WO2023190410A1 - Compound, polymerizable composition, cured product, color filter, partition wall and image display device - Google Patents

Compound, polymerizable composition, cured product, color filter, partition wall and image display device Download PDF

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WO2023190410A1
WO2023190410A1 PCT/JP2023/012336 JP2023012336W WO2023190410A1 WO 2023190410 A1 WO2023190410 A1 WO 2023190410A1 JP 2023012336 W JP2023012336 W JP 2023012336W WO 2023190410 A1 WO2023190410 A1 WO 2023190410A1
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group
alkyl
aryl
groups
different groups
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PCT/JP2023/012336
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French (fr)
Japanese (ja)
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久稔 倉
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三菱ケミカル株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/58—Derivatives of thiocarboxylic acids, the doubly-bound oxygen atoms being replaced by nitrogen atoms, e.g. imino-thio ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking

Definitions

  • the present invention relates to novel O-imino-isourea compounds and polymerizable compositions containing these O-imino-isourea compounds and at least a polymerizable compound. Furthermore, the present invention relates to a cured product obtained by curing the composition, and a color filter, partition wall, and image display device containing the cured product. Specifically, for example, a polymerizable composition used for forming pixels of each color, a black matrix, and a partition material in an image display device such as a liquid crystal display or an organic electroluminescent device (OLED), and a polymerizable composition obtained by curing this polymerizable composition. The present invention relates to a cured product and an image display device including the cured product.
  • OLED organic electroluminescent device
  • a method for producing a color filter using a colored composition is to apply a pigment-dispersed colored composition onto a substrate, dry it, and then irradiate (expose) this coating film with radiation through a mask pattern.
  • a method of obtaining pixels of each color by developing and baking is known. Further, a liquid crystal display device having the obtained color filter is known.
  • display devices having a color filter on an OLED display panel for example, an OLED display device having a plurality of insulating layers and metal layers on the OLED display panel, and a black matrix and a color resist thereon, have become popular. There is. When manufacturing such an OLED display panel, it is necessary to lower the firing temperature of the black matrix, color resist, etc. because the heat resistance of the OLED element is low.
  • black matrices and color resists baked at low temperatures using conventional coloring compositions tend to have poor heat resistance and solvent resistance.
  • Thermal polymerization initiators enable the curing of low temperature curable compositions.
  • Azo compounds or peroxide compounds are known as thermal polymerization initiators that initiate polymerization of ethylenically unsaturated bonds at relatively low temperatures.
  • thermal polymerization initiators that meet stability and safety requirements.
  • the thermal polymerization initiator is required to have good stability in a pre-bake step when removing a solvent before photolithography, and high curability in a post-bake step after photolithography.
  • Patent Document 1 discloses the use of O-imino-isourea compounds having a novel structure or salts thereof as a polymerization initiator for radical polymerization, and polymerizable compositions containing these O-imino-isourea compounds. There is.
  • Patent Document 2 discloses a monomer composition comprising (a) at least one ethylenically unsaturated monomer having a ⁇ -epithiopropyl functional group; (b) optionally having two or more ⁇ -epithiopropyl functional groups. (c) an isourea-functional polymerization initiator; and (d) a catalyst that effects a reaction between ⁇ -epithiopropyl functional groups. Discloses a polymerizable composition in which the isourea-functional polymerization initiator (c) comprises at least one of O-dialkylamino-isourea and O-imino-isourea.
  • Patent Document 3 discloses a novel dual-curing crosslinking agent for low-temperature curing that is capable of simultaneous radical polymerization and urethane curing, which contains O-imino-isourea and blocked isocyanate.
  • the dual curable crosslinker is formed by blocking the isocyanate groups of aliphatic, aromatic, or cycloaliphatic polyisocyanate compounds using O-imino-isoureas.
  • Patent Document 4 discloses that a colored image-forming material containing a peroxide compound with a 10-hour half-life temperature of 90°C or higher as a thermal polymerization initiator is used, and a post-baking process is applied at 100 to 180°C after photolithography to achieve good results. This disclosure discloses manufacturing a color filter having excellent solvent resistance.
  • Patent Document 5 discloses a composition that can form a color filter that has sufficient adhesion to a substrate even when a low-temperature treatment is used that does not cause the oxidation.
  • Non-Patent Document 1 reports on the synthesis and polymerization properties of a thermal radical initiator having an O-imino-isourea structure. It has also been reported that by using these O-imino-isourea initiators, it is possible to polymerize n-butyl acrylate at temperatures lower than 100°C.
  • Non-Patent Document 2 reports a novel dual-curing crosslinking agent that has O-imino-isourea and blocked isocyanate and is capable of simultaneous radical polymerization and urethane curing.
  • the aforementioned crosslinking agents are designed for use in automotive clear coats and enable simultaneous crosslinking of radical reactions and urethane reactions at temperatures lower than the conventional 150°C, for example at 130°C.
  • Japanese Patent No. 5693565 Japanese Patent No. 5933818 International Publication No. 2017/160016
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide an O-imino-isourea compound that exhibits good curing properties even when fired at low temperatures.
  • the present invention also provides a polymerizable composition containing the O-imino-isourea compound, a cured product obtained by curing the polymerizable composition, a partition wall and a color filter made of the cured product, and an organic electroluminescence device comprising a partition wall and a color filter.
  • An object of the present invention is to provide an image display device including an organic electroluminescent device.
  • the present inventor found that a specific O-imino-isourea compound exhibits high thermosetting properties at low temperatures of 100°C or less, and found that the above problems could be solved by using it in combination with a polymerizable compound.
  • This discovery led to the completion of the present invention. That is, the gist of the present invention is as follows.
  • R 3 and R 4 are each independently C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 1 -C 20 heteroaryl, C 7 -C 15 aralkyl, or Si( CH3 ) 3 ;
  • C 1 -C 20 alkyl and C 3 -C 20 cycloalkyl in R 3 and R 4 are O, S, N(R 6 ), C(O), C(O)O, OC(O), C( O) optionally interrupted by one or more groups selected from the group consisting of S, and SC(O), F, Cl, Br, I, NO2 , SR7 , OR8 , NR9 R may have one or more same or different groups selected from the group consisting of; C 6 -C 20 aryl, C 12 -C 20 heteroaryl, and C 7 -C 15 aralkyl in R 3 and R 4 are C 1 -C 12 alkyl, C 1
  • R 1 is C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 2 -C 20 heterocycloalkyl, C 6 -C 20 aryl or C 1 to C 20 heteroaryl;
  • C 1 -C 20 alkyl, C 2 -C 20 alkenyl and C 2 -C 20 alkynyl in R 1 are one or more of the same or different O, S, N(R 6 ), C(O), C (O) may be interrupted by groups selected from the group consisting of O and OC(O) and may have one or more identical or different groups R 1a ;
  • C 3 -C 20 cycloalkyl and C 2 -C 20 heterocycloalkyl in R 1 may be interrupted by one or more C(O) groups and may contain one or more identical or different groups.
  • R 1b It may have R 1b ; C 6 -C 20 aryl and C 1 -C 20 heteroaryl in R 1 may have one or more identical or different groups R 1c ; R 1a each independently represents F, Cl, Br, I, CN, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , C(O ) NR 13 R 14 , C 3 -C 20 cycloalkyl, optionally interrupted by one or more C(O) groups, and C 6 -C 10 aryl; C 3 -C 20 cycloalkyl and C 6 -C 10 aryl in R 1a may have one or more identical or different groups R 1aa ; R 1aa is each independently selected from the group consisting of C 1 -C 12 alkyl, C 2 -C 12 alkenyl, F, Cl, Br, I, NO 2 , SR 7 , OR 8 and NR 9 R 10 ; C 1
  • Optionally interrupted by groups F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , and C(O) may have one or more same or different groups selected from the group consisting of NR 13 R 14 ;
  • R 1b is each independently from the group consisting of C 1 -C 12 alkyl, C 2 -C 12 alkenyl, F, Cl, Br, I, CN, NO 2 , SR 7 , OR 8 and NR 9 R 10 selected;
  • C 1 -C 12 alkyl in R 1b is F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , and C( O) may have one or more same or different groups selected from the group consisting of NR 13 R 14 ;
  • R 1c is each independently C 1 -C 12 alkyl, C 2 -C 12
  • R 1aa is a hydrogen atom, C 1 to C 20 alkyl, C 2 to C 20 alkenyl, C 2 to C 20 alkynyl, C 3 to C 20 cycloalkyl, C 2 to C 20 heterocycloalkyl, C 6 to C 20 Aryl, C 1 -C 20 heteroaryl, SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , C(O)NR 13 R 14 , SO 2 R 15 , or CN;
  • C 1 -C 20 alkyl, C 2 -C 20 alkenyl and C 2 -C 20 alkynyl in R 2 are one or more of the same or different O, S, N(R 6 ), C(O), C (O) may be interrupted by groups selected from the group consisting of O, and OC(O), and may have one or more identical or different groups R 2a ;
  • R 2b C 6 -C 20 aryl and C 1 -C 20 heteroaryl in R 2 may have one or more identical or different groups R 2c ;
  • R 2a is synonymous with R 1a ;
  • R 2b is synonymous with R 1b ;
  • R 2c is synonymous with R 1c ;
  • R 2 may be combined with -SR 1 to form a ring structure containing an imino carbon atom;
  • the ring structure containing the imino carbon atom includes S-(C 1 to C 20 alkylene)-X, S-(C 2 to C 20 alkenylene)-X, S-(C 3 to C 20 cycloalkylene)-X , S-(heterocycloalkylene)-X, S-(o-phenylene)-X, S-(o-xylene)-X, S-(o-phenylene-C 1 -C 12 alkylene)-X, S- (C 1 -C 12 alkylene-o-phenylene)-
  • R 2d is optionally interrupted by groups and optionally substituted by one or more groups R 2d ; Cycloalkylene and heterocycloalkylene in the ring structures containing said imino carbon atoms may be interrupted by one or more C(O) groups and substituted by one or more identical or different groups R 2e may have been; Phenylene and o-xylylene in the ring structure containing said imino carbon atoms may be substituted by one or more identical or different groups R 2f ; R 2d is each independently F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , C(O)NR 13 R 14 selected from the group consisting of C 6 -C 10 aryl and C 1 -C 20 heteroaryl; C 6 -C 10 aryl and C 1 -C 20 heteroaryl in R 2d may have one or more groups R 2da , each R 2da being independently phen
  • C 7 -C 11 aroyl in R 6 is one or more selected from the group consisting of F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy.
  • R 7 and R 8 are each independently selected from the group consisting of hydrogen atom, C 1 -C 20 alkyl, C 2 -C 20 alkanoyl, C 6 -C 10 aryl, and C 7 -C 11 aroyl;
  • C 1 -C 20 alkyl in R 7 and R 8 is one selected from the group consisting of O, S, N (C 1 -C 12 alkyl), CO, C(O)O, and OC(O);
  • Optionally interrupted by more groups, from F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl, C 6 -C 10 aryl, OH, and SH may have one or more same or different groups selected from the group;
  • the C 2 -C 20 alkanoyl in R 7 , R 8 is interrupted by one or more groups selected from the group consisting of O, S, C(O), C(O)O, and OC(O).
  • C 6 -C 10 aryl in R 7 , R 8 is selected from the group consisting of F, Cl, Br, I, C 1 -C 6 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy.
  • C7 - C11 aroyl in R7 , R8 is selected from the group consisting of F, Cl, Br, I, C1 - C10 alkyl, C1 - C10 alkoxy, and C2 - C11 acyloxy may have one or more identical or different groups;
  • R 9 and R 10 are each independently selected from the group consisting of a hydrogen atom, C 1 -C 20 alkyl, C 2 -C 20 alkanoyl, C 7 -C 11 aroyl, C 6 -C 10 aryl;
  • C 1 -C 20 alkyl in R 9 and R 10 is selected from the group consisting of O, S, N (C 1 -C 12 alkyl), C(O), C(O)O, and OC(O).
  • R 9 , R 10 may be interrupted by one or more groups selected from the group consisting of O and S, F, Cl, Br, I, OH and C may have one or more identical or different groups selected from the group consisting of 1 to C 6 alkoxy;
  • C 7 -C 11 aroyl in R 9 and R 10 is one or more selected from the group consisting of F, Cl, Br, I, C 1 -C 6 alkyl, -OH and C 1 -C 6 alkoxy.
  • C 6 -C 10 aryl in R 9 and R 10 is one or more selected from the group consisting of F, Cl, Br, I, C 1 -C 6 alkyl, -OH and C 1 -C 6 alkoxy.
  • R 9 and R 10 together with the nitrogen atom to which they are bonded may form a saturated 5-, 6-, or 7-membered nitrogen heterocycle, and the ring may be O, S, N (C 1 -C 12 alkyl), C(O), and C(O)O as ring members, and the ring has one or more C 1 may have ⁇ C 4 alkyl; each R 11 is independently selected from the group consisting of a hydrogen atom, C 1 -C 20 alkyl, and C 6 -C 20 aryl; C 1 -C 20 alkyl may be interrupted by one or more groups selected from the group consisting of O, S and C(O), and may contain one or more identical or different R 11a May have; R 11a is each independently selected from the group consisting of F, Cl, Br, I, C 3 -C 10 cycloalkyl, heterocycloalkyl, phenyl, OH, and SH; C 6 -C 20 aryl in R 11 is one or more
  • R 12 is synonymous with R 8 ;
  • R 13 and R 14 are synonymous with R 9 and R 10 ;
  • each R 15 is independently selected from the group consisting of a hydrogen atom, C 1 -C 20 alkyl, C 6 -C 10 aryl;
  • C 1 -C 20 alkyl in R 15 is 1 or 1 selected from the group consisting of O, S, N (C 1 -C 12 alkyl), C(O), C(O)O, and OC(O)
  • Optionally interrupted by more groups, from F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl, C 6 -C 10 aryl, OH, and SH may have one or more same or different groups selected from the group;
  • C 6 -C 10 aryl in R 15 is one or more same or different groups selected from the group consisting of F, Cl, Br, I, C 1 -C 6 alkyl, and C 1 -C 6 alkoxy.
  • R 16 , R 17 , R 18 and R 19 each independently consist of a hydrogen atom, C 1 -C 20 alkyl, C 2 -C 20 alkanoyl, C 6 -C 10 aryl, C 7 -C 11 aroyl selected from the group;
  • C 1 -C 20 alkyl in R 16 , R 17 , R 18 and R 19 is O, S, N (C 1 -C 12 alkyl), C(O), C(O)O, and OC(O) optionally interrupted by one or more groups selected from the group consisting of F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl,
  • C 6 - may have one or more identical or different groups selected from the group consisting of C 10 aryl, OH, and SH;
  • the C 2 -C 20 alkanoyl in R 16 , R 17 , R 18 , R 19 is one or more selected from the group consisting of O, S
  • C 6 -C 10 aryl in R 16 , R 17 , R 18 , R 19 is selected from F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy may have one or more same or different groups selected from the group;
  • C 7 -C 11 aroyl in R 16 , R 17 , R 18 , R 19 is selected from F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy may have one or more identical or different groups selected from the group consisting of;
  • L 1 is a divalent linker when n is 2, and the linker is L 1a -C 1 -C 30 alkylene-L 1a , L 2a -C 1 -C 30 alkenylene-L 2a , L 1a -C 3 -C 16
  • R L1 is each independently selected from F, Cl, Br, I, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, and C 2 -C 11 acyloxy;
  • R 6 in L 1b and L 1c has the same meaning as R 6 ;
  • L 2 is a divalent linker when n is 2, and the linker is a single bond, L 2a -C 1 -C 30 alkylene-L 2a , L 2a -C 1 -C 30 alkenylene-L 2a , L 2a -C 6 -C 20 arylene- L 2a , L 2a -C 6 -C 20 arylene-L 2b -C 6 -C 20 arylene-L 2a ;
  • the alkylene and alkenylene in the divalent linker of L2 may each be independently interrupted by one or more identical or different groups L2c ;
  • the arylene and heteroarylene in the divalent linker of L2 may each independently have one or
  • R L2 is each independently selected from F, Cl, Br, I, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, and C 2 -C 11 acyloxy;
  • R 6 in L 2b and L 2c has the same meaning as R 6 ;
  • L 3 is a divalent linker when n is 2, and the linker is L 3a -C 1 -C 30 alkylene-L 3a , L 3a -C 3 -C 16 cycloalkylene-L 3a , L 3a -C 6 -C 20 arylene-L 3a , L 3a -C 1 -C 20 alkylene-L 3b -C 6 -C 16 cycloalkylene-L 3a , L 3a -C 6 -C 16 cycloalkylene-L 3b -C 6 -C 16 cycloalkylene-L 3a , L 3a -C 6 -C 20 cycloalkylene-L 3a
  • R 1 is C 1 to C 20 alkyl.
  • R2 is C1 - C20 alkyl, C6 -C10 aryl; C 10 aryl, or C 6 -C 10 aryl substituted with one or more identical or different C 1 -C 12 alkyl; R 3 and R 4 are each independently C 1 -C 6 alkyl, C 5 -C 12 cycloalkyl, C 6 -C 10 aryl, or C 6 -C 10 aryl substituted by one or more identical or different C 1 -C 6 alkyl; R 5 is The compound according to [1] or [2] above, which is hydrogen.
  • a polymerizable composition comprising (A) the compound described in any one of [1] to [7] above and (B) a polymerizable compound. [9] The polymerizable composition according to [8] above, further comprising (C) an alkali-soluble resin. [10] The polymerizable composition according to [8] or [9] above, further comprising (D) a photopolymerization initiator. [11] The polymerizable composition according to any one of [8] to [10] above, wherein the polymerizable compound (B) contains a (meth)acrylate compound. [12] A cured product obtained by curing the polymerizable composition according to any one of [8] to [11] above.
  • a color filter comprising the cured product according to [12] above.
  • a partition wall comprising the cured product according to [12] or [13] above.
  • An image display device comprising the cured product according to any one of [12] to [14] above.
  • Step (2) A step of exposing at least a portion of the coating film formed in step (1).
  • Step (3) A step of developing the coating film exposed in step (2).
  • Step (4) A step of baking the coating film developed in step (3).
  • total solid content means all components other than the solvent in the polymerizable composition, and even if the components other than the solvent are liquid at room temperature, they are not included in the solvent, and the total solid content is Include in minutes.
  • a numerical range expressed using " ⁇ ” means a range that includes the numerical values written before and after " ⁇ " as lower and upper limits.
  • a and/or B means one or both of A and B, and specifically means A, B, or A and B.
  • the term “(co)polymer” includes both a single polymer (homopolymer) and a copolymer (copolymer), and "polybasic acid (anhydride)” , means “polybasic acid and/or polybasic acid anhydride”.
  • the weight average molecular weight means the weight average molecular weight (Mw) in terms of polystyrene measured by GPC (gel permeation chromatography).
  • the acid value refers to the acid value in terms of effective solid content, and is calculated by neutralization titration.
  • a partition wall material refers to a bank material, a wall material, and a wall material
  • a partition wall refers to a bank, a wall, and a wall.
  • the light emitting section refers to a section that emits light when electrical energy is applied.
  • n is an integer of 1 to 4, and R 3 and R 4 are each independently C 1 to C 20 alkyl, C 3 to C 20 cycloalkyl, C 6 to C 20 aryl, C 1 to C 20 heteroaryl, C 7 -C 15 aralkyl, or Si(CH 3 ) 3 and L 1 , L 2 and L 3 are linkers.
  • L 1 is R 1
  • L 2 is R 2 and L 3 is R 5
  • L 1 is a linker
  • L 2 is R 2 and L 3 is R 5 .
  • L1 is R1 and L3 is R5 .
  • L 3 is a linker, L 1 is R 1 and L 2 is R 2 . Details of R 3 , R 4 , L 1 , L 2 and L 3 are explained in the embodiments in the text below. More specifically, there are the following aspects.
  • the compound of the first aspect of the present invention is a compound represented by the following formula (I), (II), (III) or (IV). Note that the compound of the first aspect of the present invention and the compounds of the second to fourth aspects of the present invention described below may be collectively referred to as "compound of the present invention.”
  • n is 2, 3 or 4;
  • R 1 is C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 2 -C 20 heterocycloalkyl, C 6 -C 20 aryl or C 1 to C 20 heteroaryl;
  • C 1 -C 20 alkyl, C 2 -C 20 alkenyl and C 2 -C 20 alkynyl in R 1 are one or more of the same or different O, S, N(R 6 ), C(O), C (O) may be interrupted by groups selected from the group consisting of O and OC(O) and may have one or more identical or different groups R 1a ;
  • C 3 -C 20 cycloalkyl and C 2 -C 20 heterocycloalkyl in R 1 may be interrupted by one or more C(O) groups and may contain one or more identical or different groups.
  • R 1b It may have R 1b ; C 6 -C 20 aryl and C 1 -C 20 heteroaryl in R 1 may have one or more identical or different groups R 1c ; R 1a each independently represents F, Cl, Br, I, CN, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , C(O ) NR 13 R 14 , C 3 -C 20 cycloalkyl, optionally interrupted by one or more C(O) groups, and C 6 -C 10 aryl; C 3 -C 20 cycloalkyl and C 6 -C 10 aryl in R 1a may have one or more identical or different groups R 1aa ; R 1aa is each independently selected from the group consisting of C 1 -C 12 alkyl, C 2 -C 12 alkenyl, F, Cl, Br, I, NO 2 , SR 7 , OR 8 and NR 9 R 10 ; C 1
  • Optionally interrupted by groups F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , and C(O) may have one or more same or different groups selected from the group consisting of NR 13 R 14 ;
  • R 1b is each independently from the group consisting of C 1 -C 12 alkyl, C 2 -C 12 alkenyl, F, Cl, Br, I, CN, NO 2 , SR 7 , OR 8 and NR 9 R 10 selected;
  • C 1 -C 12 alkyl in R 1b is F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , and C( O) may have one or more same or different groups selected from the group consisting of NR 13 R 14 ;
  • R 1c is each independently C 1 -C 12 alkyl, C 2 -C 12
  • R 1aa is a hydrogen atom, C 1 to C 20 alkyl, C 2 to C 20 alkenyl, C 2 to C 20 alkynyl, C 3 to C 20 cycloalkyl, C 2 to C 20 heterocycloalkyl, C 6 to C 20 Aryl, C 1 -C 20 heteroaryl, SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , C(O)NR 13 R 14 , SO 2 R 15 , or CN;
  • C 1 -C 20 alkyl, C 2 -C 20 alkenyl and C 2 -C 20 alkynyl in R 2 are one or more of the same or different O, S, N(R 6 ), C( O), C(O)O, and OC(O), and may have one or more identical or different groups R2a ;
  • C 3 -C 20 cycloalkyl and C 2 -C 20 is a hydrogen atom, C 1 to C
  • R 2b C 6 -C 20 aryl and C 1 -C 20 heteroaryl in R 2 may have one or more identical or different groups R 2c ;
  • R 2a is synonymous with R 1a ;
  • R 2b is synonymous with R 1b ;
  • R 2c is synonymous with R 1c ;
  • R 2 may be combined with -SR 1 to form a ring structure containing an imino carbon atom;
  • the ring structure containing the imino carbon atom includes S-(C 1 to C 20 alkylene)-X, S-(C 2 to C 20 alkenylene)-X, S-(C 3 to C 20 cycloalkylene)-X , S-(heterocycloalkylene)-X, S-(o-phenylene)-X, S-(o-xylene)-X, S-(o-phenylene-C 1 -C 12 alkylene)-X, S- (C 1 -C 12 alkylene-o-phenylene)-
  • R 2d is each independently F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , C(O)NR 13 R 14 selected from the group consisting of C 6 -C 10 aryl and C 1 -C 20 heteroaryl; C 6 -C 10 aryl and C 1 -C 20 heteroaryl in R 2d may have one or more groups R 2da , each R 2da being independently phenoxy, and R 1aa selected
  • C 7 -C 11 aroyl in R 6 is one or more selected from the group consisting of F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy.
  • R 7 and R 8 are each independently selected from the group consisting of hydrogen atom, C 1 -C 20 alkyl, C 2 -C 20 alkanoyl, C 6 -C 10 aryl, and C 7 -C 11 aroyl;
  • C 1 -C 20 alkyl in R 7 and R 8 is one selected from the group consisting of O, S, N (C 1 -C 12 alkyl), CO, C(O)O, and OC(O);
  • Optionally interrupted by more groups, from F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl, C 6 -C 10 aryl, OH, and SH may have one or more same or different groups selected from the group;
  • the C 2 -C 20 alkanoyl in R 7 , R 8 is interrupted by one or more groups selected from the group consisting of O, S, C(O), C(O)O, and OC(O).
  • C 6 -C 10 aryl in R 7 , R 8 is selected from the group consisting of F, Cl, Br, I, C 1 -C 6 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy.
  • C7 - C11 aroyl in R7 , R8 is selected from the group consisting of F, Cl, Br, I, C1 - C10 alkyl, C1 - C10 alkoxy, and C2 - C11 acyloxy may have one or more identical or different groups;
  • R 9 and R 10 are each independently selected from the group consisting of hydrogen atom, C 1 -C 20 alkyl, C 2 -C 20 alkanoyl, C 7 -C 11 aroyl, C 6 -C 10 aryl; 9 , C 1 -C 20 alkyl in R 10 is selected from the group consisting of O, S, N (C 1 -C 12 alkyl), C(O), C(O)O, and OC(O).
  • R 9 , R 10 may be interrupted by one or more groups selected from the group consisting of O and S, F, Cl, Br, I, OH and C may have one or more identical or different groups selected from the group consisting of 1 to C 6 alkoxy;
  • C 7 -C 11 aroyl in R 9 and R 10 is one or more selected from the group consisting of F, Cl, Br, I, C 1 -C 6 alkyl, -OH and C 1 -C 6 alkoxy.
  • C 6 -C 10 aryl in R 9 and R 10 is one or more selected from the group consisting of F, Cl, Br, I, C 1 -C 6 alkyl, -OH and C 1 -C 6 alkoxy.
  • R 9 and R 10 together with the nitrogen atom to which they are bonded may form a saturated 5-, 6-, or 7-membered nitrogen heterocycle, and the ring may be O, S, N (C 1 -C 12 alkyl), C(O), and C(O)O as ring members, and the ring has one or more C 1 may have ⁇ C 4 alkyl; each R 11 is independently selected from the group consisting of a hydrogen atom, C 1 -C 20 alkyl, and C 6 -C 20 aryl; C 1 -C 20 alkyl may be interrupted by one or more groups selected from the group consisting of O, S and C(O), and may contain one or more identical or different R 11a May have; R 11a is each independently selected from the group consisting of F, Cl, Br, I, C 3 -C 10 cycloalkyl, heterocycloalkyl, phenyl, OH, and SH; C 6 -C 20 aryl in R 11 is one or more
  • R 12 is synonymous with R 8 ;
  • R 13 and R 14 are synonymous with R 9 and R 10 ;
  • each R 15 is independently selected from the group consisting of a hydrogen atom, C 1 -C 20 alkyl, C 6 -C 10 aryl;
  • C 1 -C 20 alkyl in R 15 is 1 or 1 selected from the group consisting of O, S, N (C 1 -C 12 alkyl), C(O), C(O)O, and OC(O)
  • Optionally interrupted by more groups, from F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl, C 6 -C 10 aryl, OH, and SH may have one or more same or different groups selected from the group;
  • C 6 -C 10 aryl in R 15 is one or more same or different groups selected from the group consisting of F, Cl, Br, I, C 1 -C 6 alkyl, and C 1 -C 6 alkoxy.
  • R 16 , R 17 , R 18 and R 19 each independently consist of a hydrogen atom, C 1 -C 20 alkyl, C 2 -C 20 alkanoyl, C 6 -C 10 aryl, C 7 -C 11 aroyl selected from the group;
  • C 1 -C 20 alkyl in R 16 , R 17 , R 18 and R 19 is O, S, N (C 1 -C 12 alkyl), C(O), C(O)O, and OC(O) optionally interrupted by one or more groups selected from the group consisting of F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl,
  • C 6 - may have one or more identical or different groups selected from the group consisting of C 10 aryl, OH, and SH;
  • the C 2 -C 20 alkanoyl in R 16 , R 17 , R 18 , R 19 is one or more selected from the group consisting of O, S
  • C 6 -C 10 aryl in R 16 , R 17 , R 18 , R 19 is selected from F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy may have one or more same or different groups selected from the group;
  • C 7 -C 11 aroyl in R 16 , R 17 , R 18 , R 19 is selected from F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy may have one or more identical or different groups selected from the group consisting of;
  • L 1 is a divalent linker when n is 2, and the linker is L 1a -C 1 -C 30 alkylene-L 1a , L 2a -C 1 -C 30 alkenylene-L 2a , L 1a -C 3 -C 16
  • R L1 is each independently selected from F, Cl, Br, I, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, and C 2 -C 11 acyloxy;
  • R 6 in L 1b and L 1c has the same meaning as R 6 ;
  • L 2 is a divalent linker when n is 2, and the linker is a single bond, L 2a -C 1 -C 30 alkylene-L 2a , L 2a -C 1 -C 30 alkenylene-L 2a , L 2a -C 6 -C 20 arylene- L 2a , L 2a -C 6 -C 20 arylene-L 2b -C 6 -C 20 arylene-L 2a ;
  • the alkylene and alkenylene in the divalent linker of L2 may each be independently interrupted by one or more identical or different groups L2c ;
  • the arylene and heteroarylene in the divalent linker of L2 may each independently have one or
  • R L2 is each independently selected from F, Cl, Br, I, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, and C 2 -C 11 acyloxy;
  • R 6 in L 2b and L 2c has the same meaning as R 6 ;
  • L 3 is a divalent linker when n is 2, and the linker is L 3a -C 1 -C 30 alkylene-L 3a , L 3a -C 3 -C 16 cycloalkylene-L 3a , L 3a -C 6 -C 20 arylene-L 3a , L 3a -C 1 -C 20 alkylene-L 3b -C 6 -C 16 cycloalkylene-L 3a , L 3a -C 6 -C 16 cycloalkylene-L 3b -C 6 -C 16 cycloalkylene-L 3a , L 3a -C 6 -C 20 cycloalkylene-L 3a
  • R 6 in L 3b and L 3c has the same meaning as R 6 ;
  • R 16 in L 3a has the same meaning as;
  • L 1 and L 2 are trivalent linkers when n is 3, and the linker is a C 1 -C 30 alkanetriyl, a C 2 -C 30 alkenetriyl, a C 3 -C 16 cycloalkanetriyl.
  • the compound of the second aspect of the present invention is a compound represented by the following formula (I) or (II).
  • R 1 is C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 2 -C 20 heterocycloalkyl, C 6 -C 20 aryl or C 1 to C 20 heteroaryl;
  • C 1 -C 20 alkyl, C 2 -C 20 alkenyl and C 2 -C 20 alkynyl in R 1 are one or more of the same or different O, S, N(R 6 ), C(O), C (O) may be interrupted by groups selected from the group consisting of O and OC(O) and may have one or more identical or different groups R 1a ;
  • C 3 -C 20 cycloalkyl and C 2 -C 20 heterocycloalkyl in R 1 may be interrupted by one or more C(O) groups and may contain one or more identical or different groups.
  • R 1b It may have R 1b ; C 6 -C 20 aryl and C 1 -C 20 heteroaryl in R 1 may have one or more identical or different groups R 1c ; R 1a each independently represents F, Cl, Br, I, CN, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , C(O ) NR 13 R 14 , C 3 -C 20 cycloalkyl, optionally interrupted by one or more C(O) groups, and C 6 -C 10 aryl; C 3 -C 20 cycloalkyl and C 6 -C 10 aryl in R 1a may have one or more identical or different groups R 1aa ; R 1aa is each independently selected from the group consisting of C 1 -C 12 alkyl, C 2 -C 12 alkenyl, F, Cl, Br, I, NO 2 , SR 7 , OR 8 and NR 9 R 10 ; C 1
  • Optionally interrupted by groups F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , and C(O) may have one or more same or different groups selected from the group consisting of NR 13 R 14 ;
  • R 1b is each independently from the group consisting of C 1 -C 12 alkyl, C 2 -C 12 alkenyl, F, Cl, Br, I, CN, NO 2 , SR 7 , OR 8 and NR 9 R 10 selected;
  • C 1 -C 12 alkyl in R 1b is F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , and C( O) may have one or more same or different groups selected from the group consisting of NR 13 R 14 ;
  • R 1c is each independently C 1 -C 12 alkyl, C 2 -C 12
  • R 1aa is a hydrogen atom, C 1 to C 20 alkyl, C 2 to C 20 alkenyl, C 2 to C 20 alkynyl, C 3 to C 20 cycloalkyl, C 2 to C 20 heterocycloalkyl, C 6 to C 20 Aryl, C 1 -C 20 heteroaryl, SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , C(O)NR 13 R 14 , SO 2 R 15 , or CN;
  • C 1 -C 20 alkyl, C 2 -C 20 alkenyl and C 2 -C 20 alkynyl in R 2 are one or more of the same or different O, S, N(R 6 ), C(O), C (O) may be interrupted by groups selected from the group consisting of O, and OC(O), and may have one or more identical or different groups R 2a ;
  • R 2b C 6 -C 20 aryl and C 1 -C 20 heteroaryl in R 2 may have one or more identical or different groups R 2c ;
  • R 2a is synonymous with R 1a ;
  • R 2b is synonymous with R 1b ;
  • R 2c is synonymous with R 1c ;
  • R 2 may be combined with -SR 1 to form a ring structure containing an imino carbon atom;
  • the ring structure containing the imino carbon atom includes S-(C 1 to C 20 alkylene)-X, S-(C 2 to C 20 alkenylene)-X, S-(C 3 to C 20 cycloalkylene)-X , S-(heterocycloalkylene)-X, S-(o-phenylene)-X, S-(o-xylene)-X, S-(o-phenylene-C 1 -C 12 alkylene)-X, S- (C 1 -C 12 alkylene-o-phenylene)-
  • R 2d is optionally interrupted by groups and optionally substituted by one or more groups R 2d ; Cycloalkylene and heterocycloalkylene in the ring structures containing said imino carbon atoms may be interrupted by one or more C(O) groups and substituted by one or more identical or different groups R 2e may have been; Phenylene and o-xylylene in the ring structure containing said imino carbon atoms may be substituted by one or more identical or different groups R 2f ; R 2d is each independently F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , C(O)NR 13 R 14 selected from the group consisting of C 6 -C 10 aryl and C 1 -C 20 heteroaryl; C 6 -C 10 aryl and C 1 -C 20 heteroaryl in R 2d may have one or more groups R 2da , each R 2da being independently phen
  • C 7 -C 11 aroyl in R 6 is one or more selected from the group consisting of F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy.
  • R 7 and R 8 are each independently selected from the group consisting of hydrogen atom, C 1 -C 20 alkyl, C 2 -C 20 alkanoyl, C 6 -C 10 aryl, and C 7 -C 11 aroyl;
  • C 1 -C 20 alkyl in R 7 and R 8 is one selected from the group consisting of O, S, N (C 1 -C 12 alkyl), CO, C(O)O, and OC(O);
  • Optionally interrupted by more groups, from F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl, C 6 -C 10 aryl, OH, and SH may have one or more same or different groups selected from the group;
  • the C 2 -C 20 alkanoyl in R 7 , R 8 is interrupted by one or more groups selected from the group consisting of O, S, C(O), C(O)O, and OC(O).
  • C 6 -C 10 aryl in R 7 , R 8 is selected from the group consisting of F, Cl, Br, I, C 1 -C 6 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy.
  • C7 - C11 aroyl in R7 , R8 is selected from the group consisting of F, Cl, Br, I, C1 - C10 alkyl, C1 - C10 alkoxy, and C2 - C11 acyloxy may have one or more identical or different groups;
  • R 9 and R 10 are each independently selected from the group consisting of a hydrogen atom, C 1 -C 20 alkyl, C 2 -C 20 alkanoyl, C 7 -C 11 aroyl, C 6 -C 10 aryl;
  • C 1 -C 20 alkyl in R 9 and R 10 is selected from the group consisting of O, S, N (C 1 -C 12 alkyl), C(O), C(O)O, and OC(O).
  • R 9 , R 10 may be interrupted by one or more groups selected from the group consisting of O and S, F, Cl, Br, I, OH and C may have one or more identical or different groups selected from the group consisting of 1 to C 6 alkoxy;
  • C 7 -C 11 aroyl in R 9 and R 10 is one or more selected from the group consisting of F, Cl, Br, I, C 1 -C 6 alkyl, -OH and C 1 -C 6 alkoxy.
  • C 6 -C 10 aryl in R 9 and R 10 is one or more selected from the group consisting of F, Cl, Br, I, C 1 -C 6 alkyl, -OH and C 1 -C 6 alkoxy.
  • R 9 and R 10 together with the nitrogen atom to which they are bonded may form a saturated 5-, 6-, or 7-membered nitrogen heterocycle, and the ring may be O, S, N (C 1 -C 12 alkyl), C(O), and C(O)O as ring members, and the ring has one or more C 1 may have ⁇ C 4 alkyl; each R 11 is independently selected from the group consisting of a hydrogen atom, C 1 -C 20 alkyl, and C 6 -C 20 aryl; C 1 -C 20 alkyl may be interrupted by one or more groups selected from the group consisting of O, S and C(O), and may contain one or more identical or different R 11a May have; R 11a is each independently selected from the group consisting of F, Cl, Br, I, C 3 -C 10 cycloalkyl, heterocycloalkyl, phenyl, OH, and SH; C 6 -C 20 aryl in R 11 is one or more
  • R 12 is synonymous with R 8 ;
  • R 13 and R 14 are synonymous with R 9 and R 10 ;
  • each R 15 is independently selected from the group consisting of a hydrogen atom, C 1 -C 20 alkyl, C 6 -C 10 aryl;
  • C 1 -C 20 alkyl in R 15 is 1 or 1 selected from the group consisting of O, S, N (C 1 -C 12 alkyl), C(O), C(O)O, and OC(O)
  • Optionally interrupted by more groups, from F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl, C 6 -C 10 aryl, OH, and SH may have one or more same or different groups selected from the group;
  • C 6 -C 10 aryl in R 15 is one or more same or different groups selected from the group consisting of F, Cl, Br, I, C 1 -C 6 alkyl, and C 1 -C 6 alkoxy.
  • R 16 , R 17 , R 18 and R 19 each independently consist of a hydrogen atom, C 1 -C 20 alkyl, C 2 -C 20 alkanoyl, C 6 -C 10 aryl, C 7 -C 11 aroyl selected from the group;
  • C 1 -C 20 alkyl in R 16 , R 17 , R 18 and R 19 is O, S, N (C 1 -C 12 alkyl), C(O), C(O)O, and OC(O) optionally interrupted by one or more groups selected from the group consisting of F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl,
  • C 6 - may have one or more identical or different groups selected from the group consisting of C 10 aryl, OH, and SH;
  • the C 2 -C 20 alkanoyl in R 16 , R 17 , R 18 , R 19 is one or more selected from the group consisting of O, S
  • C 6 -C 10 aryl in R 16 , R 17 , R 18 , R 19 is selected from F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy may have one or more same or different groups selected from the group;
  • C 7 -C 11 aroyl in R 16 , R 17 , R 18 , R 19 is selected from F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy may have one or more identical or different groups selected from the group consisting of;
  • L 1 is a divalent linker, and the linker is L 1a -C 1 -C 30 alkylene-L 1a , L 2a -C 1 -C 30 alkenylene-L 2a , L 1a -C 3 -C 16 cycloal
  • R L1 is each independently selected from F, Cl, Br, I, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, and C 2 -C 11 acyloxy;
  • R 6 in L 1b and L 1c has the same meaning as R 6 .
  • the compound of the third aspect of the present invention is a compound represented by the following formula (I).
  • R 1 is C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, or C 6 -C 10 aryl;
  • C 1 -C 20 alkyl in R 1 is selected from the group consisting of one or more same or different O, S, N(R 6 ), C(O), C(O)O and OC(O) one or more identical or different groups R 1a may have;
  • C 3 -C 20 cycloalkyl in R 1 may be interrupted by one or more C(O) groups and may carry one or more identical or different groups R 1b ;
  • the C 6 -C 10 aryl in R 1 may carry one or more identical or different groups R 1c ;
  • R 1a each independently represents F, Cl, Br, I, CN, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , C(O ) NR 13 R 14 selected from the group consisting of C 3 -C 20
  • Optionally interrupted by groups F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , and C(O) may have one or more same or different groups selected from the group consisting of NR 13 R 14 ;
  • R 1b is each independently from the group consisting of C 1 -C 12 alkyl, C 2 -C 12 alkenyl, F, Cl, Br, I, CN, NO 2 , SR 7 , OR 8 and NR 9 R 10 selected;
  • C 1 -C 12 alkyl in R 1b is F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , and C( O) may have one or more same or different groups selected from the group consisting of NR 13 R 14 ;
  • R 1c is each independently C 1 -C 12 alkyl, C 2 -C 12
  • R 1aa is a hydrogen atom, C 1 to C 20 alkyl, C 6 to C 20 aryl, SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , C(O) NR 13 R 14 , SO 2 R 15 , or CN;
  • C 1 -C 20 alkyl in R 2 is from the group consisting of one or more of the same or different O, S, N(R 6 ), C(O), C(O)O, and OC(O).
  • R 2a may be interrupted by selected groups and may have one or more identical or different groups R 2a ; C 6 -C 20 aryl in R 2 may have one or more identical or different groups R 2c ; R 2a is synonymous with R 1a ; R 2c is synonymous with R 1c ; R 3 and R 4 are each independently represented by C 1 -C 6 alkyl, C 5 -C 12 cycloalkyl, C 6 -C 10 aryl, one or more of the same or different C 1 -C 6 alkyl; is a substituted C6 - C10 aryl, or Si( CH3 ) 3 ; R5 is a hydrogen atom, C(O) -C1 - C20 alkyl, -C(O) -C6 - C10 aryl, -C(O)O-C 1 -C 20 alkyl, -C(O)NH-C 1 -C 20 alkyl, or -C(O)NH-C 6 -C 10 ary
  • C 6 -C 10 aryl in R 6 is one or more selected from the group consisting of F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy.
  • R 7 and R 8 are each independently selected from the group consisting of hydrogen atom, C 1 -C 20 alkyl, C 2 -C 20 alkanoyl, C 6 -C 10 aryl, and C 7 -C 11 aroyl;
  • C 1 -C 20 alkyl in R 7 and R 8 is one selected from the group consisting of O, S, N (C 1 -C 12 alkyl), CO, C(O)O, and OC(O); one or more identical or different groups selected from the group consisting of F, Cl, Br, I, C6 - C10 aryl, OH, and SH, which may be interrupted by more groups.
  • the C 2 -C 20 alkanoyl in R 7 , R 8 is interrupted by one or more groups selected from the group consisting of O, S, C(O), C(O)O, and OC(O). may have one or more same or different groups selected from the group consisting of F, Cl, Br, I, and C 6 -C 10 aryl; C 6 -C 10 aryl in R 7 and R 8 is one or more identical groups selected from the group consisting of F, Cl, Br, I, C 1 -C 6 alkyl, and C 1 -C 6 alkoxy.
  • C7 - C11 aroyl in R7 , R8 is selected from the group consisting of F, Cl, Br, I, C1 - C10 alkyl, C1 - C10 alkoxy, and C2 - C11 acyloxy may have one or more identical or different groups;
  • R 9 and R 10 are each independently selected from the group consisting of hydrogen atom, C 1 -C 20 alkyl, C 6 -C 10 aryl;
  • C 1 -C 20 alkyl in R 9 and R 10 is selected from the group consisting of O, S, N (C 1 -C 12 alkyl), C(O), C(O)O, and OC(O).
  • C 6 -C 10 aryl in R 9 , R 10 is selected from the group consisting of F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy.
  • R 9 and R 10 together with the nitrogen atom to which they are bonded may form a saturated 5-, 6-, or 7-membered nitrogen heterocycle, and the ring may be O, S, N (C 1 -C 12 alkyl), C(O), and C(O)O as ring members, and the ring has one or more C 1 ⁇ C4 alkyl; each independently selected from the group consisting of hydrogen atoms, C1 - C20 alkyl and C6 - C20 aryl; C 1 -C 20 alkyl may be interrupted by one or more groups selected from the group consisting of O, S and C(O), and may contain one or more identical or different R 11a May have; R 11a is each independently selected from the group consisting of F, Cl, Br, I, C 3 -C 10 cycloalkyl, heterocycloalkyl, phenyl, OH, and SH; R 12 is synonymous with R 8 ; R 13 and R 14 are synonymous with R 9 and R
  • the compound of the fourth aspect of the present invention is a compound represented by the following formula (I).
  • R 1 is C 1 -C 20 alkyl, C 6 -C 10 aryl, or C 6 -C 10 aryl substituted with one or more of the same or different C 1 -C 12 alkyl
  • R 2 is C 1 -C 20 alkyl, C 6 -C 10 aryl, or C 6 -C 10 aryl substituted with one or more of the same or different C 1 -C 12 alkyl
  • R 3 and R 4 are each independently C 1 -C 6 alkyl, C 5 -C 12 cycloalkyl, C 6 -C 10 aryl, or one or more of the same or different C 1 -C 6 alkyl C 6 -C 10 aryl substituted by
  • R 5 is hydrogen.
  • alkyl in the present invention usually refers to a saturated straight or branched hydrocarbon having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms. Refers to the base.
  • alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, neo-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, and n-eicosyl
  • Alkyl may be interrupted by one or more identical or different groups selected from O, S, N(R 6 ), C(O), C(O)O, and OC(O). good. When multiple O, S, N(R 6 ), C(O), C(O)O, and OC(O) are present, they are usually separated from each other by at least one methylene group. There is. R 6 is as defined above.
  • alkyl interrupted by one or more O atoms are -CH 2 -O-CH 3 , -CH 2 CH 2 -O-CH 2 CH 3 , -[CH 2 CH 2 O] y -CH 3 (y is 1 to 9), -(CH 2 CH 2 O) y CH 2 CH 3 (y is 1 to 9), -CH 2 -CH(CH 3 )-O-CH 2 -CH 2 CH 3 , -CH 2 -CH 2 CH (CH 3 ) -O-CH 2 -CH 2 CH 3 , -CH 2 -CH 2 CH (CH 3 ) -O-CH 2 CH 3 , -CH 2 -CH2CH ( CH3 ) -O - CH3 and -CH2CH ( CH3 )-O- CH2CH3 .
  • alkenyl in the present invention refers to a monomer having 2 to 20, preferably 2 to 12, more preferably 2 to 10 carbon atoms and having one or more double bonds. It is a saturated or polyunsaturated linear or branched hydrocarbon group.
  • alkenyl having one double bond examples include ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl- 1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, alkadienyl having 4 or more carbon atoms and having two double bonds in any position, such as 1,3-butadienyl , 1,3-pentadienyl, hexa-1,4-dien-1-yl, hexa-1,4-dien-3-yl, hexa-1,4-dien-6-yl, hepta-1,4-diene -7-yl, hepta-1,5-dien-1-yl, etc.
  • alkynyl in the present invention refers to an unsaturated group having usually 2 to 20, preferably 2 to 12, more preferably 2 to 10 carbon atoms and one or more triple bonds. It is a straight or branched hydrocarbon group.
  • ethenyl, propargyl (2-propyn-1-yl), 1-propyn-1-yl, 1-methylprop-2-yn-1-yl, 2-butyn-1-yl, 3-butyn-1-yl Refers to 1-pentyn-1-yl, 3-pentyn-1-yl, 4-pentyn-1-yl, 1-methylbuty-2-yn-1-yl, 1-ethylprop-2-yn-1-yl, etc. .
  • cycloalkyl in the present invention refers to a monocyclic or polycyclic aliphatic group having usually 3 to 20 carbon atoms, preferably 3 to 16 carbon atoms, and more preferably 3 to 12 carbon atoms. Point.
  • Examples of the monocyclic aliphatic group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, with cyclopentyl and cyclohexyl being particularly preferred.
  • polycyclic ring examples include perhydroanthracil, perhydronaphthyl, perhydrofluorenyl, perhydrochrysenyl, perhydropicenyl, adamantyl, bicyclo[1.1.1]pentyl, bicyclo[ 2.2.1]heptyl, bicyclo[4.2.2]decyl, bicyclo[2.2.2]octyl, bicyclo[3.3.0]octyl, bicyclo[3.3.2]decyl, bicyclo[ 4.4.0] decyl, bicyclo [4.3.2] undecyl, bicyclo [4.3.3] dodecyl, bicyclo [3.3.3] undecyl, bicyclo [4.3.1] decyl, bicyclo [ 4.2.1]nonyl, bicyclo[3.3.1]nonyl, and bicyclo[3.2.1]octyl. Cycloalkyl may be interrupted by one or more C(O) groups.
  • heterocycloalkyl in the present invention refers generally to 3- to 8-membered, especially 5-, 6-, 7- or 8-membered monocyclic heterocyclic non-aromatic groups as well as bicyclic heterocycles.
  • the formula refers to a non-aromatic group.
  • the monocyclic and bicyclic non-aromatic groups mentioned above may be saturated or unsaturated.
  • Said monocyclic and bicyclic heterocyclic non-aromatic groups usually also contain 1, 2, 3 or 4 heteroatoms selected from N, O and S, especially 1 or 2 heteroatoms as ring members, the S atom as ring member can be present as S, SO or SO2.
  • Heterocycloalkyl may be interrupted by one or more C(O) groups, usually one or two groups.
  • saturated or unsaturated 3- to 8-membered non-aromatic heterocyclic group include oxiranyl, oxetanyl, thietanyl, thietanyl-S-oxide (S-oxothietanyl), thietanyl-S-dioxide (S-dioxothietanyl), and thietanyl-S-oxide (S-oxothietanyl).
  • pyrrolidinyl pyrazolinyl, imidazolinyl, pyrrolinyl, pyrazolinyl, imidazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1,3-dioxolanyl, dioxolenyl, thiolanyl, S-oxothiolanyl, S-dioxothiolanyl, dihydrothienyl, S-oxodihydro thienyl, S-dioxodihydrothienyl, oxazolidinyl, isoxazolidinyl, oxazolinyl, isoxazolinyl, thiazolinyl, isothiazolinyl, thiazolidinyl, isothiazolidinyl, oxathiolanyl, piperidinyl, piperazinyl, pyranyl, dihydro
  • heterocyclic ring containing one or two carbonyl groups as ring members examples include pyrrolidin-2-oneyl, pyrrolidin-2,5-dioneyl, imidazolidin-2-oneyl, oxazolidin-2-oneyl, Thiazolidin-2-oneyl is mentioned.
  • aryl in the present invention refers to monovalent monocyclic aromatic groups and polycyclic aromatic groups having a ring carbon atom.
  • monocyclic aromatic groups include phenyl.
  • Polycyclic aromatic groups include, for example, bicyclic, tricyclic or tetracyclic aromatic groups such as naphthyl, phenanthrenyl, anthracenyl or pyrenyl.
  • Preferred examples of aryl are phenyl and naphthyl.
  • Substituted phenyl is substituted with 1, 2, 3, 4 or 5 substituents.
  • Naphthyl is usually substituted with 1, 2, 3, 4, 5, 6, or 7 substituents, preferably with 1, 2, 3, or 4 substituents.
  • Substituted phenyl is, for example, pentafluorophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2-methoxyphenyl, 3-methoxy Phenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl, 4-ethoxyphenyl, 3-nitrophenyl, 4-nitrophenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 3-vinylphenyl, 4 -vinylphenyl, 4-trifluoromethylphenyl, and 3,5-diethoxycarbonylphenyl.
  • heteroaryl in the present invention generally refers to unsaturated monocyclic heterocyclic groups and polycyclic heterocyclic groups that are aromatic. Heteroaryl usually contains 1, 2, 3 or 4 heteroatoms selected from N, O and S as ring members in addition to one or more carbon atoms as ring members.
  • Examples of the monocyclic heteroaromatic group include 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 1-pyrazolyl, 3-pyrazolyl, 4- Pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isoxazolyl, 4-isoxazolyl or 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl or 5-isothiazolyl, 1-imidazolyl, 2-imidazolyl, 4-imidazolyl, 2- or 5-[1,3,4]oxadiazolyl, 4- or 5-(1,2,3-oxadiazol)yl, 3- or 5-(1,2,4-oxadiazol)yl, 2- or 5-(1,3,4-thiadiazol)yl, 2- or 5-(1,3,4
  • polycyclic heterocyclic group examples include benzofuranyl, benzothienyl, indolyl, indazolyl, benzimidazolyl, benzoxathiazolyl, benzoxadiazolyl, benzothiadiazolyl, benzoxazinyl, quinolinyl, isoquinolinyl, purinyl, 1 , 8-naphthyridyl, pteridyl, pyrido[3,2-d]pyrimidyl, pyridimidazolyl, carbazoyl or acridinyl.
  • alkanoyl in the present invention is alkyl-C(O), which is a saturated straight-chain or branched alkyl group as defined above, usually having 3 to 20 carbon atoms, and which is a carbonyl group. Refers to groups bonded through a carbon atom at any position in the alkyl group, such as acetyl, propanoyl, 2-methyl-propanoyl, butanoyl, pentanoyl, hexanoyl.
  • cycloalkanoyl in the present invention is cycloalkyl-C(O), a monocyclic or polycyclic, e.g. bicyclic or tricyclic, cycloalkyl, which It refers to a group bonded at any position in a cycloalkyl group, such as cyclobutylcarbonyl, cyclopentylcarbonyl, and cyclohexylcarbonyl.
  • aroyl in the present invention is aryl-C(O), and refers to a group bonded at any position in the aryl group defined above through the carbon atom of the carbonyl group, such as benzoyl and naphthoyl.
  • alkylene (or alkanediyl) in the context of the present invention is, in each case, an alkyl group having carbon atoms as defined above, in which one hydrogen atom in any position of the alkyl group bears one further Refers to a group that, when replaced by a binding site, forms a divalent group.
  • C 1 -C 20 alkylene thus includes divalent branched or unbranched saturated aliphatic chains having 1 to 20 carbon atoms, such as -CH 2 -, -CH 2 CH 2 - , -CH ( CH3 )-, -CH2CH2CH2- , -CH( CH3 ) CH2- , -CH2CH2CH2CH2- , -CH2CH ( CH3 ) CH2 - , -CH ( CH3 ) CH( CH3 ) - , -CH2CH2CH2CH2- , -CH2CH2CH2CH( CH3 ) -, -CH2C ( CH3 ) 2 CH 2 - is mentioned.
  • alkylene may be interrupted by one or more identical or different groups selected from O, S, N(R 6 ), C(O) and C(S).
  • Said alkylene moieties may be identical or selected from, for example, 1, 2, 3, 4, 5 or more than 5, O, S, N(R 6 ), C(O) and C(S). May contain different groups.
  • R 6 is as defined above.
  • alkenylene (or alkenediyl) in the present invention refers in each case to a straight-chain or branched alkenyl radical having usually 2 to 20, preferably 2 to 12 carbon atoms as defined above. refers to a group in which one hydrogen atom at any position on its carbon skeleton is replaced by one additional bonding site to form a divalent moiety.
  • C 2 -C 20 -alkenylene thus includes divalent straight or branched aliphatic chains having 2 to 20 carbon atoms, such as vinylene, propenylene, but-1-enylene, Examples include but-2-enylene and penta-1,3-dienylene.
  • cycloalkylene in the present invention refers to a cycloalkyl group as defined above, in which one hydrogen atom at any position of the cycloalkyl is replaced by one additional bonding site, thereby forming a divalent group. refers to a group that forms In the case of polycyclic cycloalkylenes, the points of attachment are located either in the same ring or in different rings.
  • Monocyclic rings include, for example, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene or cycloheptylene, especially cyclohexylene.
  • Examples of the polycyclic ring include perhydroanthracylene, perhydronaphthylene, perhydrofluorenylene, perhydrochrysenylene, perhydropicenylene, adamantylene, bicyclo[1.1.1]pentylene, Bicyclo[2.2.1]heptylene, bicyclo[4.2.2]decylene, bicyclo[2.2.2]octylene, bicyclo[3.3.2]decylene, bicyclo[4.3.2]undecylene, Bicyclo[4.3.3]dodecylene, bicyclo[3.3.3]undecylene, bicyclo[4.3.1]decylene, bicyclo[4.2.1]nonylene, bicyclo[3.3.1]nonylene, Bicyclo[3.2.1]octylene is mentioned. Cycloalkylene may be substituted with one or more substituents, for example by C 1 -C 4 alkyl.
  • arylene (also referred to as arenediyl) in the present invention refers to an aryl group as defined above, in which one hydrogen atom at any position of the aryl group is replaced by one further bonding site, thereby forming a double bond. Refers to a group that forms a valence group. In the case of polycyclic arylenes, the points of attachment are located either in the same ring or in different rings. Examples of arylene are phenylene, naphthylene, anthracenediyl or phenanthrenediyl. If arylene is substituted by one or more substituents, it is, for example, mono-, di-, tri-, tetra- or penta-substituted or more than penta-substituted.
  • phenylene in the present invention includes 1,2-phenylene (o-phenylene or 1,2-benzenediyl), 1,3-phenylene (m-phenylene, 1,3-benzenediyl) and 1,4-phenylene (p-phenylene or 1,4-benzenediyl).
  • naphthylene in the present invention includes 1,2-naphthylene, 1,3-naphthylene, 1,4-naphthylene, 1,5-naphthylene, 1,8-naphthylene, 2,3-naphthylene and 2,7-naphthylene. refers to
  • xylylene in the present invention refers to 1,2-xylylene (1,2-methylenephenylenemethylene, 1,2-CH 2 -C 6 H 4 -CH 2 ), 1,3-xylylene (1,3-methylene Phenylenemethylene, 1,3-CH 2 -C 6 H 4 -CH 2 ) and 1,4-xylylene (1,4-methylenephenylenemethylene, 1,4-CH 2 -C 6 H 4 -CH 2 ) .
  • heteroarylene in the present invention refers to a heteroaryl group as defined above, in which one hydrogen atom at any position of the heteroaryl group is replaced by one additional bonding site, resulting in a divalent Refers to a group that forms a group.
  • the points of attachment are located either in the same ring or in different rings.
  • Heteroarylenes may be C-attached or N-attached, where possible.
  • pyrrolediyl, imidazolediyl or pyrazolediyl may be N-attached or C-attached.
  • heteroarenediyl examples include pyridinediyl, pyrimidinediyl, pyridazinediyl, 1,2,3-triazinediyl, 1,2,4-triazinediyl, 1,2,3,4-tetrazinediyl, furandiyl, thiophene
  • diyl pyrrolediyl, thiazolediyl, thiadiazolediyl, pyrazolediyl, imidazolediyl, triazolediyl, oxazolediyl, isoxazolediyl, isothiazolediyl, and oxadiazolediyl.
  • Heteroarenediyl may be optionally substituted with one or more substituents.
  • alkantriyl in the present invention refers to an alkylene group as defined above, usually having from 1 to 30 carbon atoms, in which one hydrogen atom at any position of the alkylene is replaced by an additional bonding site. Refers to a group that forms a trivalent group when replaced. Alkantriyl is therefore a trivalent, branched or unbranched, saturated aliphatic chain. Alkantriyl may be optionally substituted with one or more substituents.
  • alkenetriyl in the present invention refers to an alkenediyl group as defined above, usually having from 2 to 30 carbon atoms, in which one hydrogen atom at any position of the alkenediyl is replaced by an additional bonding site. Refers to a group that forms a trivalent group when replaced. Alkenetriyl is therefore a trivalent, branched or unbranched, unsaturated aliphatic chain. Alkenetriyl may be optionally substituted with one or more substituents.
  • cycloalkanetriyl in the present invention refers to a cycloalkylene group as defined above, in which one hydrogen atom at any position of the cycloalkylene is replaced by one additional bonding site, resulting in a trivalent refers to a group that forms a group of In the case of polycyclic cycloalkanetriyls, their points of attachment are located either in the same ring or in different rings. Cycloalkanetriyl may be optionally substituted with one or more substituents.
  • arenetriyl in the present invention refers to an arylene group as defined above, in which one hydrogen atom at any position of the arylene group is replaced by one additional bonding site, thereby forming a trivalent group. refers to a group that forms In the case of polycyclic arenetriyls, the points of attachment are located either in the same ring or in different rings. Examples of arenetriyl are 1,2,4-benzentriyl, 1,3,5-benzentriyl, 1,3,5-naphthalenetriyl, 1,4,5-naphthalenediyl, anthracentriyl or It is a phenanthrene triyl. Arenetriyl may be optionally substituted with one or more substituents.
  • heteroarylene group in the present invention refers to a heteroarylene group as defined above, in which one hydrogen atom at any position of the heteroarylene group is further replaced by one bonding site, resulting in a trivalent refers to a group that forms a group of In the case of polycyclic heteroarenetriyls, the points of attachment are located either in the same ring or in different rings.
  • Heteroarenetriyl may be C-attached or N-attached, where possible.
  • pyrroletriyl, imidazoletriyl or pyrazoletriyl may be N-attached or C-attached.
  • alkanetetryl refers to an alkanetriyl radical as defined above, having in each case normally from 1 to 30 carbon atoms, with one hydrogen atom in any position of the alkanetriyl. is replaced by one additional bonding site to form a tetravalent group.
  • Alkanetetryl is thus a tetravalent branched or unbranched saturated aliphatic chain.
  • Alkanetetrayl may be optionally substituted with one or more substituents.
  • triacyl and tetraacyl in the present invention refer to trivalent and tetravalent groups, respectively, which form bonds through three and four carbon atoms of C(O) groups.
  • the compound of the present invention also has an S-imino structure, compared to the compound having an O-imino-isourea structure described in Patent Document 1 mentioned above.
  • S-imino structure N-O cleavage occurs more easily at low temperatures, S radicals are generated from N radicals, and the reactivity of the radicals becomes higher, so the reactivity at lower temperatures increases. improves.
  • carbodiimides are commercially available, in particular, for example, N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, N,N'-bis -(o-tolyl)-carbodiimide, N,N'-bis-(p-tolyl)-carbodiimide, N,N'-bis-(2,6-diisopropylphenyl)-carbodiimide, N,N'-bis-( trimethylsilyl)-carbodiimide, N-sec-butyl-N'-ethylcarbodiimide, N-cyclohexyl-N'-[4-(dimethylamino)- ⁇ -naphthyl]-carbodiimide, N-cyclohexyl-N'-(2-morpholino ethyl)-carbodiimide, N,N'-di-ter
  • the addition reaction may be carried out by stirring a solution of the oxime and carbodiimide in a suitable solvent such as ethyl acetate, toluene, dichloromethane, acetonitrile, tetrahydrofuran, hexane, etc.
  • a suitable solvent such as ethyl acetate, toluene, dichloromethane, acetonitrile, tetrahydrofuran, hexane, etc.
  • the reaction temperature may be from below room temperature, eg -78°C, to above room temperature, eg 150°C.
  • the catalyst used in the addition reaction is, for example, a base such as an alkali metal hydroxide, alkali metal alkoxide, alkali metal amide or alkali metal hydride, or an amine such as triethylamine or DABCO, or an amidine such as, DBU or DBN etc., or Br ⁇ nsted acids such as HCl, p-TsOH, HBF4 or H 2 SO 4 or Lewis acids such as BF 3 or Cu(O 3 SCF 3 ), and the use of these catalysts can realize improved rates and yields of the addition of oximes to carbodiimides.
  • the reaction may be carried out under conditions using a phase transfer catalyst.
  • alkylating agent R 5 -X, L 3 -X n well-known compounds can be used, such as alkyl halides, cycloalkyl halides, aralkyl halides, sulfonates, triflates, trialkyloxonium salts. can be mentioned.
  • acylating agents R 5 -X, L 3 -X n well-known compounds can be used, such as acyl halides and acyl anhydrides.
  • a suitable active Michael acceptor such as acrylonitrile or an alkyl acrylate. It can also be introduced.
  • the oximes (V, V' or V'' in Schemes 1 to 3) used in the synthesis of the compounds of the present invention can be synthesized by various methods described in the literature. For example, a synthetic method using an aldehyde as a starting material as shown in the following formula (Scheme 5) is known.
  • an aldoxime can be obtained by reacting an aldehyde described in Synthesis, 50, 1640-1650, 2018 with hydroxylamine or a salt thereof in a polar solvent such as ethanol or aqueous ethanol.
  • a polar solvent such as ethanol or aqueous ethanol.
  • a base such as sodium acetate or sodium carbonate is added to control the pH of the reaction mixture. It is well known that the rate of the reaction depends on the pH and that the base can be added initially or continuously during the reaction.
  • Basic solvents such as pyridine can also be used as base and/or solvent or co-solvent.
  • the temperature of the reaction is generally the reflux temperature of the mixture, usually about 60-120°C.
  • a convenient synthesis of the oxime is to convert the above aldoxime into an oximidoyl halide and then react it with the thiol R 1 --SH.
  • Oxime (V' in Scheme 5) can be synthesized by using polyfunctional thiol L 1 -[SH] n instead of thiol R 1 -SH.
  • Oxime (V'') can be synthesized by using a polyfunctional aldehyde as a starting material.
  • a suitable oximidoyl halide such as oximidoyl chloride or oximidoyl bromide
  • a thiol as described in WO 2012/101245.
  • these reactions are usually carried out in an inert solvent such as toluene, dioxane, tetrahydrofuran (THF), diethyl ether, dichloromethane, dimethylformamide (DMF), methanol or aqueous methanol with a base such as a tertiary amine such as triethylamine. or in the presence of metal hydroxides such as NaOH, LiOH and KOH.
  • oximidoyl halides can be prepared in combination with the corresponding aldoxime and a halogenating reagent, for example J. Org. Chem. , 45, 3916-3918, 1980, N-bromosuccinimide (NBS), chlorine or bromine or t-butyl hypochlorite as described in European Publication No. 0064091, for example. It can be obtained by reaction with acid salts. These reactions are usually carried out in inert solvents such as toluene, tetrahydrofuran (THF), dimethylformamide (DMF), chloroform, dichloromethane or in polar solvents such as methanol or aqueous methanol.
  • a halogenating reagent for example J. Org. Chem. , 45, 3916-3918, 1980, N-bromosuccinimide (NBS), chlorine or bromine or t-butyl hypochlorite as described in European Publication No. 0064091, for example
  • oximidoyl chloride Another method for synthesizing oximidoyl chloride is described, for example, in J. Org. Chem. , 48, 366-372, 1983, the oximation of glycine ethyl ester hydrochloride with sodium nitrite in aqueous HCl.
  • the polymerizable composition in the present invention contains (A) an O-imino-isourea compound and (B) a polymerizable compound, and as the (A) O-imino-isourea compound, It contains at least one of the compounds of the present invention described above.
  • the polymerizable composition of the present invention may further contain other components as necessary, such as (C) an alkali-soluble resin, (D) a photoinitiator, (E) a coloring agent, and (F) a chain. It may also contain a transfer agent or the like.
  • the components constituting the polymerizable composition of the present invention and their composition will be explained.
  • the polymerizable composition of the present invention contains (A) an O-imino-isourea compound and (B) a polymerizable compound.
  • (A) O-imino-isourea compound The content of (A) O-imino-isourea compound in the polymerizable composition of the present invention is in the total solid content of the polymerizable composition. Preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.2% by mass or more, and preferably 25% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less. % by mass or less.
  • the upper and lower limits can be arbitrarily combined, for example, preferably from 0.01 to 25% by weight, more preferably from 0.05 to 15% by weight, even more preferably from 0.2 to 10% by weight.
  • O-imino-isourea compounds may be used alone or in combination of two or more.
  • the polymerizable composition of the present invention contains (B) a polymerizable compound.
  • (B) Including the polymerizable compound is considered to increase sensitivity.
  • the polymerizable compound (B) used here refers to a compound having one or more ethylenically unsaturated bonds (ethylenic double bonds) in the molecule, but from the viewpoint of polymerizability and crosslinkability, Preferably, the compound has two or more ethylenically unsaturated bonds in the molecule. Further, it is more preferable that the unsaturated bond is derived from a (meth)acryloyloxy group, that is, a (meth)acrylate compound.
  • the polymerizable composition of the present invention it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated bonds in one molecule as the polymerizable compound (B).
  • the number of ethylenically unsaturated groups that the polyfunctional ethylenic monomer has is not particularly limited, but is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, and particularly preferably 5 or more.
  • the number is preferably 15 or less, more preferably 10 or less, still more preferably 8 or less, particularly preferably 7 or less.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 2 to 15, more preferably 3 to 10, even more preferably 4 to 8, particularly preferably 5 to 7.
  • Polymerizable compounds include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds Examples include esters obtained by an esterification reaction between a polyhydric hydroxy compound such as, and an unsaturated carboxylic acid and a polybasic carboxylic acid.
  • esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate.
  • pentaerythritol tetraacrylate dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, and other aliphatic polyhydroxy compound acrylic acid esters; methacrylic acid obtained by replacing the acrylate of these compounds with methacrylate Esters; itaconate esters in which the acrylate of these compounds is replaced with itaconate; crotonate esters in which the acrylate of these compounds is replaced with cronate; and maleate esters in which the acrylate of these compounds is replaced with maleate.
  • esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic esters and methacrylates of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.
  • esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic esters and methacrylates of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate.
  • acid esters include acid esters.
  • the ester obtained by the esterification reaction of a polyhydric hydroxy compound such as an aliphatic polyhydroxy compound or an aromatic polyhydroxy compound with an unsaturated carboxylic acid or a polybasic carboxylic acid is not necessarily a single substance, but for example, , condensates of acrylic acid, phthalic acid, and ethylene glycol; condensates of acrylic acid, maleic acid, and diethylene glycol; condensates of methacrylic acid, terephthalic acid, and pentaerythritol; condensates of acrylic acid, adipic acid, butanediol, and glycerin Examples include things.
  • Examples of the polymerizable compound (B) used in the polymerizable composition of the present invention other than the above include, for example, a polyisocyanate compound and a hydroxyl group-containing (meth)acrylic ester, or a polyisocyanate compound, a polyol, and a hydroxyl group-containing (meth)acrylate ester.
  • Urethane (meth)acrylates such as those obtained by reacting acrylic esters; Epoxy acrylates such as addition reaction products of polyvalent epoxy compounds and hydroxyl group-containing (meth)acrylic esters or (meth)acrylic acid; ethylene Acrylamides such as bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate are useful.
  • urethane (meth)acrylates examples include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U- 10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B, Examples include UV-7600B, UV-7605B, UV-7630B, and UV7640B (manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd.).
  • ester (meth)acrylates or urethane (meth)acrylates as the polymerizable compound (B) from the viewpoint of sensitivity, and dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, etc.
  • acrylate 2-tris(meth)acryloyloxymethylethyl phthalate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dibasic acid anhydride adduct of dipentaerythritol penta(meth)acrylate, It is more preferable to use a dibasic acid anhydride adduct of pentaerythritol tri(meth)acrylate. These may be used alone or in combination of two or more.
  • the molecular weight of the polymerizable compound (B) is not particularly limited, but from the viewpoint of curability and taper angle, it is preferably 100 or more, more preferably 150 or more, still more preferably 200 or more, It is even more preferably 300 or more, particularly preferably 400 or more, most preferably 500 or more, and preferably 1000 or less, more preferably 700 or less.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 100 to 1000, more preferably 150 to 1000, even more preferably 200 to 1000, even more preferably 300 to 700, particularly preferably 400 to 700, and ⁇ 700 is most preferred.
  • the number of carbon atoms in the polymerizable compound is not particularly limited, but from the viewpoint of curability and taper angle, it is preferably 7 or more, more preferably 10 or more, even more preferably 15 or more, even more preferably 20 or more, and particularly preferably is 25 or more, and is preferably 50 or less, more preferably 40 or less, still more preferably 35 or less, particularly preferably 30 or less.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 7 to 50, more preferably 10 to 50, even more preferably 15 to 40, even more preferably 20 to 35, particularly preferably 25 to 30.
  • the content of the polymerizable compound (B) in the polymerizable composition of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass in the total solid content of the polymerizable composition. Above, even more preferably 30% by mass or more, particularly preferably 40% by mass or more, preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, even more preferably 55% by mass. % or less, particularly preferably 50% by mass or less.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 5 to 80% by mass, more preferably 10 to 70% by mass, even more preferably 20 to 60% by mass, and even more preferably 30 to 55% by mass. , 40 to 50% by mass is particularly preferred.
  • the content is equal to or more than the lower limit value, there is a tendency for appropriate internal curing properties to be achieved. When the amount is below the upper limit, developability tends to be improved.
  • the polymerizable composition of the present invention may contain (C) an alkali-soluble resin.
  • the alkali-soluble resin is not particularly limited as long as it can be developed with an alkaline developer.
  • Examples of the alkali-soluble resin include various resins containing a carboxyl group and/or a hydroxyl group. Among these, resins having a carboxyl group are preferred.
  • (c) Alkali-soluble resin having ethylenic double bond In the polymerizable composition of the present invention, (C) the alkali-soluble resin is (c) an alkali-soluble resin having an ethylenic double bond (hereinafter sometimes abbreviated as "(c) alkali-soluble resin”). It is preferable to include. (c) Containing an alkali-soluble resin having an ethylenic double bond tends to increase sensitivity.
  • the specific structure of the alkali-soluble resin having an ethylenic double bond is not particularly limited, but from the viewpoint of development solubility, (c1) epoxy (meth)acrylate resin and/or (c2) acrylic copolymer resin Preferably, from the viewpoint of tapered shape, (c1) epoxy (meth)acrylate resin is more preferable. Below, (c1) epoxy (meth)acrylate resin will be explained in detail.
  • Epoxy (meth)acrylate resin is a resin obtained by adding an acid or ester compound having an ethylenically unsaturated bond (ethylenic double bond) to an epoxy resin, and further adding a polybasic acid or its anhydride.
  • Epoxy (meth)acrylate resin is a resin obtained by adding an acid or ester compound having an ethylenically unsaturated bond (ethylenic double bond) to an epoxy resin, and further adding a polybasic acid or its anhydride.
  • ethylenically unsaturated Examples include those in which a bond is added and one carboxy group of a polybasic acid anhydride is added to the hydroxyl group generated at that time.
  • (c1) epoxy (meth)acrylate resin has a chemical structure that substantially does not have an epoxy group, and is not limited to "(meth)acrylate", but is an epoxy compound (epoxy resin). is the raw material, and "(meth)acrylate” is a typical example, so it is named this way according to common usage.
  • epoxy (meth)acrylate resin (c1) from the viewpoint of patterning properties, those having an aromatic ring in the main chain can be more preferably used.
  • the epoxy resin includes a raw material compound before forming a resin by thermosetting, and the epoxy resin can be appropriately selected from known epoxy resins. Further, as the epoxy resin, a compound obtained by reacting a phenolic compound and epihalohydrin can be used.
  • the phenolic compound is preferably a compound having a divalent or divalent or higher phenolic hydroxyl group, and may be a monomer or a polymer. Specifically, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl novolac epoxy resin, trisphenol epoxy resin, phenol and dicyclopentadiene.
  • bisphenol A type epoxy resin bisphenol novolac epoxy resin, cresol novolac epoxy resin, epoxidized product of a polymer of phenol and dicyclopentadiene, 9,9-bis(4'-hydroxyphenyl) Epoxidized products of fluorene are preferred, and bisphenol A epoxy resins are more preferred.
  • acids having ethylenically unsaturated bonds include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, pentaerythritol tri(meth)acrylate succinic anhydride adduct, and pentaerythritol tri(meth)acrylate.
  • polybasic acids examples include succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, -Ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid , benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, and anhydrides thereof.
  • succinic anhydride succinic anhydride
  • maleic anhydride succinic anhydride
  • itaconic anhydride succinic anhydride is more preferred, from the viewpoint of reducing residue in pixel areas after development.
  • polyhydric alcohol By using polyhydric alcohol, it is possible to increase the molecular weight of the epoxy (meth)acrylate resin (c1) and introduce branches into the molecule, which tends to balance the molecular weight and viscosity. Furthermore, the rate of introduction of acid groups into the molecule can be increased, and sensitivity, adhesion, etc. tend to be more balanced.
  • the polyhydric alcohol include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. These may be used alone or in combination of two or more.
  • the acid value of the epoxy (meth)acrylate resin is not particularly limited, but is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, even more preferably 40 mgKOH/g or more, even more preferably 60 mgKOH/g or more, Further, it is preferably 200 mgKOH/g or less, more preferably 180 mgKOH/g or less, even more preferably 150 mgKOH/g or less, even more preferably 120 mgKOH/g or less, and particularly preferably 100 mgKOH/g or less.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 10 to 200 mgKOH/g, more preferably 10 to 180 mgKOH/g, even more preferably 20 to 150 mgKOH/g, even more preferably 40 to 120 mgKOH/g, Particularly preferred is 60 to 100 mgKOH/g.
  • Residues can be easily reduced by setting the amount to be equal to or more than the lower limit value. Further, by setting the amount to be below the upper limit, the residual film rate during development tends to improve.
  • the weight average molecular weight (Mw) of the epoxy (meth)acrylate resin is not particularly limited, but is preferably 1,000 or more, more preferably 2,000 or more, even more preferably 3,000 or more, even more preferably 4,000 or more, and even more preferably 5,000. Above, it is particularly preferably 6,000 or more, most preferably 7,000 or more, and is preferably 30,000 or less, more preferably 20,000 or less, still more preferably 15,000 or less, particularly preferably 10,000 or less.
  • the upper and lower limits can be arbitrarily combined and are preferably 1,000 to 30,000, more preferably 2,000 to 30,000, even more preferably 3,000 to 20,000, even more preferably 4,000 to 20,000, even more preferably 5,000 to 15,000, and even more preferably 6,000 to 15,000. is particularly preferred, and 7,000 to 10,000 is most preferred.
  • the amount is equal to or more than the lower limit, the remaining film rate during development tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • the content of the (c1) epoxy (meth)acrylate resin contained in the (C) alkali-soluble resin is not particularly limited, but is 30% by mass.
  • the content is preferably at least 50% by mass, more preferably at least 70% by mass, even more preferably at least 80% by mass, particularly preferably at least 90% by mass, and usually at most 100% by mass.
  • the above upper and lower limits can be arbitrarily combined. For example, it is preferably 30 to 100% by weight, more preferably 50 to 100% by weight, even more preferably 70 to 100% by weight, even more preferably 80 to 100% by weight, and particularly preferably 90 to 100% by weight.
  • the taper shape tends to be improved by making it equal to or more than the lower limit value.
  • Epoxy (meth)acrylate resin can be synthesized by a conventionally known method. Specifically, the epoxy resin is dissolved in an organic solvent, the acid or ester compound having an ethylenically unsaturated bond is added thereto in the coexistence of a catalyst and a thermal polymerization inhibitor, and then the polybasic acid or its A method can be used in which the reaction is continued by adding an anhydride.
  • Examples of the organic solvent include methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate.
  • Examples of the catalyst include tertiary amines such as triethylamine, benzyldimethylamine, and tribenzylamine; Examples include class ammonium salts; phosphorus compounds such as triphenylphosphine; and stibines such as triphenylstibine.
  • Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, and methyl hydroquinone. These may be used alone or in combination of two or more.
  • the acid or ester compound having an ethylenically unsaturated bond is preferably 0.7 to 1.3 chemical equivalents, more preferably 0.9 to 1.1 chemical equivalents per chemical equivalent of the epoxy group of the epoxy resin.
  • the amount can be used.
  • the temperature during the addition reaction is preferably 60 to 150°C, more preferably 80 to 120°C.
  • the polybasic acid (anhydride) is preferably used in an amount of 0.1 to 1.2 chemical equivalents, more preferably 0.2 to 1.1 chemical equivalents, per 1 chemical equivalent of hydroxyl group generated in the addition reaction. can be used.
  • (c1) Epoxy (meth)acrylate resin (hereinafter referred to as " (c1-1) Epoxy (meth)acrylate resin")
  • (c1-2) Epoxy (meth)acrylate resin containing a partial structure represented by the following general formula (ii) (hereinafter referred to as "( (c1-2) epoxy (meth)acrylate resin")
  • (c1-3) epoxy (meth)acrylate resin containing a partial structure represented by the following general formula (iii) hereinafter referred to as (c1-3) epoxy (meth)acrylate resin).
  • Epoxy (meth)acrylate resin includes (c1-1) epoxy (meth)acrylate resin containing a partial structure represented by the following general formula (i) from the viewpoint of developability and tapered shape. (c1-1) is more preferably an epoxy (meth)acrylate resin containing a partial structure represented by the following general formula (i).
  • R a represents a hydrogen atom or a methyl group
  • R b represents a divalent hydrocarbon group which may have a substituent.
  • the benzene ring in formula (i) may be further substituted with any substituent. * represents a bond.
  • R b represents a divalent hydrocarbon group which may have a substituent.
  • divalent hydrocarbon groups include divalent aliphatic groups, divalent aromatic ring groups, and groups in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are connected. Can be mentioned.
  • divalent aliphatic groups examples include linear, branched, and cyclic groups. Among these, linear ones are preferable from the viewpoint of development solubility, while annular ones are preferable from the viewpoint of reducing permeation of the developer into the exposed area.
  • the number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
  • the upper and lower limits can be arbitrarily combined, and are preferably from 1 to 20, more preferably from 3 to 15, even more preferably from 6 to 10. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • Examples of the divalent linear aliphatic group include methylene group, ethylene group, n-propylene group, n-butylene group, n-hexylene group, and n-heptylene group. Among these, methylene groups are preferred from the viewpoint of reducing residue.
  • Examples of the divalent branched aliphatic group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group as a side chain in addition to the above-mentioned divalent linear aliphatic group. Examples include structures having a group, a sec-butyl group, and a tert-butyl group.
  • the number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, preferably 10 or less, and more preferably 5 or less.
  • the upper and lower limits can be arbitrarily combined, and are preferably from 1 to 10, more preferably from 1 to 5, even more preferably from 2 to 5.
  • Examples of the divalent cyclic aliphatic group include groups obtained by removing two hydrogen atoms from a cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, and adamantane ring.
  • a group obtained by removing two hydrogen atoms from an adamantane ring is preferable.
  • substituents that the divalent aliphatic group may have include alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; carboxy group; From the viewpoint of ease of synthesis, non-substitution is preferred.
  • divalent aromatic ring group examples include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
  • the number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 4 to 20, more preferably 5 to 15, and even more preferably 6 to 10. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a fused ring.
  • Examples of the divalent aromatic hydrocarbon ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, Examples include triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.
  • the aromatic heterocycle in the divalent aromatic heterocyclic group may be a single ring or a condensed ring.
  • divalent aromatic heterocyclic group examples include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, and indole ring having two free valences.
  • benzene rings and naphthalene rings having two free valences are examples of benzene rings and naphthalene rings having two free valences.
  • Examples of the substituents that the divalent aromatic ring group may have include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group, and a glycidyl ether group. Among these, from the viewpoint of curability, non-substitution is preferred.
  • the group linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups includes one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic ring group.
  • Examples include groups in which one or more are linked.
  • the number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
  • the upper and lower limits can be arbitrarily combined, and are preferably from 1 to 10, more preferably from 1 to 5, and even more preferably from 2 to 3. When the amount is equal to or more than the lower limit, development adhesion tends to improve.
  • the amount of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
  • the upper and lower limits can be arbitrarily combined, and are preferably from 1 to 10, more preferably from 1 to 5, and even more preferably from 2 to 3.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve.
  • the amount to be less than or equal to the upper limit value the amount of residue tends to be reduced.
  • Examples of groups that connect one or more divalent aliphatic groups and one or more divalent aromatic ring groups include groups represented by the following formulas (i-A) to (i-F). It will be done. Among these, a group represented by the following formula (i-A) is preferred from the viewpoint of skeletal rigidity and membrane hydrophobization. * in the chemical formula represents a bond.
  • the benzene ring in formula (i) may be further substituted with any substituent.
  • substituent on the benzene ring in formula (i) include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
  • the number of substituents is not particularly limited either, and may be one or two or more as long as it is chemically permissible. From the viewpoint of curability, no substitution is preferred.
  • the partial structure represented by the formula (i) is preferably a partial structure represented by the following formula (i-1).
  • R a and R b have the same meanings as in formula (i) above.
  • R c represents a divalent hydrocarbon group having 1 to 4 carbon atoms which may have a substituent. * represents a bond.
  • the benzene ring in formula (i-1) may be further substituted with any substituent.
  • R c represents a divalent hydrocarbon group having 1 to 4 carbon atoms which may have a substituent.
  • Examples of the divalent hydrocarbon group include an alkylene group and an alkenylene group.
  • the alkylene group may be linear or branched, but is preferably linear from the viewpoint of development solubility.
  • the number of carbon atoms is not particularly limited, but is usually 1 or more, preferably 2 or more, preferably 4 or less, and more preferably 3 or less.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 1 to 4, more preferably 1 to 3, and even more preferably 2 to 3. When the amount is equal to or more than the lower limit, the remaining film rate tends to increase. Further, by setting the amount to be less than or equal to the upper limit value, the amount of outgas generated during and after firing tends to be reduced.
  • alkylene group examples include a methylene group, an ethylene group, a propylene group, and a butylene group, and from the viewpoint of reducing outgas, a methylene group or an ethylene group is preferable, and an ethylene group is more preferable.
  • the alkenylene group may be linear or branched, but is preferably linear from the viewpoint of development solubility.
  • the number of carbon atoms is not particularly limited, but is usually 2 or more, preferably 4 or less, and more preferably 3 or less. For example, 2 to 4 are preferred, and 2 to 3 are more preferred.
  • the amount is equal to or more than the lower limit, the remaining film rate tends to increase. Further, by setting the amount to be less than or equal to the upper limit value, the amount of outgas generated during and after firing tends to be reduced.
  • alkenylene group examples include ethenylene group, propenylene group, and butylene group, and ethenylene group is preferable from the viewpoint of outgas.
  • the substituent that the divalent hydrocarbon group having 1 to 4 carbon atoms may have is not particularly limited, but examples thereof include a halogen atom, an alkoxy group, a benzoyl group, and a hydroxyl group. is preferably unsubstituted.
  • R c is preferably a divalent alkylene group having 1 to 4 carbon atoms, more preferably a methylene group or an ethylene group, and even more preferably an ethylene group.
  • the partial structure represented by the above formula (i-1) contained in one molecule of the epoxy (meth)acrylate resin may be one type or two or more types.
