WO2017221620A1 - Curable composition, cured film, color filter, light-blocking film, solid-state imaging element, image display device, method for producing cured film, and polyfunctional thiol compound - Google Patents

Curable composition, cured film, color filter, light-blocking film, solid-state imaging element, image display device, method for producing cured film, and polyfunctional thiol compound Download PDF

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Publication number
WO2017221620A1
WO2017221620A1 PCT/JP2017/019297 JP2017019297W WO2017221620A1 WO 2017221620 A1 WO2017221620 A1 WO 2017221620A1 JP 2017019297 W JP2017019297 W JP 2017019297W WO 2017221620 A1 WO2017221620 A1 WO 2017221620A1
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group
curable composition
compound
cured film
formula
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PCT/JP2017/019297
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French (fr)
Japanese (ja)
Inventor
明夫 水野
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富士フイルム株式会社
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Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to KR1020207029831A priority Critical patent/KR102197489B1/en
Priority to KR1020187032850A priority patent/KR20180134984A/en
Priority to JP2018523616A priority patent/JP6818751B2/en
Publication of WO2017221620A1 publication Critical patent/WO2017221620A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/24—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/25—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
    • C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/64—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton
    • C07C323/66—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and sulfur atoms, not being part of thio groups, bound to the same carbon skeleton containing sulfur atoms of sulfo, esterified sulfo or halosulfonyl groups, bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/30—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures

Definitions

  • the present invention relates to a curable composition, a cured film, a color filter, a light shielding film, a solid-state imaging device, an image display device, a method for producing a cured film, and a polyfunctional thiol compound.
  • a color filter used in an image display device is provided with a light shielding film called a black matrix for the purpose of shielding light between colored pixels and improving contrast.
  • a light shielding film is provided for the purpose of preventing noise and improving image quality.
  • portable terminals of electronic devices such as mobile phones and PDAs (Personal Digital Assistants) are equipped with small and thin imaging units.
  • Such an imaging unit generally includes a solid-state imaging device such as a CCD (Charge Coupled Device) image sensor and a CMOS (Complementary Metal-Oxide Semiconductor) image sensor, a lens for forming a subject image on the solid-state imaging device, It has.
  • Patent Document 1 discloses that “a photosensitive resin composition for forming a partition for separating pixels in an image display device, wherein the photosensitive resin composition has a carboxyl group in the molecule as the component (A).
  • the present inventor applied the photosensitive resin composition described in Patent Document 1 onto a support and exposed the obtained photosensitive resin composition layer to produce a cured film. As a result, the exposure sensitivity was further improved. I found out that there is room for it. Specifically, it has been found that the photosensitive resin composition described in Patent Document 1 has a problem that the energy required for exposure increases when trying to obtain a finer pattern shape. Moreover, when this inventor examined the cured film obtained by said method, it also discovered that there was room for the further improvement in adhesiveness with a support body (henceforth a "board
  • this invention makes it a subject to provide the curable composition which can obtain the cured film which has the outstanding exposure sensitivity and has the outstanding adhesiveness with a support body. Moreover, this invention makes it a subject to provide the manufacturing method of a cured film, a color filter, a light shielding film, a solid-state image sensor, an image display apparatus, a cured film, and a polyfunctional thiol compound.
  • the polyfunctional thiol compound is a compound represented by the formula (2).
  • m is an integer of 3 to 14.
  • the interactive group different from the thiol group is a hydroxyl group, amino group, pyridinyl group, pyridinium group, ammonium group, phosphonium group, carboxylic acid group or salt thereof, phosphoric acid group or salt thereof, sulfonic acid group or [1] to [1] which are at least one selected from the group consisting of a salt, an aryl group, —Si (R X ) p (R Y ) 3-p , and — (OR A ) q —R Z 4].
  • the curable composition according to any one of [4].
  • R X represents a hydrolyzable group
  • R Y represents a monovalent organic group excluding the hydrolyzable group
  • p R X represents a hydrolyzable group
  • p R X represents a monovalent organic group excluding the hydrolyzable group
  • p R X represents a monovalent organic group excluding the hydrolyzable group
  • p R X represents a monovalent organic group excluding the hydrolyzable group
  • p R X represents a monovalent organic group excluding the hydrolyzable group
  • p R X represents a monovalent organic group excluding the hydrolyzable group
  • p R X represents a monovalent organic group excluding the hydrolyzable group
  • p R X represents a monovalent organic group excluding the hydrolyzable group
  • p R X represents a monovalent organic group excluding the hydrolyzable group
  • p R X represents a monovalent organic group excluding the hydrolyzable group
  • p R X represents
  • the interactive group different from the thiol group is a hydroxyl group, amino group, pyridinyl group, pyridinium group, ammonium group, phosphonium group, carboxylic acid group or salt thereof, phosphoric acid group or salt thereof, and sulfonic acid group
  • the interactive group different from the thiol group is selected from the group consisting of hydroxyl group, amino group, pyridinyl group, carboxylic acid group or salt thereof, phosphoric acid group or salt thereof, and sulfonic acid group or salt thereof.
  • An image display device comprising the cured film according to [11].
  • a curable composition layer forming step of forming a curable composition layer on a support using the curable composition according to any one of [1] to [10], and a curable composition layer The manufacturing method of the cured film containing the exposure process which exposes.
  • the curing according to [16] or [17] further comprising: a developing step for developing the exposed curable composition layer; and a washing step for washing the developed curable composition layer.
  • a method for producing a membrane A method for producing a membrane.
  • a polyfunctional thiol compound containing two or more thiol groups and an interactive group different from the thiol group [20] The polyfunctional thiol compound according to [19], which is a compound represented by the formula (1). [21] The polyfunctional thiol compound according to [19] or [20], which is a compound represented by the formula (2). [22] The polyfunctional thiol compound according to [20] or [21], wherein m is an integer of 3 to 14.
  • the interactive group different from the thiol group is a hydroxyl group, amino group, pyridinyl group, pyridinium group, ammonium group, phosphonium group, carboxylic acid group or salt thereof, phosphoric acid group or salt thereof, sulfonic acid group or [19] to [19], which is at least one selected from the group consisting of a salt thereof, an aryl group, —Si (R X ) p (R Y ) 3-p , and — (OR A ) q —R Z. 22].
  • the polyfunctional thiol compound according to any one of [22].
  • R X represents a hydrolyzable group
  • R Y represents a monovalent organic group excluding the hydrolyzable group
  • p R X represents a hydrolyzable group
  • p R X represents a monovalent organic group excluding the hydrolyzable group
  • p R X represents a monovalent organic group excluding the hydrolyzable group
  • p R X represents a monovalent organic group excluding the hydrolyzable group
  • p R X represents a monovalent organic group excluding the hydrolyzable group
  • p R X represents a monovalent organic group excluding the hydrolyzable group
  • p R X represents a monovalent organic group excluding the hydrolyzable group
  • p R X represents a monovalent organic group excluding the hydrolyzable group
  • p R X represents a monovalent organic group excluding the hydrolyzable group
  • p R X represents a monovalent organic group excluding the hydrolyzable group
  • p R X represents
  • the interactive group different from the thiol group is a hydroxyl group, amino group, pyridinyl group, pyridinium group, ammonium group, phosphonium group, carboxylic acid group or salt thereof, phosphoric acid group or salt thereof, and sulfonic acid group
  • the curable composition which has the outstanding exposure sensitivity and can obtain the cured film which has the outstanding adhesiveness with a support body
  • the present invention can provide a cured film, a color filter, a light shielding film, a solid-state imaging device, an image display device, a method for producing a cured film, and a polyfunctional thiol compound.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • group (atomic group) in this specification, the notation which does not describe substitution and unsubstitution includes what does not contain a substituent and what contains a substituent.
  • the “alkyl group” includes not only an alkyl group not containing a substituent (unsubstituted alkyl group) but also an alkyl group containing a substituent (substituted alkyl group).
  • active light or “radiation” means, for example, the emission line spectrum of a mercury lamp, deep ultraviolet light represented by an excimer laser, extreme ultraviolet lithography (EUV), X-ray, and electron beam. Etc.
  • light means actinic rays and radiation.
