WO2019031114A1 - Polymer, resin composition, resin film, method for producing patterned resin film, and electronic component - Google Patents

Polymer, resin composition, resin film, method for producing patterned resin film, and electronic component Download PDF

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Publication number
WO2019031114A1
WO2019031114A1 PCT/JP2018/025282 JP2018025282W WO2019031114A1 WO 2019031114 A1 WO2019031114 A1 WO 2019031114A1 JP 2018025282 W JP2018025282 W JP 2018025282W WO 2019031114 A1 WO2019031114 A1 WO 2019031114A1
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group
hydrocarbon group
carbon atoms
structural unit
formula
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PCT/JP2018/025282
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French (fr)
Japanese (ja)
Inventor
下川　努
誠 杉浦
貴史 土井
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Jsr株式会社
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Priority to JP2019535030A priority Critical patent/JP7056662B2/en
Publication of WO2019031114A1 publication Critical patent/WO2019031114A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • 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
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/075—Silicon-containing 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
    • G03F7/20—Exposure; Apparatus therefor
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
    • C08F212/22—Oxygen
    • C08F212/24—Phenols or alcohols

Definitions

  • the present invention relates to a polymer, a resin composition, a resin film, a method for producing a patterned resin film, and an electronic component.
  • Patent Document 1 discloses a positive photosensitive resin composition containing polyphenylene oxide (A) having a phenolic hydroxyl group and a compound (B) capable of generating an acid by light.
  • Patent Document 2 discloses a positive-type radiation-sensitive polymer containing a polymer (a) obtained by polyaddition of a polyhydric phenol compound and a vinyl ether compound, and an acid generator (b) that generates an acid upon irradiation with radiation.
  • a composition is disclosed.
  • the subject of the present invention is a resin composition capable of forming a resin film excellent in heat resistance, a polymer useful as a component of the resin composition, a resin film excellent in heat resistance, a method of producing a patterned resin film, And providing an electronic component having the resin film.
  • the present invention is, for example, the following [1] to [22].
  • a structural unit having a partial structure represented by the following formula (i) in the same or different molecule hereinafter also referred to as “structural unit (i)”
  • a compound represented by the following formula (ii-1) A polymer comprising a structural unit having a partial structure represented by and one or more hydroxyl-containing structural units (hereinafter also referred to as “structural units (ii)”) selected from structural units having a phenolic hydroxyl group, and E) Resin composition containing a solvent.
  • R 1 and R 2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, at least one carbon-carbon bond in the hydrocarbon group having 1 to 20 carbon atoms] during, -O -, - COO -, - OCO -, - OSO 2 -, - SO 3 -, - OSO 2 NR -, - NRSO 2 -, - NRCO -, - selected from NR- and -CONR- R 1 and R 2 represent a group having at least one group or a group in which a part of hydrogen atoms in these groups is substituted, and R 1 and R 2 together with the boron atom to which OR 1 and OR 2 are bonded and the number of ring members It may form 3 to 20 ring structures.
  • the R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a bond.
  • R 3 and R 4 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an electron withdrawing group, provided that the above R 3 and R 4 are each independently And at least one of them is an electron withdrawing group, and * represents a bond.
  • R 5 is an organic group having 1 to 20 carbon atoms
  • R 6 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
  • n is an integer of 0 to 3 , * Indicates a bonding hand.
  • each of R 7 and R 8 independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, at least one carbon-carbon bond in the hydrocarbon group having 1 to 20 carbon atoms] during, -O -, - COO -, - OCO -, - OSO 2 -, - SO 3 -, - OSO 2 NR 105 -, - NR 105 SO 2 -, - NR 105 CO -, - NR 105 - and -CONR 105 - represents at least one group having or part of which is a substituent of the hydrogen atoms in these groups are selected from, R 7 and R 8, oR 7 and oR 8 are bonded to each other
  • the ring structure having 3 to 20 ring members may be formed together with the phosphorus atom to be bonded, and the above R 105 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * indicates a bonding hand.
  • R 1 and R 2 each have the same meaning as the same symbol in formula (i);
  • R 11 is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or carbon
  • X 1 is an oxygen
  • R 12 represents an (a + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, at least one carbon-carbon bond in the hydrocarbon group, —O—, — At least one selected from COO-, -OCO-, -OSO 2- , -SO 3- , -OSO 2 NR 101- , -NR 101 SO 2- , -NR 101 CO-, -NR 101 -and -CONR 101- R 1 is a group having one type, or a group obtained by substituting a part of hydrogen atoms in these groups, and the above R 101 is water A prime
  • R 3 and R 4 each have the same meaning as the same symbol in formula (ii-1);
  • R 13 is a hydrogen atom, a fluorine atom, or a hydrocarbon group having 1 to 10 carbon atoms, Or a fluorinated hydrocarbon group having 1 to 10 carbon atoms;
  • X 2 is R 14 is a (b + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, at least one carbon-carbon bond in the hydrocarbon group, -O- , -COO -, - OCO -, - OSO 2 -, - SO 3 -, - OSO 2 NR 102 -, - NR 102 SO 2 -, - NR 102 CO -, - NR 102 - and -CONR 102 - selected from at least one group having the or
  • R 5 , R 6 and n each have the same meaning as the same symbol in formula (iii);
  • R 15 is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, Or a fluorinated hydrocarbon group having 1 to 10 carbon atoms;
  • X 3 is
  • R 16 is a (C + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, at least one carbon-carbon bond in the above-mentioned hydrocarbon group, —O—, , -COO -, - OCO -, - OSO 2 -, - SO 3 -, - OSO 2 NR 104 -, - NR 104 SO 2 -, - NR 104 CO -, - NR 104 - and -CONR 104
  • the polymer (A) is a structural unit having a partial structure represented by the above formula (ii-1), and one or more hydroxyl group-containing structural units selected from structural units having a phenolic hydroxyl group.
  • a method for producing a patterned resin film comprising the steps of developing a selective exposure film to obtain a patterned coating film, and curing the patterned coating film to obtain a patterned resin film.
  • a resin composition capable of forming a resin film excellent in heat resistance can be provided. Further, according to the present invention, a polymer useful as a component of the resin composition, a resin film excellent in heat resistance, a method for producing a patterned resin film, and an electronic component having the resin film can be provided. it can.
  • each component exemplified in the present specification for example, each component in the resin composition, may be used alone or in combination of two or more unless otherwise stated.
  • the "hydrocarbon group” includes a chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group.
  • the “hydrocarbon group” may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
  • Chain hydrocarbon group means a hydrocarbon group which does not contain a cyclic structure and is constituted only by a chain structure, and includes both a linear hydrocarbon group and a branched hydrocarbon group.
  • alicyclic hydrocarbon group means a hydrocarbon group containing only an alicyclic hydrocarbon structure as a cyclic structure and not containing an aromatic ring structure, and a monocyclic alicyclic hydrocarbon group and a plurality of alicyclic hydrocarbon groups and multiple cyclic hydrocarbon groups. It includes both of the alicyclic hydrocarbon groups of the ring. However, the “alicyclic hydrocarbon group” does not have to be constituted only by the structure of the alicyclic hydrocarbon, and a chain structure may be included in part thereof.
  • aromatic hydrocarbon group means a hydrocarbon group containing an aromatic ring structure as a cyclic structure.
  • aromatic hydrocarbon group does not have to be composed of only an aromatic ring structure, and a portion thereof may have a chain hydrocarbon structure and / or an alicyclic hydrocarbon structure. .
  • Patterned resin film refers to a patterned resin film.
  • the term “resin film” is used in the meaning including the patterned resin film.
  • the resin composition of the present invention contains a polymer (A) and a solvent (E) described below.
  • the polymer (A) of the present invention which is suitably used as a component of the resin composition, will also be described.
  • the resin composition of the present invention can further contain a photosensitive acid generator (B) or a photopolymerization initiator (D).
  • the resin composition of the present invention containing (B) or (D) is also referred to as a "photosensitive composition".
  • photosensitivity and photopolymerization are used to mean radiation-sensitive and radiation-sensitive polymerization corresponding to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam and X-ray.
  • the polymer (A) is a structural unit having a partial structure represented by the following formula (i) and a partial structure represented by the following formula (ii-1) in the same or different molecules, And one or more hydroxyl group-containing structural units selected from structural units having a phenolic hydroxyl group.
  • a polymer (A) may consist of one type of polymer, for example, and may consist of two or more types of polymers. When it consists of 2 or more types of polymers (blend), if it can confirm that the whole blend has structural unit (i) and structural unit (ii), for example by NMR analysis, it will be a structure in a blend
  • the polymer which does not have unit (i) or (ii) may be included.
  • the term "in the same or different molecule" (wherein molecule means a polymer molecule) is used in this sense.
  • the blend is, for example, a mixture of a polymer containing the structural unit (i) and a polymer containing the structural unit (ii).
  • the polymer (A) preferably contains the structural unit (i) and the structural unit (ii) in the same molecule.
  • the polymer (A) contains one or more structural units (i).
  • the structural unit (i) contributes to the storage stability and coatability of the resin composition, the alkali solubility of the polymer (A), and the mechanical strength and heat resistance of the resin film.
  • the coating film after exposure can be developed by alkaline developing solution by providing alkali solubility to a polymer (A).
  • R 1 and R 2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, -O-, at least one carbon-carbon bond in the hydrocarbon group having 1 to 20 carbon atoms, -COO -, - OCO -, - OSO 2 -, - SO 3 -, - OSO 2 NR -, - NRSO 2 -, - NRCO -, - NR- and -CONR- of at least one group having a (hereinafter selected “Substituted hydrocarbon group 1” or a group in which part of hydrogen atoms in these groups is substituted (hereinafter also referred to as “substituted hydrocarbon group 2”), and R 1 and R 2 And a boron atom to which OR 1 and OR 2 are bonded to form a cyclic structure having 3 to 20 ring members.
  • the R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a
  • the hydrocarbon group having 1 to 20 carbon atoms listed as R 1 , R 2 and R is a chain hydrocarbon group having 1 to 20 carbon atoms, or an alicyclic hydrocarbon group having 3 to 20 carbon atoms
  • linear hydrocarbon group having 1 to 20 carbon atoms examples include methyl group, ethyl group, i-propyl group, n-propyl group, i-butyl group, sec-butyl group, t-butyl group, n- Linear saturated hydrocarbon groups such as butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl and n-decyl; and linear unsaturated such as ethenyl, propynyl and ethynyl A hydrocarbon group is mentioned. Among these, chain saturated hydrocarbon groups are more preferable.
  • Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms include alicyclic saturated hydrocarbon groups such as cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, adamantyl group and the like; cyclobutenyl group and cyclopentenyl group And alicyclic unsaturated hydrocarbon groups such as groups. Among these, alicyclic saturated hydrocarbon groups are preferable.
  • Examples of the substituted hydrocarbon group 1 include alkyl ester alkyl groups such as methyl ester methyl group, ethyl ester methyl group and propyl ester methyl group, and alkyl ethers such as methyl ether methyl group, ethyl ether methyl group and propyl ether methyl group An alkyl group is mentioned.
  • a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) and a halogenated alkyl group are mentioned, for example.
  • R 1 and R 2 may combine with each other to form a cyclic structure having 3 to 20, preferably 3 to 15 ring members, together with the boron atom to which OR 1 and OR 2 are bonded.
  • a partial structure represented by Formula (i) which forms the said cyclic structure the partial structure represented by following formula (10) and (11) is mentioned, for example.
  • R r represents a divalent hydrocarbon group having 2 to 20 carbon atoms, at least one carbon-carbon bond in the divalent hydrocarbon group having 2 to 20 carbon atoms.
  • the R 100 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
  • the divalent hydrocarbon group having 2 to 20 carbon atoms The moiety is a group substituted with at least one member selected from a halogen atom, an alkoxy group and an alkoxycarbonyl group, and the NR 100 group may be coordinately bonded to an empty orbital of a boron atom. * Indicates a bonding hand.
  • the divalent hydrocarbon group in R r is preferably a divalent chain saturated hydrocarbon group or an alicyclic saturated hydrocarbon group, and more preferably a divalent chain saturated carbonization having 2 to 10 carbon atoms It is a hydrogen group or a divalent alicyclic saturated hydrocarbon group having 4 to 10 carbon atoms.
  • the hydrocarbon group having 1 to 20 carbon atoms in R 100 is the same as the hydrocarbon group in R in the substituted hydrocarbon group 1 described above.
  • R 1 and R 2 are preferably hydrogen atoms from the viewpoint of heat resistance.
  • Examples of the structural unit (i) include structural units represented by the following formula (1).
  • R 1 and R 2 each have the same meaning as the same symbol in formula (i).
  • R 11 is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluorinated hydrocarbon group having 1 to 10 carbon atoms.
  • R 12 represents an (a + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, and at least one carbon-carbon bond in the hydrocarbon group, —O—, —COO—, —OCO—, —OSO 2 -, -SO 3- , -OSO 2 NR 101- , -NR 101 SO 2- , -NR 101 CO-, -NR 101 -and -CONR 101- , or a group having at least one selected from these groups
  • R 101 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a halogenated alkyl group is mentioned, for example.
  • a is an integer of 1 to 3, preferably 1.
  • Examples of the hydrocarbon group having 1 to 10 carbon atoms of R 11 include, for example, a chain hydrocarbon group having 1 to 10 carbon atoms and an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and a chain hydrocarbon A group is preferable, and a methyl group and an ethyl group are more preferable.
  • Examples of the fluorinated hydrocarbon group having 1 to 10 carbon atoms of R 11 include a fluorinated chain hydrocarbon group having 1 to 10 carbon atoms, and a fluorinated alicyclic hydrocarbon group having 3 to 10 carbon atoms. Preferred is a fluorinated chain hydrocarbon group, and more preferred is a trifluoromethyl group.
  • a hydrogen atom is preferable.
  • Examples of the (a + 1) -valent hydrocarbon group having 1 to 20 carbon atoms of R 12 include linear saturated hydrocarbon groups such as methylene and alkanediyl such as ethylene, cyclopentadiyl, cyclohexanediyl And cycloalkanediyl groups such as norbornanediyl group and tetracyclododecanediyl group, and arylene groups such as phenylene group.
  • Examples of the structural unit (i) include structural units represented by the following formulas (12) to (22).
  • the polymer (A) is one or more selected from a structural unit (ii-1) having a partial structure represented by the following formula (ii-1), and a structural unit (ii-2) having a phenolic hydroxyl group Contains structural unit (ii).
  • the polymer (A) further comprises a structural unit (ii-1) having a partial structure represented by the following formula (ii-1) in the same or different molecule as the molecule containing the structural unit (i) Can.
  • the polymer (A) preferably contains the structural unit (i) and the structural unit (ii-1) in the same molecule.
  • R 3 and R 4 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an electron-withdrawing group, provided that at least one of R 3 and R 4 is an electron-accepting group It is an attractive group, and any of them is preferably an electron attractive group, and * represents a bond.
  • the hydrocarbon group having 1 to 20 carbon atoms is the same as the hydrocarbon group having 1 to 20 carbon atoms of R 1 and R 2 in the formula (i).
  • R 3 and R 4 are electron-withdrawing groups
  • the storage stability of the resin composition and the alkali solubility of the polymer (A) are preferably improved.
  • the electron withdrawing group include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; cyano groups; fluorinated hydrocarbon groups such as fluorinated alkyl group.
  • the fluorinated hydrocarbon group is a group in which part or all of hydrogen atoms in a hydrocarbon group are substituted with a fluorine atom.
  • a fluorinated hydrocarbon group having 1 to 20 carbon atoms is preferable, a fluorinated alkyl group having 1 to 20 carbon atoms is more preferable, and a fluorinated alkyl group having 1 to 10 carbon atoms is more preferable.
  • a fluorine atom, a cyano group and a fluorinated alkyl group are preferable as the electron-withdrawing group, and a fluorine atom, a cyano group, a trifluoromethyl group and a hexafluoroisopropyl group are more preferable.
  • the polymer (A) can contain one or more structural units (ii-1).
  • the structural unit (ii-1) contributes to the storage stability of the resin composition, the alkali solubility of the polymer (A), the hydrophobicity of the resin film and the low dielectric constant.
  • Examples of the structural unit (ii-1) include structural units represented by the following formula (2).
  • R 3 and R 4 each have the same meaning as the same symbol in formula (ii-1).
  • R 13 is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluorinated hydrocarbon group having 1 to 10 carbon atoms.
  • R 14 represents a (b + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, and at least one carbon-carbon bond in the hydrocarbon group, —O—, —COO—, —OCO—, —OSO 2 -, - SO 3 -, - OSO 2 NR 102 -, - NR 102 SO 2 -, - NR 102 CO -, - NR 102 - and -CONR 102 - group having at least one selected from or in these groups, And R 102 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • b is an integer of 1 to 3, preferably 1. Specific examples, preferred examples and preferred reasons for R 13 and R 14 are the same as R 11 and R 12 in the formula (1), respectively.
  • Examples of the structural unit (ii-1) include structural units (23) to (28) represented by the following formulas.
  • R ⁇ 13 > in said Formula is synonymous with the same symbol in Formula (2), respectively.
  • the polymer (A) can further include a structural unit (ii-2) having a phenolic hydroxyl group in the same or different molecule as the molecule containing the structural unit (i).
  • the polymer (A) preferably contains the structural unit (i) and the structural unit (ii-2) in the same molecule.
  • the polymer (A) can contain one or more structural units (ii-2).
  • the structural unit (ii-2) contributes to the alkali solubility of the polymer (A), the storage stability and compatibility of the resin composition, and the adhesion and mechanical strength of the resin film.
  • the polymer (A) having the structural unit (ii-2) is used, a resin film having excellent solvent resistance and heat melting property can be obtained.
  • structural unit (ii-2) having a phenolic hydroxyl group include structural units derived from a phenolic hydroxyl group-containing unsaturated compound.
  • phenolic hydroxyl group-containing unsaturated compound for example, a phenolic hydroxyl group-containing unsaturated compound which is cyclized by heating such as 2-hydroxyphenyl (meth) acrylate, 2-hydroxyphenyl (meth) acrylamide and the like and the phenolic hydroxyl group disappears; 3-hydroxyphenyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, 2,6-dimethyl-4-hydroxyphenyl (meth) acrylate, 3-hydroxyphenyl (meth) acrylamide, 4-hydroxyphenyl (meth) acrylamide Other phenols such as 2,6-dimethyl-4-hydroxyphenyl (meth) acrylamide, 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, 2,6-dimethyl-4-hydroxystyrene Hydroxyl group-containing unsaturated compounds.
  • cyclization by heating causes disappearance of the phenolic hydroxyl group and loss of hygroscopicity, and thus a low dielectric resin film is obtained, as well as copolymerization reactivity, solvent resistance of the resin film, and dielectric characteristics.
  • a phenolic hydroxyl group-containing unsaturated compound such as 2-hydroxyphenyl acrylamide or 2-hydroxyphenyl acrylate which is cyclized by heating to lose phenolic hydroxyl group.
  • the polymer (A) has a partial structure represented by the following formula (iii) in the same or different molecule as a molecule containing at least one structural unit selected from structural units (i) and (ii)
  • the structural unit (iii) can further be included.
  • the polymer (A) preferably contains the structural unit (i), the structural unit (ii) and the structural unit (iii) in the same molecule.
  • the polymer (A) can contain one or more structural units (iii).
  • the structural unit (iii) contributes to the alkali solubility of the polymer (A), the adhesion of the resin film, the mechanical strength and the heat resistance.
  • R 5 is an organic group having 1 to 20 carbon atoms (with the exception of the group corresponding to OR 6 ).
  • R 6 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, n is an integer of 0 to 3, and is preferably 0. * Indicates a bonding hand.
  • Organic group refers to a group comprising at least one carbon atom.
  • the organic group having 1 to 20 carbon atoms as R 5 is, for example, a hydrocarbon having 1 to 20 carbon atoms, such as a linear hydrocarbon group having 1 to 20 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms.
  • Examples of the hydrocarbon group having 1 to 20 carbon atoms of R 6 include a linear hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and an aromatic carbon having 6 to 20 carbon atoms.
  • a hydrogen group is mentioned.
  • linear hydrocarbon group having 1 to 20 carbon atoms and the alicyclic hydrocarbon group having 3 to 20 carbon atoms of R 6 are the groups represented by R 1 and R 2 in the formula (i) Are the same as the chain hydrocarbon group and the alicyclic hydrocarbon group described above.
  • Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms of R 6 include aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group and anthryl group; benzyl group, phenethyl group, naphthylmethyl group, an Aralkyl groups such as tolylmethyl group may be mentioned.
  • structural unit (iii) the structural unit represented by following formula (3) is mentioned, for example.
  • R 5 , R 6 and n each have the same meaning as the same symbol in formula (iii).
  • R 15 is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluorinated hydrocarbon group having 1 to 10 carbon atoms.
  • R 16 represents a (C + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, and at least one carbon-carbon bond in the hydrocarbon group, —O—, —COO—, —OCO—, —OSO 2 -, - SO 3 -, - OSO 2 NR 104 -, - NR 104 SO 2 -, - NR 104 CO -, - NR 104 - and -CONR 104 - group having at least one selected from or in these groups,
  • R 104 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • c is an integer of 1 to 3, preferably 1. Specific examples, preferred examples and preferred reasons for the R 15 and R 16 groups are the same as for R 11 and R 12 in the formula (1), respectively.
  • Examples of the structural unit (iii) include structural units (29) to (34) represented by the following formula.
  • R ⁇ 15 > in said Formula is synonymous with the same symbol in Formula (3), respectively.
  • the polymer (A) has a partial structure represented by the following formula (iv) in the same or different molecule as a molecule containing at least one structural unit selected from structural units (i) and (ii) It can further comprise a structural unit (iv).
  • the polymer (A) preferably contains the structural unit (i), the structural unit (ii) and the structural unit (iv) in the same molecule, and the polymer (A) contains the structural unit (iii) In the case where the structural unit (i), the structural unit (ii), the structural unit (iii) and the structural unit (iv) are contained in the same molecule, it is preferable.
  • the polymer (A) can contain one or more structural units (iv).
  • the structural unit (iv) contributes to the storage stability and compatibility of the resin composition, the adhesion of the resin film, the heat resistant transparency, and the antiaging property.
  • R 7 and R 8 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, -O-, at least one carbon-carbon bond in the hydrocarbon group having 1 to 20 carbon atoms, -COO -, - OCO -, - OSO 2 -, - SO 3 -, - OSO 2 NR 105 -, - NR 105 SO 2 -, - NR 105 CO -, - is selected from - NR 105 - and -CONR 105
  • R 7 and R 8 represent a group having at least one group or a group in which a part of hydrogen atoms in these groups is substituted, and R 7 and R 8 together with the phosphorus atom to which OR 7 and OR 8 are bonded are the ring members together It may form 3 to 20 ring structures.
  • the R 105 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Specific examples of each group of R 7 and R 8 are the same
  • R 7 and R 8 may be combined with each other to form a cyclic structure having 3 to 20, preferably 3 to 15 ring members, together with the phosphorus atom to which OR 7 and OR 8 are bonded.
  • Examples of the partial structure represented by the formula (iv) having a cyclic structure include partial structures represented by the following formulas (35) to (36).
  • R r1 is a divalent hydrocarbon group having 2 to 20 carbon atoms, or a part of hydrogen atoms in the divalent hydrocarbon group having 2 to 20 carbon atoms is And a group substituted with at least one selected from a halogen atom, an alkoxy group and an alkoxycarbonyl group. * Indicates a bonding hand.
  • the divalent hydrocarbon group for R r1 is preferably a divalent chain saturated hydrocarbon group or an alicyclic saturated hydrocarbon group, and more preferably a divalent chain saturated carbonization having 2 to 10 carbon atoms It is a hydrogen group or a divalent alicyclic saturated hydrocarbon group having 4 to 10 carbon atoms.
  • Each of R 7 and R 8 independently is preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms from the viewpoint of heat resistance and storage stability, and a hydrogen atom or a chain hydrocarbon group having 1 to 20 carbon atoms Is more preferable, and a hydrogen atom, a methyl group, an ethyl group and an i-propyl group are more preferable.
  • Examples of the structural unit (iv) include structural units represented by the following formula (4).
  • R 7 and R 8 each have the same meaning as the same symbol in formula (iv).
  • R 17 is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluorinated hydrocarbon group having 1 to 10 carbon atoms.
  • R 18 represents a (d + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, and at least one carbon-carbon bond in the hydrocarbon group, —O—, —COO—, —OCO—, —OSO 2 -, - SO 3 -, - OSO 2 NR 106 -, - NR 106 SO 2 -, - NR 106 CO -, - NR 106 - and -CONR 106 - group having at least one selected from or in these groups, And R 106 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • d is an integer of 1 to 3, preferably 1. Specific examples, preferred examples and preferred reasons for each group of R 17 and R 18 are the same as R 11 and R 12 in the formula (1), respectively.
  • Examples of the structural unit (iv) include structural units represented by the following formulas (37) to (45).
  • R 17 in the above-mentioned formula is respectively synonymous with the same symbol in formula (4).
  • the polymer (A) further contains a structural unit (v) having an epoxy group in the same or different molecule as a molecule containing at least one structural unit selected from structural units (i) and (ii) Can.
  • the polymer (A) preferably contains the structural unit (i), the structural unit (ii) and the structural unit (v) in the same molecule, and the polymer (A) is a structural unit (iii) and / or When it contains (iv), it is preferable to include structural unit (i), structural unit (ii), structural unit (iii) and / or (iv), and structural unit (v) in the same molecule.
  • the polymer (A) can contain one or more structural units (v).
  • the structural unit (v) contributes to the storage stability of the resin composition, the adhesion of the resin film and the mechanical strength.
  • Examples of the epoxy group include oxiranyl group (1,2-epoxy structure) and oxetanyl group (1,3-epoxy structure).
  • Specific examples of the structural unit (v) having an epoxy group include structural units derived from epoxy group-containing unsaturated compounds such as oxiranyl group-containing unsaturated compounds and oxetanyl group-containing unsaturated compounds.
  • oxiranyl group-containing unsaturated compound for example, glycidyl acrylate, glycidyl methacrylate, 2-methyl glycidyl methacrylate, glycidyl ⁇ -ethyl acrylate, glycidyl ⁇ -n-propyl acrylate, glycidyl ⁇ -n-butyl acrylate Acrylic acid 3,4-epoxybutyl, methacrylic acid 3,4-epoxybutyl, acrylic acid 6,7-epoxyheptyl, methacrylic acid 6,7-epoxyheptyl, ⁇ -ethylacrylic acid-6,7-epoxyheptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, 3,4-epoxycyclohexyl methyl meth,
  • Examples of the oxetanyl group-containing unsaturated compound include 3- (Acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (Acryloyloxymethyl) -2-pentafluoroethyl oxetane, 3- (acryloyloxymethyl) -2-phenyl oxetane, 3- (acryloyloxymethyl) -2,2-difluorooxetane, 3- (acryloyloxymethyl) -2,2,4-Trifluorooxetane, 3- (acryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (2-acryloyloxyethyl) oxe
  • 3- (acryloyloxymethyl) -3-ethyl oxetane and 3- (methacryloyloxymethyl) -3-ethyl oxetane have copolymerization reactivity, compatibility of the resin composition, and solvent resistance of the resin film. It is desirable from the viewpoint of improvement of
  • the resin composition can be cured by self-condensing the partial structure represented by the formula (i), which is presumed to contribute to the improvement of the heat resistance.
  • the partial structure represented by the formula (ii-1) is considered to suppress the self-condensation of the partial structure represented by the formula (i) during storage and to contribute to the improvement of the storage stability of the resin composition.
  • the structural unit (ii-2) is presumed to contribute to the improvement of the alkali solubility of the polymer (A) and the improvement of the crosslinking properties such as the solvent resistance of the resin film.
  • the content ratio of the structural unit (i) is usually 5 to 60 mol%, preferably 5 to 40 mol%, more preferably 5 to 20 mol%.
  • the content of the structural unit (i) is in the above range, the storage stability and coatability of the resin composition, the alkali solubility of the polymer (A), and the mechanical strength and heat resistance of the resin film tend to be improved. is there.
  • the content ratio of the structural unit (ii) is usually 5-90 mol%.
  • the content of the structural unit (ii-1) is usually 5 to 90 mol%, preferably 10 to 80 mol%, and more preferably Preferably, it is 20 to 70 mol%.
  • the content of the structural unit (ii-1) is in the above range, the storage stability of the resin composition, the alkali solubility of the polymer (A), the hydrophobicity and the low dielectric constant of the resin film tend to be improved. is there.
  • the content ratio of the structural unit (ii-2) is usually 5 to 70 mol%, preferably 10 to 40 mol%, and further Preferably, it is 15 to 30 mol%.
  • the content of the structural unit (ii-2) is in the above range, the compatibility of the resin composition, the alkali solubility of the polymer (A), and the low dielectric constant of the resin film tend to be improved.
  • the content of the structural unit (iii) is usually 5 to 50 mol%, preferably 5 to 40 mol%, more preferably 5 to 50 It is 30 mol%.
  • the content of the structural unit (iii) is in the above range, the alkali solubility of the polymer (A), the adhesion of the resin film, the mechanical strength and the heat resistance tend to be improved.
  • the content ratio of the structural unit (iv) is usually 5 to 30 mol%, preferably 5 to 25 mol%, more preferably 10 to It is 20 mol%.
  • the content ratio of the structural unit (iv) is in the above range, the storage stability and compatibility of the resin composition, the adhesion of the resin film, the heat-resistant transparency and the antiaging properties tend to be improved.
  • the content ratio of the structural unit (v) is usually 5 to 45 mol%.
  • the content ratio of the structural unit (v) is usually 5 to 40 mol%, preferably 5 to 35 mol% And more preferably 10 to 30 mol%
  • the content ratio of the structural unit (v) is usually 5 It is -45 mol%, preferably 10-45 mol%, more preferably 15-45 mol%.
  • the content ratio of each structural unit of the polymer (A) is a value in all structural units constituting the polymer (A), and can be measured by 13 C-NMR.
  • the weight average molecular weight (Mw) of the polymer (A) measured by gel permeation chromatography is the elastic modulus and crack resistance of the resin film obtained by curing the resin composition, and the resolution of the photosensitive composition.