  • the number of partial structures represented by the formula (i) contained in one molecule of epoxy (meth)acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and 3 or more. is more preferable, 10 or less is preferable, and 8 or less is even more preferable.
  • the upper and lower limits can be arbitrarily combined, and are preferably from 1 to 10, more preferably from 2 to 10, and even more preferably from 3 to 8. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • the number of partial structures represented by the formula (i-1) contained in one molecule of epoxy (meth)acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 2 or more, It is more preferably 3 or more, more preferably 10 or less, and even more preferably 8 or less.
  • the upper and lower limits can be arbitrarily combined, and are preferably from 1 to 10, more preferably from 2 to 10, and even more preferably from 3 to 8. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • the (c1) epoxy (meth)acrylate resin is (c1-2) an epoxy (meth)acrylate resin containing a partial structure represented by the following formula (ii) from the viewpoint of development adhesion. is preferred.
  • R d each independently represents a hydrogen atom or a methyl group.
  • R e represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. * represents a bond.
  • R e represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
  • the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
  • the number of rings that the aliphatic cyclic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
  • the upper and lower limits can be arbitrarily combined, and are preferably from 1 to 10, more preferably from 1 to 5, and even more preferably from 2 to 3.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • the number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 4 to 40, more preferably 4 to 30, even more preferably 6 to 20, particularly preferably 8 to 15.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • Examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring.
  • an adamantane ring is preferred from the viewpoint of development adhesion.
  • the number of rings that the aromatic ring group has is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and preferably 10 or less, more preferably 5 or less, and even more preferably 4 or less.
  • the upper and lower limits can be arbitrarily combined, and are preferably from 1 to 10, more preferably from 2 to 5, and even more preferably from 3 to 4.
  • the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, even more preferably 10 or more, particularly preferably 12 or more, and preferably 40 or less, more preferably 30 or more. , 20 or less is more preferable, and 15 or less is particularly preferable.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 4 to 40, more preferably 6 to 40, even more preferably 8 to 30, even more preferably 10 to 20, and particularly preferably 12 to 15.
  • Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.
  • Examples include rings. Among these, fluorene rings are preferred from the viewpoint of patterning properties.
  • the divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, but includes, for example, a divalent aliphatic group, a divalent aromatic ring group, and one or more divalent hydrocarbon groups. Examples include groups in which a valent aliphatic group and one or more divalent aromatic ring groups are connected.
  • divalent aliphatic groups examples include linear, branched, and cyclic groups. Among these, linear ones are preferable from the viewpoint of development solubility, while annular ones are preferable from the viewpoint of reducing permeation of the developer into the exposed area.
  • the number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 25 or less, more preferably 20 or less, and even more preferably 15 or less.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 1 to 25, more preferably 3 to 20, and even more preferably 6 to 15. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • Examples of the divalent linear aliphatic group include methylene group, ethylene group, n-propylene group, n-butylene group, n-hexylene group, and n-heptylene group. Among these, methylene group is preferred from the viewpoint of residue.
  • Examples of the divalent branched aliphatic group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group as a side chain in addition to the above-mentioned divalent linear aliphatic group. Examples include structures having a group, a sec-butyl group, and a tert-butyl group.
  • the number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 3.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • Examples of the divalent cyclic aliphatic group include groups obtained by removing two hydrogen atoms from a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring.
  • a group obtained by removing two hydrogen atoms from an adamantane ring is preferable.
  • substituents that the divalent aliphatic group may have include alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; carboxy group; From the viewpoint of ease of synthesis, non-substitution is preferred.
  • divalent aromatic ring group examples include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
  • the number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 4 to 30, more preferably 5 to 20, and even more preferably 6 to 15. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • the aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a fused ring.
  • Examples of the divalent aromatic hydrocarbon ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, Examples include triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.
  • the aromatic heterocycle in the divalent aromatic heterocyclic group may be a single ring or a condensed ring.
  • divalent aromatic heterocyclic groups include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, and indole ring, each having two free valences.
  • benzene rings and naphthalene rings having two free valences are preferred.
  • benzene rings and naphthalene rings having two free valences are preferred.
  • Examples of the substituents that the divalent aromatic ring group may have include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Among these, from the viewpoint of curability, non-substitution is preferred.
  • the group linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups includes one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic ring group. Examples include groups in which one or more are linked.
  • the number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 3. When the amount is equal to or more than the lower limit, development adhesion tends to improve.
  • the amount of residue tends to be reduced.
  • the number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 3.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve.
  • the amount to be less than or equal to the upper limit value the amount of residue tends to be reduced.
  • Examples of groups that connect one or more divalent aliphatic groups and one or more divalent aromatic ring groups include groups represented by the above formulas (i-A) to (i-F). Can be mentioned. Among these, from the viewpoint of reducing residue, the group represented by the above formula (iC) is preferable.
  • the bonding mode of the cyclic hydrocarbon group as a side chain to these divalent hydrocarbon groups is not particularly limited, but for example, one hydrogen atom of an aliphatic group or an aromatic ring group is replaced with a side chain.
  • Examples include embodiments in which a cyclic hydrocarbon group, which is a side chain, includes one carbon atom of an aliphatic group.
  • the partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-1).
  • R d has the same meaning as in formula (ii) above.
  • R f represents a monovalent cyclic hydrocarbon group which may have a substituent.
  • n is an integer of 1 or more.
  • the benzene ring in formula (ii-1) may be further substituted with any substituent. * represents a bond.
  • R f represents a monovalent cyclic hydrocarbon group which may have a substituent.
  • the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
  • the number of rings that the aliphatic cyclic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.
  • the upper and lower limits can be arbitrarily combined, and for example, 1 to 6 are preferable, 1 to 4 are more preferable, and 2 to 3 are still more preferable.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • the number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and especially 15 or less. preferable.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 4 to 40, more preferably 4 to 30, even more preferably 6 to 20, particularly preferably 8 to 15.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • Examples of the aliphatic ring in the aliphatic cyclic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring.
  • an adamantane ring is preferred from the viewpoint of development adhesion.
  • the number of rings that the aromatic ring group has is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and preferably 10 or less, and more preferably 5 or less.
  • the upper and lower limits can be arbitrarily combined, and are preferably from 1 to 10, more preferably from 2 to 10, even more preferably from 3 to 5.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 4 to 30, more preferably 5 to 20, and even more preferably 6 to 15.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring.
  • a fluorene ring is preferred from the viewpoint of development adhesion.
  • substituents that the cyclic hydrocarbon group may have include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, amyl group, Examples include alkyl groups having 1 to 5 carbon atoms such as isoamyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; and carboxy group; from the viewpoint of ease of synthesis. , unsubstituted is preferred.
  • n represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less. For example, 1 to 3 are preferred, and 1 to 2 are more preferred.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • R f is preferably a monovalent aliphatic cyclic group, and more preferably an adamantyl group.
  • the benzene ring in formula (ii-1) may be further substituted with any substituent.
  • substituents include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
  • the number of substituents is not particularly limited either, and may be one or two or more. From the viewpoint of curability, no substitution is preferred.
  • the partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-2).
  • R d has the same meaning as in formula (ii) above.
  • R g represents a divalent cyclic hydrocarbon group which may have a substituent.
  • the benzene ring in formula (ii-2) may be further substituted with any substituent.
  • * represents a bond.
  • R g represents a divalent cyclic hydrocarbon group which may have a substituent.
  • the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
  • the number of rings an aliphatic cyclic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, preferably 10 or less, and more preferably 5 or less.
  • the upper and lower limits can be arbitrarily combined, and are preferably from 1 to 10, more preferably from 2 to 5.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve.
  • the amount of residue tends to be reduced.
  • the number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 4 to 40, more preferably 6 to 35, and even more preferably 8 to 30.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. Among these, an adamantane ring is preferred from the viewpoint of development adhesion.
  • the number of rings that the aromatic ring group has is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and preferably 10 or less, and preferably 5 or less.
  • the upper and lower limits can be arbitrarily combined, and are preferably from 1 to 10, more preferably from 2 to 10, even more preferably from 3 to 5.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, even more preferably 10 or more, and preferably 40 or less, more preferably 30 or less, and still more preferably 20 or more. It is preferably 15 or less, particularly preferably 15 or less.
  • the upper and lower limits can be arbitrarily combined, and are preferably from 4 to 40, more preferably from 6 to 30, even more preferably from 8 to 20, and particularly preferably from 10 to 15. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring.
  • a fluorene ring is preferred from the viewpoint of development adhesion.
  • substituents that the cyclic hydrocarbon group may have include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, amyl group, Examples include alkyl groups having 1 to 5 carbon atoms such as isoamyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; and carboxy group. Among these, unsubstituted is preferred from the viewpoint of ease of synthesis.
  • R g is preferably a divalent aliphatic cyclic group, and more preferably a divalent adamantane cyclic group.
  • R g is preferably a divalent aromatic ring group, and more preferably a divalent fluorene ring group.
  • the benzene ring in formula (ii-2) may be further substituted with any substituent.
  • substituents on the benzene ring in formula (ii-2) include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
  • the number of substituents is not particularly limited either, and may be one or two or more. From the viewpoint of curability, no substitution is preferred.
  • the partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-3).
  • R d and R e have the same meanings as in formula (ii) above.
  • R c has the same meaning as in formula (i-1) above. * represents a bond.
  • the partial structure represented by the above formula (ii-3) contained in one molecule of the epoxy (meth)acrylate resin may be one type or two or more types.
  • the number of partial structures represented by the formula (ii) contained in one molecule of epoxy (meth)acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and It is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
  • the upper and lower limits can be arbitrarily combined, for example, preferably from 1 to 20, more preferably from 1 to 15, even more preferably from 3 to 10.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • epoxy (meth)acrylate resin (c1-3) epoxy (meth)acrylate resin includes a partial structure represented by the following general formula (iii) from the viewpoint of developability and tapered shape during development. Preferably, it is a meth)acrylate resin.
  • R h represents a hydrogen atom or a methyl group
  • R i is a single bond, -C(O)-, an alkylene group which may have a substituent, or a substituent. represents a good divalent cyclic hydrocarbon group.
  • the benzene ring in formula (iii) may be further substituted with any substituent. * represents a bond.
  • R i represents a single bond, -C(O)-, an alkylene group which may have a substituent, or a divalent cyclic hydrocarbon group which may have a substituent. represent.
  • the alkylene group may be linear or branched, but from the viewpoint of development solubility it is preferably linear, and from the viewpoint of development adhesion it is preferably branched.
  • the number of carbon atoms is not particularly limited, but is usually 1 or more, preferably 2 or more, preferably 6 or less, and more preferably 4 or less.
  • the upper and lower limits can be arbitrarily combined, and for example, 1 to 6 are preferable, and 2 to 4 are more preferable.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • alkylene group examples include methylene group, ethylene group, propylene group, butylene group, hexylene group, and heptylene group. is preferred, and dimethylmethylene group (2,2-propylene group) is more preferred.
  • alkylene group may have examples of substituents that the alkylene group may have include alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; and carboxy group; From the viewpoint of achieving both development and solubility, non-substitution is preferred.
  • divalent cyclic hydrocarbon group examples include a divalent aliphatic cyclic group and a divalent aromatic cyclic group.
  • the number of rings an aliphatic cyclic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, preferably 10 or less, and more preferably 5 or less.
  • the upper and lower limits can be arbitrarily combined, and are preferably from 1 to 10, more preferably from 2 to 5.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve.
  • the amount of residue tends to be reduced.
  • the number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 4 to 40, more preferably 6 to 35, and even more preferably 8 to 30.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • the aliphatic ring in the aliphatic cyclic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. Among these, an adamantane ring is preferred from the viewpoint of development adhesion.
  • the number of rings that the aromatic ring group has is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and preferably 10 or less, and more preferably 5 or less.
  • the upper and lower limits can be arbitrarily combined, and are preferably from 1 to 10, more preferably from 2 to 10, even more preferably from 3 to 5.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • the number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, even more preferably 10 or more, and preferably 40 or less, more preferably 30 or less, even more preferably 20 or more, 15 or less is particularly preferred.
  • the upper and lower limits can be arbitrarily combined, and are preferably from 4 to 40, more preferably from 6 to 30, even more preferably from 8 to 20, and particularly preferably from 10 to 15. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring.
  • a fluorene ring is preferred from the viewpoint of development adhesion.
  • substituents that the cyclic hydrocarbon group may have include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, amyl group, Examples include alkyl groups having 1 to 5 carbon atoms such as isoamyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; and carboxy group; from the viewpoint of simplicity of synthesis. , unsubstituted is preferred.
  • R i is preferably an alkylene group which may have a substituent, and more preferably dimethylmethylene.
  • the benzene ring in formula (iii) may be further substituted with any substituent.
  • substituents on the benzene ring in formula (iii) include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
  • the number of substituents is not particularly limited either, and may be one or two or more. From the viewpoint of curability, no substitution is preferred.
  • the partial structure represented by the formula (iii) is preferably a partial structure represented by the following formula (iii-1).
  • R h and R i have the same meanings as in formula (iii) above.
  • R c has the same meaning as in formula (i-1) above. * represents a bond.
  • the benzene ring in formula (iii-1) may be further substituted with any substituent.
  • the number of partial structures represented by the formula (iii) contained in one molecule of epoxy (meth)acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 5 or more, and 10 or more. is more preferable, 18 or less is preferable, and 15 or less is even more preferable.
  • the upper and lower limits can be arbitrarily combined, for example, preferably from 1 to 18, more preferably from 5 to 18, even more preferably from 10 to 15. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • the number of partial structures represented by the formula (iii-1) contained in one molecule of epoxy (meth)acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 3 or more, It is more preferably 5 or more, more preferably 18 or less, and even more preferably 15 or less.
  • the upper and lower limits can be arbitrarily combined, and are preferably from 1 to 18, more preferably from 3 to 18, even more preferably from 5 to 15. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • the acrylic copolymer resin preferably has an ethylenic double bond in its side chain from the viewpoint of curability.
  • (c2) acrylic copolymer resins from the viewpoint of development solubility, (c2-1) acrylic copolymer resins containing a partial structure represented by the following general formula (iv) are preferred.
  • R j and R k each independently represent a hydrogen atom or a methyl group. * represents a bond.
  • the partial structure represented by the formula (iv) is preferably a partial structure represented by the following general formula (iv-1).
  • R j and R k have the same meanings as in formula (iv) above.
  • R c has the same meaning as in formula (i-1) above.
  • the partial structure represented by the formula (iv) is preferably a partial structure represented by the following formula (iv-2).
  • R j and R k have the same meanings as in formula (iv) above.
  • (c2-1) When the acrylic copolymer resin contains a partial structure represented by the general formula (iv), (c2-1) the partial structure represented by the general formula (iv) contained in the acrylic copolymer resin
  • the content is not particularly limited, but is preferably 5 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, even more preferably 50 mol% or more, particularly preferably 70 mol% or more, and 80 mol% or more. It is most preferably at least mol%, preferably at most 99 mol%, more preferably at most 97 mol%, even more preferably at most 95 mol%.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 5 to 99 mol%, more preferably 20 to 99 mol%, even more preferably 30 to 97 mol%, even more preferably 50 to 97 mol%, Particularly preferred is 70 to 95 mol%, most preferred is 80 to 95 mol%.
  • the amount of residue is reduced by setting the amount to be equal to or more than the lower limit value. Further, by setting the amount to be less than or equal to the upper limit value, the development adhesion tends to improve.
  • the acrylic copolymer resin contains a partial structure represented by the general formula (iv-1), (c2-1) the acrylic copolymer resin contains a partial structure represented by the general formula (iv-1).
  • the content of the partial structure is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, even more preferably 8 mol% or more, even more preferably 10 mol% or more, and even more preferably 99 mol%.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 1 to 99 mol%, more preferably 1 to 60 mol%, even more preferably 5 to 40 mol%, even more preferably 8 to 30 mol%, Particularly preferred is 10 to 20 mol%.
  • the value is equal to or more than the lower limit, the sensitivity tends to increase and the amount of residue tends to decrease. Further, by setting the amount to be less than or equal to the upper limit value, the development adhesion tends to improve.
  • the acrylic copolymer resin contains a partial structure represented by the general formula (iv-2), (c2-1) the acrylic copolymer resin contains a partial structure represented by the general formula (iv-2).
  • the content of the partial structure is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, even more preferably 40 mol% or more, and even more preferably 50 mol% or more. It is particularly preferably 70 mol% or more, most preferably 99 mol% or less, more preferably 95 mol% or less, even more preferably 90 mol% or less, and particularly preferably 85 mol% or less.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 10 to 99 mol%, more preferably 20 to 99 mol%, even more preferably 30 to 95 mol%, even more preferably 40 to 95 mol%, Particularly preferred is 50 to 90 mol%, most preferred is 70 to 85 mol%.
  • the value is equal to or more than the lower limit value, the sensitivity tends to increase. Further, by setting the amount to be less than or equal to the upper limit value, there is a tendency that developability is improved.
  • the acrylic copolymer resin contains the partial structure represented by the general formula (iv)
  • other partial structures that may be included are not particularly limited, but from the viewpoint of development adhesion, for example, It is preferable to include a partial structure represented by the following general formula (iv').
  • Rl represents a hydrogen atom or a methyl group
  • Rm represents an alkyl group that may have a substituent, an aryl group that may have a substituent (an aromatic ring group) ), or an alkenyl group which may have a substituent.
  • R m represents an alkyl group that may have a substituent, an aryl group that may have a substituent, or an alkenyl group that may have a substituent.
  • alkyl group for R m include linear, branched, or cyclic alkyl groups.
  • the number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, and preferably 20 or less, more preferably 18 or less, further preferably 16 or less, even more preferably 14 or less, and even more preferably 12 or less. is particularly preferred.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 1 to 20, more preferably 1 to 18, even more preferably 3 to 16, even more preferably 3 to 14, particularly preferably 5 to 12.
  • the amount is equal to or more than the lower limit, the film strength tends to increase, and the development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • Examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, and a dodecanyl group. Among these, from the viewpoint of film strength, dicyclopentanyl group and dodecanyl group are preferred, and dicyclopentanyl group is more preferred.
  • substituents that the alkyl group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxy group. , an acryloyl group, and a methacryloyl group, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
  • Examples of the aryl group (aromatic ring group) for R m include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group.
  • the number of carbon atoms is preferably 4 or more, more preferably 6 or more, preferably 24 or less, more preferably 22 or less, even more preferably 20 or less, and particularly preferably 18 or less.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 4 to 24, more preferably 4 to 22, even more preferably 6 to 20, particularly preferably 6 to 18.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • the aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, such as a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, and a pyrene ring.
  • ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring may be a single ring or a condensed ring, such as a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, and a pyrene ring.
  • the aromatic heterocycle in the aromatic heterocyclic group may be a single ring or a condensed ring, such as a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, and an imidazole ring.
  • oxadiazole ring indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, Examples include benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring.
  • benzene ring groups and naphthalene ring groups are preferred, and benzene ring groups are more preferred.
  • substituents that the aryl group may have include methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligo
  • substituents that the aryl group may have include methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligo
  • alkenyl group for R m examples include linear, branched, or cyclic alkenyl groups.
  • the number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, even more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less.
  • the number is preferably 2 to 22, more preferably 2 to 20, even more preferably 2 to 18, even more preferably 2 to 16, and particularly preferably 2 to 14.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • alkenyl group examples include ethenyl group, propenyl group, butenyl group, and cyclohexenyl group. Among these, from the viewpoint of curability, ethenyl group and propenyl group are preferred, and ethenyl group is more preferred.
  • substituents that the alkenyl group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxy group. From the viewpoint of developability, hydroxyl groups and oligoethylene glycol groups are preferred.
  • R m is preferably an alkyl group or an alkenyl group, more preferably an alkyl group, and even more preferably a dicyclopentanyl group.
  • the acrylic copolymer resin contains a partial structure represented by the general formula (iv')
  • the acrylic copolymer resin contains a partial structure represented by the general formula (iv')
  • the content of the partial structure is not particularly limited, but is preferably 0.5 mol% or more, more preferably 1 mol% or more, even more preferably 1.5 mol% or more, particularly preferably 2 mol% or more, and 90 mol% or more. % or less, more preferably 70 mol % or less, even more preferably 50 mol % or less, even more preferably 30 mol % or less, particularly preferably 10 mol % or less.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 0.5 to 90 mol%, more preferably 0.5 to 70 mol%, even more preferably 1 to 50% mol, and 1.5 to 30 mol%. % is even more preferable, and 2 to 10 mol% is particularly preferable.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • R n represents a hydrogen atom or a methyl group
  • R o represents an alkyl group that may have a substituent, an alkenyl group that may have a substituent, a hydroxy group
  • It represents a carboxyl group, a halogen atom, an alkoxy group which may have a substituent, a thiol group, or an alkyl sulfide group which may have a substituent.
  • t represents an integer from 0 to 5.
  • R o has an alkyl group that may have a substituent, an alkenyl group that may have a substituent, a hydroxy group, a carboxy group, a halogen atom, or a substituent. represents an optionally substituted alkoxy group, a thiol group, or an optionally substituted alkyl sulfide group.
  • alkyl group in R o include linear, branched or cyclic alkyl groups.
  • the number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, and preferably 20 or less, more preferably 18 or less, further preferably 16 or less, even more preferably 14 or less, and even more preferably 12 or less. is particularly preferred.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 1 to 20, more preferably 1 to 18, even more preferably 3 to 16, even more preferably 3 to 14, particularly preferably 5 to 12. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • Examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, and a dodecanyl group. Among these, from the viewpoint of development adhesion, dicyclopentanyl group and dodecanyl group are preferred, and dicyclopentanyl group is more preferred.
  • substituents that the alkyl group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxy group. , an acryloyl group, and a methacryloyl group, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
  • Examples of the alkenyl group in R o include linear, branched, or cyclic alkenyl groups.
  • the number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, even more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less.
  • the number is preferably 2 to 22, more preferably 2 to 20, even more preferably 2 to 18, even more preferably 2 to 16, and particularly preferably 2 to 14.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • alkenyl group examples include ethenyl group, propenyl group, butenyl group, and cyclohexenyl group. Among these, from the viewpoint of curability, ethenyl group and propenyl group are preferred, and ethenyl group is more preferred.
  • substituents that the alkenyl group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxy group. From the viewpoint of developability, hydroxyl groups and oligoethylene glycol groups are preferred.
  • halogen atom in R o examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Examples of the alkoxy group in R o include linear, branched or cyclic alkoxy groups.
  • the number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less.
  • the number is preferably 1 to 20, more preferably 1 to 18, even more preferably 1 to 16, even more preferably 1 to 14, and particularly preferably 1 to 12.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • substituents that the alkoxy group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxy group. , an acryloyl group, and a methacryloyl group, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
  • alkyl sulfide group in R o examples include linear, branched, or cyclic alkyl sulfide groups.
  • the number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less. , 12 or less is particularly preferable.
  • the number is preferably 1 to 20, more preferably 1 to 18, even more preferably 1 to 16, even more preferably 1 to 14, and particularly preferably 1 to 12.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • alkyl sulfide group examples include a methyl sulfide group, an ethyl sulfide group, a propyl sulfide group, and a butyl sulfide group. Among these, from the viewpoint of developability, methyl sulfide groups and ethyl sulfide groups are preferred.
  • substituents that the alkyl group in the alkyl sulfide group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, and phenyl group. group, carboxy group, acryloyl group, and methacryloyl group, and from the viewpoint of developability, hydroxy group and oligoethylene glycol group are preferable.
  • R o is preferably a hydroxy group or a carboxy group, and more preferably a carboxy group.
  • t represents an integer from 0 to 5. From the viewpoint of developability, the number is preferably 0 to 2, more preferably 0 to 1, and even more preferably 0.
  • the acrylic copolymer resin contains a partial structure represented by the general formula (iv'')
  • the acrylic copolymer resin contains a partial structure represented by the general formula (iv'').
  • the content of the partial structure is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, even more preferably 3 mol% or more, particularly preferably 5 mol% or more, and 90 mol% or less. It is preferably 70 mol% or less, more preferably 50 mol% or less, even more preferably 30 mol% or less, particularly preferably 20 mol% or less, and most preferably 10 mol% or less.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 1 to 90 mol%, more preferably 1 to 70 mol%, even more preferably 2 to 50 mol%, even more preferably 2 to 30 mol%, Particularly preferred is 3 to 20 mol%, most preferred is 5 to 10 mol%.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • the acrylic copolymer resin includes a partial structure represented by the general formula (iv) above, it may further include a partial structure represented by the following general formula (iv''') from the viewpoint of developability. is preferred.
  • R p represents a hydrogen atom or a methyl group.
  • the acrylic copolymer resin contains a partial structure represented by the general formula (iv'''), (c2-1) the general formula (iv''') contained in the acrylic copolymer resin
  • the content of the partial structure represented by is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 30 mol% or more, and preferably 90 mol% or less, and 80 mol%. The following is more preferable, 70 mol% or less is even more preferable, and 50 mol% or less is particularly preferable.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 5 to 90 mol%, more preferably 5 to 80 mol%, even more preferably 10 to 70 mol%, and particularly preferably 30 to 50 mol%.
  • the acid value of the acrylic copolymer resin is not particularly limited, but is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, even more preferably 20 mgKOH/g or more, even more preferably 25 mgKOH/g or more, and It is preferably 100 mgKOH/g or less, more preferably 80 mgKOH/g or less, even more preferably 60 mgKOH/g or less, even more preferably 40 mgKOH/g or less.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 5 to 100 mgKOH/g, more preferably 10 to 80 mgKOH/g, even more preferably 20 to 60 mgKOH/g, even more preferably 25 to 40 mgKOH/g.
  • the weight average molecular weight (Mw) of the acrylic copolymer resin is not particularly limited, but is preferably 1,000 or more, more preferably 2,000 or more, even more preferably 3,000 or more, even more preferably 4,000 or more, particularly preferably 5,000 or more. It is also preferably 30,000 or less, more preferably 20,000 or less, still more preferably 15,000 or less, even more preferably 10,000 or less. Particularly preferably, it is 8000 or less.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 1,000 to 30,000, more preferably 2,000 to 20,000, even more preferably 3,000 to 15,000, even more preferably 4,000 to 10,000, and particularly preferably 5,000 to 8,000.
  • the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
  • the content of the (c2) acrylic copolymer resin contained in the alkali-soluble resin (C) is not particularly limited, but is preferably 5% by mass or more, The content is more preferably 10% by mass or more, further preferably 15% by mass or more, particularly preferably 20% by mass or more, and usually 100% by mass or less, more preferably 80% by mass or less, and even more preferably 50% by mass or less.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 5 to 100% by weight, more preferably 10 to 100% by weight, even more preferably 15 to 80% by weight, and particularly preferably 20 to 50% by weight.
  • the amount is equal to or more than the lower limit, the development solubility tends to be improved. By setting it below the upper limit value, the taper angle tends to become high.
  • the alkali-soluble resin may contain either (c1) epoxy (meth)acrylate resin or (c2) acrylic copolymer resin alone, or may contain both. Furthermore, the alkali-soluble resin (C) may contain an alkali-soluble resin other than the alkali-soluble resin (c).
  • the content of the alkali-soluble resin (C) in the polymerizable composition of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass in the total solid content of the polymerizable composition. % or more, even more preferably 30% by mass or more, particularly preferably 40% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 5 to 90% by weight, more preferably 10 to 90% by weight, even more preferably 20 to 80% by weight, even more preferably 30 to 70% by weight. When the amount is equal to or more than the lower limit, developability tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, curability tends to be improved.
  • the content of (c1) epoxy (meth)acrylate resin is not particularly limited, but in the total solid content of the polymerizable composition, Preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, even more preferably 30% by mass or more, particularly preferably 40% by mass or more, and more preferably 90% by mass or less.
  • the content is preferably 70% by mass or less, more preferably 60% by mass or less, particularly preferably 50% by mass or less.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 5 to 90% by mass, more preferably 10 to 90% by mass, even more preferably 20 to 70% by mass, even more preferably 30 to 60% by mass, Particularly preferred is 40 to 50% by weight.
  • the amount is equal to or more than the lower limit, developability tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, curability tends to be improved.
  • the content of (c2) acrylic copolymer resin is not particularly limited, but preferably in the total solid content of the polymerizable composition. 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, even more preferably 30% by mass or more, particularly preferably 40% by mass or more, and preferably 90% by mass or less, more preferably It is 80% by mass or less, more preferably 70% by mass or less.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 5 to 90% by weight, more preferably 10 to 90% by weight, even more preferably 20 to 80% by weight, even more preferably 30 to 70% by weight.
  • developability tends to improve.
  • by setting it below the upper limit value there is a tendency that the tapered shape becomes better.
  • the total content of (C) alkali-soluble resin and (B) polymerizable compound in the total solid content of the polymerizable composition is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 30% by mass or more, even more preferably 50% by mass or more, particularly preferably 70% by mass or more, even more particularly preferably 80% by mass or more, most preferably 90% by mass or more, and preferably 99% by mass.
  • the content is more preferably 97% by mass or less, still more preferably 95% by mass or less.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 5 to 99% by mass, more preferably 10 to 99% by mass, even more preferably 30 to 99% by mass, even more preferably 50 to 97% by mass, Particularly preferred is 70-97% by weight, particularly preferred is 80-95% by weight, and most preferred is 90-95% by weight.
  • the amount is equal to or more than the lower limit, developability tends to improve. Further, by setting the amount to be below the upper limit, the amount of the thermal polymerization initiator etc. can be increased, and the curability tends to improve.
  • the blending ratio of (C) alkali-soluble resin to (B) polymerizable compound in the polymerizable composition is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, per 100 parts by mass of (B) polymerizable compound. It is preferably 70 parts by mass or more, more preferably 80 parts by mass or more, further preferably 500 parts by mass or less, more preferably 400 parts by mass or less, and even more preferably 300 parts by mass or less.
  • the total upper and lower limits can be arbitrarily combined, for example, preferably 50 to 400 parts by weight, more preferably 60 to 300 parts by weight. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the curability tends to improve.
  • the polymerizable composition of the present invention may further contain (D) a photopolymerization initiator.
  • the photopolymerization initiator is a component that directly absorbs light, causes a decomposition reaction or a hydrogen abstraction reaction, and has a function of generating polymerization-active radicals, and polymerizes the (B) polymerizable compound.
  • it is not particularly limited as long as it is a compound that polymerizes the ethylenically unsaturated bond that the polymerizable compound (B) has.
  • a photopolymerization initiator commonly used in this field can be used as the photopolymerization initiator (D).
  • photopolymerization initiators include, for example, metallocene compounds containing titanocene compounds described in Japanese Patent Application Laid-open Nos. 59-152396 and 61-151197; Japanese Patent Applications 2000-56118; N-aryl- ⁇ such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, and N-phenylglycine described in Japanese Patent Publication No.
  • - Radical activators such as amino acids, N-aryl- ⁇ -amino acid salts, N-aryl- ⁇ -amino acid esters, ⁇ -aminoalkylphenone derivatives; Japanese Patent Publication No. 2000-80068, Japanese Patent Publication No. Examples include oxime ester compounds described in Publication No. 2006-36750 and the like.
  • metallocene compounds include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis(2,3,4,5,6-pentafluorophenyl ), dicyclopentadienyl titanium bis(2,3,5,6-tetrafluorophenyl), dicyclopentadienyl titanium bis(2,4,6-trifluorophenyl), dicyclopentadienyl titanium di( 2,6-difluorophenyl), dicyclopentadienyl titanium di(2,4-difluorophenyl), di(methylcyclopentadienyl)titanium bis(2,3,4,5,6-pentafluorophenyl), Examples include di(methylcyclopentadienyl) titanium bis(2,6-difluorophenyl) and dicyclopentadienyl titanium [2,6-di-fluoro-3-
  • biimidazole derivatives examples include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazole dimer, (4'-methoxyphenyl) )-4,5-diphenylimidazole dimer.
  • halomethylated oxadiazole derivatives examples include 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[ ⁇ -(2'- benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[ ⁇ -(2'-(6''-benzofuryl)vinyl)]-1,3,4-oxadiazole, Examples include 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.
  • halomethyl-s-triazine derivatives examples include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis( trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl) -s-triazine is mentioned.
  • Examples of ⁇ -aminoalkylphenone derivatives include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4 -morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one, 3,6-bis(2-methyl- Examples include 2-morpholinopropionyl)-9-octylcarbazole.
  • oxime ester compounds are particularly effective in terms of sensitivity and plate-making properties. For example, when using an alkali-soluble resin containing a phenolic hydroxyl group, this is particularly recommended because it is disadvantageous in terms of sensitivity. Oxime ester compounds with excellent sensitivity are useful. Oxime ester compounds are stable against thermal reactions, have a high quantum yield in photoreactions, and have high activity of generated radicals, making it possible to obtain highly sensitive polymerizable compositions in small amounts. .
  • oxime ester compounds include compounds represented by the following general formula (1).
  • R 101 represents a hydrogen atom, an alkyl group that may have a substituent, or an aromatic ring group that may have a substituent.
  • R 102 represents an arbitrary substituent containing an aromatic ring.
  • R 103 represents an alkanoyl group which may have a substituent or an aroyl group which may have a substituent.
  • n represents an integer of 0 or 1.
  • the number of carbon atoms in the alkyl group in R 101 is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, it is preferably 1 or more, more preferably 2 or more, and preferably 20 or less, more preferably 15 or less, and Preferably it is 10 or less.
  • Specific examples of the alkyl group include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, and a cyclohexylethyl group.
  • alkyl group may have include aromatic ring groups, hydroxyl groups, carboxy groups, halogen atoms, amino groups, amide groups, 4-(2-methoxy-1-methyl)ethoxy-2- Examples include methylphenyl group, N-acetyl-N-acetoxyamino group, and phenylthio group.
  • the alkyl group is preferably unsubstituted from the viewpoint of ease of synthesis.
  • Examples of the aromatic ring group for R 101 include aromatic hydrocarbon ring groups and aromatic heterocyclic groups.
  • the number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the polymerizable composition. Further, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and even more preferably 12 or less. For example, the number is preferably 5 to 30, more preferably 5 to 20, and even more preferably 5 to 12.
  • aromatic ring group examples include a phenyl group, a naphthyl group, a pyridyl group, and a furyl group.
  • a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
  • substituents that the aromatic ring group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, and a group in which these substituents are linked, From the viewpoint of developability, an alkyl group, an alkoxy group, or a group formed by connecting these groups is preferable, and a connected alkoxy group is more preferable. Among these, from the viewpoint of solubility, R 101 is preferably an alkyl group which may have a substituent.
  • R 102 is preferably an optionally substituted phenyl group, an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, an optionally substituted diphenyl sulfide group, an optionally substituted diphenyl sulfide group, or an optionally substituted diphenyl sulfide group.
  • Examples include a fluorenyl group and an optionally substituted indolyl group. Among these, from the viewpoint of sensitivity, an optionally substituted carbazolyl group or an optionally substituted diphenyl sulfide group is preferred.
  • the number of carbon atoms in the alkanoyl group in R103 is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, it is preferably 2 or more, more preferably 20 or less, more preferably 15 or less, even more preferably 10 or less, and more. More preferably, it is 5 or less.
  • Specific examples of the alkanoyl group include, for example, an acetyl group, an ethyl group, a propanoyl group, and a butanoyl group.
  • substituents that the alkanoyl group may have include aromatic ring groups, hydroxyl groups, carboxy groups, halogen atoms, amino groups, and amide groups.
  • the alkanoyl group is preferably unsubstituted from the viewpoint of ease of synthesis.
  • the number of carbon atoms in the aroyl group in R 103 is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, it is preferably 7 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
  • Specific examples of the aroyl group include benzoyl group and naphthoyl group.
  • substituents that the aroyl group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, and an alkyl group.
  • the aroyl group is preferably unsubstituted from the viewpoint of ease of synthesis.
  • R 103 is preferably an alkanoyl group that may have a substituent, more preferably an unsubstituted alkanoyl group, and even more preferably an acetyl group.
  • (D) a photopolymerization initiator in addition to the photopolymerization initiator described above, for example, Japanese Patent No. 4454067, International Publication No. 2002/100903, International Publication No. 2012 /45736 Publication, International Publication 2015/36910, International Publication 2006/18973, International Publication 2008/78678, Japanese Patent No. 4818458, International Publication 2005/80338/, International Publication 2008/75564, International Publication 2009/131189, International Publication 2009/131189, International Publication 2010/133077, International Publication 2010/102502, International Publication Year 2012/68879 Photopolymerization initiators described in publications can be used.
  • the photopolymerization initiator may contain a sensitizing dye and a polymerization accelerator depending on the wavelength of the image exposure light source, if necessary, for the purpose of increasing sensitivity.
  • the sensitizing dye include xanthene dyes described in Japanese Patent Application Laid-Open No. 4-221958 and Japanese Patent Application Publication No. 4-219756, Japanese Patent Application Publication No. 3-239703, and Japanese Patent Application Publication No. 5-289335.
  • amino group-containing sensitizing dyes are preferred, and compounds having an amino group and a phenyl group in the same molecule are more preferred.
  • amino group-containing sensitizing dyes are preferred, and compounds having an amino group and a phenyl group in the same molecule are more preferred.
  • Benzophenone compounds such as benzophenone; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2- (p-dimethylaminophenyl
  • polymerization accelerator examples include aromatic amines such as ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 4-dimethylaminoacetophenone, and 4-dimethylaminopropiophenone, and n-butylamine. , N-methyldiethanolamine, 2-dimethylaminoethyl benzoate, and the like can be used.
  • the polymerization accelerators may be used alone or in combination of two or more.
  • the content ratio of the photopolymerization initiator (D) is not particularly limited, but it is preferably 0% in the total solid content of the polymerizable composition. .01% by mass or more, more preferably 0.1% by mass or more, even more preferably 1% by mass or more, even more preferably 2% by mass or more, particularly preferably 3% by mass or more, and preferably 25% by mass.
  • the content is more preferably 20% by mass or less, still more preferably 15% by mass or less, even more preferably 10% by mass or less, particularly preferably 7% by mass or less, most preferably 5% by mass or less.
  • it is preferably 0.01 to 25% by mass, more preferably 0.01 to 20% by mass, even more preferably 0.1 to 15% by mass, even more preferably 1 to 10% by mass, and even more preferably 2 to 7% by mass. Particularly preferred is 3 to 5% by weight.
  • curability is preferably 0.01 to 25% by mass, more preferably 0.01 to 20% by mass, even more preferably 0.1 to 15% by mass, even more preferably 1 to 10% by mass, and even more preferably 2 to 7% by mass.
  • Particularly preferred is 3 to 5% by weight.
  • the blending ratio of (D) photopolymerization initiator to (B) polymerizable compound in the polymerizable composition is preferably 1 part by mass or more, and 5 parts by mass or more with respect to 100 parts by mass of (B) polymerizable compound. is more preferable, 10 parts by weight or more is still more preferable, 15 parts by weight or more is even more preferable, 20 parts by weight or more is particularly preferable, and 200 parts by weight or less is preferable, more preferably 100 parts by weight or less, 50 parts by weight or less. is more preferable, and 30 parts by mass or less is particularly preferable.
  • it is preferably 1 to 200 parts by weight, more preferably 5 to 200 parts by weight, even more preferably 10 to 100 parts by weight, even more preferably 15 to 50 parts by weight, and particularly preferably 20 to 30 parts by weight.
  • curability is preferably 1 to 200 parts by weight, more preferably 5 to 200 parts by weight, even more preferably 10 to 100 parts by weight, even more preferably 15 to 50 parts by weight, and particularly preferably 20 to 30 parts by weight.
  • the polymerizable composition of the present invention may contain (E) a colorant for the purpose of coloring the composition.
  • a colorant for the purpose of coloring the composition.
  • known colorants such as pigments and dyes can be used.
  • the type of colorant (E) used in the present invention is not particularly limited, and pigments or dyes may be used. Among these, from the viewpoint of durability, it is preferable to use pigments.
  • the colorant may contain one type or two or more types of pigments. In particular, from the viewpoint of uniformly blocking light in the visible region, it is preferable to use two or more types.
  • the type of pigment that can be used as the colorant is not particularly limited, and examples thereof include organic pigments and inorganic pigments. Among these, it is preferable to use organic pigments from the viewpoint of controlling the transmission wavelength of the polymerizable composition and curing it efficiently. Examples of organic pigments include organic colored pigments and organic black pigments.
  • the organic colored pigment refers to an organic pigment exhibiting a color other than black, and includes red pigments, orange pigments, blue pigments, violet pigments, green pigments, yellow pigments, and the like.
  • organic colored pigments it is preferable to use organic colored pigments from the viewpoint of ultraviolet absorbability.
  • One type of organic coloring pigment may be used alone, or two or more types may be used in combination.
  • organic pigments are not particularly limited, but examples thereof include azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. Specific examples of pigments that can be used are shown below using pigment numbers. Terms such as "C.I. Pigment Red 2" listed below mean color index (C.I.).
  • C. I. Pigment Red 177, 254, and 272 are preferably used.
  • red pigments with low ultraviolet absorbance from this point of view, C. I. It is more preferable to use Pigment Red 254 and 272.
  • C. I. Pigment Orange 1 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79.
  • C. I. It is preferable to use Pigment Orange 13, 43, 64, and 72.
  • C. I. Pigment Blue 1 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79.
  • C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 60 more preferably C.I. I. Pigment Blue 15:6 may be mentioned.
  • Pigment Blue 15:6, 16, and 60 When curing the polymerizable composition with ultraviolet rays, it is preferable to use a blue pigment with low ultraviolet absorption rate, and from this point of view, C .. I. It is more preferable to use Pigment Blue 60.
  • C. I. Pigment Violet 1 As a purple pigment, C. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50.
  • C.I. I. Pigment Violet 19 23, more preferably C.I. I. Pigment Violet 23 may be mentioned.
  • C. I. It is preferable to use Pigment Violet 23 and 29, and when curing the polymerizable composition with ultraviolet rays, it is preferable to use a purple pigment with a low ultraviolet absorbance.From this point of view, C.I. I. It is more preferable to use Pigment Violet 29.
  • organic coloring pigments examples include green pigments and yellow pigments.
  • green pigment C. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55.
  • yellow pigment C. I. Pigment Green 7 and 36.
  • At least one selected from the group consisting of red pigments, orange pigments, blue pigments, and violet pigments from the viewpoint of light-shielding properties and photocurability.
  • Red pigment C. I. Pigment Red 177, 254, 272
  • Orange pigment C. I. Pigment orange 43, 64, 72
  • Blue pigment C. I. Pigment Blue 15:6,60 Purple pigment: C. I. pigment violet 23, 29
  • an organic black pigment as the colorant (E).
  • the organic black pigment include aniline black, perylene black, and an organic black pigment represented by the following general formula (2). Among these, from the viewpoint of light-shielding properties and dispersibility, the organic black pigment represented by formula (2) is more preferable.
  • Inorganic pigments can also be used.
  • inorganic black pigments include carbon black, acetylene black, lamp black, bone black, graphite, iron black, cyanine black, and titanium black.
  • carbon black can be preferably used from the viewpoint of light-shielding properties and dispersibility.
  • a known dispersant or dispersion aid may be used in combination so that the pigment can stably exist in the polymerizable composition without agglomerating.
  • the content of the colorant is not particularly limited, but is preferably 1% by mass or more, more preferably 1% by mass or more based on the total solid content of the polymerizable composition.
  • the content is preferably 10% by mass or more, more preferably 60% by mass or less, and more preferably 40% by mass or less.
  • the polymerizable composition of the present invention may contain (F) a chain transfer agent.
  • F By including a chain transfer agent, radical deactivation due to oxygen inhibition in the vicinity of the surface can be improved, surface hardenability can be improved, and the taper angle tends to increase.
  • the chain transfer agent (F) include mercapto group-containing compounds and carbon tetrachloride, and mercapto group-containing compounds are more preferred since they tend to have a high chain transfer effect.
  • Mercapto group-containing compounds tend to be able to improve surface hardening properties because bond cleavage is likely to occur due to the small S--H bond energy and chain transfer reactions are likely to occur.
  • mercapto group-containing compounds having an aromatic ring and aliphatic mercapto group-containing compounds are preferred from the viewpoint of taper angle and surface hardening properties.
  • aliphatic mercapto group-containing compounds include butanediol bis(3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol bis(3-mercaptopropionate), and ethylene glycol bisthioglycolate.
  • trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2 , 4,6(1H,3H,5H)-trione are preferred, and pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate) are more preferred.
  • the polymerizable composition of the present invention may contain a coatability improver and a development improver in order to improve the coatability and development solubility.
  • a coating property improver or development improver for example, known surfactants can be used.
  • the surfactant can be used for the purpose of improving the coating properties of the polymerizable composition as a coating solution and the developability of the coating film, and among them, fluorine-based surfactants or silicone-based surfactants are preferred.
  • silicone-based surfactants are preferred because they have the effect of removing residues of the polymerizable composition from unexposed areas during development and also have the function of developing wettability. Activators are even more preferred.
  • a compound having a fluoroalkyl or fluoroalkylene group at at least one of the terminal, main chain, and side chain is suitable.
  • silicone surfactants examples include “DC3PA”, “SH7PA”, “DC11PA”, “SH21PA”, “SH28PA”, “SH29PA”, “8032Additive”, “SH8400” manufactured by Dow Corning Toray Industries, Inc., and BIC Chemie Co., Ltd. Examples include “BYK (registered trademark, hereinafter the same)” 323 and BYK330.
  • the surfactant may include other surfactants other than fluorosurfactants and silicone surfactants, such as nonionic, anionic, cationic, and amphoteric surfactants. Examples include surfactants.
  • nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, and glycerin. Fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythritol fatty acid esters, polyoxyethylene pentaerythritol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitol fatty acid esters, polyoxyethylene Examples include sorbitol fatty acid esters. Examples of these commercially available products include polyoxyethylene surfactants such as "Emulgen (registered trademark) 104P" and "Emulgen A60" manufactured by Kao Corporation.
  • anionic surfactants include alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate ester salts, higher alcohol sulfate ester salts, Aliphatic alcohol sulfate ester salts, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl phosphate ester salts, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, special polymer systems
  • surfactants include surfactants.
  • special polymer surfactants are preferred, and special polycarboxylic acid type polymer surfactants are more preferred.
  • anionic surfactants include alkyl sulfate ester salts such as "Emar (registered trademark) 10" manufactured by Kao Corporation, and alkylnaphthalene sulfonates such as “Perex (registered trademark) NB-L” manufactured by Kao Corporation.
  • special polymer surfactants include "Homogenol (registered trademark, hereinafter the same) L-18" and “Homogenol L-100” manufactured by Kao Corporation.
  • Examples of the cationic surfactant include quaternary ammonium salts, imidazoline derivatives, and alkylamine salts.
  • Examples of amphoteric surfactants include betaine type compounds, imidazolium salts, imidazolines, and amino acids. Among these, quaternary ammonium salts are preferred, and stearyltrimethylammonium salts are more preferred.
  • Examples of cationic surfactants or benign surfactants include, for example, alkylamine salts include "Acetamine (registered trademark) 24" manufactured by Kao Corporation, and examples of quaternary ammonium salts include "Cortamine (registered trademark) 24" manufactured by Kao Corporation.
  • One type of surfactant may be used alone, or two or more types may be used in combination. Examples include combinations of silicone surfactants/fluorosurfactants, silicone surfactants/special polymer surfactants, and fluorosurfactants/special polymer surfactants. . Among these, a combination of silicone surfactant/fluorosurfactant is preferred. Examples of this combination of silicone surfactant/fluorosurfactant include "BYK-300" or "BYK-330" manufactured by BYK Chemie, "DFX-18" manufactured by Neos, and "BYK-300” manufactured by BYK Chemie.
  • the content of the coatability improver or development improver is determined from the viewpoint of curability in the total solid content of the polymerizable composition.
  • each content is 20% by mass or less, and more preferably each content is 10% by mass or less.
  • the polymerizable composition of the present invention may contain an ultraviolet absorber.
  • the ultraviolet absorber is added for the purpose of controlling the photocuring distribution by causing the ultraviolet absorber to absorb a specific wavelength of the light source used for exposure. Inclusion of an ultraviolet absorber tends to produce effects such as improving the taper angle shape after development and reducing residue remaining in unexposed areas after development.
  • the ultraviolet absorber from the viewpoint of inhibiting light absorption by the photopolymerization initiator, for example, a compound having an absorption maximum in the wavelength range of 250 nm to 400 nm can be used.
  • ultraviolet absorber examples include benzotriazole compounds, triazine compounds, benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and its derivatives, dinaphthalene compounds, phenanthroline compounds, and dyes. These ultraviolet absorbers may be used alone or in combination of two or more.
  • the polymerizable composition of the present invention may contain a polymerization inhibitor. Since radical polymerization is inhibited by containing a polymerization inhibitor, it is thought that the taper angle of the obtained partition walls can be increased.
  • the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-cresol (BHT). Among these, from the viewpoint of polymerization inhibition ability, methylhydroquinone and methoxyphenol are preferred, and methylhydroquinone is more preferred.
  • One type of polymerization inhibitor may be used alone, or two or more types may be used in combination.
  • a polymerization inhibitor may be contained in the resin, and it may be used as a polymerization inhibitor contained in the polymerizable composition of the present invention, or In addition to the polymerization inhibitor contained therein, the same or different polymerization inhibitor may be added during the production of the polymerizable composition.
  • the polymerizable composition of the present invention may contain a silane coupling agent in order to improve the adhesion to the substrate.
  • a silane coupling agent for example, epoxy-based, methacrylic-based, amino-based, or imidazole-based silane coupling agents can be used. From the viewpoint of improving adhesion, epoxy-based and imidazole-based silane coupling agents are particularly preferred.
  • the content of the silane coupling agent is preferably 20% by mass or less, more preferably 20% by mass or less in the total solid content of the polymerizable composition. Preferably it is 15% by mass or less.
  • the polymerizable composition of the present invention may contain a phosphoric acid-based adhesion improver in order to improve the adhesion with the substrate.
  • a phosphoric acid-based adhesion improver (meth)acryloyloxy group-containing phosphates are preferred, and those represented by the following general formulas (3a), (3b), and (3c) are particularly preferred.
  • R q represents a hydrogen atom or a methyl group
  • r and r' are integers of 1 to 10
  • s is 1, 2, or 3.
  • the polymerizable composition of the present invention contains a phosphoric acid-based adhesion promoter
  • its content is not particularly limited, but is preferably 0.1% by mass or more in the total solid content of the polymerizable composition, and 0.2% by mass or more. It is more preferably at least 0.3% by mass, even more preferably at least 5% by mass, more preferably at most 3% by mass, even more preferably at most 1% by mass.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 0.1 to 5% by weight, more preferably 0.2 to 3% by weight, and even more preferably 0.3 to 1% by weight.
  • the amount is equal to or more than the lower limit, the adhesion to the substrate tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, surface hardening properties tend to improve.
  • the polymerizable composition of the present invention usually contains a solvent, and is used with each of the above-mentioned components dissolved or dispersed in the solvent.
  • the solvent is not particularly limited, and examples thereof include the organic solvents described below.
  • Ethylene glycol monomethyl ether ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, 3-methoxy-1-butanol, tri- Glycol monoalkyl ethers such as ethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether
  • solvents applicable to the above include, for example, Mineral Spirit, Valsol #2, Apco #18 Solvent, Apco Thinner, So Cal Solvent No. 1 and no. 2, Solvesso #150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names).
  • the solvent can dissolve or disperse each component in the polymerizable composition, and is selected depending on the method of using the polymerizable composition of the present invention.
  • the boiling point at 25 hPa) is preferably 60 to 280°C, more preferably 70 to 260°C.
  • propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, and 3-methoxy-1-butyl acetate are preferred.
  • the total solid content of the solvent in the polymerizable composition is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 18% by mass or more, and preferably 90% by mass or less, more preferably 50% by mass or more. It is preferably used in an amount of not more than 40% by mass, more preferably not more than 40% by mass, particularly preferably not more than 30% by mass.
  • the upper and lower limits can be arbitrarily combined, for example, preferably 10 to 90% by weight, more preferably 10 to 50% by weight, even more preferably 15 to 40% by weight, and particularly preferably 18 to 30% by weight.
  • the polymerizable composition of the present invention is prepared by mixing the above-mentioned components using a stirrer. Note that, in order to make the prepared polymerizable composition uniform, it may be filtered using a membrane filter or the like.
  • Step (1) A step of forming a coating film of a polymerizable composition on a substrate.
  • Step (2) A step of exposing at least a portion of the coating film formed in step (1).
  • Step (3) A step of developing the coating film exposed in step (2).
  • Step (4) A step of baking the coating film developed in step (3).
  • substrates are mainly used, but materials include, for example, polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, and epoxy resins. Examples include thermosetting resin sheets such as resins, unsaturated polyester resins, and poly(meth)acrylic resins, and various glasses. Among these, glass and heat-resistant resin are preferred from the viewpoint of heat resistance.
  • a transparent electrode such as ITO or IZO is formed on the surface of the substrate.
  • a transparent substrate it can also be formed on a TFT array or a touch panel.
  • it is suitably used in the panel structure described in Japanese Patent Application Publication No. 2021-110936.
  • the substrate may be subjected to, for example, corona discharge treatment, ozone treatment, or thin film formation treatment of various resins such as silane coupling agents and urethane resins, as necessary.
  • the thickness of the substrate is usually in the range of 0.05 to 10 mm, preferably 0.1 to 7 mm. Further, when performing a thin film formation treatment of various resins, the film thickness is usually in the range of 0.01 to 10 ⁇ m, preferably 0.05 to 5 ⁇ m.
  • the polymerizable composition of the present invention is usually supplied onto a substrate in a state dissolved or dispersed in a solvent.
  • a method for supplying it conventionally known methods such as a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, and a spray coating method can be used.
  • it may be supplied in a pattern by, for example, an inkjet method or a printing method.
  • the die coating method significantly reduces the amount of composition used, has no influence from the mist etc. that adheres when using the spin coating method, and suppresses the generation of foreign matter. Preferable from this point of view.
  • the amount of coating varies depending on the application, it is applied so that the film thickness after drying is usually 0.5 ⁇ m to 10 ⁇ m, preferably 1 ⁇ m to 9 ⁇ m, and particularly preferably 1 ⁇ m to 7 ⁇ m. It is important that the dry film thickness or the film thickness of the finally formed cured product be uniform over the entire substrate. If the variation is small, uneven defects occurring in the cured product can be suppressed.
  • the film thicknesses of the finally formed cured products will be different.
  • drying is preferably performed to form a coating film.
  • the drying is preferably performed using a hot plate, an IR oven, or a convection oven.
  • a reduced pressure drying method in which drying is performed in a reduced pressure chamber without increasing the temperature may be combined.
  • Drying conditions can be appropriately selected depending on the type of solvent component, the performance of the dryer used, etc.
  • the drying time is usually selected in the range of 15 seconds to 5 minutes at a temperature of 40°C to 100°C, preferably 50°C to 80°C, depending on the type of solvent component, the performance of the dryer used, etc.
  • the time is selected from 30 seconds to 3 minutes depending on the temperature. Note that it is preferable to carry out the firing within a range that does not exceed the firing temperature described below.
  • Step (2) Step of exposing at least a part of the coating film formed in step (1)> [4-4] Exposure method Exposure is performed by overlaying a negative mask pattern on the coating film of the polymerizable composition and irradiating it with an ultraviolet or visible light source through this mask pattern.
  • Exposure is performed by overlaying a negative mask pattern on the coating film of the polymerizable composition and irradiating it with an ultraviolet or visible light source through this mask pattern.
  • a method of projecting exposure light may also be used.
  • a scanning exposure method using laser light without using a mask pattern may also be used.
  • exposure may be carried out in an oxygen-free atmosphere or after forming an oxygen barrier layer such as a polyvinyl alcohol layer on the coating film of the polymerizable composition. It's okay.
  • the difference in film remaining ratio is caused by the difference in average light transmittance between the intermediate transmission aperture and the complete transmission aperture, that is, the difference in exposure amount.
  • a method is known in which the intermediate transmission opening is created using a matrix-like light-shielding pattern having minute polygonal light-shielding units.
  • the absorber is produced by controlling the light transmittance using a film of a chromium-based, molybdenum-based, tungsten-based, or silicon-based material, for example.
  • the light source used for the above exposure is not particularly limited.
  • Examples of light sources include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, fluorescent lamps, argon ion lasers, YAG lasers, Laser light sources include excimer lasers, nitrogen lasers, helium cadmium lasers, blue-violet semiconductor lasers, and near-infrared semiconductor lasers. When using irradiation with light of a specific wavelength, an optical filter can also be used.
  • the optical filter may be, for example, a thin film type that can control the light transmittance at the exposure wavelength, and the material in this case may be, for example, a Cr compound (Cr oxide, nitride, oxynitride, fluoride, etc.). , MoSi, Si, W, and Al.
  • a Cr compound Cr oxide, nitride, oxynitride, fluoride, etc.
  • MoSi Si, W, and Al.
  • the exposure amount is usually 1 mJ/cm 2 or more, preferably 5 mJ/cm 2 or more, more preferably 10 mJ/cm 2 or more, and preferably 300 mJ/cm 2 or less, more preferably 200 mJ/cm 2 or less. , more preferably 150 mJ/cm 2 or less.
  • the distance between the exposure target and the mask pattern is preferably 10 ⁇ m or more, more preferably 50 ⁇ m or more, even more preferably 75 ⁇ m or more, and preferably 500 ⁇ m or less, more preferably 400 ⁇ m or less. , more preferably 300 ⁇ m or less.
  • Step (3) Step of developing the coating film exposed in step (2)> [4-5] Development method After the above exposure, an image pattern can be formed on the substrate by development using an aqueous solution of an alkaline compound or an organic solvent.
  • the aqueous solution of the alkaline compound may further contain, for example, a surfactant, an organic solvent, a buffer, a complexing agent, a dye, or a pigment.
  • Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, and potassium phosphate.
  • inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-, di- or triethanolamine, mono-, di- or trimethylamine
  • Organic alkaline compounds such as mono-, di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. can be mentioned.
  • These alkaline compounds may be a mixture of two or more.
  • surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; alkylbenzene sulfonic acids
  • alkylbenzene sulfonic acids examples include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinic acid ester salts; amphoteric surfactants such as alkyl betaines and amino acids.
  • organic solvent examples include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. Two or more of these organic solvents may be used in combination. Further, the organic solvent may be used alone or in combination with water or an aqueous solution of an alkaline compound.
  • the development temperature is usually 10 to 50°C, preferably 15 to 45°C, more preferably 20 to 40°C.
  • the development method can be, for example, an immersion development method, a spray development method, a brush development method, or an ultrasonic development method.
  • the substrate may be subjected to additional exposure using a method similar to the above-described exposure method, if necessary.
  • Step of baking the coating film developed in step (3)> [4-6] Firing method The obtained coating film is preferably fired.
  • the baking method is not particularly limited, but a hot plate, IR oven, convection oven, etc. are preferably used.
  • the firing temperature is preferably 50°C or higher, more preferably 70°C or higher. Further, the temperature is preferably 150°C or lower, more preferably 100°C or lower, even more preferably 90°C or lower, and even more preferably 80°C or lower.
  • the firing time is preferably 5 minutes to 60 minutes.
  • Black Matrix When the cured product of the present invention is used as a black matrix, the width, shape, etc. of the black matrix are adjusted as appropriate depending on the specifications of the color filter to which it is applied.
  • the black matrix may be fabricated on the array or on a counter substrate.
  • the cured product of the present invention can be used as partition walls, and can also be used for light conversion layers and color filters containing luminescent nanocrystal particles. can do.
  • it can be used in a color filter that has a patterned cured product manufactured by the above-described method as a partition wall and has pixels formed in an area defined by the partition wall.
  • the pixel layer include a layer containing a colored pigment and a layer containing luminescent nanocrystal particles.
  • the color of the emitted light can be selected by changing the constituent materials and size.
  • the luminescent nanocrystal particles include quantum dots and the like. Examples include luminescent nanocrystal particles described in Japanese Patent Application Publication No. 2019-086745, a light conversion layer using the same, and a color filter.
  • Organic electroluminescent device Various organic electroluminescent devices are also manufactured using a substrate provided with a patterned cured product produced by the method described above as a partition wall.
  • the method for forming an organic electroluminescent device is not particularly limited, but preferably, after forming a barrier rib pattern on a substrate by the method described above, the functional material is sublimated in a vacuum to form an area surrounded by the barrier ribs on the substrate.
  • An organic electroluminescent device is manufactured by forming an organic layer such as a pixel by a wet process such as a vapor deposition method, a casting method, a spin coating method, or an inkjet printing method.
  • Types of organic electroluminescent devices include bottom emission type and top emission type.
  • partition walls are formed on a glass substrate laminated with transparent electrodes, and a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode layer are stacked in the opening surrounded by the partition walls. Ru.
  • the top emission type for example, partition walls are formed on a glass substrate laminated with a metal electrode layer, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer are stacked in the opening surrounded by the partition walls.
  • the light-emitting layer include organic electroluminescent layers as described in Japanese Patent Application Publication No. 2009-146691 and Japanese Patent No. 5734681.
  • quantum dots such as those described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 may be used.
  • each layer of the hole transport layer and the electron transport layer may have a laminated structure consisting of two or more layers from the viewpoint of luminous efficiency.
  • the thickness of each layer is not particularly limited, but from the viewpoint of luminous efficiency and brightness, it is usually 1 to 500 nm.
  • the organic electroluminescent element may be formed with RGB colors separated for each opening, or two or more colors may be stacked in one opening.
  • the organic electroluminescent device may include a sealing layer from the viewpoint of improving reliability.
  • the sealing layer has a function of preventing moisture in the air from adsorbing to the organic electroluminescent element and reducing luminous efficiency.
  • the organic electroluminescent device may include a low-reflection film at the interface with air from the viewpoint of improving light extraction efficiency. By arranging a low-reflection film at the interface between air and the element, it is expected that the gap in refractive index will be reduced and reflection at the interface will be suppressed. For example, a moth-eye structure or a super multilayer film technique can be applied to such a low reflection film.
  • an organic electroluminescent device When using an organic electroluminescent device as a pixel in an image display device, it is necessary to prevent light from the light emitting layer of one pixel from leaking to other pixels, and in addition, if the electrodes are made of metal, it is necessary to prevent the light from the light emitting layer of one pixel from leaking to other pixels. Since it is necessary to prevent image quality from deteriorating due to reflection of light, it is preferable to impart light-shielding properties to the partition walls constituting the organic electroluminescent device. Furthermore, in an organic electroluminescent device, since it is necessary to provide electrodes on the upper and lower surfaces of the partition wall, from the viewpoint of insulation, the partition wall preferably has high resistance and low dielectric constant. Therefore, when using a coloring agent to impart light-shielding properties to the partition walls, it is preferable to use the organic pigment that has high resistance and low dielectric constant.
  • the image display device of the present invention contains the cured product of the present invention.
  • the polymerizable composition of the present invention may be placed on a liquid crystal driving substrate (array substrate) having a black matrix or on a counter electrode substrate, and then bonded together to form a liquid crystal cell.
  • a liquid crystal driving substrate array substrate
  • an image display device such as a liquid crystal display device containing the cured product of the present invention can be manufactured.
  • a color filter having a black matrix formed from the polymerizable composition of the present invention can also be used in subpixels of an organic light emitting display panel.
  • the color filter layer can increase the light extraction rate compared to the polarizing plate, and can extend the service life of the organic light emitting display.
  • it can be used in display devices described in Japanese Patent Application Publication No. 2021-517333 and Japanese Patent Application Publication No. 2021-110936.
  • Examples of the image display device of the present invention include organic EL display devices having partition walls and organic electroluminescent elements containing the cured product of the present invention.
  • the organic EL display device includes the above-mentioned organic electroluminescent device, there are no particular restrictions on the type or structure of the image display device, and for example, the organic EL display device can be assembled according to a conventional method using an active drive type organic electroluminescent device. can. For example, it can be formed by the method described in "Organic EL Display” (Ohmsha, published August 20, 2004, written by Seiji Tokito, Chinaya Adachi, and Hideyuki Murata). For example, an image may be displayed by combining an organic electroluminescent device that emits white light and a color filter, or an image may be displayed by combining organic electroluminescent devices that emit light of different colors, such as RGB.
  • reaction vessel was cooled to ice temperature, and 2.25 g of 1-butanethiol (manufactured by Tokyo Kasei Co., Ltd.) and 2.78 g of triethylamine were added dropwise at 10° C. or lower. After completion of the dropwise addition, the mixture was returned to room temperature and stirred for 1 hour and 30 minutes.
  • the resulting reaction solution was poured into 120 ml of water, extracted with 120 ml of ethyl acetate, and the extracted layer was washed with saturated brine. The extracted layer was dried over sodium sulfate, filtered, and the solvent was distilled off using an evaporator to obtain 4.08 g of a yellow liquid (yield: 78%).
  • reaction vessel was cooled to ice temperature, and 5.59 g of p-toluenethiol (manufactured by Tokyo Kasei Co., Ltd.) and 5.57 g of triethylamine were added dropwise at 10° C. or lower. After the dropwise addition was completed, the mixture was returned to room temperature and stirred for 1 hour and 40 minutes. The obtained reaction solution was discharged into 200 ml of water, and the precipitated solid was filtered, washed with 250 ml of water, and dried in vacuum to obtain 9.11 g of oxime compound-3 as a white solid (yield: 96.7). %).
  • the obtained solid was added to hexane and stirred, then the solid was filtered off and washed with hexane. Vacuum drying yielded 0.5 g of the target compound (O-imino-isourea-9) as a white solid.
  • the structure of the obtained compound was confirmed by NMR spectrum measurement. The results are shown below.
  • the obtained solid was added to 15 ml of hexane and stirred, then the solid was filtered off and washed with hexane. The obtained solid was vacuum dried to obtain 1.38 g of the target compound (O-imino-isourea-11) as a white solid.
  • Polymerizable compound-1 (B-1): dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)
  • Alkali-soluble resin-1 (C-1): A copolymer resin containing dicyclopentanyl methacrylate/styrene/glycidyl methacrylate (molar ratio: 0.3/0.1/0.6) as a constituent monomer is subjected to an addition reaction of acrylic acid in an equal amount to the glycidyl methacrylate. , an alkali-soluble acrylic copolymer resin which is further subjected to an addition reaction with tetrahydrophthalic anhydride so that the amount becomes 0.39 mol per mol of the above copolymer resin.
  • the weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 9000, and the solid content acid value was 80 mgKOH/g.
  • Surfactant-1 Megafac F-559 (manufactured by DIC)
  • Solvent-1 Propylene glycol monomethyl ether acetate (PGMEA)
  • Example 12 to 17 ⁇ Preparation of polymerizable composition> Add each component so that the solid content ratio of each component in the total solid content of the polymerizable composition is as shown in Table 1, and add solvent-1 so that the total solid content is 17% by mass. was added, stirred, and dissolved to prepare Compositions 1 to 6. The blending ratios of the polymerizable compound, alkali-soluble resin, and thermal polymerization initiator (O-imino-isourea) in Table 1 are calculated in terms of solid content. Compositions 1 to 6 were evaluated by the method described below.
  • the solvent was distilled off from the obtained filtrate using an evaporator to obtain a white solid with a mixture of liquids. After adding 30 ml of acetonitrile to the obtained residue and stirring for a while, the acetonitrile layer was removed. After adding 30 ml of dichloromethane to the obtained residue and stirring it, it was filtered, and dichloromethane was distilled off from the obtained filtrate under reduced pressure. After repeating this operation twice, the resulting residue was vacuum dried to obtain 2.1 g of the target compound (O-imino-isourea-12) as a yellow viscous liquid.
  • a portion of the obtained liquid was purified by column using ethyl acetate/hexane solvent, and then vacuum dried to obtain 4.6 g of the target compound (O-imino-isourea-13) as a pale yellow viscous liquid. .
  • compositions 7 to 10 were prepared in the same manner as polymerizable compositions 1 to 6 so as to have the blending ratios shown in Table 3.