  • exposure in the present specification includes not only exposure with an emission line spectrum of a mercury lamp and far ultraviolet rays such as an excimer laser, X-rays and EUV light, but also an electron beam and an ion beam, etc. Also includes drawing with particle beams.
  • (meth) acrylate represents acrylate and methacrylate.
  • (meth) acryl represents acryl and methacryl.
  • (meth) acryloyl represents acryloyl and methacryloyl.
  • (meth) acrylamide represents acrylamide and methacrylamide.
  • “monomer” and “monomer” are synonymous.
  • a monomer is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less.
  • the polymerizable compound means a compound containing a polymerizable group, and may be a monomer or a polymer.
  • the polymerizable group refers to a group that participates in a polymerization reaction.
  • the curable composition is a curable composition containing a polyfunctional thiol compound, a polymerizable compound, and a photopolymerization initiator, and the polyfunctional thiol compound includes two or more thiol groups, a thiol group, Contains different interactive groups.
  • the inventor forms a curable composition layer on a support using the curable composition containing a thiol compound described in Patent Document 1, and exposes the curable composition layer to fine It has been found that the amount of exposure must be increased when trying to produce a cured film having a simple pattern shape. It is presumed that this is because when the pattern shape is made finer, the opening of the photomask becomes narrower, and as a result, the amount of light applied to the curable composition layer is further reduced. That is, since the amount of light reaching the bottom of the curable composition is reduced, it is estimated that the bottom of the curable composition layer is difficult to cure. In such a case, the amount of light reaching the bottom of the curable composition layer can be increased by increasing the exposure amount.
  • the exposure amount when the exposure amount is increased, the light diffracted at the mask opening, so-called “leakage light”, tends to increase, and the mask should be originally masked on the upper part of the curable composition layer (that is, the portion closer to the photomask). The part was exposed and the pattern shape might be deteriorated.
  • a radical reaction is initiated by the photopolymerization initiator.
  • radicals generated by the photopolymerization initiator and oxygen in the curable composition layer may be generated, and peroxy radicals may be generated. Since peroxy radicals do not have an action to advance the reaction, the polymerization reaction may stop there.
  • the curable composition contains a polyfunctional thiol compound containing two or more thiol groups. Since the thiol group generates a thiyl radical that is less susceptible to polymerization deactivation by donating hydrogen to the peroxy radical, the polymerization reaction continues. Furthermore, the polyfunctional thiol compound contains an interactive group different from the thiol group. The interactive group interacts with the support (or with the molecules constituting the overcoat layer if the support comprises an overcoat layer). Therefore, it is estimated that the polyfunctional thiol compound is likely to be unevenly distributed in a portion closer to the support (that is, the bottom portion) in the curable composition layer formed using the curable composition.
  • the action of the thiol group is more effectively exhibited. Guessed. That is, when the exposure amount is smaller, the amount of light reaching the bottom of the curable composition layer is small, but the polyfunctional thiol compound is likely to be unevenly distributed at the bottom, so that thiyl radicals are easily generated at the bottom of the curable composition layer. It is estimated that even the small amount of light is sufficiently cured to the bottom.
  • the interaction group is unevenly distributed in a portion closer to the support (that is, the bottom), so that the interaction with the support becomes stronger and has excellent adhesion to the support. Guessed.
  • components contained in the curable composition according to one embodiment of the present invention will be described.
  • the curable composition contains a predetermined polyfunctional thiol compound.
  • the polyfunctional thiol compound is not particularly limited as long as it contains two or more thiol groups (a group represented by —SH) and an interactive group different from the thiol group. Compounds can be used.
  • the number of thiol groups contained in the polyfunctional thiol compound is 2 or more, preferably 3 or more, and more preferably 4 or more.
  • the upper limit of the number of thiol groups contained in the polyfunctional thiol compound is not particularly limited, but is generally preferably 30 or less, more preferably 20 or less, and still more preferably 14 or less.
  • the number of interactive groups different from the thiol group contained in the polyfunctional thiol compound is 1 or more, and preferably 2 or more.
  • the upper limit of the interactive group different from the thiol group contained in the polyfunctional thiol compound is not particularly limited, but is generally preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less.
  • the interactive group means a group capable of interacting with other molecules.
  • the interaction includes groups capable of interacting in any manner such as intermolecular force, molecular association, electrostatic attraction, ionic bond, and / or hydrogen bond.
  • numerator which forms the support body and / or undercoat which are mentioned later is preferable. Specific examples of the interactive group will be described in detail later.
  • the content of the polyfunctional thiol compound is preferably 0.5 to 10% by mass with respect to the total solid content of the curable composition.
  • the content of the polyfunctional thiol compound is 0.5 to 10% by mass, the exposure sensitivity is more excellent.
  • a polyfunctional thiol compound may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of polyfunctional thiol compounds together, it is preferable that the total amount is in the said range.
  • polyfunctional thiol compound a compound represented by the following formula (1) is preferable.
  • L 1 and L 2 each independently represent a divalent linking group.
  • m represents an integer of 2 to 14, preferably an integer of 3 to 14, and more preferably 3 to 6.
  • n represents an integer of 1 to 15.
  • L 3 represents an m + n-valent linking group
  • R 1 represents an interactive group different from the thiol group. Note that L 1 and L 2 may be the same as or different from each other, and m L 1 , n L 2 , and n R 1 may be the same or different. Good.
  • Examples of the divalent linking group for L 1 include a divalent aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms), a divalent aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms),- O—, —S—, —N (R 4 ) — (R 4 : monovalent organic group), —C ( ⁇ O) —, —C ( ⁇ O) —O—, —O—C ( ⁇ O ) —O—, —C ( ⁇ O) —NH—, —O—C ( ⁇ O) —NH—, —S ( ⁇ O) —, —S ( ⁇ O) —O—, —S ( ⁇ O) 2 —, —S ( ⁇ O) 2 —O—, —CH ⁇ N—, —N (R) — (R: alkyl group), or a combination thereof (eg, alkyleneoxy group, alkyleneoxy group) Carbonyl group, alkylenecarbonyloxy group and the like).
  • the divalent linking group of L 2 is the same as the above aspect of L 1 .
  • L 1 and L 2 may be the same as or different from each other.
  • m L 1 and n L 2 in one molecule of the polyfunctional thiol compound may be the same or different.
  • Examples of the m + n-valent linking group of L 3 include a trimethylolpropane residue and a trivalent group such as an isocyanur ring having three — (CH 2 ) k — (k represents an integer of 2 to 6, for example).
  • a tetravalent linking group such as a pentaerythritol residue, a pentavalent linking group, a hexavalent linking group such as a dipentaerythritol residue, and combinations thereof.
  • m + n is 3 or more, preferably 4 or more.
  • m + n is 29 or less, and preferably 10 or less.
  • Examples of the m + n-valent linking group of L 3 include a group represented by any of the following formulas (A) to (D), or a group obtained by combining these groups.
  • L 4 represents a trivalent group.
  • T 3 represents a single bond or a divalent linking group, and three T 3 s may be the same as or different from each other.
  • L 5 represents a tetravalent group.
  • T 4 represents a single bond or a divalent linking group, and the four T 4 s may be the same as or different from each other.
  • L 6 represents a pentavalent group.
  • T 5 represents a single bond or a divalent linking group, and the five T 5 s may be the same as or different from each other.
  • L 7 represents a hexavalent group.
  • T 6 represents a single bond or a divalent linking group, and the six T 6 s may be the same as or different from each other.
  • the definition of the divalent linking group represented by T 3, T 4, T 5 and T 6 are the same as those defined divalent linking group represented by L 1 described above.
  • m + n-valent linking group of L 3 for example, groups represented by the following formulas (E) to (J), or a group obtained by combining these are preferable.
  • R represents a hydrogen atom or a monovalent organic group.
  • the monovalent organic group an alkyl group is preferable. * Indicates a binding position.
  • t represents an integer of 2 to 11.
  • L 3 may be a group represented by the following formulas (K) to (O), or a group obtained by combining these.
  • * represents a bonding position.
  • R 1 is the same as the embodiment of the interactive group different from the thiol group already described.