  • Mw molecular weight distribution
  • Mn is a number average molecular weight of the polymer (A) is usually 1.0 to 10.0, preferably 1.0 to 5.0, more preferably 1.0 to 3. It is 0.
  • the details of the measurement methods of Mw and Mn are as described in the examples.
  • the polymer (A) may be used alone or in combination of two or more.
  • the content of the polymer (A) is usually 30% by mass or more, preferably 40% by mass or more, based on 100% by mass in total of all components excluding the solvent (E) from the resin composition of the present invention Preferably it is 50 mass% or more.
  • the content ratio of the polymer (A) is in the above range, a resin composition capable of forming a resin film excellent in heat resistance tends to be obtained.
  • the content of the polymer (A) is usually 30 to 99% by mass, preferably 40 to 98% by mass, based on 100% by mass in total of all components excluding the solvent (E) from the photosensitive composition of the present invention. %, More preferably 50 to 95% by mass.
  • the content ratio of the polymer (A) is in the above range, it tends to be possible to obtain a photosensitive composition capable of forming a patterned resin film having excellent heat resistance and high resolution.
  • the polymer (A) can be synthesized, for example, by polymerizing a predetermined monomer leading each structural unit in a polymerization solvent in the presence of a polymerization initiator or a chain transfer agent, such as radical polymerization.
  • a polymerization initiator or a chain transfer agent such as radical polymerization.
  • monomers, a polymerization initiator and a polymerization solvent are charged in a reaction vessel, heated to a reaction temperature of about 40 to 120 ° C., and reacted for 0.1 to 10 hours under an inert gas atmosphere such as nitrogen gas.
  • polymerization initiator an azo compound and a peroxide compound are mentioned, for example.
  • the said polymerization initiator may be used by 1 type, and may use 2 or more types together.
  • Alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethylene glycol, diethylene glycol and propylene glycol; Cyclic ethers such as tetrahydrofuran and dioxane; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl Alkyl ethers of polyhydric alcohols such as ether; Alkyl ether acetates of polyhydric alcohols such as ethylene glycol ethyl ether a
  • cyclic ethers alkyl ethers of polyhydric alcohols, alkyl ether acetates of polyhydric alcohols, ketones or esters are preferable.
  • the polymerization solvents may be used alone or in combination of two or more.
  • the resin composition of the present invention can contain a photosensitive acid generator (B), and becomes a photosensitive composition by containing a photosensitive acid generator (B).
  • the photosensitive acid generator (B) is a compound which generates an acid by light.
  • An acid is generated in the exposed area on the basis of the photosensitive acid generator (B) by the treatment including the exposure treatment to the coating film formed from the photosensitive composition of the present invention, and the alkaline development of the exposed area on the basis of the action of this acid.
  • the solubility in the liquid changes.
  • the photosensitive composition may be either negative or positive.
  • the kind of photosensitive acid generator (B) can be suitably selected according to a negative type composition or a positive type composition.
  • a photosensitive acid generator (B) an onium salt compound, a halogen containing compound, a sulfone compound, a sulfonic acid compound, a sulfone imide compound, a diazomethane compound, and a compound which has a quinone diazide group are mentioned, for example.
  • the compound having a quinone diazide group is also referred to as “quinone diazide compound (b1)”, and the photosensitive acid generators other than the above exemplified ones are also referred to as “acid generator (b2)”.
  • the quinone diazide compound (b1) is a compound which decomposes a quinone diazide group to generate a carboxy group by light irradiation and contact treatment with water.
  • the coating film formed from the composition containing the quinone diazide compound (b1) is a film which is hardly soluble in an alkaline developer. A positive pattern is formed by utilizing the fact that the film is in the state of low alkali solubility and is in the state of high alkali solubility by light irradiation and contact treatment with water.
  • Examples of the quinone diazide compound (b1) include naphthoquinone diazide compounds. Specifically, a compound having one or more phenolic hydroxyl groups, 1,2-naphthoquinone diazide-4-sulfonic acid, 1,2-naphtho Ester compounds with quinonediazide-5-sulfonic acid, 1,2-naphthoquinonediazide-4-sulfonic acid chloride or 1,2-naphthoquinonediazide-5-sulfonic acid chloride may be mentioned. Specific examples of the compound having one or more phenolic hydroxyl groups include, for example, compounds described in paragraphs [0065] to [0070] of JP-A-2014-186300, which are described in the present specification. It shall be.
  • Examples of the quinone diazide compound (b1) include 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2 , 3,4,2 ′, 4′-pentahydroxybenzophenone, tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 4,6-bis [ 1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene and 1,1 Bis (4-hydroxyphenyl) -1- [4- [1- (4-hydroxyphenyl)
  • the quinone diazide compound (b1) may be used alone or in combination of two or more.
  • the content of the quinone diazide compound (b1) is preferably 100 parts by mass of the polymer (A). Is preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, and still more preferably 5 to 30 parts by mass.
  • the content of the quinone diazide compound (b1) is at least the lower limit value, the residual film ratio in the unexposed area is improved, and an image faithful to the mask pattern is easily obtained.
  • the content of the quinone diazide compound (b1) is less than or equal to the above upper limit, a resin film having an excellent pattern shape can be easily obtained, and foaming at the time of film formation tends to be prevented.
  • the acid generator (b2) is a compound which forms an acid upon irradiation with light and is a compound other than the quinone diazide compound (b1).
  • the generated acid acts on the polymer (A), the crosslinking agent (C) described later, etc. to cause crosslinking.
  • the structure is formed and the film becomes poorly soluble in alkali.
  • a negative pattern is formed by utilizing the fact that the film changes from a state of easy alkali dissolution to a state of low alkali solubility by light irradiation.
  • Examples of the acid generator (b2) include onium salt compounds such as iodonium salts, sulfonium salts, phosphonium salts, diazonium salts and pyridinium salts; halogen-containing compounds such as haloalkyl group-containing heterocyclic compounds and haloalkyl group-containing hydrocarbon compounds; Sulfone compounds such as ⁇ -ketosulfone compounds, ⁇ -sulfonylsulfone compounds and ⁇ -diazo compounds of these compounds; Sulfonic acid compounds such as alkylsulfonic acid esters, haloalkylsulfonic acid esters, arylsulfonic acid esters, iminosulfonates and the like A sulfone imide compound; and a diazomethane compound. Specific examples of these compounds include, for example, compounds described in paragraphs [0074] to [0079] of JP-A-2014-186300, which are described in the present specification.
  • onium salts include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, triphenylsulfonium trifluoromethanesulfonate, triphenyl Sulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, 4-tert-butylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-tert-butylphenyldiphenylsulfonium p-toluenesulfonate, 4,7-di-n-butoxy Naphthyltetrahydrothioph
  • the acid generator (b2) may be used alone or in combination of two or more.
  • the content of the acid generator (b2) is 100 parts by mass of the polymer (A), The amount is preferably 0.1 to 30 parts by mass, more preferably 0.3 to 20 parts by mass, and still more preferably 0.5 to 15 parts by mass.
  • the content of the acid generator (b2) is equal to or more than the lower limit, curing of the exposed portion is sufficient, and heat resistance is likely to be improved.
  • the content of the acid generator (b2) is less than or equal to the above upper limit value, a patterned resin film having a high resolution can be easily obtained without decreasing the transparency to exposure light.
  • the resin composition of the present invention can further contain a crosslinking agent (C) in order to improve the curability of the resin film.
  • the crosslinking agent (C) is a compound having two or more polymerizable groups or reactive groups.
  • the crosslinking agent (C) acts as a crosslinking component (curing component) that reacts with the polymer (A) or with each other.
  • Examples of the polymerizable group or the reactable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, an oxazolinyl group, an isocyanate group, an N-alkoxyalkylamino group, a methylol group and an alkylmethylol group.
  • crosslinking agent (C) for example, a compound having two or more (meth) acryloyl groups, a compound having two or more N-alkoxyalkylamino groups, a methylol group-containing phenol compound, an alkylmethylol group-containing phenol compound, And oxirane ring-containing compounds, oxetane ring-containing compounds, oxazoline ring-containing compounds, isocyanate group-containing compounds (including those which are blocked), aldehyde group-containing phenol compounds, and compounds having two or more (meth) acryloyl groups And compounds having two or more N-alkoxyalkylamino groups are preferred.
  • Examples of the compound having two or more (meth) acryloyl groups include bifunctional (meth) acrylic esters, and polyfunctional (meth) acrylic esters such as trifunctional or higher functional (meth) acrylic esters. .
  • difunctional (meth) acrylic acid esters examples include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexane Diol di (meth) acrylate and 1,9-nonanediol di (meth) acrylate are mentioned.
  • trifunctional or higher (meth) acrylic acid esters examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Pentaerythritol hexa (meth) acrylate, a mixture of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, tri (2- (meth) acryloyloxy Other than ethyl) phosphate, succinic acid modified pentaerythritol tri (meth) acrylate, succinic acid modified dipentaerythritol penta (meth) acrylate, A
  • Examples of the compound having two or more N-alkoxyalkylamino groups include compounds having two or more alkyletherified amino groups (hereinafter also referred to as "amino group-containing compounds"), and alkyletherified amino
  • amino group-containing compounds compounds having two or more alkyletherified amino groups
  • alkyletherified amino alkyletherified amino
  • the group is, for example, a group represented by the following formula.
  • R C1 is a methylene group or an alkylene group, preferably a methylene group or an alkylene group having 2 to 10 carbon atoms
  • R C2 is an alkyl group, preferably an alkyl group having 1 to 10 carbon atoms is there.
  • amino group-containing compound examples include active methylol groups (CH 2 OH) in nitrogen compounds such as (poly) methylolated melamine, (poly) methylolated glycoluril, (poly) methylolated benzoguanamine, and (poly) methylolated urea. And compounds in which all or part (at least two) of the groups) are alkyletherified.
  • an alkyl group which comprises an alkyl ether a methyl group, an ethyl group, a butyl group is mentioned, for example, These may mutually be same or different.
  • the methylol group which is not alkyletherified may be self-condensing within one molecule, or may be condensed between two molecules to form an oligomer component as a result.
  • hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril and the like can be used.
  • the crosslinking agent (C) may be used alone or in combination of two or more.
  • the content of the crosslinking agent (C) is usually 1 to 300 parts by mass, preferably 5 to 200 parts by mass, more preferably 10 with respect to 100 parts by mass of the polymer (A). 100 parts by mass.
  • the content of the crosslinking agent (C) is in the above range, a resin film having excellent resolution, elongation physical properties and heat resistance tends to be formed.
  • the resin composition of the present invention can contain a photopolymerization initiator (D).
  • a compound having an ethylenically unsaturated group, in particular a (meth) acryloyl group is used as the crosslinking agent (C)
  • the resin composition of the present invention has a negative photosensitive composition by using the photopolymerization initiator (D). It becomes a thing.
  • a photoinitiator (D) is a compound which generate
  • the exposure treatment for the coating film formed from the photosensitive composition generates an active species capable of initiating polymerization in the exposed area based on the photopolymerization initiator (D), and this active species causes two or more ethylenic non
  • the compound having a saturated group is polymerized to change the solubility of the exposed portion in the alkaline developer.
  • Examples of the photopolymerization initiator (D) include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, acyl phosphine oxide compounds, onium salt compounds, benzoin compounds And benzophenone compounds, ⁇ -diketone compounds, polynuclear quinone compounds, diazo compounds and imidosulfonate compounds.
  • thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyl oxime compounds and acyl phosphine oxide compounds is preferable.
  • thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-dichloro thioxanthone, 2,4- dimethyl thioxanthone, 2,4- diethyl Thioxanthone and 2,4-diisopropylthioxanthone can be mentioned.
  • acetophenone compounds include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholino).
  • Examples include phenyl) butan-1-one and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.
  • biimidazole compound examples include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and 2,2′-bis 2,4-Dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', And 5,5'-tetraphenyl-1,2'-biimidazole.
  • triazine compound examples include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-) Methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s -Triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl)
  • O-acyloxime compounds include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6 -(2-Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranyl methoxybenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- ⁇ 2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl] ) Methoxybenzoyl ⁇ -9H-carbazol-3-yl]-, 1- (O-acetyloxime).
  • NCI-831, NCI-930 above, made by ADEKA Co., Ltd.
  • OXE-03, OXE-04 above, made by BASF Co., Ltd.
  • BASF Co., Ltd. BASF Co., Ltd.
  • acyl phosphine oxide compounds include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl-phosphine oxide, bis (2 And 4,6-trimethylbenzoyl) -phenyl-phosphine oxide.
  • a sensitizer when a photopolymerization initiator other than a biimidazole compound such as an acetophenone compound is used, a sensitizer may be used in combination.
  • a sensitizer for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 4-dimethyl Ethyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone It can be mentioned.
  • a photoinitiator (D) may be used by 1 type, and may use 2 or more types together.
  • the content of the photopolymerization initiator (D) is preferably 0.01 to 120 parts by mass, more preferably 1 with respect to 100 parts by mass of the compound having an ethylenically unsaturated group.
  • the amount is about 100 parts by mass, more preferably 5 to 80 parts by mass.
  • Hardening of an exposure part becomes enough for content of a photoinitiator (D) to be more than the said lower limit, and it is easy to improve heat resistance.
  • the content of the photopolymerization initiator (D) is less than or equal to the upper limit value, it is easy to obtain a pattern with high resolution without lowering the transparency to exposure light.
  • the resin composition of the present invention contains a solvent (E).
  • the handleability of the resin composition of the present invention can be improved, the viscosity can be adjusted, and the storage stability can be improved.
  • Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate;
  • Propylene glycol monoalkyl ether such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether
  • Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether and propylene glycol dibutyl ether;
  • Cellosolves such as
  • lactic acid esters propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, alcohols and lactones are preferable; ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, tetrahydrofurfuryl alcohol, More preferred is ⁇ -butyrolactone.
  • the solvent (E) may be used alone or in combination of two or more.
  • the content of the solvent (E) is usually 40 to 900 parts by mass, preferably 60 to 900 parts by mass with respect to 100 parts by mass in total of components other than the solvent (E) in the composition. It is 400 parts by mass.
  • ⁇ Other additives (F)> In the resin composition of the present invention, various additions such as alkali-soluble polymers other than polymer (A), adhesion assistants, crosslinked fine particles, leveling agents, surfactants, sensitizers, inorganic fillers, quenchers, etc. An agent can be contained in the range which does not impair the object and the characteristic of the present invention.
  • the resin composition of the present invention can be prepared by uniformly mixing the respective components. Also, in order to remove foreign matter, the components obtained may be uniformly mixed, and then the resulting mixture may be filtered with a filter or the like.
  • the resin composition is excellent in storage stability.
  • the resin film of the present invention is a resin film (cured film) obtained by curing the resin composition of the present invention. Since the polymer (A) contained in the resin composition of the present invention is excellent in heat resistance, the resin film obtained using the resin composition of the present invention is also excellent in heat resistance.
  • the resin film of the present invention is high in mechanical strength, small in thermal expansion (linear expansion coefficient), low in dielectric constant, excellent in elongation properties, and hardly cracked even if it receives an impact.
  • the resin film of the present invention is used as a surface protective film, an interlayer insulating film and a planarizing film of electronic components such as circuit boards (semiconductor elements), semiconductor packages or display elements, and also as insulating films for high density mounting substrates It can be suitably used as a material, a photosensitive adhesive and a pressure sensitive adhesive.
  • the resin film of the present invention is produced, for example, by applying at least a resin composition of the present invention on a support to form a coated film, and curing the coated film to obtain a resin film. can do.
  • a resin composition of the present invention containing a photosensitive acid generator (B) or a photopolymerization initiator (D) is coated on a support to form a coated film.
  • Step (hereinafter also referred to as “coating step”), step of selectively exposing the coating film to obtain a selectively exposed film (hereinafter also referred to as “exposure step”), developing the selectively exposed film with an alkaline developer
  • curing step step of curing the patterned coating film to obtain a patterned resin film.
  • the resin composition of the present invention containing a photosensitive acid generator (B) or a photopolymerization initiator (D) is coated on a support, and dried if necessary. Remove the solvent (E).
  • the drying conditions are, for example, heating at usually 50 to 140 ° C. for 10 to 1000 seconds using an oven or a hot plate.
  • the film thickness of the coating film may be appropriately adjusted in accordance with the film thickness of the patterned resin film to be finally obtained.
  • the support for example, a silicon wafer, a compound semiconductor wafer, a wafer with a metal thin film, a glass substrate, a quartz substrate, a ceramic substrate, an aluminum substrate, a SUS substrate, a substrate having a semiconductor chip on the surface of these supports, and others
  • a resin sheet is mentioned.
  • the coating method include a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a silk screen method, and an ink jet method.
  • the above-mentioned coating film is selectively exposed through, for example, a reticle using, for example, a contact aligner, a stepper or a scanner to obtain a selective exposure film.
  • the exposure light for example, radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like can be mentioned, and preferably light with a wavelength of 200 to 500 nm (example: i-ray (365 nm)) is used.
  • the irradiation dose of exposure light varies depending on the type and blending ratio of each component in the photosensitive composition, the thickness of the coating film, etc. When i-line is used for the exposure light, the exposure dose is usually 100 to 1500 mJ /. It is cm 2 .
  • PEB process heat treatment may be performed on the selective coating film.
  • the PEB conditions vary depending on the kind of each component in the resin composition, the blending ratio, the thickness of the coating film, etc., but are usually 70 to 150 ° C., preferably 80 to 120 ° C., and about 1 to 60 minutes. .
  • the selective exposure film is developed with an alkaline developer to form a patterned coating film on a support.
  • the development method include a shower development method, a spray development method, an immersion development method, and a paddle development method.
  • the conditions for the development method are usually about 20 to 40 ° C. and about 1 to 10 minutes.
  • the alkaline developing solution may be, for example, an alkaline solution in which an alkaline compound such as sodium hydroxide, potassium hydroxide, ammonia water, tetramethyl ammonium hydroxide, choline or the like is dissolved to a concentration of 1 to 10% by mass.
  • An aqueous solution is mentioned.
  • An appropriate amount of, for example, a water-soluble organic solvent such as methanol or ethanol and a surfactant may be added to the alkaline aqueous solution.
  • the patterned coating film is cured by heating, for example.
  • heating is performed, for example, at a temperature of 100 to 250 ° C. for about 1 minute to 10 hours using an oven or a hot plate.
  • the electronic component of the present invention has the resin film of the present invention.
  • a circuit board semiconductor element
  • semiconductor package semiconductor package
  • a display element is mentioned, for example.
  • Example 1-1 Synthesis of Polymer (A-1)
  • 5.9 g (50 mol%) of the compound (M-1) and 10.8 g (50 mol%) of the compound (M-2) are dissolved in 45 g of propylene glycol monomethyl ether, and azo is used as a radical polymerization initiator
  • a monomer solution was prepared by adding 0.918 g (7 mol% to all monomers) of bisisobutyronitrile. Next, nitrogen bubbling was performed for 15 minutes, and the mixture was heated to 80 ° C. with stirring. The polymerization reaction was carried out for 4 hours, with the time when the solution reached 75 ° C. as the initiation time of the polymerization reaction.
  • the polymerization solution was water-cooled and cooled to 30 ° C. or less, 60 g of methanol was added, and solution liquid extraction and washing were performed five times with an equal amount of normal hexane.
  • An equal amount of propylene glycol monomethyl ether is added to a methanol solution containing a polymer after extraction and washing, methanol is distilled off with a rotary evaporator equipped with a water bath at 40 ° C., and the solution is further concentrated to about 30% to obtain a target polymer Obtained with the solution.
  • the Mw of the polymer (A-1) was 21,000, and the Mw / Mn was 2.15.
  • Example 1-2 to 1-10 Synthesis of Polymers (A-2) to (A-10)
  • polymers (A-2) to (A-10) were prepared in the same manner as in Example 1-1 except that monomers of the types and amounts shown in Table 2 were used. Got).
  • the solvent (E-1) is propylene glycol monomethyl ether.
  • Example 2-2 to 2-10 resin compositions (J-2) to (J-10) were prepared in the same manner as in Example 2-1 except that polymers of the types and amounts shown in Table 3 were used. ) Were prepared, and predetermined evaluation was performed using the obtained resin composition.
  • a hydroxystyrene-styrene copolymer product name: Styrene marker linker CST, manufactured by Maruzen Petrochemical Co., Ltd.
  • the resin composition (CJ-1) was prepared in the same manner as in Example 2-1, and predetermined evaluation was performed using the obtained resin composition.
  • the heat resistant resin compositions (J-1) to (J-10) and (CJ-1) are cured by heating at 200 ° C. for 1 hour to obtain a resin film, and then nitrogen is obtained by thermogravimetric analysis (TGA).
  • TGA thermogravimetric analysis
  • the temperature was measured at a temperature rising rate of 10 ° C./minute under an atmosphere, and evaluated at a 5 mass% thermal weight loss temperature (Td5).
  • Td5 thermogravimetric analysis
  • the width of the sample was 5 mm
  • the distance between the chucks was 20 mm
  • the tensile rate was 5 mm / min
  • the measurement temperature was about room temperature (20 to 25 ° C.).
  • the average of the measured values of five or more test pieces obtained from the cured film obtained under the same conditions is “A” when it is 70 MPa or more, “B” when it is 50 MPa or more and less than 70 MPa, “B” when it is 30 MPa or more and less than 50 MPa. C ", the case of less than 30 MPa was" D ".
  • the dielectric resin compositions (J-1) to (J-10) and (CJ-1) are coated on a SUS substrate to a film thickness of 5 ⁇ m and dried on an 80 ° C. hot plate for 3 minutes, It was heat cured in an oven at 200 ° C. for 1 hour.
  • the dielectric constant at 1 MHz of the obtained cured film (resin film) is measured, and in the case of less than 4.0, “A”, in the case of 4.0 or more and less than 4.5, “B”, 4.5 or more The case is "C".
  • Photosensitive acid generator (B-1) 4,4 '-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphthoquinone diazide- 5-sulfonic acid chloride condensate
  • Photosensitive acid generator (B-2) 4,7-di-n-butoxynaphthyltetrahydrothiophenium trifluoromethanesulfonate
  • Solvent (E-1) Propylene glycol monomethyl ether
  • Solvent (E-2) Tetrahydrofurfuryl alcohol
  • Solvent (E-3) ⁇ -butyrolactone sur
  • Example 3 a photosensitive composition (Example 3) was prepared in the same manner as Example 3-1 except that the types and amounts of the blending components were changed as shown in Table 4. PR-2) to (PR-10) and (CPR-1) were prepared. Predetermined evaluation was performed using the obtained photosensitive composition.
  • the photosensitive composition is as follows.
  • the photosensitive composition was spin-coated on a silicon wafer having a resolution and a residual film rate of 6 inches, and then heated at 110 ° C. for 3 minutes using a hot plate to prepare a uniform coated film with a thickness of 10 ⁇ m. Then, using an aligner (made by Suss Microtec, type "MA-150"), the ultraviolet light from a high pressure mercury lamp is applied to the above coated film so that the exposure amount at a wavelength of 350 nm is 500 mJ / cm 2 through a pattern mask. Irradiated. Then, the coated film after exposure was subjected to immersion development for 120 seconds at 23 ° C. using a 2.38 mass% tetramethylammonium hydroxide aqueous solution.
  • the coated film after development is washed with ultrapure water for 30 seconds, air-dried with air, then observed with a microscope (MHL110 manufactured by Olympus Corporation), and the pattern of the resolved minimum pattern
  • the dimension is a resolution (unit: ⁇ m).
  • the film thickness is measured using a stylus thickness meter P-16 manufactured by KLA-Tencor, and the residual film ratio (100% ⁇ (film thickness after development / film before development) from the film thickness difference before and after development Thickness) was calculated and evaluated by the following evaluation criteria.
  • heating was performed at 110 ° C. for 3 minutes using a hot plate.
  • C Residual film rate less than 80% 6-2.
  • the solvent resistant photosensitive compositions (PR-1) to (PR-10) and (CPR-1) are placed in a 1 mm thick metal frame placed on a Teflon sheet, and 2 in a vacuum oven with an internal temperature of 50 ° C. After time treatment, the film was pressed at 200 ° C. for 2 hours under a pressure of 0.5 t and peeled off from the Teflon sheet to obtain a cured film having a thickness of about 0.5 mm.
  • This cured film is cut into 1 cm square for testing, and after measuring the weight, it is immersed in 5 ml of NMP (N-methylpyrrolidone) at room temperature for 3 days to change the shape of the cured film (shape change by visual observation, weight change) Was evaluated.
  • the weight of the cured film after immersion in NMP was measured after the cured film after immersion in NMP was dried in a vacuum oven at an internal temperature of 80 ° C. for 3 days.
  • Each weight of the cured film before and after immersion in NMP was measured with a Sartorius precision balance BP311D. There is no change in shape by visual observation, and weight reduction is less than 3% "A", regardless of the change in visual shape change, weight reduction by 3% or more and less than 10% is "B", 10% or more In the case of “C”.

Abstract

[Problem] To provide a resin composition which has excellent heat resistance. [Solution] A resin composition which contains: a polymer that contains, in one same molecule or in different molecules, a structural unit having a partial structure of formula (i) and one or more structural units selected from among structural units having a partial structure of formula (ii-1) and structural units having a phenolic hydroxyl group; and a solvent. In the formulae, each of R1 and R2 independently represents a hydrogen atom, a hydrocarbon group having 1-20 carbon atoms, a group that has at least one moiety selected from among -O- and the like in at least one carbon-carbon bond in the above-described hydrocarbon group, or a group that is obtained by substituting some hydrogen atoms in these groups; R1 and R2 may combine with each other and form a cyclic structure having 3-20 ring members together with B to which OR1 and OR2 are bonded; each of R3 and R4 independently represents a hydrogen atom, a hydrocarbon group having 1-20 carbon atoms or an electron-withdrawing group; at least one of R3 and R4 represents an electron-withdrawing group; and * represents a bonding hand.

Description

重合体、樹脂組成物、樹脂膜、パターン化樹脂膜の製造方法、および電子部品Polymer, resin composition, resin film, method for producing patterned resin film, and electronic component
　本発明は、重合体、樹脂組成物、樹脂膜、パターン化樹脂膜の製造方法、および電子部品に関する。 The present invention relates to a polymer, a resin composition, a resin film, a method for producing a patterned resin film, and an electronic component.
　機械的強度に優れたポリアリーレンエーテルを使用したフォトレジスト材料として、従来、様々な感光性組成物が提案されている（例えば、特許文献１および２参照）。 Conventionally, various photosensitive compositions have been proposed as photoresist materials using polyarylene ethers excellent in mechanical strength (see, for example, Patent Documents 1 and 2).
　特許文献１には、フェノール性水酸基を有するポリフェニレンオキシド（Ａ）と、光により酸を発生する化合物（Ｂ）とを含有するポジ型感光性樹脂組成物が開示されている。 Patent Document 1 discloses a positive photosensitive resin composition containing polyphenylene oxide (A) having a phenolic hydroxyl group and a compound (B) capable of generating an acid by light.
　特許文献２には、多価フェノール化合物とビニルエーテル化合物とを重付加して得られる重合体（ａ）、および放射線の照射によって酸を発生する酸発生剤（ｂ）を含有するポジ型感放射線性組成物が開示されている。 Patent Document 2 discloses a positive-type radiation-sensitive polymer containing a polymer (a) obtained by polyaddition of a polyhydric phenol compound and a vinyl ether compound, and an acid generator (b) that generates an acid upon irradiation with radiation. A composition is disclosed.
特開２０００－２７５８４２号公報JP 2000-275842 特開２００５－２６６０４９号公報Japanese Patent Application Publication No. 2005-266049
　近年、半導体集積回路等を製造する分野において、大容量化、高集積化を実現するために実装技術の更なる高度化が求められており、リフロー耐性等に優れた高耐熱化が求められている。 In recent years, in the field of manufacturing semiconductor integrated circuits and the like, further advancement of mounting technology is required to realize large capacity and high integration, and high heat resistance with excellent reflow resistance etc. is required. There is.
　本発明の課題は、耐熱性に優れた樹脂膜を形成可能な樹脂組成物、当該樹脂組成物の含有成分として有用な重合体、耐熱性に優れた樹脂膜、パターン化樹脂膜の製造方法、および前記樹脂膜を有する電子部品を提供することにある。 The subject of the present invention is a resin composition capable of forming a resin film excellent in heat resistance, a polymer useful as a component of the resin composition, a resin film excellent in heat resistance, a method of producing a patterned resin film, And providing an electronic component having the resin film.
　本発明者らは上記課題を解決するため鋭意検討を行った。その結果、以下の特定構造を有する重合体を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。 The present inventors diligently studied to solve the above problems. As a result, it has been found that the above problems can be solved by using a polymer having the following specific structure, and the present invention has been completed.
　本発明は、例えば以下の［１］～［２２］である。 The present invention is, for example, the following [1] to [22].
　［１］（Ａ）同一のまたは異なる分子中に、下記式（ｉ）で表される部分構造を有する構造単位（以下「構造単位（ｉ）」ともいう）と、下記式（ii-1）で表される部分構造を有する構造単位、およびフェノール性水酸基を有する構造単位から選択される一以上の水酸基含有構造単位（以下「構造単位（ii）」ともいう）とを含む重合体、ならびに（Ｅ）溶媒を含有する樹脂組成物。 [1] (A) A structural unit having a partial structure represented by the following formula (i) in the same or different molecule (hereinafter also referred to as “structural unit (i)”), and a compound represented by the following formula (ii-1) A polymer comprising a structural unit having a partial structure represented by and one or more hydroxyl-containing structural units (hereinafter also referred to as “structural units (ii)”) selected from structural units having a phenolic hydroxyl group, and E) Resin composition containing a solvent.