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Abstract

The present invention provides a compound which is represented by formula (A). In the formula, n represents an integer of 1 to 4; each of R3 and R4 independently represents a C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C6-C20 aryl group, a C1-C20 heteroaryl group, a C7-C15 aralkyl group or an Si(CH3)3 group; and L1, L2 and L3 each represent a linker.　The present invention is able to provide an O-imino-isourea compound which is capable of achieving good curing characteristics even by means of firing at low temperatures.

Description

化合物、重合性組成物、硬化物、カラーフィルタ、隔壁及び画像表示装置Compounds, polymerizable compositions, cured products, color filters, partition walls, and image display devices
　本発明は、新規のＯ－イミノ－イソ尿素化合物、これらのＯ－イミノ－イソ尿素化合物と、少なくとも重合性化合物とを含む重合性組成物に関する。更に、本発明は、前記組成物を硬化させた硬化物、及び硬化物を含むカラーフィルタ、隔壁、画像表示装置に関する。詳しくは、例えば、液晶ディスプレイ、有機電界発光素子（ＯＬＥＤ）の画像表示装置における、各色の画素、ブラックマトリックス、隔壁材の形成に用いられる重合性組成物、この重合性組成物を硬化して得られる硬化物、およびこの硬化物を含む画像表示装置に関する。 The present invention relates to novel O-imino-isourea compounds and polymerizable compositions containing these O-imino-isourea compounds and at least a polymerizable compound. Furthermore, the present invention relates to a cured product obtained by curing the composition, and a color filter, partition wall, and image display device containing the cured product. Specifically, for example, a polymerizable composition used for forming pixels of each color, a black matrix, and a partition material in an image display device such as a liquid crystal display or an organic electroluminescent device (OLED), and a polymerizable composition obtained by curing this polymerizable composition. The present invention relates to a cured product and an image display device including the cured product.
　着色組成物を用いたカラーフィルタの製造方法としては、基板上に顔料分散型の着色組成物を塗布して乾燥した後、この塗膜に対してマスクパターンを介して放射線を照射（露光）し、現像し、焼成することにより各色の画素を得る方法が知られている。また、得られたカラーフィルタを有する液晶表示装置が知られている。 A method for producing a color filter using a colored composition is to apply a pigment-dispersed colored composition onto a substrate, dry it, and then irradiate (expose) this coating film with radiation through a mask pattern. A method of obtaining pixels of each color by developing and baking is known. Further, a liquid crystal display device having the obtained color filter is known.
　また、近年、ＯＬＥＤ表示パネル上にカラーフィルタを有する表示装置、例えば、ＯＬＥＤ表示パネル上に複数の絶縁層と金属層を備え、その上にブラックマトリクス、カラーレジストを備えるＯＬＥＤ表示装置が普及している。
　このようなＯＬＥＤ表示パネルを製造する場合、ＯＬＥＤ素子の耐熱性が低いため、ブラックマトリクスやカラーレジスト等の焼成温度を低くする必要がある。 Furthermore, in recent years, display devices having a color filter on an OLED display panel, for example, an OLED display device having a plurality of insulating layers and metal layers on the OLED display panel, and a black matrix and a color resist thereon, have become popular. There is.
When manufacturing such an OLED display panel, it is necessary to lower the firing temperature of the black matrix, color resist, etc. because the heat resistance of the OLED element is low.
　しかしながら、従来の着色組成物を用いて低温で焼成されたブラックマトリックスやカラーレジストは、耐熱性や耐溶剤性に劣る傾向がある。 However, black matrices and color resists baked at low temperatures using conventional coloring compositions tend to have poor heat resistance and solvent resistance.
　熱重合開始剤は、低温硬化性組成物の硬化を可能にする。アゾ化合物またはペルオキシド化合物は、比較的低い温度でエチレン性不飽和結合の重合を開始する熱重合開始剤として知られている。しかしながら、それらの分解温度は比較的低いため、それらを含む組成物では、製造、貯蔵、輸送の間の安定性及び安全性に関する問題がしばしば起こる。従って、安定性および安全性に対する要求を満たす熱重合開始剤が絶えず求められている。
　また、熱重合開始剤は、例えばフォトリソグラフィーの前に溶剤を除去する際のプリベーク工程での良好な安定性と、フォトリソグラフィー後のポストベーク工程における高い硬化性の実現が求められる。 Thermal polymerization initiators enable the curing of low temperature curable compositions. Azo compounds or peroxide compounds are known as thermal polymerization initiators that initiate polymerization of ethylenically unsaturated bonds at relatively low temperatures. However, because of their relatively low decomposition temperatures, compositions containing them often pose problems regarding stability and safety during manufacture, storage, and transportation. Therefore, there is a continuing need for thermal polymerization initiators that meet stability and safety requirements.
Further, the thermal polymerization initiator is required to have good stability in a pre-bake step when removing a solvent before photolithography, and high curability in a post-bake step after photolithography.
　故に、充分な安全性を有し、かつ、比較的低温での硬化性化合物の重合のための新規な熱重合開始剤の一般的な必要性がある。 There is therefore a general need for new thermal polymerization initiators for the polymerization of curable compounds at relatively low temperatures with sufficient safety.
　特許文献１は新規構造を含むＯ－イミノ－イソ尿素化合物又はそれらの塩を、ラジカル重合の重合開始剤としての使用及びそれらのＯ－イミノ－イソ尿素化合物を含む重合性組成物を開示している。 Patent Document 1 discloses the use of O-imino-isourea compounds having a novel structure or salts thereof as a polymerization initiator for radical polymerization, and polymerizable compositions containing these O-imino-isourea compounds. There is.
　特許文献２は（ａ）β－エピチオプロピル官能基を有する少なくとも１種のエチレン性不飽和モノマーを含むモノマー組成物、（ｂ）場合により、２つ以上のβ－エピチオプロピル官能基を有するが重合可能なエチレン性不飽和基は有しない化合物、（ｃ）イソ尿素官能性重合開始剤及び（ｄ）β－エピチオプロピル官能基間の反応に作用する触媒とを含む重合可能な組成物であって、該イソ尿素官能性重合開始剤（ｃ）が、Ｏ－ジアルキルアミノ－イソ尿素及びＯ－イミノ－イソ尿素のうちの少なくとも１つを含む重合可能な組成物を開示している。 Patent Document 2 discloses a monomer composition comprising (a) at least one ethylenically unsaturated monomer having a β-epithiopropyl functional group; (b) optionally having two or more β-epithiopropyl functional groups. (c) an isourea-functional polymerization initiator; and (d) a catalyst that effects a reaction between β-epithiopropyl functional groups. Discloses a polymerizable composition in which the isourea-functional polymerization initiator (c) comprises at least one of O-dialkylamino-isourea and O-imino-isourea.
　特許文献３はＯ－イミノ－イソ尿素とブロックイソシアネートを有するラジカル重合とウレタン硬化を同時に可能な低温硬化向け新規デュアル硬化性架橋剤が開示されている。
　該デュアル硬化性架橋剤はＯ－イミノ－イソ尿素を使用して、脂肪族、芳香族、あるいは脂環式ポリイソシアネート化合物のイソシアネート基をブロックすることによって形成される。 Patent Document 3 discloses a novel dual-curing crosslinking agent for low-temperature curing that is capable of simultaneous radical polymerization and urethane curing, which contains O-imino-isourea and blocked isocyanate.
The dual curable crosslinker is formed by blocking the isocyanate groups of aliphatic, aromatic, or cycloaliphatic polyisocyanate compounds using O-imino-isoureas.
　特許文献４は、熱重合開始剤として１０時間半減期温度が９０℃以上のペルオキシド化合物を含む着色画像形成材料を用い、フォトリソグラフィー後、１００～１８０℃でポストベーク工程を適用することによって、良好な耐溶剤性を有するカラーフィルタを製造することを開示している。 Patent Document 4 discloses that a colored image-forming material containing a peroxide compound with a 10-hour half-life temperature of 90°C or higher as a thermal polymerization initiator is used, and a post-baking process is applied at 100 to 180°C after photolithography to achieve good results. This disclosure discloses manufacturing a color filter having excellent solvent resistance.
　アゾ系化合物および過酸化水素の群から選ばれる少なくとも１種の熱重合開始剤を含む感放射線性組成物であって、プラスチック基板上にカラーフィルタを形成する際、該プラスチック基板が変形、黄変しないような低温処理を採用した場合でも、基板との十分な密着性を有するカラーフィルタを形成できる組成物が、特許文献５に開示されている。 A radiation-sensitive composition containing at least one thermal polymerization initiator selected from the group of azo compounds and hydrogen peroxide, which causes deformation and yellowing of the plastic substrate when forming a color filter on the plastic substrate. Patent Document 5 discloses a composition that can form a color filter that has sufficient adhesion to a substrate even when a low-temperature treatment is used that does not cause the oxidation.
　非特許文献１はＯ－イミノ－イソ尿素構造を有する熱ラジカル開始剤の合成及び重合特性について報告されている。それらのＯ－イミノ－イソ尿素開始剤を用いることで、１００℃より低い温度でｎ－ブチルアクリレートの重合が可能であることも報告されている。 Non-Patent Document 1 reports on the synthesis and polymerization properties of a thermal radical initiator having an O-imino-isourea structure. It has also been reported that by using these O-imino-isourea initiators, it is possible to polymerize n-butyl acrylate at temperatures lower than 100°C.
　非特許文献２はＯ－イミノ－イソ尿素とブロックイソシアネートを有するラジカル重合とウレタン硬化を同時に可能な新規のデュアル硬化性架橋剤が報告されている。前述の架橋剤は自動車のクリアコートに使用するために設計され、従来の１５０℃よりも低い温度条件、例えば、１３０℃でのラジカル反応とウレタン反応の同時架橋を可能にしている。 Non-Patent Document 2 reports a novel dual-curing crosslinking agent that has O-imino-isourea and blocked isocyanate and is capable of simultaneous radical polymerization and urethane curing. The aforementioned crosslinking agents are designed for use in automotive clear coats and enable simultaneous crosslinking of radical reactions and urethane reactions at temperatures lower than the conventional 150°C, for example at 130°C.
日本国特許５６９３５６５号公報Japanese Patent No. 5693565 日本国特許５９３３８１８号公報Japanese Patent No. 5933818 国際公開第２０１７／１６００１６号International Publication No. 2017/160016 日本国特開平１０－１０７１８号公報Japanese Patent Application Publication No. 10-10718 日本国特許４６６０９８６号公報Japanese Patent No. 4660986
　本発明者が検討したところ、特許文献１に記載されるＯ－イミノ－イソ尿素化合物は、１００℃以下の低温での熱硬化では、重合性組成物の硬化が不十分であることが判明した。 Upon investigation by the present inventor, it was found that the polymerizable composition of the O-imino-isourea compound described in Patent Document 1 is insufficiently cured by heat curing at a low temperature of 100°C or lower. .
　本発明は、上記事情に鑑みてなされたものであり、低温焼成においても良好な硬化特性が得られるＯ－イミノ－イソ尿素化合物を提供することを目的とする。
　また本発明は、前記Ｏ－イミノ－イソ尿素化合物を含有する重合性組成物、重合性組成物を硬化させた硬化物、硬化物からなる隔壁およびカラーフィルタ、隔壁およびカラーフィルタを備える有機電界発光素子、有機電界発光素子を含む画像表示装置を提供することを目的とする。 The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an O-imino-isourea compound that exhibits good curing properties even when fired at low temperatures.
The present invention also provides a polymerizable composition containing the O-imino-isourea compound, a cured product obtained by curing the polymerizable composition, a partition wall and a color filter made of the cured product, and an organic electroluminescence device comprising a partition wall and a color filter. An object of the present invention is to provide an image display device including an organic electroluminescent device.
　本発明者が鋭意検討した結果、特定のＯ－イミノ－イソ尿素化合物が１００℃以下の低温で高い熱硬化性を示すことを見出し、重合性化合物と組み合わせて用いることで上記課題を解決できることを見出し、本発明を完成するに至った。
　即ち本発明の要旨は以下の通りである。 As a result of intensive studies, the present inventor found that a specific O-imino-isourea compound exhibits high thermosetting properties at low temperatures of 100°C or less, and found that the above problems could be solved by using it in combination with a polymerizable compound. This discovery led to the completion of the present invention.
That is, the gist of the present invention is as follows.
［１］以下の式（Ａ）で示される化合物。 [1] A compound represented by the following formula (A).
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
　ｎは１～４の整数であり、
　Ｒ３及びＲ４は、各々独立して、Ｃ１～Ｃ２０アルキル、Ｃ３～Ｃ２０シクロアルキル、Ｃ６～Ｃ２０アリール、Ｃ１～Ｃ２０ヘテロアリール、Ｃ７～Ｃ１５アラルキル、又はＳｉ（ＣＨ３）３であり；
　Ｒ３、Ｒ４におけるＣ１～Ｃ２０アルキル及びＣ３～Ｃ２０シクロアルキルは、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、ＯＣ（Ｏ）、Ｃ（Ｏ）Ｓ、及びＳＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０からなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ３、Ｒ４におけるＣ６～Ｃ２０アリール、Ｃ１２～Ｃ２０ヘテロアリール、及びＣ７～Ｃ１５アラルキルは、Ｃ１～Ｃ１２アルキル、Ｃ１～Ｃ１２ハロアルキル、Ｃ２～Ｃ１２アルケニル、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、Ｃ（Ｏ）ＮＲ１３Ｒ１４、Ｃ６～Ｃ１０アリール、及びＣ１～Ｃ２０ヘテロアリールからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよい。
　Ｌ１、Ｌ２及びＬ３はリンカーである。
　ｎ＝１の場合、Ｌ１はＲ１であり、Ｌ２はＲ２であり、Ｌ３はＲ５である。
　ｎ＝２～４の場合、Ｌ１、Ｌ２、Ｌ３のいずれか一つがリンカーである。Ｌ１がリンカーの場合、Ｌ２はＲ２であり、Ｌ３はＲ５である。Ｌ２がリンカーの場合、Ｌ１はＲ１であり、Ｌ３はＲ５である。Ｌ３がリンカーの場合、Ｌ１はＲ１であり、Ｌ２はＲ２である。
　Ｒ１は、Ｃ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルケニル、Ｃ２～Ｃ２０アルキニル、Ｃ３～Ｃ２０シクロアルキル、Ｃ２～Ｃ２０ヘテロシクロアルキル、Ｃ６～Ｃ２０アリールまたはＣ１～Ｃ２０ヘテロアリールであり；
　Ｒ１におけるＣ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルケニル及びＣ２～Ｃ２０アルキニルは、１もしくはそれより多くの同一もしくは異なるＯ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ及びＯＣ（Ｏ）からなる群より選択される基によって中断されていてもよく、１もしくはそれより多くの同一もしくは異なる基Ｒ１ａを有していてもよく；
　Ｒ１におけるＣ３～Ｃ２０シクロアルキル及びＣ２～Ｃ２０ヘテロシクロアルキルは、１もしくはそれより多くのＣ（Ｏ）基によって中断されていてもよく、１もしくはそれより多くの同一もしくは異なる基Ｒ１ｂを有していてもよく；
　Ｒ１におけるＣ６～Ｃ２０アリール及びＣ１～Ｃ２０ヘテロアリールは、１もしくはそれより多くの同一もしくは異なる基Ｒ１ｃを有していてもよく；
　Ｒ１ａは、各々独立して、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＣＮ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、Ｃ（Ｏ）ＮＲ１３Ｒ１４、１もしくはそれより多くのＣ（Ｏ）基によって中断されていてもよいＣ３～Ｃ２０シクロアルキル、及びＣ６～Ｃ１０アリールからなる群より選択され；
　Ｒ１ａにおけるＣ３～Ｃ２０シクロアルキル及びＣ６～Ｃ１０アリールは、１もしくはそれより多くの同一もしくは異なる基Ｒ１ａａを有していてもよく；
　Ｒ１ａａは、各々独立して、Ｃ１～Ｃ１２アルキル、Ｃ２～Ｃ１２アルケニル、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、ＳＲ７、ＯＲ８及びＮＲ９Ｒ１０からなる群より選択され；
　Ｒ１ａａにおけるＣ１～Ｃ１２アルキルは、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、及びＣ（Ｏ）ＮＲ１３Ｒ１４からなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ１ｂは、各々独立して、Ｃ１～Ｃ１２アルキル、Ｃ２～Ｃ１２アルケニル、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＣＮ、ＮＯ２、ＳＲ７、ＯＲ８及びＮＲ９Ｒ１０からなる群より選択され；
　Ｒ１ｂにおけるＣ１～Ｃ１２アルキルは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、及びＣ（Ｏ）ＮＲ１３Ｒ１４からなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
Ｒ１ｃは、各々独立して、Ｃ１～Ｃ１２アルキル、Ｃ２～Ｃ１２アルケニル、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＣＮ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、Ｃ（Ｏ）ＮＲ１３Ｒ１４、Ｃ６～Ｃ１０アリール、Ｃ１～Ｃ２０ヘテロアリール、Ｃ３～Ｃ１０シクロアルキル、及びＣ２～Ｃ１０ヘテロシクロアルキルからなる群より選択され；
　Ｒ１ｃにおけるＣ１～Ｃ１２アルキルは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、及びＣ（Ｏ）ＮＲ１３Ｒ１４から選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ１ｃにおけるＣ１～Ｃ１２アルキル、Ｃ３～Ｃ１０シクロアルキル及びＣ２～Ｃ１０ヘテロシクロアルキルは、１もしくはそれより多くのＣ（Ｏ）基によって中断されていてもよく；
　Ｒ１ｃにおけるＣ６～Ｃ１０アリール、Ｃ１～Ｃ２０ヘテロアリール、Ｃ３～Ｃ１０シクロアルキル及びＣ２～Ｃ１０ヘテロシクロアルキルは、１もしくはそれより多くの同一もしくは異なる基Ｒ１ｃａを有していてもよく、該Ｒ１ｃａは、前記Ｒ１ａａと同義であり；
　Ｒ２は、水素原子、Ｃ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルケニル、Ｃ２～Ｃ２０アルキニル、Ｃ３～Ｃ２０シクロアルキル、Ｃ２～Ｃ２０ヘテロシクロアルキル、Ｃ６～Ｃ２０アリール、Ｃ１～Ｃ２０ヘテロアリール、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、Ｃ（Ｏ）ＮＲ１３Ｒ１４、ＳＯ２Ｒ１５、またはＣＮであり；
　Ｒ２におけるＣ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルケニル及びＣ２～Ｃ２０アルキニルは、１もしくはそれより多くの同一もしくは異なるＯ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される基によって中断されていてもよく、１もしくはそれより多くの同一もしくは異なる基Ｒ２ａを有していてもよく；
　Ｒ２におけるＣ３～Ｃ２０シクロアルキル及びＣ２～Ｃ２０ヘテロシクロアルキルは、１もしくはそれより多くのＣ（Ｏ）基によって中断されていてもよく、１もしくはそれより多くの同一もしくは異なる基Ｒ２ｂを有していてもよく；
　Ｒ２におけるＣ６～Ｃ２０アリール及びＣ１～Ｃ２０ヘテロアリールは、１もしくはそれより多くの同一もしくは異なる基Ｒ２ｃを有していてもよく；
　Ｒ２ａは、Ｒ１ａと同義であり；
　Ｒ２ｂは、Ｒ１ｂと同義であり；
　Ｒ２ｃは、Ｒ１ｃと同義であり；
　また、Ｒ２は、－Ｓ－Ｒ１と一緒になってイミノ炭素原子を含む環構造を形成していてもよく；
　前記イミノ炭素原子を含む環構造としては、Ｓ－（Ｃ１～Ｃ２０アルキレン）－Ｘ、Ｓ－（Ｃ２～Ｃ２０アルケニレン）－Ｘ、Ｓ－（Ｃ３～Ｃ２０シクロアルキレン）－Ｘ、Ｓ－（ヘテロシクロアルキレン）－Ｘ、Ｓ－（ｏ－フェニレン）－Ｘ、Ｓ－（ｏ－キシレン）－Ｘ、Ｓ－（ｏ－フェニレン－Ｃ１～Ｃ１２アルキレン）－Ｘ、Ｓ－（Ｃ１～Ｃ１２アルキレン－ｏ－フェニレン）－Ｘ、Ｓ－（Ｃ（Ｏ）Ｎ（Ｒ１６））－Ｘ、またはＳ－（Ｃ（Ｓ）Ｎ（Ｒ１７））－Ｘであってよく；
　Ｘは、Ｓを有するイミノ炭素原子に結合されており、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、ＯＣ（Ｏ）、Ｃ（Ｏ）Ｏ、ＳＣ（Ｏ）、Ｃ（Ｏ）Ｓ、Ｃ（Ｏ）Ｎ（Ｒ１６）、Ｎ（Ｒ１８）Ｃ（Ｏ）、Ｎ（Ｒ１９）ＳＯ２または単結合であり；
　前記イミノ炭素原子を含む環構造におけるアルキレン及びアルケニレンは、１もしくはそれより多くの同一または異なる、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）及びＣ（Ｓ）からなる群より選択される基によって中断されていてもよく、１もしくはそれより多くの基Ｒ２ｄによって置換されていてもよく；
　前記イミノ炭素原子を含む環構造におけるシクロアルキレン及びヘテロシクロアルキレンは、１もしくはそれより多くのＣ（Ｏ）基によって中断されていてもよく、１もしくはそれより多くの同一もしくは異なる基Ｒ２ｅによって置換されていてもよく；
　前記イミノ炭素原子を含む環構造におけるフェニレン及びｏ－キシリレンは、１もしくはそれより多くの同一もしくは異なる基Ｒ２ｆによって置換されていてもよく；
　Ｒ２ｄは、各々独立して、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、Ｃ（Ｏ）ＮＲ１３Ｒ１４、Ｃ６～Ｃ１０アリール及びＣ１～Ｃ２０ヘテロアリールからなる群より選択され；
　Ｒ２ｄにおけるＣ６～Ｃ１０アリール及びＣ１～Ｃ２０ヘテロアリールは、１もしくはそれより多くの基Ｒ２ｄａを有していてもよく、Ｒ２ｄａは、各々独立に、フェノキシ、及びＲ１ａａで示した基からなる群から選択され；
　Ｒ２ｅは、各々独立して、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、ＣＯＮＲ１３Ｒ１４、Ｃ１～Ｃ１２アルキル、Ｃ１～Ｃ１２ハロアルキル、Ｃ６～Ｃ１０アリール、及びＣ１～Ｃ２０ヘテロアリールからなる群より選択され；
　Ｒ２ｅにおけるＣ６～Ｃ１０アリール及びＣ１～Ｃ２０ヘテロアリールは、１もしくはそれより多くの基Ｒ２ｅａを有していてもよく、Ｒ２ｅａは、Ｒ１ａａと同義であり；
　Ｒ２ｆは、各々独立して、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、ＣＯＮＲ１３Ｒ１４、Ｃ１～Ｃ１２アルキル、Ｃ１～Ｃ１２ハロアルキル、Ｃ６～Ｃ１０アリール、及びＣ１～Ｃ２０ヘテロアリールからなる群より選択され；
　Ｒ２ｆにおけるＣ６～Ｃ１０アリール及びＣ１～Ｃ２０ヘテロアリールは、１もしくはそれより多くの基Ｒ２ｆａを有していてもよく、Ｒ２ｆａは、Ｒ１ａａと同義であり；
　Ｒ５は、水素原子、Ｃ１～Ｃ２０アルキル、Ｃ３～Ｃ２０シクロアルキル、Ｃ７～Ｃ１４アラルキル、Ｃ６～Ｃ１４アリール、またはアシル基であり；
　Ｒ５におけるアシル基は、－Ｃ（Ｏ）－Ｈ、－Ｃ（Ｏ）－Ｃ１～Ｃ１８アルキル、－Ｃ（Ｏ）－Ｃ２～Ｃ１８アルケニル、－Ｃ（Ｏ）－Ｃ６～Ｃ１４アリール、－Ｃ（Ｏ）－Ｃ２～Ｃ１８アルケニル－Ｃ６～Ｃ１４アリール、－Ｃ（Ｏ）－Ｏ－Ｃ１～Ｃ１８アルキル、－Ｃ（Ｏ）－Ｏ－Ｃ６～Ｃ１４アリール、－Ｃ（Ｏ）－ＮＨ－Ｃ１～Ｃ１８アルキル、－Ｃ（Ｏ）－ＮＨ－Ｃ６～Ｃ１４アリール及びＣ（Ｏ）－Ｎ（Ｃ１～Ｃ１８アルキル）２からなる群より選択され；
　Ｒ３及びＲ５は、それらが結合する窒素原子と共に、更なるヘテロ原子を含んでいてもよい５～１２員環を形成していてもよく；
　Ｒ６は、各々独立して、水素原子、Ｃ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルカノイル、Ｃ６～Ｃ１０アリール及びＣ７～Ｃ１１アロイルからなる群より選択され；
　Ｒ６におけるＣ１～Ｃ２０アルキルは、Ｏ、Ｓ、Ｎ（Ｃ１～Ｃ１２アルキル）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、Ｃ２～Ｃ１０ヘテロシクロアルキル、Ｃ６～Ｃ１０アリール、ＯＨ、及びＳＨからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ６におけるＣ２～Ｃ２０アルカノイルは、Ｏ、Ｓ、ＣＯ、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、Ｃ２～Ｃ１０ヘテロシクロアルキル、及びＣ６～Ｃ１０アリールからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ６におけるＣ６～Ｃ１０アリールは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１０アルキル、Ｃ１～Ｃ１０アルコキシ、及びＣ２～Ｃ１１アシロキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ６におけるＣ７～Ｃ１１アロイルは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１０アルキル、Ｃ１～Ｃ１０アルコキシ、及びＣ２～Ｃ１１アシロキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ７及びＲ８は、各々独立して、水素原子、Ｃ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルカノイル、Ｃ６～Ｃ１０アリール、及びＣ７～Ｃ１１アロイルからなる群より選択され；
　Ｒ７、Ｒ８におけるＣ１～Ｃ２０アルキルは、Ｏ、Ｓ、Ｎ（Ｃ１～Ｃ１２アルキル）、ＣＯ、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、Ｃ２～Ｃ１０ヘテロシクロアルキル、Ｃ６～Ｃ１０アリール、ＯＨ、及びＳＨからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ７、Ｒ８におけるＣ２～Ｃ２０アルカノイルは、Ｏ、Ｓ、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、Ｃ２～Ｃ１０ヘテロシクロアルキル、及びＣ６～Ｃ１０アリールからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ７、Ｒ８におけるＣ６～Ｃ１０アリールは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ６アルキル、Ｃ１～Ｃ１０アルコキシ、及びＣ２～Ｃ１１アシロキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ７、Ｒ８におけるＣ７～Ｃ１１アロイルは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１０アルキル、Ｃ１～Ｃ１０アルコキシ、及びＣ２～Ｃ１１アシロキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ９及びＲ１０は、各々独立して、水素原子、Ｃ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルカノイル、Ｃ７～Ｃ１１アロイル、Ｃ６～Ｃ１０アリールからなる群より選択され；
　Ｒ９、Ｒ１０におけるＣ１～Ｃ２０アルキルは、Ｏ、Ｓ、Ｎ（Ｃ１～Ｃ１２アルキル）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、Ｃ３～Ｃ１０シクロアルキル、ヘテロシクロアルキル、フェニル、ＯＨ、ＳＨ及びＣＮからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ９、Ｒ１０におけるＣ２～Ｃ２０アルカノイルは、Ｏ及びＳからなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＯＨ及びＣ１～Ｃ６アルコキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ９、Ｒ１０におけるＣ７～Ｃ１１アロイルは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ６アルキル、－ＯＨ及びＣ１～Ｃ６アルコキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ９、Ｒ１０におけるＣ６～Ｃ１０アリールは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ６アルキル、－ＯＨ及びＣ１～Ｃ６アルコキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ９及びＲ１０は、それらが結合される窒素原子と一緒になって、飽和の５員、６員または７員の窒素複素環を形成していてもよく、前記環はＯ、Ｓ、Ｎ（Ｃ１～Ｃ１２アルキル）、Ｃ（Ｏ）、及びＣ（Ｏ）Ｏからなる群より選択される基を環員として有していてもよく、前記環は１もしくはそれより多くのＣ１～Ｃ４アルキルを有してよく；
　Ｒ１１は各々独立して、水素原子、Ｃ１～Ｃ２０アルキル及びＣ６～Ｃ２０アリールからなる群より選択され；
　Ｃ１～Ｃ２０アルキルは、Ｏ、Ｓ及びＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、１もしくはそれより多くの同一もしくは異なるＲ１１ａを有していてもよく；
　Ｒ１１ａは、各々独立して、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、ヘテロシクロアルキル、フェニル、ＯＨ、及びＳＨからなる群より選択され；
　Ｒ１１におけるＣ６～Ｃ２０アリールは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１０アルキル、Ｃ１～Ｃ１０アルコキシ、及びＣ２～Ｃ１１アシロキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ１２は、Ｒ８と同義であり；
　Ｒ１３及びＲ１４は、Ｒ９、Ｒ１０と同義であり；
　Ｒ１５は、各々独立して、水素原子、Ｃ１～Ｃ２０アルキル、Ｃ６～Ｃ１０アリールからなる群より選択され；
　Ｒ１５におけるＣ１～Ｃ２０アルキルは、Ｏ、Ｓ、Ｎ（Ｃ１～Ｃ１２アルキル）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、Ｃ２～Ｃ１０ヘテロシクロアルキル、Ｃ６～Ｃ１０アリール、ＯＨ、及びＳＨからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ１５におけるＣ６～Ｃ１０アリールは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ６アルキル、及びＣ１～Ｃ６アルコキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ１６、Ｒ１７、Ｒ１８及びＲ１９は、各々独立して、水素原子、Ｃ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルカノイル、Ｃ６～Ｃ１０アリール、Ｃ７～Ｃ１１アロイルからなる群より選択され；
　Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９におけるＣ１～Ｃ２０アルキルは、Ｏ、Ｓ、Ｎ（Ｃ１～Ｃ１２アルキル）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、Ｃ２～Ｃ１０ヘテロシクロアルキル、Ｃ６～Ｃ１０アリール、ＯＨ、及びＳＨからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９におけるＣ２～Ｃ２０アルカノイルは、Ｏ、Ｓ、ＣＯ、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、Ｃ２～Ｃ１０ヘテロシクロアルキル、及びＣ６～Ｃ１０アリールからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９におけるＣ６～Ｃ１０アリールは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１０アルキル、Ｃ１～Ｃ１０アルコキシ、及びＣ２～Ｃ１１アシロキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９におけるＣ７～Ｃ１１アロイルは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１０アルキル、Ｃ１～Ｃ１０アルコキシ、及びＣ２～Ｃ１１アシロキシからからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｌ１は、ｎが２である場合に、二価のリンカーであり、前記リンカーは、Ｌ１ａ－Ｃ１～Ｃ３０アルキレン－Ｌ１ａ、Ｌ２ａ－Ｃ１～Ｃ３０アルケニレン－Ｌ２ａ、Ｌ１ａ－Ｃ３～Ｃ１６シクロアルキレン－Ｌ１ａ、Ｌ１ａ－Ｃ６～Ｃ２０アリーレン－Ｌ１ａ、Ｌ１ａ－Ｃ６～Ｃ２０アリーレン－Ｌ１ｂ－Ｃ６～Ｃ２０アリーレン－Ｌ１ａ、及びＬ１ａ－Ｃ１～Ｃ１３ヘテロアリーレン－Ｌ１ａからなる群より選択され；
　Ｌ１の前記リンカーにおけるアルキレン及びアルケニレンは、各々独立に、１もしくはそれより多くの同一もしくは異なる非隣接の基Ｌ１ｃによって中断されていてもよく；
　Ｌ１の前記リンカーにおけるアリーレン及びヘテロアリーレンは、各々独立に、１もしくはそれより多くの同一もしくは異なる基ＲＬ１を有していてもよく；
　Ｌ１ａは、単結合であり；
　Ｌ１ｂは、単結合、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、ＣＨ２、Ｃ（ＣＨ３）２、ＣＨ（ＯＨ）またはＣ１～Ｃ５アルキレンであり；
　Ｌ１ｃは、各々独立して、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、ＯＣ（Ｏ）、Ｃ６～Ｃ２０アリーレン及びＣ３～Ｃ１６シクロアルキレンからなる群より選択され；
　ＲＬ１は、各々独立して、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１２アルキル、Ｃ１～Ｃ１２アルコキシ、及びＣ２～Ｃ１１アシロキシから選択され；
　Ｌ１ｂ、Ｌ１ｃにおけるＲ６は、Ｒ６と同義であり；
　Ｌ２は、ｎが２である場合に、二価のリンカーであり、前記リンカーは、単結合、Ｌ２ａ－Ｃ１～Ｃ３０アルキレン－Ｌ２ａ、Ｌ２ａ－Ｃ１～Ｃ３０アルケニレン－Ｌ２ａ、Ｌ２ａ－Ｃ６～Ｃ２０アリーレン－Ｌ２ａ、Ｌ２ａ－Ｃ６～Ｃ２０アリーレン－Ｌ２ｂ－Ｃ６～Ｃ２０アリーレン－Ｌ２ａからなる群より選択され；
　Ｌ２の二価のリンカーにおけるアルキレン及びアルケニレンは、各々独立に、１もしくはそれより多くの同一もしくは異なる基Ｌ２ｃによって中断されていてもよく；
　Ｌ２の二価のリンカーにおけるアリーレン及びヘテロアリーレンは、各々独立に、１もしくはそれより多くの同一もしくは異なる基ＲＬ２を有していてもよく；
　Ｌ２ａは、各々独立して、単結合、Ｓ、Ｏ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、ＯＣ（Ｏ）またはＳＯ２であり；
　Ｌ２ｂは、単結合、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、ＣＨ２、Ｃ（ＣＨ３）２、ＣＨ（ＯＨ）またはＣ１～Ｃ５アルキレンであり；
　Ｌ２ｃは、各々独立して、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、ＯＣ（Ｏ）、Ｃ６～Ｃ２０アリーレン及びＣ３～Ｃ１６シクロアルキレンからなる群より選択され；
　ＲＬ２は、各々独立して、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１２アルキル、Ｃ１～Ｃ１２アルコキシ、及びＣ２～Ｃ１１アシロキシから選択され；
　Ｌ２ｂ、Ｌ２ｃにおけるＲ６は、Ｒ６と同義であり；
　Ｌ３は、ｎが２である場合に、二価のリンカーであり、前記リンカーは、Ｌ３ａ－Ｃ１～Ｃ３０アルキレン－Ｌ３ａ、Ｌ３ａ－Ｃ３～Ｃ１６シクロアルキレン－Ｌ３ａ、Ｌ３ａ－Ｃ６～Ｃ２０アリーレン－Ｌ３ａ、Ｌ３ａ－Ｃ１～Ｃ２０アルキレン－Ｌ３ｂ－Ｃ６～Ｃ１６シクロアルキレン－Ｌ３ａ、Ｌ３ａ－Ｃ６～Ｃ１６シクロアルキレン－Ｌ３ｂ－Ｃ６～Ｃ１６シクロアルキレン－Ｌ３ａ、Ｌ３ａ－Ｃ６～Ｃ２０アリーレン－Ｌ３ｂ－Ｃ６～Ｃ２０アリーレン－Ｌ３ａ、及びＬ３ａ－Ｃ１～Ｃ１３ヘテロアリーレン－Ｌ３ａからなる群より選択され；
　Ｌ３の二価のリンカーにおけるアルキレンは、各々独立して、１もしくはそれより多くの同一もしくは異なる非隣接の基Ｌ３ｃによって中断されていてもよく；
　Ｌ３の二価のリンカーにおけるシクロアルキレンは、各々独立して、１もしくはそれより多くの同一もしくは異なる基ＲＬ３ａを有していてもよく；
　Ｌ３の二価のリンカーにおけるアリーレン及びヘテロアリーレンは、各々独立して、１もしくはそれより多くの同一もしくは異なる基ＲＬ３ｂを有していてもよく；
　Ｌ３ａは、単結合、Ｃ（Ｏ）、Ｃ（Ｏ）ＯまたはＣ（Ｏ）Ｎ（Ｒ１６）であり；
　Ｌ３ｂは、各々独立して、単結合、Ｏ、Ｓ、Ｎ（Ｒ６）またはＣ１～Ｃ５アルキレンであり；
　Ｌ３ｃは、各々独立して、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、ＯＣ（Ｏ）、Ｃ６～Ｃ２０アリーレン、Ｃ３～Ｃ１６シクロアルキレン及びヘテロシクロアルキレンからなる群より選択され；
　ＲＬ３ａは、各々独立して、Ｃ１～Ｃ１２アルキルであり；
　ＲＬ３ｂは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１２アルコキシ、及びＣ２～Ｃ１１アシロキシからなる群より選択され；
　Ｌ３ｂ、Ｌ３ｃにおけるＲ６は、Ｒ６と同義であり；
　Ｌ３ａにおけるＲ１６は、と同義であり；
　Ｌ１及びＬ２は、ｎが３の場合、三価のリンカーであり、前記リンカーは、Ｃ１～Ｃ３０アルカントリイル、Ｃ２～Ｃ３０アルケントリイル、Ｃ３～Ｃ１６シクロアルカントリイル、ヘテロシクロアルカントリイル、Ｃ６～Ｃ２０アレーントリイル、及びヘテロアレーントリイルからなる群より選択され；
　Ｌ１、Ｌ２の三価のリンカーにおけるアルカントリイルは、１もしくはそれより多くの同一もしくは異なる基Ｌ４によって中断されていてもよく；
　Ｌ４は、各々独立して、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、ＯＣ（Ｏ）、Ｃ（Ｏ）Ｎ（Ｒ１６）、Ｎ（Ｒ１８）Ｃ（Ｏ）、Ｃ３～Ｃ２０シクロアルキレン、ヘテロシクロアルキレン、Ｃ６～Ｃ２０アリーレン及びヘテロアリーレンからなる群より選択され；
　Ｌ４におけるＲ６、Ｒ１６、Ｒ１８は各々、Ｒ６、前記Ｒ１８と同義であり；
　Ｌ３は、ｎが３の場合、三価のリンカーであり、前記リンカーは、Ｃ１～Ｃ３０アルカントリイル、Ｃ２～Ｃ３０アルケントリイル、Ｃ３～Ｃ１６シクロアルカントリイル、ヘテロシクロアルカントリイル、Ｃ６～Ｃ２０アレーントリイル、ヘテロアレーントリイル、トリアシルからなる群より選択され；
　Ｌ３の三価のリンカーにおけるアルカントリイルは、１もしくはそれより多くの同一もしくは異なる基Ｌ５によって中断されていてもよく；
　Ｌ５は、各々独立して、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、ＯＣ（Ｏ）、Ｃ（Ｏ）Ｎ（Ｒ１６）、Ｎ（Ｒ１８）Ｃ（Ｏ）、Ｃ３～Ｃ２０シクロアルキレン、ヘテロシクロアルキレン、Ｃ６～Ｃ２０アリーレン及びヘテロアリーレンからなる群より選択され；
　Ｌ５におけるＲ６、Ｒ１６、Ｒ１８は各々、Ｒ６、Ｒ１８と同義であり；
　Ｌ１及びＬ２は、ｎが４である場合、四価のリンカーであり、前記リンカーは、Ｃ１～Ｃ３０アルカンテトライルであり；
　Ｌ１、Ｌ２の４価のリンカーにおけるアルカンテトライルは、１もしくはそれより多くの同一もしくは異なる基Ｌ６によって中断されていてもよく；
　Ｌ６は、各々独立して、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、ＯＣ（Ｏ）、Ｃ（Ｏ）Ｎ（Ｒ１６）、Ｎ（Ｒ１８）Ｃ（Ｏ）、Ｃ３～Ｃ２０シクロアルキレン、ヘテロシクロアルキレン、Ｃ６～Ｃ２０アリーレン及びヘテロアリーレンからなる群より選択され；
　Ｌ６におけるＲ６、Ｒ１６、Ｒ１８は各々、Ｒ６、Ｒ１８と同義であり；
　Ｌ３は、ｎが４である場合、四価のリンカーであり、前記リンカーは、Ｃ１～Ｃ３０アルカンテトライル、テトラアシルからなる群より選択され；
　Ｌ３の４価のリンカーにおけるアルカンテトライルは、１もしくはそれより多くの同一もしくは異なる基Ｌ７によって中断されていてもよく；
　Ｌ７は、各々独立して、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、ＯＣ（Ｏ）、Ｃ（Ｏ）Ｎ（Ｒ１６）、Ｎ（Ｒ１８）Ｃ（Ｏ）、Ｃ３～Ｃ２０シクロアルキレン、ヘテロシクロアルキレン、Ｃ６～Ｃ２０アリーレン及びヘテロアリーレンからなる群より選択され；
　Ｌ７におけるＲ６、Ｒ１６、Ｒ１８は各々、Ｒ６、Ｒ１８と同義である、前記化合物。 n is an integer from 1 to 4,
R 3 and R 4 are each independently C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 1 -C 20 heteroaryl, C 7 -C 15 aralkyl, or Si( CH3 ) 3 ;
C 1 -C 20 alkyl and C 3 -C 20 cycloalkyl in R 3 and R 4 are O, S, N(R 6 ), C(O), C(O)O, OC(O), C( O) optionally interrupted by one or more groups selected from the group consisting of S, and SC(O), F, Cl, Br, I, NO2 , SR7 , OR8 , NR9 R may have one or more same or different groups selected from the group consisting of;
C 6 -C 20 aryl, C 12 -C 20 heteroaryl, and C 7 -C 15 aralkyl in R 3 and R 4 are C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 2 -C 12 alkenyl , F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , C(O)NR 13 R 14 , C 6 to C 10 aryl, and one or more identical or different groups selected from the group consisting of C 1 -C 20 heteroaryl.
L 1 , L 2 and L 3 are linkers.
When n=1, L 1 is R 1 , L 2 is R 2 and L 3 is R 5 .
When n=2 to 4, one of L 1 , L 2 , and L 3 is a linker. When L 1 is a linker, L 2 is R 2 and L 3 is R 5 . When L2 is a linker, L1 is R1 and L3 is R5 . When L 3 is a linker, L 1 is R 1 and L 2 is R 2 .
R 1 is C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 2 -C 20 heterocycloalkyl, C 6 -C 20 aryl or C 1 to C 20 heteroaryl;
C 1 -C 20 alkyl, C 2 -C 20 alkenyl and C 2 -C 20 alkynyl in R 1 are one or more of the same or different O, S, N(R 6 ), C(O), C (O) may be interrupted by groups selected from the group consisting of O and OC(O) and may have one or more identical or different groups R 1a ;
C 3 -C 20 cycloalkyl and C 2 -C 20 heterocycloalkyl in R 1 may be interrupted by one or more C(O) groups and may contain one or more identical or different groups. It may have R 1b ;
C 6 -C 20 aryl and C 1 -C 20 heteroaryl in R 1 may have one or more identical or different groups R 1c ;
R 1a each independently represents F, Cl, Br, I, CN, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , C(O ) NR 13 R 14 , C 3 -C 20 cycloalkyl, optionally interrupted by one or more C(O) groups, and C 6 -C 10 aryl;
C 3 -C 20 cycloalkyl and C 6 -C 10 aryl in R 1a may have one or more identical or different groups R 1aa ;
R 1aa is each independently selected from the group consisting of C 1 -C 12 alkyl, C 2 -C 12 alkenyl, F, Cl, Br, I, NO 2 , SR 7 , OR 8 and NR 9 R 10 ;
C 1 -C 12 alkyl in R 1aa is one or more selected from the group consisting of O, S, N(R 6 ), C(O), C(O)O, and OC(O). Optionally interrupted by groups F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , and C(O) may have one or more same or different groups selected from the group consisting of NR 13 R 14 ;
R 1b is each independently from the group consisting of C 1 -C 12 alkyl, C 2 -C 12 alkenyl, F, Cl, Br, I, CN, NO 2 , SR 7 , OR 8 and NR 9 R 10 selected;
C 1 -C 12 alkyl in R 1b is F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , and C( O) may have one or more same or different groups selected from the group consisting of NR 13 R 14 ;
R 1c is each independently C 1 -C 12 alkyl, C 2 -C 12 alkenyl, F, Cl, Br, I, CN, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O ) R 11 , C(O)OR 12 , C(O)NR 13 R 14 , C 6 -C 10 aryl, C 1 -C 20 heteroaryl, C 3 -C 10 cycloalkyl, and C 2 -C 10 hetero selected from the group consisting of cycloalkyl;
C 1 -C 12 alkyl in R 1c is F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , and C( O) may have one or more identical or different groups selected from NR 13 R 14 ;
C 1 -C 12 alkyl, C 3 -C 10 cycloalkyl and C 2 -C 10 heterocycloalkyl in R 1c may be interrupted by one or more C(O) groups;
C 6 -C 10 aryl, C 1 -C 20 heteroaryl, C 3 -C 10 cycloalkyl and C 2 -C 10 heterocycloalkyl in R 1c have one or more identical or different groups R 1ca . and the R 1ca has the same meaning as the above R 1aa ;
R 2 is a hydrogen atom, C 1 to C 20 alkyl, C 2 to C 20 alkenyl, C 2 to C 20 alkynyl, C 3 to C 20 cycloalkyl, C 2 to C 20 heterocycloalkyl, C 6 to C 20 Aryl, C 1 -C 20 heteroaryl, SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , C(O)NR 13 R 14 , SO 2 R 15 , or CN;
C 1 -C 20 alkyl, C 2 -C 20 alkenyl and C 2 -C 20 alkynyl in R 2 are one or more of the same or different O, S, N(R 6 ), C(O), C (O) may be interrupted by groups selected from the group consisting of O, and OC(O), and may have one or more identical or different groups R 2a ;
C 3 -C 20 cycloalkyl and C 2 -C 20 heterocycloalkyl in R 2 may be interrupted by one or more C(O) groups and may contain one or more identical or different groups. It may have R 2b ;
C 6 -C 20 aryl and C 1 -C 20 heteroaryl in R 2 may have one or more identical or different groups R 2c ;
R 2a is synonymous with R 1a ;
R 2b is synonymous with R 1b ;
R 2c is synonymous with R 1c ;
Furthermore, R 2 may be combined with -SR 1 to form a ring structure containing an imino carbon atom;
The ring structure containing the imino carbon atom includes S-(C 1 to C 20 alkylene)-X, S-(C 2 to C 20 alkenylene)-X, S-(C 3 to C 20 cycloalkylene)-X , S-(heterocycloalkylene)-X, S-(o-phenylene)-X, S-(o-xylene)-X, S-(o-phenylene-C 1 -C 12 alkylene)-X, S- (C 1 -C 12 alkylene-o-phenylene)-X, S-(C(O)N(R 16 ))-X, or S-(C(S)N(R 17 ))-X, often;
X is bonded to an imino carbon atom with S, O, S, N(R 6 ), C(O), OC(O), C(O)O, SC(O), C(O) S, C(O)N(R 16 ), N(R 18 )C(O), N(R 19 )SO 2 or a single bond;
The alkylene and alkenylene in the ring structure containing the imino carbon atom are selected from the group consisting of one or more of the same or different O, S, N(R 6 ), C(O) and C(S). optionally interrupted by groups and optionally substituted by one or more groups R 2d ;
Cycloalkylene and heterocycloalkylene in the ring structures containing said imino carbon atoms may be interrupted by one or more C(O) groups and substituted by one or more identical or different groups R 2e may have been;
Phenylene and o-xylylene in the ring structure containing said imino carbon atoms may be substituted by one or more identical or different groups R 2f ;
R 2d is each independently F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , C(O)NR 13 R 14 selected from the group consisting of C 6 -C 10 aryl and C 1 -C 20 heteroaryl;
C 6 -C 10 aryl and C 1 -C 20 heteroaryl in R 2d may have one or more groups R 2da , each R 2da being independently phenoxy, and R 1aa selected from the group consisting of the indicated groups;
R 2e each independently represents F, Cl, Br, I, SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , CONR 13 R 14 , C 1 - selected from the group consisting of C 12 alkyl, C 1 -C 12 haloalkyl, C 6 -C 10 aryl, and C 1 -C 20 heteroaryl;
C 6 -C 10 aryl and C 1 -C 20 heteroaryl in R 2e may have one or more groups R 2ea, R 2ea is synonymous with R 1aa ;
R 2f is each independently F, Cl, Br, I, SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , CONR 13 R 14 , C 1 - selected from the group consisting of C 12 alkyl, C 1 -C 12 haloalkyl, C 6 -C 10 aryl, and C 1 -C 20 heteroaryl;
C 6 -C 10 aryl and C 1 -C 20 heteroaryl in R 2f may have one or more groups R 2fa, R 2fa is synonymous with R 1aa ;
R 5 is a hydrogen atom, C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 7 -C 14 aralkyl, C 6 -C 14 aryl, or acyl group;
The acyl group in R 5 is -C(O)-H, -C(O)-C 1 -C 18 alkyl, -C(O)-C 2 -C 18 alkenyl, -C(O)-C 6 - C 14 aryl, -C(O)-C 2 -C 18 alkenyl-C 6 -C 14 aryl, -C(O)-O-C 1 -C 18 alkyl, -C(O)-O-C 6 - C 14 aryl, -C(O)-NH-C 1 -C 18 alkyl, -C(O)-NH-C 6 -C 14 aryl and C(O)-N(C 1 -C 18 alkyl) from 2 selected from the group;
R 3 and R 5 together with the nitrogen atom to which they are attached may form a 5- to 12-membered ring which may contain further heteroatoms;
R 6 is each independently selected from the group consisting of a hydrogen atom, C 1 -C 20 alkyl, C 2 -C 20 alkanoyl, C 6 -C 10 aryl, and C 7 -C 11 aroyl;
C 1 -C 20 alkyl in R 6 is 1 or 1 selected from the group consisting of O, S, N (C 1 -C 12 alkyl), C(O), C(O)O, and OC(O) Optionally interrupted by more groups, from F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl, C 6 -C 10 aryl, OH, and SH may have one or more same or different groups selected from the group;
The C 2 -C 20 alkanoyl in R 6 may be interrupted by one or more groups selected from the group consisting of O, S, CO, C(O)O, and OC(O), one or more same or different groups selected from the group consisting of F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl, and C 6 -C 10 aryl; May have;
C 6 -C 10 aryl in R 6 is one or more selected from the group consisting of F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy. may have more identical or different groups;
C 7 -C 11 aroyl in R 6 is one or more selected from the group consisting of F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy. may have more identical or different groups;
R 7 and R 8 are each independently selected from the group consisting of hydrogen atom, C 1 -C 20 alkyl, C 2 -C 20 alkanoyl, C 6 -C 10 aryl, and C 7 -C 11 aroyl;
C 1 -C 20 alkyl in R 7 and R 8 is one selected from the group consisting of O, S, N (C 1 -C 12 alkyl), CO, C(O)O, and OC(O); Optionally interrupted by more groups, from F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl, C 6 -C 10 aryl, OH, and SH may have one or more same or different groups selected from the group;
The C 2 -C 20 alkanoyl in R 7 , R 8 is interrupted by one or more groups selected from the group consisting of O, S, C(O), C(O)O, and OC(O). one or more selected from the group consisting of F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl, and C 6 -C 10 aryl. may have the same or different groups;
C 6 -C 10 aryl in R 7 , R 8 is selected from the group consisting of F, Cl, Br, I, C 1 -C 6 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy. may have one or more identical or different groups;
C7 - C11 aroyl in R7 , R8 is selected from the group consisting of F, Cl, Br, I, C1 - C10 alkyl, C1 - C10 alkoxy, and C2 - C11 acyloxy may have one or more identical or different groups;
R 9 and R 10 are each independently selected from the group consisting of a hydrogen atom, C 1 -C 20 alkyl, C 2 -C 20 alkanoyl, C 7 -C 11 aroyl, C 6 -C 10 aryl;
C 1 -C 20 alkyl in R 9 and R 10 is selected from the group consisting of O, S, N (C 1 -C 12 alkyl), C(O), C(O)O, and OC(O). from the group consisting of F, Cl, Br, I, NO 2 , C 3 -C 10 cycloalkyl, heterocycloalkyl, phenyl, OH, SH and CN may have one or more selected identical or different groups;
The C 2 -C 20 alkanoyl in R 9 , R 10 may be interrupted by one or more groups selected from the group consisting of O and S, F, Cl, Br, I, OH and C may have one or more identical or different groups selected from the group consisting of 1 to C 6 alkoxy;
C 7 -C 11 aroyl in R 9 and R 10 is one or more selected from the group consisting of F, Cl, Br, I, C 1 -C 6 alkyl, -OH and C 1 -C 6 alkoxy. may have the same or different groups;
C 6 -C 10 aryl in R 9 and R 10 is one or more selected from the group consisting of F, Cl, Br, I, C 1 -C 6 alkyl, -OH and C 1 -C 6 alkoxy. may have the same or different groups;
R 9 and R 10 together with the nitrogen atom to which they are bonded may form a saturated 5-, 6-, or 7-membered nitrogen heterocycle, and the ring may be O, S, N (C 1 -C 12 alkyl), C(O), and C(O)O as ring members, and the ring has one or more C 1 may have ~C 4 alkyl;
each R 11 is independently selected from the group consisting of a hydrogen atom, C 1 -C 20 alkyl, and C 6 -C 20 aryl;
C 1 -C 20 alkyl may be interrupted by one or more groups selected from the group consisting of O, S and C(O), and may contain one or more identical or different R 11a May have;
R 11a is each independently selected from the group consisting of F, Cl, Br, I, C 3 -C 10 cycloalkyl, heterocycloalkyl, phenyl, OH, and SH;
C 6 -C 20 aryl in R 11 is one or more selected from the group consisting of F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy. may have more identical or different groups;
R 12 is synonymous with R 8 ;
R 13 and R 14 are synonymous with R 9 and R 10 ;
each R 15 is independently selected from the group consisting of a hydrogen atom, C 1 -C 20 alkyl, C 6 -C 10 aryl;
C 1 -C 20 alkyl in R 15 is 1 or 1 selected from the group consisting of O, S, N (C 1 -C 12 alkyl), C(O), C(O)O, and OC(O) Optionally interrupted by more groups, from F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl, C 6 -C 10 aryl, OH, and SH may have one or more same or different groups selected from the group;
C 6 -C 10 aryl in R 15 is one or more same or different groups selected from the group consisting of F, Cl, Br, I, C 1 -C 6 alkyl, and C 1 -C 6 alkoxy. may have;
R 16 , R 17 , R 18 and R 19 each independently consist of a hydrogen atom, C 1 -C 20 alkyl, C 2 -C 20 alkanoyl, C 6 -C 10 aryl, C 7 -C 11 aroyl selected from the group;
C 1 -C 20 alkyl in R 16 , R 17 , R 18 and R 19 is O, S, N (C 1 -C 12 alkyl), C(O), C(O)O, and OC(O) optionally interrupted by one or more groups selected from the group consisting of F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl, C 6 - may have one or more identical or different groups selected from the group consisting of C 10 aryl, OH, and SH;
The C 2 -C 20 alkanoyl in R 16 , R 17 , R 18 , R 19 is one or more selected from the group consisting of O, S, CO, C(O)O, and OC(O). Optionally interrupted by groups , one or It may have more of the same or different groups;
C 6 -C 10 aryl in R 16 , R 17 , R 18 , R 19 is selected from F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy may have one or more same or different groups selected from the group;
C 7 -C 11 aroyl in R 16 , R 17 , R 18 , R 19 is selected from F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy may have one or more identical or different groups selected from the group consisting of;
L 1 is a divalent linker when n is 2, and the linker is L 1a -C 1 -C 30 alkylene-L 1a , L 2a -C 1 -C 30 alkenylene-L 2a , L 1a -C 3 -C 16 cycloalkylene-L 1a , L 1a -C 6 -C 20 arylene-L 1a , L 1a -C 6 -C 20 arylene-L 1b -C 6 -C 20 arylene-L 1a , and selected from the group consisting of L 1a -C 1 -C 13 heteroarylene-L 1a ;
The alkylene and alkenylene in the linker of L 1 may each independently be interrupted by one or more identical or different non-adjacent groups L 1c ;
The arylene and heteroarylene in the linker of L 1 may each independently have one or more identical or different groups R L 1 ;
L 1a is a single bond;
L 1b is a single bond, O, S, N(R 6 ), C(O), CH 2 , C(CH 3 ) 2 , CH(OH) or C 1 -C 5 alkylene;
L 1c each independently represents O, S, N(R 6 ), C(O), C(O)O, OC(O), C 6 -C 20 arylene, and C 3 -C 16 cycloalkylene. selected from the group;
R L1 is each independently selected from F, Cl, Br, I, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, and C 2 -C 11 acyloxy;
R 6 in L 1b and L 1c has the same meaning as R 6 ;
L 2 is a divalent linker when n is 2, and the linker is a single bond, L 2a -C 1 -C 30 alkylene-L 2a , L 2a -C 1 -C 30 alkenylene-L 2a , L 2a -C 6 -C 20 arylene- L 2a , L 2a -C 6 -C 20 arylene-L 2b -C 6 -C 20 arylene-L 2a ;
The alkylene and alkenylene in the divalent linker of L2 may each be independently interrupted by one or more identical or different groups L2c ;
The arylene and heteroarylene in the divalent linker of L2 may each independently have one or more identical or different groups R L2 ;
L2a is each independently a single bond, S, O, N( R6 ), C(O), C(O)O, OC(O) or SO2 ;
L 2b is a single bond, O, S, N(R 6 ), C(O), CH 2 , C(CH 3 ) 2 , CH(OH) or C 1 -C 5 alkylene;
L 2c each independently represents O, S, N(R 6 ), C(O), C(O)O, OC(O), C 6 -C 20 arylene, and C 3 -C 16 cycloalkylene. selected from the group;
R L2 is each independently selected from F, Cl, Br, I, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, and C 2 -C 11 acyloxy;
R 6 in L 2b and L 2c has the same meaning as R 6 ;
L 3 is a divalent linker when n is 2, and the linker is L 3a -C 1 -C 30 alkylene-L 3a , L 3a -C 3 -C 16 cycloalkylene-L 3a , L 3a -C 6 -C 20 arylene-L 3a , L 3a -C 1 -C 20 alkylene-L 3b -C 6 -C 16 cycloalkylene-L 3a , L 3a -C 6 -C 16 cycloalkylene-L 3b -C 6 -C 16 cycloalkylene-L 3a , L 3a -C 6 -C 20 arylene-L 3b -C 6 -C 20 arylene-L 3a , and L 3a -C 1 -C 13 heteroarylene-L 3a selected from the group;
The alkylene in the divalent linker of L 3 may each independently be interrupted by one or more identical or different non-adjacent groups L 3c ;
The cycloalkylenes in the divalent linker of L3 may each independently carry one or more identical or different groups R L3a ;
The arylene and heteroarylene in the divalent linker of L3 may each independently have one or more identical or different groups R L3b ;
L 3a is a single bond, C(O), C(O)O or C(O)N(R 16 );
L 3b is each independently a single bond, O, S, N(R 6 ) or C 1 -C 5 alkylene;
L 3c each independently represents O, S, N(R 6 ), C(O), C(O)O, OC(O), C 6 to C 20 arylene, C 3 to C 16 cycloalkylene, and selected from the group consisting of heterocycloalkylene;
R L3a is each independently C 1 -C 12 alkyl;
R L3b is selected from the group consisting of F, Cl, Br, I, C 1 -C 12 alkoxy, and C 2 -C 11 acyloxy;
R 6 in L 3b and L 3c has the same meaning as R 6 ;
R 16 in L 3a has the same meaning as;
L 1 and L 2 are trivalent linkers when n is 3, and the linker is a C 1 -C 30 alkanetriyl, a C 2 -C 30 alkenetriyl, a C 3 -C 16 cycloalkanetriyl. selected from the group consisting of yl, heterocycloalkanetriyl, C 6 -C 20 arenetriyl, and heteroarenetriyl;
The alkantriyl in the trivalent linker L 1 , L 2 may be interrupted by one or more identical or different groups L 4 ;
L 4 each independently represents O, S, N(R 6 ), C(O), C(O)O, OC(O), C(O)N(R 16 ), N(R 18 ) selected from the group consisting of C(O), C3 - C20 cycloalkylene, heterocycloalkylene, C6 - C20 arylene and heteroarylene;
R 6 , R 16 and R 18 in L 4 each have the same meaning as R 6 and R 18 above;
L3 is a trivalent linker when n is 3 ; selected from the group consisting of cycloalkanetriyl, C 6 -C 20 arenetriyl, heteroarenetriyl, triacyl;
The alkantriyl in the trivalent linker of L3 may be interrupted by one or more identical or different groups L5 ;
L 5 each independently represents O, S, N(R 6 ), C(O), C(O)O, OC(O), C(O)N(R 16 ), N(R 18 ) selected from the group consisting of C(O), C3 - C20 cycloalkylene, heterocycloalkylene, C6 - C20 arylene and heteroarylene;
R 6 , R 16 and R 18 in L 5 are each synonymous with R 6 and R 18 ;
L 1 and L 2 are tetravalent linkers when n is 4, and the linker is C 1 -C 30 alkanetetryl;
The alkanetetryl in the tetravalent linker of L 1 , L 2 may be interrupted by one or more identical or different groups L 6 ;
L 6 each independently represents O, S, N(R 6 ), C(O), C(O)O, OC(O), C(O)N(R 16 ), N(R 18 ) selected from the group consisting of C(O), C3 - C20 cycloalkylene, heterocycloalkylene, C6 - C20 arylene and heteroarylene;
R 6 , R 16 and R 18 in L 6 are each synonymous with R 6 and R 18 ;
L 3 is a tetravalent linker when n is 4, said linker being selected from the group consisting of C 1 -C 30 alkanetetralyl, tetraacyl;
The alkanetetryl in the tetravalent linker of L3 may be interrupted by one or more identical or different groups L7 ;
L 7 is each independently O, S, N(R 6 ), C(O), C(O)O, OC(O), C(O)N(R 16 ), N(R 18 ) selected from the group consisting of C(O), C3 - C20 cycloalkylene, heterocycloalkylene, C6 - C20 arylene and heteroarylene;
The above compound, wherein R 6 , R 16 and R 18 in L 7 have the same meanings as R 6 and R 18 , respectively.
［２］前記式（Ｉ）において、ｎ＝１であり、Ｌ１はＲ１であり、Ｌ２はＲ２であり、Ｌ３はＲ５である、上記［１］に記載の化合物。
［３］前記式（Ｉ）において、ｎ＝２であり、Ｌ１がリンカーであり、Ｌ２はＲ２であり、Ｌ３はＲ５である、上記［１］に記載の化合物。
［４］前記式（Ｉ）において、ｎ＝２であり、Ｌ２がリンカーであり、Ｌ１はＲ１であり、Ｌ３はＲ５である、上記［１］に記載の化合物。
［５］前記式（Ｉ）において、ｎ＝２であり、Ｌ３がリンカーであり、Ｌ１はＲ１であり、Ｌ２はＲ２である、上記［１］に記載の化合物。
［６］前記式（Ｉ）において、ｎ＝１であり、Ｒ１は、Ｃ１～Ｃ２０アルキル、Ｃ３～Ｃ２０シクロアルキル、またはＣ６～Ｃ１０アリールである、上記［２］に記載の化合物。
［７］前記式（Ｉ）において、ｎ＝１であり、Ｌ１はＲ１であり、Ｌ２はＲ２であり、Ｌ３はＲ５であり、Ｒ１は、Ｃ１～Ｃ２０アルキル、Ｃ６～Ｃ１０アリール、又は１もしくはそれより多くの同一もしくは異なるＣ１～Ｃ１２アルキルで置換されたＣ６～Ｃ１０アリールであり；Ｒ２はＣ１～Ｃ２０アルキル、Ｃ６～Ｃ１０アリール、又は１もしくはそれより多くの同一もしくは異なるＣ１～Ｃ１２アルキルで置換されたＣ６～Ｃ１０アリールであり；Ｒ３及びＲ４は、各々独立して、Ｃ１～Ｃ６アルキル、Ｃ５～Ｃ１２シクロアルキル、Ｃ６～Ｃ１０アリール、又は１もしくはそれより多くの同一もしくは異なるＣ１～Ｃ６アルキルによって置換されたＣ６～Ｃ１０アリールであり；Ｒ５は、水素である、上記［１］又は［２］に記載の化合物。
［８］（Ａ）上記［１］～［７］のいずれかに記載された化合物及び（Ｂ）重合性化合物を含む重合性組成物。
［９］更に（Ｃ）アルカリ可溶性樹脂を含む上記［８］に記載の重合性組成物。
［１０］更に（Ｄ）光重合開始剤を含む上記［８］又は［９］に記載の重合性組成物。
［１１］前記（Ｂ）重合性化合物が（メタ）アクリレート化合物を含む、上記［８］～［１０］のいずれかに記載の重合性組成物。
［１２］上記［８］～［１１］のいずれか１項に記載の重合性組成物を硬化させた硬化物。
［１３］上記［１２］に記載の硬化物を含むカラーフィルタ。
［１４］上記［１２］又は［１３］に記載の硬化物を含む隔壁。
［１５］上記［１２］～［１４］のいずれかに記載の硬化物を含む画像表示装置。
［１６］上記［８］～［１１］のいずれかに記載の重合性組成物を用い、少なくとも下記工程（１）～工程（４）を行う、硬化物の形成方法。
　工程（１）：重合性組成物の塗膜を基板上に形成する工程。
　工程（２）：工程（１）で形成した塗膜の少なくとも一部を露光する工程。
　工程（３）：工程（２）で露光された塗膜を現像する工程。
　工程（４）：工程（３）で現像された塗膜を焼成する工程。
［１７］前記工程（４）の焼成温度が１００℃以下である、上記［１６］に記載の硬化物の形成方法。 [2] The compound according to the above [1], wherein in the formula (I), n=1, L 1 is R 1 , L 2 is R 2 , and L 3 is R 5 .
[3] The compound according to the above [1], wherein in the formula (I), n=2, L 1 is a linker, L 2 is R 2 and L 3 is R 5 .
[4] The compound according to the above [1], wherein in the formula (I), n=2, L2 is a linker, L1 is R1 , and L3 is R5 .
[5] The compound according to the above [1], wherein in the formula (I), n=2, L 3 is a linker, L 1 is R 1 and L 2 is R 2 .
[6] In the above [2], in the formula (I), n=1 and R 1 is C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, or C 6 -C 10 aryl. Compounds described.
[7] In the formula (I), n=1, L 1 is R 1, L 2 is R 2 , L 3 is R 5 , and R 1 is C 1 to C 20 alkyl. , C6 - C10 aryl, or C6 - C10 aryl substituted with one or more identical or different C1 - C12 alkyl; R2 is C1 - C20 alkyl, C6 -C10 aryl; C 10 aryl, or C 6 -C 10 aryl substituted with one or more identical or different C 1 -C 12 alkyl; R 3 and R 4 are each independently C 1 -C 6 alkyl, C 5 -C 12 cycloalkyl, C 6 -C 10 aryl, or C 6 -C 10 aryl substituted by one or more identical or different C 1 -C 6 alkyl; R 5 is The compound according to [1] or [2] above, which is hydrogen.
[8] A polymerizable composition comprising (A) the compound described in any one of [1] to [7] above and (B) a polymerizable compound.
[9] The polymerizable composition according to [8] above, further comprising (C) an alkali-soluble resin.
[10] The polymerizable composition according to [8] or [9] above, further comprising (D) a photopolymerization initiator.
[11] The polymerizable composition according to any one of [8] to [10] above, wherein the polymerizable compound (B) contains a (meth)acrylate compound.
[12] A cured product obtained by curing the polymerizable composition according to any one of [8] to [11] above.
[13] A color filter comprising the cured product according to [12] above.
[14] A partition wall comprising the cured product according to [12] or [13] above.
[15] An image display device comprising the cured product according to any one of [12] to [14] above.
[16] A method for forming a cured product, using the polymerizable composition according to any one of [8] to [11] above, and performing at least the following steps (1) to (4).
Step (1): A step of forming a coating film of a polymerizable composition on a substrate.
Step (2): A step of exposing at least a portion of the coating film formed in step (1).
Step (3): A step of developing the coating film exposed in step (2).
Step (4): A step of baking the coating film developed in step (3).
[17] The method for forming a cured product according to the above [16], wherein the firing temperature in the step (4) is 100°C or less.
　以下、本発明を詳細に説明する。以下の記載は本発明の実施形態の一例であり、本発明はその要旨を超えない限り、これらに特定されない。
　本発明において、「（メタ）アクリル」とは、「アクリル及び／又はメタクリル」を意味する。本発明において、「全固形分」とは、重合性組成物における溶剤以外の全成分を意味し、溶剤以外の成分が常温で液体であっても、その成分は溶剤には含めず、全固形分に含める。
　本発明において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
　本発明において、「Ａ及び／又はＢ」とは、Ａ及びＢの一方又は両方を意味し、具体的には、Ａ、Ｂ、又はＡ及びＢを意味する。
　本発明において、「（共）重合体」とは、単一重合体（ホモポリマー）と共重合体（コポリマー）の双方を含むことを意味し、また、「多塩基酸（無水物）」とは、「多塩基酸及び／又は多塩基酸無水物」を意味する。
　本発明において、重量平均分子量とは、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）によるポリスチレン換算の重量平均分子量（Ｍｗ）を意味する。
　本発明において、酸価とは、有効固形分換算の酸価を表し、中和滴定により算出される。 The present invention will be explained in detail below. The following description is an example of the embodiments of the present invention, and the present invention is not limited to these unless the gist thereof is exceeded.
In the present invention, "(meth)acrylic" means "acrylic and/or methacrylic". In the present invention, "total solid content" means all components other than the solvent in the polymerizable composition, and even if the components other than the solvent are liquid at room temperature, they are not included in the solvent, and the total solid content is Include in minutes.
In the present invention, a numerical range expressed using "~" means a range that includes the numerical values written before and after "~" as lower and upper limits.
In the present invention, "A and/or B" means one or both of A and B, and specifically means A, B, or A and B.
In the present invention, the term "(co)polymer" includes both a single polymer (homopolymer) and a copolymer (copolymer), and "polybasic acid (anhydride)" , means "polybasic acid and/or polybasic acid anhydride".
In the present invention, the weight average molecular weight means the weight average molecular weight (Mw) in terms of polystyrene measured by GPC (gel permeation chromatography).
In the present invention, the acid value refers to the acid value in terms of effective solid content, and is calculated by neutralization titration.
　本発明において、隔壁材とはバンク材、壁材、ウォール材をさし、同様に、隔壁とはバンク、壁、ウォールをさす。
　本発明において、発光部（画素部）とは電気エネルギーを与えた場合に光を放出する部分をさす。 In the present invention, a partition wall material refers to a bank material, a wall material, and a wall material, and similarly, a partition wall refers to a bank, a wall, and a wall.
In the present invention, the light emitting section (pixel section) refers to a section that emits light when electrical energy is applied.
［１］化合物
　本発明の化合物は、以下の式（Ａ）で示される化合物である。 [1] Compound The compound of the present invention is a compound represented by the following formula (A).
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　ここで、ｎは１～４の整数であり、Ｒ３及びＲ４は、各々独立して、Ｃ１～Ｃ２０アルキル、Ｃ３～Ｃ２０シクロアルキル、Ｃ６～Ｃ２０アリール、Ｃ１～Ｃ２０ヘテロアリール、Ｃ７～Ｃ１５アラルキル、又はＳｉ（ＣＨ３）３であり、Ｌ１、Ｌ２及びＬ３はリンカーである。
　ｎ＝１の場合、Ｌ１はＲ１であり、Ｌ２はＲ２であり、Ｌ３はＲ５である。
　ｎ＝２～４の場合、Ｌ１、Ｌ２、Ｌ３のいずれか一つがリンカーである。Ｌ１がリンカーの場合、Ｌ２はＲ２であり、Ｌ３はＲ５である。Ｌ２がリンカーの場合、Ｌ１はＲ１であり、Ｌ３はＲ５である。Ｌ３がリンカーの場合、Ｌ１はＲ１であり、Ｌ２はＲ２である。
　Ｒ３、Ｒ４、Ｌ１、Ｌ２及びＬ３の詳細については、以下の明細書本文中の実施態様の中で説明する。
　より具体的には、以下の態様がある。 Here, n is an integer of 1 to 4, and R 3 and R 4 are each independently C 1 to C 20 alkyl, C 3 to C 20 cycloalkyl, C 6 to C 20 aryl, C 1 to C 20 heteroaryl, C 7 -C 15 aralkyl, or Si(CH 3 ) 3 and L 1 , L 2 and L 3 are linkers.
When n=1, L 1 is R 1 , L 2 is R 2 and L 3 is R 5 .
When n=2 to 4, one of L 1 , L 2 , and L 3 is a linker. When L 1 is a linker, L 2 is R 2 and L 3 is R 5 . When L2 is a linker, L1 is R1 and L3 is R5 . When L 3 is a linker, L 1 is R 1 and L 2 is R 2 .
Details of R 3 , R 4 , L 1 , L 2 and L 3 are explained in the embodiments in the text below.
More specifically, there are the following aspects.
　本発明の第１態様の化合物は、以下の式（Ｉ）、（ＩＩ）、（ＩＩＩ）又は（ＩＶ）で示される化合物である。なお、本発明の第１態様の化合物、及び後述する本発明の第２～４態様の化合物をまとめて、「本発明の化合物」と記載することがある。 The compound of the first aspect of the present invention is a compound represented by the following formula (I), (II), (III) or (IV). Note that the compound of the first aspect of the present invention and the compounds of the second to fourth aspects of the present invention described below may be collectively referred to as "compound of the present invention."
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　前記式中、
　ｎは２，３または４であり；
　Ｒ１は、Ｃ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルケニル、Ｃ２～Ｃ２０アルキニル、Ｃ３～Ｃ２０シクロアルキル、Ｃ２～Ｃ２０ヘテロシクロアルキル、Ｃ６～Ｃ２０アリールまたはＣ１～Ｃ２０ヘテロアリールであり；
　Ｒ１におけるＣ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルケニル及びＣ２～Ｃ２０アルキニルは、１もしくはそれより多くの同一もしくは異なるＯ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ及びＯＣ（Ｏ）からなる群より選択される基によって中断されていてもよく、１もしくはそれより多くの同一もしくは異なる基Ｒ１ａを有していてもよく；
　Ｒ１におけるＣ３～Ｃ２０シクロアルキル及びＣ２～Ｃ２０ヘテロシクロアルキルは、１もしくはそれより多くのＣ（Ｏ）基によって中断されていてもよく、１もしくはそれより多くの同一もしくは異なる基Ｒ１ｂを有していてもよく；
　Ｒ１におけるＣ６～Ｃ２０アリール及びＣ１～Ｃ２０ヘテロアリールは、１もしくはそれより多くの同一もしくは異なる基Ｒ１ｃを有していてもよく；
　Ｒ１ａは、各々独立して、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＣＮ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、Ｃ（Ｏ）ＮＲ１３Ｒ１４、１もしくはそれより多くのＣ（Ｏ）基によって中断されていてもよいＣ３～Ｃ２０シクロアルキル、及びＣ６～Ｃ１０アリールからなる群より選択され；
　Ｒ１ａにおけるＣ３～Ｃ２０シクロアルキル及びＣ６～Ｃ１０アリールは、１もしくはそれより多くの同一もしくは異なる基Ｒ１ａａを有していてもよく；
　Ｒ１ａａは、各々独立して、Ｃ１～Ｃ１２アルキル、Ｃ２～Ｃ１２アルケニル、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、ＳＲ７、ＯＲ８及びＮＲ９Ｒ１０からなる群より選択され；
　Ｒ１ａａにおけるＣ１～Ｃ１２アルキルは、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、及びＣ（Ｏ）ＮＲ１３Ｒ１４からなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ１ｂは、各々独立して、Ｃ１～Ｃ１２アルキル、Ｃ２～Ｃ１２アルケニル、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＣＮ、ＮＯ２、ＳＲ７、ＯＲ８及びＮＲ９Ｒ１０からなる群より選択され；
　Ｒ１ｂにおけるＣ１～Ｃ１２アルキルは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、及びＣ（Ｏ）ＮＲ１３Ｒ１４からなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ１ｃは、各々独立して、Ｃ１～Ｃ１２アルキル、Ｃ２～Ｃ１２アルケニル、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＣＮ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、Ｃ（Ｏ）ＮＲ１３Ｒ１４、Ｃ６～Ｃ１０アリール、Ｃ１～Ｃ２０ヘテロアリール、Ｃ３～Ｃ１０シクロアルキル、及びＣ２～Ｃ１０ヘテロシクロアルキルからなる群より選択され；
　Ｒ１ｃにおけるＣ１～Ｃ１２アルキルは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、及びＣ（Ｏ）ＮＲ１３Ｒ１４から選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ１ｃにおけるＣ１～Ｃ１２アルキル、Ｃ３～Ｃ１０シクロアルキル及びＣ２～Ｃ１０ヘテロシクロアルキルは、１もしくはそれより多くのＣ（Ｏ）基によって中断されていてもよく；
　Ｒ１ｃにおけるＣ６～Ｃ１０アリール、Ｃ１～Ｃ２０ヘテロアリール、Ｃ３～Ｃ１０シクロアルキル及びＣ２～Ｃ１０ヘテロシクロアルキルは、１もしくはそれより多くの同一もしくは異なる基Ｒ１ｃａを有していてもよく、該Ｒ１ｃａは、前記Ｒ１ａａと同義であり；
　Ｒ２は、水素原子、Ｃ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルケニル、Ｃ２～Ｃ２０アルキニル、Ｃ３～Ｃ２０シクロアルキル、Ｃ２～Ｃ２０ヘテロシクロアルキル、Ｃ６～Ｃ２０アリール、Ｃ１～Ｃ２０ヘテロアリール、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、Ｃ（Ｏ）ＮＲ１３Ｒ１４、ＳＯ２Ｒ１５、またはＣＮであり；　Ｒ２におけるＣ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルケニル及びＣ２～Ｃ２０アルキニルは、１もしくはそれより多くの同一もしくは異なるＯ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される基によって中断されていてもよく、１もしくはそれより多くの同一もしくは異なる基Ｒ２ａを有していてもよく；
　Ｒ２におけるＣ３～Ｃ２０シクロアルキル及びＣ２～Ｃ２０ヘテロシクロアルキルは、１もしくはそれより多くのＣ（Ｏ）基によって中断されていてもよく、１もしくはそれより多くの同一もしくは異なる基Ｒ２ｂを有していてもよく；
　Ｒ２におけるＣ６～Ｃ２０アリール及びＣ１～Ｃ２０ヘテロアリールは、１もしくはそれより多くの同一もしくは異なる基Ｒ２ｃを有していてもよく；
　Ｒ２ａは、Ｒ１ａと同義であり；
　Ｒ２ｂは、Ｒ１ｂと同義であり；
　Ｒ２ｃは、Ｒ１ｃと同義であり；
　また、Ｒ２は、－Ｓ－Ｒ１と一緒になってイミノ炭素原子を含む環構造を形成していてもよく；
　前記イミノ炭素原子を含む環構造としては、Ｓ－（Ｃ１～Ｃ２０アルキレン）－Ｘ、Ｓ－（Ｃ２～Ｃ２０アルケニレン）－Ｘ、Ｓ－（Ｃ３～Ｃ２０シクロアルキレン）－Ｘ、Ｓ－（ヘテロシクロアルキレン）－Ｘ、Ｓ－（ｏ－フェニレン）－Ｘ、Ｓ－（ｏ－キシレン）－Ｘ、Ｓ－（ｏ－フェニレン－Ｃ１～Ｃ１２アルキレン）－Ｘ、Ｓ－（Ｃ１～Ｃ１２アルキレン－ｏ－フェニレン）－Ｘ、Ｓ－（Ｃ（Ｏ）Ｎ（Ｒ１６））－Ｘ、またはＳ－（Ｃ（Ｓ）Ｎ（Ｒ１７））－Ｘであってよく；
　Ｘは、Ｓを有するイミノ炭素原子に結合されており、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、ＯＣ（Ｏ）、Ｃ（Ｏ）Ｏ、ＳＣ（Ｏ）、Ｃ（Ｏ）Ｓ、Ｃ（Ｏ）Ｎ（Ｒ１６）、Ｎ（Ｒ１８）Ｃ（Ｏ）、Ｎ（Ｒ１９）ＳＯ２または単結合であり；
　前記イミノ炭素原子を含む環構造におけるアルキレン及びアルケニレンは、１もしくはそれより多くの同一または異なる、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）及びＣ（Ｓ）からなる群より選択される基によって中断されていてもよく、１もしくはそれより多くの基Ｒ２ｄによって置換されていてもよく；
　前記イミノ炭素原子を含む環構造におけるシクロアルキレン及びヘテロシクロアルキレンは、１もしくはそれより多くのＣ（Ｏ）基によって中断されていてもよく、１もしくはそれより多くの同一もしくは異なる基Ｒ２ｅによって置換されていてもよく；　前記イミノ炭素原子を含む環構造におけるフェニレン及びｏ－キシリレンは、１もしくはそれより多くの同一もしくは異なる基Ｒ２ｆによって置換されていてもよく；
　Ｒ２ｄは、各々独立して、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、Ｃ（Ｏ）ＮＲ１３Ｒ１４、Ｃ６～Ｃ１０アリール及びＣ１～Ｃ２０ヘテロアリールからなる群より選択され；
　Ｒ２ｄにおけるＣ６～Ｃ１０アリール及びＣ１～Ｃ２０ヘテロアリールは、１もしくはそれより多くの基Ｒ２ｄａを有していてもよく、Ｒ２ｄａは、各々独立に、フェノキシ、及びＲ１ａａで示した基からなる群から選択され；
　Ｒ２ｅは、各々独立して、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、ＣＯＮＲ１３Ｒ１４、Ｃ１～Ｃ１２アルキル、Ｃ１～Ｃ１２ハロアルキル、Ｃ６～Ｃ１０アリール、及びＣ１～Ｃ２０ヘテロアリールからなる群より選択され；
　Ｒ２ｅにおけるＣ６～Ｃ１０アリール及びＣ１～Ｃ２０ヘテロアリールは、１もしくはそれより多くの基Ｒ２ｅａを有していてもよく、Ｒ２ｅａは、Ｒ１ａａと同義であり；　Ｒ２ｆは、各々独立して、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、ＣＯＮＲ１３Ｒ１４、Ｃ１～Ｃ１２アルキル、Ｃ１～Ｃ１２ハロアルキル、Ｃ６～Ｃ１０アリール、及びＣ１～Ｃ２０ヘテロアリールからなる群より選択され；
　Ｒ２ｆにおけるＣ６～Ｃ１０アリール及びＣ１～Ｃ２０ヘテロアリールは、１もしくはそれより多くの基Ｒ２ｆａを有していてもよく、Ｒ２ｆａは、Ｒ１ａａと同義であり；　Ｒ３及びＲ４は、各々独立して、Ｃ１～Ｃ２０アルキル、Ｃ３～Ｃ２０シクロアルキル、Ｃ６～Ｃ２０アリール、Ｃ１～Ｃ２０ヘテロアリール、Ｃ７～Ｃ１５アラルキル、又はＳｉ（ＣＨ３）３であり；
　Ｒ３、Ｒ４におけるＣ１～Ｃ２０アルキル及びＣ３～Ｃ２０シクロアルキルは、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、ＯＣ（Ｏ）、Ｃ（Ｏ）Ｓ、及びＳＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０からなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ３、Ｒ４におけるＣ６～Ｃ２０アリール、Ｃ１２～Ｃ２０ヘテロアリール、及びＣ７～Ｃ１５アラルキルは、Ｃ１～Ｃ１２アルキル、Ｃ１～Ｃ１２ハロアルキル、Ｃ２～Ｃ１２アルケニル、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、Ｃ（Ｏ）ＮＲ１３Ｒ１４、Ｃ６～Ｃ１０アリール、及びＣ１～Ｃ２０ヘテロアリールからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ５は、水素原子、Ｃ１～Ｃ２０アルキル、Ｃ３～Ｃ２０シクロアルキル、Ｃ７～Ｃ１４アラルキル、Ｃ６～Ｃ１４アリール、またはアシル基であり；
　Ｒ５におけるアシル基は、－Ｃ（Ｏ）－Ｈ、－Ｃ（Ｏ）－Ｃ１～Ｃ１８アルキル、－Ｃ（Ｏ）－Ｃ２～Ｃ１８アルケニル、－Ｃ（Ｏ）－Ｃ６～Ｃ１４アリール、－Ｃ（Ｏ）－Ｃ２～Ｃ１８アルケニル－Ｃ６～Ｃ１４アリール、－Ｃ（Ｏ）－Ｏ－Ｃ１～Ｃ１８アルキル、－Ｃ（Ｏ）－Ｏ－Ｃ６～Ｃ１４アリール、－Ｃ（Ｏ）－ＮＨ－Ｃ１～Ｃ１８アルキル、－Ｃ（Ｏ）－ＮＨ－Ｃ６～Ｃ１４アリール及びＣ（Ｏ）－Ｎ（Ｃ１～Ｃ１８アルキル）２からなる群より選択され；
　Ｒ３及びＲ５は、それらが結合する窒素原子と共に、更なるヘテロ原子を含んでいてもよい５～１２員環を形成していてもよく；
　Ｒ６は、各々独立して、水素原子、Ｃ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルカノイル、Ｃ６～Ｃ１０アリール及びＣ７～Ｃ１１アロイルからなる群より選択され；
　Ｒ６におけるＣ１～Ｃ２０アルキルは、Ｏ、Ｓ、Ｎ（Ｃ１～Ｃ１２アルキル）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、Ｃ２～Ｃ１０ヘテロシクロアルキル、Ｃ６～Ｃ１０アリール、ＯＨ、及びＳＨからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ６におけるＣ２～Ｃ２０アルカノイルは、Ｏ、Ｓ、ＣＯ、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、Ｃ２～Ｃ１０ヘテロシクロアルキル、及びＣ６～Ｃ１０アリールからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ６におけるＣ６～Ｃ１０アリールは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１０アルキル、Ｃ１～Ｃ１０アルコキシ、及びＣ２～Ｃ１１アシロキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ６におけるＣ７～Ｃ１１アロイルは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１０アルキル、Ｃ１～Ｃ１０アルコキシ、及びＣ２～Ｃ１１アシロキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ７及びＲ８は、各々独立して、水素原子、Ｃ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルカノイル、Ｃ６～Ｃ１０アリール、及びＣ７～Ｃ１１アロイルからなる群より選択され；
　Ｒ７、Ｒ８におけるＣ１～Ｃ２０アルキルは、Ｏ、Ｓ、Ｎ（Ｃ１～Ｃ１２アルキル）、ＣＯ、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、Ｃ２～Ｃ１０ヘテロシクロアルキル、Ｃ６～Ｃ１０アリール、ＯＨ、及びＳＨからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ７、Ｒ８におけるＣ２～Ｃ２０アルカノイルは、Ｏ、Ｓ、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、Ｃ２～Ｃ１０ヘテロシクロアルキル、及びＣ６～Ｃ１０アリールからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ７、Ｒ８におけるＣ６～Ｃ１０アリールは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ６アルキル、Ｃ１～Ｃ１０アルコキシ、及びＣ２～Ｃ１１アシロキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ７、Ｒ８におけるＣ７～Ｃ１１アロイルは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１０アルキル、Ｃ１～Ｃ１０アルコキシ、及びＣ２～Ｃ１１アシロキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ９及びＲ１０は、各々独立して、水素原子、Ｃ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルカノイル、Ｃ７～Ｃ１１アロイル、Ｃ６～Ｃ１０アリールからなる群より選択され；　Ｒ９、Ｒ１０におけるＣ１～Ｃ２０アルキルは、Ｏ、Ｓ、Ｎ（Ｃ１～Ｃ１２アルキル）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、Ｃ３～Ｃ１０シクロアルキル、ヘテロシクロアルキル、フェニル、ＯＨ、ＳＨ及びＣＮからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ９、Ｒ１０におけるＣ２～Ｃ２０アルカノイルは、Ｏ及びＳからなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＯＨ及びＣ１～Ｃ６アルコキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ９、Ｒ１０におけるＣ７～Ｃ１１アロイルは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ６アルキル、－ＯＨ及びＣ１～Ｃ６アルコキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ９、Ｒ１０におけるＣ６～Ｃ１０アリールは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ６アルキル、－ＯＨ及びＣ１～Ｃ６アルコキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ９及びＲ１０は、それらが結合される窒素原子と一緒になって、飽和の５員、６員または７員の窒素複素環を形成していてもよく、前記環はＯ、Ｓ、Ｎ（Ｃ１～Ｃ１２アルキル）、Ｃ（Ｏ）、及びＣ（Ｏ）Ｏからなる群より選択される基を環員として有していてもよく、前記環は１もしくはそれより多くのＣ１～Ｃ４アルキルを有してよく；
　Ｒ１１は各々独立して、水素原子、Ｃ１～Ｃ２０アルキル及びＣ６～Ｃ２０アリールからなる群より選択され；
　Ｃ１～Ｃ２０アルキルは、Ｏ、Ｓ及びＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、１もしくはそれより多くの同一もしくは異なるＲ１１ａを有していてもよく；
　Ｒ１１ａは、各々独立して、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、ヘテロシクロアルキル、フェニル、ＯＨ、及びＳＨからなる群より選択され；
　Ｒ１１におけるＣ６～Ｃ２０アリールは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１０アルキル、Ｃ１～Ｃ１０アルコキシ、及びＣ２～Ｃ１１アシロキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ１２は、Ｒ８と同義であり；
　Ｒ１３及びＲ１４は、Ｒ９、Ｒ１０と同義であり；
　Ｒ１５は、各々独立して、水素原子、Ｃ１～Ｃ２０アルキル、Ｃ６～Ｃ１０アリールからなる群より選択され；
　Ｒ１５におけるＣ１～Ｃ２０アルキルは、Ｏ、Ｓ、Ｎ（Ｃ１～Ｃ１２アルキル）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、Ｃ２～Ｃ１０ヘテロシクロアルキル、Ｃ６～Ｃ１０アリール、ＯＨ、及びＳＨからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ１５におけるＣ６～Ｃ１０アリールは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ６アルキル、及びＣ１～Ｃ６アルコキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ１６、Ｒ１７、Ｒ１８及びＲ１９は、各々独立して、水素原子、Ｃ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルカノイル、Ｃ６～Ｃ１０アリール、Ｃ７～Ｃ１１アロイルからなる群より選択され；
　Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９におけるＣ１～Ｃ２０アルキルは、Ｏ、Ｓ、Ｎ（Ｃ１～Ｃ１２アルキル）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、Ｃ２～Ｃ１０ヘテロシクロアルキル、Ｃ６～Ｃ１０アリール、ＯＨ、及びＳＨからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９におけるＣ２～Ｃ２０アルカノイルは、Ｏ、Ｓ、ＣＯ、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、Ｃ２～Ｃ１０ヘテロシクロアルキル、及びＣ６～Ｃ１０アリールからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９におけるＣ６～Ｃ１０アリールは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１０アルキル、Ｃ１～Ｃ１０アルコキシ、及びＣ２～Ｃ１１アシロキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９におけるＣ７～Ｃ１１アロイルは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１０アルキル、Ｃ１～Ｃ１０アルコキシ、及びＣ２～Ｃ１１アシロキシからからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｌ１は、ｎが２である場合に、二価のリンカーであり、前記リンカーは、Ｌ１ａ－Ｃ１～Ｃ３０アルキレン－Ｌ１ａ、Ｌ２ａ－Ｃ１～Ｃ３０アルケニレン－Ｌ２ａ、Ｌ１ａ－Ｃ３～Ｃ１６シクロアルキレン－Ｌ１ａ、Ｌ１ａ－Ｃ６～Ｃ２０アリーレン－Ｌ１ａ、Ｌ１ａ－Ｃ６～Ｃ２０アリーレン－Ｌ１ｂ－Ｃ６～Ｃ２０アリーレン－Ｌ１ａ、及びＬ１ａ－Ｃ１～Ｃ１３ヘテロアリーレン－Ｌ１ａからなる群より選択され；
　Ｌ１の前記リンカーにおけるアルキレン及びアルケニレンは、各々独立に、１もしくはそれより多くの同一もしくは異なる非隣接の基Ｌ１ｃによって中断されていてもよく；
　Ｌ１の前記リンカーにおけるアリーレン及びヘテロアリーレンは、各々独立に、１もしくはそれより多くの同一もしくは異なる基ＲＬ１を有していてもよく；
　Ｌ１ａは、単結合であり；
　Ｌ１ｂは、単結合、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、ＣＨ２、Ｃ（ＣＨ３）２、ＣＨ（ＯＨ）またはＣ１～Ｃ５アルキレンであり；
　Ｌ１ｃは、各々独立して、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、ＯＣ（Ｏ）、Ｃ６～Ｃ２０アリーレン及びＣ３～Ｃ１６シクロアルキレンからなる群より選択され；
　ＲＬ１は、各々独立して、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１２アルキル、Ｃ１～Ｃ１２アルコキシ、及びＣ２～Ｃ１１アシロキシから選択され；
　Ｌ１ｂ、Ｌ１ｃにおけるＲ６は、Ｒ６と同義であり；
　Ｌ２は、ｎが２である場合に、二価のリンカーであり、前記リンカーは、単結合、Ｌ２ａ－Ｃ１～Ｃ３０アルキレン－Ｌ２ａ、Ｌ２ａ－Ｃ１～Ｃ３０アルケニレン－Ｌ２ａ、Ｌ２ａ－Ｃ６～Ｃ２０アリーレン－Ｌ２ａ、Ｌ２ａ－Ｃ６～Ｃ２０アリーレン－Ｌ２ｂ－Ｃ６～Ｃ２０アリーレン－Ｌ２ａからなる群より選択され；
　Ｌ２の二価のリンカーにおけるアルキレン及びアルケニレンは、各々独立に、１もしくはそれより多くの同一もしくは異なる基Ｌ２ｃによって中断されていてもよく；
　Ｌ２の二価のリンカーにおけるアリーレン及びヘテロアリーレンは、各々独立に、１もしくはそれより多くの同一もしくは異なる基ＲＬ２を有していてもよく；
　Ｌ２ａは、各々独立して、単結合、Ｓ、Ｏ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、ＯＣ（Ｏ）またはＳＯ２であり；
　Ｌ２ｂは、単結合、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、ＣＨ２、Ｃ（ＣＨ３）２、ＣＨ（ＯＨ）またはＣ１～Ｃ５アルキレンであり；
　Ｌ２ｃは、各々独立して、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、ＯＣ（Ｏ）、Ｃ６～Ｃ２０アリーレン及びＣ３～Ｃ１６シクロアルキレンからなる群より選択され；
　ＲＬ２は、各々独立して、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１２アルキル、Ｃ１～Ｃ１２アルコキシ、及びＣ２～Ｃ１１アシロキシから選択され；
　Ｌ２ｂ、Ｌ２ｃにおけるＲ６は、Ｒ６と同義であり；
　Ｌ３は、ｎが２である場合に、二価のリンカーであり、前記リンカーは、Ｌ３ａ－Ｃ１～Ｃ３０アルキレン－Ｌ３ａ、Ｌ３ａ－Ｃ３～Ｃ１６シクロアルキレン－Ｌ３ａ、Ｌ３ａ－Ｃ６～Ｃ２０アリーレン－Ｌ３ａ、Ｌ３ａ－Ｃ１～Ｃ２０アルキレン－Ｌ３ｂ－Ｃ６～Ｃ１６シクロアルキレン－Ｌ３ａ、Ｌ３ａ－Ｃ６～Ｃ１６シクロアルキレン－Ｌ３ｂ－Ｃ６～Ｃ１６シクロアルキレン－Ｌ３ａ、Ｌ３ａ－Ｃ６～Ｃ２０アリーレン－Ｌ３ｂ－Ｃ６～Ｃ２０アリーレン－Ｌ３ａ、及びＬ３ａ－Ｃ１～Ｃ１３ヘテロアリーレン－Ｌ３ａからなる群より選択され；
　Ｌ３の二価のリンカーにおけるアルキレンは、各々独立して、１もしくはそれより多くの同一もしくは異なる非隣接の基Ｌ３ｃによって中断されていてもよく；
　Ｌ３の二価のリンカーにおけるシクロアルキレンは、各々独立して、１もしくはそれより多くの同一もしくは異なる基ＲＬ３ａを有していてもよく；
　Ｌ３の二価のリンカーにおけるアリーレン及びヘテロアリーレンは、各々独立して、１もしくはそれより多くの同一もしくは異なる基ＲＬ３ｂを有していてもよく；
　Ｌ３ａは、単結合、Ｃ（Ｏ）、Ｃ（Ｏ）ＯまたはＣ（Ｏ）Ｎ（Ｒ１６）であり；
　Ｌ３ｂは、各々独立して、単結合、Ｏ、Ｓ、Ｎ（Ｒ６）またはＣ１～Ｃ５アルキレンであり；
　Ｌ３ｃは、各々独立して、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、ＯＣ（Ｏ）、Ｃ６～Ｃ２０アリーレン、Ｃ３～Ｃ１６シクロアルキレン及びヘテロシクロアルキレンからなる群より選択され；
　ＲＬ３ａは、各々独立して、Ｃ１～Ｃ１２アルキルであり；　ＲＬ３ｂは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１２アルコキシ、及びＣ２～Ｃ１１アシロキシからなる群より選択され；
　Ｌ３ｂ、Ｌ３ｃにおけるＲ６は、Ｒ６と同義であり；
　Ｌ３ａにおけるＲ１６は、と同義であり；
　Ｌ１及びＬ２は、ｎが３の場合、三価のリンカーであり、前記リンカーは、Ｃ１～Ｃ３０アルカントリイル、Ｃ２～Ｃ３０アルケントリイル、Ｃ３～Ｃ１６シクロアルカントリイル、ヘテロシクロアルカントリイル、Ｃ６～Ｃ２０アレーントリイル、及びヘテロアレーントリイルからなる群より選択され；
　Ｌ１、Ｌ２の三価のリンカーにおけるアルカントリイルは、１もしくはそれより多くの同一もしくは異なる基Ｌ４によって中断されていてもよく；
　Ｌ４は、各々独立して、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、ＯＣ（Ｏ）、Ｃ（Ｏ）Ｎ（Ｒ１６）、Ｎ（Ｒ１８）Ｃ（Ｏ）、Ｃ３～Ｃ２０シクロアルキレン、ヘテロシクロアルキレン、Ｃ６～Ｃ２０アリーレン及びヘテロアリーレンからなる群より選択され；
　Ｌ４におけるＲ６、Ｒ１６、Ｒ１８は各々、Ｒ６、前記Ｒ１８と同義であり；
　Ｌ３は、ｎが３の場合、三価のリンカーであり、前記リンカーは、Ｃ１～Ｃ３０アルカントリイル、Ｃ２～Ｃ３０アルケントリイル、Ｃ３～Ｃ１６シクロアルカントリイル、ヘテロシクロアルカントリイル、Ｃ６～Ｃ２０アレーントリイル、ヘテロアレーントリイル、トリアシルからなる群より選択され；
　Ｌ３の三価のリンカーにおけるアルカントリイルは、１もしくはそれより多くの同一もしくは異なる基Ｌ５によって中断されていてもよく；
　Ｌ５は、各々独立して、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、ＯＣ（Ｏ）、Ｃ（Ｏ）Ｎ（Ｒ１６）、Ｎ（Ｒ１８）Ｃ（Ｏ）、Ｃ３～Ｃ２０シクロアルキレン、ヘテロシクロアルキレン、Ｃ６～Ｃ２０アリーレン及びヘテロアリーレンからなる群より選択され；
　Ｌ５におけるＲ６、Ｒ１６、Ｒ１８は各々、Ｒ６、Ｒ１８と同義であり；
　Ｌ１及びＬ２は、ｎが４である場合、四価のリンカーであり、前記リンカーは、Ｃ１～Ｃ３０アルカンテトライルであり；
　Ｌ１、Ｌ２の４価のリンカーにおけるアルカンテトライルは、１もしくはそれより多くの同一もしくは異なる基Ｌ６によって中断されていてもよく；
　Ｌ６は、各々独立して、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、ＯＣ（Ｏ）、Ｃ（Ｏ）Ｎ（Ｒ１６）、Ｎ（Ｒ１８）Ｃ（Ｏ）、Ｃ３～Ｃ２０シクロアルキレン、ヘテロシクロアルキレン、Ｃ６～Ｃ２０アリーレン及びヘテロアリーレンからなる群より選択され；
　Ｌ６におけるＲ６、Ｒ１６、Ｒ１８は各々、Ｒ６、Ｒ１８と同義であり；
　Ｌ３は、ｎが４である場合、四価のリンカーであり、前記リンカーは、Ｃ１～Ｃ３０アルカンテトライル、テトラアシルからなる群より選択され；
　Ｌ３の４価のリンカーにおけるアルカンテトライルは、１もしくはそれより多くの同一もしくは異なる基Ｌ７によって中断されていてもよく；
　Ｌ７は、各々独立して、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、ＯＣ（Ｏ）、Ｃ（Ｏ）Ｎ（Ｒ１６）、Ｎ（Ｒ１８）Ｃ（Ｏ）、Ｃ３～Ｃ２０シクロアルキレン、ヘテロシクロアルキレン、Ｃ６～Ｃ２０アリーレン及びヘテロアリーレンからなる群より選択され；
　Ｌ７におけるＲ６、Ｒ１６、Ｒ１８は各々、Ｒ６、Ｒ１８と同義である。 In the above formula,
n is 2, 3 or 4;
R 1 is C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 2 -C 20 heterocycloalkyl, C 6 -C 20 aryl or C 1 to C 20 heteroaryl;
C 1 -C 20 alkyl, C 2 -C 20 alkenyl and C 2 -C 20 alkynyl in R 1 are one or more of the same or different O, S, N(R 6 ), C(O), C (O) may be interrupted by groups selected from the group consisting of O and OC(O) and may have one or more identical or different groups R 1a ;
C 3 -C 20 cycloalkyl and C 2 -C 20 heterocycloalkyl in R 1 may be interrupted by one or more C(O) groups and may contain one or more identical or different groups. It may have R 1b ;
C 6 -C 20 aryl and C 1 -C 20 heteroaryl in R 1 may have one or more identical or different groups R 1c ;
R 1a each independently represents F, Cl, Br, I, CN, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , C(O ) NR 13 R 14 , C 3 -C 20 cycloalkyl, optionally interrupted by one or more C(O) groups, and C 6 -C 10 aryl;
C 3 -C 20 cycloalkyl and C 6 -C 10 aryl in R 1a may have one or more identical or different groups R 1aa ;
R 1aa is each independently selected from the group consisting of C 1 -C 12 alkyl, C 2 -C 12 alkenyl, F, Cl, Br, I, NO 2 , SR 7 , OR 8 and NR 9 R 10 ;
C 1 -C 12 alkyl in R 1aa is one or more selected from the group consisting of O, S, N(R 6 ), C(O), C(O)O, and OC(O). Optionally interrupted by groups F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , and C(O) may have one or more same or different groups selected from the group consisting of NR 13 R 14 ;
R 1b is each independently from the group consisting of C 1 -C 12 alkyl, C 2 -C 12 alkenyl, F, Cl, Br, I, CN, NO 2 , SR 7 , OR 8 and NR 9 R 10 selected;
C 1 -C 12 alkyl in R 1b is F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , and C( O) may have one or more same or different groups selected from the group consisting of NR 13 R 14 ;
R 1c is each independently C 1 -C 12 alkyl, C 2 -C 12 alkenyl, F, Cl, Br, I, CN, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O ) R 11 , C(O)OR 12 , C(O)NR 13 R 14 , C 6 -C 10 aryl, C 1 -C 20 heteroaryl, C 3 -C 10 cycloalkyl, and C 2 -C 10 hetero selected from the group consisting of cycloalkyl;
C 1 -C 12 alkyl in R 1c is F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , and C( O) may have one or more identical or different groups selected from NR 13 R 14 ;
C 1 -C 12 alkyl, C 3 -C 10 cycloalkyl and C 2 -C 10 heterocycloalkyl in R 1c may be interrupted by one or more C(O) groups;
C 6 -C 10 aryl, C 1 -C 20 heteroaryl, C 3 -C 10 cycloalkyl and C 2 -C 10 heterocycloalkyl in R 1c have one or more identical or different groups R 1ca . and the R 1ca has the same meaning as the above R 1aa ;
R 2 is a hydrogen atom, C 1 to C 20 alkyl, C 2 to C 20 alkenyl, C 2 to C 20 alkynyl, C 3 to C 20 cycloalkyl, C 2 to C 20 heterocycloalkyl, C 6 to C 20 Aryl, C 1 -C 20 heteroaryl, SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , C(O)NR 13 R 14 , SO 2 R 15 , or CN; C 1 -C 20 alkyl, C 2 -C 20 alkenyl and C 2 -C 20 alkynyl in R 2 are one or more of the same or different O, S, N(R 6 ), C( O), C(O)O, and OC(O), and may have one or more identical or different groups R2a ;
C 3 -C 20 cycloalkyl and C 2 -C 20 heterocycloalkyl in R 2 may be interrupted by one or more C(O) groups and may contain one or more identical or different groups. It may have R 2b ;
C 6 -C 20 aryl and C 1 -C 20 heteroaryl in R 2 may have one or more identical or different groups R 2c ;
R 2a is synonymous with R 1a ;
R 2b is synonymous with R 1b ;
R 2c is synonymous with R 1c ;
Furthermore, R 2 may be combined with -SR 1 to form a ring structure containing an imino carbon atom;
The ring structure containing the imino carbon atom includes S-(C 1 to C 20 alkylene)-X, S-(C 2 to C 20 alkenylene)-X, S-(C 3 to C 20 cycloalkylene)-X , S-(heterocycloalkylene)-X, S-(o-phenylene)-X, S-(o-xylene)-X, S-(o-phenylene-C 1 -C 12 alkylene)-X, S- (C 1 -C 12 alkylene-o-phenylene)-X, S-(C(O)N(R 16 ))-X, or S-(C(S)N(R 17 ))-X, often;
X is bonded to an imino carbon atom with S, O, S, N(R 6 ), C(O), OC(O), C(O)O, SC(O), C(O) S, C(O)N(R 16 ), N(R 18 )C(O), N(R 19 )SO 2 or a single bond;
The alkylene and alkenylene in the ring structure containing the imino carbon atom are selected from the group consisting of one or more of the same or different O, S, N(R 6 ), C(O) and C(S). optionally interrupted by groups and optionally substituted by one or more groups R 2d ;
Cycloalkylene and heterocycloalkylene in the ring structures containing said imino carbon atoms may be interrupted by one or more C(O) groups and substituted by one or more identical or different groups R 2e phenylene and o-xylylene in the ring structure containing the imino carbon atom may be substituted by one or more of the same or different groups R 2f ;
R 2d is each independently F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , C(O)NR 13 R 14 selected from the group consisting of C 6 -C 10 aryl and C 1 -C 20 heteroaryl;
C 6 -C 10 aryl and C 1 -C 20 heteroaryl in R 2d may have one or more groups R 2da , each R 2da being independently phenoxy, and R 1aa selected from the group consisting of the indicated groups;
R 2e each independently represents F, Cl, Br, I, SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , CONR 13 R 14 , C 1 - selected from the group consisting of C 12 alkyl, C 1 -C 12 haloalkyl, C 6 -C 10 aryl, and C 1 -C 20 heteroaryl;
C 6 -C 10 aryl and C 1 -C 20 heteroaryl in R 2e may have one or more groups R 2ea , R 2ea is synonymous with R 1aa ; R 2f is , each independently, F, Cl, Br, I, SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , CONR 13 R 14 , C 1 -C 12 alkyl , C 1 -C 12 haloalkyl, C 6 -C 10 aryl, and C 1 -C 20 heteroaryl;
C 6 -C 10 aryl and C 1 -C 20 heteroaryl in R 2f may have one or more groups R 2fa , R 2fa is synonymous with R 1aa ; R 3 and Each R 4 is independently C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 1 -C 20 heteroaryl, C 7 -C 15 aralkyl, or Si(CH 3 ) 3 ;
C 1 -C 20 alkyl and C 3 -C 20 cycloalkyl in R 3 and R 4 are O, S, N(R 6 ), C(O), C(O)O, OC(O), C( O) optionally interrupted by one or more groups selected from the group consisting of S, and SC(O), F, Cl, Br, I, NO2 , SR7 , OR8 , NR9 R may have one or more same or different groups selected from the group consisting of;
C 6 -C 20 aryl, C 12 -C 20 heteroaryl, and C 7 -C 15 aralkyl in R 3 and R 4 are C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 2 -C 12 alkenyl , F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , C(O)NR 13 R 14 , C 6 to C 10 aryl, and one or more identical or different groups selected from the group consisting of C 1 -C 20 heteroaryl;
R 5 is a hydrogen atom, C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 7 -C 14 aralkyl, C 6 -C 14 aryl, or acyl group;
The acyl group in R 5 is -C(O)-H, -C(O)-C 1 -C 18 alkyl, -C(O)-C 2 -C 18 alkenyl, -C(O)-C 6 - C 14 aryl, -C(O)-C 2 -C 18 alkenyl-C 6 -C 14 aryl, -C(O)-O-C 1 -C 18 alkyl, -C(O)-O-C 6 - C 14 aryl, -C(O)-NH-C 1 -C 18 alkyl, -C(O)-NH-C 6 -C 14 aryl and C(O)-N(C 1 -C 18 alkyl) from 2 selected from the group;
R 3 and R 5 together with the nitrogen atom to which they are attached may form a 5- to 12-membered ring which may contain further heteroatoms;
R 6 is each independently selected from the group consisting of a hydrogen atom, C 1 -C 20 alkyl, C 2 -C 20 alkanoyl, C 6 -C 10 aryl, and C 7 -C 11 aroyl;
C 1 -C 20 alkyl in R 6 is 1 or 1 selected from the group consisting of O, S, N (C 1 -C 12 alkyl), C(O), C(O)O, and OC(O) Optionally interrupted by more groups, from F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl, C 6 -C 10 aryl, OH, and SH may have one or more same or different groups selected from the group;
The C 2 -C 20 alkanoyl in R 6 may be interrupted by one or more groups selected from the group consisting of O, S, CO, C(O)O, and OC(O), one or more same or different groups selected from the group consisting of F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl, and C 6 -C 10 aryl; May have;
C 6 -C 10 aryl in R 6 is one or more selected from the group consisting of F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy. may have more identical or different groups;
C 7 -C 11 aroyl in R 6 is one or more selected from the group consisting of F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy. may have more identical or different groups;
R 7 and R 8 are each independently selected from the group consisting of hydrogen atom, C 1 -C 20 alkyl, C 2 -C 20 alkanoyl, C 6 -C 10 aryl, and C 7 -C 11 aroyl;
C 1 -C 20 alkyl in R 7 and R 8 is one selected from the group consisting of O, S, N (C 1 -C 12 alkyl), CO, C(O)O, and OC(O); Optionally interrupted by more groups, from F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl, C 6 -C 10 aryl, OH, and SH may have one or more same or different groups selected from the group;
The C 2 -C 20 alkanoyl in R 7 , R 8 is interrupted by one or more groups selected from the group consisting of O, S, C(O), C(O)O, and OC(O). one or more selected from the group consisting of F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl, and C 6 -C 10 aryl. may have the same or different groups;
C 6 -C 10 aryl in R 7 , R 8 is selected from the group consisting of F, Cl, Br, I, C 1 -C 6 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy. may have one or more identical or different groups;
C7 - C11 aroyl in R7 , R8 is selected from the group consisting of F, Cl, Br, I, C1 - C10 alkyl, C1 - C10 alkoxy, and C2 - C11 acyloxy may have one or more identical or different groups;
R 9 and R 10 are each independently selected from the group consisting of hydrogen atom, C 1 -C 20 alkyl, C 2 -C 20 alkanoyl, C 7 -C 11 aroyl, C 6 -C 10 aryl; 9 , C 1 -C 20 alkyl in R 10 is selected from the group consisting of O, S, N (C 1 -C 12 alkyl), C(O), C(O)O, and OC(O). optionally interrupted by one or more groups selected from the group consisting of F, Cl, Br, I, NO 2 , C 3 -C 10 cycloalkyl, heterocycloalkyl, phenyl, OH, SH and CN may have one or more identical or different groups;
The C 2 -C 20 alkanoyl in R 9 , R 10 may be interrupted by one or more groups selected from the group consisting of O and S, F, Cl, Br, I, OH and C may have one or more identical or different groups selected from the group consisting of 1 to C 6 alkoxy;
C 7 -C 11 aroyl in R 9 and R 10 is one or more selected from the group consisting of F, Cl, Br, I, C 1 -C 6 alkyl, -OH and C 1 -C 6 alkoxy. may have the same or different groups;
C 6 -C 10 aryl in R 9 and R 10 is one or more selected from the group consisting of F, Cl, Br, I, C 1 -C 6 alkyl, -OH and C 1 -C 6 alkoxy. may have the same or different groups;
R 9 and R 10 together with the nitrogen atom to which they are bonded may form a saturated 5-, 6-, or 7-membered nitrogen heterocycle, and the ring may be O, S, N (C 1 -C 12 alkyl), C(O), and C(O)O as ring members, and the ring has one or more C 1 may have ~C 4 alkyl;
each R 11 is independently selected from the group consisting of a hydrogen atom, C 1 -C 20 alkyl, and C 6 -C 20 aryl;
C 1 -C 20 alkyl may be interrupted by one or more groups selected from the group consisting of O, S and C(O), and may contain one or more identical or different R 11a May have;
R 11a is each independently selected from the group consisting of F, Cl, Br, I, C 3 -C 10 cycloalkyl, heterocycloalkyl, phenyl, OH, and SH;
C 6 -C 20 aryl in R 11 is one or more selected from the group consisting of F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy. may have more identical or different groups;
R 12 is synonymous with R 8 ;
R 13 and R 14 are synonymous with R 9 and R 10 ;
each R 15 is independently selected from the group consisting of a hydrogen atom, C 1 -C 20 alkyl, C 6 -C 10 aryl;
C 1 -C 20 alkyl in R 15 is 1 or 1 selected from the group consisting of O, S, N (C 1 -C 12 alkyl), C(O), C(O)O, and OC(O) Optionally interrupted by more groups, from F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl, C 6 -C 10 aryl, OH, and SH may have one or more same or different groups selected from the group;
C 6 -C 10 aryl in R 15 is one or more same or different groups selected from the group consisting of F, Cl, Br, I, C 1 -C 6 alkyl, and C 1 -C 6 alkoxy. may have;