  • the hydroxyl group, the amino group, the pyridinyl group, the pyridinium group, the ammonium group, and the phosphonium group are examples of the interactive group different from the thiol group in that the cured film has better adhesion to the support.
  • At least one selected from the group consisting of a salt thereof, a phosphoric acid group or a salt thereof, and a sulfonic acid group or a salt thereof More preferred is at least one selected from the group consisting of a group, a pyridinyl group, a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and a sulfonic acid group or a salt thereof.
  • the interaction group different from the thiol group is the functional group described above, the mechanism by which the cured film has better adhesion to the support is not necessarily clear. I guess.
  • the interaction is broadly classified as van der Waals interaction, ⁇ - ⁇ stacking, hydrogen- ⁇ bond, electrostatic interaction, or hydrogen bond. It is speculated that “hydrogen bonding” is the strongest, followed by “electrostatic interaction”.
  • the hydrogen- ⁇ bond which is a bond between the ⁇ electron of the phenyl group and the O—H hydrogen, is considered to be weaker than the above two, and it is presumed that the above-described effect was obtained.
  • the mechanism by which the effect of this invention is acquired is not restricted to the said estimation.
  • the amino group includes a primary amino group (NH 2 —), a secondary amino group (NR a H—), and a tertiary amino group (NR a R a —).
  • a primary amino group (NH 2 —)
  • a secondary amino group (NR a H—)
  • a tertiary amino group (NR a R a —).
  • Ra contained in a secondary amino group and a tertiary amino group will not be restrict
  • a hydrocarbon group for example, alkyl group
  • R X represents a hydrolyzable group.
  • the hydrolyzable group means a group that is directly bonded to a silicon atom (Si) and can proceed with a hydrolysis reaction.
  • Si silicon atom
  • R Y represents a monovalent organic group.
  • the monovalent organic group may be any organic group other than a hydrolyzable group, such as an alkyl group, alkenyl group, aryl group, alkylcarbonyl group, cycloalkylcarbonyl group, arylcarbonyl group, alkyloxycarbonyl group.
  • an alkyl group, an aryl group, an alkenyl group, or a combination of these is preferable.
  • the number of carbon atoms contained in the alkyl group is preferably 1 to 6, and may be any of linear, branched, and cyclic.
  • the number of carbon atoms contained in the aryl group is preferably 6-10.
  • the number of carbon atoms contained in the alkenyl group is preferably 2-12.
  • p is an integer of 1 to 3. Among these, p is preferably 3 in that the cured film has better adhesion to the support. In addition, p R X and 3-p R Y may be the same or different.
  • R Z represents a hydrogen atom, an alkyl group, or an alkoxy group, and the alkyl group and the alkyl group in the alkoxy group preferably have 1 to 6 carbon atoms. It may be any of a chain, a branch, or a ring.
  • R A represents an alkylene group having 1 to 15 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 6 carbon atoms.
  • q represents an integer of 1 to 4, more preferably an integer of 2 to 4, and still more preferably an integer of 3 to 4.
  • ⁇ Preferred embodiment 2 of polyfunctional thiol compound As the polyfunctional thiol compound, a compound represented by the following formula (2) is more preferable.
  • R 2 and R 3 each independently represent a divalent linking group having 1 or more carbon atoms.
  • the divalent linking group having 1 or more carbon atoms is not particularly limited.
  • a divalent aliphatic hydrocarbon group preferably having 1 to 8 carbon atoms
  • a divalent aromatic hydrocarbon group preferably having a carbon number 6-12
  • R 2 and R 3 may be the same as or different from each other, and m R 2 , n R 2 , and n R 3 may be the same or different from each other. .
  • m represents an integer of 2 to 14, preferably an integer of 3 to 14, and more preferably 3 to 6.
  • n represents an integer of 1 to 15, and preferably 1 to 4.
  • the value of m with respect to n (m / n) is not particularly limited, but is preferably 0.13 to 14, more preferably 1 to 5, and still more preferably 2 to 5.
  • m / n is in the range of 1 to 5, the adhesion between the cured film formed on the support using the curable composition and the support is more excellent.
  • the polyfunctional thiol compound having a smaller m / n has a more excellent pattern shape obtained by curing the curable composition, and a cured film formed on the support using the curable composition; The adhesion with the support is more excellent.
  • L 3 represents an m + n-valent linking group, and the aspect thereof is as described above.
  • R 1 represents an interactive group different from the thiol group, and the mode thereof is the same as that in formula (1) described above.
  • the n R 1 s may be the same or different.
  • the synthesis method of the polyfunctional thiol compound is not particularly limited, and can be synthesized by combining known methods.
  • a desired polyfunctional thiol compound can be synthesized by reacting a raw material compound having a plurality of thiol groups with a compound having a predetermined interactive group and having a group capable of reacting with the thiol group. it can.
  • groups capable of reacting with thiol groups include carbon-carbon double bond groups, carbon-carbon triple bond groups, epoxy groups, carboxyl groups, halogen atoms, alkyl sulfonate groups, and aryl sulfonate groups.
  • a desired polyfunctional thiol compound can be synthesized by reacting a raw material compound having a plurality of thiol groups with a (meth) acrylate compound having a predetermined interactive group by Michael addition.
  • polyfunctional thiol compounds are shown in Table 1 below. However, the polyfunctional thiol compound is not limited to these.
  • the curable composition contains a photopolymerization initiator.
  • the photopolymerization initiator is not particularly limited as long as the polymerization of the polymerizable compound can be initiated, and a known photopolymerization initiator can be used.
  • As the photopolymerization initiator for example, those having photosensitivity from the ultraviolet region to the visible light region are preferable.
  • the photopolymerization initiator may be an activator that generates an active radical by generating some action with the photoexcited sensitizer, and is an initiator that initiates cationic polymerization according to the type of the polymerizable compound. May be.
  • the photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 in the wavelength region of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).
  • the content of the photopolymerization initiator is preferably 1 to 9% by mass with respect to the total solid content of the curable composition.
  • the content of the photopolymerization initiator is 1 to 9% by mass with respect to the total solid content of the curable composition, the pattern shape of the cured film obtained by curing the curable composition is more excellent.
  • a photoinitiator may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of photoinitiators together, it is preferable that the total amount is in the said range.
  • Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those containing a triazine skeleton, those containing an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, Examples include oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones. Examples of the halogenated hydrocarbon compound containing the triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc.
  • trihalomethyltriazine compound trihalomethyltriazine compound, benzyldimethyl ketal compound, ⁇ -hydroxyketone compound, ⁇ -aminoketone compound, acylphosphine compound, phosphine oxide compound, metallocene compound, oxime compound, triallylimidazole dimer, onium compound
  • Preferred are compounds selected from the group consisting of benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds.
  • trihalomethyltriazine compounds ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, or acetophenone compounds are more preferable, trihalomethyltriazine compounds, ⁇ - More preferred is at least one compound selected from the group consisting of an aminoketone compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound.
  • hydroxyacetophenone compounds As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine initiator described in Japanese Patent No. 4225898 can also be used. Examples of the hydroxyacetophenone compound include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names, all manufactured by BASF).
  • aminoacetophenone compounds include commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (trade names, all manufactured by BASF).
  • examples of the aminoacetophenone compound include compounds described in JP-A-2009-191179 in which an absorption wavelength is matched with a long wave light source such as 365 nm or 405 nm.
  • examples of the acylphosphine compound include IRGACURE-819 and DAROCUR-TPO (trade names, both manufactured by BASF), which are commercially available products.
  • ⁇ Oxime compound> More preferred examples of the photopolymerization initiator include oxime compounds (oxime initiators).
  • the said curable composition whose photoinitiator is an oxime compound has more excellent exposure sensitivity. Oxime compounds are preferred because they are highly sensitive, have high polymerization efficiency, can cure the curable composition layer regardless of the colorant concentration, and are easy to design with a high colorant concentration.
  • Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
  • oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2- Acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxycarbonyloxyimino -1-phenylpropan-1-one and the like.
  • J.H. C. S. Perkin II (1979) pp. 1653-1660) J.M. C. S.
  • IRGACURE-OXE01 manufactured by BASF
  • IRGACURE-OXE02 manufactured by BASF
  • IRGACURE-OXE03 manufactured by BASF
  • IRGACURE-OXE04 manufactured by BASF
  • TR-PBG-304 manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.