Figure JPOXMLDOC01-appb-C000012
 ［式（ｉ）中、Ｒ1およびＲ2は、各々独立に、水素原子、炭素数１～２０の炭化水素基、前記炭素数１～２０の炭化水素基中の少なくとも１つの炭素－炭素結合間に、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＳＯ2－、－ＳＯ3－、－ＯＳＯ2ＮＲ－、－ＮＲＳＯ2－、－ＮＲＣＯ－、－ＮＲ－および－ＣＯＮＲ－から選ばれる少なくとも一種を有する基、またはこれらの基中の水素原子の一部が置換された基を示し、Ｒ1およびＲ2は、相互に結合してＯＲ1およびＯＲ2が結合するホウ素原子と共に環員数３～２０の環状構造を形成してもよい。前記Ｒは、水素原子または炭素数１～２０の炭化水素基であり、＊は結合手を示す。］
Figure JPOXMLDOC01-appb-C000012
 [In formula (i), R 1 and R 2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, at least one carbon-carbon bond in the hydrocarbon group having 1 to 20 carbon atoms] during, -O -, - COO -, - OCO -, - OSO 2 -, - SO 3 -, - OSO 2 NR -, - NRSO 2 -, - NRCO -, - selected from NR- and -CONR- R 1 and R 2 represent a group having at least one group or a group in which a part of hydrogen atoms in these groups is substituted, and R 1 and R 2 together with the boron atom to which OR 1 and OR 2 are bonded and the number of ring members It may form 3 to 20 ring structures. The R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a bond. ]
Figure JPOXMLDOC01-appb-C000013
 ［式（ii-1）中、Ｒ3およびＲ4は、各々独立に、水素原子、炭素数１～２０の炭化水素基、または電子求引性基であり、但し、上記Ｒ3およびＲ4のうち、少なくともいずれかは電子求引性基であり、＊は結合手を示す。］
　［２］重合体（Ａ）が、下記式（iii）で表される部分構造を有する構造単位（以下「構造単位（iii）」ともいう）をさらに含む、上記［１］に記載の樹脂組成物。
Figure JPOXMLDOC01-appb-C000013
 [In formula (ii-1), R 3 and R 4 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an electron withdrawing group, provided that the above R 3 and R 4 are each independently And at least one of them is an electron withdrawing group, and * represents a bond. ]
[2] The resin composition according to the above [1], wherein the polymer (A) further comprises a structural unit having a partial structure represented by the following formula (iii) (hereinafter also referred to as “structural unit (iii)”) object.
Figure JPOXMLDOC01-appb-C000014
 ［式（iii）中、Ｒ5は、炭素数１～２０の有機基であり；Ｒ6は、水素原子または炭素数１～２０の炭化水素基であり、ｎは０～３の整数であり、＊は結合手を示す。］
　［３］重合体（Ａ）が、下記式（iv）で表される部分構造を有する構造単位（以下「構造単位（iv）」ともいう）をさらに含む、上記［１］～［２］のいずれかに記載の樹脂組成物。
Figure JPOXMLDOC01-appb-C000014
 [In formula (iii), R 5 is an organic group having 1 to 20 carbon atoms; R 6 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and n is an integer of 0 to 3 , * Indicates a bonding hand. ]
[3] The polymer according to the above [1] or [2], wherein the polymer (A) further comprises a structural unit having a partial structure represented by the following formula (iv) (hereinafter also referred to as “structural unit (iv)”) The resin composition as described in any one.
Figure JPOXMLDOC01-appb-C000015
 ［式（iv）中、Ｒ7およびＲ8は、各々独立に、水素原子、炭素数１～２０の炭化水素基、前記炭素数１～２０の炭化水素基中の少なくとも１つの炭素－炭素結合間に、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＳＯ2－、－ＳＯ3－、－ＯＳＯ2ＮＲ105－、－ＮＲ105ＳＯ2－、－ＮＲ105ＣＯ－、－ＮＲ105－および－ＣＯＮＲ105－から選ばれる少なくとも一種を有する基、またはこれらの基中の水素原子の一部が置換された基を示し、Ｒ7およびＲ8は、相互に結合してＯＲ7およびＯＲ8が結合するリン原子と共に環員数３～２０の環状構造を形成してもよく、前記Ｒ105は、水素原子または炭素数１～２０の炭化水素基であり、＊は結合手を示す。］
　［４］重合体（Ａ）が、エポキシ基を有する構造単位（以下「構造単位（ｖ）」ともいう）をさらに含む、上記［１］～［３］のいずれかに記載の樹脂組成物。
Figure JPOXMLDOC01-appb-C000015
 [In formula (iv), each of R 7 and R 8 independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, at least one carbon-carbon bond in the hydrocarbon group having 1 to 20 carbon atoms] during, -O -, - COO -, - OCO -, - OSO 2 -, - SO 3 -, - OSO 2 NR 105 -, - NR 105 SO 2 -, - NR 105 CO -, - NR 105 - and -CONR 105 - represents at least one group having or part of which is a substituent of the hydrogen atoms in these groups are selected from, R 7 and R 8, oR 7 and oR 8 are bonded to each other The ring structure having 3 to 20 ring members may be formed together with the phosphorus atom to be bonded, and the above R 105 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * indicates a bonding hand. ]
[4] The resin composition according to any one of the above [1] to [3], wherein the polymer (A) further contains a structural unit having an epoxy group (hereinafter also referred to as “structural unit (v)”).
　［５］上記水酸基含有構造単位が、上記式（ii-1）で表される部分構造を有する構造単位である、上記［１］～［４］のいずれかに記載の樹脂組成物。 [5] The resin composition according to any one of the above [1] to [4], wherein the hydroxyl group-containing structural unit is a structural unit having a partial structure represented by the above formula (ii-1).
　［６］上記フェノール性水酸基を有する構造単位が、加熱により環化してフェノール性水酸基が消失するフェノール性水酸基含有不飽和化合物由来の構造単位である、上記［１］～［５］のいずれかに記載の樹脂組成物。 [6] any of the above-mentioned [1] to [5], wherein the structural unit having a phenolic hydroxyl group is a structural unit derived from a phenolic hydroxyl group-containing unsaturated compound in which the phenolic hydroxyl group disappears by cyclization upon heating and disappears The resin composition as described.
　［７］上記式（ｉ）で表される部分構造を有する構造単位が下記式（１）で表される、上記［１］～［６］のいずれかに記載の樹脂組成物。 [7] The resin composition according to any one of the above [1] to [6], wherein the structural unit having a partial structure represented by the above formula (i) is represented by the following formula (1).
Figure JPOXMLDOC01-appb-C000016
 ［式（１）中、Ｒ1およびＲ2は、それぞれ式（ｉ）中の同一記号と同義であり；Ｒ11は、水素原子、フッ素原子、炭素数１～１０の炭化水素基、または炭素数１～１０のフッ素化炭化水素基であり；Ｌ1は、単結合、酸素原子、硫黄原子、または－Ｃ（＝Ｏ）－Ｘ1－で表される基であり、Ｘ1は、酸素原子、硫黄原子またはＮＨ基であり；Ｒ12は、炭素数１～２０の（ａ＋１）価の炭化水素基、前記炭化水素基中の少なくとも１つの炭素－炭素結合間に、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＳＯ2－、－ＳＯ3－、－ＯＳＯ2ＮＲ101－、－ＮＲ101ＳＯ2－、－ＮＲ101ＣＯ－、－ＮＲ101－および－ＣＯＮＲ101－から選ばれる少なくとも一種を有する基、またはこれらの基中の水素原子の一部が置換された基であり、前記Ｒ101は、水素原子または炭素数１～２０の炭化水素基であり；ａは１～３の整数である。］
　［８］上記式（ii-1）で表される部分構造を有する構造単位が下記式（２）で表される、上記［１］～［７］のいずれかに記載の樹脂組成物。
Figure JPOXMLDOC01-appb-C000016
 [In formula (1), R 1 and R 2 each have the same meaning as the same symbol in formula (i); R 11 is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or carbon L 1 is a single bond, an oxygen atom, a sulfur atom, or a group represented by —C (= O) —X 1 —, and X 1 is an oxygen R 12 represents an (a + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, at least one carbon-carbon bond in the hydrocarbon group, —O—, — At least one selected from COO-, -OCO-, -OSO 2- , -SO 3- , -OSO 2 NR 101- , -NR 101 SO 2- , -NR 101 CO-, -NR 101 -and -CONR 101- R 1 is a group having one type, or a group obtained by substituting a part of hydrogen atoms in these groups, and the above R 101 is water A prime atom or a hydrocarbon group having 1 to 20 carbon atoms; a is an integer of 1 to 3; ]
[8] The resin composition according to any one of the above [1] to [7], wherein a structural unit having a partial structure represented by the above formula (ii-1) is represented by the following formula (2).
Figure JPOXMLDOC01-appb-C000017
 ［式（２）中、Ｒ3およびＲ4は、それぞれ式（ii-1）中の同一記号と同義であり；Ｒ13は、水素原子、フッ素原子、炭素数１～１０の炭化水素基、または炭素数１～１０のフッ素化炭化水素基であり；Ｌ2は、単結合、酸素原子、硫黄原子、または－Ｃ（＝Ｏ）－Ｘ2－で表される基であり、Ｘ2は、酸素原子、硫黄原子またはＮＨ基であり；Ｒ14は、炭素数１～２０の（ｂ＋１）価の炭化水素基、前記炭化水素基中の少なくとも１つの炭素－炭素結合間に、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＳＯ2－、－ＳＯ3－、－ＯＳＯ2ＮＲ102－、－ＮＲ102ＳＯ2－、－ＮＲ102ＣＯ－、－ＮＲ102－および－ＣＯＮＲ102－から選ばれる少なくとも一種を有する基、またはこれらの基中の水素原子の一部が置換された基であり、前記Ｒ102は、水素原子または炭素数１～２０の炭化水素基であり；ｂは１～３の整数である。］
　［９］上記式（iii）で表される部分構造を有する構造単位が下記式（３）で表される、上記［２］に記載の樹脂組成物。
Figure JPOXMLDOC01-appb-C000017
 [In formula (2), R 3 and R 4 each have the same meaning as the same symbol in formula (ii-1); R 13 is a hydrogen atom, a fluorine atom, or a hydrocarbon group having 1 to 10 carbon atoms, Or a fluorinated hydrocarbon group having 1 to 10 carbon atoms; L 2 is a single bond, an oxygen atom, a sulfur atom, or a group represented by —C (= O) —X 2 —, and X 2 is R 14 is a (b + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, at least one carbon-carbon bond in the hydrocarbon group, -O- , -COO -, - OCO -, - OSO 2 -, - SO 3 -, - OSO 2 NR 102 -, - NR 102 SO 2 -, - NR 102 CO -, - NR 102 - and -CONR 102 - selected from at least one group having the or a part of which is a substituent of the hydrogen atoms in these groups, the R 102 is that, A hydrocarbon group atom or a C 1 ~ 20; b is an integer of 1-3. ]
[9] The resin composition according to the above [2], wherein the structural unit having a partial structure represented by the above formula (iii) is represented by the following formula (3).
Figure JPOXMLDOC01-appb-C000018
 ［式（３）中、Ｒ5、Ｒ6およびｎは、それぞれ式（iii）中の同一記号と同義であり；Ｒ15は、水素原子、フッ素原子、炭素数１～１０の炭化水素基、または炭素数１～１０のフッ素化炭化水素基であり；Ｌ3は、単結合、酸素原子、硫黄原子、または－Ｃ（＝Ｏ）－Ｘ3－で表される基であり、Ｘ3は、酸素原子、硫黄原子またはＮＨ基であり；Ｒ16は、炭素数１～２０の（ｃ＋１）価の炭化水素基、前記炭化水素基中の少なくとも１つの炭素－炭素結合間に、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＳＯ2－、－ＳＯ3－、－ＯＳＯ2ＮＲ104－、－ＮＲ104ＳＯ2－、－ＮＲ104ＣＯ－、－ＮＲ104－および－ＣＯＮＲ104－から選ばれる少なくとも一種を有する基、またはこれらの基中の水素原子の一部が置換された基であり、前記Ｒ104は、水素原子または炭素数１～２０の炭化水素基であり；ｃは１～３の整数である。］
　［１０］重合体（Ａ）が、上記式（ｉ）で表される部分構造を有する構造単位を、全構造単位中、５～６０モル％含む、上記［１］～［９］のいずれかに記載の樹脂組成物。
Figure JPOXMLDOC01-appb-C000018
 [In formula (3), R 5 , R 6 and n each have the same meaning as the same symbol in formula (iii); R 15 is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, Or a fluorinated hydrocarbon group having 1 to 10 carbon atoms; L 3 is a single bond, an oxygen atom, a sulfur atom, or a group represented by —C (= O) —X 3 —, and X 3 is R 16 is a (C + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, at least one carbon-carbon bond in the above-mentioned hydrocarbon group, —O—, , -COO -, - OCO -, - OSO 2 -, - SO 3 -, - OSO 2 NR 104 -, - NR 104 SO 2 -, - NR 104 CO -, - NR 104 - and -CONR 104 - selected from group having at least one kind or a group partially substituted for hydrogen atoms in these groups, the R 104, , It is a hydrogen atom or a hydrocarbon group having a carbon number of 1 ~ 20; c is an integer of 1-3. ]
[10] Any of the above-mentioned [1] to [9], wherein the polymer (A) contains 5 to 60 mol% of structural units having a partial structure represented by the above formula (i) in all structural units The resin composition as described in.
　［１１］重合体（Ａ）が、上記式（ii-1）で表される部分構造を有する構造単位、およびフェノール性水酸基を有する構造単位から選択される一以上の水酸基含有構造単位を、全構造単位中、５～９０モル％含む、上記［１］～［１０］のいずれかに記載の樹脂組成物。 [11] The polymer (A) is a structural unit having a partial structure represented by the above formula (ii-1), and one or more hydroxyl group-containing structural units selected from structural units having a phenolic hydroxyl group. The resin composition according to any one of the above [1] to [10], containing 5 to 90 mol% in the structural unit.
　［１２］重合体（Ａ）が、上記式（iii）で表される部分構造を有する構造単位を、全構造単位中、５～５０モル％含む、上記［２］または［９］に記載の樹脂組成物。 [12] The polymer according to the above [2] or [9], wherein the polymer (A) contains 5 to 50 mol% of structural units having a partial structure represented by the above formula (iii) in all structural units. Resin composition.
　［１３］重合体（Ａ）が、前記エポキシ基を有する構造単位を、全構造単位中、５～４５モル％含む、上記［４］に記載の樹脂組成物。 [13] The resin composition as described in [4] above, wherein the polymer (A) contains 5 to 45 mol% of structural units having the epoxy group in all structural units.
　［１４］感光性酸発生剤（Ｂ）または光重合開始剤（Ｄ）をさらに含有する、上記［１］～［１３］のいずれかに記載の樹脂組成物。 [14] The resin composition according to any one of the above [1] to [13], which further contains a photosensitive acid generator (B) or a photopolymerization initiator (D).
　［１５］架橋剤（Ｃ）をさらに含有する、上記［１］～［１４］のいずれかに記載の樹脂組成物。 [15] The resin composition according to any one of the above [1] to [14], which further contains a crosslinking agent (C).
　［１６］上記式（ｉ）で表される部分構造を有する構造単位と、上記式（ii-1）で表される部分構造を有する構造単位、およびフェノール性水酸基を有する構造単位から選択される一以上の水酸基含有構造単位とを含む重合体。 [16] It is selected from a structural unit having a partial structure represented by the above formula (i), a structural unit having a partial structure represented by the above formula (ii-1), and a structural unit having a phenolic hydroxyl group Polymers comprising one or more hydroxyl group-containing structural units.
　［１７］上記式（iii）で表される部分構造を有する構造単位をさらに含む、上記［１６］に記載の重合体。 [17] The polymer according to the above [16], further comprising a structural unit having a partial structure represented by the above formula (iii).
　［１８］上記式（iv）で表される部分構造を有する構造単位をさらに含む、上記［１６］～［１７］のいずれかに記載の重合体。 [18] The polymer according to any one of the above [16] to [17], further comprising a structural unit having a partial structure represented by the above formula (iv).
　［１９］エポキシ基を有する構造単位をさらに含む、上記［１６］～［１８］のいずれかに記載の重合体。 [19] The polymer according to any one of the above [16] to [18], further comprising a structural unit having an epoxy group.
　［２０］上記［１］～［１５］のいずれかに記載の樹脂組成物を硬化させて得られる樹脂膜。 [20] A resin film obtained by curing the resin composition according to any one of the above [1] to [15].
　［２１］上記［１４］に記載の樹脂組成物を支持体上に塗布して塗布膜を形成する工程、前記塗布膜を選択的に露光して選択露光膜を得る工程、アルカリ性現像液により前記選択露光膜を現像してパターン化した塗布膜を得る工程、および前記パターン化した塗布膜を硬化させてパターン化樹脂膜を得る工程を有する、パターン化樹脂膜の製造方法。 [21] A step of applying the resin composition according to the above [14] onto a support to form a coated film, a step of selectively exposing the coated film to obtain a selectively exposed film, the above-mentioned step using an alkaline developer. A method for producing a patterned resin film, comprising the steps of developing a selective exposure film to obtain a patterned coating film, and curing the patterned coating film to obtain a patterned resin film.
　［２２］上記［２０］に記載の樹脂膜を有する電子部品。 [22] An electronic component having the resin film according to the above [20].
　本発明によれば、耐熱性に優れた樹脂膜を形成可能な樹脂組成物を提供することができる。また、本発明によれば、前記樹脂組成物の含有成分として有用な重合体、耐熱性に優れた樹脂膜、パターン化樹脂膜の製造方法、および前記樹脂膜を有する電子部品を提供することができる。 According to the present invention, a resin composition capable of forming a resin film excellent in heat resistance can be provided. Further, according to the present invention, a polymer useful as a component of the resin composition, a resin film excellent in heat resistance, a method for producing a patterned resin film, and an electronic component having the resin film can be provided. it can.
　以下、本発明を実施するための形態について好適態様も含めて説明する。 Hereinafter, modes for carrying out the present invention will be described including preferred modes.
　本明細書で例示する各成分、例えば樹脂組成物中の各成分は、特に言及しない限り、それぞれ１種単独で用いてもよく、２種以上を併用してもよい。 Each component exemplified in the present specification, for example, each component in the resin composition, may be used alone or in combination of two or more unless otherwise stated.
　本明細書において、以下の通り各用語を定義する。 In the present specification, each term is defined as follows.
　「炭化水素基」とは、鎖状炭化水素基、脂環式炭化水素基および芳香族炭化水素基を包含する。「炭化水素基」は、飽和炭化水素基でも不飽和炭化水素基でもよい。 The "hydrocarbon group" includes a chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group. The "hydrocarbon group" may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
　「鎖状炭化水素基」とは、環状構造を含まず、鎖状構造のみで構成された炭化水素基を意味し、直鎖状炭化水素基および分岐状炭化水素基の両方を包含する。 "Chain chain hydrocarbon group" means a hydrocarbon group which does not contain a cyclic structure and is constituted only by a chain structure, and includes both a linear hydrocarbon group and a branched hydrocarbon group.
　「脂環式炭化水素基」とは、環状構造としては脂環式炭化水素の構造のみを含み、芳香環構造を含まない炭化水素基を意味し、単環の脂環式炭化水素基および多環の脂環式炭化水素基の両方を包含する。但し、「脂環式炭化水素基」は、脂環式炭化水素の構造のみで構成されている必要はなく、その一部に鎖状構造を含んでいてもよい。 The term "alicyclic hydrocarbon group" means a hydrocarbon group containing only an alicyclic hydrocarbon structure as a cyclic structure and not containing an aromatic ring structure, and a monocyclic alicyclic hydrocarbon group and a plurality of alicyclic hydrocarbon groups and multiple cyclic hydrocarbon groups. It includes both of the alicyclic hydrocarbon groups of the ring. However, the “alicyclic hydrocarbon group” does not have to be constituted only by the structure of the alicyclic hydrocarbon, and a chain structure may be included in part thereof.
　「芳香族炭化水素基」とは、環状構造として芳香環構造を含む炭化水素基を意味する。但し、「芳香族炭化水素基」は、芳香環構造のみで構成されている必要はなく、その一部に鎖状炭化水素の構造および／または脂環式炭化水素の構造を含んでいてもよい。 The "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring structure as a cyclic structure. However, the "aromatic hydrocarbon group" does not have to be composed of only an aromatic ring structure, and a portion thereof may have a chain hydrocarbon structure and / or an alicyclic hydrocarbon structure. .
　「パターン化樹脂膜」とは、パターン化した樹脂膜をいう。なお、「樹脂膜」という用語は、パターン化した樹脂膜を包含する意味で用いる。 "Patterned resin film" refers to a patterned resin film. In addition, the term "resin film" is used in the meaning including the patterned resin film.
　〔樹脂組成物〕
　本発明の樹脂組成物は、以下に説明する重合体（Ａ）と溶媒（Ｅ)を含有する。以下では、前記樹脂組成物の含有成分として好適に用いられる、本発明の重合体（Ａ）もあわせて説明する。 [Resin composition]
The resin composition of the present invention contains a polymer (A) and a solvent (E) described below. Hereinafter, the polymer (A) of the present invention, which is suitably used as a component of the resin composition, will also be described.
　本発明の樹脂組成物は、感光性酸発生剤（Ｂ）または光重合開始剤（Ｄ）をさらに含有することができる。前記（Ｂ）または（Ｄ）を含有する本発明の樹脂組成物を「感光性組成物」ともいう。なお、本明細書において、感光性および光重合の用語は、可視光線、紫外線、遠紫外線、電子線、Ｘ線等の放射線に対応する、感放射線性および感放射線重合の意味で用いる。 The resin composition of the present invention can further contain a photosensitive acid generator (B) or a photopolymerization initiator (D). The resin composition of the present invention containing (B) or (D) is also referred to as a "photosensitive composition". In the present specification, the terms photosensitivity and photopolymerization are used to mean radiation-sensitive and radiation-sensitive polymerization corresponding to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam and X-ray.
　〈重合体（Ａ）〉
　重合体（Ａ）は、同一のまたは異なる分子中に、下記式（ｉ）で表される部分構造を有する構造単位と、下記式（ii-1）で表される部分構造を有する構造単位、およびフェノール性水酸基を有する構造単位から選択される一以上の水酸基含有構造単位とを含む。 <Polymer (A)>
The polymer (A) is a structural unit having a partial structure represented by the following formula (i) and a partial structure represented by the following formula (ii-1) in the same or different molecules, And one or more hydroxyl group-containing structural units selected from structural units having a phenolic hydroxyl group.
Figure JPOXMLDOC01-appb-C000019
 　上記式の説明は後述する。
Figure JPOXMLDOC01-appb-C000019
 The description of the above equation will be described later.
　重合体（Ａ）は、例えば、１種の重合体からなってもよく、２種以上の重合体からなってもよい。２種以上の重合体からなる場合（ブレンド物）は、例えばＮＭＲ分析により、ブレンド物全体が構造単位（ｉ）および構造単位（ii）を有していることを確認できれば、ブレンド物中に構造単位（ｉ）または（ii）を有していない重合体が含まれていてもよい。「同一のまたは異なる分子中」（ここでの分子とは、重合体分子を意味する）とは、このような意味で用いる。前記ブレンド物は、例えば、構造単位（ｉ）を含む重合体と、構造単位（ii）を含む重合体との混合物である。重合体（Ａ）は、同一分子中に構造単位（ｉ）と構造単位（ii）とを含むことが好ましい。 A polymer (A) may consist of one type of polymer, for example, and may consist of two or more types of polymers. When it consists of 2 or more types of polymers (blend), if it can confirm that the whole blend has structural unit (i) and structural unit (ii), for example by NMR analysis, it will be a structure in a blend The polymer which does not have unit (i) or (ii) may be included. The term "in the same or different molecule" (wherein molecule means a polymer molecule) is used in this sense. The blend is, for example, a mixture of a polymer containing the structural unit (i) and a polymer containing the structural unit (ii). The polymer (A) preferably contains the structural unit (i) and the structural unit (ii) in the same molecule.
　《構造単位（ｉ）》
　重合体（Ａ）は、１種または２種以上の構造単位（ｉ）を含む。構造単位（ｉ）は、樹脂組成物の保存安定性および塗布性、重合体（Ａ）のアルカリ溶解性、樹脂膜の機械的強度および耐熱性に寄与する。 << Structural unit (i) >>
The polymer (A) contains one or more structural units (i). The structural unit (i) contributes to the storage stability and coatability of the resin composition, the alkali solubility of the polymer (A), and the mechanical strength and heat resistance of the resin film.
　なお、重合体（Ａ）にアルカリ溶解性を付与することにより、本発明のパターン化樹脂膜の製造方法において、アルカリ性現像液により露光後の塗膜を現像することができる。 In addition, in the manufacturing method of the patterning resin film of this invention, the coating film after exposure can be developed by alkaline developing solution by providing alkali solubility to a polymer (A).
Figure JPOXMLDOC01-appb-C000020
 　式（ｉ）中の記号の意味は以下のとおりである。
Figure JPOXMLDOC01-appb-C000020
 The meanings of the symbols in formula (i) are as follows.
　Ｒ1およびＲ2は、各々独立に、水素原子、炭素数１～２０の炭化水素基、前記炭素数１～２０の炭化水素基中の少なくとも１つの炭素－炭素結合間に、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＳＯ2－、－ＳＯ3－、－ＯＳＯ2ＮＲ－、－ＮＲＳＯ2－、－ＮＲＣＯ－、－ＮＲ－および－ＣＯＮＲ－から選ばれる少なくとも一種を有する基（以下「置換炭化水素基１」ともいう）、またはこれらの基中の水素原子の一部が置換された基（以下「置換炭化水素基２」ともいう）を示し、Ｒ1およびＲ2は、相互に結合してＯＲ1およびＯＲ2が結合するホウ素原子と共に環員数３～２０の環状構造を形成してもよい。前記Ｒは、水素原子または炭素数１～２０の炭化水素基であり、＊は結合手を示す。 R 1 and R 2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, -O-, at least one carbon-carbon bond in the hydrocarbon group having 1 to 20 carbon atoms, -COO -, - OCO -, - OSO 2 -, - SO 3 -, - OSO 2 NR -, - NRSO 2 -, - NRCO -, - NR- and -CONR- of at least one group having a (hereinafter selected “Substituted hydrocarbon group 1” or a group in which part of hydrogen atoms in these groups is substituted (hereinafter also referred to as “substituted hydrocarbon group 2”), and R 1 and R 2 And a boron atom to which OR 1 and OR 2 are bonded to form a cyclic structure having 3 to 20 ring members. The R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a bond.
　上記Ｒ1、Ｒ2およびＲで列挙される炭素数１～２０の炭化水素基としては、炭素数１～２０の鎖状炭化水素基、および炭素数３～２０の脂環式炭化水素基が好ましい。このようにＲ1、Ｒ2およびＲで列挙される炭素数１～２０の炭化水素基を炭素数１～２０の鎖状炭化水素基、または炭素数３～２０の脂環式炭化水素基とすることで、耐熱性、ならびに溶媒およびアルカリ性現像液への溶解性に優れ、低誘電率の重合体を得ることができる。 The hydrocarbon groups of R 1, R 2 and the carbon number of 1 to 20 enumerated in R, a chain hydrocarbon group having 1 to 20 carbon atoms, and alicyclic hydrocarbon group having 3-20 carbon atoms preferable. Thus, the hydrocarbon group having 1 to 20 carbon atoms listed as R 1 , R 2 and R is a chain hydrocarbon group having 1 to 20 carbon atoms, or an alicyclic hydrocarbon group having 3 to 20 carbon atoms By doing this, it is possible to obtain a polymer with a low dielectric constant, which is excellent in heat resistance and solubility in solvents and alkaline developers.
　上記炭素数１～２０の鎖状炭化水素基としては、例えば、メチル基、エチル基、ｉ－プロピル基、ｎ－プロピル基、ｉ－ブチル基、ｓｅｃ－ブチル基、ｔ－ブチル基、ｎ－ブチル基、ｎ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、ｎ－オクチル基、ｎ－デシル基等の鎖状飽和炭化水素基；エテニル基、プロピニル基、エチニル基等の鎖状不飽和炭化水素基が挙げられる。これらのうち、鎖状飽和炭化水素基がより好ましい。 Examples of the above linear hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, i-propyl group, n-propyl group, i-butyl group, sec-butyl group, t-butyl group, n- Linear saturated hydrocarbon groups such as butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl and n-decyl; and linear unsaturated such as ethenyl, propynyl and ethynyl A hydrocarbon group is mentioned. Among these, chain saturated hydrocarbon groups are more preferable.
　上記炭素数３～２０の脂環式炭化水素基としては、例えば、シクロブチル基、シクロペンチル基、シクロへキシル基、シクロオクチル基、アダマンチル基等の脂環式飽和炭化水素基；シクロブテニル基、シクロペンテニル基等の脂環式不飽和炭化水素基が挙げられる。これらのうち、脂環式飽和炭化水素基が好ましい。 Examples of the alicyclic hydrocarbon group having 3 to 20 carbon atoms include alicyclic saturated hydrocarbon groups such as cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclooctyl group, adamantyl group and the like; cyclobutenyl group and cyclopentenyl group And alicyclic unsaturated hydrocarbon groups such as groups. Among these, alicyclic saturated hydrocarbon groups are preferable.
　上記置換炭化水素基１としては、例えば、メチルエステルメチル基、エチルエステルメチル基、プロピルエステルメチル基等のアルキルエステルアルキル基、メチルエーテルメチル基、エチルエーテルメチル基、プロピルエーテルメチル基等のアルキルエーテルアルキル基が挙げられる。 Examples of the substituted hydrocarbon group 1 include alkyl ester alkyl groups such as methyl ester methyl group, ethyl ester methyl group and propyl ester methyl group, and alkyl ethers such as methyl ether methyl group, ethyl ether methyl group and propyl ether methyl group An alkyl group is mentioned.
　上記置換炭化水素基２において水素原子の一部を置換する置換基としては、例えば、ハロゲン原子（フッ素原子、塩素原子、臭素原子、ヨウ素原子）、ハロゲン化アルキル基が挙げられる。 As a substituent which substitutes a part of hydrogen atom in the said substituted hydrocarbon group 2, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom) and a halogenated alkyl group are mentioned, for example.
　Ｒ1およびＲ2は、相互に結合してＯＲ1およびＯＲ2が結合するホウ素原子と共に環員数３～２０、好ましくは環員数３～１５の環状構造を形成してもよい。前記環状構造を形成する式（ｉ）で表される部分構造としては、例えば、下記式（１０）および（１１）で表される部分構造が挙げられる。 R 1 and R 2 may combine with each other to form a cyclic structure having 3 to 20, preferably 3 to 15 ring members, together with the boron atom to which OR 1 and OR 2 are bonded. As a partial structure represented by Formula (i) which forms the said cyclic structure, the partial structure represented by following formula (10) and (11) is mentioned, for example.