R 16 , R 17 , R 18 and R 19 each independently consist of a hydrogen atom, C 1 -C 20 alkyl, C 2 -C 20 alkanoyl, C 6 -C 10 aryl, C 7 -C 11 aroyl selected from the group;
C 1 -C 20 alkyl in R 16 , R 17 , R 18 and R 19 is O, S, N (C 1 -C 12 alkyl), C(O), C(O)O, and OC(O) optionally interrupted by one or more groups selected from the group consisting of F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl, C 6 - may have one or more identical or different groups selected from the group consisting of C 10 aryl, OH, and SH;
The C 2 -C 20 alkanoyl in R 16 , R 17 , R 18 , R 19 is one or more selected from the group consisting of O, S, CO, C(O)O, and OC(O). Optionally interrupted by groups , one or It may have more of the same or different groups;
C 6 -C 10 aryl in R 16 , R 17 , R 18 , R 19 is selected from F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy may have one or more same or different groups selected from the group;
C 7 -C 11 aroyl in R 16 , R 17 , R 18 , R 19 is selected from F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy may have one or more identical or different groups selected from the group consisting of;
L 1 is a divalent linker when n is 2, and the linker is L 1a -C 1 -C 30 alkylene-L 1a , L 2a -C 1 -C 30 alkenylene-L 2a , L 1a -C 3 -C 16 cycloalkylene-L 1a , L 1a -C 6 -C 20 arylene-L 1a , L 1a -C 6 -C 20 arylene-L 1b -C 6 -C 20 arylene-L 1a , and selected from the group consisting of L 1a -C 1 -C 13 heteroarylene-L 1a ;
The alkylene and alkenylene in the linker of L 1 may each independently be interrupted by one or more identical or different non-adjacent groups L 1c ;
The arylene and heteroarylene in the linker of L 1 may each independently have one or more identical or different groups R L 1 ;
L 1a is a single bond;
L 1b is a single bond, O, S, N(R 6 ), C(O), CH 2 , C(CH 3 ) 2 , CH(OH) or C 1 -C 5 alkylene;
L 1c each independently represents O, S, N(R 6 ), C(O), C(O)O, OC(O), C 6 -C 20 arylene, and C 3 -C 16 cycloalkylene. selected from the group;
R L1 is each independently selected from F, Cl, Br, I, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, and C 2 -C 11 acyloxy;
R 6 in L 1b and L 1c has the same meaning as R 6 ;
L 2 is a divalent linker when n is 2, and the linker is a single bond, L 2a -C 1 -C 30 alkylene-L 2a , L 2a -C 1 -C 30 alkenylene-L 2a , L 2a -C 6 -C 20 arylene- L 2a , L 2a -C 6 -C 20 arylene-L 2b -C 6 -C 20 arylene-L 2a ;
The alkylene and alkenylene in the divalent linker of L2 may each be independently interrupted by one or more identical or different groups L2c ;
The arylene and heteroarylene in the divalent linker of L2 may each independently have one or more identical or different groups R L2 ;
L2a is each independently a single bond, S, O, N( R6 ), C(O), C(O)O, OC(O) or SO2 ;
L 2b is a single bond, O, S, N(R 6 ), C(O), CH 2 , C(CH 3 ) 2 , CH(OH) or C 1 -C 5 alkylene;
L 2c each independently represents O, S, N(R 6 ), C(O), C(O)O, OC(O), C 6 -C 20 arylene, and C 3 -C 16 cycloalkylene. selected from the group;
R L2 is each independently selected from F, Cl, Br, I, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, and C 2 -C 11 acyloxy;
R 6 in L 2b and L 2c has the same meaning as R 6 ;
L 3 is a divalent linker when n is 2, and the linker is L 3a -C 1 -C 30 alkylene-L 3a , L 3a -C 3 -C 16 cycloalkylene-L 3a , L 3a -C 6 -C 20 arylene-L 3a , L 3a -C 1 -C 20 alkylene-L 3b -C 6 -C 16 cycloalkylene-L 3a , L 3a -C 6 -C 16 cycloalkylene-L 3b -C 6 -C 16 cycloalkylene-L 3a , L 3a -C 6 -C 20 arylene-L 3b -C 6 -C 20 arylene-L 3a , and L 3a -C 1 -C 13 heteroarylene-L 3a selected from the group;
The alkylene in the divalent linker of L 3 may each independently be interrupted by one or more identical or different non-adjacent groups L 3c ;
The cycloalkylenes in the divalent linker of L3 may each independently carry one or more identical or different groups R L3a ;
The arylene and heteroarylene in the divalent linker of L3 may each independently have one or more identical or different groups R L3b ;
L 3a is a single bond, C(O), C(O)O or C(O)N(R 16 );
L 3b is each independently a single bond, O, S, N(R 6 ) or C 1 -C 5 alkylene;
L 3c each independently represents O, S, N(R 6 ), C(O), C(O)O, OC(O), C 6 to C 20 arylene, C 3 to C 16 cycloalkylene, and selected from the group consisting of heterocycloalkylene;
R L3a is each independently C 1 -C 12 alkyl; R L3b is selected from the group consisting of F, Cl, Br, I, C 1 -C 12 alkoxy, and C 2 -C 11 acyloxy. ;
R 6 in L 3b and L 3c has the same meaning as R 6 ;
R 16 in L 3a has the same meaning as;
L 1 and L 2 are trivalent linkers when n is 3, and the linker is a C 1 -C 30 alkanetriyl, a C 2 -C 30 alkenetriyl, a C 3 -C 16 cycloalkanetriyl. selected from the group consisting of yl, heterocycloalkanetriyl, C 6 -C 20 arenetriyl, and heteroarenetriyl;
The alkantriyl in the trivalent linker L 1 , L 2 may be interrupted by one or more identical or different groups L 4 ;
L 4 each independently represents O, S, N(R 6 ), C(O), C(O)O, OC(O), C(O)N(R 16 ), N(R 18 ) selected from the group consisting of C(O), C3 - C20 cycloalkylene, heterocycloalkylene, C6 - C20 arylene and heteroarylene;
R 6 , R 16 and R 18 in L 4 each have the same meaning as R 6 and R 18 above;
L3 is a trivalent linker when n is 3 ; selected from the group consisting of cycloalkanetriyl, C 6 -C 20 arenetriyl, heteroarenetriyl, triacyl;
The alkantriyl in the trivalent linker of L3 may be interrupted by one or more identical or different groups L5 ;
L 5 each independently represents O, S, N(R 6 ), C(O), C(O)O, OC(O), C(O)N(R 16 ), N(R 18 ) selected from the group consisting of C(O), C3 - C20 cycloalkylene, heterocycloalkylene, C6 - C20 arylene and heteroarylene;
R 6 , R 16 and R 18 in L 5 are each synonymous with R 6 and R 18 ;
L 1 and L 2 are tetravalent linkers when n is 4, and the linker is C 1 -C 30 alkanetetryl;
The alkanetetryl in the tetravalent linker of L 1 , L 2 may be interrupted by one or more identical or different groups L 6 ;
L 6 each independently represents O, S, N(R 6 ), C(O), C(O)O, OC(O), C(O)N(R 16 ), N(R 18 ) selected from the group consisting of C(O), C3 - C20 cycloalkylene, heterocycloalkylene, C6 - C20 arylene and heteroarylene;
R 6 , R 16 and R 18 in L 6 are each synonymous with R 6 and R 18 ;
L 3 is a tetravalent linker when n is 4, said linker being selected from the group consisting of C 1 -C 30 alkanetetralyl, tetraacyl;
The alkanetetryl in the tetravalent linker of L3 may be interrupted by one or more identical or different groups L7 ;
L 7 is each independently O, S, N(R 6 ), C(O), C(O)O, OC(O), C(O)N(R 16 ), N(R 18 ) selected from the group consisting of C(O), C3 - C20 cycloalkylene, heterocycloalkylene, C6 - C20 arylene and heteroarylene;
R 6 , R 16 and R 18 in L 7 have the same meanings as R 6 and R 18 , respectively.
　また、本発明の第２態様の化合物は、以下の式（Ｉ）又は（ＩＩ）で示される化合物である。 Further, the compound of the second aspect of the present invention is a compound represented by the following formula (I) or (II).
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　前記式中、
　ｎ＝２であり；
　Ｒ１は、Ｃ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルケニル、Ｃ２～Ｃ２０アルキニル、Ｃ３～Ｃ２０シクロアルキル、Ｃ２～Ｃ２０ヘテロシクロアルキル、Ｃ６～Ｃ２０アリールまたはＣ１～Ｃ２０ヘテロアリールであり；
　Ｒ１におけるＣ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルケニル及びＣ２～Ｃ２０アルキニルは、１もしくはそれより多くの同一もしくは異なるＯ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ及びＯＣ（Ｏ）からなる群より選択される基によって中断されていてもよく、１もしくはそれより多くの同一もしくは異なる基Ｒ１ａを有していてもよく；
　Ｒ１におけるＣ３～Ｃ２０シクロアルキル及びＣ２～Ｃ２０ヘテロシクロアルキルは、１もしくはそれより多くのＣ（Ｏ）基によって中断されていてもよく、１もしくはそれより多くの同一もしくは異なる基Ｒ１ｂを有していてもよく；
　Ｒ１におけるＣ６～Ｃ２０アリール及びＣ１～Ｃ２０ヘテロアリールは、１もしくはそれより多くの同一もしくは異なる基Ｒ１ｃを有していてもよく；
　Ｒ１ａは、各々独立して、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＣＮ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、Ｃ（Ｏ）ＮＲ１３Ｒ１４、１もしくはそれより多くのＣ（Ｏ）基によって中断されていてもよいＣ３～Ｃ２０シクロアルキル、及びＣ６～Ｃ１０アリールからなる群より選択され；
　Ｒ１ａにおけるＣ３～Ｃ２０シクロアルキル及びＣ６～Ｃ１０アリールは、１もしくはそれより多くの同一もしくは異なる基Ｒ１ａａを有していてもよく；
　Ｒ１ａａは、各々独立して、Ｃ１～Ｃ１２アルキル、Ｃ２～Ｃ１２アルケニル、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、ＳＲ７、ＯＲ８及びＮＲ９Ｒ１０からなる群より選択され；
　Ｒ１ａａにおけるＣ１～Ｃ１２アルキルは、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、及びＣ（Ｏ）ＮＲ１３Ｒ１４からなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ１ｂは、各々独立して、Ｃ１～Ｃ１２アルキル、Ｃ２～Ｃ１２アルケニル、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＣＮ、ＮＯ２、ＳＲ７、ＯＲ８及びＮＲ９Ｒ１０からなる群より選択され；
　Ｒ１ｂにおけるＣ１～Ｃ１２アルキルは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、及びＣ（Ｏ）ＮＲ１３Ｒ１４からなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ１ｃは、各々独立して、Ｃ１～Ｃ１２アルキル、Ｃ２～Ｃ１２アルケニル、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＣＮ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、Ｃ（Ｏ）ＮＲ１３Ｒ１４、Ｃ６～Ｃ１０アリール、Ｃ１～Ｃ２０ヘテロアリール、Ｃ３～Ｃ１０シクロアルキル、及びＣ２～Ｃ１０ヘテロシクロアルキルからなる群より選択され；
　Ｒ１ｃにおけるＣ１～Ｃ１２アルキルは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、及びＣ（Ｏ）ＮＲ１３Ｒ１４から選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ１ｃにおけるＣ１～Ｃ１２アルキル、Ｃ３～Ｃ１０シクロアルキル及びＣ２～Ｃ１０ヘテロシクロアルキルは、１もしくはそれより多くのＣ（Ｏ）基によって中断されていてもよく；
　Ｒ１ｃにおけるＣ６～Ｃ１０アリール、Ｃ１～Ｃ２０ヘテロアリール、Ｃ３～Ｃ１０シクロアルキル及びＣ２～Ｃ１０ヘテロシクロアルキルは、１もしくはそれより多くの同一もしくは異なる基Ｒ１ｃａを有していてもよく、該Ｒ１ｃａは、前記Ｒ１ａａと同義であり；
　Ｒ２は、水素原子、Ｃ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルケニル、Ｃ２～Ｃ２０アルキニル、Ｃ３～Ｃ２０シクロアルキル、Ｃ２～Ｃ２０ヘテロシクロアルキル、Ｃ６～Ｃ２０アリール、Ｃ１～Ｃ２０ヘテロアリール、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、Ｃ（Ｏ）ＮＲ１３Ｒ１４、ＳＯ２Ｒ１５、またはＣＮであり；
　Ｒ２におけるＣ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルケニル及びＣ２～Ｃ２０アルキニルは、１もしくはそれより多くの同一もしくは異なるＯ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される基によって中断されていてもよく、１もしくはそれより多くの同一もしくは異なる基Ｒ２ａを有していてもよく；
　Ｒ２におけるＣ３～Ｃ２０シクロアルキル及びＣ２～Ｃ２０ヘテロシクロアルキルは、１もしくはそれより多くのＣ（Ｏ）基によって中断されていてもよく、１もしくはそれより多くの同一もしくは異なる基Ｒ２ｂを有していてもよく；
　Ｒ２におけるＣ６～Ｃ２０アリール及びＣ１～Ｃ２０ヘテロアリールは、１もしくはそれより多くの同一もしくは異なる基Ｒ２ｃを有していてもよく；
　Ｒ２ａは、Ｒ１ａと同義であり；
　Ｒ２ｂは、Ｒ１ｂと同義であり；
　Ｒ２ｃは、Ｒ１ｃと同義であり；
　また、Ｒ２は、－Ｓ－Ｒ１と一緒になってイミノ炭素原子を含む環構造を形成していてもよく；
　前記イミノ炭素原子を含む環構造としては、Ｓ－（Ｃ１～Ｃ２０アルキレン）－Ｘ、Ｓ－（Ｃ２～Ｃ２０アルケニレン）－Ｘ、Ｓ－（Ｃ３～Ｃ２０シクロアルキレン）－Ｘ、Ｓ－（ヘテロシクロアルキレン）－Ｘ、Ｓ－（ｏ－フェニレン）－Ｘ、Ｓ－（ｏ－キシレン）－Ｘ、Ｓ－（ｏ－フェニレン－Ｃ１～Ｃ１２アルキレン）－Ｘ、Ｓ－（Ｃ１～Ｃ１２アルキレン－ｏ－フェニレン）－Ｘ、Ｓ－（Ｃ（Ｏ）Ｎ（Ｒ１６））－Ｘ、またはＳ－（Ｃ（Ｓ）Ｎ（Ｒ１７））－Ｘであってよく；
　Ｘは、Ｓを有するイミノ炭素原子に結合されており、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、ＯＣ（Ｏ）、Ｃ（Ｏ）Ｏ、ＳＣ（Ｏ）、Ｃ（Ｏ）Ｓ、Ｃ（Ｏ）Ｎ（Ｒ１６）、Ｎ（Ｒ１８）Ｃ（Ｏ）、Ｎ（Ｒ１９）ＳＯ２または単結合であり；
　前記イミノ炭素原子を含む環構造におけるアルキレン及びアルケニレンは、１もしくはそれより多くの同一または異なる、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）及びＣ（Ｓ）からなる群より選択される基によって中断されていてもよく、１もしくはそれより多くの基Ｒ２ｄによって置換されていてもよく；
　前記イミノ炭素原子を含む環構造におけるシクロアルキレン及びヘテロシクロアルキレンは、１もしくはそれより多くのＣ（Ｏ）基によって中断されていてもよく、１もしくはそれより多くの同一もしくは異なる基Ｒ２ｅによって置換されていてもよく；
　前記イミノ炭素原子を含む環構造におけるフェニレン及びｏ－キシリレンは、１もしくはそれより多くの同一もしくは異なる基Ｒ２ｆによって置換されていてもよく；
　Ｒ２ｄは、各々独立して、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、Ｃ（Ｏ）ＮＲ１３Ｒ１４、Ｃ６～Ｃ１０アリール及びＣ１～Ｃ２０ヘテロアリールからなる群より選択され；
　Ｒ２ｄにおけるＣ６～Ｃ１０アリール及びＣ１～Ｃ２０ヘテロアリールは、１もしくはそれより多くの基Ｒ２ｄａを有していてもよく、Ｒ２ｄａは、各々独立に、フェノキシ、及びＲ１ａａで示した基からなる群から選択され；
　Ｒ２ｅは、各々独立して、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、ＣＯＮＲ１３Ｒ１４、Ｃ１～Ｃ１２アルキル、Ｃ１～Ｃ１２ハロアルキル、Ｃ６～Ｃ１０アリール、及びＣ１～Ｃ２０ヘテロアリールからなる群より選択され；
　Ｒ２ｅにおけるＣ６～Ｃ１０アリール及びＣ１～Ｃ２０ヘテロアリールは、１もしくはそれより多くの基Ｒ２ｅａを有していてもよく、Ｒ２ｅａは、Ｒ１ａａと同義であり；
　Ｒ２ｆは、各々独立して、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、ＣＯＮＲ１３Ｒ１４、Ｃ１～Ｃ１２アルキル、Ｃ１～Ｃ１２ハロアルキル、Ｃ６～Ｃ１０アリール、及びＣ１～Ｃ２０ヘテロアリールからなる群より選択され；
　Ｒ２ｆにおけるＣ６～Ｃ１０アリール及びＣ１～Ｃ２０ヘテロアリールは、１もしくはそれより多くの基Ｒ２ｆａを有していてもよく、Ｒ２ｆａは、Ｒ１ａａと同義であり；
　Ｒ３及びＲ４は、各々独立して、Ｃ１～Ｃ２０アルキル、Ｃ３～Ｃ２０シクロアルキル、Ｃ６～Ｃ２０アリール、Ｃ１～Ｃ２０ヘテロアリール、Ｃ７～Ｃ１５アラルキル、又はＳｉ（ＣＨ３）３であり；
　Ｒ３、Ｒ４におけるＣ１～Ｃ２０アルキル及びＣ３～Ｃ２０シクロアルキルは、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、ＯＣ（Ｏ）、Ｃ（Ｏ）Ｓ、及びＳＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０からなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ３、Ｒ４におけるＣ６～Ｃ２０アリール、Ｃ１２～Ｃ２０ヘテロアリール、及びＣ７～Ｃ１５アラルキルは、Ｃ１～Ｃ１２アルキル、Ｃ１～Ｃ１２ハロアルキル、Ｃ２～Ｃ１２アルケニル、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、Ｃ（Ｏ）ＮＲ１３Ｒ１４、Ｃ６～Ｃ１０アリール、及びＣ１～Ｃ２０ヘテロアリールからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ５は、水素原子、Ｃ１～Ｃ２０アルキル、Ｃ３～Ｃ２０シクロアルキル、Ｃ７～Ｃ１４アラルキル、Ｃ６～Ｃ１４アリール、またはアシル基であり；
　Ｒ５におけるアシル基は、－Ｃ（Ｏ）－Ｈ、－Ｃ（Ｏ）－Ｃ１～Ｃ１８アルキル、－Ｃ（Ｏ）－Ｃ２～Ｃ１８アルケニル、－Ｃ（Ｏ）－Ｃ６～Ｃ１４アリール、－Ｃ（Ｏ）－Ｃ２～Ｃ１８アルケニル－Ｃ６～Ｃ１４アリール、－Ｃ（Ｏ）－Ｏ－Ｃ１～Ｃ１８アルキル、－Ｃ（Ｏ）－Ｏ－Ｃ６～Ｃ１４アリール、－Ｃ（Ｏ）－ＮＨ－Ｃ１～Ｃ１８アルキル、－Ｃ（Ｏ）－ＮＨ－Ｃ６～Ｃ１４アリール及びＣ（Ｏ）－Ｎ（Ｃ１～Ｃ１８アルキル）２からなる群より選択され；
　Ｒ３及びＲ５は、それらが結合する窒素原子と共に、更なるヘテロ原子を含んでいてもよい５～１２員環を形成していてもよく；
　Ｒ６は、各々独立して、水素原子、Ｃ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルカノイル、Ｃ６～Ｃ１０アリール及びＣ７～Ｃ１１アロイルからなる群より選択され；
　Ｒ６におけるＣ１～Ｃ２０アルキルは、Ｏ、Ｓ、Ｎ（Ｃ１～Ｃ１２アルキル）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、Ｃ２～Ｃ１０ヘテロシクロアルキル、Ｃ６～Ｃ１０アリール、ＯＨ、及びＳＨからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ６におけるＣ２～Ｃ２０アルカノイルは、Ｏ、Ｓ、ＣＯ、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、Ｃ２～Ｃ１０ヘテロシクロアルキル、及びＣ６～Ｃ１０アリールからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ６におけるＣ６～Ｃ１０アリールは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１０アルキル、Ｃ１～Ｃ１０アルコキシ、及びＣ２～Ｃ１１アシロキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ６におけるＣ７～Ｃ１１アロイルは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１０アルキル、Ｃ１～Ｃ１０アルコキシ、及びＣ２～Ｃ１１アシロキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ７及びＲ８は、各々独立して、水素原子、Ｃ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルカノイル、Ｃ６～Ｃ１０アリール、及びＣ７～Ｃ１１アロイルからなる群より選択され；
　Ｒ７、Ｒ８におけるＣ１～Ｃ２０アルキルは、Ｏ、Ｓ、Ｎ（Ｃ１～Ｃ１２アルキル）、ＣＯ、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、Ｃ２～Ｃ１０ヘテロシクロアルキル、Ｃ６～Ｃ１０アリール、ＯＨ、及びＳＨからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ７、Ｒ８におけるＣ２～Ｃ２０アルカノイルは、Ｏ、Ｓ、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、Ｃ２～Ｃ１０ヘテロシクロアルキル、及びＣ６～Ｃ１０アリールからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ７、Ｒ８におけるＣ６～Ｃ１０アリールは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ６アルキル、Ｃ１～Ｃ１０アルコキシ、及びＣ２～Ｃ１１アシロキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ７、Ｒ８におけるＣ７～Ｃ１１アロイルは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１０アルキル、Ｃ１～Ｃ１０アルコキシ、及びＣ２～Ｃ１１アシロキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ９及びＲ１０は、各々独立して、水素原子、Ｃ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルカノイル、Ｃ７～Ｃ１１アロイル、Ｃ６～Ｃ１０アリールからなる群より選択され；
　Ｒ９、Ｒ１０におけるＣ１～Ｃ２０アルキルは、Ｏ、Ｓ、Ｎ（Ｃ１～Ｃ１２アルキル）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、Ｃ３～Ｃ１０シクロアルキル、ヘテロシクロアルキル、フェニル、ＯＨ、ＳＨ及びＣＮからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ９、Ｒ１０におけるＣ２～Ｃ２０アルカノイルは、Ｏ及びＳからなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＯＨ及びＣ１～Ｃ６アルコキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ９、Ｒ１０におけるＣ７～Ｃ１１アロイルは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ６アルキル、－ＯＨ及びＣ１～Ｃ６アルコキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ９、Ｒ１０におけるＣ６～Ｃ１０アリールは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ６アルキル、－ＯＨ及びＣ１～Ｃ６アルコキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ９及びＲ１０は、それらが結合される窒素原子と一緒になって、飽和の５員、６員または７員の窒素複素環を形成していてもよく、前記環はＯ、Ｓ、Ｎ（Ｃ１～Ｃ１２アルキル）、Ｃ（Ｏ）、及びＣ（Ｏ）Ｏからなる群より選択される基を環員として有していてもよく、前記環は１もしくはそれより多くのＣ１～Ｃ４アルキルを有してよく；
　Ｒ１１は各々独立して、水素原子、Ｃ１～Ｃ２０アルキル及びＣ６～Ｃ２０アリールからなる群より選択され；
　Ｃ１～Ｃ２０アルキルは、Ｏ、Ｓ及びＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、１もしくはそれより多くの同一もしくは異なるＲ１１ａを有していてもよく；
　Ｒ１１ａは、各々独立して、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、ヘテロシクロアルキル、フェニル、ＯＨ、及びＳＨからなる群より選択され；
　Ｒ１１におけるＣ６～Ｃ２０アリールは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１０アルキル、Ｃ１～Ｃ１０アルコキシ、及びＣ２～Ｃ１１アシロキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ１２は、Ｒ８と同義であり；
　Ｒ１３及びＲ１４は、Ｒ９、Ｒ１０と同義であり；
　Ｒ１５は、各々独立して、水素原子、Ｃ１～Ｃ２０アルキル、Ｃ６～Ｃ１０アリールからなる群より選択され；
　Ｒ１５におけるＣ１～Ｃ２０アルキルは、Ｏ、Ｓ、Ｎ（Ｃ１～Ｃ１２アルキル）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、Ｃ２～Ｃ１０ヘテロシクロアルキル、Ｃ６～Ｃ１０アリール、ＯＨ、及びＳＨからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ１５におけるＣ６～Ｃ１０アリールは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ６アルキル、及びＣ１～Ｃ６アルコキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ１６、Ｒ１７、Ｒ１８及びＲ１９は、各々独立して、水素原子、Ｃ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルカノイル、Ｃ６～Ｃ１０アリール、Ｃ７～Ｃ１１アロイルからなる群より選択され；
　Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９におけるＣ１～Ｃ２０アルキルは、Ｏ、Ｓ、Ｎ（Ｃ１～Ｃ１２アルキル）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、Ｃ２～Ｃ１０ヘテロシクロアルキル、Ｃ６～Ｃ１０アリール、ＯＨ、及びＳＨからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９におけるＣ２～Ｃ２０アルカノイルは、Ｏ、Ｓ、ＣＯ、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、Ｃ２～Ｃ１０ヘテロシクロアルキル、及びＣ６～Ｃ１０アリールからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９におけるＣ６～Ｃ１０アリールは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１０アルキル、Ｃ１～Ｃ１０アルコキシ、及びＣ２～Ｃ１１アシロキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９におけるＣ７～Ｃ１１アロイルは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１０アルキル、Ｃ１～Ｃ１０アルコキシ、及びＣ２～Ｃ１１アシロキシからからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｌ１は二価のリンカーであり、前記リンカーは、Ｌ１ａ－Ｃ１～Ｃ３０アルキレン－Ｌ１ａ、Ｌ２ａ－Ｃ１～Ｃ３０アルケニレン－Ｌ２ａ、Ｌ１ａ－Ｃ３～Ｃ１６シクロアルキレン－Ｌ１ａ、Ｌ１ａ－Ｃ６～Ｃ２０アリーレン－Ｌ１ａ、Ｌ１ａ－Ｃ６～Ｃ２０アリーレン－Ｌ１ｂ－Ｃ６～Ｃ２０アリーレン－Ｌ１ａ、及びＬ１ａ－Ｃ１～Ｃ１３ヘテロアリーレン－Ｌ１ａからなる群より選択され；
　Ｌ１の前記リンカーにおけるアルキレン及びアルケニレンは、各々独立に、１もしくはそれより多くの同一もしくは異なる非隣接の基Ｌ１ｃによって中断されていてもよく；
　Ｌ１の前記リンカーにおけるアリーレン及びヘテロアリーレンは、各々独立に、１もしくはそれより多くの同一もしくは異なる基ＲＬ１を有していてもよく；
　Ｌ１ａは、単結合であり；
　Ｌ１ｂは、単結合、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、ＣＨ２、Ｃ（ＣＨ３）２、ＣＨ（ＯＨ）またはＣ１～Ｃ５アルキレンであり；
　Ｌ１ｃは、各々独立して、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、ＯＣ（Ｏ）、Ｃ６～Ｃ２０アリーレン及びＣ３～Ｃ１６シクロアルキレンからなる群より選択され；
　ＲＬ１は、各々独立して、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１２アルキル、Ｃ１～Ｃ１２アルコキシ、及びＣ２～Ｃ１１アシロキシから選択され；
　Ｌ１ｂ、Ｌ１ｃにおけるＲ６は、Ｒ６と同義である。 In the above formula,
n=2;
R 1 is C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 2 -C 20 heterocycloalkyl, C 6 -C 20 aryl or C 1 to C 20 heteroaryl;
C 1 -C 20 alkyl, C 2 -C 20 alkenyl and C 2 -C 20 alkynyl in R 1 are one or more of the same or different O, S, N(R 6 ), C(O), C (O) may be interrupted by groups selected from the group consisting of O and OC(O) and may have one or more identical or different groups R 1a ;
C 3 -C 20 cycloalkyl and C 2 -C 20 heterocycloalkyl in R 1 may be interrupted by one or more C(O) groups and may contain one or more identical or different groups. It may have R 1b ;
C 6 -C 20 aryl and C 1 -C 20 heteroaryl in R 1 may have one or more identical or different groups R 1c ;
R 1a each independently represents F, Cl, Br, I, CN, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , C(O ) NR 13 R 14 , C 3 -C 20 cycloalkyl, optionally interrupted by one or more C(O) groups, and C 6 -C 10 aryl;
C 3 -C 20 cycloalkyl and C 6 -C 10 aryl in R 1a may have one or more identical or different groups R 1aa ;
R 1aa is each independently selected from the group consisting of C 1 -C 12 alkyl, C 2 -C 12 alkenyl, F, Cl, Br, I, NO 2 , SR 7 , OR 8 and NR 9 R 10 ;
C 1 -C 12 alkyl in R 1aa is one or more selected from the group consisting of O, S, N(R 6 ), C(O), C(O)O, and OC(O). Optionally interrupted by groups F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , and C(O) may have one or more same or different groups selected from the group consisting of NR 13 R 14 ;
R 1b is each independently from the group consisting of C 1 -C 12 alkyl, C 2 -C 12 alkenyl, F, Cl, Br, I, CN, NO 2 , SR 7 , OR 8 and NR 9 R 10 selected;
C 1 -C 12 alkyl in R 1b is F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , and C( O) may have one or more same or different groups selected from the group consisting of NR 13 R 14 ;
R 1c is each independently C 1 -C 12 alkyl, C 2 -C 12 alkenyl, F, Cl, Br, I, CN, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O ) R 11 , C(O)OR 12 , C(O)NR 13 R 14 , C 6 -C 10 aryl, C 1 -C 20 heteroaryl, C 3 -C 10 cycloalkyl, and C 2 -C 10 hetero selected from the group consisting of cycloalkyl;
C 1 -C 12 alkyl in R 1c is F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , and C( O) may have one or more identical or different groups selected from NR 13 R 14 ;
C 1 -C 12 alkyl, C 3 -C 10 cycloalkyl and C 2 -C 10 heterocycloalkyl in R 1c may be interrupted by one or more C(O) groups;
C 6 -C 10 aryl, C 1 -C 20 heteroaryl, C 3 -C 10 cycloalkyl and C 2 -C 10 heterocycloalkyl in R 1c have one or more identical or different groups R 1ca . and the R 1ca has the same meaning as the above R 1aa ;
R 2 is a hydrogen atom, C 1 to C 20 alkyl, C 2 to C 20 alkenyl, C 2 to C 20 alkynyl, C 3 to C 20 cycloalkyl, C 2 to C 20 heterocycloalkyl, C 6 to C 20 Aryl, C 1 -C 20 heteroaryl, SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , C(O)NR 13 R 14 , SO 2 R 15 , or CN;
C 1 -C 20 alkyl, C 2 -C 20 alkenyl and C 2 -C 20 alkynyl in R 2 are one or more of the same or different O, S, N(R 6 ), C(O), C (O) may be interrupted by groups selected from the group consisting of O, and OC(O), and may have one or more identical or different groups R 2a ;
C 3 -C 20 cycloalkyl and C 2 -C 20 heterocycloalkyl in R 2 may be interrupted by one or more C(O) groups and may contain one or more identical or different groups. It may have R 2b ;
C 6 -C 20 aryl and C 1 -C 20 heteroaryl in R 2 may have one or more identical or different groups R 2c ;
R 2a is synonymous with R 1a ;
R 2b is synonymous with R 1b ;
R 2c is synonymous with R 1c ;
Furthermore, R 2 may be combined with -SR 1 to form a ring structure containing an imino carbon atom;
The ring structure containing the imino carbon atom includes S-(C 1 to C 20 alkylene)-X, S-(C 2 to C 20 alkenylene)-X, S-(C 3 to C 20 cycloalkylene)-X , S-(heterocycloalkylene)-X, S-(o-phenylene)-X, S-(o-xylene)-X, S-(o-phenylene-C 1 -C 12 alkylene)-X, S- (C 1 -C 12 alkylene-o-phenylene)-X, S-(C(O)N(R 16 ))-X, or S-(C(S)N(R 17 ))-X, often;
X is bonded to an imino carbon atom with S, O, S, N(R 6 ), C(O), OC(O), C(O)O, SC(O), C(O) S, C(O)N(R 16 ), N(R 18 )C(O), N(R 19 )SO 2 or a single bond;
The alkylene and alkenylene in the ring structure containing the imino carbon atom are selected from the group consisting of one or more of the same or different O, S, N(R 6 ), C(O) and C(S). optionally interrupted by groups and optionally substituted by one or more groups R 2d ;
Cycloalkylene and heterocycloalkylene in the ring structures containing said imino carbon atoms may be interrupted by one or more C(O) groups and substituted by one or more identical or different groups R 2e may have been;
Phenylene and o-xylylene in the ring structure containing said imino carbon atoms may be substituted by one or more identical or different groups R 2f ;
R 2d is each independently F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , C(O)NR 13 R 14 selected from the group consisting of C 6 -C 10 aryl and C 1 -C 20 heteroaryl;
C 6 -C 10 aryl and C 1 -C 20 heteroaryl in R 2d may have one or more groups R 2da , each R 2da being independently phenoxy, and R 1aa selected from the group consisting of the indicated groups;
R 2e each independently represents F, Cl, Br, I, SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , CONR 13 R 14 , C 1 - selected from the group consisting of C 12 alkyl, C 1 -C 12 haloalkyl, C 6 -C 10 aryl, and C 1 -C 20 heteroaryl;
C 6 -C 10 aryl and C 1 -C 20 heteroaryl in R 2e may have one or more groups R 2ea, R 2ea is synonymous with R 1aa ;
R 2f is each independently F, Cl, Br, I, SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , CONR 13 R 14 , C 1 - selected from the group consisting of C 12 alkyl, C 1 -C 12 haloalkyl, C 6 -C 10 aryl, and C 1 -C 20 heteroaryl;
C 6 -C 10 aryl and C 1 -C 20 heteroaryl in R 2f may have one or more groups R 2fa, R 2fa is synonymous with R 1aa ;
R 3 and R 4 are each independently C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 1 -C 20 heteroaryl, C 7 -C 15 aralkyl, or Si( CH3 ) 3 ;
C 1 -C 20 alkyl and C 3 -C 20 cycloalkyl in R 3 and R 4 are O, S, N(R 6 ), C(O), C(O)O, OC(O), C( O) optionally interrupted by one or more groups selected from the group consisting of S, and SC(O), F, Cl, Br, I, NO2 , SR7 , OR8 , NR9 R may have one or more same or different groups selected from the group consisting of;
C 6 -C 20 aryl, C 12 -C 20 heteroaryl, and C 7 -C 15 aralkyl in R 3 and R 4 are C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 2 -C 12 alkenyl , F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , C(O)NR 13 R 14 , C 6 to C 10 aryl, and one or more identical or different groups selected from the group consisting of C 1 -C 20 heteroaryl;
R 5 is a hydrogen atom, C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 7 -C 14 aralkyl, C 6 -C 14 aryl, or acyl group;
The acyl group in R 5 is -C(O)-H, -C(O)-C 1 -C 18 alkyl, -C(O)-C 2 -C 18 alkenyl, -C(O)-C 6 - C 14 aryl, -C(O)-C 2 -C 18 alkenyl-C 6 -C 14 aryl, -C(O)-O-C 1 -C 18 alkyl, -C(O)-O-C 6 - C 14 aryl, -C(O)-NH-C 1 -C 18 alkyl, -C(O)-NH-C 6 -C 14 aryl and C(O)-N(C 1 -C 18 alkyl) from 2 selected from the group;
R 3 and R 5 together with the nitrogen atom to which they are attached may form a 5- to 12-membered ring which may contain further heteroatoms;
R 6 is each independently selected from the group consisting of a hydrogen atom, C 1 -C 20 alkyl, C 2 -C 20 alkanoyl, C 6 -C 10 aryl, and C 7 -C 11 aroyl;
C 1 -C 20 alkyl in R 6 is 1 or 1 selected from the group consisting of O, S, N (C 1 -C 12 alkyl), C(O), C(O)O, and OC(O) Optionally interrupted by more groups, from F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl, C 6 -C 10 aryl, OH, and SH may have one or more same or different groups selected from the group;
The C 2 -C 20 alkanoyl in R 6 may be interrupted by one or more groups selected from the group consisting of O, S, CO, C(O)O, and OC(O), one or more same or different groups selected from the group consisting of F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl, and C 6 -C 10 aryl; May have;
C 6 -C 10 aryl in R 6 is one or more selected from the group consisting of F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy. may have more identical or different groups;
C 7 -C 11 aroyl in R 6 is one or more selected from the group consisting of F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy. may have more identical or different groups;
R 7 and R 8 are each independently selected from the group consisting of hydrogen atom, C 1 -C 20 alkyl, C 2 -C 20 alkanoyl, C 6 -C 10 aryl, and C 7 -C 11 aroyl;
C 1 -C 20 alkyl in R 7 and R 8 is one selected from the group consisting of O, S, N (C 1 -C 12 alkyl), CO, C(O)O, and OC(O); Optionally interrupted by more groups, from F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl, C 6 -C 10 aryl, OH, and SH may have one or more same or different groups selected from the group;
The C 2 -C 20 alkanoyl in R 7 , R 8 is interrupted by one or more groups selected from the group consisting of O, S, C(O), C(O)O, and OC(O). one or more selected from the group consisting of F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl, and C 6 -C 10 aryl. may have the same or different groups;
C 6 -C 10 aryl in R 7 , R 8 is selected from the group consisting of F, Cl, Br, I, C 1 -C 6 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy. may have one or more identical or different groups;
C7 - C11 aroyl in R7 , R8 is selected from the group consisting of F, Cl, Br, I, C1 - C10 alkyl, C1 - C10 alkoxy, and C2 - C11 acyloxy may have one or more identical or different groups;
R 9 and R 10 are each independently selected from the group consisting of a hydrogen atom, C 1 -C 20 alkyl, C 2 -C 20 alkanoyl, C 7 -C 11 aroyl, C 6 -C 10 aryl;
C 1 -C 20 alkyl in R 9 and R 10 is selected from the group consisting of O, S, N (C 1 -C 12 alkyl), C(O), C(O)O, and OC(O). from the group consisting of F, Cl, Br, I, NO 2 , C 3 -C 10 cycloalkyl, heterocycloalkyl, phenyl, OH, SH and CN may have one or more selected identical or different groups;
The C 2 -C 20 alkanoyl in R 9 , R 10 may be interrupted by one or more groups selected from the group consisting of O and S, F, Cl, Br, I, OH and C may have one or more identical or different groups selected from the group consisting of 1 to C 6 alkoxy;
C 7 -C 11 aroyl in R 9 and R 10 is one or more selected from the group consisting of F, Cl, Br, I, C 1 -C 6 alkyl, -OH and C 1 -C 6 alkoxy. may have the same or different groups;
C 6 -C 10 aryl in R 9 and R 10 is one or more selected from the group consisting of F, Cl, Br, I, C 1 -C 6 alkyl, -OH and C 1 -C 6 alkoxy. may have the same or different groups;
R 9 and R 10 together with the nitrogen atom to which they are bonded may form a saturated 5-, 6-, or 7-membered nitrogen heterocycle, and the ring may be O, S, N (C 1 -C 12 alkyl), C(O), and C(O)O as ring members, and the ring has one or more C 1 may have ~C 4 alkyl;
each R 11 is independently selected from the group consisting of a hydrogen atom, C 1 -C 20 alkyl, and C 6 -C 20 aryl;
C 1 -C 20 alkyl may be interrupted by one or more groups selected from the group consisting of O, S and C(O), and may contain one or more identical or different R 11a May have;
R 11a is each independently selected from the group consisting of F, Cl, Br, I, C 3 -C 10 cycloalkyl, heterocycloalkyl, phenyl, OH, and SH;
C 6 -C 20 aryl in R 11 is one or more selected from the group consisting of F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy. may have more identical or different groups;
R 12 is synonymous with R 8 ;
R 13 and R 14 are synonymous with R 9 and R 10 ;
each R 15 is independently selected from the group consisting of a hydrogen atom, C 1 -C 20 alkyl, C 6 -C 10 aryl;
C 1 -C 20 alkyl in R 15 is 1 or 1 selected from the group consisting of O, S, N (C 1 -C 12 alkyl), C(O), C(O)O, and OC(O) Optionally interrupted by more groups, from F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl, C 6 -C 10 aryl, OH, and SH may have one or more same or different groups selected from the group;
C 6 -C 10 aryl in R 15 is one or more same or different groups selected from the group consisting of F, Cl, Br, I, C 1 -C 6 alkyl, and C 1 -C 6 alkoxy. may have;
R 16 , R 17 , R 18 and R 19 each independently consist of a hydrogen atom, C 1 -C 20 alkyl, C 2 -C 20 alkanoyl, C 6 -C 10 aryl, C 7 -C 11 aroyl selected from the group;
C 1 -C 20 alkyl in R 16 , R 17 , R 18 and R 19 is O, S, N (C 1 -C 12 alkyl), C(O), C(O)O, and OC(O) optionally interrupted by one or more groups selected from the group consisting of F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl, C 6 - may have one or more identical or different groups selected from the group consisting of C 10 aryl, OH, and SH;
The C 2 -C 20 alkanoyl in R 16 , R 17 , R 18 , R 19 is one or more selected from the group consisting of O, S, CO, C(O)O, and OC(O). Optionally interrupted by groups , one or It may have more of the same or different groups;
C 6 -C 10 aryl in R 16 , R 17 , R 18 , R 19 is selected from F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy may have one or more same or different groups selected from the group;
C 7 -C 11 aroyl in R 16 , R 17 , R 18 , R 19 is selected from F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy may have one or more identical or different groups selected from the group consisting of;
L 1 is a divalent linker, and the linker is L 1a -C 1 -C 30 alkylene-L 1a , L 2a -C 1 -C 30 alkenylene-L 2a , L 1a -C 3 -C 16 cycloalkylene -L 1a , L 1a -C 6 -C 20 arylene-L 1a , L 1a -C 6 -C 20 arylene-L 1b -C 6 -C 20 arylene- L 1a , and L 1a -C 1 -C 13 hetero selected from the group consisting of arylene-L 1a ;
The alkylene and alkenylene in the linker of L 1 may each independently be interrupted by one or more identical or different non-adjacent groups L 1c ;
The arylene and heteroarylene in the linker of L 1 may each independently have one or more identical or different groups R L 1 ;
L 1a is a single bond;
L 1b is a single bond, O, S, N(R 6 ), C(O), CH 2 , C(CH 3 ) 2 , CH(OH) or C 1 -C 5 alkylene;
L 1c each independently represents O, S, N(R 6 ), C(O), C(O)O, OC(O), C 6 -C 20 arylene, and C 3 -C 16 cycloalkylene. selected from the group;
R L1 is each independently selected from F, Cl, Br, I, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, and C 2 -C 11 acyloxy;
R 6 in L 1b and L 1c has the same meaning as R 6 .
　また、本発明の第３態様の化合物は、以下の式（Ｉ）で示される化合物である。 Further, the compound of the third aspect of the present invention is a compound represented by the following formula (I).
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　前記式中、
　Ｒ１は、Ｃ１～Ｃ２０アルキル、Ｃ３～Ｃ２０シクロアルキル、またはＣ６～Ｃ１０アリールであり；
　Ｒ１におけるＣ１～Ｃ２０アルキルは、１もしくはそれより多くの同一もしくは異なるＯ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ及びＯＣ（Ｏ）からなる群より選択される基によって中断されていてもよく、１もしくはそれより多くの同一もしくは異なる基Ｒ１ａ
を有していてもよく；
　Ｒ１におけるＣ３～Ｃ２０シクロアルキルは、１もしくはそれより多くのＣ（Ｏ）基によって中断されていてもよく、１もしくはそれより多くの同一もしくは異なる基Ｒ１ｂを有していてもよく；
　Ｒ１におけるＣ６～Ｃ１０アリールは、１もしくはそれより多くの同一もしくは異なる基Ｒ１ｃを有していてもよく；
　Ｒ１ａは、各々独立して、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＣＮ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、Ｃ（Ｏ）ＮＲ１３Ｒ１４、１もしくはそれより多くのＣ（Ｏ）基によって中断されていてもよいＣ３～Ｃ２０シクロアルキル及びＣ６～Ｃ１０アリールからなる群より選択され；
　Ｒ１ａにおけるＣ３～Ｃ２０シクロアルキル及びＣ６～Ｃ１０アリールは、１もしくはそれより多くの同一もしくは異なる基Ｒ１ａａを有していてもよく；
　Ｒ１ａａは、各々独立して、Ｃ１～Ｃ１２アルキル、Ｃ２～Ｃ１２アルケニル、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、ＳＲ７、ＯＲ８及びＮＲ９Ｒ１０からなる群より選択され；
　Ｒ１ａａにおけるＣ１～Ｃ１２アルキルは、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、及びＣ（Ｏ）ＮＲ１３Ｒ１４からなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ１ｂは、各々独立して、Ｃ１～Ｃ１２アルキル、Ｃ２～Ｃ１２アルケニル、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＣＮ、ＮＯ２、ＳＲ７、ＯＲ８及びＮＲ９Ｒ１０からなる群より選択され；
　Ｒ１ｂにおけるＣ１～Ｃ１２アルキルは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、及びＣ（Ｏ）ＮＲ１３Ｒ１４からなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ１ｃは、各々独立して、Ｃ１～Ｃ１２アルキル、Ｃ２～Ｃ１２アルケニル、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＣＮ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、Ｃ（Ｏ）ＮＲ１３Ｒ１４、Ｃ６～Ｃ１０アリール、Ｃ１～Ｃ２０ヘテロアリール、Ｃ３～Ｃ１０シクロアルキル、及びＣ２～Ｃ１０ヘテロシクロアルキルからなる群より選択され；
　Ｒ１ｃにおけるＣ１～Ｃ１２アルキルは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、及びＣ（Ｏ）ＮＲ１３Ｒ１４から選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ１ｃにおけるＣ１～Ｃ１２アルキル、Ｃ３～Ｃ１０シクロアルキル及びＣ２～Ｃ１０ヘテロシクロアルキルは、１もしくはそれより多くのＣ（Ｏ）基によって中断されていてもよく；
　Ｒ１ｃにおけるＣ６～Ｃ１０アリール、Ｃ１～Ｃ２０ヘテロアリール、Ｃ３～Ｃ１０シクロアルキル及びＣ２～Ｃ１０ヘテロシクロアルキルは、１もしくはそれより多くの同一もしくは異なる基Ｒ１ｃａを有していてもよく、該Ｒ１ｃａは、前記Ｒ１ａａと同義であり；
　Ｒ２は、水素原子、Ｃ１～Ｃ２０アルキル、Ｃ６～Ｃ２０アリール、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、Ｃ（Ｏ）ＮＲ１３Ｒ１４、ＳＯ２Ｒ１５、またはＣＮであり；
　Ｒ２におけるＣ１～Ｃ２０アルキルは、１もしくはそれより多くの同一もしくは異なるＯ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される基によって中断されていてもよく、１もしくはそれより多くの同一もしくは異なる基Ｒ２ａを有していてもよく；
　Ｒ２におけるＣ６～Ｃ２０アリールは、１もしくはそれより多くの同一もしくは異なる基Ｒ２ｃを有していてもよく；
　Ｒ２ａは、Ｒ１ａと同義であり；
　Ｒ２ｃは、Ｒ１ｃと同義であり；
　Ｒ３及びＲ４は、各々独立して、Ｃ１～Ｃ６アルキル、Ｃ５～Ｃ１２シクロアルキル、Ｃ６～Ｃ１０アリール、１もしくはそれより多くの同一もしくは異なるＣ１～Ｃ６アルキルによって置換されたＣ６～Ｃ１０アリール、又はＳｉ（ＣＨ３）３であり；　Ｒ５は、水素原子、Ｃ（Ｏ）－Ｃ１～Ｃ２０アルキル、－Ｃ（Ｏ）－Ｃ６～Ｃ１０アリール、－Ｃ（Ｏ）Ｏ－Ｃ１～Ｃ２０アルキル、－Ｃ（Ｏ）ＮＨ－Ｃ１～Ｃ２０アルキル、または－Ｃ（Ｏ）ＮＨ－Ｃ６～Ｃ１０アリールであり；
　Ｒ６は、各々独立して、水素原子、Ｃ１～Ｃ２０アルキル及びＣ６～Ｃ１０アリールからなる群より選択され；
　Ｒ６におけるＣ１～Ｃ２０アルキルは、Ｏ、Ｓ、Ｎ（Ｃ１～Ｃ１２アルキル）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ６～Ｃ１０アリール、ＯＨ、及びＳＨからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ６におけるＣ６～Ｃ１０アリールは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１０アルキル、Ｃ１～Ｃ１０アルコキシ、及びＣ２～Ｃ１１アシロキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ７及びＲ８は、各々独立して、水素原子、Ｃ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルカノイル、Ｃ６～Ｃ１０アリール、及びＣ７～Ｃ１１アロイルからなる群より選択され；
　Ｒ７、Ｒ８におけるＣ１～Ｃ２０アルキルは、Ｏ、Ｓ、Ｎ（Ｃ１～Ｃ１２アルキル）、ＣＯ、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ６～Ｃ１０アリール、ＯＨ、及びＳＨからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ７、Ｒ８におけるＣ２～Ｃ２０アルカノイルは、Ｏ、Ｓ、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、及びＣ６～Ｃ１０アリールからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ７、Ｒ８におけるＣ６～Ｃ１０アリールは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ６アルキル、及びＣ１～Ｃ６アルコキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ７、Ｒ８におけるＣ７～Ｃ１１アロイルは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１０アルキル、Ｃ１～Ｃ１０アルコキシ、及びＣ２～Ｃ１１アシロキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ９及びＲ１０は、各々独立して、水素原子、Ｃ１～Ｃ２０アルキル、Ｃ６～Ｃ１０アリールからなる群より選択され；
　Ｒ９、Ｒ１０におけるＣ１～Ｃ２０アルキルは、Ｏ、Ｓ、Ｎ（Ｃ１～Ｃ１２アルキル）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ６～Ｃ１０アリール、ＯＨ、及びＳＨからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ９、Ｒ１０におけるＣ６～Ｃ１０アリールは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１０アルキル、Ｃ１～Ｃ１０アルコキシ、及びＣ２～Ｃ１１アシロキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ９及びＲ１０は、それらが結合される窒素原子と一緒になって、飽和の５員、６員または７員の窒素複素環を形成していてもよく、前記環はＯ、Ｓ、Ｎ（Ｃ１～Ｃ１２アルキル）、Ｃ（Ｏ）、及びＣ（Ｏ）Ｏからなる群より選択される基を環員として有していてもよく、前記環は１もしくはそれより多くのＣ１～Ｃ４アルキルを有してよく；　各々独立して、水素原子、Ｃ１～Ｃ２０アルキル及びＣ６～Ｃ２０アリールからなる群より選択され；
　Ｃ１～Ｃ２０アルキルは、Ｏ、Ｓ及びＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、１もしくはそれより多くの同一もしくは異なるＲ１１ａを有していてもよく；
　Ｒ１１ａは、各々独立して、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、ヘテロシクロアルキル、フェニル、ＯＨ、及びＳＨからなる群より選択され；
　Ｒ１２は、Ｒ８と同義であり；
　Ｒ１３及びＲ１４は、Ｒ９、Ｒ１０と同義であり；
　Ｒ１５は、各々独立して、水素原子、Ｃ１～Ｃ２０アルキル、Ｃ６～Ｃ１０アリールからなる群より選択され；
　Ｒ１５におけるＣ１～Ｃ２０アルキルは、Ｏ、Ｓ、Ｎ（Ｃ１～Ｃ１２アルキル）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ６～Ｃ１０アリール、ＯＨ、及びＳＨからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
　Ｒ１５におけるＣ６～Ｃ１０アリールは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ６アルキル、及びＣ１～Ｃ６アルコキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよい。 In the above formula,
R 1 is C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, or C 6 -C 10 aryl;
C 1 -C 20 alkyl in R 1 is selected from the group consisting of one or more same or different O, S, N(R 6 ), C(O), C(O)O and OC(O) one or more identical or different groups R 1a
may have;
C 3 -C 20 cycloalkyl in R 1 may be interrupted by one or more C(O) groups and may carry one or more identical or different groups R 1b ;
The C 6 -C 10 aryl in R 1 may carry one or more identical or different groups R 1c ;
R 1a each independently represents F, Cl, Br, I, CN, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , C(O ) NR 13 R 14 selected from the group consisting of C 3 -C 20 cycloalkyl and C 6 -C 10 aryl, optionally interrupted by one or more C(O) groups;
C 3 -C 20 cycloalkyl and C 6 -C 10 aryl in R 1a may have one or more identical or different groups R 1aa ;
R 1aa is each independently selected from the group consisting of C 1 -C 12 alkyl, C 2 -C 12 alkenyl, F, Cl, Br, I, NO 2 , SR 7 , OR 8 and NR 9 R 10 ;
C 1 -C 12 alkyl in R 1aa is one or more selected from the group consisting of O, S, N(R 6 ), C(O), C(O)O, and OC(O). Optionally interrupted by groups F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , and C(O) may have one or more same or different groups selected from the group consisting of NR 13 R 14 ;
R 1b is each independently from the group consisting of C 1 -C 12 alkyl, C 2 -C 12 alkenyl, F, Cl, Br, I, CN, NO 2 , SR 7 , OR 8 and NR 9 R 10 selected;
C 1 -C 12 alkyl in R 1b is F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , and C( O) may have one or more same or different groups selected from the group consisting of NR 13 R 14 ;
R 1c is each independently C 1 -C 12 alkyl, C 2 -C 12 alkenyl, F, Cl, Br, I, CN, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O ) R 11 , C(O)OR 12 , C(O)NR 13 R 14 , C 6 -C 10 aryl, C 1 -C 20 heteroaryl, C 3 -C 10 cycloalkyl, and C 2 -C 10 hetero selected from the group consisting of cycloalkyl;
C 1 -C 12 alkyl in R 1c is F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , and C( O) may have one or more identical or different groups selected from NR 13 R 14 ;
C 1 -C 12 alkyl, C 3 -C 10 cycloalkyl and C 2 -C 10 heterocycloalkyl in R 1c may be interrupted by one or more C(O) groups;
C 6 -C 10 aryl, C 1 -C 20 heteroaryl, C 3 -C 10 cycloalkyl and C 2 -C 10 heterocycloalkyl in R 1c have one or more identical or different groups R 1ca . and the R 1ca has the same meaning as the above R 1aa ;
R 2 is a hydrogen atom, C 1 to C 20 alkyl, C 6 to C 20 aryl, SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , C(O) NR 13 R 14 , SO 2 R 15 , or CN;
C 1 -C 20 alkyl in R 2 is from the group consisting of one or more of the same or different O, S, N(R 6 ), C(O), C(O)O, and OC(O). may be interrupted by selected groups and may have one or more identical or different groups R 2a ;
C 6 -C 20 aryl in R 2 may have one or more identical or different groups R 2c ;
R 2a is synonymous with R 1a ;
R 2c is synonymous with R 1c ;
R 3 and R 4 are each independently represented by C 1 -C 6 alkyl, C 5 -C 12 cycloalkyl, C 6 -C 10 aryl, one or more of the same or different C 1 -C 6 alkyl; is a substituted C6 - C10 aryl, or Si( CH3 ) 3 ; R5 is a hydrogen atom, C(O) -C1 - C20 alkyl, -C(O) -C6 - C10 aryl, -C(O)O-C 1 -C 20 alkyl, -C(O)NH-C 1 -C 20 alkyl, or -C(O)NH-C 6 -C 10 aryl;
each R 6 is independently selected from the group consisting of a hydrogen atom, C 1 -C 20 alkyl, and C 6 -C 10 aryl;
C 1 -C 20 alkyl in R 6 is 1 or 1 selected from the group consisting of O, S, N (C 1 -C 12 alkyl), C(O), C(O)O, and OC(O) one or more identical or different groups selected from the group consisting of F, Cl, Br, I, C6 - C10 aryl, OH, and SH, which may be interrupted by more groups. May have;
C 6 -C 10 aryl in R 6 is one or more selected from the group consisting of F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy. may have more identical or different groups;
R 7 and R 8 are each independently selected from the group consisting of hydrogen atom, C 1 -C 20 alkyl, C 2 -C 20 alkanoyl, C 6 -C 10 aryl, and C 7 -C 11 aroyl;
C 1 -C 20 alkyl in R 7 and R 8 is one selected from the group consisting of O, S, N (C 1 -C 12 alkyl), CO, C(O)O, and OC(O); one or more identical or different groups selected from the group consisting of F, Cl, Br, I, C6 - C10 aryl, OH, and SH, which may be interrupted by more groups. May have;
The C 2 -C 20 alkanoyl in R 7 , R 8 is interrupted by one or more groups selected from the group consisting of O, S, C(O), C(O)O, and OC(O). may have one or more same or different groups selected from the group consisting of F, Cl, Br, I, and C 6 -C 10 aryl;
C 6 -C 10 aryl in R 7 and R 8 is one or more identical groups selected from the group consisting of F, Cl, Br, I, C 1 -C 6 alkyl, and C 1 -C 6 alkoxy. or may have different groups;
C7 - C11 aroyl in R7 , R8 is selected from the group consisting of F, Cl, Br, I, C1 - C10 alkyl, C1 - C10 alkoxy, and C2 - C11 acyloxy may have one or more identical or different groups;
R 9 and R 10 are each independently selected from the group consisting of hydrogen atom, C 1 -C 20 alkyl, C 6 -C 10 aryl;
C 1 -C 20 alkyl in R 9 and R 10 is selected from the group consisting of O, S, N (C 1 -C 12 alkyl), C(O), C(O)O, and OC(O). one or more identical or May have different groups;
C 6 -C 10 aryl in R 9 , R 10 is selected from the group consisting of F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy. may have one or more identical or different groups;
R 9 and R 10 together with the nitrogen atom to which they are bonded may form a saturated 5-, 6-, or 7-membered nitrogen heterocycle, and the ring may be O, S, N (C 1 -C 12 alkyl), C(O), and C(O)O as ring members, and the ring has one or more C 1 ~ C4 alkyl; each independently selected from the group consisting of hydrogen atoms, C1 - C20 alkyl and C6 - C20 aryl;
C 1 -C 20 alkyl may be interrupted by one or more groups selected from the group consisting of O, S and C(O), and may contain one or more identical or different R 11a May have;
R 11a is each independently selected from the group consisting of F, Cl, Br, I, C 3 -C 10 cycloalkyl, heterocycloalkyl, phenyl, OH, and SH;
R 12 is synonymous with R 8 ;
R 13 and R 14 are synonymous with R 9 and R 10 ;
each R 15 is independently selected from the group consisting of a hydrogen atom, C 1 -C 20 alkyl, C 6 -C 10 aryl;
C 1 -C 20 alkyl in R 15 is one selected from the group consisting of O, S, N (C 1 -C 12 alkyl), C(O), C(O)O, and OC(O); one or more identical or different groups selected from the group consisting of F, Cl, Br, I, C6 - C10 aryl, OH, and SH, which may be interrupted by more groups. May have;
C 6 -C 10 aryl in R 15 is one or more same or different groups selected from the group consisting of F, Cl, Br, I, C 1 -C 6 alkyl, and C 1 -C 6 alkoxy. It may have.
　また、本発明の第４態様の化合物は、以下の式（Ｉ）で示される化合物である。 Further, the compound of the fourth aspect of the present invention is a compound represented by the following formula (I).
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　前記式中、
　Ｒ１は、Ｃ１～Ｃ２０アルキル、Ｃ６～Ｃ１０アリール、又は１もしくはそれより多くの同一もしくは異なるＣ１～Ｃ１２アルキルで置換されたＣ６～Ｃ１０アリールであり；
　Ｒ２はＣ１～Ｃ２０アルキル、Ｃ６～Ｃ１０アリール、又は１もしくはそれより多くの同一もしくは異なるＣ１～Ｃ１２アルキルで置換されたＣ６～Ｃ１０アリールであり；
　Ｒ３及びＲ４は、各々独立して、Ｃ１～Ｃ６アルキル、Ｃ５～Ｃ１２シクロアルキル、Ｃ６～Ｃ１０アリール、又は１もしくはそれより多くの同一もしくは異なるＣ１～Ｃ６アルキルによって置換されたＣ６～Ｃ１０アリールであり；
　Ｒ５は、水素である。 In the above formula,
R 1 is C 1 -C 20 alkyl, C 6 -C 10 aryl, or C 6 -C 10 aryl substituted with one or more of the same or different C 1 -C 12 alkyl;
R 2 is C 1 -C 20 alkyl, C 6 -C 10 aryl, or C 6 -C 10 aryl substituted with one or more of the same or different C 1 -C 12 alkyl;
R 3 and R 4 are each independently C 1 -C 6 alkyl, C 5 -C 12 cycloalkyl, C 6 -C 10 aryl, or one or more of the same or different C 1 -C 6 alkyl C 6 -C 10 aryl substituted by;
R 5 is hydrogen.
　本発明における用語”アルキル”は、通常は、１～２０個、好ましくは１～１２個、より好ましくは１～１０個の炭素原子を有する、飽和の直鎖状または分枝鎖状の炭化水素基を指す。アルキル基の例は、メチル、エチル、ｎ－プロピル、イソプロピル、ｎ－ブチル、イソブチル、ｓ－ブチル、ｔ－ブチル、ｎ－ペンチル、ネオ－ペンチル、ｎ－ヘキシル、ｎ－ヘプチル、ｎ－オクチル、２－エチルへキシル、ｎ－ノニル、ｎ－デシル、ｎ－ウンデシル、ｎ－ドデシル、ｎ－トリデシル、ｎ－テトラデシル、ｎ－ヘキサデシル、ｎ－オクタデシル、およびｎ－エイコシルである。
　アルキルは、１もしくはそれより多くの同一もしくは異なる、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）から選択される基によって中断されていてもよい。
複数のＯ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）が存在する場合に、それらは、通常は、少なくとも１つのメチレン基によって互いに隔離されている。Ｒ６は、前記定義のとおりである。１もしくはそれより多くのＯ原子によって中断されたアルキルの例は、－ＣＨ２－Ｏ－ＣＨ３、－ＣＨ２ＣＨ２－Ｏ－ＣＨ２ＣＨ３、－［ＣＨ２ＣＨ２Ｏ］ｙ－ＣＨ３（ｙは、１～９である）、－（ＣＨ２ＣＨ２Ｏ）ｙＣＨ２ＣＨ３（ｙは、１～９である）、－ＣＨ２－ＣＨ（ＣＨ３）－Ｏ－ＣＨ２－ＣＨ２ＣＨ３、－ＣＨ２－ＣＨ２ＣＨ（ＣＨ３）－Ｏ－ＣＨ２－ＣＨ２ＣＨ３、－ＣＨ２－ＣＨ２ＣＨ（ＣＨ３）－Ｏ－ＣＨ２ＣＨ３、－ＣＨ２－ＣＨ２ＣＨ（ＣＨ３）－Ｏ－ＣＨ３および－ＣＨ２ＣＨ（ＣＨ３）－Ｏ－ＣＨ２ＣＨ３である。 The term "alkyl" in the present invention usually refers to a saturated straight or branched hydrocarbon having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 10 carbon atoms. Refers to the base. Examples of alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, neo-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, and n-eicosyl.
Alkyl may be interrupted by one or more identical or different groups selected from O, S, N(R 6 ), C(O), C(O)O, and OC(O). good.
When multiple O, S, N(R 6 ), C(O), C(O)O, and OC(O) are present, they are usually separated from each other by at least one methylene group. There is. R 6 is as defined above. Examples of alkyl interrupted by one or more O atoms are -CH 2 -O-CH 3 , -CH 2 CH 2 -O-CH 2 CH 3 , -[CH 2 CH 2 O] y -CH 3 (y is 1 to 9), -(CH 2 CH 2 O) y CH 2 CH 3 (y is 1 to 9), -CH 2 -CH(CH 3 )-O-CH 2 -CH 2 CH 3 , -CH 2 -CH 2 CH (CH 3 ) -O-CH 2 -CH 2 CH 3 , -CH 2 -CH 2 CH (CH 3 ) -O-CH 2 CH 3 , -CH 2 -CH2CH ( CH3 ) -O - CH3 and -CH2CH ( CH3 )-O- CH2CH3 .
　本発明における用語”アルケニル”は、２～２０個、好ましくは２～１２個の、より好ましくは２～１０個の炭素原子を有し、１もしくはそれより多くの、二重結合を有する一不飽和または多不飽和の直鎖状もしくは分枝鎖状の炭化水素基である。１つの二重結合を有するアルケニルとしては、例えばエテニル、１－プロペニル、２－プロペニル、１－メチルエテニル、１－ブテニル、２－ブテニル、３－ブテニル、１－メチル－１－プロペニル、２－メチル－１－プロペニル、１－メチル－２－プロペニル、２－メチル－２－プロペニル、４個以上の炭素原子を有し、かつ任意の位置に２つの二重結合を有するアルカジエニル、例えば１，３－ブタジエニル、１，３－ペンタジエニル、ヘキサ－１，４－ジエン－１－イル、ヘキサ－１，４－ジエン－３－イル、ヘキサ－１，４－ジエン－６－イル、ヘプタ－１，４－ジエン－７－イル、ヘプタ－１，５－ジエン－１－イルなどを指す。 The term "alkenyl" in the present invention refers to a monomer having 2 to 20, preferably 2 to 12, more preferably 2 to 10 carbon atoms and having one or more double bonds. It is a saturated or polyunsaturated linear or branched hydrocarbon group. Examples of alkenyl having one double bond include ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl- 1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, alkadienyl having 4 or more carbon atoms and having two double bonds in any position, such as 1,3-butadienyl , 1,3-pentadienyl, hexa-1,4-dien-1-yl, hexa-1,4-dien-3-yl, hexa-1,4-dien-6-yl, hepta-1,4-diene -7-yl, hepta-1,5-dien-1-yl, etc.
　本発明における用語”アルキニル”は、通常２～２０個の、好ましくは２～１２個の、より好ましくは２～１０個の炭素原子と、１もしくはそれより多くの、三重結合を有する不飽和の直鎖状もしくは分枝鎖状の炭化水素基である。例えばエテニル、プロパルギル（２－プロピン－１－イル）、１－プロピン－１－イル、１－メチルプロピ－２－イン－１－イル、２－ブチン－１－イル、３－ブチン－１－イル、１－ペンチン－１－イル、３－ペンチン－１－イル、４－ペンチン－１－イル、１－メチルブチ－２－イン－１－イル、１－エチルプロピ－２－イン－１－イルなどを指す。 The term "alkynyl" in the present invention refers to an unsaturated group having usually 2 to 20, preferably 2 to 12, more preferably 2 to 10 carbon atoms and one or more triple bonds. It is a straight or branched hydrocarbon group. For example, ethenyl, propargyl (2-propyn-1-yl), 1-propyn-1-yl, 1-methylprop-2-yn-1-yl, 2-butyn-1-yl, 3-butyn-1-yl, Refers to 1-pentyn-1-yl, 3-pentyn-1-yl, 4-pentyn-1-yl, 1-methylbuty-2-yn-1-yl, 1-ethylprop-2-yn-1-yl, etc. .
　本発明における用語”シクロアルキル”は、通常３～２０個の、好ましくは３～１６個の、より好ましくは３～１２個の炭素原子を有する、単環式または多環式の脂肪族基を指す。
　単環式の脂肪族基としては、例えば、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル、シクロヘプチル、シクロオクチルが挙げられ、特にシクロペンチル、シクロヘキシルが好ましい。
　多環式の環としては、例えば、ペルヒドロアントラシル、ペルヒドロナフチル、ペルヒドロフルオレニル、ペルヒドロクリセニル、ペルヒドロピセニル、アダマンチル、ビシクロ［１．１．１］ペンチル、ビシクロ［２．２．１］ヘプチル、ビシクロ［４．２．２］デシル、ビシクロ［２．２．２］オクチル、ビシクロ［３．３．０］オクチル、ビシクロ［３．３．２］デシル、ビシクロ［４．４．０］デシル、ビシクロ［４．３．２］ウンデシル、ビシクロ［４．３．３］ドデシル、ビシクロ［３．３．３］ウンデシル、ビシクロ［４．３．１］デシル、ビシクロ［４．２．１］ノニル、ビシクロ［３．３．１］ノニル、ビシクロ［３．２．１］オクチルである。
　シクロアルキルは、１もしくはそれより多くのＣ（Ｏ）基によって、中断されていてもよい。１個のＣ（Ｏ）によって中断されたシクロアルキルの例は、３－オキソビシクロ［２．２．１］ヘプチルである。 The term "cycloalkyl" in the present invention refers to a monocyclic or polycyclic aliphatic group having usually 3 to 20 carbon atoms, preferably 3 to 16 carbon atoms, and more preferably 3 to 12 carbon atoms. Point.
Examples of the monocyclic aliphatic group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl, with cyclopentyl and cyclohexyl being particularly preferred.
Examples of the polycyclic ring include perhydroanthracil, perhydronaphthyl, perhydrofluorenyl, perhydrochrysenyl, perhydropicenyl, adamantyl, bicyclo[1.1.1]pentyl, bicyclo[ 2.2.1]heptyl, bicyclo[4.2.2]decyl, bicyclo[2.2.2]octyl, bicyclo[3.3.0]octyl, bicyclo[3.3.2]decyl, bicyclo[ 4.4.0] decyl, bicyclo [4.3.2] undecyl, bicyclo [4.3.3] dodecyl, bicyclo [3.3.3] undecyl, bicyclo [4.3.1] decyl, bicyclo [ 4.2.1]nonyl, bicyclo[3.3.1]nonyl, and bicyclo[3.2.1]octyl.
Cycloalkyl may be interrupted by one or more C(O) groups. An example of cycloalkyl interrupted by one C(O) is 3-oxobicyclo[2.2.1]heptyl.
　本発明における用語”ヘテロシクロアルキル”は、一般に、３～８員の、特に５員、６員、７員または８員の単環式の複素環式非芳香族基ならびに二環式の複素環式非芳香族基を指す。前記の単環式および二環式の非芳香族基は、飽和または不飽和であってよい。また、前記の単環式および二環式の複素環式非芳香族基は、通常は、１、２、３または４個のＮ、ＯおよびＳから選択されるヘテロ原子を、特に１または２個のヘテロ原子を、環員として含み、その際、環員としてのＳ原子は、Ｓ、ＳＯまたはＳＯ２として存在してよい。
ヘテロシクロアルキルは、１もしくはそれより多くのＣ（Ｏ）基によって、通常は１もしくは２個の基によって中断されていてもよい。
　飽和または不飽和の３～８員の非芳香族複素環式基としては、例えば、オキシラニル、オキセタニル、チエタニル、チエタニル－Ｓ－オキシド（Ｓ－オキソチエタニル）、チエタニル－Ｓ－ジオキシド（Ｓ－ジオキソチエタニル）、ピロリジニル、ピラゾリニル、イミダゾリニル、ピロリニル、ピラゾリニル、イミダゾリニル、テトラヒドロフラニル、ジヒドロフラニル、１，３－ジオキソラニル、ジオキソレニル、チオラニル、Ｓ－オキソチオラニル、Ｓ－ジオキソチオラニル、ジヒドロチエニル、Ｓ－オキソジヒドロチエニル、Ｓ－ジオキソジヒドロチエニル、オキサゾリジニル、イソキサゾリジニル、オキサゾリニル、イソキサゾリニル、チアゾリニル、イソチアゾリニル、チアゾリジニル、イソチアゾリジニル、オキサチオラニル、ピペリジニル、ピペラジニル、ピラニル、ジヒドロピラニル、テトラヒドロピラニル、１，３－および１，４－ジオキサニル、チオピラニル、Ｓ－オキソチオピラニル、Ｓ－ジオキソチオピラニル、ジヒドロチオピラニル、Ｓ－オキソジヒドロチオピラニル、Ｓ－ジオキソジヒドロチオピラニル、テトラヒドロチオピラニル、Ｓ－オキソテトラヒドロチオピラニル、Ｓ－ジオキソテトラヒドロチオピラニル、モルホリニル、チオモルホリニル、Ｓ－オキソチオモルホリニル、Ｓ－ジオキソチオモルホリニル、チアジニルが挙げられる。
　環員として１もしくは２個のカルボニル基をも含む複素環式の環としては、例えば、ピロリジン－２－オンイル、ピロリジン－２，５－ジオンイル、イミダゾリジン－２－オンイル、オキサゾリジン－２－オンイル、チアゾリジン－２－オンイルが挙げられる。 The term "heterocycloalkyl" in the present invention refers generally to 3- to 8-membered, especially 5-, 6-, 7- or 8-membered monocyclic heterocyclic non-aromatic groups as well as bicyclic heterocycles. The formula refers to a non-aromatic group. The monocyclic and bicyclic non-aromatic groups mentioned above may be saturated or unsaturated. Said monocyclic and bicyclic heterocyclic non-aromatic groups usually also contain 1, 2, 3 or 4 heteroatoms selected from N, O and S, especially 1 or 2 heteroatoms as ring members, the S atom as ring member can be present as S, SO or SO2.
Heterocycloalkyl may be interrupted by one or more C(O) groups, usually one or two groups.
Examples of the saturated or unsaturated 3- to 8-membered non-aromatic heterocyclic group include oxiranyl, oxetanyl, thietanyl, thietanyl-S-oxide (S-oxothietanyl), thietanyl-S-dioxide (S-dioxothietanyl), and thietanyl-S-oxide (S-oxothietanyl). pyrrolidinyl, pyrazolinyl, imidazolinyl, pyrrolinyl, pyrazolinyl, imidazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1,3-dioxolanyl, dioxolenyl, thiolanyl, S-oxothiolanyl, S-dioxothiolanyl, dihydrothienyl, S-oxodihydro thienyl, S-dioxodihydrothienyl, oxazolidinyl, isoxazolidinyl, oxazolinyl, isoxazolinyl, thiazolinyl, isothiazolinyl, thiazolidinyl, isothiazolidinyl, oxathiolanyl, piperidinyl, piperazinyl, pyranyl, dihydropyranyl, tetrahydropyranyl, 1, 3- and 1,4-dioxanyl, thiopyranyl, S-oxothiopyranyl, S-dioxothiopyranyl, dihydrothiopyranyl, S-oxodihydrothiopyranyl, S-dioxodihydrothiopyranyl, tetrahydrothio Examples include pyranyl, S-oxotetrahydrothiopyranyl, S-dioxotetrahydrothiopyranyl, morpholinyl, thiomorpholinyl, S-oxothiomorpholinyl, S-dioxothiomorpholinyl, and thiazinyl.
Examples of the heterocyclic ring containing one or two carbonyl groups as ring members include pyrrolidin-2-oneyl, pyrrolidin-2,5-dioneyl, imidazolidin-2-oneyl, oxazolidin-2-oneyl, Thiazolidin-2-oneyl is mentioned.
　本発明における用語”アリール”は、環炭素原子を有する一価の単環式芳香族基ならびに多環式芳香族基を指す。単環式芳香族基としては、例えばフェニルが挙げられる。多環式芳香族基としては、例えば二環式、三環式もしくは四環式の芳香族基、例えばナフチル、フェナントレニル、アントラセニルまたはピレニルが挙げられる。アリールの好ましい例は、フェニルおよびナフチルである。置換されたフェニルは、１、２、３、４または５個の置換基によって置換されている。ナフチルは、通常は、１、２、３、４、５、６、または７個の置換基によって、好ましくは１、２、３または４個の置換基によって置換されている。置換されたフェニルは、例えば、ペンタフルオロフェニル、２－メチルフェニル、３－メチルフェニル、４－メチルフェニル、２－エチルフェニル、３－エチルフェニル、４－エチルフェニル、２－メトキシフェニル、３－メトキシフェニル、４－メトキシフェニル、２－エトキシフェニル、３－エトキシフェニル、４－エトキシフェニル、３－ニトロフェニル、４－ニトロフェニル、２－クロロフェニル、３－クロロフェニル、４－クロロフェニル、３－ビニルフェニル、４－ビニルフェニル、４－トリフルオロメチルフェニル、３，５－ジエトキシカルボニルフェニルである。 The term "aryl" in the present invention refers to monovalent monocyclic aromatic groups and polycyclic aromatic groups having a ring carbon atom. Examples of monocyclic aromatic groups include phenyl. Polycyclic aromatic groups include, for example, bicyclic, tricyclic or tetracyclic aromatic groups such as naphthyl, phenanthrenyl, anthracenyl or pyrenyl. Preferred examples of aryl are phenyl and naphthyl. Substituted phenyl is substituted with 1, 2, 3, 4 or 5 substituents. Naphthyl is usually substituted with 1, 2, 3, 4, 5, 6, or 7 substituents, preferably with 1, 2, 3, or 4 substituents. Substituted phenyl is, for example, pentafluorophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2-methoxyphenyl, 3-methoxy Phenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl, 4-ethoxyphenyl, 3-nitrophenyl, 4-nitrophenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 3-vinylphenyl, 4 -vinylphenyl, 4-trifluoromethylphenyl, and 3,5-diethoxycarbonylphenyl.
　本発明における用語”ヘテロアリール”は、一般に、不飽和の単環式複素環基ならびに多環式複素環基であって芳香族である基を指す。ヘテロアリールは、通常は、環員としての１もしくは複数の炭素原子の他に、１、２、３または４個の、Ｎ、ＯおよびＳから選択されるヘテロ原子を環員として含む。単環式複素芳香族基としては、例えば、２－フリル、３－フリル、２－チエニル、３－チエニル、１－ピロリル、２－ピロリル、３－ピロリル、１－ピラゾリル、３－ピラゾリル、４－ピラゾリル、５－ピラゾリル、２－オキサゾリル、４－オキサゾリル、５－オキサゾリル、２－チアゾリル、４－チアゾリル、５－チアゾリル、３－イソキサゾリル、４－イソキサゾリルもしくは５－イソキサゾリル、３－イソチアゾリル、４－イソチアゾリルもしくは５－イソチアゾリル、１－イミダゾリル、２－イミダゾリル、４－イミダゾリル、２－もしくは５－［１，３，４］オキサジアゾリル、４－もしくは５－（１，２，３－オキサジアゾール）イル、３－もしくは５－（１，２，４－オキサジアゾール）イル、２－もしくは５－（１，３，４－チアジアゾール）イル、２－もしくは５－（１，３，４－チアジアゾール）イル、４－もしくは５－（１，２，３－チアジアゾール）イル、３－もしくは５－（１，２，４－チアジアゾール）イル、１Ｈ－、２Ｈ－もしくは３Ｈ－１，２，３－トリアゾール－４－イル、１，３，４－トリアゾール－２－イル、２Ｈ－トリアゾール－３－イル、１Ｈ－、２－もしくは４Ｈ－１，２，４－トリアゾリル、１Ｈ－もしくは２Ｈ－テトラゾリル、２－ピリジニル、３－ピリジニル、４－ピリジニル、３－ピリダジニル、４－ピリダジニル、２－ピリミジニル、４－ピリミジニル、５－ピリミジニルおよび２－ピラジニルが挙げられる。多環式複素環基としては、例えば、ベンゾフラニル、ベンゾチエニル、インドリル、インダゾリル、ベンゾイミダゾリル、ベンゾオキサチアゾリル、ベンゾオキサジアゾリル、ベンゾチアジアゾリル、ベンゾオキサジニル、キノリニル、イソキノリニル、プリニル、１，８－ナフチリジル、プテリジル、ピリド［３，２－ｄ］ピリミジル、ピリドイミダゾリル、カルバゾイルまたはアクリジニルが挙げられる。 The term "heteroaryl" in the present invention generally refers to unsaturated monocyclic heterocyclic groups and polycyclic heterocyclic groups that are aromatic. Heteroaryl usually contains 1, 2, 3 or 4 heteroatoms selected from N, O and S as ring members in addition to one or more carbon atoms as ring members. Examples of the monocyclic heteroaromatic group include 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 1-pyrazolyl, 3-pyrazolyl, 4- Pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isoxazolyl, 4-isoxazolyl or 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl or 5-isothiazolyl, 1-imidazolyl, 2-imidazolyl, 4-imidazolyl, 2- or 5-[1,3,4]oxadiazolyl, 4- or 5-(1,2,3-oxadiazol)yl, 3- or 5-(1,2,4-oxadiazol)yl, 2- or 5-(1,3,4-thiadiazol)yl, 2- or 5-(1,3,4-thiadiazol)yl, 4- or 5-(1,2,3-thiadiazol)yl, 3- or 5-(1,2,4-thiadiazol)yl, 1H-, 2H- or 3H-1,2,3-triazol-4-yl, 1,3,4-triazol-2-yl, 2H-triazol-3-yl, 1H-, 2- or 4H-1,2,4-triazolyl, 1H- or 2H-tetrazolyl, 2-pyridinyl, 3-pyridinyl , 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl. Examples of the polycyclic heterocyclic group include benzofuranyl, benzothienyl, indolyl, indazolyl, benzimidazolyl, benzoxathiazolyl, benzoxadiazolyl, benzothiadiazolyl, benzoxazinyl, quinolinyl, isoquinolinyl, purinyl, 1 , 8-naphthyridyl, pteridyl, pyrido[3,2-d]pyrimidyl, pyridimidazolyl, carbazoyl or acridinyl.
　本発明における用語”アルカノイル”はアルキル－Ｃ（Ｏ）であり、通常３～２０個の炭素原子を有する飽和の前記定義の直鎖状もしくは分枝鎖状のアルキル基であって、カルボニル基の炭素原子を通じてそのアルキル基中の任意の位置で結合される基、例えばアセチル、プロパノイル、２－メチル－プロパノイル、ブタノイル、ペンタノイル、ヘキサノイルを指す。 The term "alkanoyl" in the present invention is alkyl-C(O), which is a saturated straight-chain or branched alkyl group as defined above, usually having 3 to 20 carbon atoms, and which is a carbonyl group. Refers to groups bonded through a carbon atom at any position in the alkyl group, such as acetyl, propanoyl, 2-methyl-propanoyl, butanoyl, pentanoyl, hexanoyl.
　本発明における用語”シクロアルカノイル”はシクロアルキル－Ｃ（Ｏ）であり、単環式のまたは多環式、例えば二環式または三環式のシクロアルキルであって、カルボニル基の炭素原子を通じてそのシクロアルキル基中の任意の位置で結合される基、例えばシクロブチルカルボニル、シクロペンチルカルボニル、シクロヘキシルカルボニルを指す。 The term "cycloalkanoyl" in the present invention is cycloalkyl-C(O), a monocyclic or polycyclic, e.g. bicyclic or tricyclic, cycloalkyl, which It refers to a group bonded at any position in a cycloalkyl group, such as cyclobutylcarbonyl, cyclopentylcarbonyl, and cyclohexylcarbonyl.
　本発明における用語”アロイル”はアリール－Ｃ（Ｏ）であり、カルボニル基の炭素原子を通じて前記定義のアリール基中の任意の位置で結合される基、例えばベンゾイルおよびナフトイルを指す。 The term "aroyl" in the present invention is aryl-C(O), and refers to a group bonded at any position in the aryl group defined above through the carbon atom of the carbonyl group, such as benzoyl and naphthoyl.
　本発明における用語”アルキレン”（またはアルカンジイル）は、それぞれの場合に、前記定義の炭素原子を有するアルキル基であって、そのアルキル基の任意の位置の１つの水素原子が、更なる１つの結合部位によって置き換えられることで、二価の基を形成する基を指す。従って、Ｃ１～Ｃ２０アルキレンとしては、１～２０個の炭素原子を有する二価の分枝鎖状もしくは非分枝鎖状の飽和脂肪族鎖、例えば－ＣＨ２－、－ＣＨ２ＣＨ２－、－ＣＨ（ＣＨ３）－、－ＣＨ２ＣＨ２ＣＨ２－、－ＣＨ（ＣＨ３）ＣＨ２－、－ＣＨ２ＣＨ２ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ（ＣＨ３）ＣＨ２－、－ＣＨ（ＣＨ３）ＣＨ（ＣＨ３）－、－ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２－、－ＣＨ２ＣＨ２ＣＨ２ＣＨ（ＣＨ３）－、－ＣＨ２Ｃ（ＣＨ３）２ＣＨ２－が挙げられる。 The term "alkylene" (or alkanediyl) in the context of the present invention is, in each case, an alkyl group having carbon atoms as defined above, in which one hydrogen atom in any position of the alkyl group bears one further Refers to a group that, when replaced by a binding site, forms a divalent group. C 1 -C 20 alkylene thus includes divalent branched or unbranched saturated aliphatic chains having 1 to 20 carbon atoms, such as -CH 2 -, -CH 2 CH 2 - , -CH ( CH3 )-, -CH2CH2CH2- , -CH( CH3 ) CH2- , -CH2CH2CH2CH2- , -CH2CH ( CH3 ) CH2 - , -CH ( CH3 ) CH( CH3 ) - , -CH2CH2CH2CH2CH2- , -CH2CH2CH2CH2CH( CH3 ) -, -CH2C ( CH3 ) 2 CH 2 - is mentioned.
　本発明における用語”アルキレンは、１もしくはそれより多くの同一または異なる、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）及びＣ（Ｓ）から選択される基によって中断されていてもよく”は、前記定義の通常１～２０個の炭素原子を有するアルキレン鎖であって、そのアルキレン鎖の連続する２個の内部メチレン基が、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）またはＣ（Ｓ）によって中断されている鎖を指す。前記のアルキレン部は、例えば１、２、３、４、５個のまたは５個より多くの、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）及びＣ（Ｓ）から選択される同一もしくは異なる基を含んでよい。Ｒ６は、前記定義のとおりである。複数のＯ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）またはＣ（Ｓ）が存在する場合に、それらは、通常は隣接していない。すなわち、それらは、少なくとも１つのメチレン基によって互いに隔離されている。これらのＯ、ＳまたはＮ（Ｒ６）から選択される中断ヘテロ原子が複数、アルキレン中に存在する場合には、これらのヘテロ原子は、通常は同一である。 In the present invention, the term "alkylene" may be interrupted by one or more identical or different groups selected from O, S, N(R 6 ), C(O) and C(S). is an alkylene chain as defined above, usually having 1 to 20 carbon atoms, in which two consecutive internal methylene groups of the alkylene chain are O, S, N(R 6 ), C(O) or Refers to a chain interrupted by a C(S). Said alkylene moieties may be identical or selected from, for example, 1, 2, 3, 4, 5 or more than 5, O, S, N(R 6 ), C(O) and C(S). May contain different groups. R 6 is as defined above. When multiple O, S, N(R 6 ), C(O) or C(S) are present, they are usually not adjacent. That is, they are separated from each other by at least one methylene group. If more than one of these interrupting heteroatoms selected from O, S or N(R 6 ) are present in the alkylene, these heteroatoms are usually the same.
　本発明における用語”アルケニレン”（またはアルケンジイル）は、それぞれの場合に、前記定義の通常２～２０個の、好ましくは２～１２個の炭素原子を有する直鎖状もしくは分枝鎖状のアルケニル基であって、その炭素骨格の任意の位置の１つの水素原子が、更なる１つの結合部位によって置き換えられることで、二価の部を形成する基を指す。従って、Ｃ２～Ｃ２０－アルケニレンとしては、２～２０個の炭素原子を有する二価の直鎖状もしくは分枝鎖状の脂肪族鎖、例えば、ビニレン、プロペニレン、ブテ－１－エニレン、ブテ－２－エニレン、ペンタ－１，３－ジエニレンが挙げられる。 The term "alkenylene" (or alkenediyl) in the present invention refers in each case to a straight-chain or branched alkenyl radical having usually 2 to 20, preferably 2 to 12 carbon atoms as defined above. refers to a group in which one hydrogen atom at any position on its carbon skeleton is replaced by one additional bonding site to form a divalent moiety. C 2 -C 20 -alkenylene thus includes divalent straight or branched aliphatic chains having 2 to 20 carbon atoms, such as vinylene, propenylene, but-1-enylene, Examples include but-2-enylene and penta-1,3-dienylene.
　本発明における用語”シクロアルキレン”は、前記定義のシクロアルキル基であって、そのシクロアルキルの任意の位置の１つの水素原子が、更なる１つの結合部位によって置き換えられることで、二価の基を形成する基を指す。多環式のシクロアルキレンの場合に、それらの結合点は、同じ環中または異なる環中のいずれかに位置している。単環式の環としては、例えば、シクロプロピレン、シクロブチレン、シクロペンチレン、シクロヘキシレンまたはシクロヘプチレン、特にシクロヘキシレンが挙げられる。多環式の環としては、例えば、ペルヒドロアントラシレン、ペルヒドロナフチレン、ペルヒドロフルオレニレン、ペルヒドロクリセニレン、ペルヒドロピセニレン、アダマンチレン、ビシクロ［１．１．１］ペンチレン、ビシクロ［２．２．１］ヘプチレン、ビシクロ［４．２．２］デシレン、ビシクロ［２．２．２］オクチレン、ビシクロ［３．３．２］デシレン、ビシクロ［４．３．２］ウンデシレン、ビシクロ［４．３．３］ドデシレン、ビシクロ［３．３．３］ウンデシレン、ビシクロ［４．３．１］デシレン、ビシクロ［４．２．１］ノニレン、ビシクロ［３．３．１］ノニレン、ビシクロ［３．２．１］オクチレンが挙げられる。
シクロアルキレンは、１もしくはそれより多くの置換基によって置換されていてもよく、例えばＣ１～Ｃ４アルキルによって置換されていてもよい。 The term "cycloalkylene" in the present invention refers to a cycloalkyl group as defined above, in which one hydrogen atom at any position of the cycloalkyl is replaced by one additional bonding site, thereby forming a divalent group. refers to a group that forms In the case of polycyclic cycloalkylenes, the points of attachment are located either in the same ring or in different rings. Monocyclic rings include, for example, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene or cycloheptylene, especially cyclohexylene. Examples of the polycyclic ring include perhydroanthracylene, perhydronaphthylene, perhydrofluorenylene, perhydrochrysenylene, perhydropicenylene, adamantylene, bicyclo[1.1.1]pentylene, Bicyclo[2.2.1]heptylene, bicyclo[4.2.2]decylene, bicyclo[2.2.2]octylene, bicyclo[3.3.2]decylene, bicyclo[4.3.2]undecylene, Bicyclo[4.3.3]dodecylene, bicyclo[3.3.3]undecylene, bicyclo[4.3.1]decylene, bicyclo[4.2.1]nonylene, bicyclo[3.3.1]nonylene, Bicyclo[3.2.1]octylene is mentioned.
Cycloalkylene may be substituted with one or more substituents, for example by C 1 -C 4 alkyl.
　本発明における用語”アリーレン”（アレーンジイルとも呼ばれる）は、前記定義のアリール基であって、そのアリール基の任意の位置の１つの水素原子が、更なる１つの結合部位によって置き換えられることで、二価の基を形成する基を指す。多環式のアリーレンの場合に、それらの結合点は、同じ環中または異なる環中のいずれかに位置している。アリーレンの例は、フェニレン、ナフチレン、アントラセンジイルまたはフェナントレンジイルである。アリーレンが、１もしくはそれより多くの置換基によって置換されている場合に、それは、例えば一置換、二置換、三置換、四置換または五置換されており、または五置換より多置換されている。 The term "arylene" (also referred to as arenediyl) in the present invention refers to an aryl group as defined above, in which one hydrogen atom at any position of the aryl group is replaced by one further bonding site, thereby forming a double bond. Refers to a group that forms a valence group. In the case of polycyclic arylenes, the points of attachment are located either in the same ring or in different rings. Examples of arylene are phenylene, naphthylene, anthracenediyl or phenanthrenediyl. If arylene is substituted by one or more substituents, it is, for example, mono-, di-, tri-, tetra- or penta-substituted or more than penta-substituted.
　本発明における用語”フェニレン”は、１，２－フェニレン（ｏ－フェニレンまたは１，２－ベンゼンジイル）、１，３－フェニレン（ｍ－フェニレン、１，３－ベンゼンジイル）および１，４－フェニレン（ｐ－フェニレンまたは１，４－ベンゼンジイル）を指す。 The term "phenylene" in the present invention includes 1,2-phenylene (o-phenylene or 1,2-benzenediyl), 1,3-phenylene (m-phenylene, 1,3-benzenediyl) and 1,4-phenylene (p-phenylene or 1,4-benzenediyl).
　本発明における用語”ナフチレン”は、１，２－ナフチレン、１，３－ナフチレン、１，４－ナフチレン、１，５－ナフチレン、１，８－ナフチレン、２，３－ナフチレンおよび２，７－ナフチレンを指す。 The term "naphthylene" in the present invention includes 1,2-naphthylene, 1,3-naphthylene, 1,4-naphthylene, 1,5-naphthylene, 1,8-naphthylene, 2,3-naphthylene and 2,7-naphthylene. refers to
　本発明における用語”キシリレン”は、１，２－キシリレン（１，２－メチレンフェニレンメチレン、１，２－ＣＨ２－Ｃ６Ｈ４－ＣＨ２）、１，３－キシリレン（１，３－メチレンフェニレンメチレン、１，３－ＣＨ２－Ｃ６Ｈ４－ＣＨ２）および１，４－キシリレン（１，４－メチレンフェニレンメチレン、１，４－ＣＨ２－Ｃ６Ｈ４－ＣＨ２）を指す。 The term "xylylene" in the present invention refers to 1,2-xylylene (1,2-methylenephenylenemethylene, 1,2-CH 2 -C 6 H 4 -CH 2 ), 1,3-xylylene (1,3-methylene Phenylenemethylene, 1,3-CH 2 -C 6 H 4 -CH 2 ) and 1,4-xylylene (1,4-methylenephenylenemethylene, 1,4-CH 2 -C 6 H 4 -CH 2 ) .
　本発明における用語”ヘテロアリーレン”は、前記定義のヘテロアリール基であって、そのヘテロアリール基の任意の位置の１つの水素原子が、更なる１つの結合部位によって置き換えられることで、二価の基を形成する基を指す。多環式のヘテロアリーレンの場合に、それらの結合点は、同じ環中または異なる環中のいずれかに位置している。ヘテロアリーレンは、可能であれば、Ｃ結合型でもＮ結合型であってもよい。例えば、ピロールジイル、イミダゾールジイルまたはピラゾールジイルは、Ｎ結合型またはＣ結合型であってよい。ヘテロアレーンジイルの例は、ピリジンジイル、ピリミジンジイル、ピリダジンジイル、１，２，３－トリアジンジイル、１，２，４－トリアジンジイル、１，２，３，４－テトラジンジイル、フランジイル、チオフェンジイル、ピロールジイル、チアゾールジイル、チアジアゾールジイル、ピラゾールジイル、イミダゾールジイル、トリアゾールジイル、オキサゾールジイル、イソキサゾールジイル、イソチアゾールジイル、オキサジアゾールジイルである。ヘテロアレーンジイルは、１もしくはそれより多くの置換基によって置換されていてもよい。 The term "heteroarylene" in the present invention refers to a heteroaryl group as defined above, in which one hydrogen atom at any position of the heteroaryl group is replaced by one additional bonding site, resulting in a divalent Refers to a group that forms a group. In the case of polycyclic heteroarylenes, the points of attachment are located either in the same ring or in different rings. Heteroarylenes may be C-attached or N-attached, where possible. For example, pyrrolediyl, imidazolediyl or pyrazolediyl may be N-attached or C-attached. Examples of heteroarenediyl are pyridinediyl, pyrimidinediyl, pyridazinediyl, 1,2,3-triazinediyl, 1,2,4-triazinediyl, 1,2,3,4-tetrazinediyl, furandiyl, thiophene These are diyl, pyrrolediyl, thiazolediyl, thiadiazolediyl, pyrazolediyl, imidazolediyl, triazolediyl, oxazolediyl, isoxazolediyl, isothiazolediyl, and oxadiazolediyl. Heteroarenediyl may be optionally substituted with one or more substituents.
　本発明における用語”アルカントリイル”は、普通１～３０個の炭素原子を有する前記定義のアルキレン基であって、そのアルキレンの任意の位置の１つの水素原子が、更なる１つの結合部位によって置き換えられることで、三価の基を形成する基を指す。従って、アルカントリイルは、三価の分枝鎖状もしくは非分枝鎖状の飽和の脂肪族鎖である。アルカントリイルは、１もしくはそれより多くの置換基によって置換されていてもよい。 The term "alkantriyl" in the present invention refers to an alkylene group as defined above, usually having from 1 to 30 carbon atoms, in which one hydrogen atom at any position of the alkylene is replaced by an additional bonding site. Refers to a group that forms a trivalent group when replaced. Alkantriyl is therefore a trivalent, branched or unbranched, saturated aliphatic chain. Alkantriyl may be optionally substituted with one or more substituents.
　本発明における用語”アルケントリイル”は、普通２～３０個の炭素原子を有する前記定義のアルケンジイル基であって、そのアルケンジイルの任意の位置の１つの水素原子が、更なる１つの結合部位によって置き換えられることで、三価の基を形成する基を指す。従って、アルケントリイルは、三価の分枝鎖状もしくは非分枝鎖状の不飽和の脂肪族鎖である。アルケントリイルは、１もしくはそれより多くの置換基によって置換されていてもよい。 The term "alkenetriyl" in the present invention refers to an alkenediyl group as defined above, usually having from 2 to 30 carbon atoms, in which one hydrogen atom at any position of the alkenediyl is replaced by an additional bonding site. Refers to a group that forms a trivalent group when replaced. Alkenetriyl is therefore a trivalent, branched or unbranched, unsaturated aliphatic chain. Alkenetriyl may be optionally substituted with one or more substituents.
　本発明における用語”シクロアルカントリイル”は、前記定義のシクロアルキレン基であって、そのシクロアルキレンの任意の位置の１つの水素原子が、更なる１つの結合部位によって置き換えられることで、三価の基を形成する基を指す。多環式のシクロアルカントリイルの場合に、それらの結合点は、同じ環中または異なる環中のいずれかに位置している。シクロアルカントリイルは、１もしくはそれより多くの置換基によって置換されていてもよい。 The term "cycloalkanetriyl" in the present invention refers to a cycloalkylene group as defined above, in which one hydrogen atom at any position of the cycloalkylene is replaced by one additional bonding site, resulting in a trivalent refers to a group that forms a group of In the case of polycyclic cycloalkanetriyls, their points of attachment are located either in the same ring or in different rings. Cycloalkanetriyl may be optionally substituted with one or more substituents.
　本発明における用語”アレーントリイル”は、前記定義のアリーレン基であって、そのアリーレン基の任意の位置の１つの水素原子が、更なる１つの結合部位によって置き換えられることで、三価の基を形成する基を指す。多環式のアレーントリイルの場合に、それらの結合点は、同じ環中または異なる環中のいずれかに位置している。アレーントリイルの例は、１，２，４－ベンゼントリイル、１，３，５－ベンゼントリイル、１，３，５－ナフタレントリイル、１，４，５－ナフタレンジイル、アントラセントリイルまたはフェナントレントリイルである。アレーントリイルは、１もしくはそれより多くの置換基によって置換されていてもよい。 The term "arenetriyl" in the present invention refers to an arylene group as defined above, in which one hydrogen atom at any position of the arylene group is replaced by one additional bonding site, thereby forming a trivalent group. refers to a group that forms In the case of polycyclic arenetriyls, the points of attachment are located either in the same ring or in different rings. Examples of arenetriyl are 1,2,4-benzentriyl, 1,3,5-benzentriyl, 1,3,5-naphthalenetriyl, 1,4,5-naphthalenediyl, anthracentriyl or It is a phenanthrene triyl. Arenetriyl may be optionally substituted with one or more substituents.
　本発明における用語”ヘテロアレーントリイル”は、前記定義のヘテロアリーレン基であって、そのヘテロアリーレン基の任意の位置の１つの水素原子が、更に１つの結合部位によって置き換えられることで、三価の基を形成する基を指す。多環式のヘテロアレーントリイルの場合に、それらの結合点は、同じ環中または異なる環中のいずれかに位置している。ヘテロアレーントリイルは、可能であれば、Ｃ結合型でもＮ結合型であってもよい。
例えば、ピロールトリイル、イミダゾールトリイルまたはピラゾールトリイルは、Ｎ結合型またはＣ結合型であってよい。 The term "heteroarenetriyl" in the present invention refers to a heteroarylene group as defined above, in which one hydrogen atom at any position of the heteroarylene group is further replaced by one bonding site, resulting in a trivalent refers to a group that forms a group of In the case of polycyclic heteroarenetriyls, the points of attachment are located either in the same ring or in different rings. Heteroarenetriyl may be C-attached or N-attached, where possible.
For example, pyrroletriyl, imidazoletriyl or pyrazoletriyl may be N-attached or C-attached.
　本発明における用語”アルカンテトライル”は、それぞれの場合に、普通１～３０個の炭素原子を有する前記定義のアルカントリイル基であって、そのアルカントリイルの任意の位置の１つの水素原子が、更なる１つの結合部位によって置き換えられることで、四価の基を形成する基を指す。従って、アルカンテトライルは、四価の分枝鎖状もしくは非分枝鎖状の飽和の脂肪族鎖である。アルカンテトライルは、１もしくはそれより多くの置換基によって置換されていてもよい。 The term "alkanetetryl" according to the invention refers to an alkanetriyl radical as defined above, having in each case normally from 1 to 30 carbon atoms, with one hydrogen atom in any position of the alkanetriyl. is replaced by one additional bonding site to form a tetravalent group. Alkanetetryl is thus a tetravalent branched or unbranched saturated aliphatic chain. Alkanetetrayl may be optionally substituted with one or more substituents.
　本発明における用語”トリアシル”及び”テトラアシル”は、それぞれ、三価及び四価の基であって、３個及び４個のＣ（Ｏ）基の炭素を通して結合を形成する基を指す。 The terms "triacyl" and "tetraacyl" in the present invention refer to trivalent and tetravalent groups, respectively, which form bonds through three and four carbon atoms of C(O) groups.
　本発明の化合物は、上述の特許文献１に記載されたＯ－イミノ－イソ尿素構造を有する化合物と比較して、Ｓ－イミノ構造も有する。
　該Ｓ－イミノ構造を有することで、Ｎ－Ｏの開裂が低温で起きやすくなること、ＮラジカルからＳラジカルが発生し、よりラジカルの反応性が高くなることから、より低温での反応性が向上する。 The compound of the present invention also has an S-imino structure, compared to the compound having an O-imino-isourea structure described in Patent Document 1 mentioned above.
By having the S-imino structure, N-O cleavage occurs more easily at low temperatures, S radicals are generated from N radicals, and the reactivity of the radicals becomes higher, so the reactivity at lower temperatures increases. improves.
［２］化合物の合成方法
　本発明の化合物の合成方法を、以下に記載する。 [2] Method for synthesizing the compound The method for synthesizing the compound of the present invention will be described below.
　式（Ｉ）、（ＩＩ）、（ＩＩＩ）、および（ＩＶ）で示される化合物は、一般的に、文献に記載される方法によって合成できる。例えば、Ｒ５＝Ｈの式（Ｉ）で示される化合物は、好適な遊離のオキシムと、カルボジイミドとを反応させることによって下記式（スキーム１）に示されるように合成できる。 Compounds of formulas (I), (II), (III), and (IV) can generally be synthesized by methods described in the literature. For example, a compound represented by formula (I) where R 5 =H can be synthesized as shown in the following formula (Scheme 1) by reacting a suitable free oxime with a carbodiimide.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　また、Ｒ５＝Ｈの式（ＩＩ）および（ＩＩＩ）の化合物についても、同様に下記式（スキーム２および３）に従って合成することができる。 Furthermore, compounds of formulas (II) and (III) where R 5 =H can be similarly synthesized according to the following formulas (Schemes 2 and 3).
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　上記スキーム１～３に従ってオキシム（スキーム１～３中のＶ、Ｖ’またはＶ’’）のカルボジイミド（スキーム１～３中のＶＩ）への付加反応によって合成することができる。上記スキーム１～３中のＲ１、Ｒ２、Ｒ３、Ｒ４およびＲ５は上記で定義された通りである。この型の付加反応は、例えば、日本国特許５６９３５６５号公報に記載されている。 It can be synthesized by addition reaction of oxime (V, V' or V'' in Schemes 1 to 3) to carbodiimide (VI in Schemes 1 to 3) according to Schemes 1 to 3 above. R 1 , R 2 , R 3 , R 4 and R 5 in Schemes 1 to 3 above are as defined above. This type of addition reaction is described, for example, in Japanese Patent No. 5,693,565.
　多くのカルボジイミド（スキーム１～３中のＶＩ）が商業的に入手可能であり、具体的には、例えば、Ｎ，Ｎ’－ジシクロヘキシルカルボジイミド、Ｎ，Ｎ’－ジイソプロピルカルボジイミド、Ｎ，Ｎ’－ビス－（ｏ－トリル）－カルボジイミド、Ｎ，Ｎ’－ビス－（ｐ－トリル）－カルボジイミド、Ｎ，Ｎ’－ビス－（２，６－ジイソプロピルフェニル）－カルボジイミド、Ｎ，Ｎ’－ビス－（トリメチルシリル）－カルボジイミド、Ｎ－ｓｅｃ－ブチル－Ｎ’－エチルカルボジイミド、Ｎ－シクロヘキシル－Ｎ’－［４－（ジメチルアミノ）－α－ナフチル］－カルボジイミド、Ｎ－シクロヘキシル－Ｎ’－（２－モルホリノエチル）－カルボジイミド、Ｎ，Ｎ’－ジ－ｔｅｒｔ－ブチルカルボジイミド、Ｎ－エチル－Ｎ’－（３－ジメチルアミノプロピル）－カルボジイミド、Ｎ，Ｎ’－ビス－（２，４，６－トリイソプロピルフェニル）－カルボジイミドが挙げられる。 Many carbodiimides (VI in Schemes 1-3) are commercially available, in particular, for example, N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, N,N'-bis -(o-tolyl)-carbodiimide, N,N'-bis-(p-tolyl)-carbodiimide, N,N'-bis-(2,6-diisopropylphenyl)-carbodiimide, N,N'-bis-( trimethylsilyl)-carbodiimide, N-sec-butyl-N'-ethylcarbodiimide, N-cyclohexyl-N'-[4-(dimethylamino)-α-naphthyl]-carbodiimide, N-cyclohexyl-N'-(2-morpholino ethyl)-carbodiimide, N,N'-di-tert-butylcarbodiimide, N-ethyl-N'-(3-dimethylaminopropyl)-carbodiimide, N,N'-bis-(2,4,6-triisopropyl) (phenyl)-carbodiimide.
　前記付加反応は、適切な溶媒、例えば、酢酸エチル、トルエン、ジクロロメタン、アセトニトリル、テトラヒドロフラン、ヘキサン等の中におけるオキシム及びカルボジイミドの溶液を撹拌することによって実施され得る。反応温度は、室温以下、例えば－７８℃から、室温以上、例えば１５０℃であってもよい。 The addition reaction may be carried out by stirring a solution of the oxime and carbodiimide in a suitable solvent such as ethyl acetate, toluene, dichloromethane, acetonitrile, tetrahydrofuran, hexane, etc. The reaction temperature may be from below room temperature, eg -78°C, to above room temperature, eg 150°C.
　前記付加反応に用いられる触媒としては、例えば、塩基である、アルカリ金属水酸化物、アルカリ金属アルコキシド、アルカリ金属アミド若しくはアルカリ金属水素化物、又はアミン、例えば、トリエチルアミン若しくはＤＡＢＣＯ等、又はアミジン、例えば、ＤＢＵ若しくはＤＢＮ等、又はブレンステッド酸、例えば、ＨＣｌ、ｐ－ＴｓＯＨ、ＨＢＦ４若しくはＨ２ＳＯ４、又はルイス酸、例えば、ＢＦ３若しくはＣｕ（Ｏ３ＳＣＦ３）が挙げられ、これらの触媒の使用は、オキシムのカルボジイミドへの付加の速度及び収率の改善を実現することができる。又は相間移動触媒を使用した条件下における反応を実施してもよい。 The catalyst used in the addition reaction is, for example, a base such as an alkali metal hydroxide, alkali metal alkoxide, alkali metal amide or alkali metal hydride, or an amine such as triethylamine or DABCO, or an amidine such as, DBU or DBN etc., or Brønsted acids such as HCl, p-TsOH, HBF4 or H 2 SO 4 or Lewis acids such as BF 3 or Cu(O 3 SCF 3 ), and the use of these catalysts can realize improved rates and yields of the addition of oximes to carbodiimides. Alternatively, the reaction may be carried out under conditions using a phase transfer catalyst.
　式（ＩＶ）で示される化合物、並びにＲ５がＨでない式（Ｉ）、（ＩＩ）および（ＩＩＩ）で示される化合物は、Ｒ５＝Ｈの式（Ｉ）、（ＩＩ）および（ＩＩＩ）で示される化合物の適切なアルキル化剤又はアシル化剤によるアルキル化又はアシル化等によって合成することができ、例えば、下記式（スキーム４）に従って合成できる。 Compounds represented by formula (IV) and compounds represented by formulas (I), (II) and (III) in which R 5 is not H are compounds represented by formulas (I), (II) and (III) in which R 5 =H. It can be synthesized by alkylation or acylation of the compound represented by with an appropriate alkylating agent or acylating agent, and for example, it can be synthesized according to the following formula (Scheme 4).
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　アルキル化剤Ｒ５－Ｘ、Ｌ３－Ｘｎとしては、周知の化合物が使用でき、例えば、ハロゲン化アルキル、ハロゲン化シクロアルキルもしくはハロゲン化アラルキル、スルホン酸塩、トリフレート、トリアルキルオキソニウム塩が挙げられる。 As the alkylating agent R 5 -X, L 3 -X n , well-known compounds can be used, such as alkyl halides, cycloalkyl halides, aralkyl halides, sulfonates, triflates, trialkyloxonium salts. can be mentioned.
　さらに、適切なアシル化剤Ｒ５－Ｘ、Ｌ３－Ｘｎは、周知の化合物が使用でき、例えば、ハロゲン化アシル、アシル無水物が挙げられる。 Further, as suitable acylating agents R 5 -X, L 3 -X n , well-known compounds can be used, such as acyl halides and acyl anhydrides.