  • Adeka Arcles NCI-831 and Adeka Arcles NCI-930 manufactured by ADEKA
  • N-1919 carboxyl hydroxybenzoic acid
  • An agent manufactured by ADEKA
  • oxime compounds other than those described above compounds described in JP-T-2009-519904 in which an oxime is linked to the carbazole N-position; compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety; dyes Compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced; Ketooxime compounds described in International Patent Publication No. 2009-131189; Triazine skeleton and oxime skeleton are the same molecule A compound described in US Pat. No.
  • the oxime compound is preferably a compound represented by the following formula (OX-1).
  • the N—O bond of the oxime compound may be an (E) oxime compound, a (Z) oxime compound, a mixture of (E) isomer and (Z) isomer. Good.
  • R and B each independently represent a monovalent substituent
  • A represents a divalent organic group
  • Ar represents an aryl group.
  • the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
  • the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. These groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
  • the substituent examples include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
  • the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the substituents described above.
  • the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the substituents described above.
  • An oxime compound containing a fluorine atom can also be used as a photopolymerization initiator.
  • Specific examples of the oxime compound containing a fluorine atom include compounds described in JP2010-262028; compounds 24 and 36 to 40 described in JP2014-500852; compounds described in JP2013-164471A (C-3); and the like. This content is incorporated herein.
  • photopolymerization initiator compounds represented by the following general formulas (1) to (4) can also be used.
  • R 1 and R 2 are each independently an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or Represents an arylalkyl group having 7 to 30 carbon atoms, and when R 1 and R 2 are phenyl groups, the phenyl groups may be bonded to each other to form a fluorene group, and R 3 and R 4 are each independently Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or carbonyl Indicates a group.
  • R 1, R 2, R 3 and R 4 have the same meanings as R 1, R 2, R 3 and R 4 in Formula (1)
  • R 5 is -R 6, -OR 6 , —SR 6 , —COR 6 , —CONR 6 R 6 , —NR 6 COR 6 , —OCOR 6 , —COOR 6 , —SCOR 6 , —OCSR 6 , —COSR 6 , —CSOR 6 , —CN
  • halogen R 6 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms.
  • X represents a direct bond or a carbonyl group
  • a represents an integer of 0-4.
  • R 1 represents an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl group having 7 to 30 carbon atoms.
  • R 3 and R 4 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a carbon number of 4 Represents a heterocyclic group of ⁇ 20, and X represents a direct bond or a carbonyl group.
  • R 1, R 3 and R 4 have the same meanings as R 1, R 3 and R 4 in the formula (3)
  • R 5 is, -R 6, -OR 6, -SR 6, Represents —COR 6 , —CONR 6 R 6 , —NR 6 COR 6 , —OCOR 6 , —COOR 6 , —SCOR 6 , —OCSR 6 , —COSR 6 , —CSOR 6 , —CN, a halogen atom or a hydroxy group;
  • R 6 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms
  • X is a direct bond Or a carbonyl group, and a represents an integer of 0 to 4.
  • R 1 and R 2 are preferably each independently a methyl group, ethyl group, n-propyl group, i-propyl group, cyclohexyl group or phenyl group.
  • R 3 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group.
  • R 4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group.
  • R 5 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group.
  • X is preferably a direct bond.
  • R 1 is preferably each independently a methyl group, ethyl group, n-propyl group, i-propyl group, cyclohexyl group or phenyl group.
  • R 3 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group.
  • R 4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group.
  • R 5 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group.
  • X is preferably a direct bond.
  • Specific examples of the compounds represented by formula (1) and formula (2) include, for example, compounds described in paragraph numbers 0076 to 0079 of JP-A No. 2014-137466. This content is incorporated herein.
  • oxime compounds preferably used in the curable composition are shown below.
  • the oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably has a maximum absorption wavelength in the wavelength region of 360 nm to 480 nm, and more preferably has a high absorbance at 365 nm and 405 nm.
  • the molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, from the viewpoint of sensitivity, and from 5,000 to 200,000. More preferably, it is 000.
  • a known method can be used for the molar extinction coefficient of the compound.
  • an ethyl acetate solvent is used at a concentration of 0.01 g / L. It is preferable to measure. You may use a photoinitiator in combination of 2 or more type as needed.
  • the curable composition contains a polymerizable compound.
  • the content of the polymerizable compound is preferably 1 to 40% by mass and more preferably 10 to 40% by mass with respect to the total solid content of the curable composition.
  • the curable composition has better exposure sensitivity.
  • a polymeric compound may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of polymeric compounds together, it is preferable that the total amount is in the said range.
  • the polymerizable compound is preferably a compound containing at least one group containing an ethylenically unsaturated bond, more preferably a compound containing 2 or more, further preferably containing 3 or more, and containing 5 or more. Is particularly preferred.
  • the upper limit is 15 or less, for example.
  • Examples of the group containing an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
  • the polymerizable compound may be in any of chemical forms such as a monomer, a prepolymer, an oligomer, a mixture thereof, and a multimer thereof, and is preferably a monomer.
  • the molecular weight of the polymerizable compound is preferably 100 to 3,000, more preferably 250 to 1,500.
  • the polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, more preferably a 3 to 6 functional (meth) acrylate compound.
  • Examples of monomers and prepolymers include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters thereof, amides, and multimers thereof.
  • unsaturated carboxylic acids eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds, and multimers thereof.
  • an addition reaction product of an unsaturated carboxylic acid ester or amide containing a nucleophilic substituent such as a hydroxy group, an amino group, or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy and A dehydration condensation reaction product of a saturated carboxylic acid ester or amide with a monofunctional or polyfunctional carboxylic acid is also preferably used.
  • reaction product of an unsaturated carboxylic acid ester or amide containing an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group A reaction product of an unsaturated carboxylic acid ester or amide containing a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable.
  • a compound group in which the unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like.
  • the compounds described in paragraphs 0095 to 0108 of JP-A-2009-288705 can also be suitably used in the present invention.
  • the polymerizable compound is also preferably a compound having one or more groups containing an ethylenically unsaturated bond and having a boiling point of 100 ° C. or higher under normal pressure.
  • compounds described in JP-A-2013-29760, paragraph 0227, and JP-A-2008-292970, paragraphs 0254 to 0257 can be referred to, the contents of which are incorporated herein.
  • Polymerizable compounds are dipentaerythritol triacrylate (KAYARAD D-330, PET-30, manufactured by Nippon Kayaku Co., Ltd. as a commercial product), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product, Nippon Kayaku Co., Ltd.) Dipentaerythritol penta (meth) acrylate (commercially available product: KAYARAD D-310, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available product: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which these (meth) acryloyl groups are mediated by ethylene glycol or propylene glycol residues (eg, commercially available from Sartomer, SR454, SR
  • oligomer types can also be used.
  • NK ester A-TMMT penentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.
  • KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd.
  • Preferred embodiments of the polymerizable compound are shown below.
  • the polymerizable compound may have an acid group such as a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group.
  • an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxy group of the aliphatic polyhydroxy compound.
  • a polymerizable compound having an acid group is more preferable, and in this ester, the aliphatic polyhydroxy compound is more preferably pentaerythritol and / or dipentaerythritol. Examples of commercially available products include Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd.
  • the preferred acid value of the polymerizable compound containing an acid group is 0.1 to 40 mgKOH / g, more preferably 5 to 30 mgKOH / g.
  • the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the development dissolution properties are good, and when it is 40 mgKOH / g or less, it is advantageous in production and / or handling. Furthermore, by being in the above range, the photopolymerization performance is good and the curability is excellent.
  • the polymerizable compound is also preferably a compound containing a caprolactone structure.
  • the compound containing a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule.
  • compounds containing a caprolactone structure represented by the following formula (Z-1) are preferred.
  • R 1 represents a hydrogen atom or a methyl group
  • m represents a number of 1 or 2
  • * represents a bond.