Figure JPOXMLDOC01-appb-C000021
 　上記式（１０）および（１１）中、Ｒrは、炭素数２～２０の２価の炭化水素基、前記炭素数２～２０の２価の炭化水素基中の少なくとも１つの炭素－炭素結合間にＮＲ100基を有する基（前記Ｒ100は、水素原子または炭素数１～２０の炭化水素基である）、または前記炭素数２～２０の２価の炭化水素基中の水素原子の一部が、ハロゲン原子、アルコキシ基およびアルコキシカルボニル基から選ばれる少なくとも１種で置換された基であり、前記ＮＲ100基はホウ素原子の空軌道に配位結合していてもよい。＊は結合手を示す。Ｒrにおける前記２価の炭化水素基は、好ましくは２価の鎖状飽和炭化水素基または脂環式飽和炭化水素基であり、より好ましくは炭素数２～１０の２価の鎖状飽和炭化水素基または炭素数４～１０の２価の脂環式飽和炭化水素基である。Ｒ100における前記炭素数１～２０の炭化水素基は、前述した置換炭化水素基１中のＲにおける炭化水素基と同様である。
Figure JPOXMLDOC01-appb-C000021
 In the above formulas (10) and (11), R r represents a divalent hydrocarbon group having 2 to 20 carbon atoms, at least one carbon-carbon bond in the divalent hydrocarbon group having 2 to 20 carbon atoms. Of the hydrogen atoms in the group having an NR 100 group between them (the R 100 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms), or the divalent hydrocarbon group having 2 to 20 carbon atoms The moiety is a group substituted with at least one member selected from a halogen atom, an alkoxy group and an alkoxycarbonyl group, and the NR 100 group may be coordinately bonded to an empty orbital of a boron atom. * Indicates a bonding hand. The divalent hydrocarbon group in R r is preferably a divalent chain saturated hydrocarbon group or an alicyclic saturated hydrocarbon group, and more preferably a divalent chain saturated carbonization having 2 to 10 carbon atoms It is a hydrogen group or a divalent alicyclic saturated hydrocarbon group having 4 to 10 carbon atoms. The hydrocarbon group having 1 to 20 carbon atoms in R 100 is the same as the hydrocarbon group in R in the substituted hydrocarbon group 1 described above.
　Ｒ1およびＲ2は、耐熱性の観点から、水素原子が好ましい。 R 1 and R 2 are preferably hydrogen atoms from the viewpoint of heat resistance.
　構造単位（ｉ）としては、例えば、下記式（１）で表される構造単位が挙げられる。 Examples of the structural unit (i) include structural units represented by the following formula (1).
Figure JPOXMLDOC01-appb-C000022
 　式（１）中の記号の意味は以下のとおりである。
Figure JPOXMLDOC01-appb-C000022
 The meanings of the symbols in the formula (1) are as follows.
　Ｒ1およびＲ2は、それぞれ式（ｉ）中の同一記号と同義である。 R 1 and R 2 each have the same meaning as the same symbol in formula (i).
　Ｒ11は、水素原子、フッ素原子、炭素数１～１０の炭化水素基、または炭素数１～１０のフッ素化炭化水素基である。Ｌ1は、単結合、酸素原子、硫黄原子、または－Ｃ（＝Ｏ）－Ｘ1－で表される基であり、Ｘ1は、酸素原子、硫黄原子またはＮＨ基である。Ｒ12は、炭素数１～２０の（ａ＋１）価の炭化水素基、前記炭化水素基中の少なくとも１つの炭素－炭素結合間に、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＳＯ2－、－ＳＯ3－、－ＯＳＯ2ＮＲ101－、－ＮＲ101ＳＯ2－、－ＮＲ101ＣＯ－、－ＮＲ101－および－ＣＯＮＲ101－から選ばれる少なくとも一種を有する基、またはこれらの基中の水素原子の一部が置換された基であり、前記Ｒ101は、水素原子または炭素数１～２０の炭化水素基である。水素原子の一部を置換する置換基としては、例えば、ハロゲン原子（フッ素原子、塩素原子、臭素原子、ヨウ素原子）、ハロゲン化アルキル基が挙げられる。ａは１～３の整数であり、好ましくは１である。 R 11 is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluorinated hydrocarbon group having 1 to 10 carbon atoms. L 1 is a single bond, an oxygen atom, a sulfur atom, or a group represented by —C (= O) —X 1 —, and X 1 is an oxygen atom, a sulfur atom or an NH group. R 12 represents an (a + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, and at least one carbon-carbon bond in the hydrocarbon group, —O—, —COO—, —OCO—, —OSO 2 -, -SO 3- , -OSO 2 NR 101- , -NR 101 SO 2- , -NR 101 CO-, -NR 101 -and -CONR 101- , or a group having at least one selected from these groups And R 101 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. As a substituent which substitutes a part of hydrogen atom, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a halogenated alkyl group is mentioned, for example. a is an integer of 1 to 3, preferably 1.
　上記Ｒ11の炭素数１～１０の炭化水素基としては、例えば、炭素数１～１０の鎖状炭化水素基、炭素数３～１０の脂環式炭化水素基が挙げられ、鎖状炭化水素基が好ましく、メチル基、エチル基がより好ましい。 Examples of the hydrocarbon group having 1 to 10 carbon atoms of R 11 include, for example, a chain hydrocarbon group having 1 to 10 carbon atoms and an alicyclic hydrocarbon group having 3 to 10 carbon atoms, and a chain hydrocarbon A group is preferable, and a methyl group and an ethyl group are more preferable.
　上記Ｒ11の炭素数１～１０のフッ素化炭化水素基としては、例えば、炭素数１～１０のフッ素化鎖状炭化水素基、炭素数３～１０のフッ素化脂環式炭化水素基が挙げられ、フッ素化鎖状炭化水素基が好ましく、トリフルオロメチル基がより好ましい。 Examples of the fluorinated hydrocarbon group having 1 to 10 carbon atoms of R 11 include a fluorinated chain hydrocarbon group having 1 to 10 carbon atoms, and a fluorinated alicyclic hydrocarbon group having 3 to 10 carbon atoms. Preferred is a fluorinated chain hydrocarbon group, and more preferred is a trifluoromethyl group.
　上記Ｒ11としては、水素原子が好ましい。 As the R 11, a hydrogen atom is preferable.
　上記Ｒ12の炭素数１～２０の（ａ＋１）価の炭化水素基としては、例えば、メチレン基、およびエチレン基等のアルカンジイル基等の鎖状飽和炭化水素基、シクロペンタンジイル基、シクロヘキサンジイル基、ノルボルナンジイル基、テトラシクロドデカンジイル基等のシクロアルカンジイル基、およびフェニレン基等のアリーレン基が挙げられる。 Examples of the (a + 1) -valent hydrocarbon group having 1 to 20 carbon atoms of R 12 include linear saturated hydrocarbon groups such as methylene and alkanediyl such as ethylene, cyclopentadiyl, cyclohexanediyl And cycloalkanediyl groups such as norbornanediyl group and tetracyclododecanediyl group, and arylene groups such as phenylene group.
　構造単位（ｉ）としては、例えば、下記式（１２）～（２２）で表される構造単位が挙げられる。 Examples of the structural unit (i) include structural units represented by the following formulas (12) to (22).
Figure JPOXMLDOC01-appb-C000023
 　《構造単位（ii）》
　重合体（Ａ）は、下記式（ii-1）で表される部分構造を有する構造単位（ii-1）、およびフェノール性水酸基を有する構造単位（ii-2）から選択される一以上の構造単位（ii）を含む。
Figure JPOXMLDOC01-appb-C000023
 << Structural unit (ii) >>
The polymer (A) is one or more selected from a structural unit (ii-1) having a partial structure represented by the following formula (ii-1), and a structural unit (ii-2) having a phenolic hydroxyl group Contains structural unit (ii).
　まず、構造単位（ii-1）について説明する。 First, structural unit (ii-1) will be described.
　重合体（Ａ）は、構造単位（ｉ）を含む分子と同一のまたは異なる分子中に、下記式（ii-1）で表される部分構造を有する構造単位（ii-1）をさらに含むことができる。これらの中でも重合体（Ａ）は同一分子中に構造単位（ｉ）と構造単位（ii-1）とを含むことが好ましい。 The polymer (A) further comprises a structural unit (ii-1) having a partial structure represented by the following formula (ii-1) in the same or different molecule as the molecule containing the structural unit (i) Can. Among these, the polymer (A) preferably contains the structural unit (i) and the structural unit (ii-1) in the same molecule.
Figure JPOXMLDOC01-appb-C000024
 　式（ii-1）中の記号の意味は以下のとおりである。
Figure JPOXMLDOC01-appb-C000024
 The meanings of the symbols in the formula (ii-1) are as follows.
　Ｒ3およびＲ4は、各々独立に、水素原子、炭素数１～２０の炭化水素基、または電子求引性基であり、但し、上記Ｒ3およびＲ4のうち、少なくともいずれかは電子求引性基であり、いずれも電子求引性基が好ましく、＊は結合手を示す。 R 3 and R 4 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an electron-withdrawing group, provided that at least one of R 3 and R 4 is an electron-accepting group It is an attractive group, and any of them is preferably an electron attractive group, and * represents a bond.
　上記炭素数１～２０の炭化水素基としては、式（ｉ）中のＲ1およびＲ2の炭素数１～２０の炭化水素基と同様である。 The hydrocarbon group having 1 to 20 carbon atoms is the same as the hydrocarbon group having 1 to 20 carbon atoms of R 1 and R 2 in the formula (i).
　上記Ｒ3およびＲ4のうち、少なくともいずれかが電子求引性基であることにより、樹脂組成物の保存安定性、重合体（Ａ）のアルカリ溶解性が向上するため好ましい。上記電子求引性基としては、例えば、フッ素原子、塩素原子、臭素原子、ヨウ素原子等のハロゲン原子；シアノ基；フッ素化アルキル基等のフッ素化炭化水素基が挙げられる。 When at least one of R 3 and R 4 is an electron-withdrawing group, the storage stability of the resin composition and the alkali solubility of the polymer (A) are preferably improved. Examples of the electron withdrawing group include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; cyano groups; fluorinated hydrocarbon groups such as fluorinated alkyl group.
　上記フッ素化炭化水素基は、炭化水素基中の水素原子の一部または全部がフッ素原子で置換された基である。フッ素化炭化水素基としては、炭素数１～２０のフッ素化炭化水素基が好ましく、炭素数１～２０のフッ素化アルキル基がより好ましく、炭素数１～１０のフッ素化アルキル基がより好ましい。 The fluorinated hydrocarbon group is a group in which part or all of hydrogen atoms in a hydrocarbon group are substituted with a fluorine atom. As the fluorinated hydrocarbon group, a fluorinated hydrocarbon group having 1 to 20 carbon atoms is preferable, a fluorinated alkyl group having 1 to 20 carbon atoms is more preferable, and a fluorinated alkyl group having 1 to 10 carbon atoms is more preferable.
　電子求引性基としては、これらの中で、フッ素原子、シアノ基、フッ素化アルキル基が好ましく、フッ素原子、シアノ基、トリフルオロメチル基、ヘキサフルオロイソプロピル基がより好ましい。 Among these, a fluorine atom, a cyano group and a fluorinated alkyl group are preferable as the electron-withdrawing group, and a fluorine atom, a cyano group, a trifluoromethyl group and a hexafluoroisopropyl group are more preferable.
　重合体（Ａ）は、１種または２種以上の構造単位（ii-1）を含むことができる。 The polymer (A) can contain one or more structural units (ii-1).
　構造単位（ii-1）は、樹脂組成物の保存安定性、重合体（Ａ）のアルカリ溶解性、樹脂膜の疎水性および低誘電率性に寄与する。 The structural unit (ii-1) contributes to the storage stability of the resin composition, the alkali solubility of the polymer (A), the hydrophobicity of the resin film and the low dielectric constant.
　構造単位（ii-1）としては、例えば、下記式（２）で表される構造単位が挙げられる。 Examples of the structural unit (ii-1) include structural units represented by the following formula (2).
Figure JPOXMLDOC01-appb-C000025
 　式（２）中の記号の意味は以下のとおりである。
Figure JPOXMLDOC01-appb-C000025
 The meanings of the symbols in the formula (2) are as follows.
　Ｒ3およびＲ4は、それぞれ式（ii-1）中の同一記号と同義である。Ｒ13は、水素原子、フッ素原子、炭素数１～１０の炭化水素基、または炭素数１～１０のフッ素化炭化水素基である。Ｌ2は、単結合、酸素原子、硫黄原子、または－Ｃ（＝Ｏ）－Ｘ2－で表される基であり、Ｘ2は、酸素原子、硫黄原子またはＮＨ基である。Ｒ14は、炭素数１～２０の（ｂ＋１）価の炭化水素基、前記炭化水素基中の少なくとも１つの炭素－炭素結合間に、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＳＯ2－、－ＳＯ3－、－ＯＳＯ2ＮＲ102－、－ＮＲ102ＳＯ2－、－ＮＲ102ＣＯ－、－ＮＲ102－および－ＣＯＮＲ102－から選ばれる少なくとも一種を有する基、またはこれらの基中の水素原子の一部が置換された基であり、前記Ｒ102は、水素原子または炭素数１～２０の炭化水素基である。ｂは１～３の整数であり、好ましくは１である。Ｒ13およびＲ14の具体例、好適例および好適理由は、それぞれ式（１）中のＲ11およびＲ12と同様である。 R 3 and R 4 each have the same meaning as the same symbol in formula (ii-1). R 13 is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluorinated hydrocarbon group having 1 to 10 carbon atoms. L 2 is a single bond, an oxygen atom, a sulfur atom, or a group represented by —C (= O) —X 2 —, and X 2 is an oxygen atom, a sulfur atom or an NH group. R 14 represents a (b + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, and at least one carbon-carbon bond in the hydrocarbon group, —O—, —COO—, —OCO—, —OSO 2 -, - SO 3 -, - OSO 2 NR 102 -, - NR 102 SO 2 -, - NR 102 CO -, - NR 102 - and -CONR 102 - group having at least one selected from or in these groups, And R 102 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. b is an integer of 1 to 3, preferably 1. Specific examples, preferred examples and preferred reasons for R 13 and R 14 are the same as R 11 and R 12 in the formula (1), respectively.
　構造単位（ii-1）としては、例えば、下記式で表される構造単位（２３）～（２８）が挙げられる。 Examples of the structural unit (ii-1) include structural units (23) to (28) represented by the following formulas.
Figure JPOXMLDOC01-appb-C000026
 　上記式中のＲ13は、それぞれ式（２）中の同一記号と同義である。
Figure JPOXMLDOC01-appb-C000026
 R < 13 > in said Formula is synonymous with the same symbol in Formula (2), respectively.
　次に、構造単位（ii-2）について説明する。 Next, structural unit (ii-2) will be described.
　重合体（Ａ）は、構造単位（ｉ）を含む分子と同一のまたは異なる分子中に、フェノール性水酸基を有する構造単位（ii-2）をさらに含むことができる。これらの中でも重合体（Ａ）は同一分子中に構造単位（ｉ）と構造単位（ii-2）とを含むことが好ましい。 The polymer (A) can further include a structural unit (ii-2) having a phenolic hydroxyl group in the same or different molecule as the molecule containing the structural unit (i). Among these, the polymer (A) preferably contains the structural unit (i) and the structural unit (ii-2) in the same molecule.
　重合体（Ａ）は、１種または２種以上の構造単位（ii-2）を含むことができる。 The polymer (A) can contain one or more structural units (ii-2).
　構造単位（ii-2）は、重合体（Ａ）のアルカリ溶解性、樹脂組成物の保存安定性および相溶性、樹脂膜の密着性および機械的強度に寄与する。また、構造単位（ii-2）を有する重合体（Ａ）を用いた場合には、耐溶剤性および熱溶融性に優れる樹脂膜を得ることができる。 The structural unit (ii-2) contributes to the alkali solubility of the polymer (A), the storage stability and compatibility of the resin composition, and the adhesion and mechanical strength of the resin film. When the polymer (A) having the structural unit (ii-2) is used, a resin film having excellent solvent resistance and heat melting property can be obtained.
　フェノール性水酸基を有する構造単位（ii-2）としては、具体的には、フェノール性水酸基含有不飽和化合物由来の構造単位が挙げられる。 Specific examples of the structural unit (ii-2) having a phenolic hydroxyl group include structural units derived from a phenolic hydroxyl group-containing unsaturated compound.
　フェノール性水酸基含有不飽和化合物としては、例えば、２－ヒドロキシフェニル（メタ）アクリレート、２－ヒドロキシフェニル（メタ）アクリルアミド等の加熱により環化してフェノール性水酸基が消失するフェノール性水酸基含有不飽和化合物；３－ヒドロキシフェニル（メタ）アクリレート、４－ヒドロキシフェニル（メタ）アクリレート、２，６－ジメチル－４－ヒドロキシフェニル（メタ）アクリレート、３－ヒドロキシフェニル（メタ）アクリルアミド、４－ヒドロキシフェニル（メタ）アクリルアミド、２，６－ジメチル－４－ヒドロキシフェニル（メタ）アクリルアミド、２－ヒドロキシスチレン、３－ヒドロキシスチレン、４－ヒドロキシスチレン、２，６－ジメチル－４－ヒドロキシスチレン等のその他フェノール性水酸基含有不飽和化合物が挙げられる。これらの中では、加熱により環化してフェノール性水酸基が消失し吸湿性がなくなり、如いては低誘電な樹脂膜が得られること、ならびに共重合反応性および樹脂膜の耐溶剤性、誘電特性の観点から、２－ヒドロキシフェニルアクリルアミドまたは２－ヒドロキシフェニルアクリレート等の加熱により環化してフェノール性水酸基が消失するフェノール性水酸基含有不飽和化合物が好ましい。 As the phenolic hydroxyl group-containing unsaturated compound, for example, a phenolic hydroxyl group-containing unsaturated compound which is cyclized by heating such as 2-hydroxyphenyl (meth) acrylate, 2-hydroxyphenyl (meth) acrylamide and the like and the phenolic hydroxyl group disappears; 3-hydroxyphenyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, 2,6-dimethyl-4-hydroxyphenyl (meth) acrylate, 3-hydroxyphenyl (meth) acrylamide, 4-hydroxyphenyl (meth) acrylamide Other phenols such as 2,6-dimethyl-4-hydroxyphenyl (meth) acrylamide, 2-hydroxystyrene, 3-hydroxystyrene, 4-hydroxystyrene, 2,6-dimethyl-4-hydroxystyrene Hydroxyl group-containing unsaturated compounds. Among these, cyclization by heating causes disappearance of the phenolic hydroxyl group and loss of hygroscopicity, and thus a low dielectric resin film is obtained, as well as copolymerization reactivity, solvent resistance of the resin film, and dielectric characteristics. From the viewpoint, it is preferable to use a phenolic hydroxyl group-containing unsaturated compound such as 2-hydroxyphenyl acrylamide or 2-hydroxyphenyl acrylate which is cyclized by heating to lose phenolic hydroxyl group.
　《構造単位（iii）》
　重合体（Ａ）は、構造単位（ｉ）および（ii）から選ばれる少なくとも１種の構造単位を含む分子と同一のまたは異なる分子中に、下記式（iii）で表される部分構造を有する構造単位（iii）をさらに含むことができる。これらの中でも重合体（Ａ）は同一分子中に構造単位（ｉ）と構造単位（ii）と構造単位（iii）とを含むことが好ましい。重合体（Ａ）は、１種または２種以上の構造単位（iii）を含むことができる。構造単位（iii）は、重合体（Ａ）のアルカリ溶解性、樹脂膜の密着性、機械的強度および耐熱性に寄与する。 << Structural unit (iii) >>
The polymer (A) has a partial structure represented by the following formula (iii) in the same or different molecule as a molecule containing at least one structural unit selected from structural units (i) and (ii) The structural unit (iii) can further be included. Among these, the polymer (A) preferably contains the structural unit (i), the structural unit (ii) and the structural unit (iii) in the same molecule. The polymer (A) can contain one or more structural units (iii). The structural unit (iii) contributes to the alkali solubility of the polymer (A), the adhesion of the resin film, the mechanical strength and the heat resistance.
Figure JPOXMLDOC01-appb-C000027
 　式（iii）中、Ｒ5は、炭素数１～２０の有機基（ただし、ＯＲ6に該当する基を除く）である。Ｒ6は、水素原子または炭素数１～２０の炭化水素基であり、ｎは０～３の整数であり、好ましくは０である。＊は結合手を示す。
Figure JPOXMLDOC01-appb-C000027
 In the formula (iii), R 5 is an organic group having 1 to 20 carbon atoms (with the exception of the group corresponding to OR 6 ). R 6 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, n is an integer of 0 to 3, and is preferably 0. * Indicates a bonding hand.
　「有機基」とは、少なくとも１個の炭素原子を含む基をいう。 "Organic group" refers to a group comprising at least one carbon atom.
　Ｒ5における炭素数１～２０の有機基としては、例えば、炭素数１～２０の鎖状炭化水素基、炭素数３～２０の脂環式炭化水素基等の炭素数１～２０の炭化水素基；前記炭素数１～２０の炭化水素基中の少なくとも１つの炭素－炭素結合間に、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＳＯ2－、－ＳＯ3－、－ＯＳＯ2ＮＲ103－、－ＮＲ103ＳＯ2－、－ＮＲ103ＣＯ－、－ＮＲ103－および－ＣＯＮＲ103－から選ばれる少なくとも一種を有する基；またはこれらの基中の水素原子の一部が置換された基が挙げられる。各基の具体例、好適例および好適理由は、式（ｉ）中のＲ1およびＲ2で説明した炭素数１～２０の炭化水素基、置換炭化水素基１および置換炭化水素基２と同様である。 The organic group having 1 to 20 carbon atoms as R 5 is, for example, a hydrocarbon having 1 to 20 carbon atoms, such as a linear hydrocarbon group having 1 to 20 carbon atoms or an alicyclic hydrocarbon group having 3 to 20 carbon atoms. groups; - between carbon bond, -O - at least one carbon in the hydrocarbon group of the carbon number of 1 ~ 20, - COO -, - OCO -, - OSO 2 -, - SO 3 -, - OSO 2 NR 103 -, - NR 103 SO 2 -, - NR 103 CO -, - NR 103 - and -CONR 103 - group having at least one selected from; or part of which is a substituent of the hydrogen atoms in these groups Can be mentioned. Specific examples, preferred examples and preferred reasons of each group are the same as the hydrocarbon group having 1 to 20 carbon atoms, substituted hydrocarbon group 1 and substituted hydrocarbon group 2 described for R 1 and R 2 in formula (i) It is.
　上記Ｒ6の炭素数１～２０の炭化水素基としては、炭素数１～２０の鎖状炭化水素基、炭素数３～２０の脂環式炭化水素基、炭素数６～２０の芳香族炭化水素基が挙げられる。 Examples of the hydrocarbon group having 1 to 20 carbon atoms of R 6 include a linear hydrocarbon group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and an aromatic carbon having 6 to 20 carbon atoms. A hydrogen group is mentioned.
　上記Ｒ6の炭素数１～２０の鎖状炭化水素基および炭素数３～２０の脂環式炭化水素基の具体例、好適例および好適理由は、式（ｉ）中のＲ1およびＲ2として説明した鎖状炭化水素基および脂環式炭化水素基と同様である。 Specific examples, preferred examples and preferred reasons for the linear hydrocarbon group having 1 to 20 carbon atoms and the alicyclic hydrocarbon group having 3 to 20 carbon atoms of R 6 are the groups represented by R 1 and R 2 in the formula (i) Are the same as the chain hydrocarbon group and the alicyclic hydrocarbon group described above.
　上記Ｒ6の炭素数６～２０の芳香族炭化水素基としては、例えば、フェニル基、トリル基、キシリル基、ナフチル基、アントリル基等のアリール基；ベンジル基、フェネチル基、ナフチルメチル基、アントリルメチル基等のアラルキル基が挙げられる。 Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms of R 6 include aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group and anthryl group; benzyl group, phenethyl group, naphthylmethyl group, an Aralkyl groups such as tolylmethyl group may be mentioned.
　構造単位（iii）としては、例えば、下記式（３）で表される構造単位が挙げられる。 As structural unit (iii), the structural unit represented by following formula (3) is mentioned, for example.
Figure JPOXMLDOC01-appb-C000028
 　式（３）中の記号の意味は以下のとおりである。
Figure JPOXMLDOC01-appb-C000028
 The meanings of the symbols in the formula (3) are as follows.
　Ｒ5、Ｒ6およびｎは、それぞれ式（iii）中の同一記号と同義である。Ｒ15は、水素原子、フッ素原子、炭素数１～１０の炭化水素基、または炭素数１～１０のフッ素化炭化水素基である。Ｌ3は、単結合、酸素原子、硫黄原子、または－Ｃ（＝Ｏ）－Ｘ3－で表される基であり、Ｘ3は、酸素原子、硫黄原子またはＮＨ基である。Ｒ16は、炭素数１～２０の（ｃ＋１）価の炭化水素基、前記炭化水素基中の少なくとも１つの炭素－炭素結合間に、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＳＯ2－、－ＳＯ3－、－ＯＳＯ2ＮＲ104－、－ＮＲ104ＳＯ2－、－ＮＲ104ＣＯ－、－ＮＲ104－および－ＣＯＮＲ104－から選ばれる少なくとも一種を有する基、またはこれらの基中の水素原子の一部が置換された基であり、前記Ｒ104は、水素原子または炭素数１～２０の炭化水素基である。ｃは１～３の整数であり、好ましくは１である。Ｒ15およびＲ16各基の具体例、好適例および好適理由は、それぞれ式（１）中のＲ11およびＲ12と同様である。 R 5 , R 6 and n each have the same meaning as the same symbol in formula (iii). R 15 is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluorinated hydrocarbon group having 1 to 10 carbon atoms. L 3 is a single bond, an oxygen atom, a sulfur atom, or a group represented by —C (= O) —X 3 —, and X 3 is an oxygen atom, a sulfur atom or an NH group. R 16 represents a (C + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, and at least one carbon-carbon bond in the hydrocarbon group, —O—, —COO—, —OCO—, —OSO 2 -, - SO 3 -, - OSO 2 NR 104 -, - NR 104 SO 2 -, - NR 104 CO -, - NR 104 - and -CONR 104 - group having at least one selected from or in these groups, And R 104 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. c is an integer of 1 to 3, preferably 1. Specific examples, preferred examples and preferred reasons for the R 15 and R 16 groups are the same as for R 11 and R 12 in the formula (1), respectively.
　構造単位（iii）としては、例えば、下記式で表される構造単位（２９）～（３４）が挙げられる。 Examples of the structural unit (iii) include structural units (29) to (34) represented by the following formula.
Figure JPOXMLDOC01-appb-C000029
 　上記式中のＲ15は、それぞれ式（３）中の同一記号と同義である。
Figure JPOXMLDOC01-appb-C000029
 R < 15 > in said Formula is synonymous with the same symbol in Formula (3), respectively.
　《構造単位（iv）》
　重合体（Ａ）は、構造単位（ｉ）および（ii）から選ばれる少なくとも１種の構造単位を含む分子と同一のまたは異なる分子中に、下記式（iv）で表される部分構造を有する構造単位（iv）をさらに含むことができる。これらの中でも重合体（Ａ）は同一分子中に構造単位（ｉ）と構造単位（ii）と構造単位（iv）とを含むことが好ましく、重合体（Ａ）が構造単位（iii）を含む場合は、同一分子中に構造単位（ｉ）と構造単位（ii）と構造単位（iii）と構造単位（iv）とを含むことが好ましい。重合体（Ａ）は、１種または２種以上の構造単位（iv）を含むことができる。構造単位（iv）は、樹脂組成物の保存安定性および相溶性、樹脂膜の密着性、耐熱透明性および老化防止性に寄与する。 << Structural unit (iv) >>
The polymer (A) has a partial structure represented by the following formula (iv) in the same or different molecule as a molecule containing at least one structural unit selected from structural units (i) and (ii) It can further comprise a structural unit (iv). Among these, the polymer (A) preferably contains the structural unit (i), the structural unit (ii) and the structural unit (iv) in the same molecule, and the polymer (A) contains the structural unit (iii) In the case where the structural unit (i), the structural unit (ii), the structural unit (iii) and the structural unit (iv) are contained in the same molecule, it is preferable. The polymer (A) can contain one or more structural units (iv). The structural unit (iv) contributes to the storage stability and compatibility of the resin composition, the adhesion of the resin film, the heat resistant transparency, and the antiaging property.
Figure JPOXMLDOC01-appb-C000030
 　式（iv）中の記号の意味は以下のとおりである。
Figure JPOXMLDOC01-appb-C000030
 The meanings of the symbols in formula (iv) are as follows.
　Ｒ7およびＲ8は、各々独立に、水素原子、炭素数１～２０の炭化水素基、前記炭素数１～２０の炭化水素基中の少なくとも１つの炭素－炭素結合間に、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＳＯ2－、－ＳＯ3－、－ＯＳＯ2ＮＲ105－、－ＮＲ105ＳＯ2－、－ＮＲ105ＣＯ－、－ＮＲ105－および－ＣＯＮＲ105－から選ばれる少なくとも一種を有する基、またはこれらの基中の水素原子の一部が置換された基を示し、Ｒ7およびＲ8は、相互に結合してＯＲ7およびＯＲ8が結合するリン原子と共に環員数３～２０の環状構造を形成してもよい。前記Ｒ105は、水素原子または炭素数１～２０の炭化水素基である。Ｒ7およびＲ8の各基の具体例は、それぞれ式（ｉ）中のＲ1およびＲ2と同様である。＊は結合手を示す。 R 7 and R 8 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, -O-, at least one carbon-carbon bond in the hydrocarbon group having 1 to 20 carbon atoms, -COO -, - OCO -, - OSO 2 -, - SO 3 -, - OSO 2 NR 105 -, - NR 105 SO 2 -, - NR 105 CO -, - is selected from - NR 105 - and -CONR 105 R 7 and R 8 represent a group having at least one group or a group in which a part of hydrogen atoms in these groups is substituted, and R 7 and R 8 together with the phosphorus atom to which OR 7 and OR 8 are bonded are the ring members together It may form 3 to 20 ring structures. The R 105 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Specific examples of each group of R 7 and R 8 are the same as R 1 and R 2 in the formula (i), respectively. * Indicates a bonding hand.