　Ｒ５がＨでない式（Ｉ）、（ＩＩ）および（ＩＩＩ）で示される化合物を得る別の方法としては、Ｒ５＝Ｈである式（Ｉ）、（ＩＩ）および（ＩＩＩ）で示される化合物とイソシアネートとの反応が挙げられる。また、適切な活性マイケル受容体、例えば、アクリロニトリル又はアクリル酸アルキルへのＲ５＝Ｈである式（Ｉ）、（ＩＩ）および（ＩＩＩ）で示される化合物のマイケル付加を介して、Ｒ５を導入することもできる。 Another way to obtain compounds of formula (I), (II) and (III) where R 5 is H is to obtain compounds of formula (I), (II) and (III) where R 5 =H. Examples include reactions between compounds and isocyanates. Alternatively, R 5 can be modified via Michael addition of compounds of formulas (I), (II) and (III), where R 5 =H, to a suitable active Michael acceptor, such as acrylonitrile or an alkyl acrylate. It can also be introduced.
　本発明の化合物の合成に使用されるオキシム（スキーム１～３中のＶ、Ｖ’またはＶ’’）は、文献に記載の様々な方法によって、合成できる。例えば、下記式（スキーム５）に示されるようなアルデヒドを出発原料とした合成法が知られている。 The oximes (V, V' or V'' in Schemes 1 to 3) used in the synthesis of the compounds of the present invention can be synthesized by various methods described in the literature. For example, a synthetic method using an aldehyde as a starting material as shown in the following formula (Scheme 5) is known.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　例えば、Ｓｙｎｔｈｅｓｉｓ，５０，　１６４０－１６５０，　２０１８に記載のアルデヒドとヒドロキシルアミンもしくはその塩とをエタノールもしくは水性エタノールなどの極性溶剤中で反応させることによってアルドキシムを得ることができる。その場合に、酢酸ナトリウムあるいは炭酸ナトリウムなどの塩基が、その反応混合物のｐＨの制御のために添加される。前記反応の速度はｐＨに依存し、かつ塩基を、最初にまたは連続的に反応の間に添加できることはよく知られている。ピリジンなどの塩基性溶剤は、また、塩基および／または溶剤もしくは助溶剤として使用することもできる。前記反応の温度は、一般に、前記混合物の還流温度であり、通常は約６０～１２０℃である。 For example, an aldoxime can be obtained by reacting an aldehyde described in Synthesis, 50, 1640-1650, 2018 with hydroxylamine or a salt thereof in a polar solvent such as ethanol or aqueous ethanol. In that case, a base such as sodium acetate or sodium carbonate is added to control the pH of the reaction mixture. It is well known that the rate of the reaction depends on the pH and that the base can be added initially or continuously during the reaction. Basic solvents such as pyridine can also be used as base and/or solvent or co-solvent. The temperature of the reaction is generally the reflux temperature of the mixture, usually about 60-120°C.
　オキシム（スキーム５中のＶ）の簡便な合成は、上記アルドキシムをオキシミドイルハロゲン化物とした後、チオールＲ１－ＳＨとの反応である。チオールＲ１－ＳＨの代わりに多官能チオールＬ１－［ＳＨ］ｎを使用することでオキシム（スキーム５中のＶ’）を合成できる。多官能アルデヒドを出発原料として用いることでオキシム（Ｖ’’）を合成できる。 A convenient synthesis of the oxime (V in Scheme 5) is to convert the above aldoxime into an oximidoyl halide and then react it with the thiol R 1 --SH. Oxime (V' in Scheme 5) can be synthesized by using polyfunctional thiol L 1 -[SH] n instead of thiol R 1 -SH. Oxime (V'') can be synthesized by using a polyfunctional aldehyde as a starting material.
　例えば、国際公開第２０１２／１０１２４５号に記載されるような、好適なオキシミドイルハロゲン化物、例えばオキシミドイル塩化物もしくはオキシミドイル臭化物とチオールとの反応である。これらの反応は、通常は、不活性溶剤、例えばトルエン、ジオキサン、テトラヒドロフラン（ＴＨＦ）、ジエチルエーテル、ジクロロメタン、ジメチルホルムアミド（ＤＭＦ）、メタノールもしくは水性メタノール中で、塩基、例えば第三級アミン、例えばトリエチルアミンもしくは金属水酸化物、例えばＮａＯＨ、ＬｉＯＨおよびＫＯＨの存在下で行われる。 For example, the reaction of a suitable oximidoyl halide, such as oximidoyl chloride or oximidoyl bromide, with a thiol, as described in WO 2012/101245. These reactions are usually carried out in an inert solvent such as toluene, dioxane, tetrahydrofuran (THF), diethyl ether, dichloromethane, dimethylformamide (DMF), methanol or aqueous methanol with a base such as a tertiary amine such as triethylamine. or in the presence of metal hydroxides such as NaOH, LiOH and KOH.
　前記のオキシミドイルハロゲン化物は、相応するアルドキシムと、ハロゲン化試薬、例えばＪ．Ｏｒｇ．Ｃｈｅｍ．，４５，３９１６－３９１８，１９８０に記載されるＮ－クロロスクシンイミド（ＮＣＳ）、Ｎ－ブロモスクシンイミド（ＮＢＳ）、例えばヨーロッパ公開特許第００６４０９１号公報に記載される塩素もしくは臭素またはｔ－ブチル次亜塩素酸塩との反応によって得ることができる。これらの反応は、通常は、不活性溶剤、例えばトルエン、テトラヒドロフラン（ＴＨＦ）、ジメチルホルムアミド（ＤＭＦ）、クロロホルム、ジクロロメタン中で、または極性溶剤、例えばメタノールもしくは水性メタノール中で行われる。 The above-mentioned oximidoyl halides can be prepared in combination with the corresponding aldoxime and a halogenating reagent, for example J. Org. Chem. , 45, 3916-3918, 1980, N-bromosuccinimide (NBS), chlorine or bromine or t-butyl hypochlorite as described in European Publication No. 0064091, for example. It can be obtained by reaction with acid salts. These reactions are usually carried out in inert solvents such as toluene, tetrahydrofuran (THF), dimethylformamide (DMF), chloroform, dichloromethane or in polar solvents such as methanol or aqueous methanol.
　オキシミドイル塩化物の別の合成法は、例えばＪ．Ｏｒｇ．Ｃｈｅｍ．，４８，３６６－３７２，１９８３に記載されるように、ＨＣｌ水溶液中でのグリシンエチルエステル塩酸塩の亜硝酸ナトリウムによるオキシム化である。 Another method for synthesizing oximidoyl chloride is described, for example, in J. Org. Chem. , 48, 366-372, 1983, the oximation of glycine ethyl ester hydrochloride with sodium nitrite in aqueous HCl.
　オキシムの種々の合成法は周知であり、上記の方法に限定されるものではない。 Various methods of synthesizing oximes are well known and are not limited to the methods described above.
　記載した合成法は、式（Ｉ）、（ＩＩ）、（ＩＩＩ）及び（ＩＶ）で示される化合物の異性体型の形成をもたらし得る。オキシミノ基の二重結合およびイソウレア基の二重結合に対しては、それぞれｓｙｎ型（Ｚ）とａｎｔｉ型（Ｅ）の両幾何異性体が存在してもよく、または前記の幾何異性体の混合物として存在してもよい。本発明においては、個々の幾何異性体と幾何異性体の任意の混合物の両方を使用することができる。従って、本発明は、また、式（Ｉ）、（ＩＩ）、（ＩＩＩ）及び（ＩＶ）で示される化合物の異性体形の混合物に関する。 The synthetic methods described may result in the formation of isomeric forms of compounds of formulas (I), (II), (III) and (IV). For the double bond of the oximino group and the double bond of the isourea group, both syn type (Z) and anti type (E) geometric isomers may exist, respectively, or a mixture of the above geometric isomers. may exist as Both individual geometric isomers and any mixtures of geometric isomers can be used in the present invention. The invention therefore also relates to mixtures of isomeric forms of the compounds of formula (I), (II), (III) and (IV).
[３]重合性組成物
　本発明における重合性組成物は、（Ａ）Ｏ－イミノ－イソ尿素化合物、及び（Ｂ）重合性化合物を含有し、（Ａ）Ｏ－イミノ－イソ尿素化合物として、前述した本発明の化合物の少なくとも１種を含有するものである。本発明の重合性組成物は、必要に応じてさらにその他の成分を含んでいてもよく、例えば（Ｃ）アルカリ可溶性樹脂、（Ｄ）光重合開始剤、（Ｅ）着色剤、（Ｆ）連鎖移動剤等を含んでいてもよい。 [3] Polymerizable composition The polymerizable composition in the present invention contains (A) an O-imino-isourea compound and (B) a polymerizable compound, and as the (A) O-imino-isourea compound, It contains at least one of the compounds of the present invention described above. The polymerizable composition of the present invention may further contain other components as necessary, such as (C) an alkali-soluble resin, (D) a photoinitiator, (E) a coloring agent, and (F) a chain. It may also contain a transfer agent or the like.
［３－１］重合性組成物の成分及び組成
　本発明の重合性組成物を構成する成分及びその組成について説明する。
　本発明の重合性組成物は、（Ａ）Ｏ－イミノ－イソ尿素化合物、及び（Ｂ）重合性化合物を含有する。 [3-1] Components and Composition of Polymerizable Composition The components constituting the polymerizable composition of the present invention and their composition will be explained.
The polymerizable composition of the present invention contains (A) an O-imino-isourea compound and (B) a polymerizable compound.
［３－１－１］（Ａ）Ｏ－イミノ－イソ尿素化合物
　本発明の重合性組成物における（Ａ）Ｏ－イミノ－イソ尿素化合物の含有量は、重合性組成物の全固形分中に好ましくは０．０１質量％以上、より好ましくは０．０５質量％以上、さらに好ましくは０．２質量％以上、また、好ましくは２５質量％以下、より好ましくは１５質量％以下、さらに好ましくは１０質量％以下である。前記上限及び下限は任意に組み合わせることができ、例えば、０．０１～２５質量％が好ましく、０．０５～１５質量％がより好ましく、０．２～１０質量％がさらに好ましい。前記下限値以上とすることで硬化性が向上する傾向がある。前記上限値以下とすることで組成物安定性が高くなる傾向がある。
　（Ａ）Ｏ－イミノ－イソ尿素化合物は、１種を単独で用いてもよく、２種以上を併用してもよい。 [3-1-1] (A) O-imino-isourea compound The content of (A) O-imino-isourea compound in the polymerizable composition of the present invention is in the total solid content of the polymerizable composition. Preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.2% by mass or more, and preferably 25% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less. % by mass or less. The upper and lower limits can be arbitrarily combined, for example, preferably from 0.01 to 25% by weight, more preferably from 0.05 to 15% by weight, even more preferably from 0.2 to 10% by weight. There is a tendency for the curability to improve when the amount is equal to or more than the lower limit. When the content is below the upper limit, the stability of the composition tends to increase.
(A) O-imino-isourea compounds may be used alone or in combination of two or more.
［３－１－２］（Ｂ）重合性化合物
　本発明の重合性組成物は（Ｂ）重合性化合物を含有する。（Ｂ）重合性化合物を含むことで、高感度となると考えられる。
　ここで使用される（Ｂ）重合性化合物としては、エチレン性不飽和結合（エチレン性二重結合）を分子内に１個以上有する化合物を意味するが、重合性及び架橋性等の点から、エチレン性不飽和結合を分子内に２個以上有する化合物であることが好ましい。また、その不飽和結合は（メタ）アクリロイルオキシ基に由来するもの、つまり、（メタ）アクリレート化合物であることがさらに好ましい。 [3-1-2] (B) Polymerizable compound The polymerizable composition of the present invention contains (B) a polymerizable compound. (B) Including the polymerizable compound is considered to increase sensitivity.
The polymerizable compound (B) used here refers to a compound having one or more ethylenically unsaturated bonds (ethylenic double bonds) in the molecule, but from the viewpoint of polymerizability and crosslinkability, Preferably, the compound has two or more ethylenically unsaturated bonds in the molecule. Further, it is more preferable that the unsaturated bond is derived from a (meth)acryloyloxy group, that is, a (meth)acrylate compound.
　本発明の重合性組成物においては、（Ｂ）重合性化合物として、特に、１分子中にエチレン性不飽和結合を２個以上有する多官能エチレン性単量体を使用することが望ましい。
多官能エチレン性単量体が有するエチレン性不飽和基の数は特に限定されないが、好ましくは２個以上、より好ましくは３個以上、さらに好ましくは４個以上、特に好ましくは５個以上であり、また、好ましくは１５個以下、より好ましくは１０個以下、さらに好ましくは８個以下、特に好ましくは７個以下である。前記上限及び下限は任意に組み合わせることができ、例えば、２～１５個が好ましく、３～１０個がより好ましく、４～８個がさらに好ましく、５～７個が特に好ましい。前記下限値以上とすることで重合性が向上して高感度となる傾向がある。前記上限値以下とすることで現像性がより良好となる傾向がある。
　（Ｂ）重合性化合物としては、例えば、脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル；芳香族ポリヒドロキシ化合物と不飽和カルボン酸とのエステル；脂肪族ポリヒドロキシ化合物、芳香族ポリヒドロキシ化合物等の多価ヒドロキシ化合物と、不飽和カルボン酸及び多塩基性カルボン酸とのエステル化反応により得られるエステル；が挙げられる。 In the polymerizable composition of the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated bonds in one molecule as the polymerizable compound (B).
The number of ethylenically unsaturated groups that the polyfunctional ethylenic monomer has is not particularly limited, but is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, and particularly preferably 5 or more. The number is preferably 15 or less, more preferably 10 or less, still more preferably 8 or less, particularly preferably 7 or less. The upper and lower limits can be arbitrarily combined, for example, preferably 2 to 15, more preferably 3 to 10, even more preferably 4 to 8, particularly preferably 5 to 7. When the amount is equal to or more than the lower limit, polymerizability tends to improve and sensitivity tends to increase. There is a tendency for the developability to become better by setting it below the above-mentioned upper limit value.
(B) Polymerizable compounds include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds Examples include esters obtained by an esterification reaction between a polyhydric hydroxy compound such as, and an unsaturated carboxylic acid and a polybasic carboxylic acid.
　脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルとしては、例えば、エチレングリコールジアクリレート、トリエチレングリコールジアクリレート、トリメチロールプロパントリアクリレート、トリメチロールエタントリアクリレート、ペンタエリスリトールジアクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールテトラアクリレート、ジペンタエリスリトールテトラアクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールヘキサアクリレート、グリセロールアクリレート等の脂肪族ポリヒドロキシ化合物のアクリル酸エステル；これらの化合物のアクリレートをメタクリレートに代えたメタクリル酸エステル；これらの化合物のアクリレートをイタコネートに代えたイタコン酸エステル；これらの化合物のアクリレートをクロネートに代えたクロトン酸エステル；これらの化合物のアクリレートをマレエートに代えたマレイン酸エステル；が挙げられる。 Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate. , pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, and other aliphatic polyhydroxy compound acrylic acid esters; methacrylic acid obtained by replacing the acrylate of these compounds with methacrylate Esters; itaconate esters in which the acrylate of these compounds is replaced with itaconate; crotonate esters in which the acrylate of these compounds is replaced with cronate; and maleate esters in which the acrylate of these compounds is replaced with maleate.
　芳香族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルとしては、例えば、ハイドロキノンジアクリレート、ハイドロキノンジメタクリレート、レゾルシンジアクリレート、レゾルシンジメタクリレート、ピロガロールトリアクリレート等の芳香族ポリヒドロキシ化合物のアクリル酸エステル及びメタクリル酸エステルが挙げられる。
　脂肪族ポリヒドロキシ化合物、芳香族ポリヒドロキシ化合物等の多価ヒドロキシ化合物と、不飽和カルボン酸及び多塩基性カルボン酸とのエステル化反応により得られるエステルとしては、必ずしも単一物ではないが、例えば、アクリル酸、フタル酸、及びエチレングリコールの縮合物；アクリル酸、マレイン酸、及びジエチレングリコールの縮合物；メタクリル酸、テレフタル酸及びペンタエリスリトールの縮合物；アクリル酸、アジピン酸、ブタンジオール及びグリセリンの縮合物；が挙げられる。 Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic esters and methacrylates of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. Examples include acid esters.
The ester obtained by the esterification reaction of a polyhydric hydroxy compound such as an aliphatic polyhydroxy compound or an aromatic polyhydroxy compound with an unsaturated carboxylic acid or a polybasic carboxylic acid is not necessarily a single substance, but for example, , condensates of acrylic acid, phthalic acid, and ethylene glycol; condensates of acrylic acid, maleic acid, and diethylene glycol; condensates of methacrylic acid, terephthalic acid, and pentaerythritol; condensates of acrylic acid, adipic acid, butanediol, and glycerin Examples include things.
　本発明の重合性組成物に用いられる（Ｂ）重合性化合物の上記以外の例としては、例えば、ポリイソシアネート化合物と水酸基含有（メタ）アクリル酸エステル又はポリイソシアネート化合物とポリオール及び水酸基含有（メタ）アクリル酸エステルを反応させて得られるようなウレタン（メタ）アクリレート類；多価エポキシ化合物と水酸基含有（メタ）アクリル酸エステル又は（メタ）アクリル酸との付加反応物のようなエポキシアクリレート類；エチレンビスアクリルアミド等のアクリルアミド類；フタル酸ジアリル等のアリルエステル類；ジビニルフタレート等のビニル基含有化合物が有用である。
　ウレタン（メタ）アクリレート類としては、例えば、ＤＰＨＡ－４０Ｈ、ＵＸ－５０００、ＵＸ－５００２Ｄ－Ｐ２０、ＵＸ－５００３Ｄ、ＵＸ－５００５（日本化薬社製）、Ｕ－２ＰＰＡ、Ｕ－６ＬＰＡ、Ｕ－１０ＰＡ、Ｕ－３３Ｈ、ＵＡ－５３Ｈ、ＵＡ－３２Ｐ、ＵＡ－１１００Ｈ（新中村化学工業社製）、ＵＡ－３０６Ｈ、ＵＡ－５１０Ｈ、ＵＦ－８００１Ｇ（協栄社化学社製）、ＵＶ－１７００Ｂ、ＵＶ－７６００Ｂ、ＵＶ－７６０５Ｂ、ＵＶ－７６３０Ｂ、ＵＶ７６４０Ｂ（日本合成化学工業社製）が挙げられる。 Examples of the polymerizable compound (B) used in the polymerizable composition of the present invention other than the above include, for example, a polyisocyanate compound and a hydroxyl group-containing (meth)acrylic ester, or a polyisocyanate compound, a polyol, and a hydroxyl group-containing (meth)acrylate ester. Urethane (meth)acrylates such as those obtained by reacting acrylic esters; Epoxy acrylates such as addition reaction products of polyvalent epoxy compounds and hydroxyl group-containing (meth)acrylic esters or (meth)acrylic acid; ethylene Acrylamides such as bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate are useful.
Examples of urethane (meth)acrylates include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U- 10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B, Examples include UV-7600B, UV-7605B, UV-7630B, and UV7640B (manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd.).
　これらの中でも、感度の観点から（Ｂ）重合性化合物として、エステル（メタ）アクリレート類又はウレタン（メタ）アクリレート類を用いることが好ましく、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、２－トリス（メタ）アクリロイロキシメチルエチルフタル酸、ペンタエリスリトールテトラ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレートの二塩基酸無水物付加物、ペンタエリスリトールトリ（メタ）アクリレートの二塩基酸無水物付加物を用いることがより好ましい。
　これらは１種を単独で用いてもよく、２種以上を併用してもよい。 Among these, it is preferable to use ester (meth)acrylates or urethane (meth)acrylates as the polymerizable compound (B) from the viewpoint of sensitivity, and dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, etc. ) acrylate, 2-tris(meth)acryloyloxymethylethyl phthalate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dibasic acid anhydride adduct of dipentaerythritol penta(meth)acrylate, It is more preferable to use a dibasic acid anhydride adduct of pentaerythritol tri(meth)acrylate.
These may be used alone or in combination of two or more.
　本発明の重合性組成物において、（Ｂ）重合性化合物の分子量は特に限定されないが、硬化性、テーパ角の観点から、好ましくは１００以上、より好ましくは１５０以上で、さらに好ましくは２００以上、よりさらに好ましくは３００以上、特に好ましくは４００以上、最も好ましくは５００以上であり、また、好ましくは１０００以下、より好ましくは７００以下である。前記上限及び下限は任意に組み合わせることができ、例えば、１００～１０００が好ましく、１５０～１０００がより好ましく、２００～１０００がさらに好ましく、３００～７００がよりさらに好ましく、４００～７００が特に好ましく、５００～７００が最も好ましい。 In the polymerizable composition of the present invention, the molecular weight of the polymerizable compound (B) is not particularly limited, but from the viewpoint of curability and taper angle, it is preferably 100 or more, more preferably 150 or more, still more preferably 200 or more, It is even more preferably 300 or more, particularly preferably 400 or more, most preferably 500 or more, and preferably 1000 or less, more preferably 700 or less. The upper and lower limits can be arbitrarily combined, for example, preferably 100 to 1000, more preferably 150 to 1000, even more preferably 200 to 1000, even more preferably 300 to 700, particularly preferably 400 to 700, and ~700 is most preferred.
　（Ｂ）重合性化合物の炭素数は特に限定されないが、硬化性、テーパ角の観点から、好ましくは７以上、より好ましくは１０以上、さらに好ましくは１５以上、よりさらに好ましくは２０以上、特に好ましくは２５以上であり、また、好ましくは５０以下、より好ましくは４０以下、さらに好ましくは３５以下、特に好ましくは３０以下である。前記上限及び下限は任意に組み合わせることができ、例えば、７～５０が好ましく、１０～５０がより好ましく、１５～４０がさらに好ましく、２０～３５がよりさらに好ましく、２５～３０が特に好ましい。 (B) The number of carbon atoms in the polymerizable compound is not particularly limited, but from the viewpoint of curability and taper angle, it is preferably 7 or more, more preferably 10 or more, even more preferably 15 or more, even more preferably 20 or more, and particularly preferably is 25 or more, and is preferably 50 or less, more preferably 40 or less, still more preferably 35 or less, particularly preferably 30 or less. The upper and lower limits can be arbitrarily combined, for example, preferably 7 to 50, more preferably 10 to 50, even more preferably 15 to 40, even more preferably 20 to 35, particularly preferably 25 to 30.
　本発明の重合性組成物における（Ｂ）重合性化合物の含有量は、重合性組成物の全固形分中に好ましくは５質量％以上、より好ましくは１０質量％以上、さらに好ましくは２０質量％以上、よりさらに好ましくは３０質量％以上、特に好ましくは４０質量％以上、また、好ましくは８０質量％以下、より好ましくは７０質量％以下、さらに好ましくは６０質量％以下、よりさらに好ましくは５５質量％以下、特に好ましくは５０質量％以下である。前記上限及び下限は任意に組み合わせることができ、例えば、５～８０質量％が好ましく、１０～７０質量％がより好ましく、２０～６０質量％がさらに好ましく、３０～５５質量％以がよりさらに好ましく、４０～５０質量％が特に好ましい。前記下限値以上とすることで適切な内部硬化性となる傾向がある。前記上限値以下とすることで現像性が良好となる傾向がある。 The content of the polymerizable compound (B) in the polymerizable composition of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass in the total solid content of the polymerizable composition. Above, even more preferably 30% by mass or more, particularly preferably 40% by mass or more, preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, even more preferably 55% by mass. % or less, particularly preferably 50% by mass or less. The upper and lower limits can be arbitrarily combined, for example, preferably 5 to 80% by mass, more preferably 10 to 70% by mass, even more preferably 20 to 60% by mass, and even more preferably 30 to 55% by mass. , 40 to 50% by mass is particularly preferred. When the content is equal to or more than the lower limit value, there is a tendency for appropriate internal curing properties to be achieved. When the amount is below the upper limit, developability tends to be improved.
［３－１－３］（Ｃ）アルカリ可溶性樹脂
　本発明の重合性組成物は、（Ｃ）アルカリ可溶性樹脂を含有してもよい。アルカリ可溶性樹脂としてはアルカリ現像液で現像可能な樹脂であれば特に限定されない。アルカリ可溶性樹脂としては、カルボキシ基及び／又は水酸基を含有する各種樹脂が挙げられる。その中でも、カルボキシ基を有する樹脂が好ましい。 [3-1-3] (C) Alkali-soluble resin The polymerizable composition of the present invention may contain (C) an alkali-soluble resin. The alkali-soluble resin is not particularly limited as long as it can be developed with an alkaline developer. Examples of the alkali-soluble resin include various resins containing a carboxyl group and/or a hydroxyl group. Among these, resins having a carboxyl group are preferred.
［（ｃ）エチレン性二重結合を有するアルカリ可溶性樹脂］
　本発明の重合性組成物において、（Ｃ）アルカリ可溶性樹脂は、（ｃ）エチレン性二重結合を有するアルカリ可溶性樹脂（以下、「（ｃ）アルカリ可溶性樹脂」と略記する場合がある。）を含むことが好ましい。（ｃ）エチレン性二重結合を有するアルカリ可溶性樹脂を含むことで、感度が高くなる傾向がある。 [(c) Alkali-soluble resin having ethylenic double bond]
In the polymerizable composition of the present invention, (C) the alkali-soluble resin is (c) an alkali-soluble resin having an ethylenic double bond (hereinafter sometimes abbreviated as "(c) alkali-soluble resin"). It is preferable to include. (c) Containing an alkali-soluble resin having an ethylenic double bond tends to increase sensitivity.
　（ｃ）エチレン性二重結合を有するアルカリ可溶性樹脂の具体的構造は特に限定されないが、現像溶解性の観点から、（ｃ１）エポキシ（メタ）アクリレート樹脂及び／又は（ｃ２）アクリル共重合樹脂が好ましく、テーパ形状の観点からは（ｃ１）エポキシ（メタ）アクリレート樹脂がより好ましい。
　以下に、（ｃ１）エポキシ（メタ）アクリレート樹脂について詳述する。 (c) The specific structure of the alkali-soluble resin having an ethylenic double bond is not particularly limited, but from the viewpoint of development solubility, (c1) epoxy (meth)acrylate resin and/or (c2) acrylic copolymer resin Preferably, from the viewpoint of tapered shape, (c1) epoxy (meth)acrylate resin is more preferable.
Below, (c1) epoxy (meth)acrylate resin will be explained in detail.
［（ｃ１）エポキシ（メタ）アクリレート樹脂］
　（ｃ１）エポキシ（メタ）アクリレート樹脂は、エポキシ樹脂にエチレン性不飽和結合（エチレン性二重結合）を有する酸又はエステル化合物を付加し、さらに多塩基酸又はその無水物を付加させた樹脂である。例えば、エポキシ樹脂のエポキシ基に、エチレン性不飽和結合を有する酸のカルボキシ基が開環付加されることにより、エポキシ樹脂にエステル結合（－Ｃ（Ｏ）Ｏ－）を介してエチレン性不飽和結合が付加されると共に、その際生じた水酸基に、多塩基酸無水物の一方のカルボキシ基が付加されたものが挙げられる。また多塩基酸無水物を付加するときに、多価アルコールを同時に添加して付加されたものも挙げられる。さらに、上記反応で得られた樹脂のカルボキシ基に、さらに反応し得る官能基を有する化合物を反応させて得られる樹脂も、（ｃ１）エポキシ（メタ）アクリレート樹脂に含まれる。
　このように、（ｃ１）エポキシ（メタ）アクリレート樹脂は化学構造上、実質的にエポキシ基を有さず、かつ「（メタ）アクリレート」に限定されるものではないが、エポキシ化合物（エポキシ樹脂）が原料であり、かつ、「（メタ）アクリレート」が代表例であるので慣用に従いこのように命名されている。
　また、（ｃ１）エポキシ（メタ）アクリレート系樹脂としては、パターニング性の観点から、主鎖に芳香族環を有するものをより好適に用いることができる。 [(c1) Epoxy (meth)acrylate resin]
(c1) Epoxy (meth)acrylate resin is a resin obtained by adding an acid or ester compound having an ethylenically unsaturated bond (ethylenic double bond) to an epoxy resin, and further adding a polybasic acid or its anhydride. be. For example, when a carboxyl group of an acid having an ethylenically unsaturated bond is ring-opened and added to the epoxy group of an epoxy resin, ethylenically unsaturated Examples include those in which a bond is added and one carboxy group of a polybasic acid anhydride is added to the hydroxyl group generated at that time. Also included are those in which a polyhydric alcohol is added simultaneously when a polybasic acid anhydride is added. Furthermore, a resin obtained by reacting a compound having a functional group that can further react with the carboxy group of the resin obtained by the above reaction is also included in the (c1) epoxy (meth)acrylate resin.
In this way, (c1) epoxy (meth)acrylate resin has a chemical structure that substantially does not have an epoxy group, and is not limited to "(meth)acrylate", but is an epoxy compound (epoxy resin). is the raw material, and "(meth)acrylate" is a typical example, so it is named this way according to common usage.
Moreover, as the epoxy (meth)acrylate resin (c1), from the viewpoint of patterning properties, those having an aromatic ring in the main chain can be more preferably used.
　ここでエポキシ樹脂とは、熱硬化により樹脂を形成する以前の原料化合物をも含めて言うこととし、そのエポキシ樹脂としては、公知のエポキシ樹脂の中から適宜選択して用いることができる。また、エポキシ樹脂は、フェノール性化合物とエピハロヒドリンとを反応させて得られる化合物を用いることができる。フェノール性化合物としては、２価もしくは２価以上のフェノール性水酸基を有する化合物が好ましく、単量体でも重合体でもよい。
　具体的には、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、フェノールノボラックエポキシ樹脂、クレゾールノボラックエポキシ樹脂、ビフェニルノボラックエポキシ樹脂、トリスフェノールエポキシ樹脂、フェノールとジシクロペンタジエンとの重合体のエポキシ化物、ジハイドロオキシルフルオレン型エポキシ樹脂、ジハイドロオキシルアルキレンオキシルフルオレン型エポキシ樹脂、９，９－ビス（４’－ヒドロキシフェニル）フルオレンのジグリシジルエーテル化物、１，１－ビス（４’－ヒドロキシフェニル）アダマンタンのジグリシジルエーテル化物が挙げられ、主鎖に芳香族環を有するものを好適に用いることができる。 Here, the epoxy resin includes a raw material compound before forming a resin by thermosetting, and the epoxy resin can be appropriately selected from known epoxy resins. Further, as the epoxy resin, a compound obtained by reacting a phenolic compound and epihalohydrin can be used. The phenolic compound is preferably a compound having a divalent or divalent or higher phenolic hydroxyl group, and may be a monomer or a polymer.
Specifically, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl novolac epoxy resin, trisphenol epoxy resin, phenol and dicyclopentadiene. epoxidized product of polymer with, dihydroxylfluorene type epoxy resin, dihydroxylalkyleneoxylfluorene type epoxy resin, diglycidyl etherified product of 9,9-bis(4'-hydroxyphenyl)fluorene, 1,1-bis Examples include diglycidyl etherified products of (4'-hydroxyphenyl)adamantane, and those having an aromatic ring in the main chain can be preferably used.
　中でも、硬化膜強度の観点から、ビスフェノールＡ型エポキシ樹脂、フェノールノボラックエポキシ樹脂、クレゾールノボラックエポキシ樹脂、フェノールとジシクロペンタジエンとの重合体のエポキシ化物、９，９－ビス（４’－ヒドロキシフェニル）フルオレンのエポキシ化物が好ましく、ビスフェノールＡ型エポキシ樹脂がさらに好ましい。 Among them, from the viewpoint of cured film strength, bisphenol A type epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, epoxidized product of a polymer of phenol and dicyclopentadiene, 9,9-bis(4'-hydroxyphenyl) Epoxidized products of fluorene are preferred, and bisphenol A epoxy resins are more preferred.
　エチレン性不飽和結合を有する酸としては、例えば、（メタ）アクリル酸、クロトン酸、マレイン酸、フマル酸、シトラコン酸、ペンタエリスリトールトリ（メタ）アクリレート無水コハク酸付加物、ペンタエリスリトールトリ（メタ）アクリレートテトラヒドロ無水フタル酸付加物、ジペンタエリスリトールペンタ（メタ）アクリレート無水コハク酸付加物、ジペンタエリスリトールペンタ（メタ）アクリレート無水フタル酸付加物、ジペンタエリスリトールペンタ（メタ）アクリレートテトラヒドロ無水フタル酸付加物、（メタ）アクリル酸とε－カプロラクトンとの反応生成物が挙げられる。中でも、感度の観点から、（メタ）アクリル酸が好ましい。 Examples of acids having ethylenically unsaturated bonds include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, pentaerythritol tri(meth)acrylate succinic anhydride adduct, and pentaerythritol tri(meth)acrylate. Acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta(meth)acrylate succinic anhydride adduct, dipentaerythritol penta(meth)acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta(meth)acrylate tetrahydrophthalic anhydride adduct , a reaction product of (meth)acrylic acid and ε-caprolactone. Among these, (meth)acrylic acid is preferred from the viewpoint of sensitivity.
　多塩基酸（無水物）としては、例えば、コハク酸、マレイン酸、イタコン酸、フタル酸、テトラヒドロフタル酸、３－メチルテトラヒドロフタル酸、４－メチルテトラヒドロフタル酸、３－エチルテトラヒドロフタル酸、４－エチルテトラヒドロフタル酸、ヘキサヒドロフタル酸、３－メチルヘキサヒドロフタル酸、４－メチルヘキサヒドロフタル酸、３－エチルヘキサヒドロフタル酸、４－エチルヘキサヒドロフタル酸、トリメリット酸、ピロメリット酸、ベンゾフェノンテトラカルボン酸、ビフェニルテトラカルボン酸、及びそれらの無水物が挙げられる。これらは１種を単独でも用いてもよく、２種以上を併用してもよい。これらの中でも、現像後の画素部の残渣低減の観点から、コハク酸無水物、マレイン酸無水物、イタコン酸無水物が好ましく、コハク酸無水物がより好ましい。 Examples of polybasic acids (anhydrides) include succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, -Ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid , benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, and anhydrides thereof. These may be used alone or in combination of two or more. Among these, succinic anhydride, maleic anhydride, and itaconic anhydride are preferred, and succinic anhydride is more preferred, from the viewpoint of reducing residue in pixel areas after development.
　多価アルコールを用いることで、（ｃ１）エポキシ（メタ）アクリレート樹脂の分子量を増大させ、分子中に分岐を導入することが出来、分子量と粘度のバランスをとることができる傾向がある。また、分子中への酸基の導入率を増やすことができ、感度や密着性等のバランスがとれやすい傾向がある。
　多価アルコールとしては、例えば、トリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリメチロールエタン、１，２，３－プロパントリオールが挙げられる。これらは１種を単独で用いてもよく、２種以上を併用してもよい。 By using polyhydric alcohol, it is possible to increase the molecular weight of the epoxy (meth)acrylate resin (c1) and introduce branches into the molecule, which tends to balance the molecular weight and viscosity. Furthermore, the rate of introduction of acid groups into the molecule can be increased, and sensitivity, adhesion, etc. tend to be more balanced.
Examples of the polyhydric alcohol include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. These may be used alone or in combination of two or more.
　（ｃ１）エポキシ（メタ）アクリレート樹脂の酸価は特に限定されないが、１０ｍｇＫＯＨ／ｇ以上が好ましく、２０ｍｇＫＯＨ／ｇ以上がより好ましく、４０ｍｇＫＯＨ／ｇ以上がさらに好ましく、６０ｍｇＫＯＨ／ｇ以上がよりさらに好ましく、また、２００ｍｇＫＯＨ／ｇ以下が好ましく、１８０ｍｇＫＯＨ／ｇ以下がより好ましく、１５０ｍｇＫＯＨ／ｇ以下がさらに好ましく、１２０ｍｇＫＯＨ／ｇ以下がよりさらに好ましく、１００ｍｇＫＯＨ／ｇ以下が特に好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、１０～２００ｍｇＫＯＨ／ｇが好ましく、１０～１８０ｍｇＫＯＨ／ｇがより好ましく、２０～１５０ｍｇＫＯＨ／ｇがさらに好ましく、４０～１２０ｍｇＫＯＨ／ｇがよりさらに好ましく、６０～１００ｍｇＫＯＨ／ｇが特に好ましい。前記下限値以上とすることで残渣が低減しやすい。また、前記上限値以下とすることで現像時の残膜率が良化する傾向がある。 (c1) The acid value of the epoxy (meth)acrylate resin is not particularly limited, but is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, even more preferably 40 mgKOH/g or more, even more preferably 60 mgKOH/g or more, Further, it is preferably 200 mgKOH/g or less, more preferably 180 mgKOH/g or less, even more preferably 150 mgKOH/g or less, even more preferably 120 mgKOH/g or less, and particularly preferably 100 mgKOH/g or less. The upper and lower limits can be arbitrarily combined, for example, preferably 10 to 200 mgKOH/g, more preferably 10 to 180 mgKOH/g, even more preferably 20 to 150 mgKOH/g, even more preferably 40 to 120 mgKOH/g, Particularly preferred is 60 to 100 mgKOH/g. Residues can be easily reduced by setting the amount to be equal to or more than the lower limit value. Further, by setting the amount to be below the upper limit, the residual film rate during development tends to improve.
　（ｃ１）エポキシ（メタ）アクリレート樹脂の重量平均分子量（Ｍｗ）は特に限定されないが、好ましくは１０００以上、より好ましくは２０００以上、さらに好ましくは３０００以上、よりさらに好ましくは４０００以上、ことさら好ましくは５０００以上、特に好ましくは６０００以上、最も好ましくは７０００以上であり、また、好ましくは３００００以下、より好ましくは２００００以下、さらに好ましくは１５０００以下、特に好ましくは１００００以下である。前記上限及び下限は任意に組み合わせることができ、１０００～３００００が好ましく、２０００～３００００がより好ましく、３０００～２００００がさらに好ましく、４０００～２００００がよりさらに好ましく、５０００～１５０００がことさら好ましく、６０００～１５０００が特に好ましく、７０００～１００００が最も好ましい。前記下限値以上とすることで現像時の残膜率が良化する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。 (c1) The weight average molecular weight (Mw) of the epoxy (meth)acrylate resin is not particularly limited, but is preferably 1,000 or more, more preferably 2,000 or more, even more preferably 3,000 or more, even more preferably 4,000 or more, and even more preferably 5,000. Above, it is particularly preferably 6,000 or more, most preferably 7,000 or more, and is preferably 30,000 or less, more preferably 20,000 or less, still more preferably 15,000 or less, particularly preferably 10,000 or less. The upper and lower limits can be arbitrarily combined and are preferably 1,000 to 30,000, more preferably 2,000 to 30,000, even more preferably 3,000 to 20,000, even more preferably 4,000 to 20,000, even more preferably 5,000 to 15,000, and even more preferably 6,000 to 15,000. is particularly preferred, and 7,000 to 10,000 is most preferred. When the amount is equal to or more than the lower limit, the remaining film rate during development tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
　（Ｃ）アルカリ可溶性樹脂が（ｃ１）エポキシ（メタ）アクリレート樹脂を含む場合、（Ｃ）アルカリ可溶性樹脂に含まれる（ｃ１）エポキシ（メタ）アクリレート樹脂の含有量は特に限定されないが、３０質量％以上が好ましく、５０質量％以上がより好ましく、７０質量％以上がさらに好ましく、８０質量％以上がよりさらに好ましく、９０質量％以上が特に好ましく、また、通常１００質量％以下である。前記上限及び下限は任意に組み合わせることができ。例えば、３０～１００質量％が好ましく、５０～１００質量％がより好ましく、７０～１００質量％がさらに好ましく、８０～１００質量％がよりさらに好ましく、９０～１００質量％が特に好ましい。前記下限値以上とすることでテーパ形状が良化する傾向がある。 When the (C) alkali-soluble resin includes (c1) an epoxy (meth)acrylate resin, the content of the (c1) epoxy (meth)acrylate resin contained in the (C) alkali-soluble resin is not particularly limited, but is 30% by mass. The content is preferably at least 50% by mass, more preferably at least 70% by mass, even more preferably at least 80% by mass, particularly preferably at least 90% by mass, and usually at most 100% by mass. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 30 to 100% by weight, more preferably 50 to 100% by weight, even more preferably 70 to 100% by weight, even more preferably 80 to 100% by weight, and particularly preferably 90 to 100% by weight. The taper shape tends to be improved by making it equal to or more than the lower limit value.
　（ｃ１）エポキシ（メタ）アクリレート樹脂は、従来公知の方法により合成することができる。具体的には、前記エポキシ樹脂を有機溶剤に溶解させ、触媒と熱重合禁止剤の共存下、前記エチレン性不飽和結合を有する酸又はエステル化合物を加えて付加反応させ、さらに多塩基酸又はその無水物を加えて反応を続ける方法を用いることができる。 (c1) Epoxy (meth)acrylate resin can be synthesized by a conventionally known method. Specifically, the epoxy resin is dissolved in an organic solvent, the acid or ester compound having an ethylenically unsaturated bond is added thereto in the coexistence of a catalyst and a thermal polymerization inhibitor, and then the polybasic acid or its A method can be used in which the reaction is continued by adding an anhydride.
　有機溶剤としては、例えば、メチルエチルケトン、シクロヘキサノン、ジエチレングリコールエチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテートが挙げられる。触媒としては、例えば、トリエチルアミン、ベンジルジメチルアミン、トリベンジルアミン等の第３級アミン類；テトラメチルアンモニウムクロライド、メチルトリエチルアンモニウムクロライド、テトラエチルアンモニウムクロライド、テトラブチルアンモニウムクロライド、トリメチルベンジルアンモニウムクロライド等の第４級アンモニウム塩類；トリフェニルホスフィン等の燐化合物；トリフェニルスチビンなどのスチビン類；が挙げられる。熱重合禁止剤としては、例えば、ハイドロキノン、ハイドロキノンモノメチルエーテル、メチルハイドロキノンが挙げられる。
　これらは１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of the organic solvent include methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate. Examples of the catalyst include tertiary amines such as triethylamine, benzyldimethylamine, and tribenzylamine; Examples include class ammonium salts; phosphorus compounds such as triphenylphosphine; and stibines such as triphenylstibine. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, and methyl hydroquinone.
These may be used alone or in combination of two or more.
　エチレン性不飽和結合を有する酸又はエステル化合物は、エポキシ樹脂のエポキシ基の１化学当量に対して、好ましくは０．７～１．３化学当量、より好ましくは０．９～１．１化学当量となる量を用いることができる。付加反応時の温度は、好ましくは６０～１５０℃、より好ましくは８０～１２０℃である。多塩基酸（無水物）は、付加反応で生じた水酸基の１化学当量に対して、好ましくは０．１～１．２化学当量、より好ましくは０．２～１．１化学当量となる量を用いることができる。 The acid or ester compound having an ethylenically unsaturated bond is preferably 0.7 to 1.3 chemical equivalents, more preferably 0.9 to 1.1 chemical equivalents per chemical equivalent of the epoxy group of the epoxy resin. The amount can be used. The temperature during the addition reaction is preferably 60 to 150°C, more preferably 80 to 120°C. The polybasic acid (anhydride) is preferably used in an amount of 0.1 to 1.2 chemical equivalents, more preferably 0.2 to 1.1 chemical equivalents, per 1 chemical equivalent of hydroxyl group generated in the addition reaction. can be used.
　（ｃ１）エポキシ（メタ）アクリレート樹脂は、テーパ形状、残膜率の観点から、（ｃ１－１）下記一般式（ｉ）で表される部分構造を含むエポキシ（メタ）アクリレート樹脂（以下、「（ｃ１－１）エポキシ（メタ）アクリレート樹脂」と称する場合がある。）、（ｃ１－２）下記一般式（ｉｉ）で表される部分構造を含むエポキシ（メタ）アクリレート樹脂（以下、「（ｃ１－２）エポキシ（メタ）アクリレート樹脂」と称する場合がある。）、及び（ｃ１－３）下記一般式（ｉｉｉ）で表される部分構造を含むエポキシ（メタ）アクリレート樹脂（以下、「（ｃ１－３）エポキシ（メタ）アクリレート樹脂」と称する場合がある。）からなる群から選ばれる少なくとも１種を含有することが好ましい。 (c1) Epoxy (meth)acrylate resin (hereinafter referred to as " (c1-1) Epoxy (meth)acrylate resin"), (c1-2) Epoxy (meth)acrylate resin containing a partial structure represented by the following general formula (ii) (hereinafter referred to as "( (c1-2) epoxy (meth)acrylate resin"), and (c1-3) epoxy (meth)acrylate resin containing a partial structure represented by the following general formula (iii) (hereinafter referred to as (c1-3) epoxy (meth)acrylate resin).
　（ｃ１）エポキシ（メタ）アクリレート樹脂は、これらの中でも現像性、テーパ形状の観点から、（ｃ１－１）下記一般式（ｉ）で表される部分構造を含むエポキシ（メタ）アクリレート樹脂を含むことが好ましく、（ｃ１－１）下記一般式（ｉ）で表される部分構造を含むエポキシ（メタ）アクリレート樹脂であることがより好ましい。 (c1) Epoxy (meth)acrylate resin includes (c1-1) epoxy (meth)acrylate resin containing a partial structure represented by the following general formula (i) from the viewpoint of developability and tapered shape. (c1-1) is more preferably an epoxy (meth)acrylate resin containing a partial structure represented by the following general formula (i).
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　式（ｉ）中、Ｒａは水素原子又はメチル基を表し、Ｒｂは置換基を有していてもよい２価の炭化水素基を表す。式（ｉ）中のベンゼン環は、さらに任意の置換基により置換されていてもよい。＊は結合手を表す。 In formula (i), R a represents a hydrogen atom or a methyl group, and R b represents a divalent hydrocarbon group which may have a substituent. The benzene ring in formula (i) may be further substituted with any substituent. * represents a bond.
　前記式（ｉ）において、Ｒｂは置換基を有していてもよい２価の炭化水素基を表す。２価の炭化水素基としては、２価の脂肪族基、２価の芳香族環基、１以上の２価の脂肪族基と１以上の２価の芳香族環基とを連結した基が挙げられる。 In the formula (i), R b represents a divalent hydrocarbon group which may have a substituent. Examples of divalent hydrocarbon groups include divalent aliphatic groups, divalent aromatic ring groups, and groups in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are connected. Can be mentioned.
　２価の脂肪族基は、直鎖状、分岐鎖状、環状のものが挙げられる。これらの中でも現像溶解性の観点からは直鎖状のものが好ましく、一方で露光部への現像液の浸透低減の観点からは環状のものが好ましい。その炭素数は通常１以上であり、３以上が好ましく、６以上がより好ましく、また、２０以下が好ましく、１５以下がより好ましく、１０以下がさらに好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、１～２０が好ましく、３～１５がより好ましく、６～１０がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。 Examples of divalent aliphatic groups include linear, branched, and cyclic groups. Among these, linear ones are preferable from the viewpoint of development solubility, while annular ones are preferable from the viewpoint of reducing permeation of the developer into the exposed area. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The upper and lower limits can be arbitrarily combined, and are preferably from 1 to 20, more preferably from 3 to 15, even more preferably from 6 to 10. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
　２価の直鎖状脂肪族基としては、例えば、メチレン基、エチレン基、ｎ－プロピレン基、ｎ－ブチレン基、ｎ－ヘキシレン基、ｎ－ヘプチレン基が挙げられる。これらの中でも残渣低減の観点から、メチレン基が好ましい。
　２価の分岐鎖状脂肪族基としては、例えば、前述の２価の直鎖状脂肪族基に、側鎖としてメチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基を有する構造が挙げられる。
　２価の環状の脂肪族基が有する環の数は特に限定されないが、通常１以上、２以上が好ましく、また、１０以下が好ましく、５以下がより好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、１～１０が好ましく、１～５がより好ましく、２～５がさらに好ましい。前記下限値以上とすることで残膜率が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。２価の環状の脂肪族基としては、例えば、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環の環から水素原子を２つ除した基が挙げられる。これらの中でも現像密着性の観点から、アダマンタン環から水素原子を２つ除した基が好ましい。 Examples of the divalent linear aliphatic group include methylene group, ethylene group, n-propylene group, n-butylene group, n-hexylene group, and n-heptylene group. Among these, methylene groups are preferred from the viewpoint of reducing residue.
Examples of the divalent branched aliphatic group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group as a side chain in addition to the above-mentioned divalent linear aliphatic group. Examples include structures having a group, a sec-butyl group, and a tert-butyl group.
The number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, preferably 10 or less, and more preferably 5 or less. The upper and lower limits can be arbitrarily combined, and are preferably from 1 to 10, more preferably from 1 to 5, even more preferably from 2 to 5. There is a tendency for the residual film rate to improve by setting it as the lower limit value or more. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced. Examples of the divalent cyclic aliphatic group include groups obtained by removing two hydrogen atoms from a cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, and adamantane ring. Among these, from the viewpoint of development adhesion, a group obtained by removing two hydrogen atoms from an adamantane ring is preferable.
　２価の脂肪族基が有していてもよい置換基としては、例えば、メトキシ基、エトキシ基等の炭素数１～５のアルコキシ基；水酸基；ニトロ基；シアノ基；カルボキシ基が挙げられ、合成容易性の観点から、無置換が好ましい。 Examples of substituents that the divalent aliphatic group may have include alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; carboxy group; From the viewpoint of ease of synthesis, non-substitution is preferred.
　２価の芳香族環基としては、２価の芳香族炭化水素環基及び２価の芳香族複素環基が挙げられる。その炭素数は通常４以上であり、５以上が好ましく、６以上がより好ましく、また、２０以下が好ましく、１５以下がより好ましく、１０以下がさらに好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、４～２０が好ましく、５～１５がより好ましく、６～１０がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。 Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The upper and lower limits can be arbitrarily combined, for example, preferably 4 to 20, more preferably 5 to 15, and even more preferably 6 to 10. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
　２価の芳香族炭化水素環基における芳香族炭化水素環としては、単環であっても縮合環であってもよい。２価の芳香族炭化水素環基としては、例えば、２個の遊離原子価を有する、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環が挙げられる。
　２価の芳香族複素環基における芳香族複素環としては、単環であっても縮合環であってもよい。２価の芳香族複素環基としては、例えば、２個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環が挙げられる。これらの中でも光硬化性の観点から、２個の遊離原子価を有するベンゼン環、ナフタレン環が好ましく、２個の遊離原子価を有するベンゼン環がより好ましい。 The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a fused ring. Examples of the divalent aromatic hydrocarbon ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, Examples include triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.
The aromatic heterocycle in the divalent aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the divalent aromatic heterocyclic group include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, and indole ring having two free valences. ring, carbazole ring, pyrroloimidazole ring, pyrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, Examples include pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring. Among these, from the viewpoint of photocurability, benzene rings and naphthalene rings having two free valences are preferred, and benzene rings having two free valences are more preferred.
　２価の芳香族環基が有していてもよい置換基としては、例えば、ヒドロキシ基、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシ基、グリシジルエーテル基が挙げられる。これらの中でも硬化性の観点から、無置換が好ましい。 Examples of the substituents that the divalent aromatic ring group may have include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group, and a glycidyl ether group. Among these, from the viewpoint of curability, non-substitution is preferred.
　１以上の２価の脂肪族基と１以上の２価の芳香族環基とを連結した基としては、前述の２価の脂肪族基を１以上と、前述の２価の芳香族環基を１以上とを連結した基が挙げられる。
　２価の脂肪族基の数は特に限定されないが、通常１以上、２以上が好ましく、また、１０以下が好ましく、５以下がより好ましく、３以下がさらに好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、１～１０が好ましく、１～５がより好ましく、２～３がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。
　２価の芳香族環基の数は特に限定されないが、通常１以上、２以上が好ましく、また、１０以下が好ましく、５以下がより好ましく、３以下がさらに好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、１～１０が好ましく、１～５がより好ましく、２～３がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。 The group linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups includes one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic ring group. Examples include groups in which one or more are linked.
The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. The upper and lower limits can be arbitrarily combined, and are preferably from 1 to 10, more preferably from 1 to 5, and even more preferably from 2 to 3. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. The upper and lower limits can be arbitrarily combined, and are preferably from 1 to 10, more preferably from 1 to 5, and even more preferably from 2 to 3. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
　１以上の２価の脂肪族基と１以上の２価の芳香族環基とを連結した基としては、例えば、下記式（ｉ－Ａ）～（ｉ－Ｆ）で表される基が挙げられる。これらの中でも骨格の剛直性と膜の疎水化の観点から、下記式（ｉ－Ａ）で表される基が好ましい。化学式中の＊は結合手を表す。 Examples of groups that connect one or more divalent aliphatic groups and one or more divalent aromatic ring groups include groups represented by the following formulas (i-A) to (i-F). It will be done. Among these, a group represented by the following formula (i-A) is preferred from the viewpoint of skeletal rigidity and membrane hydrophobization. * in the chemical formula represents a bond.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　前記のとおり、式（ｉ）中のベンゼン環は、さらに任意の置換基により置換されていてもよい。式（ｉ）中のベンゼン環の置換基としては、例えば、ヒドロキシ基、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシ基が挙げられる。置換基の数も特に限定されず、化学的に許容される限りにおいて、１つでもよいし、２つ以上でもよい。
　硬化性の観点から、無置換が好ましい。 As mentioned above, the benzene ring in formula (i) may be further substituted with any substituent. Examples of the substituent on the benzene ring in formula (i) include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is not particularly limited either, and may be one or two or more as long as it is chemically permissible.
From the viewpoint of curability, no substitution is preferred.
　前記式（ｉ）で表される部分構造は、現像溶解性の観点から、下記式（ｉ－１）で表される部分構造であることが好ましい。 From the viewpoint of development solubility, the partial structure represented by the formula (i) is preferably a partial structure represented by the following formula (i-1).
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　式（ｉ－１）中、Ｒａ及びＲｂは、前記式（ｉ）のものと同義である。Ｒｃは置換基を有していてもよい炭素数１～４の２価の炭化水素基を表す。＊は結合手を表す。式（ｉ－１）中のベンゼン環は、さらに任意の置換基により置換されていてもよい。 In formula (i-1), R a and R b have the same meanings as in formula (i) above. R c represents a divalent hydrocarbon group having 1 to 4 carbon atoms which may have a substituent. * represents a bond. The benzene ring in formula (i-1) may be further substituted with any substituent.
　前記一般式（ｉ－１）において、Ｒｃは置換基を有していてもよい炭素数１～４の２価の炭化水素基を表す。２価の炭化水素基としては、アルキレン基、アルケニレン基が挙げられる。 In the general formula (i-1), R c represents a divalent hydrocarbon group having 1 to 4 carbon atoms which may have a substituent. Examples of the divalent hydrocarbon group include an alkylene group and an alkenylene group.
　アルキレン基は直鎖でも、分岐鎖でもよいが、現像溶解性の観点から直鎖であることが好ましい。その炭素数は特に限定されないが、通常１以上、２以上が好ましく、また、４以下が好ましく、３以下がより好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、１～４が好ましく、１～３がより好ましく、２～３がさらに好ましい。前記下限値以上とすることで残膜率が高くなる傾向がある。また、前記上限値以下とすることで焼成時、焼成後のアウトガス発生量が少なくなる傾向がある。 The alkylene group may be linear or branched, but is preferably linear from the viewpoint of development solubility. The number of carbon atoms is not particularly limited, but is usually 1 or more, preferably 2 or more, preferably 4 or less, and more preferably 3 or less. The upper and lower limits can be arbitrarily combined, for example, preferably 1 to 4, more preferably 1 to 3, and even more preferably 2 to 3. When the amount is equal to or more than the lower limit, the remaining film rate tends to increase. Further, by setting the amount to be less than or equal to the upper limit value, the amount of outgas generated during and after firing tends to be reduced.
　アルキレン基の具体例としては、メチレン基、エチレン基、プロピレン基、ブチレン基が挙げられ、アウトガス低減の観点から、メチレン基又はエチレン基が好ましく、エチレン基がより好ましい。 Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, and a butylene group, and from the viewpoint of reducing outgas, a methylene group or an ethylene group is preferable, and an ethylene group is more preferable.
　アルケニレン基は直鎖でも、分岐鎖でもよいが、現像溶解性の観点から直鎖であることが好ましい。その炭素数は特に限定されないが、通常２以上であり、また４以下が好ましく、３以下がより好ましい。例えば、２～４が好ましく、２～３がより好ましい。前記下限値以上とすることで残膜率が高くなる傾向がある。また、前記上限値以下とすることで焼成時、焼成後のアウトガス発生量が少なくなる傾向がある。 The alkenylene group may be linear or branched, but is preferably linear from the viewpoint of development solubility. The number of carbon atoms is not particularly limited, but is usually 2 or more, preferably 4 or less, and more preferably 3 or less. For example, 2 to 4 are preferred, and 2 to 3 are more preferred. When the amount is equal to or more than the lower limit, the remaining film rate tends to increase. Further, by setting the amount to be less than or equal to the upper limit value, the amount of outgas generated during and after firing tends to be reduced.
　アルケニレン基の具体例としては、エテニレン基、プロペニレン基、ブチレニレン基が挙げられ、アウトガスの観点から、エテニレン基が好ましい。 Specific examples of the alkenylene group include ethenylene group, propenylene group, and butylene group, and ethenylene group is preferable from the viewpoint of outgas.
　炭素数１～４の２価の炭化水素基が有していてもよい置換基は特に限定されないが、例えば、ハロゲン原子、アルコキシ基、ベンゾイル基、水酸基が挙げられ、合成の容易さの観点からは無置換が好ましい。 The substituent that the divalent hydrocarbon group having 1 to 4 carbon atoms may have is not particularly limited, but examples thereof include a halogen atom, an alkoxy group, a benzoyl group, and a hydroxyl group. is preferably unsubstituted.
　これらの中でもアウトガス低減の観点から、Ｒｃが炭素数１～４の２価のアルキレン基であることが好ましく、メチレン基又はエチレン基であることがより好ましく、エチレン基であることがさらに好ましい。 Among these, from the viewpoint of reducing outgas, R c is preferably a divalent alkylene group having 1 to 4 carbon atoms, more preferably a methylene group or an ethylene group, and even more preferably an ethylene group.
　（ｃ１－１）エポキシ（メタ）アクリレート樹脂１分子中に含まれる、前記式（ｉ－１）で表される部分構造は、１種でも２種以上でもよい。 (c1-1) The partial structure represented by the above formula (i-1) contained in one molecule of the epoxy (meth)acrylate resin may be one type or two or more types.
　（ｃ１－１）エポキシ（メタ）アクリレート樹脂１分子中に含まれる、前記式（ｉ）で表される部分構造の数は特に限定されないが、１以上が好ましく、２以上がより好ましく、３以上がさらに好ましく、また、１０以下が好ましく、８以下がさらに好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、１～１０が好ましく、２～１０がより好ましく、３～８がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。 (c1-1) The number of partial structures represented by the formula (i) contained in one molecule of epoxy (meth)acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 2 or more, and 3 or more. is more preferable, 10 or less is preferable, and 8 or less is even more preferable. The upper and lower limits can be arbitrarily combined, and are preferably from 1 to 10, more preferably from 2 to 10, and even more preferably from 3 to 8. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
　（ｃ１－１）エポキシ（メタ）アクリレート樹脂１分子中に含まれる、前記式（ｉ－１）で表される部分構造の数は特に限定されないが、１以上が好ましく、２以上がより好ましく、３以上がさらに好ましく、また、１０以下が好ましく、８以下がさらに好ましい。
前記上限及び下限は任意に組み合わせることができ、例えば、１～１０が好ましく、２～１０がより好ましく、３～８がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。 (c1-1) The number of partial structures represented by the formula (i-1) contained in one molecule of epoxy (meth)acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 2 or more, It is more preferably 3 or more, more preferably 10 or less, and even more preferably 8 or less.
The upper and lower limits can be arbitrarily combined, and are preferably from 1 to 10, more preferably from 2 to 10, and even more preferably from 3 to 8. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
　以下に（ｃ１－１）エポキシ（メタ）アクリレート樹脂の具体例を挙げる。 Specific examples of (c1-1) epoxy (meth)acrylate resin are listed below.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　別の態様として、（ｃ１）エポキシ（メタ）アクリレート樹脂は、現像密着性の観点から、下記式（ｉｉ）で表される部分構造を含む（ｃ１－２）エポキシ（メタ）アクリレート樹脂であることが好ましい。 In another embodiment, the (c1) epoxy (meth)acrylate resin is (c1-2) an epoxy (meth)acrylate resin containing a partial structure represented by the following formula (ii) from the viewpoint of development adhesion. is preferred.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　式（ｉｉ）中、Ｒｄは各々独立に、水素原子又はメチル基を表す。Ｒｅは、環状炭化水素基を側鎖として有する２価の炭化水素基を表す。＊は結合手を表す。 In formula (ii), R d each independently represents a hydrogen atom or a methyl group. R e represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. * represents a bond.
　前記式（ｉｉ）において、Ｒｅは、環状炭化水素基を側鎖として有する２価の炭化水素基を表す。
　環状炭化水素基としては、脂肪族環基又は芳香族環基が挙げられる。 In the formula (ii), R e represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
　脂肪族環基が有する環の数は特に限定されないが、通常１以上、２以上が好ましく、また、１０以下が好ましく、５以下がより好ましく、３以下がさらに好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、１～１０が好ましく、１～５がより好ましく、２～３がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。
　脂肪族環基の炭素数は通常４以上であり、６以上が好ましく、８以上がより好ましく、また、４０以下が好ましく、３０以下がより好ましく、２０以下がさらに好ましく、１５以下が特に好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、４～４０が好ましく、４～３０がより好ましく、６～２０がさらに好ましく、８～１５が特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。
　脂肪族環基における脂肪族環しては、例えば、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環が挙げられる。これらの中でも現像密着性の観点から、アダマンタン環が好ましい。 The number of rings that the aliphatic cyclic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. The upper and lower limits can be arbitrarily combined, and are preferably from 1 to 10, more preferably from 1 to 5, and even more preferably from 2 to 3. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
The number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and particularly preferably 15 or less. The upper and lower limits can be arbitrarily combined, for example, preferably 4 to 40, more preferably 4 to 30, even more preferably 6 to 20, particularly preferably 8 to 15. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
Examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. Among these, an adamantane ring is preferred from the viewpoint of development adhesion.
　芳香族環基が有する環の数は特に限定されないが、通常１以上、２以上が好ましく、３以上がより好ましく、また、１０以下が好ましく、５以下がより好ましく、４以下がさらに好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、１～１０が好ましく、２～５がより好ましく、３～４がさらに好ましい。前記下限値以上とすることで残渣が低減する傾向がある。また、前記上限値以下とすることで現像密着性が向上する傾向がある。
　芳香族環基としては、芳香族炭化水素環基、芳香族複素環基が挙げられる。芳香族環基の炭素数は通常４以上であり、６以上が好ましく、８以上がより好ましく、１０以上がよりさらに好ましく、１２以上が特に好ましく、また、４０以下が好ましく、３０以下がより好ましく、２０以下がさらに好ましく、１５以下が特に好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、４～４０が好ましく、６～４０がより好ましく、８～３０がさらに好ましく、１０～２０がよりさらに好ましく、１２～１５が特に好ましい。前記下限値以上とすることで残渣が低減する傾向がある。また、前記上限値以下とすることで現像密着性が向上する傾向がある。
　芳香族環基における芳香族環としては、例えば、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環が挙げられる。これらの中でもパターニング特性の観点から、フルオレン環が好ましい。 The number of rings that the aromatic ring group has is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and preferably 10 or less, more preferably 5 or less, and even more preferably 4 or less. The upper and lower limits can be arbitrarily combined, and are preferably from 1 to 10, more preferably from 2 to 5, and even more preferably from 3 to 4. There is a tendency for the amount of residue to be reduced by setting the amount to be equal to or more than the lower limit value. Further, by setting the amount to be less than or equal to the upper limit value, the development adhesion tends to improve.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, even more preferably 10 or more, particularly preferably 12 or more, and preferably 40 or less, more preferably 30 or more. , 20 or less is more preferable, and 15 or less is particularly preferable. The upper and lower limits can be arbitrarily combined, for example, preferably 4 to 40, more preferably 6 to 40, even more preferably 8 to 30, even more preferably 10 to 20, and particularly preferably 12 to 15. There is a tendency for the amount of residue to be reduced by setting the amount to be equal to or more than the lower limit value. Further, by setting the amount to be less than or equal to the upper limit value, the development adhesion tends to improve.
Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring. Examples include rings. Among these, fluorene rings are preferred from the viewpoint of patterning properties.
　環状炭化水素基を側鎖として有する２価の炭化水素基における、２価の炭化水素基は特に限定されないが、例えば、２価の脂肪族基、２価の芳香族環基、１以上の２価の脂肪族基と１以上の２価の芳香族環基とを連結した基が挙げられる。 The divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, but includes, for example, a divalent aliphatic group, a divalent aromatic ring group, and one or more divalent hydrocarbon groups. Examples include groups in which a valent aliphatic group and one or more divalent aromatic ring groups are connected.
　２価の脂肪族基は、直鎖状、分岐鎖状、環状のものが挙げられる。これらの中でも現像溶解性の観点からは直鎖状のものが好ましく、一方で露光部への現像液の浸透低減の観点からは環状のものが好ましい。その炭素数は通常１以上であり、３以上が好ましく、６以上がより好ましく、また、２５以下が好ましく、２０以下がより好ましく、１５以下がさらに好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、１～２５が好ましく、３～２０がより好ましく、６～１５がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。 Examples of divalent aliphatic groups include linear, branched, and cyclic groups. Among these, linear ones are preferable from the viewpoint of development solubility, while annular ones are preferable from the viewpoint of reducing permeation of the developer into the exposed area. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 25 or less, more preferably 20 or less, and even more preferably 15 or less. The upper and lower limits can be arbitrarily combined, for example, preferably 1 to 25, more preferably 3 to 20, and even more preferably 6 to 15. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
　２価の直鎖状脂肪族基としては、例えば、メチレン基、エチレン基、ｎ－プロピレン基、ｎ－ブチレン基、ｎ－ヘキシレン基、ｎ－ヘプチレン基が挙げられる。これらの中でも残渣の観点から、メチレン基が好ましい。
　２価の分岐鎖状脂肪族基としては、例えば、前述の２価の直鎖状脂肪族基に、側鎖としてメチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基を有する構造が挙げられる。
　２価の環状の脂肪族基が有する環の数は特に限定されないが、通常１以上、２以上が好ましく、また、１０以下が好ましく、５以下がより好ましく、３以下がさらに好ましい。
前記上限及び下限は任意に組み合わせることができ、例えば、１～１０が好ましく、１～５がより好ましく、２～３がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。
　２価の環状の脂肪族基としては、例えば、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環から水素原子を２つ除した基が挙げられる。これらの中でも現像密着性の観点から、アダマンタン環から水素原子を２つ除した基が好ましい。 Examples of the divalent linear aliphatic group include methylene group, ethylene group, n-propylene group, n-butylene group, n-hexylene group, and n-heptylene group. Among these, methylene group is preferred from the viewpoint of residue.
Examples of the divalent branched aliphatic group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group as a side chain in addition to the above-mentioned divalent linear aliphatic group. Examples include structures having a group, a sec-butyl group, and a tert-butyl group.
The number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less.
The upper and lower limits can be arbitrarily combined, for example, preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 3. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
Examples of the divalent cyclic aliphatic group include groups obtained by removing two hydrogen atoms from a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. Among these, from the viewpoint of development adhesion, a group obtained by removing two hydrogen atoms from an adamantane ring is preferable.
　２価の脂肪族基が有していてもよい置換基としては、例えば、メトキシ基、エトキシ基等の炭素数１～５のアルコキシ基；水酸基；ニトロ基；シアノ基；カルボキシ基が挙げられ、合成容易性の観点から、無置換が好ましい。 Examples of substituents that the divalent aliphatic group may have include alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; carboxy group; From the viewpoint of ease of synthesis, non-substitution is preferred.
　２価の芳香族環基としては、２価の芳香族炭化水素環基及び２価の芳香族複素環基が挙げられる。その炭素数は通常４以上であり、５以上が好ましく、６以上がより好ましく、また、３０以下が好ましく、２０以下がより好ましく、１５以下がさらに好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、４～３０が好ましく、５～２０がより好ましく、６～１５がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。 Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. The upper and lower limits can be arbitrarily combined, for example, preferably 4 to 30, more preferably 5 to 20, and even more preferably 6 to 15. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
　２価の芳香族炭化水素環基における芳香族炭化水素環としては、単環であっても縮合環であってもよい。２価の芳香族炭化水素環基としては、例えば、２個の遊離原子価を有する、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環が挙げられる。
　２価の芳香族複素環基における芳香族複素環としては、単環であっても縮合環であってもよい。２価の芳香族複素環基としては、例えば、２個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環が挙げられる。これらの中でも光硬化性の観点から、２個の遊離原子価を有するベンゼン環、ナフタレン環が好ましく、２個の遊離原子価を有するベンゼン環がより好ましい。 The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a fused ring. Examples of the divalent aromatic hydrocarbon ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, Examples include triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.
The aromatic heterocycle in the divalent aromatic heterocyclic group may be a single ring or a condensed ring. Examples of divalent aromatic heterocyclic groups include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, and indole ring, each having two free valences. ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, Examples include pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring. Among these, from the viewpoint of photocurability, benzene rings and naphthalene rings having two free valences are preferred, and benzene rings having two free valences are more preferred.
　２価の芳香族環基が有していてもよい置換基としては、例えば、ヒドロキシ基、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシ基が挙げられる。これらの中でも硬化性の観点から、無置換が好ましい。 Examples of the substituents that the divalent aromatic ring group may have include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Among these, from the viewpoint of curability, non-substitution is preferred.
　１以上の２価の脂肪族基と１以上の２価の芳香族環基とを連結した基としては、前述の２価の脂肪族基を１以上と、前述の２価の芳香族環基を１以上とを連結した基が挙げられる。
　２価の脂肪族基の数は特に限定されないが、通常１以上、２以上が好ましく、また、１０以下が好ましく、５以下がより好ましく、３以下がさらに好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、１～１０が好ましく、１～５がより好ましく、２～３がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。
　２価の芳香族環基の数は特に限定されないが、通常１以上、２以上が好ましく、また、１０以下が好ましく、５以下がより好ましく、３以下がさらに好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、１～１０が好ましく、１～５がより好ましく、２～３がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。 The group linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups includes one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic ring group. Examples include groups in which one or more are linked.
The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. The upper and lower limits can be arbitrarily combined, for example, preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 3. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. The upper and lower limits can be arbitrarily combined, for example, preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 3. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
　１以上の２価の脂肪族基と１以上の２価の芳香族環基とを連結した基としては、例えば、前記式（ｉ－Ａ）～（ｉ－Ｆ）で表される基等が挙げられる。これらの中でも残渣低減の観点から、前記式（ｉ－Ｃ）で表される基が好ましい。 Examples of groups that connect one or more divalent aliphatic groups and one or more divalent aromatic ring groups include groups represented by the above formulas (i-A) to (i-F). Can be mentioned. Among these, from the viewpoint of reducing residue, the group represented by the above formula (iC) is preferable.
　これらの２価の炭化水素基に対して、側鎖である環状炭化水素基の結合態様は特に限定されないが、例えば、脂肪族基や芳香族環基の水素原子１つを側鎖で置換した態様や、脂肪族基の炭素原子の１つを含めて側鎖である環状炭化水素基を構成した態様が挙げられる。 The bonding mode of the cyclic hydrocarbon group as a side chain to these divalent hydrocarbon groups is not particularly limited, but for example, one hydrogen atom of an aliphatic group or an aromatic ring group is replaced with a side chain. Examples include embodiments in which a cyclic hydrocarbon group, which is a side chain, includes one carbon atom of an aliphatic group.
　前記式（ｉｉ）で表される部分構造は、現像密着性の観点から、下記式（ｉｉ－１）で表される部分構造であることが好ましい。 From the viewpoint of development adhesion, the partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-1).
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
　式（ｉｉ－１）中、Ｒｄは前記式（ｉｉ）と同義である。Ｒｆは、置換基を有していてもよい１価の環状炭化水素基を表す。ｎは１以上の整数である。式（ｉｉ－１）中のベンゼン環は、さらに任意の置換基により置換されていてもよい。＊は結合手を表す。 In formula (ii-1), R d has the same meaning as in formula (ii) above. R f represents a monovalent cyclic hydrocarbon group which may have a substituent. n is an integer of 1 or more. The benzene ring in formula (ii-1) may be further substituted with any substituent. * represents a bond.
（Ｒｆ）
　前記式（ｉｉ－１）において、Ｒｆは、置換基を有していてもよい１価の環状炭化水素基を表す。
　環状炭化水素基としては、脂肪族環基又は芳香族環基が挙げられる。 (R f )
In the formula (ii-1), R f represents a monovalent cyclic hydrocarbon group which may have a substituent.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
　脂肪族環基が有する環の数は特に限定されないが、通常１以上、２以上が好ましく、また、６以下が好ましく、４以下がより好ましく、３以下がさらに好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、１～６が好ましく、１～４がより好ましく、２～３がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。
　また、脂肪族環基の炭素数は通常４以上であり、６以上が好ましく、８以上がより好ましく、また、４０以下が好ましく、３０以下がより好ましく、２０以下がさらに好ましく、１５以下が特に好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、４～４０が好ましく、４～３０がより好ましく、６～２０がさらに好ましく、８～１５が特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。
　脂肪族環基における脂肪族環としては、例えば、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環が挙げられる。これらの中でも現像密着性の観点から、アダマンタン環が好ましい。 The number of rings that the aliphatic cyclic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less. The upper and lower limits can be arbitrarily combined, and for example, 1 to 6 are preferable, 1 to 4 are more preferable, and 2 to 3 are still more preferable. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
The number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and especially 15 or less. preferable. The upper and lower limits can be arbitrarily combined, for example, preferably 4 to 40, more preferably 4 to 30, even more preferably 6 to 20, particularly preferably 8 to 15. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
Examples of the aliphatic ring in the aliphatic cyclic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. Among these, an adamantane ring is preferred from the viewpoint of development adhesion.
　芳香族環基が有する環の数は特に限定されないが、通常１以上、２以上が好ましく、３以上がより好ましく、また、１０以下が好ましく、５以下がより好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、１～１０が好ましく、２～１０がより好ましく、３～５がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。
　芳香族環基としては、芳香族炭化水素環基、芳香族複素環基が挙げられる。また、芳香族環基の炭素数は通常４以上であり、５以上が好ましく、６以上がより好ましく、また、３０以下が好ましく、２０以下がより好ましく、１５以下がさらに好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、４～３０が好ましく、５～２０がより好ましく、６～１５がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。
　芳香族環基における芳香族環としては、例えば、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、フルオレン環が挙げられる。これらの中でも現像密着性の観点から、フルオレン環が好ましい。 The number of rings that the aromatic ring group has is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and preferably 10 or less, and more preferably 5 or less. The upper and lower limits can be arbitrarily combined, and are preferably from 1 to 10, more preferably from 2 to 10, even more preferably from 3 to 5. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. Further, the number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. The upper and lower limits can be arbitrarily combined, for example, preferably 4 to 30, more preferably 5 to 20, and even more preferably 6 to 15. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among these, a fluorene ring is preferred from the viewpoint of development adhesion.
　環状炭化水素基が有していてもよい置換基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、アミル基、イソアミル基等の炭素数１～５のアルキル基；メトキシ基、エトキシ基等の炭素数１～５のアルコキシ基；水酸基；ニトロ基；シアノ基；カルボキシ基が挙げられ、合成の容易性の観点から、無置換が好ましい。 Examples of substituents that the cyclic hydrocarbon group may have include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, amyl group, Examples include alkyl groups having 1 to 5 carbon atoms such as isoamyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; and carboxy group; from the viewpoint of ease of synthesis. , unsubstituted is preferred.
　ｎは１以上の整数を表すが、２以上が好ましく、また、３以下が好ましい。例えば、１～３が好ましく、１～２がより好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。 n represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less. For example, 1 to 3 are preferred, and 1 to 2 are more preferred. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
　これらの中でも、強固な膜硬化度と電気特性の観点から、Ｒｆが１価の脂肪族環基であることが好ましく、アダマンチル基であることがより好ましい。 Among these, from the viewpoint of strong film hardening degree and electrical properties, R f is preferably a monovalent aliphatic cyclic group, and more preferably an adamantyl group.
　前記のとおり、式（ｉｉ－１）中のベンゼン環は、さらに任意の置換基により置換されていてもよい。置換基としては、例えば、ヒドロキシ基、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシ基が挙げられる。置換基の数も特に限定されず、１つでもよいし、２つ以上でもよい。硬化性の観点から、無置換が好ましい。 As described above, the benzene ring in formula (ii-1) may be further substituted with any substituent. Examples of the substituent include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is not particularly limited either, and may be one or two or more. From the viewpoint of curability, no substitution is preferred.
　以下に前記式（ｉｉ－１）で表される部分構造の具体例を挙げる。 Specific examples of the partial structure represented by the above formula (ii-1) are listed below.
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
　前記式（ｉｉ）で表される部分構造は、現像密着性の観点から、下記式（ｉｉ－２）で表される部分構造であることが好ましい。 From the viewpoint of development adhesion, the partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-2).
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
　式（ｉｉ－２）中、Ｒｄは前記式（ｉｉ）と同義である。Ｒｇは、置換基を有していてもよい２価の環状炭化水素基を表す。式（ｉｉ－２）中のベンゼン環は、さらに任意の置換基により置換されていてもよい。＊は結合手を表す。 In formula (ii-2), R d has the same meaning as in formula (ii) above. R g represents a divalent cyclic hydrocarbon group which may have a substituent. The benzene ring in formula (ii-2) may be further substituted with any substituent. * represents a bond.
　前記式（ｉｉ－２）において、Ｒｇは、置換基を有していてもよい２価の環状炭化水素基を表す。
　環状炭化水素基としては、脂肪族環基又は芳香族環基が挙げられる。 In the formula (ii-2), R g represents a divalent cyclic hydrocarbon group which may have a substituent.
Examples of the cyclic hydrocarbon group include an aliphatic ring group and an aromatic ring group.
　脂肪族環基が有する環の数は特に限定されないが、通常１以上、２以上が好ましく、また、１０以下が好ましく、５以下がより好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、１～１０が好ましく、２～５がより好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。
　また、脂肪族環基の炭素数は通常４以上であり、６以上が好ましく、８以上がより好ましく、また、４０以下が好ましく、３５以下がより好ましく、３０以下がさらに好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、４～４０が好ましく、６～３５がより好ましく、８～３０がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。
　脂肪族環基における脂肪族環としては、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環が挙げられる。これらの中でも現像密着性の観点から、アダマンタン環が好ましい。 The number of rings an aliphatic cyclic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, preferably 10 or less, and more preferably 5 or less. The upper and lower limits can be arbitrarily combined, and are preferably from 1 to 10, more preferably from 2 to 5. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
Further, the number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less. The upper and lower limits can be arbitrarily combined, for example, preferably 4 to 40, more preferably 6 to 35, and even more preferably 8 to 30. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
Examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. Among these, an adamantane ring is preferred from the viewpoint of development adhesion.
　芳香族環基が有する環の数は特に限定されないが、通常１以上、２以上が好ましく、３以上がより好ましく、また、１０以下が好ましく、５以下が好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、１～１０が好ましく、２～１０がより好ましく、３～５がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。
　芳香族環基としては、芳香族炭化水素環基、芳香族複素環基が挙げられる。また、芳香族環基の炭素数は通常４以上であり、６以上が好ましく、８以上がより好ましく、１０以上がさらに好ましく、また、４０以下が好ましく、３０以下がより好ましく、２０以下がさらに好ましく、１５以下が特に好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、４～４０が好ましく、６～３０がより好ましく、８～２０がさらに好ましく、１０～１５が特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。
　芳香族環基における芳香族環としては、例えば、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、フルオレン環が挙げられる。これらの中でも現像密着性の観点から、フルオレン環が好ましい。 The number of rings that the aromatic ring group has is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and preferably 10 or less, and preferably 5 or less. The upper and lower limits can be arbitrarily combined, and are preferably from 1 to 10, more preferably from 2 to 10, even more preferably from 3 to 5. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, even more preferably 10 or more, and preferably 40 or less, more preferably 30 or less, and still more preferably 20 or more. It is preferably 15 or less, particularly preferably 15 or less. The upper and lower limits can be arbitrarily combined, and are preferably from 4 to 40, more preferably from 6 to 30, even more preferably from 8 to 20, and particularly preferably from 10 to 15. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among these, a fluorene ring is preferred from the viewpoint of development adhesion.
　環状炭化水素基が有していてもよい置換基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、アミル基、イソアミル基等の炭素数１～５のアルキル基；メトキシ基、エトキシ基等の炭素数１～５のアルコキシ基；水酸基；ニトロ基；シアノ基；カルボキシ基が挙げられる。これらの中でも合成の簡易性の観点から、無置換が好ましい。 Examples of substituents that the cyclic hydrocarbon group may have include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, amyl group, Examples include alkyl groups having 1 to 5 carbon atoms such as isoamyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; and carboxy group. Among these, unsubstituted is preferred from the viewpoint of ease of synthesis.
　これらの中でも、硬化性の観点から、Ｒｇが２価の脂肪族環基であることが好ましく、２価のアダマンタン環基であることがより好ましい。
　別の態様として、現像密着性の観点から、Ｒｇが２価の芳香族環基であることが好ましく、２価のフルオレン環基であることがより好ましい。 Among these, from the viewpoint of curability, R g is preferably a divalent aliphatic cyclic group, and more preferably a divalent adamantane cyclic group.
As another embodiment, from the viewpoint of development adhesion, R g is preferably a divalent aromatic ring group, and more preferably a divalent fluorene ring group.
　前記のとおり、式（ｉｉ－２）中のベンゼン環は、さらに任意の置換基により置換されていてもよい。式（ｉｉ－２）中のベンゼン環の置換基としては、例えば、ヒドロキシ基、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシ基が挙げられる。置換基の数も特に限定されず、１つでもよいし、２つ以上でもよい。硬化性の観点から、無置換が好ましい。 As described above, the benzene ring in formula (ii-2) may be further substituted with any substituent. Examples of the substituent on the benzene ring in formula (ii-2) include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. The number of substituents is not particularly limited either, and may be one or two or more. From the viewpoint of curability, no substitution is preferred.
　以下に前記式（ｉｉ－２）で表される部分構造の具体例を挙げる。 Specific examples of the partial structure represented by the above formula (ii-2) are listed below.
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
　前記式（ｉｉ）で表される部分構造は、硬化性の観点から、下記式（ｉｉ－３）で表される部分構造であることが好ましい。 From the viewpoint of curability, the partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-3).
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
　式（ｉｉ－３）中、Ｒｄ及びＲｅは前記式（ｉｉ）と同義である。Ｒｃは前記式（ｉ－１）と同義である。＊は結合手を表す。 In formula (ii-3), R d and R e have the same meanings as in formula (ii) above. R c has the same meaning as in formula (i-1) above. * represents a bond.
　（ｃ１－２）エポキシ（メタ）アクリレート樹脂１分子中に含まれる、前記式（ｉｉ－３）で表される部分構造は、１種でも２種以上でもよい。 (c1-2) The partial structure represented by the above formula (ii-3) contained in one molecule of the epoxy (meth)acrylate resin may be one type or two or more types.
　（ｃ１－２）エポキシ（メタ）アクリレート樹脂１分子中に含まれる、前記式（ｉｉ）で表される部分構造の数は特に限定されないが、１以上が好ましく、３以上がより好ましく、また、２０以下が好ましく、１５以下がより好ましく、１０以下がさらに好ましい。
　前記上限及び下限は任意に組み合わせることができ、例えば、１～２０が好ましく、１～１５がより好ましく、３～１０がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。 (c1-2) The number of partial structures represented by the formula (ii) contained in one molecule of epoxy (meth)acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 3 or more, and It is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less.
The upper and lower limits can be arbitrarily combined, for example, preferably from 1 to 20, more preferably from 1 to 15, even more preferably from 3 to 10. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
　さらに別の態様として、（ｃ１）エポキシ（メタ）アクリレート樹脂は、現像性、現像時のテーパ形状の観点から、下記一般式（ｉｉｉ）で表される部分構造を含む（ｃ１－３）エポキシ（メタ）アクリレート樹脂であることが好ましい。 As yet another aspect, (c1) epoxy (meth)acrylate resin (c1-3) epoxy (meth)acrylate resin includes a partial structure represented by the following general formula (iii) from the viewpoint of developability and tapered shape during development. Preferably, it is a meth)acrylate resin.
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
　式（ｉｉｉ）中、Ｒｈは水素原子又はメチル基を表し、Ｒｉは単結合、－Ｃ（Ｏ）－、置換基を有していてもよいアルキレン基、又は置換基を有していてもよい２価の環状炭化水素基を表す。式（ｉｉｉ）中のベンゼン環は、さらに任意の置換基により置換されていてもよい。＊は結合手を表す。 In formula (iii), R h represents a hydrogen atom or a methyl group, and R i is a single bond, -C(O)-, an alkylene group which may have a substituent, or a substituent. represents a good divalent cyclic hydrocarbon group. The benzene ring in formula (iii) may be further substituted with any substituent. * represents a bond.
（Ｒｉ）
　前記式（ｉｉｉ）において、Ｒｉは単結合、－Ｃ（Ｏ）－、置換基を有していてもよいアルキレン基、又は置換基を有していてもよい２価の環状炭化水素基を表す。 (R i )
In the formula (iii), R i represents a single bond, -C(O)-, an alkylene group which may have a substituent, or a divalent cyclic hydrocarbon group which may have a substituent. represent.
　アルキレン基は直鎖状でも、分岐鎖状でもよいが、現像溶解性の観点からは直鎖状であることが好ましく、現像密着性の観点からは分岐鎖状であることが好ましい。その炭素数は特に限定されないが、通常１以上、２以上が好ましく、また、６以下が好ましく、４以下がより好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、１～６が好ましく、２～４がより好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。 The alkylene group may be linear or branched, but from the viewpoint of development solubility it is preferably linear, and from the viewpoint of development adhesion it is preferably branched. The number of carbon atoms is not particularly limited, but is usually 1 or more, preferably 2 or more, preferably 6 or less, and more preferably 4 or less. The upper and lower limits can be arbitrarily combined, and for example, 1 to 6 are preferable, and 2 to 4 are more preferable. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
　アルキレン基としては、例えば、メチレン基、エチレン基、プロピレン基、ブチレン基、へキシレン基、ヘプチレン基が挙げられ、現像密着性と現像溶解性の両立の観点から、メチレン基、エチレン基、プロピレン基が好ましく、ジメチルメチレン基（２，２－プロピレン基）がより好ましい。 Examples of the alkylene group include methylene group, ethylene group, propylene group, butylene group, hexylene group, and heptylene group. is preferred, and dimethylmethylene group (2,2-propylene group) is more preferred.
　アルキレン基が有していてもよい置換基としては、例えば、メトキシ基、エトキシ基等の炭素数１～５のアルコキシ基；水酸基；ニトロ基；シアノ基；カルボキシ基が挙げられ、現像密着性と現像溶解性の両立の観点から、無置換が好ましい。 Examples of the substituents that the alkylene group may have include alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; and carboxy group; From the viewpoint of achieving both development and solubility, non-substitution is preferred.
　２価の環状炭化水素基としては、２価の脂肪族環基又は２価の芳香族環基が挙げられる。 Examples of the divalent cyclic hydrocarbon group include a divalent aliphatic cyclic group and a divalent aromatic cyclic group.
　脂肪族環基が有する環の数は特に限定されないが、通常１以上、２以上が好ましく、また、１０以下が好ましく、５以下がより好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、１～１０が好ましく、２～５がより好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。
　また、脂肪族環基の炭素数は通常４以上であり、６以上が好ましく、８以上がより好ましく、また、４０以下が好ましく、３５以下がより好ましく、３０以下がさらに好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、４～４０が好ましく、６～３５がより好ましく、８～３０がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。
　脂肪族環基における脂肪族環としては、例えば、シクロヘキサン環、シクロヘプタン環、シクロデカン環、シクロドデカン環、ノルボルナン環、イソボルナン環、アダマンタン環が挙げられる。これらの中でも現像密着性の観点から、アダマンタン環が好ましい。 The number of rings an aliphatic cyclic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, preferably 10 or less, and more preferably 5 or less. The upper and lower limits can be arbitrarily combined, and are preferably from 1 to 10, more preferably from 2 to 5. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
Further, the number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less. The upper and lower limits can be arbitrarily combined, for example, preferably 4 to 40, more preferably 6 to 35, and even more preferably 8 to 30. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
Examples of the aliphatic ring in the aliphatic cyclic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring. Among these, an adamantane ring is preferred from the viewpoint of development adhesion.