  • R 1 represents a hydrogen atom or a methyl group
  • * represents a bond
  • Polymerizable compounds containing a caprolactone structure are commercially available from Nippon Kayaku, for example, as the KAYARAD DPCA series. 2) the number of groups represented by 2 and R 1 are all hydrogen atoms), DPCA-30 (wherein m is 1 and the number of groups represented by formula (Z-2) is 3). , Compounds in which R 1 is all hydrogen atoms), DPCA-60 (a compound in which m is 1, the number of groups represented by formula (Z-2) is 6, and R 1 is all hydrogen atoms) DPCA-120 (a compound in which m is 2, the number of groups represented by formula (Z-2) is 6, and all R 1 are hydrogen atoms).
  • a compound represented by the following formula (Z-4) or (Z-5) can also be used.
  • each E independently represents-((CH 2 ) y CH 2 O)-or ((CH 2 ) y CH (CH 3 ) O)-.
  • Y represents an integer of 0 to 10 each independently,
  • X each independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxylic acid group.
  • the total number of (meth) acryloyl groups is 3 or 4
  • each m independently represents an integer of 0 to 10
  • the total of each m is an integer of 0 to 40.
  • the total number of (meth) acryloyl groups is 5 or 6
  • each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.
  • m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
  • the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and still more preferably an integer of 4 to 8.
  • n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
  • the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and still more preferably an integer of 6 to 12.
  • -((CH 2 ) y CH 2 O)-or ((CH 2 ) y CH (CH 3 ) O)-in formula (Z-4) or formula (Z-5) is A form bonded to X is preferred.
  • the compounds represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more.
  • all six Xs are acryloyl groups
  • all six Xs are acryloyl groups
  • An embodiment which is a mixture with a compound having at least one hydrogen atom is preferred. With such a configuration, the developability can be further improved.
  • the total content of the compound represented by the formula (Z-4) or the formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.
  • the compound represented by the formula (Z-4) or the formula (Z-5) is a conventionally known process, which is a pentaerythritol or dipentaerythritol by a ring-opening addition reaction with ethylene oxide or propylene oxide. It can be synthesized from the step of bonding a ring-opening skeleton and the step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with the terminal hydroxy group of the ring-opening skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (Z-4) or (Z-5).
  • pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.
  • Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”).
  • exemplary compounds (a), (f) b), (e) and (f) are preferred.
  • Examples of commercially available polymerizable compounds represented by the formulas (Z-4) and (Z-5) include SR-494, a tetrafunctional acrylate containing four ethyleneoxy chains manufactured by Sartomer, Nippon Kayaku Examples thereof include DPCA-60, which is a hexafunctional acrylate containing six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate containing three isobutyleneoxy chains.
  • Examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765; Urethane compounds containing an ethylene oxide skeleton described in JP-A-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable.
  • urethane oligomers UAS-10, UAB-140 (Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (Shin Nakamura Chemical Co., Ltd.), DPHA-40H (Nippon Kayaku Co., Ltd.), UA-306H, UA- 306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.
  • the polymerizable compound preferably has an SP (Solubility Parameter) value of 9.50 or more, more preferably 10.40 or more, and still more preferably 10.60 or more.
  • SP Solubility Parameter
  • the SP value is obtained by the Hoy method (HL Hoy Journal of Paining, 1970, Vol. 42, 76-118). The SP value is shown with the unit omitted, but the unit is cal 1/2 cm ⁇ 3/2 .
  • the curable composition contains a polymerizable compound containing a cardo skeleton from the viewpoint of improving the development residue.
  • a polymerizable compound containing a cardo skeleton a polymerizable compound containing a 9,9-bisarylfluorene skeleton is preferable, and a compound represented by the following formula (Q3) is more preferable.
  • Ar 11 to Ar 14 each independently represents an aryl group containing a benzene ring surrounded by a broken line.
  • X 1 to X 4 each independently represents a substituent containing a polymerizable group, and the carbon atom in the substituent may be substituted with a hetero atom.
  • a and b each independently represents an integer of 1 to 5, and c and d each independently represents an integer of 0 to 5.
  • R 1 to R 4 each independently represents a substituent, e, f, g and h each independently represents an integer of 0 or more, and the upper limit values of e, f, g and h are Ar 11 to Ar 14 respectively.
  • X 1 to X 4 and R 1 to R 4 are Each may be independently substituted with a benzene ring surrounded by a broken line, or may be substituted with a ring other than the benzene ring surrounded by a broken line.
  • the aryl group containing a benzene ring surrounded by a broken line represented by Ar 11 to Ar 14 is preferably an aryl group having 6 to 14 carbon atoms, and an aryl group having 6 to 10 carbon atoms (
  • a phenyl group or a naphthyl group is more preferable, and a phenyl group (only a benzene ring surrounded by a broken line) is more preferable.
  • X 1 to X 4 each independently represents a substituent containing a polymerizable group, and the carbon atom in the substituent may be substituted with a hetero atom.
  • the substituent containing a polymerizable group represented by X 1 to X 4 is not particularly limited, but is preferably an aliphatic group containing a polymerizable group.
  • the aliphatic group containing a polymerizable group represented by X 1 to X 4 is not particularly limited, but is preferably an alkylene group having 1 to 12 carbon atoms other than the polymerizable group, and 2 to 10 carbon atoms. And more preferably an alkylene group having 2 to 5 carbon atoms.
  • aliphatic group containing a polymerizable group represented by X 1 to X 4 when the aliphatic group is substituted with a heteroatom, it is substituted with —NR— (R is a substituent), an oxygen atom, or a sulfur atom.
  • R is a substituent
  • the non-adjacent —CH 2 — in the aliphatic group is preferably substituted with an oxygen atom or a sulfur atom, and the non-adjacent —CH 2 — in the aliphatic group is oxygen More preferably, it is substituted with an atom.
  • the aliphatic group containing a polymerizable group represented by X 1 to X 4 is preferably substituted at one or two positions with a hetero atom, more preferably at one position with a hetero atom, and Ar 11 to More preferably, one position adjacent to the aryl group containing a benzene ring surrounded by a broken line represented by Ar 14 is substituted with a hetero atom.
  • the polymerizable group contained in the aliphatic group containing the polymerizable group represented by X 1 to X 4 is a radically polymerizable or cationically polymerizable group (hereinafter also referred to as a radically polymerizable group and a cationically polymerizable group, respectively). ) Is preferred.
  • radically polymerizable groups As the radically polymerizable group, generally known radically polymerizable groups can be used, and preferable examples thereof include a polymerizable group containing an ethylenically unsaturated bond capable of radical polymerization, Can include a vinyl group, a (meth) acryloyloxy group, and the like. Among these, a (meth) acryloyloxy group is preferable, and an acryloyloxy group is more preferable.
  • cationic polymerizable group generally known cationic polymerizable groups can be used.
  • alicyclic ether group, cyclic acetal group, cyclic lactone group, cyclic thioether group, spiro orthoester group, vinyloxy group Groups and the like are preferable, and epoxy groups, oxetanyl groups, and vinyloxy groups are particularly preferable.
  • the polymerizable group contained in the substituent contained in Ar 11 to Ar 14 is preferably a radical polymerizable group.
  • Two or more of Ar 11 ⁇ Ar 14 comprises a substituent containing a polymerizable group, preferably contains a substituent 2-4 of Ar 11 ⁇ Ar 14 contains a polymerizable group, Ar More preferably, 2 or 3 of 11 to Ar 14 contain a substituent containing a polymerizable group, and two of Ar 11 to Ar 14 contain a substituent containing a polymerizable group. Further preferred.
  • Ar 11 to Ar 14 are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, X 1 to X 4 are each independently surrounded by a broken line Even if it is substituted with a benzene ring, it may be substituted with a ring other than the benzene ring surrounded by a broken line.
  • a and b each independently represent an integer of 1 to 5, preferably 1 or 2, and more preferably a and b are all 1.
  • c and d each independently represent an integer of 0 to 5, preferably 0 or 1, and more preferably c and d are both 0.
  • R 1 to R 4 each independently represents a substituent.
  • the substituent represented by R 1 to R 4 is not particularly limited, and examples thereof include halogen atoms, halogenated alkyl groups, alkyl groups, alkenyl groups, acyl groups, hydroxy groups, hydroxyalkyl groups, alkoxy groups, aryl groups, hetero groups. An aryl group, an alicyclic group, etc. can be mentioned.