　Ｒ7およびＲ8は、相互に結合してＯＲ7およびＯＲ8が結合するリン原子と共に環員数３～２０、好ましくは環員数３～１５の環状構造を形成してもよい。前記環状構造を有する式（iv）で表される部分構造としては、例えば、下記式（３５）～（３６）で表される部分構造が挙げられる。 R 7 and R 8 may be combined with each other to form a cyclic structure having 3 to 20, preferably 3 to 15 ring members, together with the phosphorus atom to which OR 7 and OR 8 are bonded. Examples of the partial structure represented by the formula (iv) having a cyclic structure include partial structures represented by the following formulas (35) to (36).
Figure JPOXMLDOC01-appb-C000031
 　上記式（３５）および（３６）中、Ｒr1は、炭素数２～２０の２価の炭化水素基、または前記炭素数２～２０の２価の炭化水素基中の水素原子の一部が、ハロゲン原子、アルコキシ基およびアルコキシカルボニル基から選ばれる少なくとも１種で置換された基である。＊は結合手を示す。Ｒr1における前記２価の炭化水素基は、好ましくは２価の鎖状飽和炭化水素基または脂環式飽和炭化水素基であり、より好ましくは炭素数２～１０の２価の鎖状飽和炭化水素基または炭素数４～１０の２価の脂環式飽和炭化水素基である。
Figure JPOXMLDOC01-appb-C000031
 In the above formulas (35) and (36), R r1 is a divalent hydrocarbon group having 2 to 20 carbon atoms, or a part of hydrogen atoms in the divalent hydrocarbon group having 2 to 20 carbon atoms is And a group substituted with at least one selected from a halogen atom, an alkoxy group and an alkoxycarbonyl group. * Indicates a bonding hand. The divalent hydrocarbon group for R r1 is preferably a divalent chain saturated hydrocarbon group or an alicyclic saturated hydrocarbon group, and more preferably a divalent chain saturated carbonization having 2 to 10 carbon atoms It is a hydrogen group or a divalent alicyclic saturated hydrocarbon group having 4 to 10 carbon atoms.
　Ｒ7およびＲ8は、耐熱性、保存安定性の観点から、各々独立に、水素原子または炭素数１～２０の炭化水素基が好ましく、水素原子または炭素数１～２０の鎖状炭化水素基がより好ましく、水素原子、メチル基、エチル基、ｉ－プロピル基がさらに好ましい。 Each of R 7 and R 8 independently is preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms from the viewpoint of heat resistance and storage stability, and a hydrogen atom or a chain hydrocarbon group having 1 to 20 carbon atoms Is more preferable, and a hydrogen atom, a methyl group, an ethyl group and an i-propyl group are more preferable.
　構造単位（iv）としては、例えば、下記式（４）で表される構造単位が挙げられる。 Examples of the structural unit (iv) include structural units represented by the following formula (4).
Figure JPOXMLDOC01-appb-C000032
 　式（４）中の記号の意味は以下のとおりである。
Figure JPOXMLDOC01-appb-C000032
 The meanings of the symbols in the formula (4) are as follows.
　Ｒ7およびＲ8は、それぞれ式（iv）中の同一記号と同義である。Ｒ17は、水素原子、フッ素原子、炭素数１～１０の炭化水素基、または炭素数１～１０のフッ素化炭化水素基である。Ｌ4は、単結合、酸素原子、硫黄原子、または－Ｃ（＝Ｏ）－Ｘ4－で表される基であり、Ｘ4は、酸素原子、硫黄原子またはＮＨ基である。Ｒ18は、炭素数１～２０の（ｄ＋１）価の炭化水素基、前記炭化水素基中の少なくとも１つの炭素－炭素結合間に、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＳＯ2－、－ＳＯ3－、－ＯＳＯ2ＮＲ106－、－ＮＲ106ＳＯ2－、－ＮＲ106ＣＯ－、－ＮＲ106－および－ＣＯＮＲ106－から選ばれる少なくとも一種を有する基、またはこれらの基中の水素原子の一部が置換された基であり、前記Ｒ106は、水素原子または炭素数１～２０の炭化水素基である。ｄは１～３の整数であり、好ましくは１である。Ｒ17およびＲ18の各基の具体例、好適例および好適理由は、それぞれ式（１）中のＲ11およびＲ12と同様である。 R 7 and R 8 each have the same meaning as the same symbol in formula (iv). R 17 is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or a fluorinated hydrocarbon group having 1 to 10 carbon atoms. L 4 is a single bond, an oxygen atom, a sulfur atom, or a group represented by —C (= O) —X 4 —, and X 4 is an oxygen atom, a sulfur atom or an NH group. R 18 represents a (d + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, and at least one carbon-carbon bond in the hydrocarbon group, —O—, —COO—, —OCO—, —OSO 2 -, - SO 3 -, - OSO 2 NR 106 -, - NR 106 SO 2 -, - NR 106 CO -, - NR 106 - and -CONR 106 - group having at least one selected from or in these groups, And R 106 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. d is an integer of 1 to 3, preferably 1. Specific examples, preferred examples and preferred reasons for each group of R 17 and R 18 are the same as R 11 and R 12 in the formula (1), respectively.
　構造単位（iv）としては、例えば、下記式（３７）～（４５）で表される構造単位が挙げられる。 Examples of the structural unit (iv) include structural units represented by the following formulas (37) to (45).
Figure JPOXMLDOC01-appb-C000033
 　上記式中のＲ17は、それぞれ式（４）中の同一記号と同義である。
Figure JPOXMLDOC01-appb-C000033
 R 17 in the above-mentioned formula is respectively synonymous with the same symbol in formula (4).
　《構造単位（ｖ）》
　重合体（Ａ）は、構造単位（ｉ）および（ii）から選ばれる少なくとも１種の構造単位を含む分子と同一のまたは異なる分子中に、エポキシ基を有する構造単位（ｖ）をさらに含むことができる。これらの中でも重合体（Ａ）は同一分子中に構造単位（ｉ）と構造単位（ii）と構造単位（ｖ）とを含むことが好ましく、重合体（Ａ）が構造単位（iii）及び／又は（iv）を含む場合は、同一分子中に構造単位（ｉ）と構造単位（ii）と構造単位（iii）及び／又は（iv）と構造単位（ｖ）とを含むことが好ましい。重合体（Ａ）は、１種または２種以上の構造単位（ｖ）を含むことができる。構造単位（ｖ）は、樹脂組成物の保存安定性、樹脂膜の密着性および機械的強度に寄与する。 << Structural unit (v) >>
The polymer (A) further contains a structural unit (v) having an epoxy group in the same or different molecule as a molecule containing at least one structural unit selected from structural units (i) and (ii) Can. Among these, the polymer (A) preferably contains the structural unit (i), the structural unit (ii) and the structural unit (v) in the same molecule, and the polymer (A) is a structural unit (iii) and / or When it contains (iv), it is preferable to include structural unit (i), structural unit (ii), structural unit (iii) and / or (iv), and structural unit (v) in the same molecule. The polymer (A) can contain one or more structural units (v). The structural unit (v) contributes to the storage stability of the resin composition, the adhesion of the resin film and the mechanical strength.
　エポキシ基としては、例えば、オキシラニル基（１，２－エポキシ構造）、オキセタニル基（１，３－エポキシ構造）が挙げられる。エポキシ基を有する構造単位（ｖ）としては、具体的には、オキシラニル基含有不飽和化合物やオキセタニル基含有不飽和化合物等のエポキシ基含有不飽和化合物由来の構造単位が挙げられる。 Examples of the epoxy group include oxiranyl group (1,2-epoxy structure) and oxetanyl group (1,3-epoxy structure). Specific examples of the structural unit (v) having an epoxy group include structural units derived from epoxy group-containing unsaturated compounds such as oxiranyl group-containing unsaturated compounds and oxetanyl group-containing unsaturated compounds.
　オキシラニル基含有不飽和化合物としては、例えば、アクリル酸グリシジル、メタクリル酸グリシジル、メタクリル酸２－メチルグリシジル、α－エチルアクリル酸グリシジル、α－ｎ－プロピルアクリル酸グリシジル、α－ｎ－ブチルアクリル酸グリシジル、アクリル酸３，４－エポキシブチル、メタクリル酸３，４－エポキシブチル、アクリル酸６，７－エポキシヘプチル、メタクリル酸６，７－エポキシヘプチル、α－エチルアクリル酸－６，７－エポキシヘプチル、ｏ－ビニルベンジルグリシジルエーテル、ｍ－ビニルベンジルグリシジルエーテル、ｐ－ビニルベンジルグリシジルエーテル、メタクリル酸３，４－エポキシシクロへキシルメチルが挙げられる。 As the oxiranyl group-containing unsaturated compound, for example, glycidyl acrylate, glycidyl methacrylate, 2-methyl glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate Acrylic acid 3,4-epoxybutyl, methacrylic acid 3,4-epoxybutyl, acrylic acid 6,7-epoxyheptyl, methacrylic acid 6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, 3,4-epoxycyclohexyl methyl methacrylate.
　これらのうち、メタクリル酸グリシジル、メタクリル酸２－メチルグリシジル、メタクリル酸－６，７－エポキシヘプチル、ｏ－ビニルベンジルグリシジルエーテル、ｍ－ビニルベンジルグリシジルエーテル、ｐ－ビニルベンジルグリシジルエーテル、メタクリル酸３，４－エポキシシクロヘキシルが、共重合反応性および層間絶縁膜の耐溶剤性等の向上の観点から好ましい。 Among these, glycidyl methacrylate, 2-methyl glycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, methacrylic acid 3, 4-epoxycyclohexyl is preferable from the viewpoint of improving the copolymerization reactivity and the solvent resistance of the interlayer insulating film.
　オキセタニル基含有不飽和化合物としては、例えば、
　３－（アクリロイルオキシメチル）オキセタン、３－（アクリロイルオキシメチル）－２－メチルオキセタン、３－（アクリロイルオキシメチル）－３－エチルオキセタン、３－（アクリロイルオキシメチル）－２－トリフルオロメチルオキセタン、３－（アクリロイルオキシメチル）－２－ペンタフルオロエチルオキセタン、３－（アクリロイルオキシメチル）－２－フェニルオキセタン、３－（アクリロイルオキシメチル）－２，２－ジフルオロオキセタン、３－（アクリロイルオキシメチル）－２，２，４－トリフルオロオキセタン、３－（アクリロイルオキシメチル）－２，２，４，４－テトラフルオロオキセタン、３－（２－アクリロイルオキシエチル）オキセタン、３－（２－アクリロイルオキシエチル）－２－エチルオキセタン、３－（２－アクリロイルオキシエチル）－３－エチルオキセタン、３－（２－アクリロイルオキシエチル）－２－トリフルオロメチルオキセタン、３－（２－アクリロイルオキシエチル）－２－ペンタフルオロエチルオキセタン、３－（２－アクリロイルオキシエチル）－２－フェニルオキセタン、３－（２－アクリロイルオキシエチル）－２，２－ジフルオロオキセタン、３－（２－アクリロイルオキシエチル）－２，２，４－トリフルオロオキセタン、３－（２－アクリロイルオキシエチル）－２，２，４，４－テトラフルオロオキセタン等のアクリル酸エステル；
　３－（メタクリロイルオキシメチル）オキセタン、３－（メタクリロイルオキシメチル）－２－メチルオキセタン、３－（メタクリロイルオキシメチル）－３－エチルオキセタン、３－（メタクリロイルオキシメチル）－２－トリフルオロメチルオキセタン、３－（メタクリロイルオキシメチル）－２－ペンタフルオロエチルオキセタン、３－（メタクリロイルオキシメチル）－２－フェニルオキセタン、３－（メタクリロイルオキシメチル）－２，２－ジフルオロオキセタン、３－（メタクリロイルオキシメチル）－２，２，４－トリフルオロオキセタン、３－（メタクリロイルオキシメチル）－２，２，４，４－テトラフルオロオキセタン、３－（２－メタクリロイルオキシエチル）オキセタン、３－（２－メタクリロイルオキシエチル）－２－エチルオキセタン、３－（２－メタクリロイルオキシエチル）－３－エチルオキセタン、３－（２－メタクリロイルオキシエチル）－２－トリフルオロメチルオキセタン、３－（２－メタクリロイルオキシエチル）－２－ペンタフルオロエチルオキセタン、３－（２－メタクリロイルオキシエチル）－２－フェニルオキセタン、３－（２－メタクリロイルオキシエチル）－２，２－ジフルオロオキセタン、３－（２－メタクリロイルオキシエチル）－２，２，４－トリフルオロオキセタン、３－（２－メタクリロイルオキシエチル）－２，２，４，４－テトラフルオロオキセタン等のメタクリル酸エステル；が挙げられる。 Examples of the oxetanyl group-containing unsaturated compound include
3- (Acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (Acryloyloxymethyl) -2-pentafluoroethyl oxetane, 3- (acryloyloxymethyl) -2-phenyl oxetane, 3- (acryloyloxymethyl) -2,2-difluorooxetane, 3- (acryloyloxymethyl) -2,2,4-Trifluorooxetane, 3- (acryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (2-acryloyloxyethyl) oxetane, 3- (2-acryloyloxyethyl) ) -2-Ethyl oxeta 3- (2-acryloyloxyethyl) -3-ethyl oxetane, 3- (2-acryloyloxyethyl) -2-trifluoromethyl oxetane, 3- (2-acryloyloxyethyl) -2-pentafluoroethyl oxetane, 3- (2-Acryloyloxyethyl) -2-phenyloxetane, 3- (2-acryloyloxyethyl) -2,2-difluorooxetane, 3- (2-acryloyloxyethyl) -2,2,4-trifluoro Acrylic acid esters such as oxetane, 3- (2-acryloyloxyethyl) -2,2,4,4-tetrafluorooxetane;
3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-methyl oxetane, 3- (methacryloyloxymethyl) -3-ethyl oxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyl oxetane, 3- (Methacryloyloxymethyl) -2-pentafluoroethyl oxetane, 3- (methacryloyloxymethyl) -2-phenyl oxetane, 3- (methacryloyloxymethyl) -2,2-difluorooxetane, 3- (methacryloyloxymethyl) -2,2,4-Trifluorooxetane, 3- (methacryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) -2-ethyl oxetane, 3- (2-methacryloyloxyethyl) -3-ethyl oxetane, 3- (2-methacryloyloxyethyl) -2-trifluoromethyl oxetane, 3- (2-methacryloyloxyethyl) -2- Pentafluoroethyl oxetane, 3- (2-methacryloyloxyethyl) -2-phenyl oxetane, 3- (2-methacryloyloxyethyl) -2,2-difluorooxetane, 3- (2-methacryloyloxyethyl) -2,2 And methacrylic acid esters such as 3,4-trifluorooxetane and 3- (2-methacryloyloxyethyl) -2,2,4,4-tetrafluorooxetane.
　これらのうち、３－（アクリロイルオキシメチル）－３－エチルオキセタン、３－（メタクリロイルオキシメチル）－３－エチルオキセタンが、共重合反応性、樹脂組成物の相溶性、および樹脂膜の耐溶剤性等の向上の観点から望ましい。 Among these, 3- (acryloyloxymethyl) -3-ethyl oxetane and 3- (methacryloyloxymethyl) -3-ethyl oxetane have copolymerization reactivity, compatibility of the resin composition, and solvent resistance of the resin film. It is desirable from the viewpoint of improvement of
　《重合体（Ａ）の構成》
　重合体（Ａ）において、式（ｉ）で表される部分構造を自己縮合させることにより、樹脂組成物を硬化させることができ、耐熱性向上に寄与すると推察される。式（ii-1）で表される部分構造は、保存時に式（ｉ）で表される部分構造の自己縮合を抑制し、樹脂組成物の保存安定性向上に寄与すると推察される。構造単位（ii-2）は、重合体（Ａ）のアルカリ溶解性の向上および樹脂膜の耐溶剤性などの架橋物性の向上に寄与すると推察される。式（iii）で表される部分構造を自己縮合させることにより、樹脂組成物を硬化させることができ、耐熱性向上に寄与すると推察される。式（iv）で表される部分構造を自己縮合させることにより、樹脂組成物を硬化させることができ、耐熱性向上に寄与すると推察される。 << Configuration of Polymer (A) >>
In the polymer (A), the resin composition can be cured by self-condensing the partial structure represented by the formula (i), which is presumed to contribute to the improvement of the heat resistance. The partial structure represented by the formula (ii-1) is considered to suppress the self-condensation of the partial structure represented by the formula (i) during storage and to contribute to the improvement of the storage stability of the resin composition. The structural unit (ii-2) is presumed to contribute to the improvement of the alkali solubility of the polymer (A) and the improvement of the crosslinking properties such as the solvent resistance of the resin film. By self-condensing the partial structure represented by Formula (iii), it is guessed that a resin composition can be hardened and it contributes to heat resistance improvement. By self-condensing the partial structure represented by Formula (iv), it is possible that the resin composition can be cured and contributes to the improvement of the heat resistance.
　重合体（Ａ）において、構造単位（ｉ）の含有割合は、通常は５～６０モル％、好ましくは５～４０モル％、さらに好ましくは５～２０モル％である。構造単位（ｉ）の含有割合が前記範囲にあると、樹脂組成物の保存安定性および塗布性、重合体（Ａ）のアルカリ溶解性、樹脂膜の機械的強度および耐熱性が向上する傾向にある。 In the polymer (A), the content ratio of the structural unit (i) is usually 5 to 60 mol%, preferably 5 to 40 mol%, more preferably 5 to 20 mol%. When the content of the structural unit (i) is in the above range, the storage stability and coatability of the resin composition, the alkali solubility of the polymer (A), and the mechanical strength and heat resistance of the resin film tend to be improved. is there.
　重合体（Ａ）において、構造単位（ii）の含有割合は、通常は５～９０モル％である。 In the polymer (A), the content ratio of the structural unit (ii) is usually 5-90 mol%.
　また、重合体（Ａ）が構造単位（ii-1）を含む場合には、構造単位（ii-1）の含有割合は、通常は５～９０モル％、好ましくは１０～８０モル％、さらに好ましくは２０～７０モル％である。構造単位（ii-1）の含有割合が前記範囲にあると、樹脂組成物の保存安定性、重合体（Ａ）のアルカリ溶解性、樹脂膜の疎水性および低誘電率性が向上する傾向にある。 When the polymer (A) contains the structural unit (ii-1), the content of the structural unit (ii-1) is usually 5 to 90 mol%, preferably 10 to 80 mol%, and more preferably Preferably, it is 20 to 70 mol%. When the content of the structural unit (ii-1) is in the above range, the storage stability of the resin composition, the alkali solubility of the polymer (A), the hydrophobicity and the low dielectric constant of the resin film tend to be improved. is there.
　また、重合体（Ａ）が構造単位（ii-2）を含む場合には、構造単位（ii-2）の含有割合は、通常は５～７０モル％、好ましくは１０～４０モル％、さらに好ましくは１５～３０モル％である。構造単位（ii-2）の含有割合が前記範囲にあると、樹脂組成物の相溶性、重合体（Ａ）のアルカリ溶解性、樹脂膜の低誘電率性が向上する傾向にある。 When the polymer (A) contains the structural unit (ii-2), the content ratio of the structural unit (ii-2) is usually 5 to 70 mol%, preferably 10 to 40 mol%, and further Preferably, it is 15 to 30 mol%. When the content of the structural unit (ii-2) is in the above range, the compatibility of the resin composition, the alkali solubility of the polymer (A), and the low dielectric constant of the resin film tend to be improved.
　また、重合体（Ａ）が構造単位（iii）を含む場合には、構造単位（iii）の含有割合は、通常は５～５０モル％、好ましくは５～４０モル％、さらに好ましくは５～３０モル％である。構造単位（iii）の含有割合が前記範囲にあると、重合体（Ａ）のアルカリ溶解性、樹脂膜の密着性、機械的強度および耐熱性が向上する傾向にある。 When the polymer (A) contains the structural unit (iii), the content of the structural unit (iii) is usually 5 to 50 mol%, preferably 5 to 40 mol%, more preferably 5 to 50 It is 30 mol%. When the content of the structural unit (iii) is in the above range, the alkali solubility of the polymer (A), the adhesion of the resin film, the mechanical strength and the heat resistance tend to be improved.
　また、重合体（Ａ）が構造単位（iv）を含む場合には、構造単位（iv）の含有割合は、通常は５～３０モル％、好ましくは５～２５モル％、さらに好ましくは１０～２０モル％である。構造単位（iv）の含有割合が前記範囲にあると、樹脂組成物の保存安定性および相溶性、樹脂膜の密着性、耐熱透明性および老化防止性が向上する傾向にある。 When the polymer (A) contains a structural unit (iv), the content ratio of the structural unit (iv) is usually 5 to 30 mol%, preferably 5 to 25 mol%, more preferably 10 to It is 20 mol%. When the content ratio of the structural unit (iv) is in the above range, the storage stability and compatibility of the resin composition, the adhesion of the resin film, the heat-resistant transparency and the antiaging properties tend to be improved.
　また、重合体（Ａ）が構造単位（ｖ）を含む場合には、構造単位（ｖ）の含有割合は、通常は５～４５モル％である。重合体（Ａ）が構造単位（ii-1）及び構造単位（ｖ）を含む場合には、構造単位（ｖ）の含有割合は、通常は５～４０モル％、好ましくは５～３５モル％、さらに好ましくは１０～３０モル％であり、重合体（Ａ）が構造単位（ii-2）及び構造単位（ｖ）を含む場合には、構造単位（ｖ）の含有割合は、通常は５～４５モル％、好ましくは１０～４５モル％、さらに好ましくは１５～４５モル％である。構造単位（ｖ）の含有割合が前記範囲にあると、樹脂組成物の塗布性および相溶性、樹脂膜の密着性および機械的強度が向上する傾向にある。 When the polymer (A) contains the structural unit (v), the content ratio of the structural unit (v) is usually 5 to 45 mol%. When the polymer (A) contains the structural unit (ii-1) and the structural unit (v), the content ratio of the structural unit (v) is usually 5 to 40 mol%, preferably 5 to 35 mol% And more preferably 10 to 30 mol%, and when the polymer (A) contains the structural unit (ii-2) and the structural unit (v), the content ratio of the structural unit (v) is usually 5 It is -45 mol%, preferably 10-45 mol%, more preferably 15-45 mol%. When the content ratio of the structural unit (v) is in the above range, the coating properties and compatibility of the resin composition, and the adhesion and mechanical strength of the resin film tend to be improved.
　重合体（Ａ）の各構造単位の含有割合は、重合体（Ａ）を構成する全構造単位中の値であり、13Ｃ－ＮＭＲにより測定することができる。 The content ratio of each structural unit of the polymer (A) is a value in all structural units constituting the polymer (A), and can be measured by 13 C-NMR.
　重合体（Ａ）のゲルパーミエーションクロマトグラフィー法により測定される重量平均分子量（Ｍｗ）は、樹脂組成物を硬化させて得られる樹脂膜の弾性率、クラック耐性、感光性組成物の解像性の観点から、ポリスチレン換算で、通常は１，０００～２００，０００、好ましくは２，０００～１００，０００、さらに好ましくは５，０００～５０，０００である。重合体（Ａ）の分子量分布（Ｍｗ／Ｍｎ；Ｍｎは数平均分子量）は、通常は１．０～１０．０、好ましくは１．０～５．０、より好ましくは１．０～３．０である。ＭｗおよびＭｎの測定方法の詳細は、実施例に記載したとおりである。 The weight average molecular weight (Mw) of the polymer (A) measured by gel permeation chromatography is the elastic modulus and crack resistance of the resin film obtained by curing the resin composition, and the resolution of the photosensitive composition. In terms of polystyrene, it is usually 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 5,000 to 50,000. The molecular weight distribution (Mw / Mn; Mn is a number average molecular weight) of the polymer (A) is usually 1.0 to 10.0, preferably 1.0 to 5.0, more preferably 1.0 to 3. It is 0. The details of the measurement methods of Mw and Mn are as described in the examples.
　重合体（Ａ）は１種で用いてもよく、２種以上を併用してもよい。 The polymer (A) may be used alone or in combination of two or more.
　重合体（Ａ）の含有割合は、本発明の樹脂組成物から溶媒（Ｅ）を除いた全成分の合計１００質量％に対して、通常は３０質量％以上、好ましくは４０質量％以上、さらに好ましくは５０質量％以上である。重合体（Ａ）の含有割合が前記範囲にあると、耐熱性に優れた樹脂膜を形成可能な樹脂組成物が得られる傾向にある。 The content of the polymer (A) is usually 30% by mass or more, preferably 40% by mass or more, based on 100% by mass in total of all components excluding the solvent (E) from the resin composition of the present invention Preferably it is 50 mass% or more. When the content ratio of the polymer (A) is in the above range, a resin composition capable of forming a resin film excellent in heat resistance tends to be obtained.
　重合体（Ａ）の含有割合は、本発明の感光性組成物から溶剤（Ｅ）を除いた全成分の合計１００質量％に対して、通常は３０～９９質量％、好ましくは４０～９８質量％、さらに好ましくは５０～９５質量％である。重合体（Ａ）の含有割合が前記範囲にあると、耐熱性に優れ、解像度が高いパターン化樹脂膜を形成可能な感光性組成物が得られる傾向にある。 The content of the polymer (A) is usually 30 to 99% by mass, preferably 40 to 98% by mass, based on 100% by mass in total of all components excluding the solvent (E) from the photosensitive composition of the present invention. %, More preferably 50 to 95% by mass. When the content ratio of the polymer (A) is in the above range, it tends to be possible to obtain a photosensitive composition capable of forming a patterned resin film having excellent heat resistance and high resolution.
　《重合体（Ａ）の合成方法》
　重合体（Ａ）は、例えば、重合開始剤や連鎖移動剤の存在下、重合溶媒中で、各構造単位を導く所定の単量体をラジカル重合等の重合をさせることによって合成することができる。例えば、反応容器内に単量体、重合開始剤および重合溶媒を仕込み、窒素ガス等の不活性ガス雰囲気下で、反応温度４０～１２０℃程度に加熱し、０．１～１０時間反応させる。 << Synthesis Method of Polymer (A) >>
The polymer (A) can be synthesized, for example, by polymerizing a predetermined monomer leading each structural unit in a polymerization solvent in the presence of a polymerization initiator or a chain transfer agent, such as radical polymerization. . For example, monomers, a polymerization initiator and a polymerization solvent are charged in a reaction vessel, heated to a reaction temperature of about 40 to 120 ° C., and reacted for 0.1 to 10 hours under an inert gas atmosphere such as nitrogen gas.
　上記重合開始剤としては、例えば、アゾ化合物、過酸化物化合物が挙げられる。上記重合開始剤は１種で用いてもよく、２種以上を併用してもよい。 As said polymerization initiator, an azo compound and a peroxide compound are mentioned, for example. The said polymerization initiator may be used by 1 type, and may use 2 or more types together.
　上記重合溶媒としては、例えば、
　メタノール、エタノール、１－プロパノール、２－プロパノール、１－ブタノール、２－ブタノール、エチレングリコール、ジエチレングリコール、プロピレングリコール等のアルコール類；
　テトラヒドロフラン、ジオキサン等の環状エーテル類；
　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エチルメチルエーテル、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等の多価アルコールのアルキルエーテル類；
　エチレングリコールエチルエーテルアセテート、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等の多価アルコールのアルキルエーテルアセテート類；
　トルエン、キシレン等の芳香族炭化水素類；
　アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン、４－ヒドロキシ－４－メチル－２－ペンタノン、ジアセトンアルコール等のケトン類；
　酢酸エチル、酢酸ブチル、２－ヒドロキシプロピオン酸メチル、２－ヒドロキシ－２－メチルプロピオン酸エチル、２－ヒドロキシ－２－メチルプロピオン酸エチル、エトキシ酢酸エチル、ヒドロキシ酢酸エチル、２－ヒドロキシ－３－メチルブタン酸メチル、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－エトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル等のエステル類が挙げられる。 As the above-mentioned polymerization solvent, for example,
Alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethylene glycol, diethylene glycol and propylene glycol;
Cyclic ethers such as tetrahydrofuran and dioxane;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl Alkyl ethers of polyhydric alcohols such as ether;
Alkyl ether acetates of polyhydric alcohols such as ethylene glycol ethyl ether acetate, diethylene glycol ethyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol monomethyl ether acetate;
Aromatic hydrocarbons such as toluene and xylene;
Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, diacetone alcohol;
Ethyl acetate, butyl acetate, methyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutane Esters such as methyl acid, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate and the like can be mentioned.
　これらのうち、環状エーテル類、多価アルコールのアルキルエーテル類、多価アルコールのアルキルエーテルアセテート類、ケトン類またはエステル類が好ましい。 Among these, cyclic ethers, alkyl ethers of polyhydric alcohols, alkyl ether acetates of polyhydric alcohols, ketones or esters are preferable.
　上記重合溶媒は１種で用いてもよく、２種以上を併用してもよい。 The polymerization solvents may be used alone or in combination of two or more.
　〈感光性酸発生剤（Ｂ）〉
　本発明の樹脂組成物は、感光性酸発生剤（Ｂ）を含有することができ、感光性酸発生剤（Ｂ）を含有することで感光性組成物となる。 <Photosensitive acid generator (B)>
The resin composition of the present invention can contain a photosensitive acid generator (B), and becomes a photosensitive composition by containing a photosensitive acid generator (B).
　感光性酸発生剤（Ｂ）は、光により酸を発生する化合物である。本発明の感光性組成物から形成された塗布膜に対する露光処理を含む処理によって、感光性酸発生剤（Ｂ）に基づき露光部に酸が発生し、この酸の作用に基づき露光部のアルカリ性現像液への溶解性が変化する。 The photosensitive acid generator (B) is a compound which generates an acid by light. An acid is generated in the exposed area on the basis of the photosensitive acid generator (B) by the treatment including the exposure treatment to the coating film formed from the photosensitive composition of the present invention, and the alkaline development of the exposed area on the basis of the action of this acid. The solubility in the liquid changes.