　芳香族環基が有する環の数は特に限定されないが、通常１以上、２以上が好ましく、３以上がより好ましく、また、１０以下が好ましく、５以下がより好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、１～１０が好ましく、２～１０がより好ましく、３～５がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。
　芳香族環基としては、芳香族炭化水素環基、芳香族複素環基が挙げられる。芳香族環基の炭素数は通常４以上であり、６以上が好ましく、８以上がより好ましく、１０以上がさらに好ましく、また、４０以下が好ましく、３０以下がより好ましく、２０以下がさらに好ましく、１５以下が特に好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、４～４０が好ましく、６～３０がより好ましく、８～２０がさらに好ましく、１０～１５が特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。
　芳香族環基における芳香族環としては、例えば、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、フルオレン環が挙げられる。これらの中でも現像密着性の観点から、フルオレン環が好ましい。 The number of rings that the aromatic ring group has is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and preferably 10 or less, and more preferably 5 or less. The upper and lower limits can be arbitrarily combined, and are preferably from 1 to 10, more preferably from 2 to 10, even more preferably from 3 to 5. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, even more preferably 10 or more, and preferably 40 or less, more preferably 30 or less, even more preferably 20 or more, 15 or less is particularly preferred. The upper and lower limits can be arbitrarily combined, and are preferably from 4 to 40, more preferably from 6 to 30, even more preferably from 8 to 20, and particularly preferably from 10 to 15. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among these, a fluorene ring is preferred from the viewpoint of development adhesion.
　環状炭化水素基が有していてもよい置換基としては、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｓｅｃ－ブチル基、ｔｅｒｔ－ブチル基、アミル基、イソアミル基等の炭素数１～５のアルキル基；メトキシ基、エトキシ基等の炭素数１～５のアルコキシ基；水酸基；ニトロ基；シアノ基；カルボキシ基が挙げられ、合成の簡易性の観点から、無置換が好ましい。 Examples of substituents that the cyclic hydrocarbon group may have include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, amyl group, Examples include alkyl groups having 1 to 5 carbon atoms such as isoamyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; and carboxy group; from the viewpoint of simplicity of synthesis. , unsubstituted is preferred.
　これらの中でも、残渣低減の観点から、Ｒｉが置換基を有していてもよいアルキレン基であることが好ましく、ジメチルメチレンであることがより好ましい。 Among these, from the viewpoint of reducing residue, R i is preferably an alkylene group which may have a substituent, and more preferably dimethylmethylene.
　前記のとおり、式（ｉｉｉ）中のベンゼン環は、さらに任意の置換基により置換されていてもよい。式（ｉｉｉ）中のベンゼン環の置換基としては、例えば、ヒドロキシ基、メチル基、メトキシ基、エチル基、エトキシ基、プロピル基、プロポキシ基が挙げられる。
　置換基の数も特に限定されず、１つでもよいし、２つ以上でもよい。硬化性の観点から、無置換が好ましい。 As described above, the benzene ring in formula (iii) may be further substituted with any substituent. Examples of the substituent on the benzene ring in formula (iii) include a hydroxy group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group.
The number of substituents is not particularly limited either, and may be one or two or more. From the viewpoint of curability, no substitution is preferred.
　前記式（ｉｉｉ）で表される部分構造は、現像溶解性の観点から、下記式（ｉｉｉ－１）で表される部分構造であることが好ましい。 From the viewpoint of development solubility, the partial structure represented by the formula (iii) is preferably a partial structure represented by the following formula (iii-1).
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
　式（ｉｉｉ－１）中、Ｒｈ及びＲｉは前記式（ｉｉｉ）と同義である。Ｒｃは前記式（ｉ－１）のものと同義である。＊は結合手を表す。式（ｉｉｉ－１）中のベンゼン環は、さらに任意の置換基により置換されていてもよい。 In formula (iii-1), R h and R i have the same meanings as in formula (iii) above. R c has the same meaning as in formula (i-1) above. * represents a bond. The benzene ring in formula (iii-1) may be further substituted with any substituent.
　（ｃ１－３）エポキシ（メタ）アクリレート樹脂１分子中に含まれる、前記式（ｉｉｉ）で表される部分構造の数は特に限定されないが、１以上が好ましく、５以上がより好ましく、１０以上がさらに好ましく、また、１８以下が好ましく、１５以下がさらに好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、１～１８が好ましく、５～１８がより好ましく、１０～１５がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。 (c1-3) The number of partial structures represented by the formula (iii) contained in one molecule of epoxy (meth)acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 5 or more, and 10 or more. is more preferable, 18 or less is preferable, and 15 or less is even more preferable. The upper and lower limits can be arbitrarily combined, for example, preferably from 1 to 18, more preferably from 5 to 18, even more preferably from 10 to 15. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
　（ｃ１－３）エポキシ（メタ）アクリレート樹脂１分子中に含まれる、前記式（ｉｉｉ－１）で表される部分構造の数は特に限定されないが、１以上が好ましく、３以上がより好ましく、５以上がさらに好ましく、また、１８以下が好ましく、１５以下がさらに好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、１～１８が好ましく、３～１８がより好ましく、５～１５がさらに好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。 (c1-3) The number of partial structures represented by the formula (iii-1) contained in one molecule of epoxy (meth)acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 3 or more, It is more preferably 5 or more, more preferably 18 or less, and even more preferably 15 or less. The upper and lower limits can be arbitrarily combined, and are preferably from 1 to 18, more preferably from 3 to 18, even more preferably from 5 to 15. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
　以下に（ｃ１－３）エポキシ（メタ）アクリレート樹脂の具体例を挙げる。 Specific examples of the (c1-3) epoxy (meth)acrylate resin are listed below.
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
［（ｃ２）アクリル共重合樹脂］
　（ｃ２）アクリル共重合樹脂は、硬化性の観点から、側鎖にエチレン性二重結合を有するものであることが好ましい。 [(c2) Acrylic copolymer resin]
(c2) The acrylic copolymer resin preferably has an ethylenic double bond in its side chain from the viewpoint of curability.
　（ｃ２）アクリル共重合樹脂の中でも、現像溶解性の観点から、（ｃ２－１）下記一般式（ｉｖ）で表される部分構造を含むアクリル共重合樹脂が好ましい。 Among (c2) acrylic copolymer resins, from the viewpoint of development solubility, (c2-1) acrylic copolymer resins containing a partial structure represented by the following general formula (iv) are preferred.
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
　式（ｉｖ）中、Ｒｊ及びＲｋは各々独立に、水素原子又はメチル基を表す。＊は結合手を表す。 In formula (iv), R j and R k each independently represent a hydrogen atom or a methyl group. * represents a bond.
　前記式（ｉｖ）で表される部分構造は、現像性の観点から、下記一般式（ｉｖ－１）で表される部分構造であることが好ましい。 From the viewpoint of developability, the partial structure represented by the formula (iv) is preferably a partial structure represented by the following general formula (iv-1).
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000042
　式（ｉｖ－１）中、Ｒｊ及びＲｋは、前記式（ｉｖ）のものと同義である。Ｒｃは前記式（ｉ－１）のものと同義である。 In formula (iv-1), R j and R k have the same meanings as in formula (iv) above. R c has the same meaning as in formula (i-1) above.
　前記式（ｉｖ）で表される部分構造は、感度の観点から、下記式（ｉｖ－２）で表される部分構造であることが好ましい。 From the viewpoint of sensitivity, the partial structure represented by the formula (iv) is preferably a partial structure represented by the following formula (iv-2).
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000043
　式（ｉｖ－２）中、Ｒｊ及びＲｋは、前記式（ｉｖ）のものと同義である。 In formula (iv-2), R j and R k have the same meanings as in formula (iv) above.
　（ｃ２－１）アクリル共重合樹脂が前記一般式（ｉｖ）で表される部分構造を含む場合、（ｃ２－１）アクリル共重合樹脂に含まれる前記一般式（ｉｖ）で表される部分構造の含有量は特に限定されないが、５モル％以上が好ましく、２０モル％以上がより好ましく、３０モル％以上がさらに好ましく、５０モル％以上がよりさらに好ましく、７０モル％以上が特に好ましく、８０モル％以上が最も好ましく、また、９９モル％以下が好ましく、９７モル％以下がより好ましく、９５モル％以下がさらに好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、５～９９モル％が好ましく、２０～９９モル％がより好ましく、３０～９７モル％がさらに好ましく、５０～９７モル％がよりさらに好ましく、７０～９５モル％が特に好ましく、８０～９５モル％が最も好ましい。前記下限値以上とすることで残渣が低減する傾向がある。また、前記上限値以下とすることで現像密着性が向上する傾向がある。 (c2-1) When the acrylic copolymer resin contains a partial structure represented by the general formula (iv), (c2-1) the partial structure represented by the general formula (iv) contained in the acrylic copolymer resin The content is not particularly limited, but is preferably 5 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, even more preferably 50 mol% or more, particularly preferably 70 mol% or more, and 80 mol% or more. It is most preferably at least mol%, preferably at most 99 mol%, more preferably at most 97 mol%, even more preferably at most 95 mol%. The upper and lower limits can be arbitrarily combined, for example, preferably 5 to 99 mol%, more preferably 20 to 99 mol%, even more preferably 30 to 97 mol%, even more preferably 50 to 97 mol%, Particularly preferred is 70 to 95 mol%, most preferred is 80 to 95 mol%. There is a tendency for the amount of residue to be reduced by setting the amount to be equal to or more than the lower limit value. Further, by setting the amount to be less than or equal to the upper limit value, the development adhesion tends to improve.
　（ｃ２－１）アクリル共重合樹脂が前記一般式（ｉｖ－１）で表される部分構造を含む場合、（ｃ２－１）アクリル共重合樹脂に含まれる前記一般式（ｉｖ－１）で表される部分構造の含有量は特に限定されないが、１モル％以上が好ましく、５モル％以上がより好ましく、８モル％以上がさらに好ましく、１０モル％以上がよりさらに好ましく、また、９９モル％以下が好ましく、６０モル％以下がより好ましく、４０モル％以下がさらに好ましく、３０モル％以下がよりさらに好ましく、２０モル％以下が特に好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、１～９９モル％が好ましく、１～６０モル％がより好ましく、５～４０モル％がさらに好ましく、８～３０モル％がよりさらに好ましく、１０～２０モル％が特に好ましい。前記下限値以上とすることで感度が高くなり、残渣が低減する傾向がある。また、前記上限値以下とすることで現像密着性が向上する傾向がある。 (c2-1) When the acrylic copolymer resin contains a partial structure represented by the general formula (iv-1), (c2-1) the acrylic copolymer resin contains a partial structure represented by the general formula (iv-1). The content of the partial structure is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, even more preferably 8 mol% or more, even more preferably 10 mol% or more, and even more preferably 99 mol%. The following is preferable, 60 mol% or less is more preferable, 40 mol% or less is even more preferable, even more preferably 30 mol% or less, and particularly preferably 20 mol% or less. The upper and lower limits can be arbitrarily combined, for example, preferably 1 to 99 mol%, more preferably 1 to 60 mol%, even more preferably 5 to 40 mol%, even more preferably 8 to 30 mol%, Particularly preferred is 10 to 20 mol%. When the value is equal to or more than the lower limit, the sensitivity tends to increase and the amount of residue tends to decrease. Further, by setting the amount to be less than or equal to the upper limit value, the development adhesion tends to improve.
　（ｃ２－１）アクリル共重合樹脂が前記一般式（ｉｖ－２）で表される部分構造を含む場合、（ｃ２－１）アクリル共重合樹脂に含まれる前記一般式（ｉｖ－２）で表される部分構造の含有量は特に限定されないが、１０モル％以上が好ましく、２０モル％以上がより好ましく、３０モル％以上がさらに好ましく、４０モル％以上がよりさらに好ましく、５０モル％以上が特に好ましく、７０モル％以上が最も好ましく、また、９９モル％以下が好ましく、９５モル％以下がより好ましく、９０モル％以下がさらに好ましく、８５モル％以下が特に好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、１０～９９モル％が好ましく、２０～９９モル％がより好ましく、３０～９５モル％がさらに好ましく、４０～９５モル％がよりさらに好ましく、５０～９０モル％が特に好ましく、７０～８５モル％が最も好ましい。前記下限値以上とすることで感度が高くなる傾向がある。また、前記上限値以下とすることで現像性が向上する傾向がある。 (c2-1) When the acrylic copolymer resin contains a partial structure represented by the general formula (iv-2), (c2-1) the acrylic copolymer resin contains a partial structure represented by the general formula (iv-2). The content of the partial structure is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, even more preferably 40 mol% or more, and even more preferably 50 mol% or more. It is particularly preferably 70 mol% or more, most preferably 99 mol% or less, more preferably 95 mol% or less, even more preferably 90 mol% or less, and particularly preferably 85 mol% or less. The upper and lower limits can be arbitrarily combined, for example, preferably 10 to 99 mol%, more preferably 20 to 99 mol%, even more preferably 30 to 95 mol%, even more preferably 40 to 95 mol%, Particularly preferred is 50 to 90 mol%, most preferred is 70 to 85 mol%. When the value is equal to or more than the lower limit value, the sensitivity tends to increase. Further, by setting the amount to be less than or equal to the upper limit value, there is a tendency that developability is improved.
　（ｃ２－１）アクリル共重合樹脂が前記一般式（ｉｖ）で表される部分構造を含む場合、他に含んでいてもよい部分構造は特に限定されないが、現像密着性の観点から、例えば、下記一般式（ｉｖ’）で表される部分構造を含むことが好ましい。 (c2-1) When the acrylic copolymer resin contains the partial structure represented by the general formula (iv), other partial structures that may be included are not particularly limited, but from the viewpoint of development adhesion, for example, It is preferable to include a partial structure represented by the following general formula (iv').
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
　上記式（ｉｖ’）中、Ｒｌは水素原子又はメチル基を表し、Ｒｍは置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基（芳香族環基）、又は置換基を有していてもよいアルケニル基を表す。 In the above formula (iv'), Rl represents a hydrogen atom or a methyl group, Rm represents an alkyl group that may have a substituent, an aryl group that may have a substituent (an aromatic ring group) ), or an alkenyl group which may have a substituent.
　前記式（ｉｖ’）において、Ｒｍは置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基、又は置換基を有していてもよいアルケニル基を表す。
　Ｒｍにおけるアルキル基としては直鎖状、分岐鎖状又は環状のアルキル基が挙げられる。その炭素数は、１以上が好ましく、３以上がより好ましく、５以上がさらに好ましく、また、２０以下が好ましく、１８以下がより好ましく、１６以下がさらに好ましく、１４以下がよりさらに好ましく、１２以下が特に好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、１～２０が好ましく、１～１８がより好ましく、３～１６がさらに好ましく、３～１４がよりさらに好ましく、５～１２が特に好ましい。前記下限値以上とすることで膜強度が高くなり、現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。 In the formula (iv'), R m represents an alkyl group that may have a substituent, an aryl group that may have a substituent, or an alkenyl group that may have a substituent.
Examples of the alkyl group for R m include linear, branched, or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, and preferably 20 or less, more preferably 18 or less, further preferably 16 or less, even more preferably 14 or less, and even more preferably 12 or less. is particularly preferred. The upper and lower limits can be arbitrarily combined, for example, preferably 1 to 20, more preferably 1 to 18, even more preferably 3 to 16, even more preferably 3 to 14, particularly preferably 5 to 12. When the amount is equal to or more than the lower limit, the film strength tends to increase, and the development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
　アルキル基としては、例えば、メチル基、エチル基、シクロヘキシル基、ジシクロペンタニル基、ドデカニル基が挙げられる。これらの中でも膜強度の観点から、ジシクロペンタニル基、ドデカニル基が好ましく、ジシクロペンタニル基がより好ましい。
　アルキル基が有していてもよい置換基としては、例えば、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシ基、アクリロイル基、メタクリロイル基が挙げられ、現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, and a dodecanyl group. Among these, from the viewpoint of film strength, dicyclopentanyl group and dodecanyl group are preferred, and dicyclopentanyl group is more preferred.
Examples of substituents that the alkyl group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxy group. , an acryloyl group, and a methacryloyl group, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
　Ｒｍにおけるアリール基（芳香族環基）としては、１価の芳香族炭化水素環基、１価の芳香族複素環基が挙げられる。その炭素数は４以上が好ましく、６以上がより好ましく、また、２４以下が好ましく、２２以下がより好ましく、２０以下がさらに好ましく、１８以下が特に好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、４～２４が好ましく、４～２２がより好ましく、６～２０がさらに好ましく、６～１８が特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。
　芳香族炭化水素環基における芳香族炭化水素環としては、単環であっても縮合環であってもよく、例えば、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環が挙げられる。
　芳香族複素環基における芳香族複素環としては、単環であっても縮合環であってもよく、例えば、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環が挙げられる。これらの中でも硬化性の観点から、ベンゼン環基、ナフタレン環基が好ましく、ベンゼン環基がより好ましい。
　アリール基が有していてもよい置換基としては、例えば、メチル基、エチル基、プロピル基、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシ基が挙げられ、現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Examples of the aryl group (aromatic ring group) for R m include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. The number of carbon atoms is preferably 4 or more, more preferably 6 or more, preferably 24 or less, more preferably 22 or less, even more preferably 20 or less, and particularly preferably 18 or less. The upper and lower limits can be arbitrarily combined, for example, preferably 4 to 24, more preferably 4 to 22, even more preferably 6 to 20, particularly preferably 6 to 18. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, such as a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, and a pyrene ring. ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.
The aromatic heterocycle in the aromatic heterocyclic group may be a single ring or a condensed ring, such as a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, and an imidazole ring. , oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, Examples include benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring. . Among these, from the viewpoint of curability, benzene ring groups and naphthalene ring groups are preferred, and benzene ring groups are more preferred.
Examples of substituents that the aryl group may have include methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligo Examples include ethylene glycol group, phenyl group, and carboxy group, and from the viewpoint of developability, hydroxy group and oligoethylene glycol group are preferable.
　Ｒｍにおけるアルケニル基としては、直鎖状、分岐鎖状又は環状のアルケニル基が挙げられる。その炭素数は、２以上が好ましく、また、２２以下が好ましく、２０以下がより好ましく、１８以下がさらに好ましく、１６以下がよりさらに好ましく、１４以下が特に好ましい。例えば、２～２２が好ましく、２～２０がより好ましく、２～１８がさらに好ましく、２～１６がよりさらに好ましく、２～１４が特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。 Examples of the alkenyl group for R m include linear, branched, or cyclic alkenyl groups. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, even more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less. For example, the number is preferably 2 to 22, more preferably 2 to 20, even more preferably 2 to 18, even more preferably 2 to 16, and particularly preferably 2 to 14. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
　アルケニル基としては、例えば、エテニル基、プロペニル基、ブテニル基、シクロヘキセニル基が挙げられる。これらの中でも硬化性の観点から、エテニル基、プロペニル基が好ましく、エテニル基がより好ましい。
　アルケニル基が有していてもよい置換基としては、例えば、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシ基が挙げられ、現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Examples of the alkenyl group include ethenyl group, propenyl group, butenyl group, and cyclohexenyl group. Among these, from the viewpoint of curability, ethenyl group and propenyl group are preferred, and ethenyl group is more preferred.
Examples of substituents that the alkenyl group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxy group. From the viewpoint of developability, hydroxyl groups and oligoethylene glycol groups are preferred.
　これらの中でも現像性の観点から、Ｒｍとしては、アルキル基、アルケニル基が好ましく、アルキル基がより好ましく、ジシクロペンタニル基がさらに好ましい。 Among these, from the viewpoint of developability, R m is preferably an alkyl group or an alkenyl group, more preferably an alkyl group, and even more preferably a dicyclopentanyl group.
　（ｃ２－１）アクリル共重合樹脂が前記一般式（ｉｖ’）で表される部分構造を含む場合、（ｃ２－１）アクリル共重合樹脂に含まれる前記一般式（ｉｖ’）で表される部分構造の含有量は特に限定されないが、０．５モル％以上が好ましく、１モル％以上がより好ましく、１．５モル％以上がさらに好ましく、２モル％以上が特に好ましく、また、９０モル％以下が好ましく、７０モル％以下がより好ましく、５０％モル以下がさらに好ましく、３０モル％以下がよりさらに好ましく、１０モル％以下が特に好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、０．５～９０モル％が好ましく、０．５～７０モル％がより好ましく、１～５０％モルがさらに好ましく、１．５～３０モル％がよりさらに好ましく、２～１０モル％が特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。 (c2-1) When the acrylic copolymer resin contains a partial structure represented by the general formula (iv'), (c2-1) the acrylic copolymer resin contains a partial structure represented by the general formula (iv') The content of the partial structure is not particularly limited, but is preferably 0.5 mol% or more, more preferably 1 mol% or more, even more preferably 1.5 mol% or more, particularly preferably 2 mol% or more, and 90 mol% or more. % or less, more preferably 70 mol % or less, even more preferably 50 mol % or less, even more preferably 30 mol % or less, particularly preferably 10 mol % or less. The upper and lower limits can be arbitrarily combined, for example, preferably 0.5 to 90 mol%, more preferably 0.5 to 70 mol%, even more preferably 1 to 50% mol, and 1.5 to 30 mol%. % is even more preferable, and 2 to 10 mol% is particularly preferable. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
　（ｃ２－１）アクリル共重合樹脂が前記一般式（ｉｖ）で表される部分構造を含む場合、耐熱性、膜強度の観点から、下記一般式（ｉｖ’’）で表される部分構造をさらに含むことが好ましい。 (c2-1) When the acrylic copolymer resin contains a partial structure represented by the general formula (iv) above, from the viewpoint of heat resistance and film strength, the partial structure represented by the following general formula (iv'') is It is preferable to further include.
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
　上記式（ｉｖ’’）中、Ｒｎは水素原子又はメチル基を表し、Ｒｏは置換基を有していてもよいアルキル基、置換基を有していてもよいアルケニル基、ヒドロキシ基、カルボキシ基、ハロゲン原子、置換基を有していてもよいアルコキシ基、チオール基、又は置換基を有していてもよいアルキルスルフィド基を表す。ｔは０～５の整数を表す。 In the above formula (iv''), R n represents a hydrogen atom or a methyl group, and R o represents an alkyl group that may have a substituent, an alkenyl group that may have a substituent, a hydroxy group, It represents a carboxyl group, a halogen atom, an alkoxy group which may have a substituent, a thiol group, or an alkyl sulfide group which may have a substituent. t represents an integer from 0 to 5.
　前記式（ｉｖ’’）においてＲｏは置換基を有していてもよいアルキル基、置換基を有していてもよいアルケニル基、ヒドロキシ基、カルボキシ基、ハロゲン原子、置換基を有していてもよいアルコキシ基、チオール基、又は置換基を有していてもよいアルキルスルフィド基を表す。
　Ｒｏにおけるアルキル基としては、直鎖状、分岐鎖状又は環状のアルキル基が挙げられる。その炭素数は、１以上が好ましく、３以上がより好ましく、５以上がさらに好ましく、また、２０以下が好ましく、１８以下がより好ましく、１６以下がさらに好ましく、１４以下がよりさらに好ましく、１２以下が特に好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、１～２０が好ましく、１～１８がより好ましく、３～１６がさらに好ましく、３～１４がよりさらに好ましく、５～１２が特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。 In the formula (iv''), R o has an alkyl group that may have a substituent, an alkenyl group that may have a substituent, a hydroxy group, a carboxy group, a halogen atom, or a substituent. represents an optionally substituted alkoxy group, a thiol group, or an optionally substituted alkyl sulfide group.
Examples of the alkyl group in R o include linear, branched or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, and preferably 20 or less, more preferably 18 or less, further preferably 16 or less, even more preferably 14 or less, and even more preferably 12 or less. is particularly preferred. The upper and lower limits can be arbitrarily combined, for example, preferably 1 to 20, more preferably 1 to 18, even more preferably 3 to 16, even more preferably 3 to 14, particularly preferably 5 to 12. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
　アルキル基としては、例えば、メチル基、エチル基、シクロヘキシル基、ジシクロペンタニル基、ドデカニル基が挙げられる。これらの中でも現像密着性の観点から、ジシクロペンタニル基、ドデカニル基が好ましく、ジシクロペンタニル基がより好ましい。
　アルキル基が有していてもよい置換基としては、例えば、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシ基、アクリロイル基、メタクリロイル基が挙げられ、現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, and a dodecanyl group. Among these, from the viewpoint of development adhesion, dicyclopentanyl group and dodecanyl group are preferred, and dicyclopentanyl group is more preferred.
Examples of substituents that the alkyl group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxy group. , an acryloyl group, and a methacryloyl group, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
　Ｒｏにおけるアルケニル基としては、直鎖状、分岐鎖状又は環状のアルケニル基が挙げられる。その炭素数は、２以上が好ましく、また、２２以下が好ましく、２０以下がより好ましく、１８以下がさらに好ましく、１６以下がよりさらに好ましく、１４以下が特に好ましい。例えば、２～２２が好ましく、２～２０がより好ましく、２～１８がさらに好ましく、２～１６がよりさらに好ましく、２～１４が特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。 Examples of the alkenyl group in R o include linear, branched, or cyclic alkenyl groups. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, even more preferably 18 or less, even more preferably 16 or less, and particularly preferably 14 or less. For example, the number is preferably 2 to 22, more preferably 2 to 20, even more preferably 2 to 18, even more preferably 2 to 16, and particularly preferably 2 to 14. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
　アルケニル基としては、例えば、エテニル基、プロペニル基、ブテニル基、シクロヘキセニル基が挙げられる。これらの中でも硬化性の観点から、エテニル基、プロペニル基が好ましく、エテニル基がより好ましい。
　アルケニル基が有していてもよい置換基としては、例えば、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシ基が挙げられ、現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Examples of the alkenyl group include ethenyl group, propenyl group, butenyl group, and cyclohexenyl group. Among these, from the viewpoint of curability, ethenyl group and propenyl group are preferred, and ethenyl group is more preferred.
Examples of substituents that the alkenyl group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxy group. From the viewpoint of developability, hydroxyl groups and oligoethylene glycol groups are preferred.
　Ｒｏにおけるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。 Examples of the halogen atom in R o include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
　Ｒｏにおけるアルコキシ基としては、直鎖状、分岐鎖状又は環状のアルコキシ基が挙げられる。その炭素数は、１以上が好ましく、また、２０以下が好ましく、１８以下がより好ましく、１６以下がさらに好ましく、１４以下がよりさらに好ましく、１２以下が特に好ましい。例えば、１～２０が好ましく、１～１８がより好ましく、１～１６がさらに好ましく、１～１４がよりさらに好ましく、１～１２が特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。 Examples of the alkoxy group in R o include linear, branched or cyclic alkoxy groups. The number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. For example, the number is preferably 1 to 20, more preferably 1 to 18, even more preferably 1 to 16, even more preferably 1 to 14, and particularly preferably 1 to 12. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
　アルコキシ基が有していてもよい置換基としては、例えば、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシ基、アクリロイル基、メタクリロイル基が挙げられ、現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Examples of substituents that the alkoxy group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxy group. , an acryloyl group, and a methacryloyl group, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.
　Ｒｏにおけるアルキルスルフィド基としては、直鎖状、分岐鎖状又は環状のアルキルスルフィド基が挙げられる。その炭素数は、１以上であることが好ましく、また、２０以下であることが好ましく、１８以下であることがより好ましく、１６以下であることがさらに好ましく、１４以下であることがよりさらに好ましく、１２以下であることが特に好ましい。例えば、１～２０が好ましく、１～１８がより好ましく、１～１６がさらに好ましく、１～１４がよりさらに好ましく、１～１２が特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。 Examples of the alkyl sulfide group in R o include linear, branched, or cyclic alkyl sulfide groups. The number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less. , 12 or less is particularly preferable. For example, the number is preferably 1 to 20, more preferably 1 to 18, even more preferably 1 to 16, even more preferably 1 to 14, and particularly preferably 1 to 12. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
　アルキルスルフィド基としては、例えば、メチルスルフィド基、エチルスルフィド基、プロピルスルフィド基、ブチルスルフィド基が挙げられる。これらの中でも現像性の観点から、メチルスルフィド基、エチルスルフィド基が好ましい。
　アルキルスルフィド基におけるアルキル基が有していてもよい置換基としては、例えば、メトキシ基、エトキシ基、クロロ基、ブロモ基、フルオロ基、ヒドロキシ基、アミノ基、エポキシ基、オリゴエチレングリコール基、フェニル基、カルボキシ基、アクリロイル基、メタクリロイル基が挙げられ、現像性の観点から、ヒドロキシ基、オリゴエチレングリコール基が好ましい。 Examples of the alkyl sulfide group include a methyl sulfide group, an ethyl sulfide group, a propyl sulfide group, and a butyl sulfide group. Among these, from the viewpoint of developability, methyl sulfide groups and ethyl sulfide groups are preferred.
Examples of substituents that the alkyl group in the alkyl sulfide group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, and phenyl group. group, carboxy group, acryloyl group, and methacryloyl group, and from the viewpoint of developability, hydroxy group and oligoethylene glycol group are preferable.
　これらの中でも現像性の観点から、Ｒｏとしては、ヒドロキシ基、カルボキシ基が好ましく、カルボキシ基がより好ましい。 Among these, from the viewpoint of developability, R o is preferably a hydroxy group or a carboxy group, and more preferably a carboxy group.
（ｔ）
　前記式（ｉｖ’’）においてｔは０～５の整数を表す。現像性の観点から、０～２が好ましく、０～１がより好ましく、０がさらに好ましい。 (t)
In the formula (iv''), t represents an integer from 0 to 5. From the viewpoint of developability, the number is preferably 0 to 2, more preferably 0 to 1, and even more preferably 0.
　（ｃ２－１）アクリル共重合樹脂が前記一般式（ｉｖ’’）で表される部分構造を含む場合、（ｃ２－１）アクリル共重合樹脂に含まれる前記一般式（ｉｖ’’）で表される部分構造の含有量は特に限定されないが、１モル％以上が好ましく、２モル％以上がより好ましく、３モル％以上がさらに好ましく、５モル％以上が特に好ましく、また、９０モル％以下が好ましく、７０モル％以下がより好ましく、５０モル％以下がさらに好ましく、３０モル％以下がよりさらに好ましく、２０モル％以下が特に好ましく、１０モル％以下が最も好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、１～９０モル％が好ましく、１～７０モル％がより好ましく、２～５０モル％がさらに好ましく、２～３０モル％がよりさらに好ましく、３～２０モル％が特に好ましく、５～１０モル％が最も好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。 (c2-1) When the acrylic copolymer resin contains a partial structure represented by the general formula (iv''), (c2-1) the acrylic copolymer resin contains a partial structure represented by the general formula (iv''). The content of the partial structure is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, even more preferably 3 mol% or more, particularly preferably 5 mol% or more, and 90 mol% or less. It is preferably 70 mol% or less, more preferably 50 mol% or less, even more preferably 30 mol% or less, particularly preferably 20 mol% or less, and most preferably 10 mol% or less. The upper and lower limits can be arbitrarily combined, for example, preferably 1 to 90 mol%, more preferably 1 to 70 mol%, even more preferably 2 to 50 mol%, even more preferably 2 to 30 mol%, Particularly preferred is 3 to 20 mol%, most preferred is 5 to 10 mol%. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
　（ｃ２－１）アクリル共重合樹脂が前記一般式（ｉｖ）で表される部分構造を含む場合、現像性の観点から下記一般式（ｉｖ’’’）で表される部分構造をさらに含むことが好ましい。 (c2-1) When the acrylic copolymer resin includes a partial structure represented by the general formula (iv) above, it may further include a partial structure represented by the following general formula (iv''') from the viewpoint of developability. is preferred.
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000046
　上記式（ｉｖ’’’）中、Ｒｐは水素原子又はメチル基を表す。 In the above formula (iv'''), R p represents a hydrogen atom or a methyl group.
　（ｃ２－１）アクリル共重合樹脂が前記一般式（ｉｖ’’’）で表される部分構造を含む場合、（ｃ２－１）アクリル共重合樹脂に含まれる前記一般式（ｉｖ’’’）で表される部分構造の含有量は特に限定されないが、５モル％以上が好ましく、１０モル％以上がより好ましく、３０モル％以上がさらに好ましく、また、９０モル％以下が好ましく、８０モル％以下がより好ましく、７０モル％以下がさらに好ましく、５０モル％以下が特に好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、５～９０モル％が好ましく、５～８０モル％がより好ましく、１０～７０モル％がさらに好ましく、３０～５０モル％が特に好ましい。前記下限値以上とすることで残渣が低減する傾向がある。
　また、前記上限値以下とすることで現像密着性が向上する傾向がある。 (c2-1) When the acrylic copolymer resin contains a partial structure represented by the general formula (iv'''), (c2-1) the general formula (iv''') contained in the acrylic copolymer resin The content of the partial structure represented by is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 30 mol% or more, and preferably 90 mol% or less, and 80 mol%. The following is more preferable, 70 mol% or less is even more preferable, and 50 mol% or less is particularly preferable. The upper and lower limits can be arbitrarily combined, for example, preferably 5 to 90 mol%, more preferably 5 to 80 mol%, even more preferably 10 to 70 mol%, and particularly preferably 30 to 50 mol%. There is a tendency for the amount of residue to be reduced by setting the amount to be equal to or more than the lower limit value.
Further, by setting the amount to be less than or equal to the upper limit value, the development adhesion tends to improve.
　（ｃ２）アクリル共重合樹脂の酸価は特に限定されないが、５ｍｇＫＯＨ／ｇ以上が好ましく、１０ｍｇＫＯＨ／ｇ以上がより好ましく、２０ｍｇＫＯＨ／ｇ以上がさらに好ましく、２５ｍｇＫＯＨ／ｇ以上がよりさらに好ましく、また、１００ｍｇＫＯＨ／ｇ以下が好ましく、８０ｍｇＫＯＨ／ｇ以下がより好ましく、６０ｍｇＫＯＨ／ｇ以下がさらに好ましく、４０ｍｇＫＯＨ／ｇ以下がよりさらに好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、５～１００ｍｇＫＯＨ／ｇが好ましく、１０～８０ｍｇＫＯＨ／ｇがより好ましく、２０～６０ｍｇＫＯＨ／ｇがさらに好ましく、２５～４０ｍｇＫＯＨ／ｇがよりさらに好ましい。前記下限値以上とすることで残渣が低減する傾向がある。また、前記上限値以下とすることで現像密着性が向上する傾向がある。 (c2) The acid value of the acrylic copolymer resin is not particularly limited, but is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, even more preferably 20 mgKOH/g or more, even more preferably 25 mgKOH/g or more, and It is preferably 100 mgKOH/g or less, more preferably 80 mgKOH/g or less, even more preferably 60 mgKOH/g or less, even more preferably 40 mgKOH/g or less. The upper and lower limits can be arbitrarily combined, for example, preferably 5 to 100 mgKOH/g, more preferably 10 to 80 mgKOH/g, even more preferably 20 to 60 mgKOH/g, even more preferably 25 to 40 mgKOH/g. There is a tendency for the amount of residue to be reduced by setting the amount to be equal to or more than the lower limit value. Further, by setting the amount to be less than or equal to the upper limit value, the development adhesion tends to improve.
　（ｃ２）アクリル共重合樹脂の重量平均分子量（Ｍｗ）は特に限定されないが、好ましくは１０００以上、より好ましくは２０００以上、さらに好ましくは３０００以上、よりさらに好ましくは４０００以上、特に好ましくは５０００以上であり、また、好ましくは３００００以下、より好ましくは２００００以下、さらに好ましくは１５０００以下、よりさらに好ましくは１００００以下である。特に好ましくは８０００以下である。前記上限及び下限は任意に組み合わせることができ、例えば、１０００～３００００が好ましく、２０００～２００００がより好ましく、３０００～１５０００がさらに好ましく、４０００～１００００がよりさらに好ましく、５０００～８０００が特に好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで残渣が低減する傾向がある。 (c2) The weight average molecular weight (Mw) of the acrylic copolymer resin is not particularly limited, but is preferably 1,000 or more, more preferably 2,000 or more, even more preferably 3,000 or more, even more preferably 4,000 or more, particularly preferably 5,000 or more. It is also preferably 30,000 or less, more preferably 20,000 or less, still more preferably 15,000 or less, even more preferably 10,000 or less. Particularly preferably, it is 8000 or less. The upper and lower limits can be arbitrarily combined, for example, preferably 1,000 to 30,000, more preferably 2,000 to 20,000, even more preferably 3,000 to 15,000, even more preferably 4,000 to 10,000, and particularly preferably 5,000 to 8,000. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the amount of residue tends to be reduced.
　（Ｃ）アルカリ可溶性樹脂が（ｃ２）アクリル共重合樹脂を含む場合、（Ｃ）アルカリ可溶性樹脂に含まれる（ｃ２）アクリル共重合樹脂の含有量は特に限定されないが、５質量％以上が好ましく、１０質量％以上がより好ましく、１５質量％以上がさらに好ましく、２０質量％以上が特に好ましく、また、通常１００質量％以下が好ましく、８０質量％以下がより好ましく、５０質量％以下がさらに好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、５～１００質量％が好ましく、１０～１００質量％がより好ましく、１５～８０質量％がさらに好ましく、２０～５０質量％が特に好ましい。前記下限値以上とすることで現像溶解性が良好となる傾向がある。前記上限値以下とすることでテーパ角が高くなる傾向がある。 When the alkali-soluble resin (C) contains (c2) an acrylic copolymer resin, the content of the (c2) acrylic copolymer resin contained in the alkali-soluble resin (C) is not particularly limited, but is preferably 5% by mass or more, The content is more preferably 10% by mass or more, further preferably 15% by mass or more, particularly preferably 20% by mass or more, and usually 100% by mass or less, more preferably 80% by mass or less, and even more preferably 50% by mass or less. The upper and lower limits can be arbitrarily combined, for example, preferably 5 to 100% by weight, more preferably 10 to 100% by weight, even more preferably 15 to 80% by weight, and particularly preferably 20 to 50% by weight. When the amount is equal to or more than the lower limit, the development solubility tends to be improved. By setting it below the upper limit value, the taper angle tends to become high.
　（Ｃ）アルカリ可溶性樹脂中には、（ｃ１）エポキシ（メタ）アクリレート樹脂及び（ｃ２）アクリル共重合樹脂のいずれかが単独で含まれていてもよく、両者が含まれていてもよい。さらに、（Ｃ）アルカリ可溶性樹脂中には（ｃ）アルカリ可溶性樹脂以外のアルカリ可溶性樹脂が含まれていてもよい。 (C) The alkali-soluble resin may contain either (c1) epoxy (meth)acrylate resin or (c2) acrylic copolymer resin alone, or may contain both. Furthermore, the alkali-soluble resin (C) may contain an alkali-soluble resin other than the alkali-soluble resin (c).
　本発明の重合性組成物における（Ｃ）アルカリ可溶性樹脂の含有量は、重合性組成物の全固形分中に、好ましくは５質量％以上、より好ましくは１０質量％以上、さらに好ましくは２０質量％以上、よりさらに好ましくは３０質量％以上、特に好ましくは４０質量％以上、また、好ましくは９０質量％以下、より好ましくは８０質量％以下、さらに好ましくは７０質量％以下である。前記上限及び下限は任意に組み合わせることができ、例えば、５～９０質量％が好ましく、１０～９０質量％がより好ましく、２０～８０質量％がさらに好ましく、３０～７０質量％がよりさらに好ましい。前記下限値以上とすることで現像性が向上する傾向がある。また、前記上限値以下とすることで硬化性が良好となる傾向がある。 The content of the alkali-soluble resin (C) in the polymerizable composition of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass in the total solid content of the polymerizable composition. % or more, even more preferably 30% by mass or more, particularly preferably 40% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less. The upper and lower limits can be arbitrarily combined, for example, preferably 5 to 90% by weight, more preferably 10 to 90% by weight, even more preferably 20 to 80% by weight, even more preferably 30 to 70% by weight. When the amount is equal to or more than the lower limit, developability tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, curability tends to be improved.
　本発明の重合性組成物が（ｃ１）エポキシ（メタ）アクリレート樹脂を含む場合、（ｃ１）エポキシ（メタ）アクリレート樹脂の含有量は特に限定されないが、重合性組成物の全固形分中に、好ましくは５質量％以上、より好ましくは１０質量％以上、さらに好ましくは２０質量％以上、よりさらに好ましくは３０質量％以上、特に好ましくは４０質量％以上、また、好ましくは９０質量％以下、より好ましくは７０質量％以下、さらに好ましくは６０質量％以下、特に好ましくは５０質量％以下である。前記上限及び下限は任意に組み合わせることができ、例えば、５～９０質量％が好ましく、１０～９０質量％がより好ましく、２０～７０質量％がさらに好ましく、３０～６０質量％がよりさらに好ましく、４０～５０質量％が特に好ましい。前記下限値以上とすることで現像性が向上する傾向がある。また、前記上限値以下とすることで硬化性が良好となる傾向がある。 When the polymerizable composition of the present invention contains (c1) epoxy (meth)acrylate resin, the content of (c1) epoxy (meth)acrylate resin is not particularly limited, but in the total solid content of the polymerizable composition, Preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, even more preferably 30% by mass or more, particularly preferably 40% by mass or more, and more preferably 90% by mass or less. The content is preferably 70% by mass or less, more preferably 60% by mass or less, particularly preferably 50% by mass or less. The upper and lower limits can be arbitrarily combined, for example, preferably 5 to 90% by mass, more preferably 10 to 90% by mass, even more preferably 20 to 70% by mass, even more preferably 30 to 60% by mass, Particularly preferred is 40 to 50% by weight. When the amount is equal to or more than the lower limit, developability tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, curability tends to be improved.
　また、本発明の重合性組成物が（ｃ２）アクリル共重合樹脂を含む場合、（ｃ２）アクリル共重合樹脂の含有量は特に限定されないが、重合性組成物の全固形分中に、好ましくは５質量％以上、より好ましくは１０質量％以上、さらに好ましくは２０質量％以上、よりさらに好ましくは３０質量％以上、特に好ましくは４０質量％以上、また、好ましくは９０質量％以下、より好ましくは８０質量％以下、さらに好ましくは７０質量％以下、である。前記上限及び下限は任意に組み合わせることができ、例えば、５～９０質量％が好ましく、１０～９０質量％がより好ましく、２０～８０質量％がさらに好ましく、３０～７０質量％がよりさらに好ましい。前記下限値以上とすることで現像性が向上する傾向がある。また、前記上限値以下とすることでテーパ形状が良好となる傾向がある。 Further, when the polymerizable composition of the present invention contains (c2) acrylic copolymer resin, the content of (c2) acrylic copolymer resin is not particularly limited, but preferably in the total solid content of the polymerizable composition. 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, even more preferably 30% by mass or more, particularly preferably 40% by mass or more, and preferably 90% by mass or less, more preferably It is 80% by mass or less, more preferably 70% by mass or less. The upper and lower limits can be arbitrarily combined, for example, preferably 5 to 90% by weight, more preferably 10 to 90% by weight, even more preferably 20 to 80% by weight, even more preferably 30 to 70% by weight. When the amount is equal to or more than the lower limit, developability tends to improve. In addition, by setting it below the upper limit value, there is a tendency that the tapered shape becomes better.
　また、重合性組成物の全固形分中における（Ｃ）アルカリ可溶性樹脂及び（Ｂ）重合性化合物の含有量の合計は、好ましくは５質量％以上、より好ましくは１０質量％以上、さらに好ましくは３０質量％以上、よりさらに好ましくは５０質量％以上、特に好ましくは７０質量％以上、さらに特に好ましくは８０質量％以上であり、最も好ましくは９０質量％以上であり、また、好ましくは９９質量％以下、より好ましくは９７質量％以下、さらに好ましくは９５質量％以下である。前記上限及び下限は任意に組み合わせることができ、例えば、５～９９質量％が好ましく、１０～９９質量％がより好ましく、３０～９９質量％がさらに好ましく、５０～９７質量％がよりさらに好ましく、７０～９７質量％がことさら好ましく、８０～９５質量％が特に好ましく、９０～９５質量％が最も好ましい。
　前記下限値以上とすることで現像性が向上する傾向がある。また、前記上限値以下とすることで熱重合開始剤等を増量させることができ、硬化性が向上する傾向がある。 Further, the total content of (C) alkali-soluble resin and (B) polymerizable compound in the total solid content of the polymerizable composition is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 30% by mass or more, even more preferably 50% by mass or more, particularly preferably 70% by mass or more, even more particularly preferably 80% by mass or more, most preferably 90% by mass or more, and preferably 99% by mass. The content is more preferably 97% by mass or less, still more preferably 95% by mass or less. The upper and lower limits can be arbitrarily combined, for example, preferably 5 to 99% by mass, more preferably 10 to 99% by mass, even more preferably 30 to 99% by mass, even more preferably 50 to 97% by mass, Particularly preferred is 70-97% by weight, particularly preferred is 80-95% by weight, and most preferred is 90-95% by weight.
When the amount is equal to or more than the lower limit, developability tends to improve. Further, by setting the amount to be below the upper limit, the amount of the thermal polymerization initiator etc. can be increased, and the curability tends to improve.
　重合性組成物における（Ｂ）重合性化合物に対する（Ｃ）アルカリ可溶性樹脂の配合比としては、（Ｂ）重合性化合物１００質量部に対して、５０質量部以上が好ましく、６０質量部以上がより好ましく、７０質量部以上がさらに好ましく、８０質量部以上が特に好ましく、また、５００質量部以下が好ましく、４００質量部以下がより好ましく、３００質量部以下がさらに好ましい。全上限及び下限は任意に組み合わせることができ、例えば、５０～４００質量部が好ましく、６０～３００質量部がより好ましい。前記下限値以上とすることで現像密着性が向上する傾向がある。また、前記上限値以下とすることで硬化性が向上する傾向がある。 The blending ratio of (C) alkali-soluble resin to (B) polymerizable compound in the polymerizable composition is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, per 100 parts by mass of (B) polymerizable compound. It is preferably 70 parts by mass or more, more preferably 80 parts by mass or more, further preferably 500 parts by mass or less, more preferably 400 parts by mass or less, and even more preferably 300 parts by mass or less. The total upper and lower limits can be arbitrarily combined, for example, preferably 50 to 400 parts by weight, more preferably 60 to 300 parts by weight. When the amount is equal to or more than the lower limit, development adhesion tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, the curability tends to improve.
［３－１－４］（Ｄ）光重合開始剤
　本発明の重合性組成物は、さらに（Ｄ）光重合開始剤を含有してもよい。（Ｄ）光重合開始剤は、光を直接吸収し、分解反応又は水素引き抜き反応を起こし、重合活性ラジカルを発生する機能を有する成分であり、（Ｂ）重合性化合物を重合させる。例えば、（Ｂ）重合性化合物が有するエチレン性不飽和結合を重合させる化合物であれば特に限定されない。 [3-1-4] (D) Photopolymerization initiator The polymerizable composition of the present invention may further contain (D) a photopolymerization initiator. (D) The photopolymerization initiator is a component that directly absorbs light, causes a decomposition reaction or a hydrogen abstraction reaction, and has a function of generating polymerization-active radicals, and polymerizes the (B) polymerizable compound. For example, it is not particularly limited as long as it is a compound that polymerizes the ethylenically unsaturated bond that the polymerizable compound (B) has.
　本発明の重合性組成物は、（Ｄ）光重合開始剤として、この分野で通常用いられている光重合開始剤を使用することができる。このような光重合開始剤としては、例えば、日本国特開昭５９－１５２３９６号公報、日本国特開昭６１－１５１１９７号公報に記載のチタノセン化合物を含むメタロセン化合物；日本国特開２０００－５６１１８号公報に記載のヘキサアリールビイミダゾール誘導体類；日本国特開平１０－３９５０３号公報記載のハロメチル化オキサジアゾール誘導体類、ハロメチル－ｓ－トリアジン誘導体類、Ｎ－フェニルグリシン等のＮ－アリール－α－アミノ酸類、Ｎ－アリール－α－アミノ酸塩類、Ｎ－アリール－α－アミノ酸エステル類等のラジカル活性剤、α－アミノアルキルフェノン誘導体類；日本国特開２０００－８００６８号公報、日本国特開２００６－３６７５０号公報等に記載されているオキシムエステル系化合物が挙げられる。 In the polymerizable composition of the present invention, a photopolymerization initiator commonly used in this field can be used as the photopolymerization initiator (D). Such photopolymerization initiators include, for example, metallocene compounds containing titanocene compounds described in Japanese Patent Application Laid-open Nos. 59-152396 and 61-151197; Japanese Patent Applications 2000-56118; N-aryl-α such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, and N-phenylglycine described in Japanese Patent Publication No. 10-39503; - Radical activators such as amino acids, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; Japanese Patent Publication No. 2000-80068, Japanese Patent Publication No. Examples include oxime ester compounds described in Publication No. 2006-36750 and the like.
　具体的には、例えば、メタロセン化合物としては、ジシクロペンタジエニルチタニウムジクロリド、ジシクロペンタジエニルチタニウムビスフェニル、ジシクロペンタジエニルチタニウムビス（２，３，４，５，６－ペンタフルオロフェニル）、ジシクロペンタジエニルチタニウムビス（２，３，５，６－テトラフルオロフェニル）、ジシクロペンタジエニルチタニウムビス（２，４，６－トリフルオロフェニル）、ジシクロペンタジエニルチタニウムジ（２，６－ジフルオロフェニル）、ジシクロペンタジエニルチタニウムジ（２，４－ジフルオロフェニル）、ジ（メチルシクロペンタジエニル）チタニウムビス（２，３，４，５，６－ペンタフルオロフェニル）、ジ（メチルシクロペンタジエニル）チタニウムビス（２，６－ジフルオロフェニル）、ジシクロペンタジエニルチタニウム〔２，６－ジ－フルオロ－３－（ピロ－１－イル）－フェニル〕が挙げられる。 Specifically, for example, metallocene compounds include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis(2,3,4,5,6-pentafluorophenyl ), dicyclopentadienyl titanium bis(2,3,5,6-tetrafluorophenyl), dicyclopentadienyl titanium bis(2,4,6-trifluorophenyl), dicyclopentadienyl titanium di( 2,6-difluorophenyl), dicyclopentadienyl titanium di(2,4-difluorophenyl), di(methylcyclopentadienyl)titanium bis(2,3,4,5,6-pentafluorophenyl), Examples include di(methylcyclopentadienyl) titanium bis(2,6-difluorophenyl) and dicyclopentadienyl titanium [2,6-di-fluoro-3-(pyrro-1-yl)-phenyl].
　ビイミダゾール誘導体類としては、例えば、２－（２’－クロロフェニル）－４，５－ジフェニルイミダゾール２量体、２－（２’－クロロフェニル）－４，５－ビス（３’－メトキシフェニル）イミダゾール２量体、２－（２’－フルオロフェニル）－４，５－ジフェニルイミダゾール２量体、２－（２’－メトキシフェニル）－４，５－ジフェニルイミダゾール２量体、（４’－メトキシフェニル）－４，５－ジフェニルイミダゾール２量体が挙げられる。 Examples of biimidazole derivatives include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazole dimer, (4'-methoxyphenyl) )-4,5-diphenylimidazole dimer.
　ハロメチル化オキサジアゾール誘導体類としては、例えば、２－トリクロロメチル－５－（２’－ベンゾフリル）－１，３，４－オキサジアゾール、２－トリクロロメチル－５－〔β－（２’－ベンゾフリル）ビニル〕－１，３，４－オキサジアゾール、２－トリクロロメチル－５－〔β－（２’－（６’’－ベンゾフリル）ビニル）〕－１，３，４－オキサジアゾール、２－トリクロロメチル－５－フリル－１，３，４－オキサジアゾールが挙げられる。 Examples of halomethylated oxadiazole derivatives include 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'- benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6''-benzofuryl)vinyl)]-1,3,4-oxadiazole, Examples include 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.
　ハロメチル－ｓ－トリアジン誘導体類としては、例えば、２－（４－メトキシフェニル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－メトキシナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－エトキシナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－エトキシカルボニルナフチル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジンが挙げられる。 Examples of halomethyl-s-triazine derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis( trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl) -s-triazine is mentioned.
　α－アミノアルキルフェノン誘導体類としては、例えば、２－メチル－１－〔４－（メチルチオ）フェニル〕－２－モルフォリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）ブタン－１－オン、２－ジメチルアミノ－２－（４－メチルベンジル）－１－(４－モルフォリノフェニル)ブタン－１－オン、３，６－ビス（２－メチル－２－モルフォリノプロピオニル）－９－オクチルカルバゾールが挙げられる。 Examples of α-aminoalkylphenone derivatives include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4 -morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one, 3,6-bis(2-methyl- Examples include 2-morpholinopropionyl)-9-octylcarbazole.
　光重合開始剤としては、特に、感度や製版性の点でオキシムエステル系化合物が有効であり、例えばフェノール性水酸基を含むアルカリ可溶性樹脂を用いる場合は、感度の点で不利になるため、特にこのような感度に優れたオキシムエステル系化合物が有用である。
　オキシムエステル系化合物は、熱反応に対して安定であり、光反応の量子収率が高く、生成するラジカルの活性が高いために、少量で高感度な重合性組成物を得ることが可能である。 As a photopolymerization initiator, oxime ester compounds are particularly effective in terms of sensitivity and plate-making properties. For example, when using an alkali-soluble resin containing a phenolic hydroxyl group, this is particularly recommended because it is disadvantageous in terms of sensitivity. Oxime ester compounds with excellent sensitivity are useful.
Oxime ester compounds are stable against thermal reactions, have a high quantum yield in photoreactions, and have high activity of generated radicals, making it possible to obtain highly sensitive polymerizable compositions in small amounts. .
　オキシムエステル系化合物としては、例えば、下記一般式（１）で表される化合物が挙げられる。 Examples of oxime ester compounds include compounds represented by the following general formula (1).
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000047
　式（１）中、
　Ｒ１０１は、水素原子、置換基を有していてもよいアルキル基、又は、置換基を有していてもよい芳香族環基を示す。
　Ｒ１０２は芳香環を含む任意の置換基を示す。
　Ｒ１０３は、置換基を有していてもよいアルカノイル基、又は、置換基を有していてもよいアロイル基を示す。
　ｎは０または１の整数を示す。 In formula (1),
R 101 represents a hydrogen atom, an alkyl group that may have a substituent, or an aromatic ring group that may have a substituent.
R 102 represents an arbitrary substituent containing an aromatic ring.
R 103 represents an alkanoyl group which may have a substituent or an aroyl group which may have a substituent.
n represents an integer of 0 or 1.
　Ｒ１０１におけるアルキル基の炭素数は特に限定されないが、溶媒への溶解性、感度の観点から、好ましくは１以上、より好ましくは２以上、また、好ましくは２０以下、より好ましくは１５以下、さらに好ましくは１０以下である。アルキル基の具体例としては、例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、シクロペンチルメチル基、シクロペンチルエチル基、シクロヘキシルメチル基、シクロヘキシルエチル基が挙げられる。
　アルキル基が有していてもよい置換基としては、例えば、芳香族環基、水酸基、カルボキシ基、ハロゲン原子、アミノ基、アミド基、４－（２－メトキシ－１－メチル）エトキシ－２－メチルフェニル基、Ｎ－アセチル－Ｎ－アセトキシアミノ基、フェニルチオ基が挙げられる。アルキル基としては、合成容易性の観点からは、無置換であることが好ましい。 The number of carbon atoms in the alkyl group in R 101 is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, it is preferably 1 or more, more preferably 2 or more, and preferably 20 or less, more preferably 15 or less, and Preferably it is 10 or less. Specific examples of the alkyl group include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, and a cyclohexylethyl group.
Examples of substituents that the alkyl group may have include aromatic ring groups, hydroxyl groups, carboxy groups, halogen atoms, amino groups, amide groups, 4-(2-methoxy-1-methyl)ethoxy-2- Examples include methylphenyl group, N-acetyl-N-acetoxyamino group, and phenylthio group. The alkyl group is preferably unsubstituted from the viewpoint of ease of synthesis.
　Ｒ１０１における芳香族環基としては、芳香族炭化水素環基及び芳香族複素環基が挙げられる。芳香族環基の炭素数は特に限定されないが、重合性組成物への溶解性の観点から５以上であることが好ましい。また、現像性の観点から３０以下であることが好ましく、２０以下であることがより好ましく、１２以下であることがさらに好ましい。例えば、５～３０が好ましく、５～２０がより好ましく、５～１２がさらに好ましい。 Examples of the aromatic ring group for R 101 include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the polymerizable composition. Further, from the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and even more preferably 12 or less. For example, the number is preferably 5 to 30, more preferably 5 to 20, and even more preferably 5 to 12.
　芳香族環基の具体例としては、例えば、フェニル基、ナフチル基、ピリジル基、フリル基が挙げられ、これらの中でも現像性の観点から、フェニル基又はナフチル基が好ましく、フェニル基がより好ましい。
　芳香族環基が有していてもよい置換基としては、例えば、水酸基、カルボキシ基、ハロゲン原子、アミノ基、アミド基、アルキル基、アルコキシ基、これらの置換基が連結した基が挙げられ、現像性の観点からアルキル基、アルコキシ基、これらを連結した基が好ましく、連結したアルコキシ基がより好ましい。
　これらの中でも、溶解性の観点から、Ｒ１０１が置換基を有していてもよいアルキル基であることが好ましい。 Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, and a furyl group. Among these, from the viewpoint of developability, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
Examples of substituents that the aromatic ring group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, and a group in which these substituents are linked, From the viewpoint of developability, an alkyl group, an alkoxy group, or a group formed by connecting these groups is preferable, and a connected alkoxy group is more preferable.
Among these, from the viewpoint of solubility, R 101 is preferably an alkyl group which may have a substituent.
　Ｒ１０２としては、好ましくは置換されていてもよいフェニル基、置換されていてもよいカルバゾリル基、置換されていてもよいチオキサントニル基、置換されていてもよいジフェニルスルフィド基、置換されていてもよいフルオレニル基、または置換されていてもよいインドリル基が挙げられる。これらの中でも、感度の観点から、置換されていてもよいカルバゾリル基又は置換されていてもよいジフェニルスルフィド基が好ましい。 R 102 is preferably an optionally substituted phenyl group, an optionally substituted carbazolyl group, an optionally substituted thioxanthonyl group, an optionally substituted diphenyl sulfide group, an optionally substituted diphenyl sulfide group, or an optionally substituted diphenyl sulfide group. Examples include a fluorenyl group and an optionally substituted indolyl group. Among these, from the viewpoint of sensitivity, an optionally substituted carbazolyl group or an optionally substituted diphenyl sulfide group is preferred.
　Ｒ１０３におけるアルカノイル基の炭素数は特に限定されないが、溶媒への溶解性や感度の観点から、好ましくは２以上、また、好ましくは２０以下、より好ましくは１５以下、さらに好ましくは１０以下、よりさらに好ましくは５以下である。アルカノイル基の具体例としては、例えば、アセチル基、エチロイル基、プロパノイル基、ブタノイル基が挙げられる。
　アルカノイル基が有していてもよい置換基としては、例えば、芳香族環基、水酸基、カルボキシ基、ハロゲン原子、アミノ基、アミド基が挙げられる。アルカノイル基としては、合成容易性の観点からは、無置換であることが好ましい。 The number of carbon atoms in the alkanoyl group in R103 is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, it is preferably 2 or more, more preferably 20 or less, more preferably 15 or less, even more preferably 10 or less, and more. More preferably, it is 5 or less. Specific examples of the alkanoyl group include, for example, an acetyl group, an ethyl group, a propanoyl group, and a butanoyl group.
Examples of substituents that the alkanoyl group may have include aromatic ring groups, hydroxyl groups, carboxy groups, halogen atoms, amino groups, and amide groups. The alkanoyl group is preferably unsubstituted from the viewpoint of ease of synthesis.
　Ｒ１０３におけるアロイル基の炭素数は特に限定されないが、溶媒への溶解性や感度の観点から、好ましくは７以上、また、好ましくは２０以下、より好ましくは１５以下、さらに好ましくは１０以下である。アロイル基の具体例としては、例えば、ベンゾイル基、ナフトイル基が挙げられる。
　アロイル基が有していてもよい置換基としては、例えば、水酸基、カルボキシ基、ハロゲン原子、アミノ基、アミド基、アルキル基が挙げられる。アロイル基としては、合成容易性の観点からは、無置換であることが好ましい。
　これらの中でも、感度の観点から、Ｒ１０３が置換基を有していてもよいアルカノイル基であることが好ましく、無置換のアルカノイル基であることがより好ましく、アセチル基であることがさらに好ましい。 The number of carbon atoms in the aroyl group in R 103 is not particularly limited, but from the viewpoint of solubility in solvents and sensitivity, it is preferably 7 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. . Specific examples of the aroyl group include benzoyl group and naphthoyl group.
Examples of substituents that the aroyl group may have include a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, and an alkyl group. The aroyl group is preferably unsubstituted from the viewpoint of ease of synthesis.
Among these, from the viewpoint of sensitivity, R 103 is preferably an alkanoyl group that may have a substituent, more preferably an unsubstituted alkanoyl group, and even more preferably an acetyl group.
　本発明の重合性組成物は、（Ｄ）光重合開始剤として、上記の光重合開始剤以外にも、例えば、日本国特許４４５４０６７号公報、国際公開２００２年／１００９０３号公報、国際公開２０１２年／４５７３６号公報、国際公開２０１５年／３６９１０号公報、国際公開２００６年／１８９７３号公報、国際公開２００８／７８６７８号公報、日本国特許４８１８４５８号公報、国際公開２００５年／８０３３８号／公報、国際公開２００８年／７５５６４号公報、国際公開２００９／１３１１８９号／公報、国際公報２００９年／１３１１８９号公報、国際公報２０１０年／１３３０７７号公報、国際公報２０１０年／１０２５０２号公報、国際公報年２０１２／６８８７９号公報に記載されている光重合開始剤などが使用できる。 In the polymerizable composition of the present invention, as (D) a photopolymerization initiator, in addition to the photopolymerization initiator described above, for example, Japanese Patent No. 4454067, International Publication No. 2002/100903, International Publication No. 2012 /45736 Publication, International Publication 2015/36910, International Publication 2006/18973, International Publication 2008/78678, Japanese Patent No. 4818458, International Publication 2005/80338/, International Publication 2008/75564, International Publication 2009/131189, International Publication 2009/131189, International Publication 2010/133077, International Publication 2010/102502, International Publication Year 2012/68879 Photopolymerization initiators described in publications can be used.
　光重合開始剤は、１種類を単独で用いても、２種類以上を組み合わせて使用してもよい。光重合開始剤には、必要に応じて、感度を高める目的で、画像露光光源の波長に応じた増感色素、重合促進剤を配合させることができる。増感色素としては、例えば、日本国特開平４－２２１９５８号公報、日本国特開平４－２１９７５６号公報に記載のキサンテン色素、日本国特開平３－２３９７０３号公報、日本国特開平５－２８９３３５号公報に記載の複素環を有するクマリン色素、日本国特開平３－２３９７０３号公報、日本国特開平５－２８９３３５号公報に記載の３－ケトクマリン化合物、日本国特開平６－１９２４０号公報に記載のピロメテン色素、日本国特開昭４７－２５２８号公報、日本国特開昭５４－１５５２９２号公報、日本国特公昭４５－３７３７７号公報、日本国特開昭４８－８４１８３号公報、日本国特開昭５２－１１２６８１号公報、日本国特開昭５８－１５５０３号公報、日本国特開昭６０－８８００５号公報、日本国特開昭５９－５６４０３号公報、日本国特開平２－６９号公報、日本国特開昭５７－１６８０８８号公報、日本国特開平５－１０７７６１号公報、日本国特開平５－２１０２４０号公報、日本国特開平４－２８８８１８号公報に記載のジアルキルアミノベンゼン骨格を有する色素を挙げることができる。 One type of photopolymerization initiator may be used alone, or two or more types may be used in combination. The photopolymerization initiator may contain a sensitizing dye and a polymerization accelerator depending on the wavelength of the image exposure light source, if necessary, for the purpose of increasing sensitivity. Examples of the sensitizing dye include xanthene dyes described in Japanese Patent Application Laid-Open No. 4-221958 and Japanese Patent Application Publication No. 4-219756, Japanese Patent Application Publication No. 3-239703, and Japanese Patent Application Publication No. 5-289335. Coumarin dyes having a heterocycle as described in Japanese Patent Publication No. 3-239703, 3-ketocoumarin compounds described in Japanese Patent Application Publication No. 5-289335, as described in Japanese Patent Application Publication No. 6-19240 Pyrromethene dye, Japanese Patent Publication No. 47-2528, Japanese Patent Application Publication No. 54-155292, Japanese Patent Publication No. 1982-37377, Japanese Patent Application Publication No. 48-84183, Japanese Patent Application Publication No. 1984-84183, Japanese Unexamined Patent Publication No. 52-112681, Japanese Unexamined Patent Application No. 58-15503, Unexamined Japanese Patent Application No. 60-88005, Unexamined Japanese Patent Application No. 59-56403, Unexamined Japanese Patent Application No. 2-69 Hei 2-69 , having a dialkylaminobenzene skeleton as described in Japanese Patent Application Publication No. 57-168088, Japanese Publication No. 5-107761, Japanese Patent Application Publication No. 5-210240, and Japanese Patent Application Publication No. 4-288818. Dyes can be mentioned.
　これらの増感色素のうち、アミノ基含有増感色素が好ましく、アミノ基及びフェニル基を同一分子内に有する化合物がより好ましい。例えば、４，４’－ジメチルアミノベンゾフェノン、４，４’－ジエチルアミノベンゾフェノン、２－アミノベンゾフェノン、４－アミノベンゾフェノン、４，４’－ジアミノベンゾフェノン、３，３’－ジアミノベンゾフェノン、３，４－ジアミノベンゾフェノン等のベンゾフェノン系化合物；２－（ｐ－ジメチルアミノフェニル）ベンゾオキサゾール、２－（ｐ－ジエチルアミノフェニル）ベンゾオキサゾール、２－（ｐ－ジメチルアミノフェニル）ベンゾ［４，５］ベンゾオキサゾール、２－（ｐ－ジメチルアミノフェニル）ベンゾ［６，７］ベンゾオキサゾール、２，５－ビス（ｐ－ジエチルアミノフェニル）－１，３，４－オキサゾール、２－（ｐ－ジメチルアミノフェニル）ベンゾチアゾール、２－（ｐ－ジエチルアミノフェニル）ベンゾチアゾール、２－（ｐ－ジメチルアミノフェニル）ベンズイミダゾール、２－（ｐ－ジエチルアミノフェニル）ベンズイミダゾール、２，５－ビス（ｐ－ジエチルアミノフェニル）－１，３，４－チアジアゾール、（ｐ－ジメチルアミノフェニル）ピリジン、（ｐ－ジエチルアミノフェニル）ピリジン、（ｐ－ジメチルアミノフェニル）キノリン、（ｐ－ジエチルアミノフェニル）キノリン、（ｐ－ジメチルアミノフェニル）ピリミジン、（ｐ－ジエチルアミノフェニル）ピリミジン等のｐ－ジアルキルアミノフェニル基含有化合物がさらに好ましい。これらの中でも、４，４’－ジアルキルアミノベンゾフェノンが特に好ましい。
　増感色素は、１種を単独で用いてもよく、２種以上を併用してもよい。 Among these sensitizing dyes, amino group-containing sensitizing dyes are preferred, and compounds having an amino group and a phenyl group in the same molecule are more preferred. For example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4-diaminobenzophenone Benzophenone compounds such as benzophenone; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzoxazole, 2- (p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-oxazole, 2-(p-dimethylaminophenyl)benzothiazole, 2- (p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)-1,3,4- Thiadiazole, (p-dimethylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, (p-diethylaminophenyl) ) P-dialkylaminophenyl group-containing compounds such as pyrimidine are more preferred. Among these, 4,4'-dialkylaminobenzophenone is particularly preferred.
The sensitizing dyes may be used alone or in combination of two or more.
　重合促進剤としては、例えば、４－ジメチルアミノ安息香酸エチル、４－ジメチルアミノ安息香酸２－エチルへキシル、４－ジメチルアミノアセトフェノン、４－ジメチルアミノプロピオフェノン等の芳香族アミン、ｎ－ブチルアミン、Ｎ－メチルジエタノールアミン、安息香酸２－ジメチルアミノエチル等の脂肪族アミンを用いることができる。重合促進剤は、１種を単独で用いても、２種以上を併用してもよい。 Examples of the polymerization accelerator include aromatic amines such as ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 4-dimethylaminoacetophenone, and 4-dimethylaminopropiophenone, and n-butylamine. , N-methyldiethanolamine, 2-dimethylaminoethyl benzoate, and the like can be used. The polymerization accelerators may be used alone or in combination of two or more.
　本発明の重合性組成物が（Ｄ）光重合開始剤を含有する場合、（Ｄ）光重合開始剤の含有割合は特に限定されないが、重合性組成物の全固形分中に、好ましくは０．０１質量％以上、より好ましくは０．１質量％以上、さらに好ましくは１質量％以上、よりさらに好ましくは２質量％以上、特に好ましくは３質量％以上であり、また、好ましくは２５質量％以下、より好ましくは２０質量％以下、さらに好ましくは１５質量％以下、よりさらに好ましくは１０質量％以下、特に好ましくは７質量％以下、最も好ましくは５質量％以下である。例えば、０．０１～２５質量％が好ましく、０．０１～２０質量％がより好ましく、０．１～１５質量％がさらに好ましく、１～１０質量％がよりさらに好ましく、２～７質量％がことさら好ましく、３～５質量％が特に好ましい。前記下限値以上とすることで硬化性が向上する傾向がある。前記上限値以下とすることで残渣が低減する傾向がある。 When the polymerizable composition of the present invention contains (D) a photopolymerization initiator, the content ratio of the photopolymerization initiator (D) is not particularly limited, but it is preferably 0% in the total solid content of the polymerizable composition. .01% by mass or more, more preferably 0.1% by mass or more, even more preferably 1% by mass or more, even more preferably 2% by mass or more, particularly preferably 3% by mass or more, and preferably 25% by mass. The content is more preferably 20% by mass or less, still more preferably 15% by mass or less, even more preferably 10% by mass or less, particularly preferably 7% by mass or less, most preferably 5% by mass or less. For example, it is preferably 0.01 to 25% by mass, more preferably 0.01 to 20% by mass, even more preferably 0.1 to 15% by mass, even more preferably 1 to 10% by mass, and even more preferably 2 to 7% by mass. Particularly preferred is 3 to 5% by weight. There is a tendency for the curability to improve when the amount is equal to or more than the lower limit. There is a tendency for the amount of residue to be reduced by setting the amount to be less than or equal to the upper limit value.
　重合性組成物中の（Ｂ）重合性化合物に対する（Ｄ）光重合開始剤の配合比としては、（Ｂ）重合性化合物１００質量部に対して、１質量部以上が好ましく、５質量部以上がより好ましく、１０質量部以上がさらに好ましく、１５質量部以上がよりさらに好ましく、２０質量部以上が特に好ましく、また、２００質量部以下が好ましく、１００質量部以下がより好ましく、５０質量部以下がさらに好ましく、３０質量部以下が特に好ましい。例えば、１～２００質量部が好ましく、５～２００質量部がより好ましく、１０～１００質量部がさらに好ましく、１５～５０質量部がよりさらに好ましく、２０～３０質量部が特に好ましい。前記下限値以上とすることで硬化性が向上する傾向がある。前記上限値以下とすることで残渣が低減する傾向がある。 The blending ratio of (D) photopolymerization initiator to (B) polymerizable compound in the polymerizable composition is preferably 1 part by mass or more, and 5 parts by mass or more with respect to 100 parts by mass of (B) polymerizable compound. is more preferable, 10 parts by weight or more is still more preferable, 15 parts by weight or more is even more preferable, 20 parts by weight or more is particularly preferable, and 200 parts by weight or less is preferable, more preferably 100 parts by weight or less, 50 parts by weight or less. is more preferable, and 30 parts by mass or less is particularly preferable. For example, it is preferably 1 to 200 parts by weight, more preferably 5 to 200 parts by weight, even more preferably 10 to 100 parts by weight, even more preferably 15 to 50 parts by weight, and particularly preferably 20 to 30 parts by weight. There is a tendency for the curability to improve when the amount is equal to or more than the lower limit. There is a tendency for the amount of residue to be reduced by setting the amount to be less than or equal to the upper limit value.
［３－１－５］（Ｅ）着色剤
　本発明の重合性組成物は、組成物を着色させる目的で（Ｅ）着色剤を含有してもよい。
　（Ｅ）着色剤としては、顔料、染料等公知の着色剤を用いることができる。
　本発明で用いる（Ｅ）着色剤の種類は特に限定されず、顔料を用いてもよいし、染料を用いてもよい。これらの中でも、耐久性の観点から、顔料を用いることが好ましい。 [3-1-5] (E) Colorant The polymerizable composition of the present invention may contain (E) a colorant for the purpose of coloring the composition.
(E) As the colorant, known colorants such as pigments and dyes can be used.
The type of colorant (E) used in the present invention is not particularly limited, and pigments or dyes may be used. Among these, from the viewpoint of durability, it is preferable to use pigments.
　（Ｅ）着色剤に含まれる顔料は、１種でも２種以上でもよい。特に、可視領域において均一に遮光するとの観点からは、２種以上であることが好ましい。
　（Ｅ）着色剤として用いることができる顔料の種類は特に限定されないが、例えば、有機顔料や無機顔料が挙げられる。これらの中でも、重合性組成物の透過波長をコントロールして効率的に硬化させるとの観点からは、有機顔料を用いることが好ましい。
　有機顔料としては、有機着色顔料や有機黒色顔料が挙げられる。ここで、有機着色顔料とは、黒色以外の色を呈する有機顔料のことを意味し、赤色顔料、橙色顔料、青色顔料、紫色顔料、緑色顔料、黄色顔料等が挙げられる。 (E) The colorant may contain one type or two or more types of pigments. In particular, from the viewpoint of uniformly blocking light in the visible region, it is preferable to use two or more types.
(E) The type of pigment that can be used as the colorant is not particularly limited, and examples thereof include organic pigments and inorganic pigments. Among these, it is preferable to use organic pigments from the viewpoint of controlling the transmission wavelength of the polymerizable composition and curing it efficiently.
Examples of organic pigments include organic colored pigments and organic black pigments. Here, the organic colored pigment refers to an organic pigment exhibiting a color other than black, and includes red pigments, orange pigments, blue pigments, violet pigments, green pigments, yellow pigments, and the like.
　有機顔料の中でも、紫外線吸収性の観点から有機着色顔料を用いることが好ましい。
　有機着色顔料は、１種を単独で用いてもよく、２種以上を併用してもよい。特に、遮光性の用途に用いる場合には、色の異なる有機着色顔料を組み合わせて用いることがより好ましく、黒に近い色を呈する有機着色顔料の組み合わせを用いることがさらに好ましい。 Among the organic pigments, it is preferable to use organic colored pigments from the viewpoint of ultraviolet absorbability.
One type of organic coloring pigment may be used alone, or two or more types may be used in combination. In particular, when used for light-shielding applications, it is more preferable to use a combination of organic coloring pigments of different colors, and it is even more preferable to use a combination of organic coloring pigments that exhibit a color close to black.
　これらの有機顔料の化学構造は特に限定されないが、例えば、アゾ系、フタロシアニン系、キナクリドン系、ベンズイミダゾロン系、イソインドリノン系、ジオキサジン系、インダンスレン系、ペリレン系が挙げられる。以下、使用できる顔料の具体例をピグメントナンバーで示す。以下に挙げる「Ｃ．Ｉ．ピグメントレッド２」等の用語は、カラーインデックス（Ｃ．Ｉ．）を意味する。 The chemical structure of these organic pigments is not particularly limited, but examples thereof include azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. Specific examples of pigments that can be used are shown below using pigment numbers. Terms such as "C.I. Pigment Red 2" listed below mean color index (C.I.).
　赤色顔料としては、Ｃ．Ｉ．ピグメントレッド１、２、３、４、５、６、７、８、９、１２、１４、１５、１６、１７、２１、２２、２３、３１、３２、３７、３８、４１、４７、４８、４８：１、４８：２、４８：３、４８：４、４９、４９：１、４９：２、５０：１、５２：１、５２：２、５３、５３：１、５３：２、５３：３、５７、５７：１、５７：２、５８：４、６０、６３、６３：１、６３：２、６４、６４：１、６８、６９、８１、８１：１、８１：２、８１：３、８１：４、８３、８８、９０：１、１０１、１０１：１、１０４、１０８、１０８：１、１０９、１１２、１１３、１１４、１２２、１２３、１４４、１４６、１４７、１４９、１５１、１６６、１６８、１６９、１７０、１７２、１７３、１７４、１７５、１７６、１７７、１７８、１７９、１８１、１８４、１８５、１８７、１８８、１９０、１９３、１９４、２００、２０２、２０６、２０７、２０８、２０９、２１０、２１４、２１６、２２０、２２１、２２４、２３０、２３１、２３２、２３３、２３５、２３６、２３７、２３８、２３９、２４２、２４３、２４５、２４７、２４９、２５０、２５１、２５３、２５４、２５５、２５６、２５７、２５８、２５９、２６０、２６２、２６３、２６４、２６５、２６６、２６７、２６８、２６９、２７０、２７１、２７２、２７３、２７４、２７５、２７６を挙げることができる。
　この中でも、遮光性、分散性の観点から好ましくはＣ．Ｉ．ピグメントレッド４８：１、１２２、１４９、１６８、１７７、１７９、１９４、２０２、２０６、２０７、２０９、２２４、２４２、２５４、さらに好ましくはＣ．Ｉ．ピグメントレッド１７７、２０９、２２４、２５４を挙げることができる。
　なお、分散性や遮光性の点で、Ｃ．Ｉ．ピグメントレッド１７７、２５４、２７２を用いることが好ましく、重合性組成物を紫外線で硬化させる場合には、赤色顔料としては紫外線吸収率の低いものを使用することが好ましく、係る観点からはＣ．Ｉ．ピグメントレッド２５４、２７２を用いることがより好ましい。 As a red pigment, C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81: 3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276.
Among these, C.I. I. Pigment Red 48:1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment Red 177, 209, 224, and 254.
In addition, in terms of dispersibility and light blocking properties, C. I. Pigment Red 177, 254, and 272 are preferably used. When curing the polymerizable composition with ultraviolet rays, it is preferable to use red pigments with low ultraviolet absorbance; from this point of view, C. I. It is more preferable to use Pigment Red 254 and 272.
　橙色（オレンジ）顔料としては、Ｃ．Ｉ．ピグメントオレンジ１、２、５、１３、１６、１７、１９、２０、２１、２２、２３、２４、３４、３６、３８、３９、４３、４６、４８、４９、６１、６２、６４、６５、６７、６８、６９、７０、７１、７２、７３、７４、７５、７７、７８、７９を挙げることができる。
　この中でも分散性や遮光性の観点から、Ｃ．Ｉ．ピグメントオレンジ１３、４３、６４、７２を用いることが好ましく、重合性組成物を紫外線で硬化させる場合には、オレンジ顔料としては紫外線吸収率の低いものを使用することが好ましく、係る観点からはＣ．Ｉ．ピグメントオレンジ６４、７２を用いることがより好ましい。 As the orange pigment, C. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79.
Among these, C. I. It is preferable to use Pigment Orange 13, 43, 64, and 72. When curing the polymerizable composition with ultraviolet rays, it is preferable to use orange pigments with low ultraviolet absorbance, and from this point of view, C ．． I. It is more preferable to use Pigment Orange 64 and 72.
　青色顔料としては、Ｃ．Ｉ．ピグメントブルー１、１：２、９、１４、１５、１５：１、１５：２、１５：３、１５：４、１５：６、１６、１７、１９、２５、２７、２８、２９、３３、３５、３６、５６、５６：１、６０、６１、６１：１、６２、６３、６６、６７、６８、７１、７２、７３、７４、７５、７６、７８、７９を挙げることができる。
　この中でも、遮光性の観点から、好ましくはＣ．Ｉ．ピグメントブルー１５、１５：１、１５：２、１５：３、１５：４、１５：６、６０、さらに好ましくはＣ．Ｉ．ピグメントブルー１５：６を挙げることができる。
　なお、分散性や遮光性の点で、Ｃ．Ｉ．ピグメントブルー１５：６、１６、６０を用いることが好ましく、重合性組成物を紫外線で硬化させる場合には、青色顔料としては紫外線吸収率の低いものを使用することが好ましく、かかる観点からはＣ．Ｉ．ピグメントブルー６０を用いることがより好ましい。 As a blue pigment, C. I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79.
Among these, from the viewpoint of light-shielding properties, C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 60, more preferably C.I. I. Pigment Blue 15:6 may be mentioned.
In addition, in terms of dispersibility and light blocking properties, C. I. It is preferable to use Pigment Blue 15:6, 16, and 60. When curing the polymerizable composition with ultraviolet rays, it is preferable to use a blue pigment with low ultraviolet absorption rate, and from this point of view, C ．． I. It is more preferable to use Pigment Blue 60.
　紫色顔料としては、Ｃ．Ｉ．ピグメントバイオレット１、１：１、２、２：２、３、３：１、３：３、５、５：１、１４、１５、１６、１９、２３、２５、２７、２９、３１、３２、３７、３９、４２、４４、４７、４９、５０を挙げることができる。
　この中でも、遮光性の観点から、好ましくはＣ．Ｉ．ピグメントバイオレット１９、２３、さらに好ましくはＣ．Ｉ．ピグメントバイオレット２３を挙げることができる。
　なお、分散性や遮光性の点で、Ｃ．Ｉ．ピグメントバイオレット２３、２９を用いることが好ましく、重合性組成物を紫外線で硬化させる場合には、紫色顔料としては紫外線吸収率の低いものを使用することが好ましく、係る観点からはＣ．Ｉ．ピグメントバイオレット２９を用いることがより好ましい。 As a purple pigment, C. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50.
Among these, from the viewpoint of light-shielding properties, C.I. I. Pigment Violet 19, 23, more preferably C.I. I. Pigment Violet 23 may be mentioned.
In addition, in terms of dispersibility and light blocking properties, C. I. It is preferable to use Pigment Violet 23 and 29, and when curing the polymerizable composition with ultraviolet rays, it is preferable to use a purple pigment with a low ultraviolet absorbance.From this point of view, C.I. I. It is more preferable to use Pigment Violet 29.
　赤色顔料、橙色顔料、青色顔料、紫色顔料の他に用いることができる有機着色顔料としては例えば、緑色顔料、黄色顔料等を挙げることができる。
　緑色顔料としては、Ｃ．Ｉ．ピグメントグリーン１、２、４、７、８、１０、１３、１４、１５、１７、１８、１９、２６、３６、４５、４８、５０、５１、５４、５５を挙げることができる。
　この中でも、好ましくはＣ．Ｉ．ピグメントグリーン７、３６を挙げることができる。
　黄色顔料としては、Ｃ．Ｉ．ピグメントイエロー１、１：１、２、３、４、５、６、９、１０、１２、１３、１４、１６、１７、２４、３１、３２、３４、３５、３５：１、３６、３６：１、３７、３７：１、４０、４１、４２、４３、４８、５３、５５、６１、６２、６２：１、６３、６５、７３、７４、７５、８１、８３、８７、９３、９４、９５、９７、１００、１０１、１０４、１０５、１０８、１０９、１１０、１１１、１１６、１１７、１１９、１２０、１２６、１２７、１２７：１、１２８、１２９、１３３、１３４、１３６、１３８、１３９、１４２、１４７、１４８、１５０、１５１、１５３、１５４、１５５、１５７、１５８、１５９、１６０、１６１、１６２、１６３、１６４、１６５、１６６、１６７、１６８、１６９、１７０、１７２、１７３、１７４、１７５、１７６、１８０、１８１、１８２、１８３、１８４、１８５、１８８、１８９、１９０、１９１、１９１：１、１９２、１９３、１９４、１９５、１９６、１９７、１９８、１９９、２００、２０２、２０３、２０４、２０５、２０６、２０７、２０８を挙げることができる。
　この中でも、好ましくはＣ．Ｉ．ピグメントイエロー８３、１１７、１２９、１３８、１３９、１５０、１５４、１５５、１８０、１８５、さらに好ましくはＣ．Ｉ．ピグメントイエロー８３、１３８、１３９、１５０、１８０を挙げることができる。 Examples of organic coloring pigments that can be used in addition to red pigments, orange pigments, blue pigments, and purple pigments include green pigments and yellow pigments.
As a green pigment, C. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55.
Among these, C. I. Pigment Green 7 and 36 can be mentioned.
As a yellow pigment, C. I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, and 208 can be mentioned.
Among these, C. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment Yellow 83, 138, 139, 150, and 180.
　これらの中でも、遮光性や、光硬化性の観点から、赤色顔料、橙色顔料、青色顔料及び紫色顔料からなる群から選ばれる少なくとも１種を用いることが好ましい。 Among these, it is preferable to use at least one selected from the group consisting of red pigments, orange pigments, blue pigments, and violet pigments from the viewpoint of light-shielding properties and photocurability.
　これらの中でも、硬化性や、光硬化性の観点からは、以下の顔料のうち少なくとも１種以上を含有するものとすることが好ましい。
　赤色顔料：Ｃ．Ｉ．ピグメントレッド１７７、２５４、２７２
　橙色顔料：Ｃ．Ｉ．ピグメントオレンジ４３、６４、７２
　青色顔料：Ｃ．Ｉ．ピグメントブルー１５：６、６０
　紫色顔料：Ｃ．Ｉ．ピグメントバイオレット２３、２９ Among these, from the viewpoint of curability and photocurability, it is preferable to contain at least one or more of the following pigments.
Red pigment: C. I. Pigment Red 177, 254, 272
Orange pigment: C. I. Pigment orange 43, 64, 72
Blue pigment: C. I. Pigment Blue 15:6,60
Purple pigment: C. I. pigment violet 23, 29
　また、遮光性の観点から、（Ｅ）着色剤として有機黒色顔料を用いることが好ましい。
　有機黒色顔料としては、アニリンブラック、ペリレンブラックや以下一般式（２）で表される有機黒色顔料が挙げられる。このうち、遮光性、分散性の観点から、式（２）で表される有機黒色顔料がより好ましい。 Moreover, from the viewpoint of light-shielding properties, it is preferable to use an organic black pigment as the colorant (E).
Examples of the organic black pigment include aniline black, perylene black, and an organic black pigment represented by the following general formula (2). Among these, from the viewpoint of light-shielding properties and dispersibility, the organic black pigment represented by formula (2) is more preferable.
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000048
　また無機顔料を使用することもできる。無機黒色顔料としては、カーボンブラック、アセチレンブラック、ランプブラック、ボーンブラック、黒鉛、鉄黒、シアニンブラック、チタンブラック等が挙げられる。これらの中でも、遮光性、分散性の観点からカーボンブラックを好ましく用いることができる。 Inorganic pigments can also be used. Examples of inorganic black pigments include carbon black, acetylene black, lamp black, bone black, graphite, iron black, cyanine black, and titanium black. Among these, carbon black can be preferably used from the viewpoint of light-shielding properties and dispersibility.
　顔料を用いる際に、その顔料が凝集せずに安定して重合性組成物中に存在できるように、公知の分散剤や分散助剤が併用されてもよい。 When using a pigment, a known dispersant or dispersion aid may be used in combination so that the pigment can stably exist in the polymerizable composition without agglomerating.
　本発明の重合性組成物が（Ｅ）着色剤を含有する場合、着色剤の含有量としては、特に限定されないが、重合性組成物の全固形分中に、好ましくは１質量％以上、より好ましくは１０質量％以上であり、また、好ましくは６０質量％以下、より好ましくは４０質量％以下である。
　下限値以上とすることで、色特性、遮光性が良化する傾向があり、上限値以下とすることで、硬化性が良化する傾向がある。 When the polymerizable composition of the present invention contains the colorant (E), the content of the colorant is not particularly limited, but is preferably 1% by mass or more, more preferably 1% by mass or more based on the total solid content of the polymerizable composition. The content is preferably 10% by mass or more, more preferably 60% by mass or less, and more preferably 40% by mass or less.
When the amount is at least the lower limit, color properties and light shielding properties tend to be improved, and when it is at most the upper limit, the curability tends to be improved.
［３－１－６］（Ｆ）連鎖移動剤
　本発明の重合性組成物は、（Ｆ）連鎖移動剤を含有してもよい。（Ｆ）連鎖移動剤を含むことで、表面近傍における酸素阻害等によるラジカル失活が改善されて表面硬化性を高めることができ、テーパ角が高くなる傾向がある。
　（Ｆ）連鎖移動剤としては、例えば、メルカプト基含有化合物や、四塩化炭素が挙げられ、連鎖移動効果が高い傾向があることからメルカプト基含有化合物がより好ましい。メルカプト基含有化合物は、Ｓ－Ｈ結合エネルギーが小さいことによって結合開裂が起こりやすく、連鎖移動反応を起こしやすいため、表面硬化性を高めることができる傾向がある。 [3-1-6] (F) Chain transfer agent The polymerizable composition of the present invention may contain (F) a chain transfer agent. (F) By including a chain transfer agent, radical deactivation due to oxygen inhibition in the vicinity of the surface can be improved, surface hardenability can be improved, and the taper angle tends to increase.
Examples of the chain transfer agent (F) include mercapto group-containing compounds and carbon tetrachloride, and mercapto group-containing compounds are more preferred since they tend to have a high chain transfer effect. Mercapto group-containing compounds tend to be able to improve surface hardening properties because bond cleavage is likely to occur due to the small S--H bond energy and chain transfer reactions are likely to occur.
　連鎖移動剤の中でも、テーパ角、表面硬化性の観点から、芳香族環を有するメルカプト基含有化合物と脂肪族系のメルカプト基含有化合物が好ましい。
　脂肪族系のメルカプト基含有化合物としては、例えば、ブタンジオールビス（３－メルカプトプロピオネート）、ブタンジオールビスチオグリコレート、エチレングリコールビス（３－メルカプトプロピオネート）、エチレングリコールビスチオグリコレート、トリメチロールプロパントリス（３－メルカプトプロピオネート）、トリメチロールプロパントリスチオグリコレート、トリスヒドロキシエチルトリスチオプロピオネート、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、ペンタエリスリトールトリス（３－メルカプトプロピオネート）、ブタンジオールビス（３－メルカプトブチレート）、エチレングリコールビス（３－メルカプトブチレート）、トリメチロールプロパントリス（３－メルカプトブチレート）、ペンタエリスリトールテトラキス（３－メルカプトブチレート）、ペンタエリスリトールトリス（３－メルカプトブチレート）、１，３，５－トリス（３－メルカプトブチルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオンが挙げられる。 Among the chain transfer agents, mercapto group-containing compounds having an aromatic ring and aliphatic mercapto group-containing compounds are preferred from the viewpoint of taper angle and surface hardening properties.
Examples of aliphatic mercapto group-containing compounds include butanediol bis(3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol bis(3-mercaptopropionate), and ethylene glycol bisthioglycolate. , trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tristhioglycolate, trishydroxyethyltristhiopropionate, pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate) propionate), butanediol bis(3-mercaptobutyrate), ethylene glycol bis(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), Pentaerythritol tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione Can be mentioned.
　これらのうち、トリメチロールプロパントリス（３－メルカプトプロピオネート）、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、ペンタエリスリトールトリス（３－メルカプトプロピオネート）、トリメチロールプロパントリス（３－メルカプトブチレート）、ペンタエリスリトールテトラキス（３－メルカプトブチレート）、ペンタエリスリトールトリス（３－メルカプトブチレート）、１，３，５－トリス（３－メルカプトブチルオキシエチル）－１，３，５－トリアジン－２，４，６（１Ｈ，３Ｈ，５Ｈ）－トリオンが好ましく、ペンタエリスリトールテトラキス（３－メルカプトプロピオネート）、ペンタエリスリトールテトラキス（３－メルカプトブチレート）がより好ましい。 Among these, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2 , 4,6(1H,3H,5H)-trione are preferred, and pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate) are more preferred.
　これらは１種を単独で用いてもよく、２種以上を併用してもよい。 These may be used alone or in combination of two or more.
［３－１－７］塗布性向上剤、現像改良剤
　本発明の重合性組成物は、塗布性や現像溶解性を向上するために塗布性向上剤や現像改良剤を含有してもよい。
　塗布性向上剤あるいは現像改良剤としては、例えば、公知の界面活性剤を用いることができる。
　界面活性剤は、重合性組成物の塗布液としての塗布性、及び塗布膜の現像性の向上などを目的として用いることができ、中でもフッ素系界面活性剤又はシリコーン系界面活性剤が好ましい。
　特に、現像の際、未露光部から重合性組成物の残渣を除去する作用があり、また、濡れ性を発現する機能を有することから、シリコーン系界面活性剤が好ましく、ポリエーテル変性シリコーン系界面活性剤がさらに好ましい。 [3-1-7] Spreadability improver and development improver The polymerizable composition of the present invention may contain a coatability improver and a development improver in order to improve the coatability and development solubility.
As the coating property improver or development improver, for example, known surfactants can be used.