  • the substituent represented by R 1 to R 4 is preferably an alkyl group, an alkoxy group or an aryl group, more preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a phenyl group.
  • R 1 to R 4 are each independently May be substituted with a benzene ring surrounded by a broken line, or may be substituted with a ring other than the benzene ring surrounded by a broken line.
  • e, f, g and h each independently represent an integer of 0 or more, and the upper limit values of e, f, g and h are the substituents that Ar 11 to Ar 14 can contain, respectively. It is a value obtained by subtracting a, b, c or d from the number.
  • e, f, g and h are each independently preferably 0 to 8, more preferably 0 to 2, and still more preferably 0.
  • Ar 11 to Ar 14 are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, e, f, g and h may be 0 or 1 Preferably, it is 0.
  • Examples of the compound represented by the formula (Q3) include 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene.
  • Examples of the polymerizable compound containing a 9,9-bisarylfluorene skeleton compounds described in JP 2010-254732 A can also be suitably used.
  • Examples of the polymerizable compound containing a cardo skeleton include, but are not limited to, on-coat EX series (manufactured by Nagase Sangyo Co., Ltd.) and Ogsol (manufactured by Osaka Gas Chemical Co., Ltd.).
  • the curable composition preferably contains a colorant.
  • the colorant is at least one selected from the group consisting of pigments and dyes, and may be a chromatic colorant or a black colorant, but preferably contains a black pigment.
  • the content of the colorant in the curable composition is not particularly limited, but when a cured film obtained from the above curable composition is used as a light-shielding film, a more excellent light-shielding property can be obtained. 50 mass% or more is preferable with respect to the total solid.
  • the upper limit of the content of the colorant is not particularly limited, but generally 70% by mass or less is preferable with respect to the total solid content of the curable composition. When the content of the colorant is not more than the upper limit value, the curable composition has more excellent coatability.
  • the pigment is not particularly limited, and a known inorganic pigment and / or organic pigment can be used.
  • inorganic pigment It does not restrict
  • inorganic pigments include zinc white, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, red lead, iron oxide red, yellow lead, zinc yellow (one zinc yellow, 2 types of zinc yellow), ultramarine blue, prussian blue (potassium ferrocyanide) zircon gray, praseodymium yellow, chrome titanium yellow, chrome green, peacock, Victoria green, bitumen (unrelated to Prussian blue), vanadium zirconium blue, Examples include chrome tin pink, ceramic red, and salmon pink.
  • the black inorganic pigment includes a metal oxide containing one or more metal elements selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. , Metal nitrides, metal oxynitrides, and the like.
  • the inorganic pigment carbon black, titanium black, metal pigment, etc. (hereinafter referred to as “black pigment”) in that a curable composition capable of forming a cured film having at least a high optical density is obtained.
  • black pigment examples include a metal oxide containing one or more metal elements selected from the group consisting of Nb, V, Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. And metal nitrides.
  • the inorganic pigment contains at least one selected from the group consisting of titanium nitride, titanium oxynitride, niobium nitride, vanadium nitride, silver, or tin-containing metal pigments, and silver and tin-containing metal pigments. It is preferable to contain at least one selected from the group consisting of titanium nitride, titanium oxynitride, niobium nitride, and vanadium nitride. Niobium nitride and vanadium nitride may be niobium oxynitride and vanadium oxynitride.
  • Carbon black can also be used as the inorganic pigment. Specific examples of carbon black are commercially available C.I. I. Pigment Black 1 and other organic pigments C.I. I. Examples thereof include inorganic pigments such as CI Pigment Black 7, but are not limited thereto.
  • pigments having infrared absorptivity other than the pigments described as black pigments can also be used.
  • a tungsten compound, a metal boride, and the like are preferable, and among them, a tungsten compound is preferable from the viewpoint of excellent light-shielding properties at wavelengths in the infrared region.
  • a tungsten compound is preferable from the viewpoint of excellent light absorption wavelength region of a photopolymerization initiator related to curing efficiency by exposure and transparency of visible light region.
  • a black pigment or an infrared light-shielding pigment has red, green, yellow, orange, purple, blue, or the like.
  • the aspect which mixes a coloring pigment or dye mentioned later is mentioned. It is preferable to mix a red pigment or dye, or a purple pigment or dye with a black pigment or a pigment having infrared light shielding properties, and it is more preferable to mix a red pigment with a black pigment or a pigment having infrared light shielding properties. . Furthermore, you may add the near-infrared absorber and infrared absorber which are mentioned later.
  • the black pigment preferably contains titanium black and / or niobium oxynitride.
  • Titanium black is black particles containing titanium atoms. Preferred are low-order titanium oxide, titanium oxynitride, titanium nitride, and the like.
  • the surface of titanium black particles can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation. It can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide, and treatment with a water-repellent substance as disclosed in JP-A-2007-302836 is also possible. Is possible. Titanium black is typically titanium black particles, and it is preferable that both the primary particle diameter and the average primary particle diameter of each particle are small. The same applies to niobium oxynitride. Specifically, an average primary particle diameter in the range of 10 nm to 45 nm is preferable.
  • the average primary particle diameter of a pigment can be measured using a transmission electron microscope (Transmission Electron Microscope, TEM).
  • TEM Transmission Electron Microscope
  • the transmission electron microscope for example, a transmission microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used.
  • the average primary particle diameter of the pigment is the maximum length of a particle image obtained using a transmission electron microscope (Dmax: the maximum length at two points on the contour of the particle image), and the maximum vertical length ( DV-max: When an image is sandwiched between two straight lines parallel to the maximum length, the shortest length connecting the two straight lines vertically is measured, and the geometric mean value (Dmax ⁇ DV-max) 1 / 2 was the particle size.
  • the average primary particle diameter of the pigment is determined by measuring the particle diameter of 100 particles by this method and intending the arithmetic average value thereof.
  • the specific surface area of titanium black and niobium oxynitride is not particularly limited. However, since the water repellency after surface treatment of titanium black and niobium oxynitride with a water repellent becomes a predetermined performance, BET (Brunauer, Emmett, Teller) The value measured by the method is preferably 5 m 2 / g or more and 150 m 2 / g or less, more preferably 20 m 2 / g or more and 120 m 2 / g or less.
  • titanium black examples include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade name, manufactured by Mitsubishi Materials Corporation), Tilack D (trade name, manufactured by Ako Kasei Co., Ltd.), titanium nitride 50 nm (trade name, manufactured by Wako Pure Chemical Industries, Ltd.), and the like.
  • Titanium oxynitride, titanium nitride, or niobium oxynitride is preferably used as the colorant, and titanium nitride or niobium oxynitride is more preferable, and niobium oxynitride is more preferable because the resulting cured film has better moisture resistance. preferable. This is presumably because these colorants are hydrophobic.
  • titanium black is contained as a dispersion in the curable composition, and the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.00 on a mass basis.
  • the to-be-dispersed bodies include both those in which titanium black is in the state of primary particles and those in the state of aggregates (secondary particles).
  • the following means can be used.
  • titanium black particles and silica particles are dispersed by using a disperser to obtain a dispersion, and the dispersion is subjected to reduction treatment at a high temperature (for example, 850 to 1,000 ° C.) to thereby obtain titanium black particles. It is possible to obtain a to-be-dispersed body containing Si and Ti as a main component.
  • the reduction treatment can also be performed in an atmosphere of a reducing gas such as ammonia.
  • titanium oxide include TTO-51N (trade name, manufactured by Ishihara Sangyo).
  • Examples of commercially available silica particles include AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, 380 (trade name, manufactured by Evonik).
  • a dispersing agent may be used for the dispersion of titanium oxide and silica particles.
  • the dispersant include those described in the section of the dispersant described later.
  • the dispersion may be performed in a solvent.
  • the solvent include water and organic solvents. What is demonstrated in the column of the organic solvent mentioned later is mentioned. Titanium black whose content ratio (Si / Ti) is adjusted to, for example, 0.05 or more is described, for example, in paragraph numbers [0005] and paragraphs [0016] to [0021] of JP-A-2008-266045. It can produce by the method of.
  • Curing including this dispersion by adjusting the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion including titanium black and Si atoms to a suitable range (for example, 0.05 or more).