　前記感光性組成物は、ネガ型またはポジ型のいずれであってもよい。感光性酸発生剤（Ｂ）の種類は、ネガ型の組成物またはポジ型の組成物に応じて、適宜選択することができる。 The photosensitive composition may be either negative or positive. The kind of photosensitive acid generator (B) can be suitably selected according to a negative type composition or a positive type composition.
　感光性酸発生剤（Ｂ）としては、例えば、オニウム塩化合物、ハロゲン含有化合物、スルホン化合物、スルホン酸化合物、スルホンイミド化合物、ジアゾメタン化合物、キノンジアジド基を有する化合物が挙げられる。以下、キノンジアジド基を有する化合物を「キノンジアジド化合物（ｂ１）」ともいい、これ以外の前記例示の感光性酸発生剤を「酸発生剤（ｂ２）」ともいう。 As a photosensitive acid generator (B), an onium salt compound, a halogen containing compound, a sulfone compound, a sulfonic acid compound, a sulfone imide compound, a diazomethane compound, and a compound which has a quinone diazide group are mentioned, for example. Hereinafter, the compound having a quinone diazide group is also referred to as “quinone diazide compound (b1)”, and the photosensitive acid generators other than the above exemplified ones are also referred to as “acid generator (b2)”.
　《キノンジアジド化合物（ｂ１）》
　キノンジアジド化合物（ｂ１）は、光照射および水との接触処理により、キノンジアジド基が分解してカルボキシ基を生じる化合物である。キノンジアジド化合物（ｂ１）を含有する組成物から形成された塗布膜は、アルカリ性現像液に対して難溶な膜である。光照射および水との接触処理により前記膜がアルカリ難溶の状態からアルカリ易溶の状態になることを利用することにより、ポジ型のパターンが形成される。 << quinone diazide compound (b1) >>
The quinone diazide compound (b1) is a compound which decomposes a quinone diazide group to generate a carboxy group by light irradiation and contact treatment with water. The coating film formed from the composition containing the quinone diazide compound (b1) is a film which is hardly soluble in an alkaline developer. A positive pattern is formed by utilizing the fact that the film is in the state of low alkali solubility and is in the state of high alkali solubility by light irradiation and contact treatment with water.
　キノンジアジド化合物（ｂ１）としては、例えば、ナフトキノンジアジド化合物が挙げられ、具体的には、フェノール性水酸基を１つ以上有する化合物と、１，２－ナフトキノンジアジド－４－スルホン酸、１，２－ナフトキノンジアジド－５－スルホン酸、１，２－ナフトキノンジアジド－４－スルホン酸クロリドまたは１，２－ナフトキノンジアジド－５－スルホン酸クロリドとのエステル化合物が挙げられる。フェノール性水酸基を１つ以上有する化合物の具体例としては、例えば、特開２０１４－１８６３００号公報の段落［００６５］～［００７０］に記載された化合物が挙げられ、これらは本明細書に記載されているものとする。 Examples of the quinone diazide compound (b1) include naphthoquinone diazide compounds. Specifically, a compound having one or more phenolic hydroxyl groups, 1,2-naphthoquinone diazide-4-sulfonic acid, 1,2-naphtho Ester compounds with quinonediazide-5-sulfonic acid, 1,2-naphthoquinonediazide-4-sulfonic acid chloride or 1,2-naphthoquinonediazide-5-sulfonic acid chloride may be mentioned. Specific examples of the compound having one or more phenolic hydroxyl groups include, for example, compounds described in paragraphs [0065] to [0070] of JP-A-2014-186300, which are described in the present specification. It shall be.
　キノンジアジド化合物（ｂ１）としては、例えば、４，４'－ジヒドロキシジフェニルメタン、４，４'－ジヒドロキシジフェニルエーテル、２，３，４－トリヒドロキシベンゾフェノン、２，３，４，４'－テトラヒドロキシベンゾフェノン、２，３，４，２'，４'－ペンタヒドロキシベンゾフェノン、トリス（４－ヒドロキシフェニル）メタン、トリス（４－ヒドロキシフェニル）エタン、１，１－ビス（４－ヒドロキシフェニル）－１－フェニルエタン、１，３－ビス［１－（４－ヒドロキシフェニル）－１－メチルエチル］ベンゼン、１，４－ビス［１－（４－ヒドロキシフェニル）－１－メチルエチル］ベンゼン、４，６－ビス［１－（４－ヒドロキシフェニル）－１－メチルエチル］－１，３－ジヒドロキシベンゼンおよび１，１－ビス（４－ヒドロキシフェニル）－１－［４－［１－（４－ヒドロキシフェニル）－１－メチルエチル］フェニル］エタン（別名：４，４'－［１－［４－［１－（４－ヒドロキシフェニル）－１－メチルエチル］フェニル］エチリデン］ビスフェノール）から選ばれる化合物と、１，２－ナフトキノンジアジド－４－スルホン酸、１，２－ナフトキノンジアジド－５－スルホン酸、１，２－ナフトキノンジアジド－４－スルホン酸クロリドまたは１，２－ナフトキノンジアジド－５－スルホン酸クロリドとのエステル化合物が挙げられる。 Examples of the quinone diazide compound (b1) include 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, 2,3,4-trihydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2 , 3,4,2 ′, 4′-pentahydroxybenzophenone, tris (4-hydroxyphenyl) methane, tris (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 4,6-bis [ 1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene and 1,1 Bis (4-hydroxyphenyl) -1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethane (alias: 4,4 '-[1- [4- [1- (4) -Hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol), 1,2-naphthoquinonediazide-4-sulfonic acid, 1,2-naphthoquinonediazide-5-sulfonic acid, and 1,2- And ester compounds with naphthoquinone diazide-4-sulfonic acid chloride or 1,2-naphthoquinone diazide-5-sulfonic acid chloride.
　キノンジアジド化合物（ｂ１）は１種で用いてもよく、２種以上を併用してもよい。 The quinone diazide compound (b1) may be used alone or in combination of two or more.
　本発明の感光性組成物において、感光性酸発生剤（Ｂ）としてキノンジアジド化合物（ｂ１）を用いる場合、キノンジアジド化合物（ｂ１）の含有量は、重合体（Ａ）１００質量部に対して、好ましくは１～５０質量部、より好ましくは３～３０質量部、さらに好ましくは５～３０質量部である。キノンジアジド化合物（ｂ１）の含有量が前記下限値以上であると、未露光部の残膜率が向上し、マスクパターンに忠実な像が得られやすい。キノンジアジド化合物（ｂ１）の含有量が前記上限値以下であると、パターン形状に優れた樹脂膜が得られやすく、製膜時の発泡も防止できる傾向にある。 In the photosensitive composition of the present invention, when the quinone diazide compound (b1) is used as the photosensitive acid generator (B), the content of the quinone diazide compound (b1) is preferably 100 parts by mass of the polymer (A). Is preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, and still more preferably 5 to 30 parts by mass. When the content of the quinone diazide compound (b1) is at least the lower limit value, the residual film ratio in the unexposed area is improved, and an image faithful to the mask pattern is easily obtained. When the content of the quinone diazide compound (b1) is less than or equal to the above upper limit, a resin film having an excellent pattern shape can be easily obtained, and foaming at the time of film formation tends to be prevented.
　《キノンジアジド化合物（ｂ１）以外の酸発生剤（ｂ２）》
　酸発生剤（ｂ２）は、光照射により、酸を形成する化合物であってキノンジアジド化合物（ｂ１）以外の化合物である。酸発生剤（ｂ２）を含有する組成物から形成された塗布膜に対して光照射することで、発生する前記酸が重合体（Ａ）、後述する架橋剤（Ｃ）等に作用して架橋構造が形成され、アルカリ難溶な膜となる。光照射により前記膜がアルカリ易溶の状態からアルカリ難溶の状態に変化することを利用することにより、ネガ型のパターンが形成される。 << Acid Generator (b2) Other than Quinone Diazide Compound (b1) >>
The acid generator (b2) is a compound which forms an acid upon irradiation with light and is a compound other than the quinone diazide compound (b1). By irradiating the coating film formed from the composition containing the acid generator (b2) with light, the generated acid acts on the polymer (A), the crosslinking agent (C) described later, etc. to cause crosslinking. The structure is formed and the film becomes poorly soluble in alkali. A negative pattern is formed by utilizing the fact that the film changes from a state of easy alkali dissolution to a state of low alkali solubility by light irradiation.
　酸発生剤（ｂ２）は、例えば、ヨードニウム塩、スルホニウム塩、ホスホニウム塩、ジアゾニウム塩、ピリジニウム塩等のオニウム塩化合物；ハロアルキル基含有複素環式化合物、ハロアルキル基含有炭化水素化合物等のハロゲン含有化合物；β－ケトスルホン化合物、β－スルホニルスルホン化合物およびこれらの化合物のα－ジアゾ化合物等のスルホン化合物；アルキルスルホン酸エステル類、ハロアルキルスルホン酸エステル類、アリールスルホン酸エステル類、イミノスルホネート類等のスルホン酸化合物；スルホンイミド化合物；ジアゾメタン化合物が挙げられる。これらの化合物の具体例としては、例えば、特開２０１４－１８６３００号公報の段落［００７４］～［００７９］に記載された化合物が挙げられ、これらは本明細書に記載されているものとする。 Examples of the acid generator (b2) include onium salt compounds such as iodonium salts, sulfonium salts, phosphonium salts, diazonium salts and pyridinium salts; halogen-containing compounds such as haloalkyl group-containing heterocyclic compounds and haloalkyl group-containing hydrocarbon compounds; Sulfone compounds such as β-ketosulfone compounds, β-sulfonylsulfone compounds and α-diazo compounds of these compounds; Sulfonic acid compounds such as alkylsulfonic acid esters, haloalkylsulfonic acid esters, arylsulfonic acid esters, iminosulfonates and the like A sulfone imide compound; and a diazomethane compound. Specific examples of these compounds include, for example, compounds described in paragraphs [0074] to [0079] of JP-A-2014-186300, which are described in the present specification.
　オニウム塩の具体例としては、ジフェニルヨードニウムトリフルオロメタンスルホネート、ジフェニルヨードニウムｐ－トルエンスルホネート、ジフェニルヨードニウムヘキサフルオロアンチモネート、ジフェニルヨードニウムヘキサフルオロホスフェート、ジフェニルヨードニウムテトラフルオロボレート、トリフェニルスルホニウムトリフリオロメタンスルホネート、トリフェニルスルホニウムｐ－トルエンスルホネート、トリフェニルスルホニウムヘキサフルオロアンチモネート、４－ｔ－ブチルフェニル・ジフェニルスルホニウムトリフルオロメタンスルホネート、４－ｔ－ブチルフェニル・ジフェニルスルホニウムｐ－トルエンスルホネート、４，７－ジ－ｎ－ブトキシナフチルテトラヒドロチオフェニウムトリフルオロメタンスルホネート、４－（フェニルチオ）フェニルジフェニルスルホニウムトリス（ペンタフルオロエチル）トリフルオロホスフェート、４－（フェニルチオ）フェニルジフェニルスルホニウムヘキサフルオロホスファートが挙げられる。 Specific examples of onium salts include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, triphenylsulfonium trifluoromethanesulfonate, triphenyl Sulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, 4-tert-butylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-tert-butylphenyldiphenylsulfonium p-toluenesulfonate, 4,7-di-n-butoxy Naphthyltetrahydrothiophenium trifluoromethane Sulfonates, 4- (phenylthio) phenyl diphenyl sulfonium tris (pentafluoroethyl) trifluoro phosphate, 4- (phenylthio) phenyl diphenyl sulfonium hexafluorophosphate and the like.
　酸発生剤（ｂ２）は１種で用いてもよく、２種以上を併用してもよい。 The acid generator (b2) may be used alone or in combination of two or more.
　本発明の樹脂組成物において、感光性酸発生剤（Ｂ）として酸発生剤（ｂ２）を用いる場合、酸発生剤（ｂ２）の含有量は、重合体（Ａ）１００質量部に対して、好ましくは０．１～３０質量部、より好ましくは０．３～２０質量部、さらに好ましくは０．５～１５質量部である。酸発生剤（ｂ２）の含有量が前記下限値以上であると、露光部の硬化が充分となり、耐熱性が向上しやすい。酸発生剤（ｂ２）の含有量が前記上限値以下であると、露光光に対する透明性が低下することなく、解像度が高いパターン化樹脂膜が得られやすい。 In the resin composition of the present invention, when using an acid generator (b2) as the photosensitive acid generator (B), the content of the acid generator (b2) is 100 parts by mass of the polymer (A), The amount is preferably 0.1 to 30 parts by mass, more preferably 0.3 to 20 parts by mass, and still more preferably 0.5 to 15 parts by mass. When the content of the acid generator (b2) is equal to or more than the lower limit, curing of the exposed portion is sufficient, and heat resistance is likely to be improved. When the content of the acid generator (b2) is less than or equal to the above upper limit value, a patterned resin film having a high resolution can be easily obtained without decreasing the transparency to exposure light.
　〈架橋剤（Ｃ）〉
　本発明の樹脂組成物は、樹脂膜の硬化性を向上させるため、架橋剤（Ｃ）をさらに含有することができる。架橋剤（Ｃ）は、２個以上の重合可能な基又は反応可能な基を有する化合物である。架橋剤（Ｃ）は、重合体（Ａ）と、または架橋剤同士で反応する架橋成分（硬化成分）として作用する。重合可能な基又は反応可能な基としては、例えば、エチレン性不飽和基、オキシラニル基、オキセタニル基、オキサゾリニル基、イソシアネート基、Ｎ－アルコキシアルキルアミノ基、メチロール基、アルキルメチロール基が挙げられる。 <Crosslinking agent (C)>
The resin composition of the present invention can further contain a crosslinking agent (C) in order to improve the curability of the resin film. The crosslinking agent (C) is a compound having two or more polymerizable groups or reactive groups. The crosslinking agent (C) acts as a crosslinking component (curing component) that reacts with the polymer (A) or with each other. Examples of the polymerizable group or the reactable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, an oxazolinyl group, an isocyanate group, an N-alkoxyalkylamino group, a methylol group and an alkylmethylol group.
　架橋剤（Ｃ）としては、例えば、２個以上の（メタ）アクリロイル基を有する化合物、２個以上のＮ－アルコキシアルキルアミノ基を有する化合物、メチロール基含有フェノール化合物、アルキルメチロール基含有フェノール化合物、オキシラン環含有化合物、オキセタン環含有化合物、オキサゾリン環含有化合物、イソシアネート基含有化合物（ブロック化されたものを含む）、アルデヒド基含有フェノール化合物が挙げられ、２個以上の（メタ）アクリロイル基を有する化合物、および２個以上のＮ－アルコキシアルキルアミノ基を有する化合物が好ましい。 As the crosslinking agent (C), for example, a compound having two or more (meth) acryloyl groups, a compound having two or more N-alkoxyalkylamino groups, a methylol group-containing phenol compound, an alkylmethylol group-containing phenol compound, And oxirane ring-containing compounds, oxetane ring-containing compounds, oxazoline ring-containing compounds, isocyanate group-containing compounds (including those which are blocked), aldehyde group-containing phenol compounds, and compounds having two or more (meth) acryloyl groups And compounds having two or more N-alkoxyalkylamino groups are preferred.
　２個以上の（メタ）アクリロイル基を有する化合物としては、例えば、２官能（メタ）アクリル酸エステルや、３官能以上の（メタ）アクリル酸エステル等の多官能（メタ）アクリル酸エステルが挙げられる。 Examples of the compound having two or more (meth) acryloyl groups include bifunctional (meth) acrylic esters, and polyfunctional (meth) acrylic esters such as trifunctional or higher functional (meth) acrylic esters. .
　２官能（メタ）アクリル酸エステルとしては、例えば、エチレングリコールジ（メタ）アクリレート、プロピレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、テトラエチレングリコールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレートが挙げられる。 Examples of difunctional (meth) acrylic acid esters include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexane Diol di (meth) acrylate and 1,9-nonanediol di (meth) acrylate are mentioned.
　３官能以上の（メタ）アクリル酸エステルとしては、例えば、トリメチロールプロパントリ（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、ペンタエリスリトールテトラ（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、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）アクリレートとジペンタエリスリトールヘキサ（メタ）アクリレートとの混合物、エチレンオキサイド変性ジペンタエリスリトールヘキサ（メタ）アクリレート、トリ（２－（メタ）アクリロイルオキシエチル）フォスフェート、コハク酸変性ペンタエリスリトールトリ（メタ）アクリレート、コハク酸変性ジペンタエリスリトールペンタ（メタ）アクリレートの他、直鎖アルキレン基及び脂環式構造を有し、かつ２個以上のイソシアネート基を有する化合物と、分子内に１個以上のヒドロキシ基を有し、かつ３個、４個又は５個の（メタ）アクリロイルオキシ基を有する化合物とを反応させて得られる多官能ウレタン（メタ）アクリレート系化合物が挙げられる。 Examples of trifunctional or higher (meth) acrylic acid esters include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Pentaerythritol hexa (meth) acrylate, a mixture of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, tri (2- (meth) acryloyloxy Other than ethyl) phosphate, succinic acid modified pentaerythritol tri (meth) acrylate, succinic acid modified dipentaerythritol penta (meth) acrylate, A compound having a chain alkylene group and an alicyclic structure and having two or more isocyanate groups, and one, three or more hydroxy groups in the molecule and three, four or five (meth) The polyfunctional urethane (meth) acrylate type compound obtained by making it react with the compound which has an acryloyloxy group is mentioned.
　２個以上のＮ－アルコキシアルキルアミノ基を有する化合物としては、アルキルエーテル化されたアミノ基を２つ以上有する化合物（以下「アミノ基含有化合物」ともいう）が挙げられ、アルキルエーテル化されたアミノ基は、例えば、下記式で表される基である。 Examples of the compound having two or more N-alkoxyalkylamino groups include compounds having two or more alkyletherified amino groups (hereinafter also referred to as "amino group-containing compounds"), and alkyletherified amino The group is, for example, a group represented by the following formula.
Figure JPOXMLDOC01-appb-C000034
 　上記式中、ＲC1はメチレン基またはアルキレン基であり、好ましくはメチレン基または炭素数２～１０のアルキレン基であり、ＲC2はアルキル基であり、好ましくは炭素数１～１０のアルキル基である。
Figure JPOXMLDOC01-appb-C000034
 In the above formula, R C1 is a methylene group or an alkylene group, preferably a methylene group or an alkylene group having 2 to 10 carbon atoms, R C2 is an alkyl group, preferably an alkyl group having 1 to 10 carbon atoms is there.
　アミノ基含有化合物としては、例えば、（ポリ）メチロール化メラミン、（ポリ）メチロール化グリコールウリル、（ポリ）メチロール化ベンゾグアナミン、（ポリ）メチロール化ウレア等の窒素化合物中の活性メチロール基（ＣＨ2ＯＨ基）の全部または一部（少なくとも２個）がアルキルエーテル化された化合物が挙げられる。ここで、アルキルエーテルを構成するアルキル基としては、例えば、メチル基、エチル基、ブチル基が挙げられ、これらは互いに同一であってもよいし、異なっていてもよい。また、アルキルエーテル化されていないメチロール基は、一分子内で自己縮合していてもよく、二分子間で縮合して、その結果、オリゴマー成分が形成されていてもよい。具体的には、ヘキサメトキシメチルメラミン、ヘキサブトキシメチルメラミン、テトラメトキシメチルグリコールウリル、テトラブトキシメチルグリコールウリル等を用いることができる。 Examples of the amino group-containing compound include active methylol groups (CH 2 OH) in nitrogen compounds such as (poly) methylolated melamine, (poly) methylolated glycoluril, (poly) methylolated benzoguanamine, and (poly) methylolated urea. And compounds in which all or part (at least two) of the groups) are alkyletherified. Here, as an alkyl group which comprises an alkyl ether, a methyl group, an ethyl group, a butyl group is mentioned, for example, These may mutually be same or different. Moreover, the methylol group which is not alkyletherified may be self-condensing within one molecule, or may be condensed between two molecules to form an oligomer component as a result. Specifically, hexamethoxymethylmelamine, hexabutoxymethylmelamine, tetramethoxymethylglycoluril, tetrabutoxymethylglycoluril and the like can be used.
　架橋剤（Ｃ）は１種で用いてもよく、２種以上を併用してもよい。 The crosslinking agent (C) may be used alone or in combination of two or more.
　本発明の樹脂組成物において、架橋剤（Ｃ）の含有量は、重合体（Ａ）１００質量部に対して、通常は１～３００質量部、好ましくは５～２００質量部、より好ましくは１０～１００質量部である。架橋剤（Ｃ）の含有量が前記範囲にあると、解像度、伸び物性および耐熱性に優れた樹脂膜が形成される傾向にある。 In the resin composition of the present invention, the content of the crosslinking agent (C) is usually 1 to 300 parts by mass, preferably 5 to 200 parts by mass, more preferably 10 with respect to 100 parts by mass of the polymer (A). 100 parts by mass. When the content of the crosslinking agent (C) is in the above range, a resin film having excellent resolution, elongation physical properties and heat resistance tends to be formed.
　〈光重合開始剤（Ｄ）〉
　本発明の樹脂組成物は、光重合開始剤（Ｄ）を含有することができる。架橋剤（Ｃ）としてエチレン性不飽和基、特に（メタ）アクリロイル基を有する化合物を用いる場合、光重合開始剤（Ｄ）を用いることで、本発明の樹脂組成物はネガ型の感光性組成物となる。 <Photoinitiator (D)>
The resin composition of the present invention can contain a photopolymerization initiator (D). When a compound having an ethylenically unsaturated group, in particular a (meth) acryloyl group, is used as the crosslinking agent (C), the resin composition of the present invention has a negative photosensitive composition by using the photopolymerization initiator (D). It becomes a thing.
　光重合開始剤（Ｄ）は、可視光線、紫外線、遠紫外線、電子線、Ｘ線等の放射線の露光により、重合性化合物の重合を開始しうる活性種を発生する化合物である。前記感光性組成物から形成された塗布膜に対する露光処理によって、光重合開始剤（Ｄ）に基づき露光部に重合を開始しうる活性種が発生し、この活性種により２個以上のエチレン性不飽和基を有する化合物が重合し露光部のアルカリ性現像液への溶解性が変化する。 A photoinitiator (D) is a compound which generate | occur | produces the active species which can start superposition | polymerization of a polymeric compound by exposure of radiations, such as a visible ray, an ultraviolet-ray, far ultraviolet rays, an electron beam, X ray. The exposure treatment for the coating film formed from the photosensitive composition generates an active species capable of initiating polymerization in the exposed area based on the photopolymerization initiator (D), and this active species causes two or more ethylenic non The compound having a saturated group is polymerized to change the solubility of the exposed portion in the alkaline developer.
　光重合開始剤（Ｄ）としては、例えば、チオキサントン系化合物、アセトフェノン系化合物、ビイミダゾール系化合物、トリアジン系化合物、Ｏ－アシルオキシム系化合物、アシルホスフィンオキサイド系化合物、オニウム塩系化合物、ベンゾイン系化合物、ベンゾフェノン系化合物、α－ジケトン系化合物、多核キノン系化合物、ジアゾ系化合物、イミドスルホナート系化合物が挙げられる。これらのうち、チオキサントン系化合物、アセトフェノン系化合物、ビイミダゾール系化合物、トリアジン系化合物、Ｏ－アシルオキシム系化合物およびアシルホスフィンオキサイド系化合物から選ばれる少なくとも１種が好ましい。 Examples of the photopolymerization initiator (D) include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, acyl phosphine oxide compounds, onium salt compounds, benzoin compounds And benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, diazo compounds and imidosulfonate compounds. Among these, at least one selected from thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyl oxime compounds and acyl phosphine oxide compounds is preferable.
　チオキサントン系化合物の具体例としては、チオキサントン、２－クロロチオキサントン、２－メチルチオキサントン、２－イソプロピルチオキサントン、４－イソプロピルチオキサントン、２，４－ジクロロチオキサントン、２，４－ジメチルチオキサントン、２，４－ジエチルチオキサントン、２，４－ジイソプロピルチオキサントンが挙げられる。 Specific examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-dichloro thioxanthone, 2,4- dimethyl thioxanthone, 2,4- diethyl Thioxanthone and 2,4-diisopropylthioxanthone can be mentioned.
　アセトフェノン系化合物の具体例としては、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－（４－メチルベンジル）－２－（ジメチルアミノ）－１－（４－モルフォリノフェニル）ブタン－１－オンが挙げられる。 Specific examples of acetophenone compounds include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholino). Examples include phenyl) butan-1-one and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.
　ビイミダゾール系化合物の具体例としては、２，２'－ビス（２－クロロフェニル）－４，４'，５，５'－テトラフェニル－１，２'－ビイミダゾール、２，２'－ビス（２，４－ジクロロフェニル）－４，４'，５，５'－テトラフェニル－１，２'－ビイミダゾール、２，２'－ビス（２，４，６－トリクロロフェニル）－４，４'，５，５'－テトラフェニル－１，２'－ビイミダゾールが挙げられる。 Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and 2,2′-bis 2,4-Dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', And 5,5'-tetraphenyl-1,2'-biimidazole.
　トリアジン化合物の具体例としては、２，４，６－トリス（トリクロロメチル）－ｓ－トリアジン、２－メチル－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－〔２－（５－メチルフラン－２－イル）エテニル〕－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－〔２－（フラン－２－イル）エテニル〕－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－〔２－（４－ジエチルアミノ－２－メチルフェニル）エテニル〕－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－〔２－（３，４－ジメトキシフェニル）エテニル〕－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－メトキシフェニル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－エトキシスチリル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－ｎ－ブトキシフェニル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン等のハロメチル基を有するトリアジン化合物が挙げられる。 Specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-) Methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s -Triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxysty) Triazine compounds having a halomethyl group such as 4-, 4-bis (trichloromethyl) -s-triazine and 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine It can be mentioned.
　Ｏ－アシルオキシム系化合物の具体例としては、１，２－オクタンジオン，１－〔４－（フェニルチオ）フェニル〕－，２－（Ｏ－ベンゾイルオキシム）、エタノン，１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－，１－（Ｏ－アセチルオキシム）、エタノン，１－〔９－エチル－６－（２－メチル－４－テトラヒドロフラニルメトキシベンゾイル）－９Ｈ－カルバゾール－３－イル〕－，１－（Ｏ－アセチルオキシム）、エタノン，１－〔９－エチル－６－｛２－メチル－４－（２，２－ジメチル－１，３－ジオキソラニル）メトキシベンゾイル｝－９Ｈ－カルバゾール－３－イル〕－，１－（Ｏ－アセチルオキシム）が挙げられる。Ｏ－アシルオキシム系化合物の市販品としては、ＮＣＩ－８３１、ＮＣＩ－９３０（以上、株式会社ＡＤＥＫＡ社製））、ＯＸＥ－０３、ＯＸＥ－０４（以上、ＢＡＳＦ社製）等を使用することもできる。 Specific examples of O-acyloxime compounds include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6 -(2-Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranyl methoxybenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl] ) Methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime). As commercially available products of O-acyloxime compounds, NCI-831, NCI-930 (above, made by ADEKA Co., Ltd.), OXE-03, OXE-04 (above, made by BASF Co., Ltd.), etc. may also be used. it can.
　アシルホスフィンオキサイド系化合物の具体例としては、２，４，６－トリメチルベンゾイル－ジフェニル－ホスフィンオキサイド、ビス（２，６－ジメトキシベンゾイル）－２，４，４－トリメチルペンチル－ホスフィンオキサイド、ビス（２，４，６－トリメチルベンゾイル）－フェニル－ホスフィンオキサイドが挙げられる。 Specific examples of the acyl phosphine oxide compounds include 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl-phosphine oxide, bis (2 And 4,6-trimethylbenzoyl) -phenyl-phosphine oxide.
　本発明において、アセトフェノン系化合物等の、ビイミダゾール系化合物以外の光重合開始剤を用いる場合には、増感剤を併用することもできる。このような増感剤としては、例えば、４，４'－ビス（ジメチルアミノ）ベンゾフェノン、４，４'－ビス（ジエチルアミノ）ベンゾフェノン、４－ジエ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、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－エチルヘキシル、２，５－ビス（４－ジエチルアミノベンザル）シクロヘキサノン、７－ジエチルアミノ－３－（４－ジエチルアミノベンゾイル）クマリン、４－（ジエチルアミノ）カルコンが挙げられる。 In the present invention, when a photopolymerization initiator other than a biimidazole compound such as an acetophenone compound is used, a sensitizer may be used in combination. As such a sensitizer, for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 4-dimethyl Ethyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone It can be mentioned.
　光重合開始剤（Ｄ）は１種で用いてもよく、２種以上を併用してもよい。 A photoinitiator (D) may be used by 1 type, and may use 2 or more types together.
　本発明の樹脂組成物において、光重合開始剤（Ｄ）の含有量は、前記エチレン性不飽和基を有する化合物１００質量部に対して、好ましくは０．０１～１２０質量部、より好ましくは１～１００質量部、さらに好ましくは５～８０質量部である。光重合開始剤（Ｄ）の含有量が前記下限値以上であると、露光部の硬化が充分となり、耐熱性が向上しやすい。光重合開始剤（Ｄ）の含有量が前記上限値以下であると、露光光に対する透明性が低下することなく、解像度が高いパターンが得られやすい。 In the resin composition of the present invention, the content of the photopolymerization initiator (D) is preferably 0.01 to 120 parts by mass, more preferably 1 with respect to 100 parts by mass of the compound having an ethylenically unsaturated group. The amount is about 100 parts by mass, more preferably 5 to 80 parts by mass. Hardening of an exposure part becomes enough for content of a photoinitiator (D) to be more than the said lower limit, and it is easy to improve heat resistance. When the content of the photopolymerization initiator (D) is less than or equal to the upper limit value, it is easy to obtain a pattern with high resolution without lowering the transparency to exposure light.
　〈溶媒（Ｅ）〉
　本発明の樹脂組成物は、溶媒（Ｅ）を含有する。溶媒（Ｅ）を用いることで、本発明の樹脂組成物の取扱い性を向上させたり、粘度を調節したり、保存安定性を向上させたりすることができる。 <Solvent (E)>
The resin composition of the present invention contains a solvent (E). By using the solvent (E), the handleability of the resin composition of the present invention can be improved, the viscosity can be adjusted, and the storage stability can be improved.