The surfactant can be used for the purpose of improving the coating properties of the polymerizable composition as a coating solution and the developability of the coating film, and among them, fluorine-based surfactants or silicone-based surfactants are preferred.
In particular, silicone-based surfactants are preferred because they have the effect of removing residues of the polymerizable composition from unexposed areas during development and also have the function of developing wettability. Activators are even more preferred.
　フッ素系界面活性剤としては、末端、主鎖及び側鎖の少なくとも何れかの部位にフルオロアルキル又はフルオロアルキレン基を有する化合物が好適である。具体的には、１，１，２，２－テトラフロロオクチル（１，１，２，２－テトラフロロプロピル）エーテル、１，１，２，２－テトラフロロオクチルヘキシルエーテル、オクタエチレングリコールジ（１，１，２，２－テトラフロロブチル）エーテル、ヘキサエチレングリコールジ（１，１，２，２，３，３－ヘキサフロロペンチル）エーテル、オクタプロピレングリコールジ（１，１，２，２－テトラフロロブチル）エーテル、ヘキサプロピレングリコールジ（１，１，２，２，３，３－ヘキサフロロペンチル）エーテル、パーフロロドデシルスルホン酸ナトリウム、１，１，２，２，８，８，９，９，１０，１０－デカフロロドデカン、１，１，２，２，３，３－ヘキサフロロデカンなどを挙げることができる。これらの市販品としては、例えば、ＢＭ　Ｃｈｅｍｉｅ社製「ＢＭ－１０００」、「ＢＭ－１１００」、ＤＩＣ社製「メガファックＦ４７０」、「メガファックＦ４７５」、「メガファックＦ５５４」、「メガファックＦ５５９」、スリーエムジャパン社製「ＦＣ４３０」、ネオス社製「ＤＦＸ－１８」を挙げることができる。 As the fluorosurfactant, a compound having a fluoroalkyl or fluoroalkylene group at at least one of the terminal, main chain, and side chain is suitable. Specifically, 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether, octaethylene glycol di( 1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol di(1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di(1,1,2,2- tetrafluorobutyl) ether, hexapropylene glycol di(1,1,2,2,3,3-hexafluoropentyl)ether, sodium perfluorododecyl sulfonate, 1,1,2,2,8,8,9, Examples include 9,10,10-decafluorododecane and 1,1,2,2,3,3-hexafluorodecane. These commercially available products include, for example, "BM-1000" and "BM-1100" manufactured by BM Chemie, "Megafac F470", "Megafac F475", "Megafac F554", and "Megafac F559" manufactured by DIC Corporation. ", "FC430" manufactured by 3M Japan, and "DFX-18" manufactured by Neos.
　シリコーン系界面活性剤としては、例えば、東レ・ダウコーニング社製「ＤＣ３ＰＡ」、「ＳＨ７ＰＡ」、「ＤＣ１１ＰＡ」、「ＳＨ２１ＰＡ」、「ＳＨ２８ＰＡ」、「ＳＨ２９ＰＡ」、「８０３２Ａｄｄｉｔｉｖｅ」、「ＳＨ８４００」、ビックケミー社製「ＢＹＫ（登録商標、以下同じ。）３２３」、「ＢＹＫ３３０」を挙げることができる。
　界面活性剤として、フッ素系界面活性剤及びシリコーン系界面活性剤以外のその他の界面活性剤を含んでいてもよく、その他の界面活性剤としては、例えば、ノニオン性、アニオン性、カチオン性、両性界面活性剤が挙げられる。 Examples of silicone surfactants include "DC3PA", "SH7PA", "DC11PA", "SH21PA", "SH28PA", "SH29PA", "8032Additive", "SH8400" manufactured by Dow Corning Toray Industries, Inc., and BIC Chemie Co., Ltd. Examples include "BYK (registered trademark, hereinafter the same)" 323 and BYK330.
The surfactant may include other surfactants other than fluorosurfactants and silicone surfactants, such as nonionic, anionic, cationic, and amphoteric surfactants. Examples include surfactants.
　ノニオン性界面活性剤としては、例えば、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンポリオキシプロピレンアルキルエーテル類、ポリオキシエチレンアルキルフェニルエーテル類、ポリオキシエチレンアルキルエステル類、ポリオキシエチレン脂肪酸エステル類、グリセリン脂肪酸エステル類、ポリオキシエチレングリセリン脂肪酸エステル類、ペンタエリスリット脂肪酸エステル類、ポリオキシエチレンペンタエリスリット脂肪酸エステル類、ソルビタン脂肪酸エステル類、ポリオキシエチレンソルビタン脂肪酸エステル類、ソルビット脂肪酸エステル類、ポリオキシエチレンソルビット脂肪酸エステル類が挙げられる。これらの市販品としては、例えば、花王社製の「エマルゲン（登録商標。以下同じ。）１０４Ｐ」、「エマルゲンＡ６０」などのポリオキシエチレン系界面活性剤などが挙げられる。 Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, and glycerin. Fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythritol fatty acid esters, polyoxyethylene pentaerythritol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitol fatty acid esters, polyoxyethylene Examples include sorbitol fatty acid esters. Examples of these commercially available products include polyoxyethylene surfactants such as "Emulgen (registered trademark) 104P" and "Emulgen A60" manufactured by Kao Corporation.
　アニオン性界面活性剤としては、例えば、アルキルスルホン酸塩類、アルキルベンゼンスルホン酸塩類、アルキルナフタレンスルホン酸塩類、ポリオキシエチレンアルキルエーテルスルホン酸塩類、アルキル硫酸塩類、アルキル硫酸エステル塩類、高級アルコール硫酸エステル塩類、脂肪族アルコール硫酸エステル塩類、ポリオキシエチレンアルキルエーテル硫酸塩類、ポリオキシエチレンアルキルフェニルエーテル硫酸塩類、アルキル燐酸エステル塩類、ポリオキシエチレンアルキルエーテル燐酸塩類、ポリオキシエチレンアルキルフェニルエーテル燐酸塩類、特殊高分子系界面活性剤が挙げられる。中でも、特殊高分子系界面活性剤が好ましく、特殊ポリカルボン酸型高分子系界面活性剤がさらに好ましい。アニオン性界面活性剤としては、例えば、アルキル硫酸エステル塩類では、花王社製「エマール（登録商標。）１０」等、アルキルナフタレンスルホン酸塩類では花王社製「ペレックス（登録商標。）ＮＢ－Ｌ」など、特殊高分子系界面活性剤では花王社製「ホモゲノール（登録商標、以下同じ。）Ｌ－１８」、「ホモゲノールＬ－１００」などが挙げられる。 Examples of anionic surfactants include alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate ester salts, higher alcohol sulfate ester salts, Aliphatic alcohol sulfate ester salts, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl phosphate ester salts, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, special polymer systems Examples include surfactants. Among these, special polymer surfactants are preferred, and special polycarboxylic acid type polymer surfactants are more preferred. Examples of anionic surfactants include alkyl sulfate ester salts such as "Emar (registered trademark) 10" manufactured by Kao Corporation, and alkylnaphthalene sulfonates such as "Perex (registered trademark) NB-L" manufactured by Kao Corporation. Examples of special polymer surfactants include "Homogenol (registered trademark, hereinafter the same) L-18" and "Homogenol L-100" manufactured by Kao Corporation.
　カチオン性界面活性剤としては、例えば、第４級アンモニウム塩類、イミダゾリン誘導体類、アルキルアミン塩類が挙げられる。両性界面活性剤としては、例えば、ベタイン型化合物類、イミダゾリウム塩類、イミダゾリン類、アミノ酸類が挙げられる。これらのうち、第４級アンモニウム塩類が好ましく、ステアリルトリメチルアンモニウム塩類がさらに好ましい。カチオン性界面活性剤又は良性界面活性剤としては、例えば、アルキルアミン塩類としては、花王社製「アセタミン（登録商標。）２４」が挙げられ、第４級アンモニウム塩類としては、花王社製「コータミン（登録商標、以下同じ。）２４Ｐ」、「コータミン８６Ｗ」が挙げられる。
　界面活性剤は１種を単独で用いてもよく、２種以上を併用してもよい。例えば、シリコーン系界面活性剤／フッ素系界面活性剤の組み合わせ、シリコーン系界面活性剤／特殊高分子系界面活性剤の組み合わせ、フッ素系界面活性剤／特殊高分子系界面活性剤の組み合わせが挙げられる。中でも、シリコーン系界面活性剤／フッ素系界面活性剤の組み合わせが好ましい。このシリコーン系界面活性剤／フッ素系界面活性剤の組み合わせでは、例えば、ビックケミー社製「ＢＹＫ－３００」又は「ＢＹＫ－３３０」／ネオス社製「ＤＦＸ－１８」、ビックケミー社製「ＢＹＫ－３００」、「ＢＹＫ－３３０」／ＡＧＣセイミケミカル社製「Ｓ－３９３」、ビックケミー社製「ＢＹＫ－３００」又は「ＢＹＫ－３３０」／ＤＩＣ社製「Ｆ－５５４」又は「Ｆ－５５９」、信越シリコーン社製「ＫＰ３４０」／ＤＩＣ社製「Ｆ－４７８」又は「Ｆ－４７５」、東レ・ダウコーニング社製「ＳＨ７ＰＡ」／ダイキン社製「ＤＳ－４０１」、ＮＵＣ社製「Ｌ－７７」／スリーエムジャパン社製「ＦＣ４４３０」が挙げられる。
　現像改良剤として、例えば、有機カルボン酸又はその無水物を含む公知の現像改良剤を用いることもできる。
　本発明の重合性組成物が塗布性向上剤や現像改良剤を含む場合、塗布性向上剤や現像改良剤の含有量は、硬化性の観点から、重合性組成物の全固形分中に、好ましくはそれぞれ２０質量％以下、より好ましくはそれぞれ１０質量％以下である。 Examples of the cationic surfactant include quaternary ammonium salts, imidazoline derivatives, and alkylamine salts. Examples of amphoteric surfactants include betaine type compounds, imidazolium salts, imidazolines, and amino acids. Among these, quaternary ammonium salts are preferred, and stearyltrimethylammonium salts are more preferred. Examples of cationic surfactants or benign surfactants include, for example, alkylamine salts include "Acetamine (registered trademark) 24" manufactured by Kao Corporation, and examples of quaternary ammonium salts include "Cortamine (registered trademark) 24" manufactured by Kao Corporation. (registered trademark, the same applies hereinafter) 24P" and "Cortamine 86W".
One type of surfactant may be used alone, or two or more types may be used in combination. Examples include combinations of silicone surfactants/fluorosurfactants, silicone surfactants/special polymer surfactants, and fluorosurfactants/special polymer surfactants. . Among these, a combination of silicone surfactant/fluorosurfactant is preferred. Examples of this combination of silicone surfactant/fluorosurfactant include "BYK-300" or "BYK-330" manufactured by BYK Chemie, "DFX-18" manufactured by Neos, and "BYK-300" manufactured by BYK Chemie. , "BYK-330" / "S-393" manufactured by AGC Seimi Chemical, "BYK-300" or "BYK-330" manufactured by BYK Chemie / "F-554" or "F-559" manufactured by DIC, Shin-Etsu Silicone "KP340" manufactured by DIC / "F-478" or "F-475" manufactured by DIC, "SH7PA" manufactured by Toray Dow Corning / "DS-401" manufactured by Daikin, "L-77" manufactured by 3M One example is "FC4430" manufactured by Japan Co., Ltd.
As the development improver, for example, known development improvers containing organic carboxylic acids or their anhydrides can also be used.
When the polymerizable composition of the present invention contains a coatability improver or a development improver, the content of the coatability improver or development improver is determined from the viewpoint of curability in the total solid content of the polymerizable composition. Preferably, each content is 20% by mass or less, and more preferably each content is 10% by mass or less.
［３－１－８］紫外線吸収剤
　本発明の重合性組成物は、紫外線吸収剤を含有してもよい。紫外線吸収剤は、露光に用いられる光源の特定の波長を紫外線吸収剤によって吸収させることにより、光硬化分布を制御する目的で添加されるものである。紫外線吸収剤を含むことにより、現像後のテーパ角形状を改善したり、現像後に非露光部に残る残渣を低減したりするなどの効果が得られる傾向がある。紫外線吸収剤としては、光重合開始剤による光吸収を阻害するとの観点から、例えば、波長２５０ｎｍから４００ｎｍの間に吸収極大を有する化合物を用いることができる。
　紫外線吸収剤としては、例えば、ベンゾトリアゾール系化合物、トリアジン系化合物、ベンゾフェノン化合物、ベンゾエート化合物、桂皮酸誘導体、ナフタレン誘導体、アントラセン及びその誘導体、ジナフタレン化合物、フェナントロリン化合物、染料が挙げられる。
　これらの紫外線吸収剤は、１種を単独で用いてもよく、２種以上を併用してもよい。 [3-1-8] Ultraviolet absorber The polymerizable composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber is added for the purpose of controlling the photocuring distribution by causing the ultraviolet absorber to absorb a specific wavelength of the light source used for exposure. Inclusion of an ultraviolet absorber tends to produce effects such as improving the taper angle shape after development and reducing residue remaining in unexposed areas after development. As the ultraviolet absorber, from the viewpoint of inhibiting light absorption by the photopolymerization initiator, for example, a compound having an absorption maximum in the wavelength range of 250 nm to 400 nm can be used.
Examples of the ultraviolet absorber include benzotriazole compounds, triazine compounds, benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and its derivatives, dinaphthalene compounds, phenanthroline compounds, and dyes.
These ultraviolet absorbers may be used alone or in combination of two or more.
［３－１－９］重合禁止剤
　本発明の重合性組成物は、重合禁止剤を含有してもよい。重合禁止剤を含有することでラジカル重合が阻害されることから、得られる隔壁のテーパ角を大きくすることができると考えられる。
　重合禁止剤としては、例えば、ハイドロキノン、ハイドロキノンモノメチルエーテル、メチルハイドロキノン、メトキシフェノール、２，６－ジ－ｔｅｒｔ－ブチル－４－クレゾール（ＢＨＴ）が挙げられる。これらの中でも重合禁止能力の観点から、メチルハイドロキノン、メトキシフェノールが好ましく、メチルハイドロキノンがより好ましい。 [3-1-9] Polymerization inhibitor The polymerizable composition of the present invention may contain a polymerization inhibitor. Since radical polymerization is inhibited by containing a polymerization inhibitor, it is thought that the taper angle of the obtained partition walls can be increased.
Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-cresol (BHT). Among these, from the viewpoint of polymerization inhibition ability, methylhydroquinone and methoxyphenol are preferred, and methylhydroquinone is more preferred.
　重合禁止剤は、１種を単独で用いてもよく、２種以上を併用してもよい。通常、（Ｂ）アルカリ可溶性樹脂を製造する際に、樹脂中に重合禁止剤が含まれることがあり、それを本発明の重合性組成物に含まれる重合禁止剤として用いてもよいし、樹脂中に含まれる重合禁止剤の他に、それと同一、又は異なる重合禁止剤を重合性組成物の製造時に添加してもよい。 One type of polymerization inhibitor may be used alone, or two or more types may be used in combination. Usually, when manufacturing the alkali-soluble resin (B), a polymerization inhibitor may be contained in the resin, and it may be used as a polymerization inhibitor contained in the polymerizable composition of the present invention, or In addition to the polymerization inhibitor contained therein, the same or different polymerization inhibitor may be added during the production of the polymerizable composition.
［３－１－１０］シランカップリング剤
　本発明の重合性組成物は、基板との密着性を改善するため、シランカップリング剤を含有してもよい。シランカップリング剤としては、例えば、エポキシ系、メタクリル系、アミノ系、イミダゾール系のシランカップリング剤が使用できる。密着性向上の観点から、特にエポキシ系、イミダゾール系のシランカップリング剤が好ましい。
　本発明の重合性組成物がシランカップリング剤を含む場合、シランカップリング剤の含有量は、密着性の観点から、重合性組成物の全固形分中に、好ましくは２０質量％以下、より好ましくは１５質量％以下である。 [3-1-10] Silane coupling agent The polymerizable composition of the present invention may contain a silane coupling agent in order to improve the adhesion to the substrate. As the silane coupling agent, for example, epoxy-based, methacrylic-based, amino-based, or imidazole-based silane coupling agents can be used. From the viewpoint of improving adhesion, epoxy-based and imidazole-based silane coupling agents are particularly preferred.
When the polymerizable composition of the present invention contains a silane coupling agent, from the viewpoint of adhesion, the content of the silane coupling agent is preferably 20% by mass or less, more preferably 20% by mass or less in the total solid content of the polymerizable composition. Preferably it is 15% by mass or less.
［３－１－１１］リン酸系密着向上剤
　本発明の重合性組成物は、基板との密着性を改善するため、リン酸系密着向上剤を含有してもよい。リン酸系密着向上剤としては、（メタ）アクリロイルオキシ基含有ホスフェート類が好ましく、中でも下記一般式（３ａ）、（３ｂ）、（３ｃ）で表されるものが好ましい。 [3-1-11] Phosphoric acid-based adhesion improver The polymerizable composition of the present invention may contain a phosphoric acid-based adhesion improver in order to improve the adhesion with the substrate. As the phosphoric acid-based adhesion improver, (meth)acryloyloxy group-containing phosphates are preferred, and those represented by the following general formulas (3a), (3b), and (3c) are particularly preferred.
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000049
　上記一般式（３ａ）、（３ｂ）、（３ｃ）において、Ｒｑは水素原子又はメチル基を示し、ｒ及びｒ’は１～１０の整数、ｓは１、２又は３である。 In the above general formulas (3a), (3b), and (3c), R q represents a hydrogen atom or a methyl group, r and r' are integers of 1 to 10, and s is 1, 2, or 3.
　本発明の重合性組成物がリン酸系密着向上剤を含有する場合、その含有量は特に限定されないが、重合性組成物の全固形分中に０．１質量％以上が好ましく、０．２質量％以上がより好ましく、０．３質量％以上がさらに好ましく、また、５質量％以下が好ましく、３質量％以下がより好ましく、１質量％以下がさらに好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、０．１～５質量％が好ましく、０．２～３質量％がより好ましく、０．３～１質量％がさらに好ましい。前記下限値以上とすることで基板との密着性が向上する傾向がある。また、前記上限値以下とすることで表面硬化性が向上する傾向がある。 When the polymerizable composition of the present invention contains a phosphoric acid-based adhesion promoter, its content is not particularly limited, but is preferably 0.1% by mass or more in the total solid content of the polymerizable composition, and 0.2% by mass or more. It is more preferably at least 0.3% by mass, even more preferably at least 5% by mass, more preferably at most 3% by mass, even more preferably at most 1% by mass. The upper and lower limits can be arbitrarily combined, for example, preferably 0.1 to 5% by weight, more preferably 0.2 to 3% by weight, and even more preferably 0.3 to 1% by weight. When the amount is equal to or more than the lower limit, the adhesion to the substrate tends to improve. Further, by setting the amount to be less than or equal to the upper limit value, surface hardening properties tend to improve.
［３－１－１２］溶剤
　本発明の重合性組成物は、通常溶剤を含有し、前述の各成分を溶剤に溶解又は分散させた状態で使用される。溶剤としては、特に制限は無いが、例えば、以下に記載する有機溶剤が挙げられる。 [3-1-12] Solvent The polymerizable composition of the present invention usually contains a solvent, and is used with each of the above-mentioned components dissolved or dispersed in the solvent. The solvent is not particularly limited, and examples thereof include the organic solvents described below.
　エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノ－ｎ－ブチルエーテル、プロピレングリコール－ｔ－ブチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノ－ｎ－ブチルエーテル、メトキシメチルペンタノール、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノメチルエーテル、３－メチル－３－メトキシブタノール、３－メトキシ－１－ブタノール、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、トリプロピレングリコールメチルエーテル等のグリコールモノアルキルエーテル類；エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジプロピルエーテル、ジエチレングリコールジブチルエーテル、ジプロピレングリコールジメチルエーテル等のグリコールジアルキルエーテル類；エチレングリコールモノメチルエーテルアセテート、エチレングリコールモノエチルエーテルアセテート、エチレングリコールモノ－ｎ－ブチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、プロピレングリコールモノプロピルエーテルアセテート、プロピレングリコールモノブチルエーテルアセテート、メトキシブチルアセテート、３－メトキシブチルアセテート、メトキシペンチルアセテート、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノ－ｎ－ブチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート、トリエチレングリコールモノメチルエーテルアセテート、トリエチレングリコールモノエチルエーテルアセテート、３－メチル－３－メトキシブチルアセテート、３－メトキシ－１－ブチルアセテート等のグリコールアルキルエーテルアセテート類；エチレングリコールジアセテート、１，３－ブチレングリコールジアセテート、１，６－ヘキサノールジアセテート等のグリコールジアセテート類；シクロヘキサノールアセテート等のアルキルアセテート類；アミルエーテル、ジエチルエーテル、ジプロピルエーテル、ジイソプロピルエーテル、ジブチルエーテル、ジアミルエーテル、エチルイソブチルエーテル、ジヘキシルエーテル等のエーテル類；アセトン、メチルエチルケトン、メチルアミルケトン、メチルイソプロピルケトン、メチルイソアミルケトン、ジイソプロピルケトン、ジイソブチルケトン、メチルイソブチルケトン、シクロヘキサノン、エチルアミルケトン、メチルブチルケトン、メチルヘキシルケトン、メチルノニルケトン、メトキシメチルペンタノン等のケトン類；メタノール、エタノール、プロパノール、ブタノール、ヘキサノール、シクロヘキサノール、エチレングリコール、プロピレングリコール、ブタンジオール、ジエチレングリコール、ジプロピレングリコール、トリエチレングリコール、メトキシメチルペンタノール、グリセリン、ベンジルアルコール等の１価又は多価アルコール類；ｎ－ペンタン、ｎ－オクタン、ジイソブチレン、ｎ－ヘキサン、ヘキセン、イソプレン、ジペンテン、ドデカン等の脂肪族炭化水素類；シクロヘキサン、メチルシクロヘキサン、メチルシクロヘキセン、ビシクロヘキシル等の脂環式炭化水素類；ベンゼン、トルエン、キシレン、クメン等の芳香族炭化水素類；アミルホルメート、エチルホルメート、酢酸エチル、酢酸ブチル、酢酸プロピル、酢酸アミル、メチルイソブチレート、エチレングリコールアセテート、エチルプロピオネート、プロピルプロピオネート、酪酸ブチル、酪酸イソブチル、イソ酪酸メチル、エチルカプリレート、ブチルステアレート、エチルベンゾエート、３－エトキシプロピオン酸メチル、３－エトキシプロピオン酸エチル、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－メトキシプロピオン酸プロピル、３－メトキシプロピオン酸ブチル、γ－ブチロラクトン等の鎖状又は環状エステル類；３－メトキシプロピオン酸、３－エトキシプロピオン酸等のアルコキシカルボン酸類；ブチルクロライド、アミルクロライド等のハロゲン化炭化水素類；メトキシメチルペンタノン等のエーテルケトン類；アセトニトリル、ベンゾニトリル等のニトリル類：テトラヒドロフラン、ジメチルテトラヒドロフラン、ジメトキシテトラヒドロフラン等のテトラヒドロフラン類などである。 Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, 3-methoxy-1-butanol, tri- Glycol monoalkyl ethers such as ethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, Glycol dialkyl ethers such as dipropylene glycol dimethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl Ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, tri- Glycol alkyl ether acetates such as ethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, 3-methoxy-1-butyl acetate; ethylene glycol diacetate, 1,3-butylene Glycol diacetates such as glycol diacetate and 1,6-hexanol diacetate; Alkyl acetates such as cyclohexanol acetate; amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether , dihexyl ether and other ethers; acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl Ketones such as ketones and methoxymethylpentanone; methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, Monohydric or polyhydric alcohols such as benzyl alcohol; aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane; cyclohexane, methylcyclohexane, methylcyclohexene, Alicyclic hydrocarbons such as bicyclohexyl; aromatic hydrocarbons such as benzene, toluene, xylene, cumene; amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate , ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, Chain or cyclic esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone; 3-methoxypropionic acid, 3-ethoxypropion Alkoxycarboxylic acids such as acids; Halogenated hydrocarbons such as butyl chloride and amyl chloride; Ether ketones such as methoxymethylpentanone; Nitriles such as acetonitrile and benzonitrile; Tetrahydrofuran such as tetrahydrofuran, dimethyltetrahydrofuran, and dimethoxytetrahydrofuran. etc.
　上記に該当する市販の溶剤としては、例えば、ミネラルスピリット、バルソル＃２、アプコ＃１８ソルベント、アプコシンナー、ソーカルソルベントＮｏ．１及びＮｏ．２、ソルベッソ＃１５０、シェルＴＳ２８ソルベント、カルビトール、エチルカルビトール、ブチルカルビトール、メチルセロソルブ、エチルセロソルブ、エチルセロソルブアセテート、メチルセロソルブアセテート、ジグライム（いずれも商品名）が挙げられる。 Commercially available solvents applicable to the above include, for example, Mineral Spirit, Valsol #2, Apco #18 Solvent, Apco Thinner, So Cal Solvent No. 1 and no. 2, Solvesso #150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names).
　溶剤は、重合性組成物中の各成分を溶解又は分散させることができ、本発明の重合性組成物の使用方法に応じて選択されるが、塗布性の観点から、大気圧下（１０１３．２５ｈＰａ）における沸点が６０～２８０℃であるものが好ましく、７０～２６０℃であるものがより好ましい。例えば、プロピレングリコールモノメチルエーテル、３－メトキシ－１－ブタノール、プロピレングリコールモノメチルエーテルアセテート、３－メトキシ－１－ブチルアセテートが好ましい。 The solvent can dissolve or disperse each component in the polymerizable composition, and is selected depending on the method of using the polymerizable composition of the present invention. The boiling point at 25 hPa) is preferably 60 to 280°C, more preferably 70 to 260°C. For example, propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, and 3-methoxy-1-butyl acetate are preferred.
　溶剤は１種を単独で用いてもよく、２種以上を併用してもよい。
　溶剤は、重合性組成物中の全固形分が、好ましくは１０質量％以上、より好ましくは１５質量％以上、さらに好ましくは１８質量％以上、また、好ましくは９０質量％以下、より好ましくは５０質量％以下、さらに好ましくは４０質量％以下、特に好ましくは３０質量％以下となるように使用されることが好ましい。前記上限及び下限は任意に組み合わせることができ、例えば、１０～９０質量％が好ましく、１０～５０質量％がより好ましく、１５～４０質量％がさらに好ましく、１８～３０質量％が特に好ましい。前記下限値以上とすることで高い膜厚に対しても塗膜が得られる傾向がある。また、前記上限値以下とすることで適度な塗布均一性が得られる傾向がある。 One type of solvent may be used alone, or two or more types may be used in combination.
The total solid content of the solvent in the polymerizable composition is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 18% by mass or more, and preferably 90% by mass or less, more preferably 50% by mass or more. It is preferably used in an amount of not more than 40% by mass, more preferably not more than 40% by mass, particularly preferably not more than 30% by mass. The upper and lower limits can be arbitrarily combined, for example, preferably 10 to 90% by weight, more preferably 10 to 50% by weight, even more preferably 15 to 40% by weight, and particularly preferably 18 to 30% by weight. By setting the amount above the lower limit, a coating film tends to be obtained even with a high film thickness. Further, by setting the amount to be less than or equal to the upper limit value, appropriate coating uniformity tends to be obtained.
［３－２］重合性組成物の調製方法
　本発明の重合性組成物は、上記の各成分を撹拌機で混合することにより調製される。なお、調製された重合性組成物が均一なものとなるよう、メンブランフィルタ等を用いて濾過してもよい。 [3-2] Method for preparing polymerizable composition The polymerizable composition of the present invention is prepared by mixing the above-mentioned components using a stirrer. Note that, in order to make the prepared polymerizable composition uniform, it may be filtered using a membrane filter or the like.
［４］硬化物の形成方法
　本発明の重合性組成物を硬化させることで、硬化物が得られる。
　次に、本発明の重合性組成物を用いた硬化物の形成方法について説明する。本発明においては、少なくとも下記の工程（１）～工程（４）を行って硬化物を形成方法することが好ましい。
　工程（１）：重合性組成物の塗膜を基板上に形成する工程。
　工程（２）：工程（１）で形成した塗膜の少なくとも一部を露光する工程。
　工程（３）：工程（２）で露光された塗膜を現像する工程。
　工程（４）：工程（３）で現像された塗膜を焼成する工程。 [4] Method for forming cured product A cured product can be obtained by curing the polymerizable composition of the present invention.
Next, a method for forming a cured product using the polymerizable composition of the present invention will be explained. In the present invention, it is preferable to perform at least the following steps (1) to (4) to form a cured product.
Step (1): A step of forming a coating film of a polymerizable composition on a substrate.
Step (2): A step of exposing at least a portion of the coating film formed in step (1).
Step (3): A step of developing the coating film exposed in step (2).
Step (4): A step of baking the coating film developed in step (3).
＜工程（１）：重合性組成物の塗膜を基板上に形成する工程＞
　［４－１］基板
　硬化物を形成するため基板としては、適度の強度があれば、その材質は特に限定されるものではない。主に透明基板が使用されるが、材質としては、例えば、ポリエチレンテレフタレート等のポリエステル系樹脂、ポリプロピレン、ポリエチレン等のポリオレフィン系樹脂、ポリカーボネート、ポリメチルメタクリレート、ポリスルフォン等の熱可塑性樹脂製シート、エポキシ樹脂、不飽和ポリエステル樹脂、ポリ（メタ）アクリル系樹脂等の熱硬化性樹脂シート、各種ガラスが挙げられる。中でも、耐熱性の観点からガラス、耐熱性樹脂が好ましい。また、基板の表面にＩＴＯ、ＩＺＯ等の透明電極が成膜されている場合もある。透明基板以外では、ＴＦＴアレイ上や、タッチパネル上に形成することも可能である。例えば日本国特開２０２１－１１０９３６号公報に記載されるパネル構造などで、好適に用いられる。 <Step (1): Step of forming a coating film of the polymerizable composition on the substrate>
[4-1] Substrate The material of the substrate for forming the cured product is not particularly limited as long as it has appropriate strength. Transparent substrates are mainly used, but materials include, for example, polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, thermoplastic resin sheets such as polycarbonate, polymethyl methacrylate, and polysulfone, and epoxy resins. Examples include thermosetting resin sheets such as resins, unsaturated polyester resins, and poly(meth)acrylic resins, and various glasses. Among these, glass and heat-resistant resin are preferred from the viewpoint of heat resistance. In some cases, a transparent electrode such as ITO or IZO is formed on the surface of the substrate. In addition to a transparent substrate, it can also be formed on a TFT array or a touch panel. For example, it is suitably used in the panel structure described in Japanese Patent Application Publication No. 2021-110936.
　基板には、接着性等の表面物性の改良のため、必要に応じ、例えば、コロナ放電処理、オゾン処理、シランカップリング剤やウレタン系樹脂等の各種樹脂の薄膜形成処理を行ってもよい。
　基板の厚さは、通常０．０５～１０ｍｍ、好ましくは０．１～７ｍｍの範囲とされる。
　また、各種樹脂の薄膜形成処理を行う場合、その膜厚は、通常０．０１～１０μｍ、好ましくは０．０５～５μｍの範囲である。 In order to improve surface properties such as adhesion, the substrate may be subjected to, for example, corona discharge treatment, ozone treatment, or thin film formation treatment of various resins such as silane coupling agents and urethane resins, as necessary.
The thickness of the substrate is usually in the range of 0.05 to 10 mm, preferably 0.1 to 7 mm.
Further, when performing a thin film formation treatment of various resins, the film thickness is usually in the range of 0.01 to 10 μm, preferably 0.05 to 5 μm.
［４－２］基板への重合性組成物の供給方法
　本発明の重合性組成物は、通常、溶剤に溶解或いは分散された状態で、基板上へ供給される。その供給方法としては、従来公知の方法、例えば、スピナー法、ワイヤーバー法、フローコート法、ダイコート法、ロールコート法、スプレーコート法によって行うことができる。また、例えば、インクジェット法や印刷法により、パターン状に供給されてもよい。中でも、ダイコート法によれば、組成物の使用量が大幅に削減され、かつ、スピンコート法によった際に付着するミスト等の影響が全くない、異物発生が抑制される等、総合的な観点から好ましい。 [4-2] Method of supplying polymerizable composition to substrate The polymerizable composition of the present invention is usually supplied onto a substrate in a state dissolved or dispersed in a solvent. As a method for supplying it, conventionally known methods such as a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, and a spray coating method can be used. Alternatively, it may be supplied in a pattern by, for example, an inkjet method or a printing method. Among these, the die coating method significantly reduces the amount of composition used, has no influence from the mist etc. that adheres when using the spin coating method, and suppresses the generation of foreign matter. Preferable from this point of view.
　塗布量は用途により異なるが、乾燥後の膜厚として、通常０．５μｍ～１０μｍ、好ましくは１μｍ～９μｍ、特に好ましくは１μｍ～７μｍとなるように塗布される。乾燥膜厚あるいは最終的に形成された硬化物の膜厚が、基板全域に渡って均一であることが重要である。ばらつきが小さければ、硬化物に生じるムラ欠陥を抑制することができる。 Although the amount of coating varies depending on the application, it is applied so that the film thickness after drying is usually 0.5 μm to 10 μm, preferably 1 μm to 9 μm, and particularly preferably 1 μm to 7 μm. It is important that the dry film thickness or the film thickness of the finally formed cured product be uniform over the entire substrate. If the variation is small, uneven defects occurring in the cured product can be suppressed.
　本発明の重合性組成物を用いて、後述の、膜厚の異なる硬化物を一括形成する場合は、最終的に形成された硬化物の膜厚は異なるものとなる。 When the polymerizable composition of the present invention is used to collectively form cured products having different film thicknesses as described below, the film thicknesses of the finally formed cured products will be different.
［４－３］乾燥方法
　基板上に重合性組成物を供給した後、好ましくは乾燥を行い塗膜が形成される。乾燥は、ホットプレート、ＩＲオーブン、コンベクションオーブンを使用した乾燥方法によるのが好ましい。温度を高めず、減圧チャンバー内で乾燥を行う、減圧乾燥法を組み合わせてもよい。 [4-3] Drying method After supplying the polymerizable composition onto the substrate, drying is preferably performed to form a coating film. The drying is preferably performed using a hot plate, an IR oven, or a convection oven. A reduced pressure drying method in which drying is performed in a reduced pressure chamber without increasing the temperature may be combined.
　乾燥の条件は、溶剤成分の種類、使用する乾燥機の性能等に応じて適宜選択することができる。乾燥時間は、溶剤成分の種類、使用する乾燥機の性能等に応じて、通常は、４０℃～１００℃の温度で１５秒～５分間の範囲で選ばれ、好ましくは５０℃～８０℃の温度で３０秒～３分間の範囲で選ばれる。
　なお後述の焼成温度を超えない範囲で行うことが好ましい。 Drying conditions can be appropriately selected depending on the type of solvent component, the performance of the dryer used, etc. The drying time is usually selected in the range of 15 seconds to 5 minutes at a temperature of 40°C to 100°C, preferably 50°C to 80°C, depending on the type of solvent component, the performance of the dryer used, etc. The time is selected from 30 seconds to 3 minutes depending on the temperature.
Note that it is preferable to carry out the firing within a range that does not exceed the firing temperature described below.
＜工程（２）：工程（１）で形成した塗膜の少なくとも一部を露光する工程＞
［４－４］露光方法
　露光は、重合性組成物の塗膜上に、ネガのマスクパターンを重ね、このマスクパターンを介し、紫外線又は可視光線の光源を照射して行う。露光マスクを用いて露光を行う場合には、露光マスクを重合性組成物の塗膜に近接させる方法や、露光マスクを重合性組成物の塗膜から離れた位置に配置し、露光マスクを介した露光光を投影する方法によってもよい。マスクパターンを用いないレーザー光による走査露光方式によってもよい。必要に応じ、酸素による塗膜の感度の低下を防ぐため、脱酸素雰囲気下で行ったり、重合性組成物の塗膜上にポリビニルアルコール層等の酸素遮断層を形成した後に露光を行ったりしてもよい。 <Step (2): Step of exposing at least a part of the coating film formed in step (1)>
[4-4] Exposure method Exposure is performed by overlaying a negative mask pattern on the coating film of the polymerizable composition and irradiating it with an ultraviolet or visible light source through this mask pattern. When performing exposure using an exposure mask, there are two methods: placing the exposure mask close to the coating film of the polymerizable composition, or placing the exposure mask at a position away from the coating film of the polymerizable composition, and using the exposure mask through the exposure mask. A method of projecting exposure light may also be used. A scanning exposure method using laser light without using a mask pattern may also be used. If necessary, in order to prevent the sensitivity of the coating film from decreasing due to oxygen, exposure may be carried out in an oxygen-free atmosphere or after forming an oxygen barrier layer such as a polyvinyl alcohol layer on the coating film of the polymerizable composition. It's okay.
　膜厚の異なる硬化物を同時に形成する場合は、例えば、遮光部（光透過率０％）と、複数の開口部として、平均光透過率の最も高い開口部（完全透過開口部）に対して平均光透過率の小さい開口部（中間透過開口部）を有する露光マスクを用いる。この方法により、中間透過開口部と完全透過開口部の平均光透過率の差、即ち露光量の差により、残膜率の差異を生じさせる。
　中間透過開口部は、例えば、微小な多角形の遮光ユニットを有するマトリックス状遮光パターンによって作成する方法が知られている。また吸収体として、例えば、クロム系、モリブデン系、タングステン系、シリコン系材料の膜によって、光透過率を制御し作成する方法が知られている。 When forming cured products with different film thicknesses at the same time, for example, for a light shielding part (light transmittance 0%) and for multiple openings, for the opening with the highest average light transmittance (completely transmitting opening) An exposure mask having an opening with a small average light transmittance (intermediate transmission opening) is used. With this method, the difference in film remaining ratio is caused by the difference in average light transmittance between the intermediate transmission aperture and the complete transmission aperture, that is, the difference in exposure amount.
For example, a method is known in which the intermediate transmission opening is created using a matrix-like light-shielding pattern having minute polygonal light-shielding units. Furthermore, methods are known in which the absorber is produced by controlling the light transmittance using a film of a chromium-based, molybdenum-based, tungsten-based, or silicon-based material, for example.
　上記の露光に使用される光源は、特に限定されるものではない。光源としては、例えば、キセノンランプ、ハロゲンランプ、タングステンランプ、高圧水銀灯、超高圧水銀灯、メタルハライドランプ、中圧水銀灯、低圧水銀灯、カーボンアーク、蛍光ランプ等のランプ光源や、アルゴンイオンレーザー、ＹＡＧレーザー、エキシマレーザー、窒素レーザー、ヘリウムカドミニウムレーザー、青紫色半導体レーザー、近赤外半導体レーザー等のレーザー光源が挙げられる。特定の波長の光を照射して使用する場合には、光学フィルターを利用することもできる。 The light source used for the above exposure is not particularly limited. Examples of light sources include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, fluorescent lamps, argon ion lasers, YAG lasers, Laser light sources include excimer lasers, nitrogen lasers, helium cadmium lasers, blue-violet semiconductor lasers, and near-infrared semiconductor lasers. When using irradiation with light of a specific wavelength, an optical filter can also be used.
　光学フィルターとしては、例えば薄膜で露光波長における光透過率を制御可能なタイプでもよく、その場合の材質としては、例えば、Ｃｒ化合物（Ｃｒの酸化物、窒化物、酸窒化物、フッ化物等）、ＭｏＳｉ、Ｓｉ、Ｗ、Ａｌが挙げられる。 The optical filter may be, for example, a thin film type that can control the light transmittance at the exposure wavelength, and the material in this case may be, for example, a Cr compound (Cr oxide, nitride, oxynitride, fluoride, etc.). , MoSi, Si, W, and Al.
　露光量としては、通常、１ｍＪ／ｃｍ2以上、好ましくは５ｍＪ／ｃｍ2以上、より好ましくは１０ｍＪ／ｃｍ2以上であり、また、好ましくは３００ｍＪ／ｃｍ2以下、より好ましくは２００ｍＪ／ｃｍ2以下、さらに好ましくは１５０ｍＪ／ｃｍ2以下である。
　近接露光方式の場合には、露光対象とマスクパターンとの距離としては、好ましくは１０μｍ以上、より好ましくは５０μｍ以上、さらに好ましくは７５μｍ以上であり、また、好ましくは５００μｍ以下、より好ましくは４００μｍ以下、さらに好ましくは３００μｍ以下である。 The exposure amount is usually 1 mJ/cm 2 or more, preferably 5 mJ/cm 2 or more, more preferably 10 mJ/cm 2 or more, and preferably 300 mJ/cm 2 or less, more preferably 200 mJ/cm 2 or less. , more preferably 150 mJ/cm 2 or less.
In the case of a close exposure method, the distance between the exposure target and the mask pattern is preferably 10 μm or more, more preferably 50 μm or more, even more preferably 75 μm or more, and preferably 500 μm or less, more preferably 400 μm or less. , more preferably 300 μm or less.
＜工程（３）：工程（２）で露光された塗膜を現像する工程＞
［４－５］現像方法
　上記の露光を行った後、アルカリ性化合物の水溶液、又は有機溶剤を用いる現像によって、基板上に画像パターンを形成することができる。アルカリ性化合物の水溶液は、さらに、例えば、界面活性剤、有機溶剤、緩衝剤、錯化剤、染料又は顔料が含まれていてもよい。 <Step (3): Step of developing the coating film exposed in step (2)>
[4-5] Development method After the above exposure, an image pattern can be formed on the substrate by development using an aqueous solution of an alkaline compound or an organic solvent. The aqueous solution of the alkaline compound may further contain, for example, a surfactant, an organic solvent, a buffer, a complexing agent, a dye, or a pigment.
　アルカリ性化合物としては、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、炭酸ナトリウム、炭酸カリウム、炭酸水素ナトリウム、炭酸水素カリウム、ケイ酸ナトリウム、ケイ酸カリウム、メタケイ酸ナトリウム、リン酸ナトリウム、リン酸カリウム、リン酸水素ナトリウム、リン酸水素カリウム、リン酸二水素ナトリウム、リン酸二水素カリウム、水酸化アンモニウム等の無機アルカリ性化合物、モノ－、ジ－又はトリエタノールアミン、モノ－、ジ－又はトリメチルアミン、モノ－、ジ－又はトリエチルアミン、モノ－又はジイソプロピルアミン、ｎ－ブチルアミン、モノ－、ジ－又はトリイソプロパノールアミン、エチレンイミン、エチレンジイミン、テトラメチルアンモニウムヒドロキシド（ＴＭＡＨ）、コリン等の有機アルカリ性化合物が挙げられる。これらのアルカリ性化合物は、２種以上の混合物であってもよい。 Alkaline compounds include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, and potassium phosphate. , inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-, di- or triethanolamine, mono-, di- or trimethylamine, Organic alkaline compounds such as mono-, di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. can be mentioned. These alkaline compounds may be a mixture of two or more.
　界面活性剤としては、例えば、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルアリールエーテル類、ポリオキシエチレンアルキルエステル類、ソルビタンアルキルエステル類、モノグリセリドアルキルエステル類等のノニオン系界面活性剤；アルキルベンゼンスルホン酸塩類、アルキルナフタレンスルホン酸塩類、アルキル硫酸塩類、アルキルスルホン酸塩類、スルホコハク酸エステル塩類等のアニオン性界面活性剤；アルキルベタイン類、アミノ酸類等の両性界面活性剤が挙げられる。 Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters; alkylbenzene sulfonic acids Examples include anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinic acid ester salts; amphoteric surfactants such as alkyl betaines and amino acids.
　有機溶剤としては、例えば、イソプロピルアルコール、ベンジルアルコール、エチルセロソルブ、ブチルセロソルブ、フェニルセロソルブ、プロピレングリコール、ジアセトンアルコールが挙げられる。これらの有機溶剤は、２種以上を併用してもよい。また、有機溶剤は、単独で使用してもよく、水やアルカリ性化合物の水溶液と併用してもよい。 Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. Two or more of these organic solvents may be used in combination. Further, the organic solvent may be used alone or in combination with water or an aqueous solution of an alkaline compound.
　現像処理の条件は特に制限はなく、通常、現像温度は１０～５０℃、好ましくは１５～４５℃、より好ましくは２０～４０℃である。現像方法は、例えば、浸漬現像法、スプレー現像法、ブラシ現像法、超音波現像法によることができる。
　現像処理の後の基板には、必要により上記の露光方法と同様な方法により追加露光を行ってもよい。 There are no particular restrictions on the conditions for the development process, and the development temperature is usually 10 to 50°C, preferably 15 to 45°C, more preferably 20 to 40°C. The development method can be, for example, an immersion development method, a spray development method, a brush development method, or an ultrasonic development method.
After the development process, the substrate may be subjected to additional exposure using a method similar to the above-described exposure method, if necessary.
＜工程（４）：工程（３）で現像された塗膜を焼成する工程＞
［４－６］焼成方法
　得られた塗膜は、焼成を行うことが好ましい。
　焼成の方法はとくに限定されないが、ホットプレート、ＩＲオーブン、コンベクションオーブンなどが好適に使用される。焼成温度は、５０℃以上が好ましく、７０℃以上がより好ましい。また、１５０℃以下が好ましく、１００℃以下がより好ましく、９０℃以下がさらに好ましく、８０℃以下がよりさらに好ましい。焼成時間は５分間～６０分間が好ましい。 <Step (4): Step of baking the coating film developed in step (3)>
[4-6] Firing method The obtained coating film is preferably fired.
The baking method is not particularly limited, but a hot plate, IR oven, convection oven, etc. are preferably used. The firing temperature is preferably 50°C or higher, more preferably 70°C or higher. Further, the temperature is preferably 150°C or lower, more preferably 100°C or lower, even more preferably 90°C or lower, and even more preferably 80°C or lower. The firing time is preferably 5 minutes to 60 minutes.
［５］ブラックマトリックス
　本発明の硬化物をブラックマトリックスとして使用する場合、ブラックマトリックスの幅や形状等は、これを適用するカラーフィルタの仕様によって適宜調整される。ブラックマトリックスはアレイ上に作成してもよく、あるいは対向基板上に作成してもよい。 [5] Black Matrix When the cured product of the present invention is used as a black matrix, the width, shape, etc. of the black matrix are adjusted as appropriate depending on the specifications of the color filter to which it is applied. The black matrix may be fabricated on the array or on a counter substrate.
［６］隔壁、発光性ナノ結晶粒子を含む光変換層、カラーフィルタ
　本発明の硬化物は、隔壁として使用することができ、また、発光性ナノ結晶粒子を含む光変換層やカラーフィルタに使用することができる。
　例えば、上述した方法により製造されたパターン化された硬化物を隔壁として有し、隔壁で区画された領域に画素を形成したカラーフィルタに使用することができる。画素層としては、着色顔料を含む層や、発光性ナノ結晶粒子を含む層が挙げられる。発光性ナノ結晶粒子を用いる場合には、構成材料及びサイズを変更することにより、発光色を選択することができる。発光性ナノ結晶粒子としては、量子ドット等が挙げられる。
　例えば、日本国特開２０１９－０８６７４５号公報に記載される発光性ナノ結晶粒子や、それを用いた光変換層、カラーフィルタが挙げられる。 [6] Partition walls, light conversion layers containing luminescent nanocrystal particles, and color filters The cured product of the present invention can be used as partition walls, and can also be used for light conversion layers and color filters containing luminescent nanocrystal particles. can do.
For example, it can be used in a color filter that has a patterned cured product manufactured by the above-described method as a partition wall and has pixels formed in an area defined by the partition wall. Examples of the pixel layer include a layer containing a colored pigment and a layer containing luminescent nanocrystal particles. When using luminescent nanocrystal particles, the color of the emitted light can be selected by changing the constituent materials and size. Examples of the luminescent nanocrystal particles include quantum dots and the like.
Examples include luminescent nanocrystal particles described in Japanese Patent Application Publication No. 2019-086745, a light conversion layer using the same, and a color filter.
［７］有機電界発光素子
　また、上述した方法により製造されたパターン化された硬化物を隔壁として備える基板を用いて、種々の有機電界発光素子が製造される。有機電界発光素子を形成する方法は特に限定されないが、好ましくは、上述した方法により基板上に隔壁のパターンを形成した後に、機能材料を真空状態で昇華させ、基板上の隔壁により囲まれた領域内に付着させて成膜する蒸着法や、キャスト法、スピンコート法、インクジェット印刷法といったウェットプロセスにて画素等の有機層を形成することによって、有機電界発光素子が製造される。 [7] Organic electroluminescent device Various organic electroluminescent devices are also manufactured using a substrate provided with a patterned cured product produced by the method described above as a partition wall. The method for forming an organic electroluminescent device is not particularly limited, but preferably, after forming a barrier rib pattern on a substrate by the method described above, the functional material is sublimated in a vacuum to form an area surrounded by the barrier ribs on the substrate. An organic electroluminescent device is manufactured by forming an organic layer such as a pixel by a wet process such as a vapor deposition method, a casting method, a spin coating method, or an inkjet printing method.
　有機電界発光素子のタイプとしては、ボトムエミッション型やトップエミッション型が挙げられる。
　ボトムエミッション型では、例えば、透明電極を積層したガラス基板上に隔壁を形成し、隔壁で囲まれた開口部に正孔輸送層、発光層、電子輸送層、金属電極層を積層して作成される。一方でトップエミッション型では、例えば、金属電極層を積層したガラス基板上に隔壁を形成し、隔壁で囲まれた開口部に電子輸送層、発光層、正孔輸送層、透明電極層を積層して作成される。
　なお、発光層としては、日本国特開２００９－１４６６９１号公報や日本国特許第５７３４６８１号公報に記載されているような有機電界発光層が挙げられる。また、日本国特許第５６５３３８７号公報や日本国特許第５６５３１０１号公報に記載されているような量子ドットを用いてもよい。 Types of organic electroluminescent devices include bottom emission type and top emission type.
In the bottom emission type, for example, partition walls are formed on a glass substrate laminated with transparent electrodes, and a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode layer are stacked in the opening surrounded by the partition walls. Ru. On the other hand, in the top emission type, for example, partition walls are formed on a glass substrate laminated with a metal electrode layer, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer are stacked in the opening surrounded by the partition walls. Created by
Note that examples of the light-emitting layer include organic electroluminescent layers as described in Japanese Patent Application Publication No. 2009-146691 and Japanese Patent No. 5734681. Alternatively, quantum dots such as those described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 may be used.
　層構成はこれに限定されず、例えば、正孔輸送層、電子輸送層の各層は発光効率の観点から二層以上からなる積層構成でもよい。各層の厚みは特に限定されないが、発光効率や輝度の観点から、通常１～５００ｎｍである。 The layer structure is not limited to this, and for example, each layer of the hole transport layer and the electron transport layer may have a laminated structure consisting of two or more layers from the viewpoint of luminous efficiency. The thickness of each layer is not particularly limited, but from the viewpoint of luminous efficiency and brightness, it is usually 1 to 500 nm.
　有機電界発光素子は、開口部ごとにＲＧＢ各色を分けて形成してもよく、１つの開口部に二色以上を積層してもよい。有機電界発光素子は信頼性向上の観点から、封止層を備えていてもよい。封止層は空気中の水分が有機電界発光素子に吸着し、発光効率を低下することを防ぐ機能を有する。有機電界発光素子は、光取り出し効率向上の観点から、空気との界面に低反射膜を備えていてもよい。低反射膜を空気と素子との界面に配置することで屈折率のギャップを小さくし、界面での反射を抑制することが期待できる。このような低反射膜には、例えば、モスアイ構造、超多層膜の技術が適用されうる。 The organic electroluminescent element may be formed with RGB colors separated for each opening, or two or more colors may be stacked in one opening. The organic electroluminescent device may include a sealing layer from the viewpoint of improving reliability. The sealing layer has a function of preventing moisture in the air from adsorbing to the organic electroluminescent element and reducing luminous efficiency. The organic electroluminescent device may include a low-reflection film at the interface with air from the viewpoint of improving light extraction efficiency. By arranging a low-reflection film at the interface between air and the element, it is expected that the gap in refractive index will be reduced and reflection at the interface will be suppressed. For example, a moth-eye structure or a super multilayer film technique can be applied to such a low reflection film.
　有機電界発光素子を画像表示装置の画素として使用する場合には、ある画素の発光層の光が他の画素に漏れることを防止する必要があり、さらに、電極等が金属である場合には外光の反射に伴う画像品質の低下を防止する必要があるため、有機電界発光素子を構成する隔壁に遮光性を付与することが好ましい。
　また、有機電界発光素子においては、隔壁の上面及び下面に電極を付与することが必要であるため、絶縁性の観点から、隔壁は高抵抗、低誘電率であることが好ましい。そのため、隔壁に遮光性を付与するために着色剤を使用する場合には、高抵抗かつ低誘電率である前記有機顔料を用いることが好ましい。 When using an organic electroluminescent device as a pixel in an image display device, it is necessary to prevent light from the light emitting layer of one pixel from leaking to other pixels, and in addition, if the electrodes are made of metal, it is necessary to prevent the light from the light emitting layer of one pixel from leaking to other pixels. Since it is necessary to prevent image quality from deteriorating due to reflection of light, it is preferable to impart light-shielding properties to the partition walls constituting the organic electroluminescent device.
Furthermore, in an organic electroluminescent device, since it is necessary to provide electrodes on the upper and lower surfaces of the partition wall, from the viewpoint of insulation, the partition wall preferably has high resistance and low dielectric constant. Therefore, when using a coloring agent to impart light-shielding properties to the partition walls, it is preferable to use the organic pigment that has high resistance and low dielectric constant.
［８］画像表示装置
　本発明の画像表示装置は、本発明の硬化物を含む。
　例えば、本発明の重合性組成物で形成されたブラックマトリックスを有する液晶駆動基板（アレイ基板）上、または対極基板側に設置し、これらを貼り合わせて液晶セルを形成し、形成した液晶セルに液晶を注入することで、本発明の硬化物を含む、液晶表示装置等の画像表示装置を製造することができる。 [8] Image display device The image display device of the present invention contains the cured product of the present invention.
For example, the polymerizable composition of the present invention may be placed on a liquid crystal driving substrate (array substrate) having a black matrix or on a counter electrode substrate, and then bonded together to form a liquid crystal cell. By injecting liquid crystal, an image display device such as a liquid crystal display device containing the cured product of the present invention can be manufactured.
　また、本発明の重合性組成物から形成されたブラックマトリックスを有するカラーフィルタを、有機発光表示パネルの副画素に用いることもできる。カラーフィルタ層は偏光板と比較して、光の取り出し率を増加させることができ、有機発光表示装置の使用寿命を延ばすことができる。例えば、日本国特表２０２１－５１７３３３号公報、日本国特開２０２１－１１０９３６号公報に記載された表示装置に用いることができる。 Furthermore, a color filter having a black matrix formed from the polymerizable composition of the present invention can also be used in subpixels of an organic light emitting display panel. The color filter layer can increase the light extraction rate compared to the polarizing plate, and can extend the service life of the organic light emitting display. For example, it can be used in display devices described in Japanese Patent Application Publication No. 2021-517333 and Japanese Patent Application Publication No. 2021-110936.
　本発明の画像表示装置としては、本発明の硬化物を含む隔壁や有機電界発光素子を有する有機ＥＬ表示装置も挙げることができる。
　有機ＥＬ表示装置は、上述の有機電界発光素子を含むものであれば画像表示装置の型式や構造については特に制限はなく、例えば、アクティブ駆動型有機電界発光素子を用いて常法に従って組み立てることができる。例えば、「有機ＥＬディスプレイ」（オーム社、平成１６年８月２０日発行、時任静士、安達千波矢、村田英幸著）に記載されているような方法で形成することができる。例えば、白色光を発光する有機電界発光素子とカラーフィルタとを組み合わせて画像表示させてもよいし、ＲＧＢ等の発光色の異なる有機電界発光素子を組み合わせて画像表示させてもよい。 Examples of the image display device of the present invention include organic EL display devices having partition walls and organic electroluminescent elements containing the cured product of the present invention.
As long as the organic EL display device includes the above-mentioned organic electroluminescent device, there are no particular restrictions on the type or structure of the image display device, and for example, the organic EL display device can be assembled according to a conventional method using an active drive type organic electroluminescent device. can. For example, it can be formed by the method described in "Organic EL Display" (Ohmsha, published August 20, 2004, written by Seiji Tokito, Chinaya Adachi, and Hideyuki Murata). For example, an image may be displayed by combining an organic electroluminescent device that emits white light and a color filter, or an image may be displayed by combining organic electroluminescent devices that emit light of different colors, such as RGB.
　次に、本発明の化合物及び重合性組成物について、具体的な実施例を挙げて説明するが、本発明はその要旨を超えない限り、以下の実施例に限定されるものではない。 Next, the compound and polymerizable composition of the present invention will be explained by giving specific examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.
［実施例１］
＜Ｏ－イミノ－イソ尿素－１の合成＞
（合成例１．１　オキシム化合物－１の合成） [Example 1]
<Synthesis of O-imino-isourea-1>
(Synthesis Example 1.1 Synthesis of oxime compound-1)
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000050
　２００ｍｌの４口フラスコにアセトアルドキシム（東京化成社製）２．９５ｇを入れ、ＤＭＦ２１ｍｌに溶解させた。反応溶液を４０℃に加熱し、Ｎ－クロロスクシンイミド（富士フィルム和光純薬社製）６．６８ｇを４０～４５℃で添加した後、室温で３０分攪拌した。
　その後、反応容器を氷温で冷却し、ｐ－トルエンチオール（東京化成社製）５．５９ｇ、トリエチルアミン５．５７ｇを１０℃以下で滴下した。滴下終了後は、室温に戻し１時間４０分攪拌した。
　得られた反応溶液を水１００ｍｌ中に放出し、析出した固体を濾別し、真空乾燥して白色固体のオキシム化合物－１　７．６１ｇを得た（収率８４％）。 2.95 g of acetaldoxime (manufactured by Tokyo Kasei Co., Ltd.) was placed in a 200 ml four-necked flask and dissolved in 21 ml of DMF. The reaction solution was heated to 40° C., 6.68 g of N-chlorosuccinimide (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added at 40 to 45° C., and then stirred at room temperature for 30 minutes.
Thereafter, the reaction vessel was cooled to ice temperature, and 5.59 g of p-toluenethiol (manufactured by Tokyo Kasei Co., Ltd.) and 5.57 g of triethylamine were added dropwise at 10° C. or lower. After the dropwise addition was completed, the mixture was returned to room temperature and stirred for 1 hour and 40 minutes.
The resulting reaction solution was poured into 100 ml of water, and the precipitated solid was filtered off and dried under vacuum to obtain 7.61 g of oxime compound-1 as a white solid (yield: 84%).
（合成例１．２　Ｏ－イミノ－イソ尿素－１の合成） (Synthesis Example 1.2 Synthesis of O-imino-isourea-1)
Figure JPOXMLDOC01-appb-C000051
Figure JPOXMLDOC01-appb-C000051
　１００ｍｌのナスフラスコに合成例１．１で得られたオキシム化合物－１　１．４５ｇをＴＨＦ１２ｍｌに溶解し、水酸化ナトリウム０．０３ｇ、Ｎ，Ｎ‘－ジイソプロピルカルボジイミド（富士フィルム和光純薬社製）１．１１ｇを添加し、室温で７時間３０分攪拌した。反応溶液をろ過し、得られたろ液の溶媒をエバポレーターで留去し白色固体２．４２ｇを得た。得られた固体１．２８ｇをクロロホルム／メタノール溶媒でカラム精製を行い、目的の化合物（Ｏ－イミノ－イソ尿素－１）０．９５ｇを得た。 In a 100 ml eggplant flask, dissolve 1.45 g of oxime compound-1 obtained in Synthesis Example 1.1 in 12 ml of THF, add 0.03 g of sodium hydroxide, and N,N'-diisopropylcarbodiimide (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.). 1.11 g was added and stirred at room temperature for 7 hours and 30 minutes. The reaction solution was filtered, and the solvent of the obtained filtrate was distilled off using an evaporator to obtain 2.42 g of a white solid. 1.28 g of the obtained solid was purified by column using chloroform/methanol solvent to obtain 0.95 g of the target compound (O-imino-isourea-1).
　得られた化合物に対し、ＮＭＲスペクトル測定による構造確認を行った。結果を以下に示す。
　１Ｈ－ＮＭＲ（ＣＤＣｌ３）　δ（ｐｐｍ）１．１４－１．２７（ｍ，１２Ｈ，Ｎ－ＣＨ（ＣＨ３）２）、１．８４（ｓ，３Ｈ，Ｃ（＝Ｎ）－ＣＨ３）、２．４２（ｓ，３Ｈ，Ｐｈ－ＣＨ３）、３．８４－４．０３（ｍ，２Ｈ，Ｎ－ＣＨ）、５．００（ｓ，１Ｈ，Ｎ－Ｈ）、７．２２－７．２４（ｄ，２Ｈ，ＣＨ３Ｐｈ－Ｈ）、７．４５－７．４７（ｄ，２Ｈ，ＣＨ３Ｐｈ－Ｈ） The structure of the obtained compound was confirmed by NMR spectrum measurement. The results are shown below.
1 H-NMR (CDCl 3 ) δ (ppm) 1.14-1.27 (m, 12H, N-CH(CH 3 ) 2 ), 1.84 (s, 3H, C(=N)-CH 3 ), 2.42 (s, 3H, Ph-CH 3 ), 3.84-4.03 (m, 2H, N-CH), 5.00 (s, 1H, NH), 7.22- 7.24 (d, 2H, CH 3 Ph-H), 7.45-7.47 (d, 2H, CH 3 Ph-H)
［実施例２］
＜Ｏ－イミノ－イソ尿素－２の合成＞ [Example 2]
<Synthesis of O-imino-isourea-2>
Figure JPOXMLDOC01-appb-C000052
Figure JPOXMLDOC01-appb-C000052
　１００ｍｌのナスフラスコに合成例１．１で得られたオキシム化合物－１　１．４５ｇをＴＨＦ１２ｍｌに溶解し、水酸化ナトリウム０．０３ｇ、Ｎ，Ｎ‘－ジシクロヘキシルカルボジイミド（東京化成社製）１．７３ｇを室温で添加し、室温で７時間３０分攪拌した。反応溶液をろ過し、得られたろ液をエバポレーターで溶媒を留去して白色固体３．０２ｇを得た。１．９２ｇをクロロホルム／メタノール溶媒でカラム精製を行い、目的の化合物（Ｏ－イミノ－イソ尿素－２）１．２ｇ白色固体として得た。 Dissolve 1.45 g of oxime compound-1 obtained in Synthesis Example 1.1 in 12 ml of THF in a 100 ml eggplant flask, add 0.03 g of sodium hydroxide, and 1.73 g of N,N'-dicyclohexylcarbodiimide (manufactured by Tokyo Kasei Co., Ltd.). was added at room temperature, and stirred at room temperature for 7 hours and 30 minutes. The reaction solution was filtered, and the solvent was distilled off from the obtained filtrate using an evaporator to obtain 3.02 g of a white solid. 1.92 g was purified by column using chloroform/methanol solvent to obtain 1.2 g of the target compound (O-imino-isourea-2) as a white solid.
　得られた化合物に対し、ＮＭＲスペクトル測定による構造確認を行った。結果を以下に示す。
　１Ｈ－ＮＭＲ（ＣＤＣｌ３）　δ（ｐｐｍ）０．９９－２．０５（ｍ，２０Ｈ，－ＣＨ２－）、１．７３（ｓ，３Ｈ，Ｃ（＝Ｎ）－ＣＨ３）、２．３２（ｓ，３Ｈ，Ｐｈ－ＣＨ３）、３．３９－３．５５（ｍ，２Ｈ，Ｎ－ＣＨ）、４．９４（ｓ，１Ｈ，Ｎ－Ｈ）、７．１３－７．１５（ｄ，２Ｈ，ＣＨ３Ｐｈ－Ｈ）、７．３６－７．３８（ｄ，２Ｈ，ＣＨ３Ｐｈ－Ｈ） The structure of the obtained compound was confirmed by NMR spectrum measurement. The results are shown below.
1 H-NMR (CDCl 3 ) δ (ppm) 0.99-2.05 (m, 20H, -CH 2 -), 1.73 (s, 3H, C (=N) - CH 3 ), 2. 32 (s, 3H, Ph-CH 3 ), 3.39-3.55 (m, 2H, N-CH), 4.94 (s, 1H, NH), 7.13-7.15 ( d, 2H, CH 3 Ph-H), 7.36-7.38 (d, 2H, CH 3 Ph-H)
［実施例３］
＜Ｏ－イミノ－イソ尿素－３の合成＞ [Example 3]
<Synthesis of O-imino-isourea-3>
Figure JPOXMLDOC01-appb-C000053
Figure JPOXMLDOC01-appb-C000053
　１００ｍｌのナスフラスコに合成例１．１で得られたオキシム化合物－１　２．７２ｇをＴＨＦ２３ｍｌに溶解し、水酸化ナトリウム０．０６ｇ、ビス（２，６-ジイソプロピルフェニル）カルボジイミド（東京化成社製）５．４４ｇを室温で添加し、室温で７時間３０分攪拌した。反応溶液をろ過し、得られたろ液の溶媒をエバポレーターで留去して白色固体７．９２ｇを得た。得られた固体の１．７５ｇをクロロホルム／メタノール溶媒でカラム精製を行い、目的の化合物（Ｏ－イミノ－イソ尿素－３）１．１５ｇ白色固体として得た。 In a 100 ml eggplant flask, 2.72 g of oxime compound-1 obtained in Synthesis Example 1.1 was dissolved in 23 ml of THF, and 0.06 g of sodium hydroxide and bis(2,6-diisopropylphenyl)carbodiimide (manufactured by Tokyo Kasei Co., Ltd.) were added. 5.44 g was added at room temperature and stirred at room temperature for 7 hours and 30 minutes. The reaction solution was filtered, and the solvent of the obtained filtrate was distilled off using an evaporator to obtain 7.92 g of a white solid. 1.75 g of the obtained solid was purified by column using chloroform/methanol solvent to obtain 1.15 g of the target compound (O-imino-isourea-3) as a white solid.
　得られた化合物に対し、ＮＭＲスペクトル測定による構造確認を行った。結果を以下に示す。
　１Ｈ－ＮＭＲ（ＣＤＣｌ３）　δ（ｐｐｍ）１．００－１．４６（ｍ，２４Ｈ，Ｐｈ－ＣＨ（ＣＨ３）２）、１．８２（ｓ，３Ｈ，Ｃ（＝Ｎ）－ＣＨ３）、２．３８（ｓ，３Ｈ，Ｐｈ－ＣＨ３）、３．０７－３．２６（ｍ，２Ｈ，Ｐｈ－ＣＨ）、３．４４－３．６４（ｍ，２Ｈ，Ｐｈ－ＣＨ）、６．８１－７．２７（ｍ，６Ｈ，（ｉＰｒ）２Ｐｈ－Ｈ）、７．１６－７．１８（ｄ，２Ｈ，ＣＨ３Ｐｈ－Ｈ）、７．３２－７．３４（ｄ，２Ｈ，ＣＨ３Ｐｈ－Ｈ） The structure of the obtained compound was confirmed by NMR spectrum measurement. The results are shown below.
1 H-NMR (CDCl 3 ) δ (ppm) 1.00-1.46 (m, 24H, Ph-CH(CH 3 ) 2 ), 1.82 (s, 3H, C(=N)-CH 3 ), 2.38 (s, 3H, Ph-CH 3 ), 3.07-3.26 (m, 2H, Ph-CH), 3.44-3.64 (m, 2H, Ph-CH), 6.81-7.27 (m, 6H, (iPr) 2 Ph-H), 7.16-7.18 (d, 2H, CH 3 Ph-H), 7.32-7.34 (d, 2H, CH 3 Ph-H)
［実施例４］
＜Ｏ－イミノ－イソ尿素－４の合成＞
（合成例４．１　オキシム化合物－２の合成） [Example 4]
<Synthesis of O-imino-isourea-4>
(Synthesis Example 4.1 Synthesis of oxime compound-2)
Figure JPOXMLDOC01-appb-C000054
Figure JPOXMLDOC01-appb-C000054
　２００ｍｌの４口フラスコにα－ベンズアルドキシム（東京化成社製）３．０３ｇを入れ、ＤＭＦ３０ｍｌに溶解させた。反応溶液の入ったフラスコを水浴につけ、Ｎ－クロロスクシンイミド（富士フィルム和光純薬社製）３．５１ｇを２０～２５℃で添加し、室温で４５分攪拌し、さらにＮ－クロロスクシンイミド０．２１ｇを追加して室温で１時間攪拌した。その後、反応容器を氷温で冷却し、１－ブタンチオール（東京化成社製）２．２５ｇ、トリエチルアミン２．７８ｇを１０℃以下で滴下した。滴下終了後は、室温に戻し１時間３０分攪拌した。得られた反応溶液を水１２０ｍｌ中に放出し、酢酸エチル１２０ｍｌを加え抽出し、抽出層は飽和食塩水で洗浄した。抽出層を硫酸ナトリウムで乾燥させた後、ろ過し、溶媒をエバポレーターで留去して、黄色液体４．０８ｇを得た（収率７８％）。 3.03 g of α-benzaldoxime (manufactured by Tokyo Kasei Co., Ltd.) was placed in a 200 ml four-necked flask and dissolved in 30 ml of DMF. The flask containing the reaction solution was placed in a water bath, 3.51 g of N-chlorosuccinimide (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added at 20 to 25°C, stirred for 45 minutes at room temperature, and further 0.21 g of N-chlorosuccinimide was added. was added and stirred at room temperature for 1 hour. Thereafter, the reaction vessel was cooled to ice temperature, and 2.25 g of 1-butanethiol (manufactured by Tokyo Kasei Co., Ltd.) and 2.78 g of triethylamine were added dropwise at 10° C. or lower. After completion of the dropwise addition, the mixture was returned to room temperature and stirred for 1 hour and 30 minutes. The resulting reaction solution was poured into 120 ml of water, extracted with 120 ml of ethyl acetate, and the extracted layer was washed with saturated brine. The extracted layer was dried over sodium sulfate, filtered, and the solvent was distilled off using an evaporator to obtain 4.08 g of a yellow liquid (yield: 78%).
（合成例４．２　Ｏ－イミノ－イソ尿素－４の合成） (Synthesis Example 4.2 Synthesis of O-imino-isourea-4)
Figure JPOXMLDOC01-appb-C000055
Figure JPOXMLDOC01-appb-C000055
　１００ｍｌのナスフラスコに合成例4．１で得られたオキシム化合物－２　１．５７ｇをＴＨＦ１１ｍｌに溶解し、水酸化ナトリウム０．０３４ｇ、Ｎ，Ｎ‘－ジイソプロピルカルボジイミド（富士フィルム和光純薬社製）０．９９ｇを室温で添加し、室温で６時間攪拌した。反応溶液をろ過し、得られたろ液の溶媒をエバポレーターで留去して無色液体２．０ｇを得た。２．０ｇをクロロホルム／メタノール溶媒でカラム精製を行い、目的の化合物（Ｏ－イミノ－イソ尿素－４）１．１５ｇを無色液体として得た。 Dissolve 1.57 g of oxime compound-2 obtained in Synthesis Example 4.1 in 11 ml of THF in a 100 ml eggplant flask, add 0.034 g of sodium hydroxide, and N,N'-diisopropylcarbodiimide (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.). 0.99 g was added at room temperature and stirred at room temperature for 6 hours. The reaction solution was filtered, and the solvent of the obtained filtrate was distilled off using an evaporator to obtain 2.0 g of a colorless liquid. Column purification of 2.0 g was performed using a chloroform/methanol solvent to obtain 1.15 g of the target compound (O-imino-isourea-4) as a colorless liquid.
　得られた化合物に対し、ＮＭＲスペクトル測定による構造確認を行った。結果を以下に示す。
　１Ｈ－ＮＭＲ（ＣＤＣｌ３）　δ（ｐｐｍ）０．７５－０．８４（ｔ，３Ｈ，ＳＣＨ２ＣＨ２ＣＨ２－ＣＨ３）、１．１１－１．２２（ｍ，１２Ｈ，Ｎ－ＣＨ（ＣＨ３）２）、１．２２－１．３２（ｍ，２Ｈ，ＳＣＨ２ＣＨ２－ＣＨ２－）、１．３９－１．４９（ｍ，２Ｈ，ＳＣＨ２－ＣＨ２－）、２．５２－２．６１（ｔ，２Ｈ，Ｓ－ＣＨ２－）、３．８２－４．０７（ｍ，２Ｈ，Ｎ－ＣＨ）、７．４０－７．５８（ｍ，５Ｈ，Ｐｈ－Ｈ） The structure of the obtained compound was confirmed by NMR spectrum measurement. The results are shown below.
1 H-NMR (CDCl 3 ) δ (ppm) 0.75-0.84 (t, 3H, SCH 2 CH 2 CH 2 -CH 3 ), 1.11-1.22 (m, 12H, N-CH (CH 3 ) 2 ), 1.22-1.32 (m, 2H, SCH 2 CH 2 -CH 2 -), 1.39-1.49 (m, 2H, SCH 2 -CH 2 -), 2 .52-2.61 (t, 2H, S-CH 2 -), 3.82-4.07 (m, 2H, N-CH), 7.40-7.58 (m, 5H, Ph-H )
［実施例５］
＜Ｏ－イミノ－イソ尿素－５の合成＞ [Example 5]
<Synthesis of O-imino-isourea-5>
Figure JPOXMLDOC01-appb-C000056
Figure JPOXMLDOC01-appb-C000056
　１００ｍｌのナスフラスコに合成例４．１で得られたオキシム化合物－２　１．２６ｇをＴＨＦ１１ｍｌに溶解し、水酸化ナトリウム０．０３ｇ、Ｎ，Ｎ‘－ジシクロヘキシルカルボジイミド（東京化成社製）１．３ｇを室温で添加し、室温で６時間攪拌した。反応溶液をろ過し、得られたろ液をエバポレーターで溶媒を留去して黄色液体２．６３ｇを得た。２．０ｇをクロロホルム／メタノール溶媒でカラム精製を行い、目的の化合物（Ｏ－イミノ－イソ尿素－５）０．７８ｇ液体として得た。 Dissolve 1.26 g of oxime compound-2 obtained in Synthesis Example 4.1 in 11 ml of THF in a 100 ml eggplant flask, add 0.03 g of sodium hydroxide, and 1.3 g of N,N'-dicyclohexylcarbodiimide (manufactured by Tokyo Kasei Co., Ltd.). was added at room temperature and stirred at room temperature for 6 hours. The reaction solution was filtered, and the solvent was distilled off from the obtained filtrate using an evaporator to obtain 2.63 g of a yellow liquid. 2.0 g was purified by column using chloroform/methanol solvent to obtain 0.78 g of the target compound (O-imino-isourea-5) as a liquid.
　得られた化合物に対し、ＮＭＲスペクトル測定による構造確認を行った。結果を以下に示す。
　１Ｈ－ＮＭＲ（ＣＤＣｌ３）　δ（ｐｐｍ）０．６７－０．７４（ｔ，３Ｈ，ＳＣＨ２ＣＨ２ＣＨ２－ＣＨ３）、０．９９－１．９７（ｍ，２０Ｈ，－ＣＨ２－）、１．０９－１．１７（ｍ，２Ｈ，ＳＣＨ２ＣＨ２－ＣＨ２－）、１．２５－１．３２（ｍ，２Ｈ，ＳＣＨ２－ＣＨ２－）、２．４５－２．５３（ｔ，２Ｈ，Ｓ－ＣＨ２－）、３．３８－３．６２（ｍ，２Ｈ，Ｎ－ＣＨ）、７．３４－７．４５（ｍ，５Ｈ，Ｐｈ－Ｈ） The structure of the obtained compound was confirmed by NMR spectrum measurement. The results are shown below.
1 H-NMR (CDCl 3 ) δ (ppm) 0.67-0.74 (t, 3H, SCH 2 CH 2 CH 2 -CH 3 ), 0.99-1.97 (m, 20H, -CH 2 -), 1.09-1.17 (m, 2H, SCH 2 CH 2 -CH 2 -), 1.25-1.32 (m, 2H, SCH 2 -CH 2 -), 2.45-2 .53 (t, 2H, S-CH 2 -), 3.38-3.62 (m, 2H, N-CH), 7.34-7.45 (m, 5H, Ph-H)
［実施例６］
＜Ｏ－イミノ－イソ尿素－６の合成＞ [Example 6]
<Synthesis of O-imino-isourea-6>
Figure JPOXMLDOC01-appb-C000057
Figure JPOXMLDOC01-appb-C000057
　１００ｍｌのナスフラスコに合成例４．１で得られたオキシム化合物－２　０．８４ｇをＴＨＦ１１ｍｌに溶解し、水酸化ナトリウム０．０３ｇ、ビス（２，６－ジイソプロピルフェニル）カルボジイミド（東京化成社製）１．４５ｇを室温で添加し、室温で６時間攪拌した。反応溶液をろ過し、得られたろ液の溶媒をエバポレーターで留去して白色固体２．３３ｇを得た。２．３ｇをクロロホルム／ヘキサン溶媒でカラム精製を行った後、ヘキサンで洗浄および乾燥後、目的の化合物（Ｏ－イミノ－イソ尿素－６）０．５５ｇ白色固体として得た。 In a 100 ml eggplant flask, dissolve 0.84 g of oxime compound-2 obtained in Synthesis Example 4.1 in 11 ml of THF, add 0.03 g of sodium hydroxide, and bis(2,6-diisopropylphenyl)carbodiimide (manufactured by Tokyo Kasei Co., Ltd.). 1.45 g was added at room temperature and stirred at room temperature for 6 hours. The reaction solution was filtered, and the solvent of the obtained filtrate was distilled off using an evaporator to obtain 2.33 g of a white solid. After column purification of 2.3 g with chloroform/hexane solvent, washing with hexane and drying, 0.55 g of the target compound (O-imino-isourea-6) was obtained as a white solid.
　得られた化合物に対し、ＮＭＲスペクトル測定による構造確認を行った。結果を以下に示す。
　１Ｈ－ＮＭＲ（ＣＤＣｌ３）　δ（ｐｐｍ）０．８０－０．８３（ｔ，３Ｈ，ＳＣＨ２ＣＨ２ＣＨ２－ＣＨ３）、０．９９－１．９７（ｍ，２４Ｈ，Ｐｈ－ＣＨ（ＣＨ３）２）、１．０９－１．１７（ｍ，２Ｈ，ＳＣＨ２ＣＨ２－ＣＨ２－）、１．１２－１．２９（ｍ，２Ｈ，ＳＣＨ２－ＣＨ２－）、２．３５－２．４７（ｔ，２Ｈ，Ｓ－ＣＨ２－）、３．０９－３．２７（ｍ，２Ｈ，Ｐｈ－ＣＨ）、３．４２－３．６１（ｍ，２Ｈ，Ｐｈ－ＣＨ）、６．９０－７．３７（ｍ，６Ｈ，（ｉＰｒ）２Ｐｈ－Ｈ）、７．３９－７．６７（ｍ，５Ｈ，Ｃ（＝Ｎ）－Ｐｈ－Ｈ） The structure of the obtained compound was confirmed by NMR spectrum measurement. The results are shown below.
1 H-NMR (CDCl 3 ) δ (ppm) 0.80-0.83 (t, 3H, SCH 2 CH 2 CH 2 -CH 3 ), 0.99-1.97 (m, 24H, Ph-CH (CH 3 ) 2 ), 1.09-1.17 (m, 2H, SCH 2 CH 2 -CH 2 -), 1.12-1.29 (m, 2H, SCH 2 -CH 2 -), 2 .35-2.47 (t, 2H, S-CH 2 -), 3.09-3.27 (m, 2H, Ph-CH), 3.42-3.61 (m, 2H, Ph-CH ), 6.90-7.37 (m, 6H, (iPr) 2 Ph-H), 7.39-7.67 (m, 5H, C(=N)-Ph-H)
［実施例７］
＜Ｏ－イミノ－イソ尿素－７の合成＞
（合成例７．１　オキシム化合物－３の合成） [Example 7]
<Synthesis of O-imino-isourea-7>
(Synthesis Example 7.1 Synthesis of oxime compound-3)
Figure JPOXMLDOC01-appb-C000058
Figure JPOXMLDOC01-appb-C000058
　２００ｍｌの４口フラスコにブチルアルドキシム（東京化成社製）４．３６ｇを入れ、ＤＭＦ３０ｍｌに溶解させた。反応溶液の入ったフラスコを水浴につけ、Ｎ－クロロスクシンイミド（富士フィルム和光純薬社製）６．６８ｇを４０℃以下で添加した後、室温で９０分攪拌した。その後、反応容器を氷温で冷却し、ｐ－トルエンチオール（東京化成社製）５．５９ｇ、トリエチルアミン５．５７ｇを１０℃以下で滴下した。滴下終了後は、室温に戻し１時間４０分攪拌した。得られた反応溶液を水２００ｍｌ中に放出し、析出した固体を濾別し、水２５０ｍｌで洗浄後、真空乾燥して白色固体のオキシム化合物－３　９．１１ｇを得た（収率９６．７％）。 4.36 g of butyraldoxime (manufactured by Tokyo Kasei Co., Ltd.) was placed in a 200 ml four-necked flask and dissolved in 30 ml of DMF. The flask containing the reaction solution was placed in a water bath, and 6.68 g of N-chlorosuccinimide (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added at 40° C. or below, followed by stirring at room temperature for 90 minutes. Thereafter, the reaction vessel was cooled to ice temperature, and 5.59 g of p-toluenethiol (manufactured by Tokyo Kasei Co., Ltd.) and 5.57 g of triethylamine were added dropwise at 10° C. or lower. After the dropwise addition was completed, the mixture was returned to room temperature and stirred for 1 hour and 40 minutes. The obtained reaction solution was discharged into 200 ml of water, and the precipitated solid was filtered, washed with 250 ml of water, and dried in vacuum to obtain 9.11 g of oxime compound-3 as a white solid (yield: 96.7). %).
（合成例７．２　Ｏ－イミノ－イソ尿素－７の合成） (Synthesis Example 7.2 Synthesis of O-imino-isourea-7)
Figure JPOXMLDOC01-appb-C000059
Figure JPOXMLDOC01-appb-C000059
　１００ｍｌのナスフラスコに合成例７．１で得られたオキシム化合物-３　３．１４ｇをＴＨＦ３０ｍｌに溶解し、水酸化ナトリウム０．１ｇ、ビス（２，６－ジイソプロピルフェニル）カルボジイミド（東京化成社製）５．４４ｇを室温で添加し、室温で３時間４５分攪拌し、一晩後さらに４時間撹拌した。反応溶液をろ過し、得られたろ液の溶媒をエバポレーターで留去して白色固体８．７８ｇを得た。得られた固体の２．１ｇをクロロホルム／ヘキサン溶媒でカラム精製を行い、目的の化合物（Ｏ－イミノ－イソ尿素－７）１．５５ｇを白色固体として得た。 In a 100 ml eggplant flask, 3.14 g of oxime compound-3 obtained in Synthesis Example 7.1 was dissolved in 30 ml of THF, and 0.1 g of sodium hydroxide and bis(2,6-diisopropylphenyl)carbodiimide (manufactured by Tokyo Kasei Co., Ltd.) were added. 5.44 g was added at room temperature, stirred at room temperature for 3 hours and 45 minutes, and then stirred for an additional 4 hours after overnight. The reaction solution was filtered, and the solvent of the obtained filtrate was distilled off using an evaporator to obtain 8.78 g of a white solid. 2.1 g of the obtained solid was purified by column using chloroform/hexane solvent to obtain 1.55 g of the target compound (O-imino-isourea-7) as a white solid.
　得られた化合物に対し、ＮＭＲスペクトル測定による構造確認を行った。結果を以下に示す。
　１Ｈ－ＮＭＲ（ＣＤＣｌ３）　δ（ｐｐｍ）０．６２－０．７８（ｔ，３Ｈ，Ｃ（＝Ｎ）ＣＨ２ＣＨ２－ＣＨ３）、０．８９－１．３０（ｍ，２４Ｈ，Ｐｈ－ＣＨ（ＣＨ３））、１．３０－１．４２（ｍ，２Ｈ，Ｃ（＝Ｎ）ＣＨ２－ＣＨ２－）、１．９５－２．０６（ｔ，２Ｈ，Ｃ（＝Ｎ）－ＣＨ２－）、２．２９（ｓ，３Ｈ，Ｐｈ－ＣＨ３）、２．９７－３．１８（ｍ，２Ｈ，Ｐｈ－ＣＨ）、３．３２－３．５５（ｍ，２Ｈ，Ｐｈ－ＣＨ）、６．７５－７．１８（ｍ，６Ｈ，（ｉＰｒ）２Ｐｈ－Ｈ）、７．０６－７．０８（ｄ，２Ｈ，ＣＨ３Ｐｈ－Ｈ）、７．２２－７．２４（ｄ，２Ｈ，ＣＨ３Ｐｈ－Ｈ） The structure of the obtained compound was confirmed by NMR spectrum measurement. The results are shown below.
1 H-NMR (CDCl 3 ) δ (ppm) 0.62-0.78 (t, 3H, C(=N) CH 2 CH 2 -CH 3 ), 0.89-1.30 (m, 24H, Ph-CH( CH3 )), 1.30-1.42(m,2H,C(=N) CH2 - CH2- ), 1.95-2.06(t,2H,C(=N )-CH 2 -), 2.29 (s, 3H, Ph-CH 3 ), 2.97-3.18 (m, 2H, Ph-CH), 3.32-3.55 (m, 2H, Ph-CH), 6.75-7.18 (m, 6H, (iPr) 2 Ph-H), 7.06-7.08 (d, 2H, CH 3 Ph-H), 7.22-7 .24(d,2H, CH3Ph -H)
［実施例８］
＜Ｏ－イミノ－イソ尿素－８の合成＞
（合成例８．１　オキシム化合物－４の合成） [Example 8]
<Synthesis of O-imino-isourea-8>
(Synthesis Example 8.1 Synthesis of oxime compound-4)
Figure JPOXMLDOC01-appb-C000060
Figure JPOXMLDOC01-appb-C000060
　５０ｍｌの４口フラスコにアセトアルドキシム（東京化成社製）　０．５９ｇを入れ、ＤＭＦ　１２ｍｌに溶解させた。ここにＮ－クロロスクシンイミド（富士フィルム和光純薬社製）１．４ｇを室温で添加した後、室温で３０分攪拌した。その後、反応容器を氷温で冷却し、１，４－ベンゼンジチオール（東京化成社製）０．６４ｇ、トリエチルアミン１．１１ｇを１０℃以下で滴下した。滴下終了後は、室温に戻し１時間３０分攪拌した。得られた反応溶液を水１００ｍｌ中に放出し、析出した固体を濾別し、水８０ｍｌおよびメタノール３０ｍｌで洗浄し、真空乾燥して白色固体のオキシム化合物－４　０．８９ｇを得た（収率７７．４％）。 0.59 g of acetaldoxime (manufactured by Tokyo Kasei Co., Ltd.) was placed in a 50 ml four-necked flask and dissolved in 12 ml of DMF. After adding 1.4 g of N-chlorosuccinimide (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) at room temperature, the mixture was stirred at room temperature for 30 minutes. Thereafter, the reaction vessel was cooled to ice temperature, and 0.64 g of 1,4-benzenedithiol (manufactured by Tokyo Kasei Co., Ltd.) and 1.11 g of triethylamine were added dropwise at 10° C. or lower. After completion of the dropwise addition, the mixture was returned to room temperature and stirred for 1 hour and 30 minutes. The obtained reaction solution was discharged into 100 ml of water, and the precipitated solid was filtered, washed with 80 ml of water and 30 ml of methanol, and dried in vacuum to obtain 0.89 g of oxime compound-4 as a white solid (yield: 77.4%).
（合成例８．２　Ｏ－イミノ－イソ尿素－８の合成） (Synthesis Example 8.2 Synthesis of O-imino-isourea-8)
Figure JPOXMLDOC01-appb-C000061
Figure JPOXMLDOC01-appb-C000061
　５０ｍｌのナスフラスコに合成例８．１で得られたオキシム化合物－４　０．３８ｇをＴＨＦ２０ｍｌに溶解し、水酸化ナトリウム０．０３ｇ、ビス（２，６－ジイソプロピルフェニル）カルボジイミド（東京化成社製）１．０９ｇを室温で添加し、室温で７時間４５分攪拌した。一晩後、さらに8時間撹拌した。反応溶液をろ過し、得られたろ液の溶媒をエバポレーターで留去して得られた固体をヘキサン１５ｍｌで洗浄し、乾燥の後、白色固体１．１６ｇを得た。０．６ｇをクロロホルム／メタノール溶媒でカラム精製を行った後、目的の化合物（Ｏ－イミノ－イソ尿素－８）０．１２ｇを白色固体として得た。 In a 50 ml eggplant flask, dissolve 0.38 g of oxime compound-4 obtained in Synthesis Example 8.1 in 20 ml of THF, add 0.03 g of sodium hydroxide, and bis(2,6-diisopropylphenyl)carbodiimide (manufactured by Tokyo Kasei Co., Ltd.). 1.09 g was added at room temperature and stirred at room temperature for 7 hours and 45 minutes. After overnight stirring was continued for an additional 8 hours. The reaction solution was filtered, and the solvent of the obtained filtrate was distilled off using an evaporator. The solid obtained was washed with 15 ml of hexane, and after drying, 1.16 g of a white solid was obtained. After column purification of 0.6 g using chloroform/methanol solvent, 0.12 g of the target compound (O-imino-isourea-8) was obtained as a white solid.
　得られた化合物に対し、ＮＭＲスペクトル測定による構造確認を行った。結果を以下に示す。
　１Ｈ－ＮＭＲ（ＣＤＣｌ３）　δ（ｐｐｍ）　０．９１－１．３４（ｍ，４８Ｈ，Ｐｈ－ＣＨ（ＣＨ３）２）、１．７３（ｓ，６Ｈ，Ｃ（＝Ｎ）－ＣＨ３）、２．９７－３．１４（ｍ，４Ｈ，Ｐｈ－ＣＨ）、３．３２－３．４９（ｍ，４Ｈ，Ｐｈ－ＣＨ）、６．６３－７．２８（ｍ，１２Ｈ，（ｉＰｒ）２Ｐｈ－Ｈ）、７．３６（ｓ，４Ｈ，Ｓ２Ｐｈ－Ｈ） The structure of the obtained compound was confirmed by NMR spectrum measurement. The results are shown below.
1 H-NMR (CDCl 3 ) δ (ppm) 0.91-1.34 (m, 48H, Ph-CH(CH 3 ) 2 ), 1.73 (s, 6H, C(=N)-CH 3 ), 2.97-3.14 (m, 4H, Ph-CH), 3.32-3.49 (m, 4H, Ph-CH), 6.63-7.28 (m, 12H, (iPr ) 2 Ph-H), 7.36 (s, 4H, S 2 Ph-H)
［実施例９］
＜Ｏ－イミノ－イソ尿素－９の合成＞
　反応式は以下である。 [Example 9]
<Synthesis of O-imino-isourea-9>
The reaction formula is as follows.
Figure JPOXMLDOC01-appb-C000062
Figure JPOXMLDOC01-appb-C000062
　２０ｍｌのナスフラスコにチオアセトヒドロキサム酸メチル（富士フィルム和光純薬社製）０．１８ｇをＴＨＦ４ｍｌに溶解し、水酸化ナトリウム０．０２ｇ、ビス（２，６－ジイソプロピルフェニル）カルボジイミド（東京化成社製）０．６２ｇを添加し、室温で３時間４５分攪拌した。そのまま反応溶液を３日間静置した後、反応溶液をろ過し、得られたろ液をエバポレーターで溶媒を留去して白色固体を得た。得られた固体をヘキサンに加え、攪拌した後、固体を濾別し、ヘキサンで洗浄した。真空乾燥して、目的の化合物（Ｏ－イミノ－イソ尿素－９）０．５ｇを白色固体として得た。
　得られた化合物に対し、ＮＭＲスペクトル測定による構造確認を行った。結果を以下に示す。
　１Ｈ－ＮＭＲ（ＣＤＣｌ３）　δ（ｐｐｍ）　０．９１－１．４６（ｍ，２４Ｈ，－ＣＨ２－（ＣＨ３）２）、２．２１（ｓ，３Ｈ，Ｃ（＝Ｎ）－ＣＨ３）、２．２２（ｓ，３Ｈ，Ｓ－ＣＨ３）、３．０４－３．２２（ｍ，２Ｈ，ＣＨ－（ＣＨ３）２）、３．３６－３．６０（ｍ，２Ｈ，ＣＨ－（ＣＨ３）２）、６．７７－７．３６（ｍ，１２Ｈ，Ｐｈ－Ｈ） In a 20 ml eggplant flask, dissolve 0.18 g of methyl thioacetohydroxamate (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) in 4 ml of THF, add 0.02 g of sodium hydroxide, and bis(2,6-diisopropylphenyl)carbodiimide (manufactured by Tokyo Kasei Co., Ltd.). ) and stirred at room temperature for 3 hours and 45 minutes. After the reaction solution was allowed to stand for 3 days, the reaction solution was filtered, and the solvent was distilled off from the obtained filtrate using an evaporator to obtain a white solid. The obtained solid was added to hexane and stirred, then the solid was filtered off and washed with hexane. Vacuum drying yielded 0.5 g of the target compound (O-imino-isourea-9) as a white solid.
The structure of the obtained compound was confirmed by NMR spectrum measurement. The results are shown below.
1 H-NMR (CDCl 3 ) δ (ppm) 0.91-1.46 (m, 24H, -CH 2 -(CH 3 ) 2 ), 2.21 (s, 3H, C(=N) -CH 3 ), 2.22 (s, 3H, S-CH 3 ), 3.04-3.22 (m, 2H, CH-(CH 3 ) 2 ), 3.36-3.60 (m, 2H, CH-( CH3 ) 2 ), 6.77-7.36(m, 12H, Ph-H)
［実施例１０］
＜Ｏ－イミノ－イソ尿素－１０の合成＞
（合成例１０．１　オキシム化合物－５の合成）
　反応式は以下である。 [Example 10]
<Synthesis of O-imino-isourea-10>
(Synthesis Example 10.1 Synthesis of oxime compound-5)
The reaction formula is as follows.
Figure JPOXMLDOC01-appb-C000063
Figure JPOXMLDOC01-appb-C000063
　５０ｍｌの４口フラスコにアセトアルドキシム（東京化成社製）１．９ｇを入れ、ＤＭＦ７．７ｍｌに溶解させた。室温で、Ｎ－クロロスクシンイミド（富士フィルム和光純薬社製）４．４０ｇを７０分かけて添加した。
　その後、反応容器を氷温で冷却し、４－（メチルチオ）ベンゼンチオール（東京化成社製）５．２９ｇをＤＭＦ１．２ｍｌに溶解させ、５分かけて添加した後、トリエチルアミン３．６９ｇを滴下した。滴下終了後は、室温に戻し１時間３０分攪拌した。
　得られた反応溶液に水２１ｍｌを添加し、析出した固体を濾別し、水で洗浄した。得られた固体を真空乾燥して白色固体のオキシム化合物－５　６．５７ｇを得た（収率９４．１％）。 1.9 g of acetaldoxime (manufactured by Tokyo Kasei Co., Ltd.) was placed in a 50 ml four-necked flask and dissolved in 7.7 ml of DMF. At room temperature, 4.40 g of N-chlorosuccinimide (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added over 70 minutes.
Thereafter, the reaction container was cooled to ice temperature, 5.29 g of 4-(methylthio)benzenethiol (manufactured by Tokyo Kasei Co., Ltd.) was dissolved in 1.2 ml of DMF, and the solution was added over 5 minutes, followed by dropwise addition of 3.69 g of triethylamine. . After completion of the dropwise addition, the mixture was returned to room temperature and stirred for 1 hour and 30 minutes.
21 ml of water was added to the resulting reaction solution, and the precipitated solid was filtered off and washed with water. The obtained solid was vacuum dried to obtain 6.57 g of oxime compound-5 as a white solid (yield 94.1%).
Figure JPOXMLDOC01-appb-C000064
Figure JPOXMLDOC01-appb-C000064
（合成例１０．２　Ｏ－イミノ－イソ尿素－１０の合成）
　１００ｍｌの４口ナスフラスコに合成例１０．１で得られたオキシム化合物－５　６．５７ｇをＴＨＦ３６ｍｌに溶解し、水酸化ナトリウム０．１２５ｇ、ビス（２，６-ジイソプロピルフェニル）カルボジイミド（東京化成社製）１２．２ｇを室温で添加し、室温で４７時間攪拌した。反応溶液をろ過し、得られたろ液の溶媒をエバポレーターで留去して白色固体１９．１ｇを得た。得られた固体にｎ－へプタン１００ｍｌを加えて３０分攪拌した後、固体を濾別し、ｎ－へプタン３０ｍｌで洗浄した。得られた固体を乾燥し、目的の化合物（Ｏ－イミノ－イソ尿素－１０）１４．５ｇ白色固体として得た（収率８１．７％）。 (Synthesis Example 10.2 Synthesis of O-imino-isourea-10)
In a 100 ml four-necked eggplant flask, 6.57 g of oxime compound-5 obtained in Synthesis Example 10.1 was dissolved in 36 ml of THF. 12.2 g (manufactured by M.D.) was added at room temperature, and the mixture was stirred at room temperature for 47 hours. The reaction solution was filtered, and the solvent of the obtained filtrate was distilled off using an evaporator to obtain 19.1 g of a white solid. After adding 100 ml of n-heptane to the obtained solid and stirring for 30 minutes, the solid was filtered off and washed with 30 ml of n-heptane. The obtained solid was dried to obtain 14.5 g of the target compound (O-imino-isourea-10) as a white solid (yield: 81.7%).
　得られた化合物に対し、ＮＭＲスペクトル測定による構造確認を行った。結果を以下に示す。
　１Ｈ－ＮＭＲ（ＣＤＣｌ３）　δ（ｐｐｍ）０．９２－１．４５（ｍ，２４Ｈ，Ｐｈ－ＣＨ（ＣＨ３）２）、１．８１（ｓ，３Ｈ，Ｃ（＝Ｎ）－ＣＨ３）、２．４８（ｓ，３Ｈ，Ｓ－ＣＨ３）、３．０５－３．２４（ｍ，２Ｈ，Ｐｈ－ＣＨ）、３．４０－３．５８（ｍ，２Ｈ，Ｐｈ－ＣＨ）、６．７５－７．３５（ｍ，１０Ｈ，（ｉＰｒ）２Ｐｈ－Ｈ，ＣＨ３ＳＰｈ－Ｈ） The structure of the obtained compound was confirmed by NMR spectrum measurement. The results are shown below.
1 H-NMR (CDCl 3 ) δ (ppm) 0.92-1.45 (m, 24H, Ph-CH(CH 3 ) 2 ), 1.81 (s, 3H, C(=N)-CH 3 ), 2.48 (s, 3H, S-CH 3 ), 3.05-3.24 (m, 2H, Ph-CH), 3.40-3.58 (m, 2H, Ph-CH), 6.75-7.35 (m, 10H, (iPr) 2 Ph-H, CH 3 SPh-H)
［実施例１１］
＜Ｏ－イミノ－イソ尿素－１１の合成＞
（合成例１１．１　オキシム化合物－６の合成） [Example 11]
<Synthesis of O-imino-isourea-11>
(Synthesis Example 11.1 Synthesis of oxime compound-6)
Figure JPOXMLDOC01-appb-C000065
Figure JPOXMLDOC01-appb-C000065
　５０ｍｌの４口フラスコにブチルアルドキシム（東京化成社製）１．３１ｇを入れ、ＤＭＦ１３ｍｌに溶解させた。Ｎ－クロロスクシンイミド（富士フィルム和光純薬社製）２．００ｇを室温で添加した後、室温で１時間攪拌した。
　その後、反応容器を氷温で冷却し、４－（メチルチオ）ベンゼンチオール（東京化成社製）２．１１ｇ、トリエチルアミン１．６７ｇを１０℃以下で滴下した。滴下終了後は、室温に戻し１時間攪拌した。
　得られた反応溶液を水１００ｍｌ中に放出し、析出した固体を濾別し、さらに水１００ｍｌに加え、攪拌した後、固体を濾別し、水で洗浄した。得られた固体を真空乾燥し、白色固体のオキシム化合物－６　３．１６ｇを得た（収率９６．９％）。 1.31 g of butyraldoxime (manufactured by Tokyo Kasei Co., Ltd.) was placed in a 50 ml four-necked flask and dissolved in 13 ml of DMF. After adding 2.00 g of N-chlorosuccinimide (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) at room temperature, the mixture was stirred at room temperature for 1 hour.
Thereafter, the reaction vessel was cooled to ice temperature, and 2.11 g of 4-(methylthio)benzenethiol (manufactured by Tokyo Kasei Co., Ltd.) and 1.67 g of triethylamine were added dropwise at 10° C. or lower. After completion of the dropwise addition, the mixture was returned to room temperature and stirred for 1 hour.
The resulting reaction solution was discharged into 100 ml of water, and the precipitated solid was filtered off. After adding to 100 ml of water and stirring, the solid was filtered off and washed with water. The obtained solid was vacuum dried to obtain 3.16 g of oxime compound-6 as a white solid (yield 96.9%).
Figure JPOXMLDOC01-appb-C000066
Figure JPOXMLDOC01-appb-C000066
（合成例１１．２　Ｏ－イミノ－イソ尿素－１１の合成）
　５０ｍｌのナスフラスコに合成例１１．１で得られたオキシム化合物－６　０．７２ｇをＴＨＦ１２ｍｌに溶解し、水酸化ナトリウム０．０３ｇ、ビス（２，６－ジイソプロピルフェニル）カルボジイミド（東京化成社製）１．０９ｇを室温で添加し、室温で１０時間攪拌した後、３日間静置した。反応溶液をろ過し、得られたろ液の溶媒をエバポレーターで留去して白色固体を得た。得られた固体をヘキサン１５ｍｌに加え攪拌した後、固体を濾別し、ヘキサンで洗浄した。得られた固体を真空乾燥し、目的の化合物（Ｏ－イミノ－イソ尿素－１１）１．３８ｇを白色固体として得た。 (Synthesis Example 11.2 Synthesis of O-imino-isourea-11)
In a 50 ml eggplant flask, 0.72 g of oxime compound-6 obtained in Synthesis Example 11.1 was dissolved in 12 ml of THF, and 0.03 g of sodium hydroxide and bis(2,6-diisopropylphenyl)carbodiimide (manufactured by Tokyo Kasei Co., Ltd.) were added. 1.09 g was added at room temperature, stirred at room temperature for 10 hours, and then allowed to stand for 3 days. The reaction solution was filtered, and the solvent of the obtained filtrate was distilled off using an evaporator to obtain a white solid. The obtained solid was added to 15 ml of hexane and stirred, then the solid was filtered off and washed with hexane. The obtained solid was vacuum dried to obtain 1.38 g of the target compound (O-imino-isourea-11) as a white solid.
　得られた化合物に対し、ＮＭＲスペクトル測定による構造確認を行った。結果を以下に示す。
　１Ｈ－ＮＭＲ（ＣＤＣｌ３）　δ（ｐｐｍ）０．７２－０．８６（ｔ，３Ｈ，Ｃ（＝Ｎ）ＣＨ２ＣＨ２－ＣＨ３）、１．００－１．４０（ｍ，２４Ｈ，Ｐｈ－ＣＨ（ＣＨ３）２）、１．４０－１．５０（ｍ，２Ｈ，Ｃ（＝Ｎ）ＣＨ２－ＣＨ２－）、２．０２－２．１５（ｔ，２Ｈ，Ｃ（＝Ｎ）－ＣＨ２－）、２．４８（ｓ，３Ｈ，Ｓ－ＣＨ３）、３．０１－３．２３（ｍ，２Ｈ，Ｐｈ－ＣＨ）、３．３８－３．６２（ｍ，２Ｈ，Ｐｈ－ＣＨ）、６．７５－７．３４（ｍ，１０Ｈ，（ｉＰｒ）２Ｐｈ－Ｈ，ＣＨ３ＳＰｈ－Ｈ） The structure of the obtained compound was confirmed by NMR spectrum measurement. The results are shown below.
1 H-NMR (CDCl 3 ) δ (ppm) 0.72-0.86 (t, 3H, C(=N) CH 2 CH 2 -CH 3 ), 1.00-1.40 (m, 24H, Ph-CH( CH3 ) 2 ), 1.40-1.50(m,2H,C(=N) CH2 - CH2- ), 2.02-2.15(t,2H,C(= N)-CH 2 -), 2.48 (s, 3H, S-CH 3 ), 3.01-3.23 (m, 2H, Ph-CH), 3.38-3.62 (m, 2H , Ph-CH), 6.75-7.34 (m, 10H, (iPr) 2 Ph-H, CH 3 SPh-H)
　以下の実施例で用いた重合性組成物の構成成分は次の通りである。 The constituent components of the polymerizable composition used in the following examples are as follows.
　重合性化合物－１（Ｂ－１）：ジペンタエリスリトールヘキサアクリレート（ＫＡＹＡＲＡＤ　ＤＰＨＡ、日本化薬社製） Polymerizable compound-1 (B-1): dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)
アルカリ可溶性樹脂－１（Ｃ－１）：
　ジシクロペンタニルメタクリレート／スチレン／グリシジルメタクリレート（モル比：０．３／０．１／０．６）を構成モノマーとする共重合樹脂に、アクリル酸を前記グリシジルメタクリレートに対して等量付加反応させ、さらに無水テトラヒドロフタル酸を上記の共重合樹脂１モルに対して０．３９モルになるように付加反応させた、アルカリ可溶性のアクリル共重合樹脂。ＧＰＣで測定したポリスチレン換算の重量平均分子量（Ｍｗ）は９０００、固形分酸価は８０ｍｇＫＯＨ／ｇ。 Alkali-soluble resin-1 (C-1):
A copolymer resin containing dicyclopentanyl methacrylate/styrene/glycidyl methacrylate (molar ratio: 0.3/0.1/0.6) as a constituent monomer is subjected to an addition reaction of acrylic acid in an equal amount to the glycidyl methacrylate. , an alkali-soluble acrylic copolymer resin which is further subjected to an addition reaction with tetrahydrophthalic anhydride so that the amount becomes 0.39 mol per mol of the above copolymer resin. The weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 9000, and the solid content acid value was 80 mgKOH/g.
　界面活性剤－１：メガファック　Ｆ―５５９（ＤＩＣ社製）
　溶剤－１：プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ） Surfactant-1: Megafac F-559 (manufactured by DIC)
Solvent-1: Propylene glycol monomethyl ether acetate (PGMEA)
Figure JPOXMLDOC01-appb-T000067
Figure JPOXMLDOC01-appb-T000067
［実施例１２～１７］
＜重合性組成物の調製＞
　重合性組成物の全固形分中の各成分の固形分の比率が表１の配合割合となるように各成分を加え、さらに全固形分の含有割合が１７質量％となるように溶剤－１を加え、攪拌、溶解させて、組成物１～６を調製した。
　なお、表１中の重合性化合物、アルカリ可溶性樹脂、熱重合開始剤（Ｏ－イミノ－イソ尿素）の配合割合は固形分換算値である。
　組成物１～６について、以下に記載の方法で評価を行った。 [Examples 12 to 17]
<Preparation of polymerizable composition>
Add each component so that the solid content ratio of each component in the total solid content of the polymerizable composition is as shown in Table 1, and add solvent-1 so that the total solid content is 17% by mass. was added, stirred, and dissolved to prepare Compositions 1 to 6.
The blending ratios of the polymerizable compound, alkali-soluble resin, and thermal polymerization initiator (O-imino-isourea) in Table 1 are calculated in terms of solid content.
Compositions 1 to 6 were evaluated by the method described below.
（アクリレートの二重結合反応率測定）
　シリコンウエハ基板上にスピナーを用いて、乾燥後に２.０μｍの厚みになるように組成物を塗布した。その後、６０℃で２分間ホットプレート上で加熱乾燥し、得られた塗膜を、オーブン中８５℃または１００℃で１時間加熱硬化させ、熱硬化前後のＩＲ吸収スペクトルをＦＴ-ＩＲ分光光度計で測定した。スペクトルの８１０ｃｍ－１の吸光度から、アクリレートの二重結合反応率を見積もった。結果を表２に示す。 (Acrylate double bond reaction rate measurement)
The composition was coated onto a silicon wafer substrate using a spinner so that it would have a thickness of 2.0 μm after drying. Thereafter, the resulting coating film was dried by heating on a hot plate for 2 minutes at 60°C, and the resulting coating was cured by heating at 85°C or 100°C for 1 hour in an oven. It was measured with The double bond reaction rate of the acrylate was estimated from the absorbance at 810 cm −1 of the spectrum. The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000068
 