  • a suitable range for example, 0.05 or more.
  • the residue includes components derived from a curable composition such as titanium black particles and a resin component. The reason why the residue is reduced is not yet clear, but the above-described dispersion tends to have a small particle diameter (for example, a particle diameter of 30 nm or less), and further contains Si atoms of the dispersion.
  • Titanium black is excellent in light-shielding property for light in a wide wavelength range from ultraviolet light to infrared light.
  • a cured film formed using a material having a mass conversion of 0.05 or more exhibits excellent light shielding properties.
  • the content ratio (Si / Ti) of Si atoms to Ti atoms in the dispersion is, for example, the method (1-1) or the method (1-2) described in paragraph 0033 of JP2013-249417A ).
  • Whether the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.05 or more with respect to the dispersion to be contained in the cured film obtained by curing the curable composition Can be determined by the method (2) described in paragraph 0035 of JP2013-249417A.
  • the above-described titanium black can be used.
  • complex oxides such as Cu, Fe, Mn, V, Ni, cobalt oxide, iron oxide, carbon black, aniline black, etc.
  • ⁇ atoms may be used in combination with titanium black, if desired, for the purpose of adjusting the light shielding property and the like, as long as the effects of the present invention are not impaired.
  • materials used for introducing Si atoms into the dispersion will be described.
  • a Si-containing material such as silica may be used. Examples of silica that can be used include precipitated silica, fumed silica, colloidal silica, and synthetic silica. These may be appropriately selected and used.
  • the particle diameter of the silica particles is smaller than the film thickness when the cured film is formed, the light-shielding property is more excellent, so it is preferable to use fine particle type silica.
  • the fine particle type silica include silica described in paragraph 0039 of JP2013-249417A, and the contents thereof are incorporated in the present specification.
  • the curable composition can use a tungsten compound and / or a metal boride as a pigment.
  • Tungsten compounds and metal borides have high absorption with respect to infrared rays (light having a wavelength of about 800 to 1,200 nm) (that is, they have high light shielding properties (shielding properties) with respect to infrared rays), and with respect to visible light. Infrared shielding material with low absorption. For this reason, a curable composition can form a pattern with high light-shielding property in an infrared region, and high translucency in a visible light region by containing a tungsten compound and / or a metal boride.
  • Tungsten compounds and metal borides have low absorption even for light shorter than the visible range used for exposure of high pressure mercury lamps, KrF, ArF and the like used for image formation. For this reason, by combining with the above-mentioned polymerizable compound, photopolymerization initiator, and alkali-soluble resin described later, an excellent pattern can be obtained, and development residue can be further suppressed in pattern formation.
  • tungsten compound examples include a tungsten oxide compound, a tungsten boride compound, a tungsten sulfide compound, and the like, and a tungsten oxide compound represented by the following general formula (composition formula) (I) is preferable.
  • composition formula) (I) M x W y O z (I) M represents a metal, W represents tungsten, and O represents oxygen. 0.001 ⁇ x / y ⁇ 1.1 2.2 ⁇ z / y ⁇ 3.0
  • alkali metal for example, alkali metal, alkaline earth metal, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, Rb, Cs and the like can be mentioned, and alkali metals are preferable. 1 type or 2 types or more may be sufficient as the metal of M.
  • M is preferably an alkali metal, more preferably Rb or Cs, and even more preferably Cs.
  • infrared rays can be sufficiently shielded, and when it is 1.1 or less, generation of an impurity phase in the tungsten compound can be more reliably avoided. it can.
  • z / y is 2.2 or more, chemical stability as a material can be further improved, and when it is 3.0 or less, infrared rays can be sufficiently shielded.
  • tungsten oxide compound represented by the general formula (I) examples include Cs 0.33 WO 3 , Rb 0.33 WO 3 , K 0.33 WO 3 , Ba 0.33 WO 3 and the like. Cs 0.33 WO 3 or Rb 0.33 WO 3 is preferable, and Cs 0.33 WO 3 is more preferable.
  • the tungsten compound is preferably fine particles.
  • the average primary particle diameter of the tungsten fine particles is preferably 800 nm or less, more preferably 400 nm or less, and even more preferably 200 nm or less.
  • the average primary particle size is preferably as small as possible.
  • the average primary particle size of the tungsten fine particles is usually 1 nm or more.
  • Two or more tungsten compounds can be used.
  • Tungsten compounds are commercially available.
  • the tungsten oxide compound is, for example, a tungsten oxide compound
  • the tungsten oxide compound can be obtained by a method of heat-treating the tungsten compound in an inert gas atmosphere or a reducing gas atmosphere (see Japanese Patent No. 4096205).
  • the tungsten oxide compound is also available as a dispersion of tungsten fine particles such as YMF-02 manufactured by Sumitomo Metal Mining Co., Ltd.
  • lanthanum boride LaB 6
  • PrB 6 praseodymium boride
  • NdB 6 cerium boride
  • CeB 6 cerium boride
  • YB 6 yttrium boride
  • titanium boride TiB 2
  • zirconium boride ZrB 2
  • hafnium boride HfB 2
  • vanadium boride VB 2
  • tantalum boride TaB 2
  • CrB, CrB 2 chromium boride
  • molybdenum boride One or more of MoB 2 , Mo 2 B 5 , MoB), tungsten boride (W 2 B 5 ) and the like can be mentioned, and lanthanum boride (LaB 6 ) is preferable.
  • the metal boride is preferably fine particles.
  • the average primary particle diameter of the metal boride fine particles is preferably 800 nm or less, more preferably 300 nm or less, and further preferably 100 nm or less. When the average primary particle diameter is in such a range, the metal boride fine particles are less likely to block visible light by light scattering, and thus the translucency in the visible light region can be further ensured. From the viewpoint of avoiding light scattering, the average primary particle size is preferably as small as possible. However, for reasons such as ease of handling during production, the average primary particle size of the metal boride fine particles is usually 1 nm or more.
  • Two or more metal borides may be used.
  • the metal boride is available as a commercial product, for example, as a dispersion of metal boride fine particles such as KHF-7 manufactured by Sumitomo Metal Mining Co., Ltd.
  • titanium nitride-containing particles containing Fe atoms can also be used.
  • a gas phase reaction method is usually used, and specific examples include an electric furnace method and a thermal plasma method.
  • the thermal plasma method is preferable because it is less contaminated with impurities, easily has a uniform particle diameter, and has high productivity.
  • the method for generating thermal plasma include direct current arc discharge, multiphase arc discharge, radio frequency (RF) plasma, hybrid plasma, and the like, and high frequency plasma with less impurities from the electrodes is preferable.
  • RF radio frequency
  • titanium powder is evaporated by high-frequency thermal plasma, nitrogen is introduced into the apparatus as a carrier gas, and titanium powder is nitrided in the cooling process. And a method of synthesizing titanium nitride-containing particles.
  • the thermal plasma method is not limited to the above.
  • the method for producing titanium nitride-containing particles is not particularly limited, but the production methods described in paragraphs ⁇ 0037> to ⁇ 0089> of International Publication No. 2010/147098 can be referred to.
  • the Ag powder of International Publication No. 2010/147098 instead of the Ag powder of International Publication No. 2010/147098, using a component containing Fe and / or a component containing Si, which will be described later, and a mixture of this and a titanium powder material (titanium particles) as a raw material
  • titanium nitride-containing particles contained in the curable composition of the present invention can be produced.
  • the titanium powder material (titanium particles) used for the production of titanium nitride-containing particles is preferably of high purity.
  • the titanium powder material is not particularly limited, but a titanium element having a purity of 99.99% or more is preferable, and a material having 99.999% or more is more preferably used.
  • the titanium powder material (titanium particles) used for the production of titanium nitride-containing particles may contain atoms other than titanium atoms.
  • examples of other atoms that can be contained in the titanium powder material include Fe atoms and Si atoms.
  • the content of Fe atoms is preferably more than 0.001% by mass with respect to the total mass of the titanium powder material.
  • the titanium powder material contains Si atoms the content of Si atoms is preferably more than 0.002% by mass and less than 0.3% by mass with respect to the total mass of the titanium powder material.