　溶媒（Ｅ）としては、例えば、
　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等のエチレングリコールモノアルキルエーテルアセテート類；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プロピルエーテル、プロピレングリコールモノブチルエーテル等のプロピレングリコールモノアルキルエーテル類；プロピレングリコールジメチルエーテル、プロピレングリコールジエチルエーテル、プロピレングリコールジプロピルエーテル、プロピレングリコールジブチルエーテル等のプロピレングリコールジアルキルエーテル類；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等のプロピレングリコールモノアルキルエーテルアセテート類；
　エチルセロソルブ、ブチルセロソルブ等のセロソルブ類；ブチルカルビトール等のカルビトール類；乳酸メチル、乳酸エチル、乳酸ｎ－プロピル、乳酸イソプロピル等の乳酸エステル類；酢酸エチル、酢酸ｎ－プロピル、酢酸イソプロピル、酢酸ｎ－ブチル、酢酸イソブチル、酢酸ｎ－アミル、酢酸イソアミル、プロピオン酸イソプロピル、プロピオン酸ｎ－ブチル、プロピオン酸イソブチル等の脂肪族カルボン酸エステル類；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－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、ピルビン酸メチル、ピルビン酸エチル等の他のエステル類；
　メタノール、エタノール、１－プロパノール、２－プロパノール、１－ブタノール、２－ブタノール、エチレングリコール、ジエチレングリコール、プロピレングリコール、テトラヒドロフルフリルアルコール等のアルコール類；
　２－ヘプタノン、３－ヘプタノン、４－ヘプタノン、シクロヘキサノン等のケトン類；Ｎ－ジメチルホルムアミド、Ｎ－メチルアセトアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチルピロリドン等のアミド類；γ－ブチロラクトン等のラクトン類；
　トルエン、キシレン等の芳香族炭化水素類；
が挙げられる。 As the solvent (E), for example,
Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; Propylene glycol monoalkyl ether such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether and propylene glycol dibutyl ether; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene Recall monopropyl ether acetate, propylene glycol monoalkyl ether acetates such as propylene glycol monobutyl ether acetate;
Cellosolves such as ethyl cellosolve and butyl cellosolve; carbitols such as butyl carbitol; lactic acid esters such as methyl lactate, ethyl lactate, n-propyl lactate and isopropyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-acetate Aliphatic carboxylic acid esters such as -butyl, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate and isobutyl propionate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Other esters such as methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate;
Alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, ethylene glycol, diethylene glycol, propylene glycol and tetrahydrofurfuryl alcohol;
Ketones such as 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone; Amides such as N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide and N-methylpyrrolidone; Lactones such as γ-butyrolactone Kind;
Aromatic hydrocarbons such as toluene and xylene;
Can be mentioned.
　これらの中でも、乳酸エステル類、プロピレングリコールモノアルキルエーテルアセテート類、プロピレングリコールモノアルキルエーテル類、アルコール類、ラクトン類が好ましく；乳酸エチル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル、テトラヒドロフルフリルアルコール、γ－ブチロラクトンがより好ましい。 Among these, lactic acid esters, propylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, alcohols and lactones are preferable; ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, tetrahydrofurfuryl alcohol, More preferred is γ-butyrolactone.
　溶媒（Ｅ）は１種で用いてもよく、２種以上を併用してもよい。 The solvent (E) may be used alone or in combination of two or more.
　本発明の樹脂組成物において、溶媒（Ｅ）の含有量は、当該組成物中の溶媒（Ｅ）以外の成分の合計１００質量部に対して、通常は４０～９００質量部、好ましくは６０～４００質量部である。 In the resin composition of the present invention, the content of the solvent (E) is usually 40 to 900 parts by mass, preferably 60 to 900 parts by mass with respect to 100 parts by mass in total of components other than the solvent (E) in the composition. It is 400 parts by mass.
　〈その他添加剤（Ｆ）〉
　本発明の樹脂組成物には、その他、重合体（Ａ）以外のアルカリ可溶性重合体、密着助剤、架橋微粒子、レベリング剤、界面活性剤、増感剤、無機フィラー、クエンチャー等の各種添加剤を、本発明の目的および特性を損わない範囲で含有させることができる。 <Other additives (F)>
In the resin composition of the present invention, various additions such as alkali-soluble polymers other than polymer (A), adhesion assistants, crosslinked fine particles, leveling agents, surfactants, sensitizers, inorganic fillers, quenchers, etc. An agent can be contained in the range which does not impair the object and the characteristic of the present invention.
　〈樹脂組成物の調製方法〉
　本発明の樹脂組成物は、各成分を均一に混合することにより調製できる。また、異物を取り除くために、各成分を均一に混合した後、得られた混合物をフィルター等で濾過してもよい。前記樹脂組成物は、保存安定性に優れている。 <Method of Preparing Resin Composition>
The resin composition of the present invention can be prepared by uniformly mixing the respective components. Also, in order to remove foreign matter, the components obtained may be uniformly mixed, and then the resulting mixture may be filtered with a filter or the like. The resin composition is excellent in storage stability.
　〔樹脂膜〕
　本発明の樹脂膜は、具体的には、本発明の樹脂組成物を硬化させて得られる樹脂膜（硬化膜）である。本発明の樹脂組成物に含まれる重合体（Ａ）は耐熱性に優れることから、本発明の樹脂組成物を用いて得られる樹脂膜も耐熱性に優れる。 [Resin film]
Specifically, the resin film of the present invention is a resin film (cured film) obtained by curing the resin composition of the present invention. Since the polymer (A) contained in the resin composition of the present invention is excellent in heat resistance, the resin film obtained using the resin composition of the present invention is also excellent in heat resistance.
　さらに、本発明の樹脂膜は、機械的強度が高く、熱膨張性（線膨張率）が小さく、誘電率が低く、また伸び物性に優れ、衝撃を受けてもクラックが発生しづらい。 Furthermore, the resin film of the present invention is high in mechanical strength, small in thermal expansion (linear expansion coefficient), low in dielectric constant, excellent in elongation properties, and hardly cracked even if it receives an impact.
　したがって、本発明の樹脂膜は、回路基板（半導体素子）、半導体パッケージまたは表示素子等の電子部品が有する、表面保護膜、層間絶縁膜および平坦化膜として、また、高密度実装基板用絶縁膜材料、感光性接着剤および感圧接着剤として好適に用いることができる。 Therefore, the resin film of the present invention is used as a surface protective film, an interlayer insulating film and a planarizing film of electronic components such as circuit boards (semiconductor elements), semiconductor packages or display elements, and also as insulating films for high density mounting substrates It can be suitably used as a material, a photosensitive adhesive and a pressure sensitive adhesive.
　本発明の樹脂膜は、例えば、少なくとも、本発明の樹脂組成物を支持体上に塗布して塗布膜を形成する工程、および前記塗布膜を硬化させて樹脂膜を得る工程を行うことにより製造することができる。 The resin film of the present invention is produced, for example, by applying at least a resin composition of the present invention on a support to form a coated film, and curing the coated film to obtain a resin film. can do.
　〔パターン化樹脂膜の製造方法〕
　本発明のパターン化樹脂膜の製造方法は、感光性酸発生剤（Ｂ）または光重合開始剤（Ｄ）を含有する本発明の樹脂組成物を支持体上に塗布して塗布膜を形成する工程（以下「塗布工程」ともいう）、前記塗布膜を選択的に露光して選択露光膜を得る工程（以下「露光工程」ともいう）、アルカリ性現像液により前記選択露光膜を現像してパターン化した塗布膜を得る工程（以下「現像工程」ともいう）、および前記パターン化した塗布膜を硬化させてパターン化樹脂膜を得る工程（以下「硬化工程」ともいう）を有する。 [Method for producing patterned resin film]
In the method for producing a patterned resin film of the present invention, a resin composition of the present invention containing a photosensitive acid generator (B) or a photopolymerization initiator (D) is coated on a support to form a coated film. Step (hereinafter also referred to as "coating step"), step of selectively exposing the coating film to obtain a selectively exposed film (hereinafter also referred to as "exposure step"), developing the selectively exposed film with an alkaline developer And the step of curing the patterned coating film to obtain a patterned resin film (hereinafter, also referred to as a "curing step").
　［１］塗布工程
　塗布工程では、感光性酸発生剤（Ｂ）または光重合開始剤（Ｄ）を含有する本発明の樹脂組成物を、支持体上に塗布し、必要に応じて乾燥して溶媒（Ｅ）を除去する。前記乾燥の条件は、例えば、オーブンやホットプレートを用いて、通常は５０～１４０℃で１０～１０００秒間加熱する。このようにして支持体上に塗布膜を形成する。塗布膜の膜厚は、最終的に得られるパターン化樹脂膜の膜厚に応じて、適宜、調整すればよい。 [1] Coating Step In the coating step, the resin composition of the present invention containing a photosensitive acid generator (B) or a photopolymerization initiator (D) is coated on a support, and dried if necessary. Remove the solvent (E). The drying conditions are, for example, heating at usually 50 to 140 ° C. for 10 to 1000 seconds using an oven or a hot plate. Thus, a coating film is formed on the support. The film thickness of the coating film may be appropriately adjusted in accordance with the film thickness of the patterned resin film to be finally obtained.
　支持体としては、例えば、シリコンウエハ、化合物半導体ウエハ、金属薄膜付きウエハ、ガラス基板、石英基板、セラミックス基板、アルミ基板、ＳＵＳ基板、およびこれらの支持体の表面に半導体チップを有する基板、その他、樹脂製シートが挙げられる。塗布方法としては、例えば、ディッピング法、スプレー法、バーコート法、ロールコート法、スピンコート法、カーテンコート法、グラビア印刷法、シルクスクリーン法、インクジェット法が挙げられる。 As the support, for example, a silicon wafer, a compound semiconductor wafer, a wafer with a metal thin film, a glass substrate, a quartz substrate, a ceramic substrate, an aluminum substrate, a SUS substrate, a substrate having a semiconductor chip on the surface of these supports, and others A resin sheet is mentioned. Examples of the coating method include a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a silk screen method, and an ink jet method.
　［２］露光工程
　露光工程では、例えばレチクルを介して、例えばコンタクトアライナー、ステッパーまたはスキャナーを用いて、上記塗布膜を選択的に露光し、選択露光膜を得る。露光光としては、例えば、可視光線、紫外線、遠紫外線、電子線、Ｘ線等の放射線が挙げられ、好ましくは、波長２００～５００ｎｍの光（例：ｉ線（３６５ｎｍ））を用いる。露光光の照射量は、感光性組成物中の各成分の種類、配合割合、塗布膜の厚さ等によって異なるが、露光光にｉ線を使用する場合、露光量は通常は１００～１５００ｍＪ／ｃｍ2である。 [2] Exposure Step In the exposure step, the above-mentioned coating film is selectively exposed through, for example, a reticle using, for example, a contact aligner, a stepper or a scanner to obtain a selective exposure film. As the exposure light, for example, radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like can be mentioned, and preferably light with a wavelength of 200 to 500 nm (example: i-ray (365 nm)) is used. The irradiation dose of exposure light varies depending on the type and blending ratio of each component in the photosensitive composition, the thickness of the coating film, etc. When i-line is used for the exposure light, the exposure dose is usually 100 to 1500 mJ /. It is cm 2 .
　その後、前記選択塗布膜に対して加熱処理を行うこともできる。以下、この処理を「ＰＥＢ処理」ともいう。前記ＰＥＢ条件は、樹脂組成物中の各成分の種類、配合割合、塗布膜の厚さ等によって異なるが、通常は７０～１５０℃、好ましくは８０～１２０℃で、１～６０分間程度である。 Thereafter, heat treatment may be performed on the selective coating film. Hereinafter, this process is also referred to as "PEB process". The PEB conditions vary depending on the kind of each component in the resin composition, the blending ratio, the thickness of the coating film, etc., but are usually 70 to 150 ° C., preferably 80 to 120 ° C., and about 1 to 60 minutes. .
　［３］現像工程
　現像工程では、例えば、アルカリ性現像液により前記選択露光膜を現像して、支持体上にパターン化した塗布膜を形成する。現像方法としては、シャワー現像法、スプレー現像法、浸漬現像法、パドル現像法等が挙げられる。前記現像方法の条件としては、通常は２０～４０℃で１～１０分間程度である。 [3] Development Step In the development step, for example, the selective exposure film is developed with an alkaline developer to form a patterned coating film on a support. Examples of the development method include a shower development method, a spray development method, an immersion development method, and a paddle development method. The conditions for the development method are usually about 20 to 40 ° C. and about 1 to 10 minutes.
　前記アルカリ性現像液としては、例えば、水酸化ナトリウム、水酸化カリウム、アンモニア水、テトラメチルアンモニウムハイドロキサイド、コリン等のアルカリ性化合物を、１～１０質量％濃度となるように水に溶解させたアルカリ性水溶液が挙げられる。前記アルカリ性水溶液には、例えば、メタノール、エタノール等の水溶性の有機溶媒および界面活性剤などを適量添加することもできる。なお、アルカリ性現像液で上記選択露光膜を現像した後は、水で洗浄し、乾燥してもよい。 The alkaline developing solution may be, for example, an alkaline solution in which an alkaline compound such as sodium hydroxide, potassium hydroxide, ammonia water, tetramethyl ammonium hydroxide, choline or the like is dissolved to a concentration of 1 to 10% by mass. An aqueous solution is mentioned. An appropriate amount of, for example, a water-soluble organic solvent such as methanol or ethanol and a surfactant may be added to the alkaline aqueous solution. After developing the selective exposure film with an alkaline developer, the film may be washed with water and dried.
　［４］硬化工程
　現像工程後、例えば、加熱により上記パターン化した塗布膜を硬化させる。硬化条件としては、オーブンやホットプレートを用いて、例えば１００～２５０℃の温度で１分間～１０時間程度加熱する。 [4] Curing Step After the developing step, the patterned coating film is cured by heating, for example. As curing conditions, heating is performed, for example, at a temperature of 100 to 250 ° C. for about 1 minute to 10 hours using an oven or a hot plate.
　〔電子部品〕
　本発明の電子部品は、本発明の樹脂膜を有する。前記電子部品としては、例えば、回路基板（半導体素子）、半導体パッケージまたは表示素子が挙げられる。 [Electronic parts]
The electronic component of the present invention has the resin film of the present invention. As said electronic component, a circuit board (semiconductor element), a semiconductor package, or a display element is mentioned, for example.
　以下、本発明を実施例に基づいてさらに具体的に説明するが、本発明はこれら実施例に限定されない。以下の実施例等の記載において、特に言及しない限り、「部」は「質量部」の意味で用いる。 Hereinafter, the present invention will be more specifically described based on examples, but the present invention is not limited to these examples. In the description of the following examples and the like, "part" is used in the meaning of "part by mass" unless otherwise stated.
　１．物性の測定方法
　重合体（Ａ）その他の重合体の平均分子量（Ｍｗ、Ｍｎ）の測定方法
　下記条件下でゲルパーミエーションクロマトグラフィー法にて重量平均分子量（Ｍｗ）、および数平均分子量（Ｍｎ）を測定した。
・カラム：東ソー社製カラムのＴＳＫ－ＭおよびＴＳＫ２５００を直列に接続
・溶媒：Ｎ，Ｎ－ジメチルホルムアミド
・温度：４０℃
・検出方法：屈折率法
・標準物質：ポリスチレン
　２．重合体の合成
　重合体の合成に用いた化合物（Ｍ－１）～（Ｍ－８）を以下に示す。 1. Method of measuring physical properties Method of measuring average molecular weight (Mw, Mn) of polymer (A) and other polymers Weight average molecular weight (Mw), and number average molecular weight (Mn) by gel permeation chromatography under the following conditions Was measured.
・ Column: TSK-M and TSK2500 of Tosoh columns are connected in series ・ Solvent: N, N-dimethylformamide ・ Temperature: 40 ° C
Detection method: refractive index method Standard substance: polystyrene 2. The compounds (M-1) to (M-8) used for the synthesis of the polymer synthesis polymer are shown below.
Figure JPOXMLDOC01-appb-T000035
 　［実施例１－１］（重合体（Ａ－１）の合成）
　３００ｍＬの三口フラスコに化合物（Ｍ－１）５．９ｇ（５０モル％）および化合物（Ｍ－２）１０．８ｇ（５０モル％）をプロピレングリコールモノメチルエーテル４５ｇに溶解し、ラジカル重合開始剤としてアゾビスイソブチロニトリル０．９１８ｇ（全単量体に対して７モル％）を添加して単量体溶液を調製した。次いで１５分窒素バブリングを行った後、攪拌しながら８０℃に加熱した。溶液が７５℃となった時点を重合反応の開始時間として、重合反応を４時間実施した。重合反応終了後、重合溶液を水冷して３０℃以下に冷却し、メタノール６０ｇを加え、溶液と等量のノルマルヘキサンで５回液液抽出洗浄を行った。抽出洗浄後の重合体を含むメタノール溶液に等量のプロピレングリコールモノメチルエーテルを加えて、４０℃の水浴を備えたロータリーエバポレーターでメタノールを留去した上、さらに３０％程度まで濃縮し目的の重合体溶液と得た。重合体（Ａ－１）のＭｗは２１，０００であり、Ｍｗ／Ｍｎは２．１５であった。
Figure JPOXMLDOC01-appb-T000035
 Example 1-1 Synthesis of Polymer (A-1)
In a 300 mL three-necked flask, 5.9 g (50 mol%) of the compound (M-1) and 10.8 g (50 mol%) of the compound (M-2) are dissolved in 45 g of propylene glycol monomethyl ether, and azo is used as a radical polymerization initiator A monomer solution was prepared by adding 0.918 g (7 mol% to all monomers) of bisisobutyronitrile. Next, nitrogen bubbling was performed for 15 minutes, and the mixture was heated to 80 ° C. with stirring. The polymerization reaction was carried out for 4 hours, with the time when the solution reached 75 ° C. as the initiation time of the polymerization reaction. After completion of the polymerization reaction, the polymerization solution was water-cooled and cooled to 30 ° C. or less, 60 g of methanol was added, and solution liquid extraction and washing were performed five times with an equal amount of normal hexane. An equal amount of propylene glycol monomethyl ether is added to a methanol solution containing a polymer after extraction and washing, methanol is distilled off with a rotary evaporator equipped with a water bath at 40 ° C., and the solution is further concentrated to about 30% to obtain a target polymer Obtained with the solution. The Mw of the polymer (A-1) was 21,000, and the Mw / Mn was 2.15.
　［実施例１－２～１－１０］（重合体（Ａ－２）～（Ａ－１０）の合成）
　実施例１－２～１－１０では、表２に示す種類および量の単量体を用いたこと以外は実施例１－１と同様にして、重合体（Ａ－２）～（Ａ－１０）を得た。 [Examples 1-2 to 1-10] (Synthesis of Polymers (A-2) to (A-10))
In Examples 1-2 to 1-10, polymers (A-2) to (A-10) were prepared in the same manner as in Example 1-1 except that monomers of the types and amounts shown in Table 2 were used. Got).
Figure JPOXMLDOC01-appb-T000036
 　３．樹脂組成物の調製
　［実施例２－１］
　重合体（Ａ－１）１００部を溶媒（Ｅ－１）２５０部に２５℃で溶解させ、樹脂組成物（Ｊ－１）を調製した。得られた樹脂組成物を用いて、所定の評価を行った。
Figure JPOXMLDOC01-appb-T000036
 3. Preparation of Resin Composition [Example 2-1]
100 parts of the polymer (A-1) was dissolved in 250 parts of the solvent (E-1) at 25 ° C. to prepare a resin composition (J-1). Predetermined evaluation was performed using the obtained resin composition.
　溶媒（Ｅ－１）は、プロピレングリコールモノメチルエーテルである。 The solvent (E-1) is propylene glycol monomethyl ether.
　［実施例２－２～２－１０、比較例２－１］
　実施例２－２～２－１０では、表３に示す種類および量の重合体を用いたこと以外は実施例２－１と同様にして、樹脂組成物（Ｊ－２）～（Ｊ－１０）を調製し、得られた樹脂組成物を用いて、所定の評価を行った。また、比較例２－１では、重合体（ＣＡ－１）として表３に示す量のヒドロキシスチレン－スチレン共重合体（製品名スチレンマルカリンカーＣＳＴ、丸善石油化学株式会社製)を用いたこと以外は実施例２－１と同様にして、樹脂組成物（ＣＪ－１）を調製し、得られた樹脂組成物を用いて、所定の評価を行った。 [Examples 2-2 to 2-10, comparative example 2-1]
In Examples 2-2 to 2-10, resin compositions (J-2) to (J-10) were prepared in the same manner as in Example 2-1 except that polymers of the types and amounts shown in Table 3 were used. ) Were prepared, and predetermined evaluation was performed using the obtained resin composition. In addition, in Comparative Example 2-1, a hydroxystyrene-styrene copolymer (product name: Styrene marker linker CST, manufactured by Maruzen Petrochemical Co., Ltd.) in an amount shown in Table 3 as the polymer (CA-1) was used. The resin composition (CJ-1) was prepared in the same manner as in Example 2-1, and predetermined evaluation was performed using the obtained resin composition.
　４．評価
　樹脂組成物の評価方法は以下のとおりである。 4. Evaluation Method The evaluation method of the resin composition is as follows.
　４－１．耐熱性
　樹脂組成物（Ｊ－１）～（Ｊ－１０）、（ＣＪ－１）を２００℃、１時間で加熱硬化させて樹脂膜を得た後、熱重量分析法（ＴＧＡ）により、窒素雰囲気下、昇温速度１０℃／分にて測定し、５質量％熱重量減少温度（Ｔｄ５）で評価した。５質量％熱重量減少温度が３５０℃以上の場合を「Ａ」、３００℃以上３５０℃未満の場合を「Ｂ」、３００℃未満の場合を「Ｃ」とした。 4-1. The heat resistant resin compositions (J-1) to (J-10) and (CJ-1) are cured by heating at 200 ° C. for 1 hour to obtain a resin film, and then nitrogen is obtained by thermogravimetric analysis (TGA). The temperature was measured at a temperature rising rate of 10 ° C./minute under an atmosphere, and evaluated at a 5 mass% thermal weight loss temperature (Td5). When the 5% by mass thermal weight loss temperature is 350 ° C. or higher is “A”, when it is 300 ° C. to less than 350 ° C. “B”, and when it is less than 300 ° C. “C”.
　４－２．保存安定性
　樹脂組成物（Ｊ－１）～（Ｊ－１０）、（ＣＪ－１）を５℃で１ヶ月間保存した後の粘度を測定した。粘度は、Ｅ型粘度計（東機産業社の「ＶＩＳＣＯＮＩＣ  ＥＬＤ．Ｒ」）を用いて２５℃で測定した。５℃１ヶ月間保存後の粘度上昇率が５％未満の場合を「Ａ」、５％以上１０％未満の場合を「Ｂ」、１０％以上１５％未満の場合を「Ｃ」、１５％以上の場合を「Ｄ」とした。「－」は未測定を意味する。 4-2. Storage stability Resin compositions (J-1) to (J-10) and (CJ-1) were measured for viscosity after stored at 5 ° C. for 1 month. The viscosity was measured at 25 ° C. using an E-type viscometer (“VISCONIC ELD. R” manufactured by Toki Sangyo Co., Ltd.). "A" when viscosity increase rate after storage for 1 month at 5 ° C is less than 5%, "B" when it is 5% or more and less than 10%, "C" when it is 10% or more and less than 15% The above case is referred to as "D". "-" Means unmeasured.
　４－３．アルカリ溶解性
　樹脂組成物（Ｊ－１）～（Ｊ－１０）、（ＣＪ－１）をシリコンウエハ上に、膜厚５μｍとなるように塗布し、８０℃のホットプレートで３分間乾燥して樹脂組成物の塗布膜を得た。次いで、２．３８質量％濃度のテトラメチルアンモニウムハイドロキサイド水溶液に前記塗布膜を２３℃で１２０秒間浸漬した。前記塗布膜が完全に溶解した場合を「Ａ」、少し残渣が見られた場合を「Ｂ」、溶け残った場合を「Ｃ」とした。 4-3. Apply alkali soluble resin compositions (J-1) to (J-10) and (CJ-1) on a silicon wafer to a film thickness of 5 μm, and dry for 3 minutes on a hot plate at 80 ° C. The coating film of the resin composition was obtained. Then, the coating film was immersed in a 2.38% by mass tetramethyl ammonium hydroxide aqueous solution at 23 ° C. for 120 seconds. The case where the coating film was completely dissolved was referred to as “A”, the case where a little residue was observed was referred to as “B”, and the case where it remained undissolved was “C”.
　４－４．機械的強度
　樹脂組成物（Ｊ－１）～（Ｊ－１０）、（ＣＪ－１）をテフロン（登録商標）シート上に均一に塗布し、８０℃のオーブンで１０分間乾燥して樹脂組成物の塗布膜を形成した。次いで、前記塗布膜に対して２００℃のオーブンで１時間加熱処理をした後、テフロンシートから剥離して厚さ約３０μｍとなる硬化膜（樹脂膜）を得た。剥離した硬化膜の機械的強度を引張試験機で測定した。測定の際、試料の幅は５ｍｍ、チャック間は２０ｍｍとし、引っ張り速度は５ｍｍ／分で、測定温度は室温（２０～２５℃）程度とした。同一条件で得た硬化膜から得た５本以上の試験片の測定値の平均が７０ＭＰａ以上の場合を「Ａ」、５０ＭＰａ以上７０ＭＰａ未満の場合を「Ｂ」、３０ＭＰａ以上５０ＭＰａ未満の場合を「Ｃ」、３０ＭＰａ未満の場合を「Ｄ」とした。 4-4. Mechanical strength resin compositions (J-1) to (J-10) and (CJ-1) were uniformly coated on a Teflon (registered trademark) sheet and dried in an oven at 80 ° C. for 10 minutes to obtain a resin composition. Was formed. Next, the coated film was heat-treated in an oven at 200 ° C. for 1 hour, and then peeled from the Teflon sheet to obtain a cured film (resin film) having a thickness of about 30 μm. The mechanical strength of the peeled cured film was measured by a tensile tester. At the time of measurement, the width of the sample was 5 mm, the distance between the chucks was 20 mm, the tensile rate was 5 mm / min, and the measurement temperature was about room temperature (20 to 25 ° C.). The average of the measured values of five or more test pieces obtained from the cured film obtained under the same conditions is “A” when it is 70 MPa or more, “B” when it is 50 MPa or more and less than 70 MPa, “B” when it is 30 MPa or more and less than 50 MPa. C ", the case of less than 30 MPa was" D ".
　４－５．線膨張係数（平均線膨張率）
　上述の「４－４」において得た硬化膜（樹脂膜）の線膨張係数を熱機械的分析装置で測定した。試料の幅は３ｍｍ、チャック間は１０ｍｍとした。荷重は９．８ｍＮで、昇温速度は５℃／分であった。１００～１５０℃の平均線膨張率が１００ｐｐｍ未満の場合を「Ａ」、１００ｐｐｍ以上１４０ｐｐｍ未満の場合を「Ｂ」、１４０ｐｐｍ以上１８０ｐｐｍ未満の場合を「Ｃ」、１８０ｐｐｍ以上の場合を「Ｄ」とした。 4-5. Coefficient of linear expansion (average coefficient of linear expansion)
The linear expansion coefficient of the cured film (resin film) obtained in the above-mentioned "4-4" was measured by a thermomechanical analyzer. The width of the sample was 3 mm and the distance between the chucks was 10 mm. The load was 9.8 mN, and the temperature rising rate was 5 ° C./min. When the average linear expansion coefficient at 100 to 150 ° C is less than 100 ppm, "A", for 100 ppm to less than 140 ppm, "B", for 140 ppm to less than 180 ppm, "C", for 180 ppm or more, "D" did.
　４－６．誘電率
　樹脂組成物（Ｊ－１）～（Ｊ－１０）、（ＣＪ－１）をＳＵＳ基板上に、膜厚５μｍとなるように塗布し、８０℃のホットプレートで３分間乾燥した後、２００℃のオーブンで１時間加熱硬化させた。得られた硬化膜（樹脂膜）の１ＭＨｚでの誘電率を測定し、４．０未満の場合を「Ａ」、４．０以上４．５未満の場合を「Ｂ」、４．５以上の場合を「Ｃ」とした。 4-6. The dielectric resin compositions (J-1) to (J-10) and (CJ-1) are coated on a SUS substrate to a film thickness of 5 μm and dried on an 80 ° C. hot plate for 3 minutes, It was heat cured in an oven at 200 ° C. for 1 hour. The dielectric constant at 1 MHz of the obtained cured film (resin film) is measured, and in the case of less than 4.0, “A”, in the case of 4.0 or more and less than 4.5, “B”, 4.5 or more The case is "C".
Figure JPOXMLDOC01-appb-T000037
 　５．感光性組成物の調製
　感光性組成物の調製に用いた各成分を以下に示す。
Figure JPOXMLDOC01-appb-T000037
 5. Preparation of photosensitive composition Each component used for preparation of photosensitive composition is shown below.