Figure JPOXMLDOC01-appb-T000068
 
　表２の実施例１２～１７の結果より、本発明のＯ－イミノ－イソ尿素化合物を用いることで、１００℃以下での低温焼成においても、高い二重結合反応率を達成可能であり、良好な熱硬化特性を得られることが示された。 From the results of Examples 12 to 17 in Table 2, by using the O-imino-isourea compound of the present invention, it is possible to achieve a high double bond reaction rate even in low-temperature calcination at 100°C or less, and it is favorable. It was shown that excellent thermosetting properties could be obtained.
［比較例１］
＜Ｏ－イミノ―イソ尿素－１２の合成＞ [Comparative example 1]
<Synthesis of O-imino-isourea-12>
Figure JPOXMLDOC01-appb-C000069
Figure JPOXMLDOC01-appb-C000069
　２００ｍｌのナスフラスコにシクロヘキサノンオキシム（東京化成社製）３．３９ｇをＴＨＦ４１ｍｌに溶解し、水酸化ナトリウム０．１２ｇ、Ｎ，Ｎ‘－ジシクロヘキシルカルボジイミド（東京化成社製）６．８１ｇを添加し、室温で７時間３０分攪拌した。そのまま反応溶液を３日間静置した後、反応溶液にジクロロメタンを５０ｍｌ加え、しばらく攪拌した後、ろ過した。得られたろ液をエバポレーターで溶媒を留去して液体の混合した白色固体を得た。得られた残渣にアセトニトリル３０ｍｌを加えしばらく攪拌した後、アセトニトリル層を除去した。得られた残渣にジクロロメタン３０ｍｌを加え攪拌した後、ろ過し、得られたろ液からジクロロメタンを減圧で留去した。この操作を２回繰り返した後、得られた残渣を真空乾燥して、目的の化合物（Ｏ－イミノ－イソ尿素－１２）２．１ｇを黄色粘性液体として得た。 In a 200 ml eggplant flask, 3.39 g of cyclohexanone oxime (manufactured by Tokyo Kasei Co., Ltd.) was dissolved in 41 ml of THF, 0.12 g of sodium hydroxide and 6.81 g of N,N'-dicyclohexylcarbodiimide (manufactured by Tokyo Kasei Co., Ltd.) were added, and the mixture was heated to room temperature. The mixture was stirred for 7 hours and 30 minutes. After the reaction solution was allowed to stand for 3 days, 50 ml of dichloromethane was added to the reaction solution, stirred for a while, and then filtered. The solvent was distilled off from the obtained filtrate using an evaporator to obtain a white solid with a mixture of liquids. After adding 30 ml of acetonitrile to the obtained residue and stirring for a while, the acetonitrile layer was removed. After adding 30 ml of dichloromethane to the obtained residue and stirring it, it was filtered, and dichloromethane was distilled off from the obtained filtrate under reduced pressure. After repeating this operation twice, the resulting residue was vacuum dried to obtain 2.1 g of the target compound (O-imino-isourea-12) as a yellow viscous liquid.
　得られた化合物に対し、ＮＭＲスペクトル測定による構造確認を行った。結果を以下に示す。
　１Ｈ－ＮＭＲ（ＣＤＣｌ３）　δ（ｐｐｍ）０．９８－２．１９（ｍ，２６Ｈ，－ＣＨ２－）、２．２１－２．３５（ｔ，２Ｈ，Ｃ（＝Ｎ）－ＣＨ２－）、２．５１－２．６６（ｔ，２Ｈ，Ｃ（＝Ｎ）－ＣＨ２－）、３．３５－３．６４（ｍ，２Ｈ，Ｎ－ＣＨ）、５．０３－５．３０（ｓ，１Ｈ，Ｎ－Ｈ） The structure of the obtained compound was confirmed by NMR spectrum measurement. The results are shown below.
1 H-NMR (CDCl 3 ) δ (ppm) 0.98-2.19 (m, 26H, -CH 2 -), 2.21-2.35 (t, 2H, C (=N) - CH 2 -), 2.51-2.66 (t, 2H, C(=N)-CH 2 -), 3.35-3.64 (m, 2H, N-CH), 5.03-5.30 (s, 1H, NH)
［比較例２］
＜Ｏ－イミノ－イソ尿素－１３の合成＞ [Comparative example 2]
<Synthesis of O-imino-isourea-13>
Figure JPOXMLDOC01-appb-C000070
 
Figure JPOXMLDOC01-appb-C000070
 
　１００ｍｌのナスフラスコに２－ブタノンオキシム（東京化成社製）５．０２２ｇをＴＨＦ３２ｍｌに溶解し、水酸化ナトリウム０．１６３ｇ、Ｎ，Ｎ‘－ジシクロヘキシルカルボジイミド（東京化成社製）１１．８６７ｇを添加し、室温で８時間攪拌した。反応溶液をろ過し、得られたろ液からエバポレーターで溶媒を留去して淡黄色粘性液体を得た。得られた液体の一部を酢酸エチル／ヘキサン溶媒でカラム精製を行った後、真空乾燥して、目的の化合物（Ｏ－イミノ―イソ尿素－１３）４．６ｇを淡黄色粘性液体として得た。 In a 100 ml eggplant flask, 5.022 g of 2-butanone oxime (manufactured by Tokyo Kasei Co., Ltd.) was dissolved in 32 ml of THF, and 0.163 g of sodium hydroxide and 11.867 g of N,N'-dicyclohexylcarbodiimide (manufactured by Tokyo Kasei Co., Ltd.) were added. and stirred at room temperature for 8 hours. The reaction solution was filtered, and the solvent was distilled off from the resulting filtrate using an evaporator to obtain a pale yellow viscous liquid. A portion of the obtained liquid was purified by column using ethyl acetate/hexane solvent, and then vacuum dried to obtain 4.6 g of the target compound (O-imino-isourea-13) as a pale yellow viscous liquid. .
　得られた化合物に対し、ＮＭＲスペクトル測定による構造確認を行った。結果を以下に示す。
　１Ｈ－ＮＭＲ（ＣＤＣｌ３）　δ（ｐｐｍ）１．１０－２．００（ｍ，２５Ｈ，－ＣＨ２－／Ｃ（＝Ｎ）－ＣＨ２－ＣＨ３）、１．９６（ｓ，３Ｈ，Ｃ（＝Ｎ）－ＣＨ３）、３．４０－３．５５（ｍ，２Ｈ，Ｎ－ＣＨ）、５．１４（ｓ，１Ｈ，ＮＨ） The structure of the obtained compound was confirmed by NMR spectrum measurement. The results are shown below.
1 H-NMR (CDCl 3 ) δ (ppm) 1.10-2.00 (m, 25H, -CH 2 -/C(=N)-CH 2 -CH 3 ), 1.96 (s, 3H, C (=N)-CH 3 ), 3.40-3.55 (m, 2H, N-CH), 5.14 (s, 1H, NH)
［比較例３～６］
＜重合性組成物の調製＞
　重合性組成物１～６と同様に表３の配合割合になるように組成物７～１０を調製した。 [Comparative Examples 3 to 6]
<Preparation of polymerizable composition>
Compositions 7 to 10 were prepared in the same manner as polymerizable compositions 1 to 6 so as to have the blending ratios shown in Table 3.
Figure JPOXMLDOC01-appb-T000071
Figure JPOXMLDOC01-appb-T000071
（アクリレートの二重結合反応率測定）
　組成物７～１０について、組成物１～６と同様の方法でアクリレートの二重結合反応率の評価を行った。結果を表４に示す。 (Acrylate double bond reaction rate measurement)
For Compositions 7 to 10, the double bond reaction rate of acrylate was evaluated in the same manner as for Compositions 1 to 6. The results are shown in Table 4.
Figure JPOXMLDOC01-appb-T000072
Figure JPOXMLDOC01-appb-T000072
　表４の比較例３～６の結果より、本発明の範囲から逸脱するＯ－イミノ－イソ尿素化合物を用いた場合には、１００℃以下での低温焼成では、二重結合反応率が極めて低く、本発明のＯ－イミノ－イソ尿素化合物を用いることで、比較化合物を用いた場合と比較して、極めて良好な熱硬化特性が得られることが実証された。

  From the results of Comparative Examples 3 to 6 in Table 4, when O-imino-isourea compounds that deviate from the scope of the present invention are used, the double bond reaction rate is extremely low when fired at a low temperature of 100°C or less. It has been demonstrated that by using the O-imino-isourea compound of the present invention, extremely good thermosetting properties can be obtained compared to the case where a comparative compound is used.

Claims (17)

  1. 　以下の式（Ａ）で示される化合物。
    Figure JPOXMLDOC01-appb-C000001
    　ｎは１～４の整数であり、
    　Ｒ３及びＲ４は、各々独立して、Ｃ１～Ｃ２０アルキル、Ｃ３～Ｃ２０シクロアルキル、Ｃ６～Ｃ２０アリール、Ｃ１～Ｃ２０ヘテロアリール、Ｃ７～Ｃ１５アラルキル、又はＳｉ（ＣＨ３）３であり；
    　Ｒ３、Ｒ４におけるＣ１～Ｃ２０アルキル及びＣ３～Ｃ２０シクロアルキルは、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、ＯＣ（Ｏ）、Ｃ（Ｏ）Ｓ、及びＳＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０からなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
    　Ｒ３、Ｒ４におけるＣ６～Ｃ２０アリール、Ｃ１２～Ｃ２０ヘテロアリール、及びＣ７～Ｃ１５アラルキルは、Ｃ１～Ｃ１２アルキル、Ｃ１～Ｃ１２ハロアルキル、Ｃ２～Ｃ１２アルケニル、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、Ｃ（Ｏ）ＮＲ１３Ｒ１４、Ｃ６～Ｃ１０アリール、及びＣ１～Ｃ２０ヘテロアリールからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよい。
    　Ｌ１、Ｌ２及びＬ３はリンカーである。
    　ｎ＝１の場合、Ｌ１はＲ１であり、Ｌ２はＲ２であり、Ｌ３はＲ５である。
    　ｎ＝２～４の場合、Ｌ１、Ｌ２、Ｌ３のいずれか一つがリンカーである。Ｌ１がリンカーの場合、Ｌ２はＲ２であり、Ｌ３はＲ５である。Ｌ２がリンカーの場合、Ｌ１はＲ１であり、Ｌ３はＲ５である。Ｌ３がリンカーの場合、Ｌ１はＲ１であり、Ｌ２はＲ２である。
    　Ｒ１は、Ｃ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルケニル、Ｃ２～Ｃ２０アルキニル、Ｃ３～Ｃ２０シクロアルキル、Ｃ２～Ｃ２０ヘテロシクロアルキル、Ｃ６～Ｃ２０アリールまたはＣ１～Ｃ２０ヘテロアリールであり；
    　Ｒ１におけるＣ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルケニル及びＣ２～Ｃ２０アルキニルは、１もしくはそれより多くの同一もしくは異なるＯ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ及びＯＣ（Ｏ）からなる群より選択される基によって中断されていてもよく、１もしくはそれより多くの同一もしくは異なる基Ｒ１ａを有していてもよく；
    　Ｒ１におけるＣ３～Ｃ２０シクロアルキル及びＣ２～Ｃ２０ヘテロシクロアルキルは、１もしくはそれより多くのＣ（Ｏ）基によって中断されていてもよく、１もしくはそれより多くの同一もしくは異なる基Ｒ１ｂを有していてもよく；
    　Ｒ１におけるＣ６～Ｃ２０アリール及びＣ１～Ｃ２０ヘテロアリールは、１もしくはそれより多くの同一もしくは異なる基Ｒ１ｃを有していてもよく；
    　Ｒ１ａは、各々独立して、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＣＮ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、Ｃ（Ｏ）ＮＲ１３Ｒ１４、１もしくはそれより多くのＣ（Ｏ）基によって中断されていてもよいＣ３～Ｃ２０シクロアルキル、及びＣ６～Ｃ１０アリールからなる群より選択され；
    　Ｒ１ａにおけるＣ３～Ｃ２０シクロアルキル及びＣ６～Ｃ１０アリールは、１もしくはそれより多くの同一もしくは異なる基Ｒ１ａａを有していてもよく；
    　Ｒ１ａａは、各々独立して、Ｃ１～Ｃ１２アルキル、Ｃ２～Ｃ１２アルケニル、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、ＳＲ７、ＯＲ８及びＮＲ９Ｒ１０からなる群より選択され；
    　Ｒ１ａａにおけるＣ１～Ｃ１２アルキルは、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、及びＣ（Ｏ）ＮＲ１３Ｒ１４からなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
    　Ｒ１ｂは、各々独立して、Ｃ１～Ｃ１２アルキル、Ｃ２～Ｃ１２アルケニル、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＣＮ、ＮＯ２、ＳＲ７、ＯＲ８及びＮＲ９Ｒ１０からなる群より選択され；
    　Ｒ１ｂにおけるＣ１～Ｃ１２アルキルは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、及びＣ（Ｏ）ＮＲ１３Ｒ１４からなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
    Ｒ１ｃは、各々独立して、Ｃ１～Ｃ１２アルキル、Ｃ２～Ｃ１２アルケニル、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＣＮ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、Ｃ（Ｏ）ＮＲ１３Ｒ１４、Ｃ６～Ｃ１０アリール、Ｃ１～Ｃ２０ヘテロアリール、Ｃ３～Ｃ１０シクロアルキル、及びＣ２～Ｃ１０ヘテロシクロアルキルからなる群より選択され；
    　Ｒ１ｃにおけるＣ１～Ｃ１２アルキルは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、及びＣ（Ｏ）ＮＲ１３Ｒ１４から選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
    　Ｒ１ｃにおけるＣ１～Ｃ１２アルキル、Ｃ３～Ｃ１０シクロアルキル及びＣ２～Ｃ１０ヘテロシクロアルキルは、１もしくはそれより多くのＣ（Ｏ）基によって中断されていてもよく；
    　Ｒ１ｃにおけるＣ６～Ｃ１０アリール、Ｃ１～Ｃ２０ヘテロアリール、Ｃ３～Ｃ１０シクロアルキル及びＣ２～Ｃ１０ヘテロシクロアルキルは、１もしくはそれより多くの同一もしくは異なる基Ｒ１ｃａを有していてもよく、該Ｒ１ｃａは、前記Ｒ１ａａと同義であり；
    　Ｒ２は、水素原子、Ｃ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルケニル、Ｃ２～Ｃ２０アルキニル、Ｃ３～Ｃ２０シクロアルキル、Ｃ２～Ｃ２０ヘテロシクロアルキル、Ｃ６～Ｃ２０アリール、Ｃ１～Ｃ２０ヘテロアリール、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、Ｃ（Ｏ）ＮＲ１３Ｒ１４、ＳＯ２Ｒ１５、またはＣＮであり；
    　Ｒ２におけるＣ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルケニル及びＣ２～Ｃ２０アルキニルは、１もしくはそれより多くの同一もしくは異なるＯ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される基によって中断されていてもよく、１もしくはそれより多くの同一もしくは異なる基Ｒ２ａを有していてもよく；
    　Ｒ２におけるＣ３～Ｃ２０シクロアルキル及びＣ２～Ｃ２０ヘテロシクロアルキルは、１もしくはそれより多くのＣ（Ｏ）基によって中断されていてもよく、１もしくはそれより多くの同一もしくは異なる基Ｒ２ｂを有していてもよく；
    　Ｒ２におけるＣ６～Ｃ２０アリール及びＣ１～Ｃ２０ヘテロアリールは、１もしくはそれより多くの同一もしくは異なる基Ｒ２ｃを有していてもよく；
    　Ｒ２ａは、Ｒ１ａと同義であり；
    　Ｒ２ｂは、Ｒ１ｂと同義であり；
    　Ｒ２ｃは、Ｒ１ｃと同義であり；
    　また、Ｒ２は、－Ｓ－Ｒ１と一緒になってイミノ炭素原子を含む環構造を形成していてもよく；
    　前記イミノ炭素原子を含む環構造としては、Ｓ－（Ｃ１～Ｃ２０アルキレン）－Ｘ、Ｓ－（Ｃ２～Ｃ２０アルケニレン）－Ｘ、Ｓ－（Ｃ３～Ｃ２０シクロアルキレン）－Ｘ、Ｓ－（ヘテロシクロアルキレン）－Ｘ、Ｓ－（ｏ－フェニレン）－Ｘ、Ｓ－（ｏ－キシレン）－Ｘ、Ｓ－（ｏ－フェニレン－Ｃ１～Ｃ１２アルキレン）－Ｘ、Ｓ－（Ｃ１～Ｃ１２アルキレン－ｏ－フェニレン）－Ｘ、Ｓ－（Ｃ（Ｏ）Ｎ（Ｒ１６））－Ｘ、またはＳ－（Ｃ（Ｓ）Ｎ（Ｒ１７））－Ｘであってよく；
    　Ｘは、Ｓを有するイミノ炭素原子に結合されており、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、ＯＣ（Ｏ）、Ｃ（Ｏ）Ｏ、ＳＣ（Ｏ）、Ｃ（Ｏ）Ｓ、Ｃ（Ｏ）Ｎ（Ｒ１６）、Ｎ（Ｒ１８）Ｃ（Ｏ）、Ｎ（Ｒ１９）ＳＯ２または単結合であり；
    　前記イミノ炭素原子を含む環構造におけるアルキレン及びアルケニレンは、１もしくはそれより多くの同一または異なる、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）及びＣ（Ｓ）からなる群より選択される基によって中断されていてもよく、１もしくはそれより多くの基Ｒ２ｄによって置換されていてもよく；
    　前記イミノ炭素原子を含む環構造におけるシクロアルキレン及びヘテロシクロアルキレンは、１もしくはそれより多くのＣ（Ｏ）基によって中断されていてもよく、１もしくはそれより多くの同一もしくは異なる基Ｒ２ｅによって置換されていてもよく；
    　前記イミノ炭素原子を含む環構造におけるフェニレン及びｏ－キシリレンは、１もしくはそれより多くの同一もしくは異なる基Ｒ２ｆによって置換されていてもよく；
    　Ｒ２ｄは、各々独立して、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、Ｃ（Ｏ）ＮＲ１３Ｒ１４、Ｃ６～Ｃ１０アリール及びＣ１～Ｃ２０ヘテロアリールからなる群より選択され；
    　Ｒ２ｄにおけるＣ６～Ｃ１０アリール及びＣ１～Ｃ２０ヘテロアリールは、１もしくはそれより多くの基Ｒ２ｄａを有していてもよく、Ｒ２ｄａは、各々独立に、フェノキシ、及びＲ１ａａで示した基からなる群から選択され；
    　Ｒ２ｅは、各々独立して、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、ＣＯＮＲ１３Ｒ１４、Ｃ１～Ｃ１２アルキル、Ｃ１～Ｃ１２ハロアルキル、Ｃ６～Ｃ１０アリール、及びＣ１～Ｃ２０ヘテロアリールからなる群より選択され；
    　Ｒ２ｅにおけるＣ６～Ｃ１０アリール及びＣ１～Ｃ２０ヘテロアリールは、１もしくはそれより多くの基Ｒ２ｅａを有していてもよく、Ｒ２ｅａは、Ｒ１ａａと同義であり；
    　Ｒ２ｆは、各々独立して、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＳＲ７、ＯＲ８、ＮＲ９Ｒ１０、Ｃ（Ｏ）Ｒ１１、Ｃ（Ｏ）ＯＲ１２、ＣＯＮＲ１３Ｒ１４、Ｃ１～Ｃ１２アルキル、Ｃ１～Ｃ１２ハロアルキル、Ｃ６～Ｃ１０アリール、及びＣ１～Ｃ２０ヘテロアリールからなる群より選択され；
    　Ｒ２ｆにおけるＣ６～Ｃ１０アリール及びＣ１～Ｃ２０ヘテロアリールは、１もしくはそれより多くの基Ｒ２ｆａを有していてもよく、Ｒ２ｆａは、Ｒ１ａａと同義であり；
    　Ｒ５は、水素原子、Ｃ１～Ｃ２０アルキル、Ｃ３～Ｃ２０シクロアルキル、Ｃ７～Ｃ１４アラルキル、Ｃ６～Ｃ１４アリール、またはアシル基であり；
    　Ｒ５におけるアシル基は、－Ｃ（Ｏ）－Ｈ、－Ｃ（Ｏ）－Ｃ１～Ｃ１８アルキル、－Ｃ（Ｏ）－Ｃ２～Ｃ１８アルケニル、－Ｃ（Ｏ）－Ｃ６～Ｃ１４アリール、－Ｃ（Ｏ）－Ｃ２～Ｃ１８アルケニル－Ｃ６～Ｃ１４アリール、－Ｃ（Ｏ）－Ｏ－Ｃ１～Ｃ１８アルキル、－Ｃ（Ｏ）－Ｏ－Ｃ６～Ｃ１４アリール、－Ｃ（Ｏ）－ＮＨ－Ｃ１～Ｃ１８アルキル、－Ｃ（Ｏ）－ＮＨ－Ｃ６～Ｃ１４アリール及びＣ（Ｏ）－Ｎ（Ｃ１～Ｃ１８アルキル）２からなる群より選択され；
    　Ｒ３及びＲ５は、それらが結合する窒素原子と共に、更なるヘテロ原子を含んでいてもよい５～１２員環を形成していてもよく；
    　Ｒ６は、各々独立して、水素原子、Ｃ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルカノイル、Ｃ６～Ｃ１０アリール及びＣ７～Ｃ１１アロイルからなる群より選択され；
    　Ｒ６におけるＣ１～Ｃ２０アルキルは、Ｏ、Ｓ、Ｎ（Ｃ１～Ｃ１２アルキル）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、Ｃ２～Ｃ１０ヘテロシクロアルキル、Ｃ６～Ｃ１０アリール、ＯＨ、及びＳＨからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
    　Ｒ６におけるＣ２～Ｃ２０アルカノイルは、Ｏ、Ｓ、ＣＯ、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、Ｃ２～Ｃ１０ヘテロシクロアルキル、及びＣ６～Ｃ１０アリールからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
    　Ｒ６におけるＣ６～Ｃ１０アリールは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１０アルキル、Ｃ１～Ｃ１０アルコキシ、及びＣ２～Ｃ１１アシロキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
    　Ｒ６におけるＣ７～Ｃ１１アロイルは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１０アルキル、Ｃ１～Ｃ１０アルコキシ、及びＣ２～Ｃ１１アシロキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
    　Ｒ７及びＲ８は、各々独立して、水素原子、Ｃ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルカノイル、Ｃ６～Ｃ１０アリール、及びＣ７～Ｃ１１アロイルからなる群より選択され；
    　Ｒ７、Ｒ８におけるＣ１～Ｃ２０アルキルは、Ｏ、Ｓ、Ｎ（Ｃ１～Ｃ１２アルキル）、ＣＯ、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、Ｃ２～Ｃ１０ヘテロシクロアルキル、Ｃ６～Ｃ１０アリール、ＯＨ、及びＳＨからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
    　Ｒ７、Ｒ８におけるＣ２～Ｃ２０アルカノイルは、Ｏ、Ｓ、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、Ｃ２～Ｃ１０ヘテロシクロアルキル、及びＣ６～Ｃ１０アリールからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
    　Ｒ７、Ｒ８におけるＣ６～Ｃ１０アリールは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ６アルキル、Ｃ１～Ｃ１０アルコキシ、及びＣ２～Ｃ１１アシロキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
    　Ｒ７、Ｒ８におけるＣ７～Ｃ１１アロイルは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１０アルキル、Ｃ１～Ｃ１０アルコキシ、及びＣ２～Ｃ１１アシロキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
    　Ｒ９及びＲ１０は、各々独立して、水素原子、Ｃ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルカノイル、Ｃ７～Ｃ１１アロイル、Ｃ６～Ｃ１０アリールからなる群より選択され；
    　Ｒ９、Ｒ１０におけるＣ１～Ｃ２０アルキルは、Ｏ、Ｓ、Ｎ（Ｃ１～Ｃ１２アルキル）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＮＯ２、Ｃ３～Ｃ１０シクロアルキル、ヘテロシクロアルキル、フェニル、ＯＨ、ＳＨ及びＣＮからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
    　Ｒ９、Ｒ１０におけるＣ２～Ｃ２０アルカノイルは、Ｏ及びＳからなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、ＯＨ及びＣ１～Ｃ６アルコキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
    　Ｒ９、Ｒ１０におけるＣ７～Ｃ１１アロイルは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ６アルキル、－ＯＨ及びＣ１～Ｃ６アルコキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
    　Ｒ９、Ｒ１０におけるＣ６～Ｃ１０アリールは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ６アルキル、－ＯＨ及びＣ１～Ｃ６アルコキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
    　Ｒ９及びＲ１０は、それらが結合される窒素原子と一緒になって、飽和の５員、６員または７員の窒素複素環を形成していてもよく、前記環はＯ、Ｓ、Ｎ（Ｃ１～Ｃ１２アルキル）、Ｃ（Ｏ）、及びＣ（Ｏ）Ｏからなる群より選択される基を環員として有していてもよく、前記環は１もしくはそれより多くのＣ１～Ｃ４アルキルを有してよく；
    　Ｒ１１は各々独立して、水素原子、Ｃ１～Ｃ２０アルキル及びＣ６～Ｃ２０アリールからなる群より選択され；
    　Ｃ１～Ｃ２０アルキルは、Ｏ、Ｓ及びＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、１もしくはそれより多くの同一もしくは異なるＲ１１ａを有していてもよく；
    　Ｒ１１ａは、各々独立して、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、ヘテロシクロアルキル、フェニル、ＯＨ、及びＳＨからなる群より選択され；
    　Ｒ１１におけるＣ６～Ｃ２０アリールは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１０アルキル、Ｃ１～Ｃ１０アルコキシ、及びＣ２～Ｃ１１アシロキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
    　Ｒ１２は、Ｒ８と同義であり；
    　Ｒ１３及びＲ１４は、Ｒ９、Ｒ１０と同義であり；
    　Ｒ１５は、各々独立して、水素原子、Ｃ１～Ｃ２０アルキル、Ｃ６～Ｃ１０アリールからなる群より選択され；
    　Ｒ１５におけるＣ１～Ｃ２０アルキルは、Ｏ、Ｓ、Ｎ（Ｃ１～Ｃ１２アルキル）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、Ｃ２～Ｃ１０ヘテロシクロアルキル、Ｃ６～Ｃ１０アリール、ＯＨ、及びＳＨからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
    　Ｒ１５におけるＣ６～Ｃ１０アリールは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ６アルキル、及びＣ１～Ｃ６アルコキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
    　Ｒ１６、Ｒ１７、Ｒ１８及びＲ１９は、各々独立して、水素原子、Ｃ１～Ｃ２０アルキル、Ｃ２～Ｃ２０アルカノイル、Ｃ６～Ｃ１０アリール、Ｃ７～Ｃ１１アロイルからなる群より選択され；
    　Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９におけるＣ１～Ｃ２０アルキルは、Ｏ、Ｓ、Ｎ（Ｃ１～Ｃ１２アルキル）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、Ｃ２～Ｃ１０ヘテロシクロアルキル、Ｃ６～Ｃ１０アリール、ＯＨ、及びＳＨからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
    　Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９におけるＣ２～Ｃ２０アルカノイルは、Ｏ、Ｓ、ＣＯ、Ｃ（Ｏ）Ｏ、及びＯＣ（Ｏ）からなる群より選択される１もしくはそれより多くの基によって中断されていてもよく、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ３～Ｃ１０シクロアルキル、Ｃ２～Ｃ１０ヘテロシクロアルキル、及びＣ６～Ｃ１０アリールからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
    　Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９におけるＣ６～Ｃ１０アリールは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１０アルキル、Ｃ１～Ｃ１０アルコキシ、及びＣ２～Ｃ１１アシロキシからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
    　Ｒ１６、Ｒ１７、Ｒ１８、Ｒ１９におけるＣ７～Ｃ１１アロイルは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１０アルキル、Ｃ１～Ｃ１０アルコキシ、及びＣ２～Ｃ１１アシロキシからからなる群より選択される１もしくはそれより多くの同一もしくは異なる基を有していてもよく；
    　Ｌ１は、ｎが２である場合に、二価のリンカーであり、前記リンカーは、Ｌ１ａ－Ｃ１～Ｃ３０アルキレン－Ｌ１ａ、Ｌ２ａ－Ｃ１～Ｃ３０アルケニレン－Ｌ２ａ、Ｌ１ａ－Ｃ３～Ｃ１６シクロアルキレン－Ｌ１ａ、Ｌ１ａ－Ｃ６～Ｃ２０アリーレン－Ｌ１ａ、Ｌ１ａ－Ｃ６～Ｃ２０アリーレン－Ｌ１ｂ－Ｃ６～Ｃ２０アリーレン－Ｌ１ａ、及びＬ１ａ－Ｃ１～Ｃ１３ヘテロアリーレン－Ｌ１ａからなる群より選択され；
    　Ｌ１の前記リンカーにおけるアルキレン及びアルケニレンは、各々独立に、１もしくはそれより多くの同一もしくは異なる非隣接の基Ｌ１ｃによって中断されていてもよく；
    　Ｌ１の前記リンカーにおけるアリーレン及びヘテロアリーレンは、各々独立に、１もしくはそれより多くの同一もしくは異なる基ＲＬ１を有していてもよく；
    　Ｌ１ａは、単結合であり；
    　Ｌ１ｂは、単結合、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、ＣＨ２、Ｃ（ＣＨ３）２、ＣＨ（ＯＨ）またはＣ１～Ｃ５アルキレンであり；
    　Ｌ１ｃは、各々独立して、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、ＯＣ（Ｏ）、Ｃ６～Ｃ２０アリーレン及びＣ３～Ｃ１６シクロアルキレンからなる群より選択され；
    　ＲＬ１は、各々独立して、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１２アルキル、Ｃ１～Ｃ１２アルコキシ、及びＣ２～Ｃ１１アシロキシから選択され；
    　Ｌ１ｂ、Ｌ１ｃにおけるＲ６は、Ｒ６と同義であり；
    　Ｌ２は、ｎが２である場合に、二価のリンカーであり、前記リンカーは、単結合、Ｌ２ａ－Ｃ１～Ｃ３０アルキレン－Ｌ２ａ、Ｌ２ａ－Ｃ１～Ｃ３０アルケニレン－Ｌ２ａ、Ｌ２ａ－Ｃ６～Ｃ２０アリーレン－Ｌ２ａ、Ｌ２ａ－Ｃ６～Ｃ２０アリーレン－Ｌ２ｂ－Ｃ６～Ｃ２０アリーレン－Ｌ２ａからなる群より選択され；
    　Ｌ２の二価のリンカーにおけるアルキレン及びアルケニレンは、各々独立に、１もしくはそれより多くの同一もしくは異なる基Ｌ２ｃによって中断されていてもよく；
    　Ｌ２の二価のリンカーにおけるアリーレン及びヘテロアリーレンは、各々独立に、１もしくはそれより多くの同一もしくは異なる基ＲＬ２を有していてもよく；
    　Ｌ２ａは、各々独立して、単結合、Ｓ、Ｏ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、ＯＣ（Ｏ）またはＳＯ２であり；
    　Ｌ２ｂは、単結合、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、ＣＨ２、Ｃ（ＣＨ３）２、ＣＨ（ＯＨ）またはＣ１～Ｃ５アルキレンであり；
    　Ｌ２ｃは、各々独立して、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、ＯＣ（Ｏ）、Ｃ６～Ｃ２０アリーレン及びＣ３～Ｃ１６シクロアルキレンからなる群より選択され；
    　ＲＬ２は、各々独立して、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１２アルキル、Ｃ１～Ｃ１２アルコキシ、及びＣ２～Ｃ１１アシロキシから選択され；
    　Ｌ２ｂ、Ｌ２ｃにおけるＲ６は、Ｒ６と同義であり；
    　Ｌ３は、ｎが２である場合に、二価のリンカーであり、前記リンカーは、Ｌ３ａ－Ｃ１～Ｃ３０アルキレン－Ｌ３ａ、Ｌ３ａ－Ｃ３～Ｃ１６シクロアルキレン－Ｌ３ａ、Ｌ３ａ－Ｃ６～Ｃ２０アリーレン－Ｌ３ａ、Ｌ３ａ－Ｃ１～Ｃ２０アルキレン－Ｌ３ｂ－Ｃ６～Ｃ１６シクロアルキレン－Ｌ３ａ、Ｌ３ａ－Ｃ６～Ｃ１６シクロアルキレン－Ｌ３ｂ－Ｃ６～Ｃ１６シクロアルキレン－Ｌ３ａ、Ｌ３ａ－Ｃ６～Ｃ２０アリーレン－Ｌ３ｂ－Ｃ６～Ｃ２０アリーレン－Ｌ３ａ、及びＬ３ａ－Ｃ１～Ｃ１３ヘテロアリーレン－Ｌ３ａからなる群より選択され；
    　Ｌ３の二価のリンカーにおけるアルキレンは、各々独立して、１もしくはそれより多くの同一もしくは異なる非隣接の基Ｌ３ｃによって中断されていてもよく；
    　Ｌ３の二価のリンカーにおけるシクロアルキレンは、各々独立して、１もしくはそれより多くの同一もしくは異なる基ＲＬ３ａを有していてもよく；
    　Ｌ３の二価のリンカーにおけるアリーレン及びヘテロアリーレンは、各々独立して、１もしくはそれより多くの同一もしくは異なる基ＲＬ３ｂを有していてもよく；
    　Ｌ３ａは、単結合、Ｃ（Ｏ）、Ｃ（Ｏ）ＯまたはＣ（Ｏ）Ｎ（Ｒ１６）であり；
    　Ｌ３ｂは、各々独立して、単結合、Ｏ、Ｓ、Ｎ（Ｒ６）またはＣ１～Ｃ５アルキレンであり；
    　Ｌ３ｃは、各々独立して、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、ＯＣ（Ｏ）、Ｃ６～Ｃ２０アリーレン、Ｃ３～Ｃ１６シクロアルキレン及びヘテロシクロアルキレンからなる群より選択され；
    　ＲＬ３ａは、各々独立して、Ｃ１～Ｃ１２アルキルであり；
    　ＲＬ３ｂは、Ｆ、Ｃｌ、Ｂｒ、Ｉ、Ｃ１～Ｃ１２アルコキシ、及びＣ２～Ｃ１１アシロキシからなる群より選択され；
    　Ｌ３ｂ、Ｌ３ｃにおけるＲ６は、Ｒ６と同義であり；
    　Ｌ３ａにおけるＲ１６は、と同義であり；
    　Ｌ１及びＬ２は、ｎが３の場合、三価のリンカーであり、前記リンカーは、Ｃ１～Ｃ３０アルカントリイル、Ｃ２～Ｃ３０アルケントリイル、Ｃ３～Ｃ１６シクロアルカントリイル、ヘテロシクロアルカントリイル、Ｃ６～Ｃ２０アレーントリイル、及びヘテロアレーントリイルからなる群より選択され；
    　Ｌ１、Ｌ２の三価のリンカーにおけるアルカントリイルは、１もしくはそれより多くの同一もしくは異なる基Ｌ４によって中断されていてもよく；
    　Ｌ４は、各々独立して、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、ＯＣ（Ｏ）、Ｃ（Ｏ）Ｎ（Ｒ１６）、Ｎ（Ｒ１８）Ｃ（Ｏ）、Ｃ３～Ｃ２０シクロアルキレン、ヘテロシクロアルキレン、Ｃ６～Ｃ２０アリーレン及びヘテロアリーレンからなる群より選択され；
    　Ｌ４におけるＲ６、Ｒ１６、Ｒ１８は各々、Ｒ６、前記Ｒ１８と同義であり；
    　Ｌ３は、ｎが３の場合、三価のリンカーであり、前記リンカーは、Ｃ１～Ｃ３０アルカントリイル、Ｃ２～Ｃ３０アルケントリイル、Ｃ３～Ｃ１６シクロアルカントリイル、ヘテロシクロアルカントリイル、Ｃ６～Ｃ２０アレーントリイル、ヘテロアレーントリイル、トリアシルからなる群より選択され；
    　Ｌ３の三価のリンカーにおけるアルカントリイルは、１もしくはそれより多くの同一もしくは異なる基Ｌ５によって中断されていてもよく；
    　Ｌ５は、各々独立して、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、ＯＣ（Ｏ）、Ｃ（Ｏ）Ｎ（Ｒ１６）、Ｎ（Ｒ１８）Ｃ（Ｏ）、Ｃ３～Ｃ２０シクロアルキレン、ヘテロシクロアルキレン、Ｃ６～Ｃ２０アリーレン及びヘテロアリーレンからなる群より選択され；
    　Ｌ５におけるＲ６、Ｒ１６、Ｒ１８は各々、Ｒ６、Ｒ１８と同義であり；
    　Ｌ１及びＬ２は、ｎが４である場合、四価のリンカーであり、前記リンカーは、Ｃ１～Ｃ３０アルカンテトライルであり；
    　Ｌ１、Ｌ２の４価のリンカーにおけるアルカンテトライルは、１もしくはそれより多くの同一もしくは異なる基Ｌ６によって中断されていてもよく；
    　Ｌ６は、各々独立して、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、ＯＣ（Ｏ）、Ｃ（Ｏ）Ｎ（Ｒ１６）、Ｎ（Ｒ１８）Ｃ（Ｏ）、Ｃ３～Ｃ２０シクロアルキレン、ヘテロシクロアルキレン、Ｃ６～Ｃ２０アリーレン及びヘテロアリーレンからなる群より選択され；
    　Ｌ６におけるＲ６、Ｒ１６、Ｒ１８は各々、Ｒ６、Ｒ１８と同義であり；
    　Ｌ３は、ｎが４である場合、四価のリンカーであり、前記リンカーは、Ｃ１～Ｃ３０アルカンテトライル、テトラアシルからなる群より選択され；
    　Ｌ３の４価のリンカーにおけるアルカンテトライルは、１もしくはそれより多くの同一もしくは異なる基Ｌ７によって中断されていてもよく；
    　Ｌ７は、各々独立して、Ｏ、Ｓ、Ｎ（Ｒ６）、Ｃ（Ｏ）、Ｃ（Ｏ）Ｏ、ＯＣ（Ｏ）、Ｃ（Ｏ）Ｎ（Ｒ１６）、Ｎ（Ｒ１８）Ｃ（Ｏ）、Ｃ３～Ｃ２０シクロアルキレン、ヘテロシクロアルキレン、Ｃ６～Ｃ２０アリーレン及びヘテロアリーレンからなる群より選択され；
    　Ｌ７におけるＲ６、Ｒ１６、Ｒ１８は各々、Ｒ６、Ｒ１８と同義である、前記化合物。     A compound represented by the following formula (A).
    Figure JPOXMLDOC01-appb-C000001
    n is an integer from 1 to 4,
    R 3 and R 4 are each independently C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 6 -C 20 aryl, C 1 -C 20 heteroaryl, C 7 -C 15 aralkyl, or Si( CH3 ) 3 ;
    C 1 -C 20 alkyl and C 3 -C 20 cycloalkyl in R 3 and R 4 are O, S, N(R 6 ), C(O), C(O)O, OC(O), C( O) optionally interrupted by one or more groups selected from the group consisting of S, and SC(O), F, Cl, Br, I, NO2 , SR7 , OR8 , NR9 R may have one or more same or different groups selected from the group consisting of;
    C 6 -C 20 aryl, C 12 -C 20 heteroaryl, and C 7 -C 15 aralkyl in R 3 and R 4 are C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 2 -C 12 alkenyl , F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , C(O)NR 13 R 14 , C 6 to C 10 aryl, and one or more identical or different groups selected from the group consisting of C 1 -C 20 heteroaryl.
    L 1 , L 2 and L 3 are linkers.
    When n=1, L 1 is R 1 , L 2 is R 2 and L 3 is R 5 .
    When n=2 to 4, one of L 1 , L 2 , and L 3 is a linker. When L 1 is a linker, L 2 is R 2 and L 3 is R 5 . When L2 is a linker, L1 is R1 and L3 is R5 . When L 3 is a linker, L 1 is R 1 and L 2 is R 2 .
    R 1 is C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 3 -C 20 cycloalkyl, C 2 -C 20 heterocycloalkyl, C 6 -C 20 aryl or C 1 to C 20 heteroaryl;
    C 1 -C 20 alkyl, C 2 -C 20 alkenyl and C 2 -C 20 alkynyl in R 1 are one or more of the same or different O, S, N(R 6 ), C(O), C (O) may be interrupted by groups selected from the group consisting of O and OC(O) and may have one or more identical or different groups R 1a ;
    C 3 -C 20 cycloalkyl and C 2 -C 20 heterocycloalkyl in R 1 may be interrupted by one or more C(O) groups and may contain one or more identical or different groups. It may have R 1b ;
    C 6 -C 20 aryl and C 1 -C 20 heteroaryl in R 1 may have one or more identical or different groups R 1c ;
    R 1a each independently represents F, Cl, Br, I, CN, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , C(O ) NR 13 R 14 , C 3 -C 20 cycloalkyl, optionally interrupted by one or more C(O) groups, and C 6 -C 10 aryl;
    C 3 -C 20 cycloalkyl and C 6 -C 10 aryl in R 1a may have one or more identical or different groups R 1aa ;
    R 1aa is each independently selected from the group consisting of C 1 -C 12 alkyl, C 2 -C 12 alkenyl, F, Cl, Br, I, NO 2 , SR 7 , OR 8 and NR 9 R 10 ;
    C 1 -C 12 alkyl in R 1aa is one or more selected from the group consisting of O, S, N(R 6 ), C(O), C(O)O, and OC(O). Optionally interrupted by groups F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , and C(O) may have one or more same or different groups selected from the group consisting of NR 13 R 14 ;
    R 1b is each independently from the group consisting of C 1 -C 12 alkyl, C 2 -C 12 alkenyl, F, Cl, Br, I, CN, NO 2 , SR 7 , OR 8 and NR 9 R 10 selected;
    C 1 -C 12 alkyl in R 1b is F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , and C( O) may have one or more same or different groups selected from the group consisting of NR 13 R 14 ;
    R 1c is each independently C 1 -C 12 alkyl, C 2 -C 12 alkenyl, F, Cl, Br, I, CN, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O ) R 11 , C(O)OR 12 , C(O)NR 13 R 14 , C 6 -C 10 aryl, C 1 -C 20 heteroaryl, C 3 -C 10 cycloalkyl, and C 2 -C 10 hetero selected from the group consisting of cycloalkyl;
    C 1 -C 12 alkyl in R 1c is F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , and C( O) may have one or more identical or different groups selected from NR 13 R 14 ;
    C 1 -C 12 alkyl, C 3 -C 10 cycloalkyl and C 2 -C 10 heterocycloalkyl in R 1c may be interrupted by one or more C(O) groups;
    C 6 -C 10 aryl, C 1 -C 20 heteroaryl, C 3 -C 10 cycloalkyl and C 2 -C 10 heterocycloalkyl in R 1c have one or more identical or different groups R 1ca . and the R 1ca has the same meaning as the above R 1aa ;
    R 2 is a hydrogen atom, C 1 to C 20 alkyl, C 2 to C 20 alkenyl, C 2 to C 20 alkynyl, C 3 to C 20 cycloalkyl, C 2 to C 20 heterocycloalkyl, C 6 to C 20 Aryl, C 1 -C 20 heteroaryl, SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , C(O)NR 13 R 14 , SO 2 R 15 , or CN;
    C 1 -C 20 alkyl, C 2 -C 20 alkenyl and C 2 -C 20 alkynyl in R 2 are one or more of the same or different O, S, N(R 6 ), C(O), C (O) may be interrupted by groups selected from the group consisting of O, and OC(O), and may have one or more identical or different groups R 2a ;
    C 3 -C 20 cycloalkyl and C 2 -C 20 heterocycloalkyl in R 2 may be interrupted by one or more C(O) groups and may contain one or more identical or different groups. It may have R 2b ;
    C 6 -C 20 aryl and C 1 -C 20 heteroaryl in R 2 may have one or more identical or different groups R 2c ;
    R 2a is synonymous with R 1a ;
    R 2b is synonymous with R 1b ;
    R 2c is synonymous with R 1c ;
    Furthermore, R 2 may be combined with -SR 1 to form a ring structure containing an imino carbon atom;
    The ring structure containing the imino carbon atom includes S-(C 1 to C 20 alkylene)-X, S-(C 2 to C 20 alkenylene)-X, S-(C 3 to C 20 cycloalkylene)-X , S-(heterocycloalkylene)-X, S-(o-phenylene)-X, S-(o-xylene)-X, S-(o-phenylene-C 1 -C 12 alkylene)-X, S- (C 1 -C 12 alkylene-o-phenylene)-X, S-(C(O)N(R 16 ))-X, or S-(C(S)N(R 17 ))-X, often;
    X is bonded to an imino carbon atom with S, O, S, N(R 6 ), C(O), OC(O), C(O)O, SC(O), C(O) S, C(O)N(R 16 ), N(R 18 )C(O), N(R 19 )SO 2 or a single bond;
    The alkylene and alkenylene in the ring structure containing the imino carbon atom are selected from the group consisting of one or more of the same or different O, S, N(R 6 ), C(O) and C(S). optionally interrupted by groups and optionally substituted by one or more groups R 2d ;
    Cycloalkylene and heterocycloalkylene in the ring structures containing said imino carbon atoms may be interrupted by one or more C(O) groups and substituted by one or more identical or different groups R 2e may have been;
    Phenylene and o-xylylene in the ring structure containing said imino carbon atoms may be substituted by one or more identical or different groups R 2f ;
    R 2d is each independently F, Cl, Br, I, NO 2 , SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , C(O)NR 13 R 14 selected from the group consisting of C 6 -C 10 aryl and C 1 -C 20 heteroaryl;
    C 6 -C 10 aryl and C 1 -C 20 heteroaryl in R 2d may have one or more groups R 2da , each R 2da being independently phenoxy, and R 1aa selected from the group consisting of the indicated groups;
    R 2e each independently represents F, Cl, Br, I, SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , CONR 13 R 14 , C 1 - selected from the group consisting of C 12 alkyl, C 1 -C 12 haloalkyl, C 6 -C 10 aryl, and C 1 -C 20 heteroaryl;
    C 6 -C 10 aryl and C 1 -C 20 heteroaryl in R 2e may have one or more groups R 2ea, R 2ea is synonymous with R 1aa ;
    R 2f is each independently F, Cl, Br, I, SR 7 , OR 8 , NR 9 R 10 , C(O)R 11 , C(O)OR 12 , CONR 13 R 14 , C 1 - selected from the group consisting of C 12 alkyl, C 1 -C 12 haloalkyl, C 6 -C 10 aryl, and C 1 -C 20 heteroaryl;
    C 6 -C 10 aryl and C 1 -C 20 heteroaryl in R 2f may have one or more groups R 2fa, R 2fa is synonymous with R 1aa ;
    R 5 is a hydrogen atom, C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, C 7 -C 14 aralkyl, C 6 -C 14 aryl, or acyl group;
    The acyl group in R 5 is -C(O)-H, -C(O)-C 1 -C 18 alkyl, -C(O)-C 2 -C 18 alkenyl, -C(O)-C 6 - C 14 aryl, -C(O)-C 2 -C 18 alkenyl-C 6 -C 14 aryl, -C(O)-O-C 1 -C 18 alkyl, -C(O)-O-C 6 - C 14 aryl, -C(O)-NH-C 1 -C 18 alkyl, -C(O)-NH-C 6 -C 14 aryl and C(O)-N(C 1 -C 18 alkyl) from 2 selected from the group;
    R 3 and R 5 together with the nitrogen atom to which they are attached may form a 5- to 12-membered ring which may contain further heteroatoms;
    R 6 is each independently selected from the group consisting of a hydrogen atom, C 1 -C 20 alkyl, C 2 -C 20 alkanoyl, C 6 -C 10 aryl, and C 7 -C 11 aroyl;
    C 1 -C 20 alkyl in R 6 is 1 or 1 selected from the group consisting of O, S, N (C 1 -C 12 alkyl), C(O), C(O)O, and OC(O) Optionally interrupted by more groups, from F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl, C 6 -C 10 aryl, OH, and SH may have one or more same or different groups selected from the group;
    The C 2 -C 20 alkanoyl in R 6 may be interrupted by one or more groups selected from the group consisting of O, S, CO, C(O)O, and OC(O), one or more same or different groups selected from the group consisting of F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl, and C 6 -C 10 aryl; May have;
    C 6 -C 10 aryl in R 6 is one or more selected from the group consisting of F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy. may have more identical or different groups;
    C 7 -C 11 aroyl in R 6 is one or more selected from the group consisting of F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy. may have more identical or different groups;
    R 7 and R 8 are each independently selected from the group consisting of hydrogen atom, C 1 -C 20 alkyl, C 2 -C 20 alkanoyl, C 6 -C 10 aryl, and C 7 -C 11 aroyl;
    C 1 -C 20 alkyl in R 7 and R 8 is one selected from the group consisting of O, S, N (C 1 -C 12 alkyl), CO, C(O)O, and OC(O); Optionally interrupted by more groups, from F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl, C 6 -C 10 aryl, OH, and SH may have one or more same or different groups selected from the group;
    The C 2 -C 20 alkanoyl in R 7 , R 8 is interrupted by one or more groups selected from the group consisting of O, S, C(O), C(O)O, and OC(O). one or more selected from the group consisting of F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl, and C 6 -C 10 aryl. may have the same or different groups;
    C 6 -C 10 aryl in R 7 , R 8 is selected from the group consisting of F, Cl, Br, I, C 1 -C 6 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy. may have one or more identical or different groups;
    C7 - C11 aroyl in R7 , R8 is selected from the group consisting of F, Cl, Br, I, C1 - C10 alkyl, C1 - C10 alkoxy, and C2 - C11 acyloxy may have one or more identical or different groups;
    R 9 and R 10 are each independently selected from the group consisting of a hydrogen atom, C 1 -C 20 alkyl, C 2 -C 20 alkanoyl, C 7 -C 11 aroyl, C 6 -C 10 aryl;
    C 1 -C 20 alkyl in R 9 and R 10 is selected from the group consisting of O, S, N (C 1 -C 12 alkyl), C(O), C(O)O, and OC(O). from the group consisting of F, Cl, Br, I, NO 2 , C 3 -C 10 cycloalkyl, heterocycloalkyl, phenyl, OH, SH and CN may have one or more selected identical or different groups;
    The C 2 -C 20 alkanoyl in R 9 , R 10 may be interrupted by one or more groups selected from the group consisting of O and S, F, Cl, Br, I, OH and C may have one or more identical or different groups selected from the group consisting of 1 to C 6 alkoxy;
    C 7 -C 11 aroyl in R 9 and R 10 is one or more selected from the group consisting of F, Cl, Br, I, C 1 -C 6 alkyl, -OH and C 1 -C 6 alkoxy. may have the same or different groups;
    C 6 -C 10 aryl in R 9 and R 10 is one or more selected from the group consisting of F, Cl, Br, I, C 1 -C 6 alkyl, -OH and C 1 -C 6 alkoxy. may have the same or different groups;
    R 9 and R 10 together with the nitrogen atom to which they are bonded may form a saturated 5-, 6-, or 7-membered nitrogen heterocycle, and the ring may be O, S, N (C 1 -C 12 alkyl), C(O), and C(O)O as ring members, and the ring has one or more C 1 may have ~C 4 alkyl;
    each R 11 is independently selected from the group consisting of a hydrogen atom, C 1 -C 20 alkyl, and C 6 -C 20 aryl;
    C 1 -C 20 alkyl may be interrupted by one or more groups selected from the group consisting of O, S and C(O), and may contain one or more identical or different R 11a May have;
    R 11a is each independently selected from the group consisting of F, Cl, Br, I, C 3 -C 10 cycloalkyl, heterocycloalkyl, phenyl, OH, and SH;
    C 6 -C 20 aryl in R 11 is one or more selected from the group consisting of F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy. may have more identical or different groups;
    R 12 is synonymous with R 8 ;
    R 13 and R 14 are synonymous with R 9 and R 10 ;
    each R 15 is independently selected from the group consisting of a hydrogen atom, C 1 -C 20 alkyl, C 6 -C 10 aryl;
    C 1 -C 20 alkyl in R 15 is 1 or 1 selected from the group consisting of O, S, N (C 1 -C 12 alkyl), C(O), C(O)O, and OC(O) Optionally interrupted by more groups, from F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl, C 6 -C 10 aryl, OH, and SH may have one or more same or different groups selected from the group;
    C 6 -C 10 aryl in R 15 is one or more same or different groups selected from the group consisting of F, Cl, Br, I, C 1 -C 6 alkyl, and C 1 -C 6 alkoxy. may have;
    R 16 , R 17 , R 18 and R 19 each independently consist of a hydrogen atom, C 1 -C 20 alkyl, C 2 -C 20 alkanoyl, C 6 -C 10 aryl, C 7 -C 11 aroyl selected from the group;
    C 1 -C 20 alkyl in R 16 , R 17 , R 18 and R 19 is O, S, N (C 1 -C 12 alkyl), C(O), C(O)O, and OC(O) optionally interrupted by one or more groups selected from the group consisting of F, Cl, Br, I, C 3 -C 10 cycloalkyl, C 2 -C 10 heterocycloalkyl, C 6 - may have one or more identical or different groups selected from the group consisting of C 10 aryl, OH, and SH;
    The C 2 -C 20 alkanoyl in R 16 , R 17 , R 18 , R 19 is one or more selected from the group consisting of O, S, CO, C(O)O, and OC(O). Optionally interrupted by groups , one or It may have more of the same or different groups;
    C 6 -C 10 aryl in R 16 , R 17 , R 18 , R 19 is selected from F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy may have one or more same or different groups selected from the group;
    C 7 -C 11 aroyl in R 16 , R 17 , R 18 , R 19 is selected from F, Cl, Br, I, C 1 -C 10 alkyl, C 1 -C 10 alkoxy, and C 2 -C 11 acyloxy may have one or more identical or different groups selected from the group consisting of;
    L 1 is a divalent linker when n is 2, and the linker is L 1a -C 1 -C 30 alkylene-L 1a , L 2a -C 1 -C 30 alkenylene-L 2a , L 1a -C 3 -C 16 cycloalkylene-L 1a , L 1a -C 6 -C 20 arylene-L 1a , L 1a -C 6 -C 20 arylene-L 1b -C 6 -C 20 arylene-L 1a , and selected from the group consisting of L 1a -C 1 -C 13 heteroarylene-L 1a ;
    The alkylene and alkenylene in the linker of L 1 may each independently be interrupted by one or more identical or different non-adjacent groups L 1c ;
    The arylene and heteroarylene in the linker of L 1 may each independently have one or more identical or different groups R L 1 ;
    L 1a is a single bond;
    L 1b is a single bond, O, S, N(R 6 ), C(O), CH 2 , C(CH 3 ) 2 , CH(OH) or C 1 -C 5 alkylene;
    L 1c each independently represents O, S, N(R 6 ), C(O), C(O)O, OC(O), C 6 -C 20 arylene, and C 3 -C 16 cycloalkylene. selected from the group;
    R L1 is each independently selected from F, Cl, Br, I, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, and C 2 -C 11 acyloxy;
    R 6 in L 1b and L 1c has the same meaning as R 6 ;
    L 2 is a divalent linker when n is 2, and the linker is a single bond, L 2a -C 1 -C 30 alkylene-L 2a , L 2a -C 1 -C 30 alkenylene-L 2a , L 2a -C 6 -C 20 arylene- L 2a , L 2a -C 6 -C 20 arylene-L 2b -C 6 -C 20 arylene-L 2a ;
    The alkylene and alkenylene in the divalent linker of L2 may each be independently interrupted by one or more identical or different groups L2c ;
    The arylene and heteroarylene in the divalent linker of L2 may each independently have one or more identical or different groups R L2 ;
    L2a is each independently a single bond, S, O, N( R6 ), C(O), C(O)O, OC(O) or SO2 ;
    L 2b is a single bond, O, S, N(R 6 ), C(O), CH 2 , C(CH 3 ) 2 , CH(OH) or C 1 -C 5 alkylene;
    L 2c each independently represents O, S, N(R 6 ), C(O), C(O)O, OC(O), C 6 -C 20 arylene, and C 3 -C 16 cycloalkylene. selected from the group;
    R L2 is each independently selected from F, Cl, Br, I, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, and C 2 -C 11 acyloxy;
    R 6 in L 2b and L 2c has the same meaning as R 6 ;
    L 3 is a divalent linker when n is 2, and the linker is L 3a -C 1 -C 30 alkylene-L 3a , L 3a -C 3 -C 16 cycloalkylene-L 3a , L 3a -C 6 -C 20 arylene-L 3a , L 3a -C 1 -C 20 alkylene-L 3b -C 6 -C 16 cycloalkylene-L 3a , L 3a -C 6 -C 16 cycloalkylene-L 3b -C 6 -C 16 cycloalkylene-L 3a , L 3a -C 6 -C 20 arylene-L 3b -C 6 -C 20 arylene-L 3a , and L 3a -C 1 -C 13 heteroarylene-L 3a selected from the group;
    The alkylene in the divalent linker of L 3 may each independently be interrupted by one or more identical or different non-adjacent groups L 3c ;
    The cycloalkylenes in the divalent linker of L3 may each independently carry one or more identical or different groups R L3a ;
    The arylene and heteroarylene in the divalent linker of L3 may each independently have one or more identical or different groups R L3b ;
    L 3a is a single bond, C(O), C(O)O or C(O)N(R 16 );
    L 3b is each independently a single bond, O, S, N(R 6 ) or C 1 -C 5 alkylene;
    L 3c each independently represents O, S, N(R 6 ), C(O), C(O)O, OC(O), C 6 to C 20 arylene, C 3 to C 16 cycloalkylene, and selected from the group consisting of heterocycloalkylene;
    R L3a is each independently C 1 -C 12 alkyl;
    R L3b is selected from the group consisting of F, Cl, Br, I, C 1 -C 12 alkoxy, and C 2 -C 11 acyloxy;
    R 6 in L 3b and L 3c has the same meaning as R 6 ;
    R 16 in L 3a has the same meaning as;
    L 1 and L 2 are trivalent linkers when n is 3, and the linker is a C 1 -C 30 alkanetriyl, a C 2 -C 30 alkenetriyl, a C 3 -C 16 cycloalkanetriyl. selected from the group consisting of yl, heterocycloalkanetriyl, C 6 -C 20 arenetriyl, and heteroarenetriyl;
    The alkantriyl in the trivalent linker L 1 , L 2 may be interrupted by one or more identical or different groups L 4 ;
    L 4 each independently represents O, S, N(R 6 ), C(O), C(O)O, OC(O), C(O)N(R 16 ), N(R 18 ) selected from the group consisting of C(O), C3 - C20 cycloalkylene, heterocycloalkylene, C6 - C20 arylene and heteroarylene;
    R 6 , R 16 and R 18 in L 4 each have the same meaning as R 6 and R 18 above;
    L3 is a trivalent linker when n is 3 ; selected from the group consisting of cycloalkanetriyl, C 6 -C 20 arenetriyl, heteroarenetriyl, triacyl;
    The alkantriyl in the trivalent linker of L3 may be interrupted by one or more identical or different groups L5 ;
    L 5 each independently represents O, S, N(R 6 ), C(O), C(O)O, OC(O), C(O)N(R 16 ), N(R 18 ) selected from the group consisting of C(O), C3 - C20 cycloalkylene, heterocycloalkylene, C6 - C20 arylene and heteroarylene;
    R 6 , R 16 and R 18 in L 5 are each synonymous with R 6 and R 18 ;
    L 1 and L 2 are tetravalent linkers when n is 4, and the linker is C 1 -C 30 alkanetetryl;
    The alkanetetryl in the tetravalent linker of L 1 , L 2 may be interrupted by one or more identical or different groups L 6 ;
    L 6 each independently represents O, S, N(R 6 ), C(O), C(O)O, OC(O), C(O)N(R 16 ), N(R 18 ) selected from the group consisting of C(O), C3 - C20 cycloalkylene, heterocycloalkylene, C6 - C20 arylene and heteroarylene;
    R 6 , R 16 and R 18 in L 6 are each synonymous with R 6 and R 18 ;
    L 3 is a tetravalent linker when n is 4, said linker being selected from the group consisting of C 1 -C 30 alkanetetralyl, tetraacyl;
    The alkanetetryl in the tetravalent linker of L3 may be interrupted by one or more identical or different groups L7 ;
    L 7 is each independently O, S, N(R 6 ), C(O), C(O)O, OC(O), C(O)N(R 16 ), N(R 18 ) selected from the group consisting of C(O), C3 - C20 cycloalkylene, heterocycloalkylene, C6 - C20 arylene and heteroarylene;
    The above compound, wherein R 6 , R 16 and R 18 in L 7 have the same meanings as R 6 and R 18 , respectively.
  2. 　前記式（Ｉ）において、ｎ＝１であり、Ｌ１はＲ１であり、Ｌ２はＲ２であり、Ｌ３はＲ５である、請求項１に記載の化合物。 2. The compound according to claim 1, wherein in the formula (I), n=1, L1 is R1 , L2 is R2 , and L3 is R5 .
  3. 　前記式（Ｉ）において、ｎ＝２であり、Ｌ１がリンカーであり、Ｌ２はＲ２であり、Ｌ３はＲ５である、請求項１に記載の化合物。 2. The compound according to claim 1, wherein in the formula (I), n=2, L1 is a linker, L2 is R2 , and L3 is R5 .
  4. 　前記式（Ｉ）において、ｎ＝２であり、Ｌ２がリンカーであり、Ｌ１はＲ１であり、Ｌ３はＲ５である、請求項１に記載の化合物。 2. The compound according to claim 1, wherein in the formula (I), n=2, L2 is a linker, L1 is R1 , and L3 is R5 .
  5. 　前記式（Ｉ）において、ｎ＝２であり、Ｌ３がリンカーであり、Ｌ１はＲ１であり、Ｌ２はＲ２である、請求項１に記載の化合物。 2. The compound according to claim 1, wherein in the formula (I), n=2, L3 is a linker, L1 is R1 , and L2 is R2 .
  6. 　前記式（Ｉ）において、ｎ＝１であり、
    　Ｒ１は、Ｃ１～Ｃ２０アルキル、Ｃ３～Ｃ２０シクロアルキル、またはＣ６～Ｃ１０アリールである、請求項１に記載の化合物。     In the formula (I), n=1,
    2. The compound of claim 1, wherein R 1 is C 1 -C 20 alkyl, C 3 -C 20 cycloalkyl, or C 6 -C 10 aryl.
  7. 　前記式（Ｉ）において、ｎ＝１であり、Ｌ１はＲ１であり、Ｌ２はＲ２であり、Ｌ３はＲ５であり、
    　Ｒ１は、Ｃ１～Ｃ２０アルキル、Ｃ６～Ｃ１０アリール、又は１もしくはそれより多くの同一もしくは異なるＣ１～Ｃ１２アルキルで置換されたＣ６～Ｃ１０アリールであり；
    　Ｒ２はＣ１～Ｃ２０アルキル、Ｃ６～Ｃ１０アリール、又は１もしくはそれより多くの同一もしくは異なるＣ１～Ｃ１２アルキルで置換されたＣ６～Ｃ１０アリールであり；
    　Ｒ３及びＲ４は、各々独立して、Ｃ１～Ｃ６アルキル、Ｃ５～Ｃ１２シクロアルキル、Ｃ６～Ｃ１０アリール、又は１もしくはそれより多くの同一もしくは異なるＣ１～Ｃ６アルキルによって置換されたＣ６～Ｃ１０アリールであり；
    　Ｒ５は、水素である、請求項１に記載の化合物。     In the formula (I), n=1, L1 is R1 , L2 is R2 , L3 is R5 ,
    R 1 is C 1 -C 20 alkyl, C 6 -C 10 aryl, or C 6 -C 10 aryl substituted with one or more of the same or different C 1 -C 12 alkyl;
    R 2 is C 1 -C 20 alkyl, C 6 -C 10 aryl, or C 6 -C 10 aryl substituted with one or more of the same or different C 1 -C 12 alkyl;
    R 3 and R 4 are each independently C 1 -C 6 alkyl, C 5 -C 12 cycloalkyl, C 6 -C 10 aryl, or one or more of the same or different C 1 -C 6 alkyl C 6 -C 10 aryl substituted by;
    2. A compound according to claim 1, wherein R5 is hydrogen.
  8. 　（Ａ）請求項１～７のいずれか１項に記載された化合物及び（Ｂ）重合性化合物を含む重合性組成物。 A polymerizable composition comprising (A) the compound according to any one of claims 1 to 7 and (B) a polymerizable compound.
  9. 　更に（Ｃ）アルカリ可溶性樹脂を含む請求項８に記載の重合性組成物。 The polymerizable composition according to claim 8, further comprising (C) an alkali-soluble resin.
  10. 　更に（Ｄ）光重合開始剤を含む請求項８に記載の重合性組成物。 The polymerizable composition according to claim 8, further comprising (D) a photopolymerization initiator.
  11. 　前記（Ｂ）重合性化合物が（メタ）アクリレート化合物を含む、請求項８に記載の重合性組成物。 The polymerizable composition according to claim 8, wherein the (B) polymerizable compound contains a (meth)acrylate compound.
  12. 　請求項８に記載の重合性組成物を硬化させた硬化物。 A cured product obtained by curing the polymerizable composition according to claim 8.
  13. 　請求項１２に記載の硬化物を含むカラーフィルタ。 A color filter comprising the cured product according to claim 12.
  14. 　請求項１２に記載の硬化物を含む隔壁。 A partition wall comprising the cured product according to claim 12.
  15. 　請求項１２に記載の硬化物を含む画像表示装置。 An image display device comprising the cured product according to claim 12.
  16. 　請求項８に記載の重合性組成物を用い、少なくとも下記工程（１）～工程（４）を行う、硬化物の形成方法。
    　工程（１）：重合性組成物の塗膜を基板上に形成する工程。
    　工程（２）：工程（１）で形成した塗膜の少なくとも一部を露光する工程。
    　工程（３）：工程（２）で露光された塗膜を現像する工程。
    　工程（４）：工程（３）で現像された塗膜を焼成する工程。     A method for forming a cured product, using the polymerizable composition according to claim 8, and performing at least the following steps (1) to (4).
    Step (1): A step of forming a coating film of a polymerizable composition on a substrate.
    Step (2): A step of exposing at least a portion of the coating film formed in step (1).
    Step (3): A step of developing the coating film exposed in step (2).
    Step (4): A step of baking the coating film developed in step (3).
  17. 　前記工程（４）の焼成温度が１００℃以下である、請求項１６に記載の硬化物の形成方法。
     

          The method for forming a cured product according to claim 16, wherein the firing temperature in the step (4) is 100°C or less.
PCT/JP2023/012336 2022-03-28 2023-03-27 Compound, polymerizable composition, cured product, color filter, partition wall and image display device WO2023190410A1 (en)

Applications Claiming Priority (2)

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