　感光性酸発生剤（Ｂ－１）：４，４'－［１－［４－［１－（４－ヒドロキシフェニル）－１－メチルエチル］フェニル］エチリデン］ビスフェノールと１，２－ナフトキノンジアジド－５－スルホン酸クロリドの縮合物
　感光性酸発生剤（Ｂ－２）：４，７－ジ－ｎ－ブトキシナフチルテトラヒドロチオフェニウムトリフルオロメタンスルホネート
　架橋剤（Ｃ－１）：ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートとの混合物
　光重合開始剤（Ｄ－１）：２，４，６－トリメチルベンゾイル－ジフェニル－フォスフィンオキサイド
　溶媒（Ｅ－１）：プロピレングリコールモノメチルエーテル
　溶剤（Ｅ－２）：テトラヒドロフルフリルアルコール
　溶剤（Ｅ－３）：γ―ブチロラクトン
　界面活性剤（Ｆ－１）：ＦＴＸ－２１８（（株）ネオス製）
　［実施例３－１］
　重合体（Ａ－１）１００部、架橋剤（Ｃ－１）８０部、光重合開始剤（Ｄ－１）３０部、界面活性剤（Ｆ－１）０．１部を溶媒（Ｅ－１）４９０部に２５℃で溶解させ、感光性組成物（ＰＲ－１）を調製した。得られた感光性組成物を用いて、所定の評価を行った。 Photosensitive acid generator (B-1): 4,4 '-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphthoquinone diazide- 5-sulfonic acid chloride condensate Photosensitive acid generator (B-2): 4,7-di-n-butoxynaphthyltetrahydrothiophenium trifluoromethanesulfonate Crosslinker (C-1): dipentaerythritol pentaacrylate and Mixture with dipentaerythritol hexaacrylate Photoinitiator (D-1): 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide Solvent (E-1): Propylene glycol monomethyl ether Solvent (E-2): Tetrahydrofurfuryl alcohol Solvent (E-3): γ-butyrolactone surfactant (F -1): FTX-218 (manufactured by Neos Corporation)
Example 3-1
100 parts of polymer (A-1), 80 parts of crosslinking agent (C-1), 30 parts of photopolymerization initiator (D-1), 0.1 part of surfactant (F-1) in solvent (E-1) The mixture was dissolved in 490 parts at 25 ° C. to prepare a photosensitive composition (PR-1). Predetermined evaluation was performed using the obtained photosensitive composition.
　［実施例３－２～３－１０、比較例３－１］
　実施例３－２～３－１０、比較例３－１では、表４に示すとおりに配合成分の種類および量を変更したこと以外は実施例３－１と同様にして、感光性組成物（ＰＲ－２）～（ＰＲ－１０）、（ＣＰＲ－１）を調製した。得られた感光性組成物を用いて、所定の評価を行った。 [Examples 3-2 to 3-10, Comparative Example 3-1]
In Examples 3-2 to 3-10 and Comparative Example 3-1, a photosensitive composition (Example 3) was prepared in the same manner as Example 3-1 except that the types and amounts of the blending components were changed as shown in Table 4. PR-2) to (PR-10) and (CPR-1) were prepared. Predetermined evaluation was performed using the obtained photosensitive composition.
　６－１．フォトリソグラフィー評価
　感光性組成物の評価方法は以下のとおりである。 6-1. Evaluation method of photolithographic evaluation The photosensitive composition is as follows.
　解像度および残膜率
　６インチのシリコンウエハに感光性組成物をスピンコートし、その後、ホットプレートを用いて１１０℃で３分間加熱し、厚さ１０μｍの均一な塗布膜を作製した。次いで、アライナー（Ｓｕｓｓ　Ｍｉｃｒｏｔｅｃ社製、型式「ＭＡ－１５０」）を用い、高圧水銀灯からの紫外線を、パターンマスクを介して、波長３５０ｎｍにおける露光量が５００ｍＪ／ｃｍ2となるように前記塗布膜に照射した。次いで、露光後の前記塗布膜を、２．３８質量％濃度のテトラメチルアンモニウムハイドロキサイド水溶液を用いて２３℃で１２０秒間、浸漬現像した。次いで、現像後の前記塗布膜を、超純水にて３０秒間洗浄し、エアーにて風乾した後、顕微鏡（オリンパス（株）社製、ＭＨＬ１１０）にて観察し、解像した最小パターンのパターン寸法を解像度（単位：μｍ）とした。また、KLA-Tencor社製触針式膜厚計P-16を用いて膜厚を測定し、現像前後の膜厚差から残膜率（１００％×（現像後の膜厚／現像前の膜厚））を算出し、下記評価基準にて評価した。なお、実施例３－２～３－６の場合、露光後にホットプレートを用いて１１０℃で３分間加熱した。 The photosensitive composition was spin-coated on a silicon wafer having a resolution and a residual film rate of 6 inches, and then heated at 110 ° C. for 3 minutes using a hot plate to prepare a uniform coated film with a thickness of 10 μm. Then, using an aligner (made by Suss Microtec, type "MA-150"), the ultraviolet light from a high pressure mercury lamp is applied to the above coated film so that the exposure amount at a wavelength of 350 nm is 500 mJ / cm 2 through a pattern mask. Irradiated. Then, the coated film after exposure was subjected to immersion development for 120 seconds at 23 ° C. using a 2.38 mass% tetramethylammonium hydroxide aqueous solution. Next, the coated film after development is washed with ultrapure water for 30 seconds, air-dried with air, then observed with a microscope (MHL110 manufactured by Olympus Corporation), and the pattern of the resolved minimum pattern The dimension is a resolution (unit: μm). In addition, the film thickness is measured using a stylus thickness meter P-16 manufactured by KLA-Tencor, and the residual film ratio (100% × (film thickness after development / film before development) from the film thickness difference before and after development Thickness) was calculated and evaluated by the following evaluation criteria. In the case of Examples 3-2 to 3-6, after exposure, heating was performed at 110 ° C. for 3 minutes using a hot plate.
　Ａ：残膜率９０％以上
　Ｂ：残膜率８０％以上９０％未満
　Ｃ：残膜率８０％未満
　６－２．耐溶剤性
　感光性組成物（ＰＲ－１）～（ＰＲ－１０）、（ＣＰＲ－１）をテフロンシート上に置いた厚さ１ｍｍの金枠内に入れ、内温５０℃の真空オーブンで２時間処理した後に０．５ｔの重圧をかけて２００℃×２時間プレスし、テフロンシートから剥離し厚さ約０．５ｍｍの硬化膜を得た。この硬化膜を試験用に１ｃｍ角にカットし、重量を測定した後、５ｍｌのＮＭＰ（Ｎ－メチルピロリドン）に室温３日間浸漬し、硬化膜形状の変化（目視での形状変化、重量変化）を評価した。ＮＭＰ浸漬後の硬化膜の重量は、ＮＭＰ浸漬後の硬化膜を内温８０℃の真空オーブンで３日間乾燥した後に測定した。ＮＭＰ浸漬前後の硬化膜の各重量は、ザルトリウス製精密天秤ＢＰ３１１Ｄにて測定した。目視での形状の変化がなく、かつ重量減少が３％未満の場合を「Ａ」、目視形状の変化にかかわらず、重量減少が３％以上１０％未満の場合を「Ｂ」、１０％以上の場合を「Ｃ」とした。 A: Residual film rate 90% or more B: Residual film rate 80% or more and less than 90% C: Residual film rate less than 80% 6-2. The solvent resistant photosensitive compositions (PR-1) to (PR-10) and (CPR-1) are placed in a 1 mm thick metal frame placed on a Teflon sheet, and 2 in a vacuum oven with an internal temperature of 50 ° C. After time treatment, the film was pressed at 200 ° C. for 2 hours under a pressure of 0.5 t and peeled off from the Teflon sheet to obtain a cured film having a thickness of about 0.5 mm. This cured film is cut into 1 cm square for testing, and after measuring the weight, it is immersed in 5 ml of NMP (N-methylpyrrolidone) at room temperature for 3 days to change the shape of the cured film (shape change by visual observation, weight change) Was evaluated. The weight of the cured film after immersion in NMP was measured after the cured film after immersion in NMP was dried in a vacuum oven at an internal temperature of 80 ° C. for 3 days. Each weight of the cured film before and after immersion in NMP was measured with a Sartorius precision balance BP311D. There is no change in shape by visual observation, and weight reduction is less than 3% "A", regardless of the change in visual shape change, weight reduction by 3% or more and less than 10% is "B", 10% or more In the case of “C”.
　６－３．熱溶融性
　感光性組成物（ＰＲ－１）～（ＰＲ－１０）、（ＣＰＲ－１）について上記「６－２」と同様の手法で得た１ｃｍ角の硬化膜試験片２枚を重ね、厚さ１ミリの５ｃｍ角ステンレス基板で上下を挟んで０．５ｔの重圧をかけて２００℃×１時間プレスし、形状の変化を熱溶融性として評価した。２枚の硬化膜試験片が溶融変形し一体化している場合を「ｍ１」、２枚の硬化膜試験片は溶融変形するが一体化はしていない場合を「ｍ２」、硬化膜試験片が溶融変形せず一体化もしてしない場合を「ｍ３」とした。 6-3. For heat-meltable photosensitive compositions (PR-1) to (PR-10) and (CPR-1), two 1 cm square cured film test pieces obtained by the same method as the above-mentioned "6-2" are stacked, A pressure of 0.5 t was applied to the upper and lower sides of a 1 mm thick 5 cm square stainless steel substrate and pressed at 200 ° C. for 1 hour, and the change in shape was evaluated as the heat melting property. “M1” when two cured film test pieces are melted and deformed and integrated, “m2” and two cured film test pieces are melted and deformed but not integrated when “m2” is used. The case where it did not carry out fusion | melting deformation and was not integrated was set to "m3."
Figure JPOXMLDOC01-appb-T000038
Figure JPOXMLDOC01-appb-T000038

Claims (22)

  1. （Ａ）同一のまたは異なる分子中に、
    　　　下記式（ｉ）で表される部分構造を有する構造単位と、
    　　　下記式（ii-1）で表される部分構造を有する構造単位、およびフェノール性水酸基を有する構造単位から選択される一以上の水酸基含有構造単位と
    　　　を含む重合体、ならびに
    （Ｅ）溶媒
    を含有する樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
     ［式（ｉ）中、Ｒ1およびＲ2は、各々独立に、水素原子、炭素数１～２０の炭化水素基、前記炭素数１～２０の炭化水素基中の少なくとも１つの炭素－炭素結合間に、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＳＯ2－、－ＳＯ3－、－ＯＳＯ2ＮＲ－、－ＮＲＳＯ2－、－ＮＲＣＯ－、－ＮＲ－および－ＣＯＮＲ－から選ばれる少なくとも一種を有する基、またはこれらの基中の水素原子の一部が置換された基を示し、Ｒ1およびＲ2は、相互に結合してＯＲ1およびＯＲ2が結合するホウ素原子と共に環員数３～２０の環状構造を形成してもよい。前記Ｒは、水素原子または炭素数１～２０の炭化水素基であり、＊は結合手を示す。］
    Figure JPOXMLDOC01-appb-C000002
     ［式（ii-1）中、Ｒ3およびＲ4は、各々独立に、水素原子、炭素数１～２０の炭化水素基、または電子求引性基であり、但し、上記Ｒ3およびＲ4のうち、少なくともいずれかは電子求引性基であり、＊は結合手を示す。］     (A) in the same or different molecules,
    A structural unit having a partial structure represented by the following formula (i):
    A polymer comprising: a structural unit having a partial structure represented by the following formula (ii-1); and one or more hydroxyl group-containing structural units selected from structural units having a phenolic hydroxyl group; and (E) a solvent Resin composition.
    Figure JPOXMLDOC01-appb-C000001
     [In formula (i), R 1 and R 2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, at least one carbon-carbon bond in the hydrocarbon group having 1 to 20 carbon atoms] during, -O -, - COO -, - OCO -, - OSO 2 -, - SO 3 -, - OSO 2 NR -, - NRSO 2 -, - NRCO -, - selected from NR- and -CONR- R 1 and R 2 represent a group having at least one group or a group in which a part of hydrogen atoms in these groups is substituted, and R 1 and R 2 together with the boron atom to which OR 1 and OR 2 are bonded and the number of ring members It may form 3 to 20 ring structures. The R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a bond. ]
    Figure JPOXMLDOC01-appb-C000002
     [In formula (ii-1), R 3 and R 4 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an electron withdrawing group, provided that the above R 3 and R 4 are each independently And at least one of them is an electron withdrawing group, and * represents a bond. ]
  2. 　重合体（Ａ）が、下記式（iii）で表される部分構造を有する構造単位をさらに含む、請求項１に記載の樹脂組成物。
    Figure JPOXMLDOC01-appb-C000003
     ［式（iii）中、Ｒ5は、炭素数１～２０の有機基であり；Ｒ6は、水素原子または炭素数１～２０の炭化水素基であり、ｎは０～３の整数であり、＊は結合手を示す。］     The resin composition of Claim 1 in which a polymer (A) further contains the structural unit which has a partial structure represented by following formula (iii).
    Figure JPOXMLDOC01-appb-C000003
     [In formula (iii), R 5 is an organic group having 1 to 20 carbon atoms; R 6 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and n is an integer of 0 to 3 , * Indicates a bonding hand. ]
  3. 　重合体（Ａ）が、下記式（iv）で表される部分構造を有する構造単位をさらに含む、請求項１～２のいずれか１項に記載の樹脂組成物。
    Figure JPOXMLDOC01-appb-C000004
     ［式（iv）中、Ｒ7およびＲ8は、各々独立に、水素原子、炭素数１～２０の炭化水素基、前記炭素数１～２０の炭化水素基中の少なくとも１つの炭素－炭素結合間に、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＳＯ2－、－ＳＯ3－、－ＯＳＯ2ＮＲ105－、－ＮＲ105ＳＯ2－、－ＮＲ105ＣＯ－、－ＮＲ105－および－ＣＯＮＲ105－から選ばれる少なくとも一種を有する基、またはこれらの基中の水素原子の一部が置換された基を示し、Ｒ7およびＲ8は、相互に結合してＯＲ7およびＯＲ8が結合するリン原子と共に環員数３～２０の環状構造を形成してもよく、前記Ｒ105は、水素原子または炭素数１～２０の炭化水素基であり、＊は結合手を示す。］     The resin composition according to any one of claims 1 to 2, wherein the polymer (A) further comprises a structural unit having a partial structure represented by the following formula (iv).
    Figure JPOXMLDOC01-appb-C000004
     [In formula (iv), each of R 7 and R 8 independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, at least one carbon-carbon bond in the hydrocarbon group having 1 to 20 carbon atoms] during, -O -, - COO -, - OCO -, - OSO 2 -, - SO 3 -, - OSO 2 NR 105 -, - NR 105 SO 2 -, - NR 105 CO -, - NR 105 - and -CONR 105 - represents at least one group having or part of which is a substituent of the hydrogen atoms in these groups are selected from, R 7 and R 8, oR 7 and oR 8 are bonded to each other The ring structure having 3 to 20 ring members may be formed together with the phosphorus atom to be bonded, and the above R 105 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * indicates a bonding hand. ]
  4. 　重合体（Ａ）が、エポキシ基を有する構造単位をさらに含む、請求項１～３のいずれか１項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 3, wherein the polymer (A) further comprises a structural unit having an epoxy group.
  5. 　上記水酸基含有構造単位が、上記式（ii-1）で表される部分構造を有する構造単位である、請求項１～４のいずれか１項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 4, wherein the hydroxyl group-containing structural unit is a structural unit having a partial structure represented by the above formula (ii-1).
  6. 　上記フェノール性水酸基を有する構造単位が、加熱により環化してフェノール性水酸基が消失するフェノール性水酸基含有不飽和化合物由来の構造単位である、請求項１～５のいずれか１項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 5, wherein the structural unit having a phenolic hydroxyl group is a structural unit derived from a phenolic hydroxyl group-containing unsaturated compound which is cyclized by heating to lose the phenolic hydroxyl group. object.
  7. 　上記式（ｉ）で表される部分構造を有する構造単位が下記式（１）で表される、請求項１～６のいずれか１項に記載の樹脂組成物。
    Figure JPOXMLDOC01-appb-C000005
     ［式（１）中、Ｒ1およびＲ2は、それぞれ式（ｉ）中の同一記号と同義であり；Ｒ11は、水素原子、フッ素原子、炭素数１～１０の炭化水素基、または炭素数１～１０のフッ素化炭化水素基であり；Ｌ1は、単結合、酸素原子、硫黄原子、または－Ｃ（＝Ｏ）－Ｘ1－で表される基であり、Ｘ1は、酸素原子、硫黄原子またはＮＨ基であり；Ｒ12は、炭素数１～２０の（ａ＋１）価の炭化水素基、前記炭化水素基中の少なくとも１つの炭素－炭素結合間に、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＳＯ2－、－ＳＯ3－、－ＯＳＯ2ＮＲ101－、－ＮＲ101ＳＯ2－、－ＮＲ101ＣＯ－、－ＮＲ101－および－ＣＯＮＲ101－から選ばれる少なくとも一種を有する基、またはこれらの基中の水素原子の一部が置換された基であり、前記Ｒ101は、水素原子または炭素数１～２０の炭化水素基であり；ａは１～３の整数である。］     The resin composition according to any one of claims 1 to 6, wherein a structural unit having a partial structure represented by the above formula (i) is represented by the following formula (1).
    Figure JPOXMLDOC01-appb-C000005
     [In formula (1), R 1 and R 2 each have the same meaning as the same symbol in formula (i); R 11 is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, or carbon L 1 is a single bond, an oxygen atom, a sulfur atom, or a group represented by —C (= O) —X 1 —, and X 1 is an oxygen R 12 represents an (a + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, at least one carbon-carbon bond in the hydrocarbon group, —O—, — At least one selected from COO-, -OCO-, -OSO 2- , -SO 3- , -OSO 2 NR 101- , -NR 101 SO 2- , -NR 101 CO-, -NR 101 -and -CONR 101- R 1 is a group having one type, or a group obtained by substituting a part of hydrogen atoms in these groups, and the above R 101 is water A prime atom or a hydrocarbon group having 1 to 20 carbon atoms; a is an integer of 1 to 3; ]
  8. 　上記式（ii-1）で表される部分構造を有する構造単位が下記式（２）で表される、請求項１～７のいずれか１項に記載の樹脂組成物。
    Figure JPOXMLDOC01-appb-C000006
     ［式（２）中、Ｒ3およびＲ4は、それぞれ式（ii-1）中の同一記号と同義であり；Ｒ13は、水素原子、フッ素原子、炭素数１～１０の炭化水素基、または炭素数１～１０のフッ素化炭化水素基であり；Ｌ2は、単結合、酸素原子、硫黄原子、または－Ｃ（＝Ｏ）－Ｘ2－で表される基であり、Ｘ2は、酸素原子、硫黄原子またはＮＨ基であり；Ｒ14は、炭素数１～２０の（ｂ＋１）価の炭化水素基、前記炭化水素基中の少なくとも１つの炭素－炭素結合間に、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＳＯ2－、－ＳＯ3－、－ＯＳＯ2ＮＲ102－、－ＮＲ102ＳＯ2－、－ＮＲ102ＣＯ－、－ＮＲ102－および－ＣＯＮＲ102－から選ばれる少なくとも一種を有する基、またはこれらの基中の水素原子の一部が置換された基であり、前記Ｒ102は、水素原子または炭素数１～２０の炭化水素基であり；ｂは１～３の整数である。］     The resin composition according to any one of claims 1 to 7, wherein the structural unit having a partial structure represented by the above formula (ii-1) is represented by the following formula (2).
    Figure JPOXMLDOC01-appb-C000006
     [In formula (2), R 3 and R 4 each have the same meaning as the same symbol in formula (ii-1); R 13 is a hydrogen atom, a fluorine atom, or a hydrocarbon group having 1 to 10 carbon atoms, Or a fluorinated hydrocarbon group having 1 to 10 carbon atoms; L 2 is a single bond, an oxygen atom, a sulfur atom, or a group represented by —C (= O) —X 2 —, and X 2 is R 14 is a (b + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, at least one carbon-carbon bond in the hydrocarbon group, -O- , -COO -, - OCO -, - OSO 2 -, - SO 3 -, - OSO 2 NR 102 -, - NR 102 SO 2 -, - NR 102 CO -, - NR 102 - and -CONR 102 - selected from at least one group having the or a part of which is a substituent of the hydrogen atoms in these groups, the R 102 is that, A hydrocarbon group atom or a C 1 ~ 20; b is an integer of 1-3. ]
  9. 　上記式（iii）で表される部分構造を有する構造単位が下記式（３）で表される、請求項２に記載の樹脂組成物。
    Figure JPOXMLDOC01-appb-C000007
     ［式（３）中、Ｒ5、Ｒ6およびｎは、それぞれ式（iii）中の同一記号と同義であり；Ｒ15は、水素原子、フッ素原子、炭素数１～１０の炭化水素基、または炭素数１～１０のフッ素化炭化水素基であり；Ｌ3は、単結合、酸素原子、硫黄原子、または－Ｃ（＝Ｏ）－Ｘ3－で表される基であり、Ｘ3は、酸素原子、硫黄原子またはＮＨ基であり；Ｒ16は、炭素数１～２０の（ｃ＋１）価の炭化水素基、前記炭化水素基中の少なくとも１つの炭素－炭素結合間に、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＳＯ2－、－ＳＯ3－、－ＯＳＯ2ＮＲ104－、－ＮＲ104ＳＯ2－、－ＮＲ104ＣＯ－、－ＮＲ104－および－ＣＯＮＲ104－から選ばれる少なくとも一種を有する基、またはこれらの基中の水素原子の一部が置換された基であり、前記Ｒ104は、水素原子または炭素数１～２０の炭化水素基であり；ｃは１～３の整数である。］     The resin composition of Claim 2 in which the structural unit which has a partial structure represented by the said Formula (iii) is represented by following formula (3).
    Figure JPOXMLDOC01-appb-C000007
     [In formula (3), R 5 , R 6 and n each have the same meaning as the same symbol in formula (iii); R 15 is a hydrogen atom, a fluorine atom, a hydrocarbon group having 1 to 10 carbon atoms, Or a fluorinated hydrocarbon group having 1 to 10 carbon atoms; L 3 is a single bond, an oxygen atom, a sulfur atom, or a group represented by —C (= O) —X 3 —, and X 3 is R 16 is a (C + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, at least one carbon-carbon bond in the above-mentioned hydrocarbon group, —O—, , -COO -, - OCO -, - OSO 2 -, - SO 3 -, - OSO 2 NR 104 -, - NR 104 SO 2 -, - NR 104 CO -, - NR 104 - and -CONR 104 - selected from group having at least one kind or a group partially substituted for hydrogen atoms in these groups, the R 104, , It is a hydrogen atom or a hydrocarbon group having a carbon number of 1 ~ 20; c is an integer of 1-3. ]
  10. 　重合体（Ａ）が、上記式（ｉ）で表される部分構造を有する構造単位を、全構造単位中、５～６０モル％含む、請求項１～９のいずれか１項に記載の樹脂組成物。 The resin according to any one of claims 1 to 9, wherein the polymer (A) contains 5 to 60% by mole of structural units having a partial structure represented by the above formula (i) in all structural units. Composition.
  11. 　重合体（Ａ）が、上記式（ii-1）で表される部分構造を有する構造単位、およびフェノール性水酸基を有する構造単位から選択される一以上の水酸基含有構造単位を、全構造単位中、５～９０モル％含む、請求項１～１０のいずれか１項に記載の樹脂組成物。 The polymer (A) is one or more hydroxyl group-containing structural units selected from structural units having a partial structure represented by the above formula (ii-1) and structural units having a phenolic hydroxyl group in all structural units The resin composition according to any one of claims 1 to 10, containing 5 to 90 mol%.
  12. 　重合体（Ａ）が、上記式（iii）で表される部分構造を有する構造単位を、全構造単位中、５～５０モル％含む、請求項２または９に記載の樹脂組成物。 The resin composition according to claim 2 or 9, wherein the polymer (A) contains 5 to 50% by mole of structural units having a partial structure represented by the above formula (iii) in all structural units.
  13. 　重合体（Ａ）が、前記エポキシ基を有する構造単位を、全構造単位中、５～４５モル％含む、請求項４に記載の樹脂組成物。 The resin composition according to claim 4, wherein the polymer (A) contains 5 to 45 mol% of structural units having the epoxy group in all structural units.
  14. 　感光性酸発生剤（Ｂ）または光重合開始剤（Ｄ）をさらに含有する、請求項１～１３のいずれか１項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 13, further comprising a photosensitive acid generator (B) or a photopolymerization initiator (D).
  15. 　架橋剤（Ｃ）をさらに含有する、請求項１～１４のいずれか１項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 14, further comprising a crosslinking agent (C).
  16. 　下記式（ｉ）で表される部分構造を有する構造単位と、
    　下記式（ii-1）で表される部分構造を有する構造単位、およびフェノール性水酸基を有する構造単位から選択される一以上の水酸基含有構造単位と
    を含む重合体。
    Figure JPOXMLDOC01-appb-C000008
     ［式（ｉ）中、Ｒ1およびＲ2は、各々独立に、水素原子、炭素数１～２０の炭化水素基、前記炭素数１～２０の炭化水素基中の少なくとも１つの炭素－炭素結合間に、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＳＯ2－、－ＳＯ3－、－ＯＳＯ2ＮＲ－、－ＮＲＳＯ2－、－ＮＲＣＯ－、－ＮＲ－および－ＣＯＮＲ－から選ばれる少なくとも一種を有する基、またはこれらの基中の水素原子の一部が置換された基を示し、Ｒ1およびＲ2は、相互に結合してＯＲ1およびＯＲ2が結合するホウ素原子と共に環員数３～２０の環状構造を形成してもよい。前記Ｒは、水素原子または炭素数１～２０の炭化水素基であり、＊は結合手を示す。］
    Figure JPOXMLDOC01-appb-C000009
     ［式（ii-1）中、Ｒ3およびＲ4は、各々独立に、水素原子、炭素数１～２０の炭化水素基、または電子求引性基であり、但し、上記Ｒ3およびＲ4のうち、少なくともいずれかは電子求引性基であり、＊は結合手を示す。］     A structural unit having a partial structure represented by the following formula (i):
    A polymer comprising a structural unit having a partial structure represented by the following formula (ii-1) and one or more hydroxyl group-containing structural units selected from structural units having a phenolic hydroxyl group.
    Figure JPOXMLDOC01-appb-C000008
     [In formula (i), R 1 and R 2 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, at least one carbon-carbon bond in the hydrocarbon group having 1 to 20 carbon atoms] during, -O -, - COO -, - OCO -, - OSO 2 -, - SO 3 -, - OSO 2 NR -, - NRSO 2 -, - NRCO -, - selected from NR- and -CONR- R 1 and R 2 represent a group having at least one group or a group in which a part of hydrogen atoms in these groups is substituted, and R 1 and R 2 together with the boron atom to which OR 1 and OR 2 are bonded and the number of ring members It may form 3 to 20 ring structures. The R is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a bond. ]
    Figure JPOXMLDOC01-appb-C000009
     [In formula (ii-1), R 3 and R 4 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or an electron withdrawing group, provided that the above R 3 and R 4 are each independently And at least one of them is an electron withdrawing group, and * represents a bond. ]
  17. 　下記式（iii）で表される部分構造を有する構造単位をさらに含む、請求項１６に記載の重合体。
    Figure JPOXMLDOC01-appb-C000010
     ［式（iii）中、Ｒ5は、炭素数１～２０の有機基であり；Ｒ6は、水素原子または炭素数１～２０の炭化水素基であり、ｎは０～３の整数であり、＊は結合手を示す。］     The polymer according to claim 16, further comprising a structural unit having a partial structure represented by the following formula (iii).
    Figure JPOXMLDOC01-appb-C000010
     [In formula (iii), R 5 is an organic group having 1 to 20 carbon atoms; R 6 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and n is an integer of 0 to 3 , * Indicates a bonding hand. ]
  18. 　下記式（iv）で表される部分構造を有する構造単位をさらに含む、請求項１６～１７のいずれか１項に記載の重合体。
    Figure JPOXMLDOC01-appb-C000011
     ［式（iv）中、Ｒ7およびＲ8は、各々独立に、水素原子、炭素数１～２０の炭化水素基、前記炭素数１～２０の炭化水素基中の少なくとも１つの炭素－炭素結合間に、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、－ＯＳＯ2－、－ＳＯ3－、－ＯＳＯ2ＮＲ105－、－ＮＲ105ＳＯ2－、－ＮＲ105ＣＯ－、－ＮＲ105－および－ＣＯＮＲ105－から選ばれる少なくとも一種を有する基、またはこれらの基中の水素原子の一部が置換された基を示し、Ｒ7およびＲ8は、相互に結合してＯＲ7およびＯＲ8が結合するリン原子と共に環員数３～２０の環状構造を形成してもよく、前記Ｒ105は、水素原子または炭素数１～２０の炭化水素基であり、＊は結合手を示す。］     The polymer according to any one of claims 16 to 17, further comprising a structural unit having a partial structure represented by the following formula (iv).
    Figure JPOXMLDOC01-appb-C000011
     [In formula (iv), each of R 7 and R 8 independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, at least one carbon-carbon bond in the hydrocarbon group having 1 to 20 carbon atoms] during, -O -, - COO -, - OCO -, - OSO 2 -, - SO 3 -, - OSO 2 NR 105 -, - NR 105 SO 2 -, - NR 105 CO -, - NR 105 - and -CONR 105 - represents at least one group having or part of which is a substituent of the hydrogen atoms in these groups are selected from, R 7 and R 8, oR 7 and oR 8 are bonded to each other The ring structure having 3 to 20 ring members may be formed together with the phosphorus atom to be bonded, and the above R 105 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * indicates a bonding hand. ]
  19. 　エポキシ基を有する構造単位をさらに含む、請求項１６～１８のいずれか１項に記載の重合体。 The polymer according to any one of claims 16 to 18, further comprising a structural unit having an epoxy group.
  20. 　請求項１～１５のいずれか１項に記載の樹脂組成物を硬化させて得られる樹脂膜。 A resin film obtained by curing the resin composition according to any one of claims 1 to 15.
  21. 　請求項１４に記載の樹脂組成物を支持体上に塗布して塗布膜を形成する工程、前記塗布膜を選択的に露光して選択露光膜を得る工程、アルカリ性現像液により前記選択露光膜を現像してパターン化した塗布膜を得る工程、および前記パターン化した塗布膜を硬化させてパターン化樹脂膜を得る工程を有する、パターン化樹脂膜の製造方法。 A step of applying a resin composition according to claim 14 onto a support to form a coating film, a step of selectively exposing the coating film to obtain a selective exposure film, an alkaline developer to form the selective exposure film A method for producing a patterned resin film, comprising the steps of developing to obtain a patterned coating film, and curing the patterned coating film to obtain a patterned resin film.
  22. 　請求項２０に記載の樹脂膜を有する電子部品。 An electronic component comprising the resin film according to claim 20.
PCT/JP2018/025282 2017-08-10 2018-07-03 Polymer, resin composition, resin film, method for producing patterned resin film, and electronic component WO2019031114A1 (en)

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