  • the content is more preferably from 0.15% by mass, and even more preferably from 0.02 to 0.1% by mass.
  • the patterning property of the cured film is further improved.
  • the content of Si atoms is less than 0.3% by mass, the polarity of the outermost layer of the obtained titanium nitride-containing particles is further stabilized.
  • the water content in the titanium powder material (titanium particles) used for the production of titanium nitride-containing particles is preferably less than 1% by mass and less than 0.1% by mass with respect to the total mass of the titanium powder material. It is more preferable that it is not substantially contained.
  • the titanium nitride-containing particles are obtained by using a thermal plasma method, whereby a diffraction angle 2 ⁇ of a peak derived from the (200) plane when CuK ⁇ rays are used as an X-ray source (details will be described later) is 42.6. It becomes easy to adjust to a range of more than 4 ° to 43.5 °.
  • the method for causing the titanium nitride-containing particles to contain Fe atoms is not particularly limited.
  • Fe atoms are introduced in the stage of obtaining titanium particles (titanium powder) used as a raw material for the above-described titanium nitride-containing particles.
  • the method etc. are mentioned. More specifically, when titanium is produced by the crawl method or the like, a reaction vessel made of a material containing Fe atoms such as stainless steel is used, or a press machine and a crusher for crushing titanium are used.
  • a material containing Fe atoms as a material, Fe atoms can be attached to the surface of the titanium particles.
  • the titanium nitride-containing particles can contain Fe atoms.
  • Fe atoms contained in titanium nitride-containing particles are ions, metal compounds (including complex compounds), intermetallic compounds, alloys, oxides, composite oxides, nitrides, oxynitrides, sulfides, and oxysulfides. And may be included in any form.
  • the Fe atom contained in the titanium nitride-containing particle may exist as an impurity at a position between crystal lattices, or may exist as an impurity in an amorphous state at a crystal grain boundary.
  • the present inventor has found that the content of Fe atoms in the titanium nitride-containing particles is related to the patterning property and the corrosion resistance of the electrode.
  • the Fe atoms contained in the titanium nitride-containing particles are excellent in adhesion to the electrode and the substrate, and the titanium nitride in the titanium nitride-containing particles is considered to adhere to the electrode and the substrate through the Fe atoms.
  • the patterning property of the cured film is improved by setting the content of Fe atoms in the titanium nitride-containing particles to a predetermined amount or more.
  • the content of Fe atoms contained in the titanium nitride-containing particles is too large, the amount of Fe atoms remaining on the electrode and the substrate increases, which is considered to cause corrosion of the electrode. Therefore, it is estimated that the corrosion resistance of the electrode is improved by setting the content of Fe atoms in the titanium nitride-containing particles to a predetermined amount or less.
  • the content of Fe atoms in the titanium nitride-containing particles is preferably more than 0.001% by mass and less than 0.4% by mass with respect to the total mass of the titanium nitride-containing particles. Of these, 0.01 to 0.2% by mass is more preferable, and 0.02 to 0.1% by mass is even more preferable.
  • the content of Fe atoms is more than 0.001% by mass, the patterning property of the cured film is further improved.
  • the content of Fe atoms is less than 0.4% by mass, the corrosion resistance of the electrode by the cured film is further improved (the cured film can be inhibited from corroding the electrode).
  • the content of Fe atoms in the titanium nitride-containing particles is within the above range, excellent patterning properties of the cured film and anticorrosion properties of the electrodes can be obtained.
  • the content of Fe atoms in the titanium nitride-containing particles can be measured by ICP (Inductively Coupled Plasma) emission spectroscopy.
  • the titanium nitride-containing particles preferably further contain Si atoms (silicon atoms). Thereby, the patterning property of a cured film improves more.
  • the reason why the patterning property is improved by containing Si atoms is considered to be the same as the above-described Fe atoms.
  • the content of Si atoms in the titanium nitride-containing particles is preferably more than 0.002% by mass and less than 0.3% by mass with respect to the total mass of the titanium nitride-containing particles, and 0.01 to 0.15 The mass is more preferably 0.02 to 0.1% by mass. When the content of Si atoms is more than 0.002% by mass, the patterning property of the cured film is further improved.
  • the Si atom content is less than 0.3% by mass, the polarity of the outermost layer of the titanium nitride-containing particles is further stabilized.
  • the adsorptivity of the dispersant to the titanium nitride-containing particles is improved, the undispersed titanium nitride-containing particles are reduced, and the generation of particles can be suppressed. It is done.
  • the content of Si atoms in the titanium nitride-containing particles can be measured by the same method as that for Fe atoms.
  • the method for incorporating Si atoms into the titanium nitride-containing particles is not particularly limited.
  • Si atoms are introduced at the stage of obtaining titanium particles (titanium powder) used as a raw material for the above-described titanium nitride-containing particles.
  • the method etc. are mentioned. More specifically, when titanium is produced by a crawl method or the like, a reaction vessel made of a material containing Si atoms is used, or Si atom is used as a material for a press machine and a crusher when crushing titanium. Si atoms can be attached to the surface of the titanium particles.
  • titanium nitride-containing particles in addition to the titanium particles that are raw materials, components such as Si particles and Si oxide are added, and these are nitrided by the thermal plasma method.
  • the titanium nitride-containing particles can contain Si atoms.
  • Si atoms contained in titanium nitride-containing particles are ions, metal compounds (including complex compounds), intermetallic compounds, alloys, oxides, complex oxides, nitrides, oxynitrides, sulfides, and oxysulfides. And may be included in any form.
  • Si atoms contained in the titanium nitride-containing particles may be present as impurities at the position between the crystal lattices, or may be present as impurities in the amorphous state at the crystal grain boundaries.
  • the content of titanium atoms (Ti atoms) in the titanium nitride-containing particles is preferably 10 to 85% by mass and preferably 15 to 75% by mass with respect to the total mass of the titanium nitride-containing particles. More preferred is 20 to 70% by mass.
  • the content of Ti atoms in the titanium nitride-containing particles can be measured by ICP emission spectroscopy.
  • the content of nitrogen atoms (N atoms) in the titanium nitride-containing particles is preferably 3 to 60% by mass and preferably 5 to 50% by mass with respect to the total mass of the titanium nitride-containing particles. More preferably, it is 10 to 40% by mass.
  • the nitrogen atom content can be analyzed by an inert gas melting-thermal conductivity method.
  • Titanium nitride-containing particles contain titanium nitride (TiN) as a main component, and are usually noticeable when oxygen is mixed during the synthesis and when the particle size is small. , A part of oxygen atoms may be contained.
  • the content of oxygen atoms in the titanium nitride-containing particles is preferably 1 to 40% by mass, more preferably 1 to 35% by mass with respect to the total mass of the titanium nitride-containing particles. More preferably, it is ⁇ 30% by mass.
  • the oxygen atom content can be analyzed by an inert gas melting-infrared absorption method.
  • the specific surface area is preferably 5 m 2 / g or more 100 m 2 / g or less of titanium nitride-containing particles, 10 m 2 / g or more 60 m 2 / g or less is more preferable.
  • the specific surface area can be determined by the BET (Brunauer, Emmett, Teller) method.
  • the titanium nitride-containing particles may be composite fine particles composed of titanium nitride particles and metal fine particles.
  • Composite fine particles refer to particles in which titanium nitride particles and metal fine particles are complexed or in a highly dispersed state.
  • “composite” means that the particles are composed of both titanium nitride and metal components
  • “highly dispersed” means that the titanium nitride particles and metal particles are It means that the particles exist individually and the small amount of particles are not aggregated and are uniformly and uniformly dispersed.
  • the metal fine particles are not particularly limited.
  • at least one selected from copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium and iridium, and alloys thereof is preferable, and copper, silver, gold, platinum and tin, and these More preferably, it is at least one selected from these alloys. From the viewpoint of better moisture resistance, silver is preferred.
  • the content of the metal fine particles in the titanium nitride-containing particles is preferably 5% by mass or more and 50% by mass or less, and preferably 10% by mass or more and 30% by mass or less with respect to the total mass of the titanium nitride-containing particles. Is more preferable.
  • the titanium nitride-containing particles preferably have a diffraction angle 2 ⁇ of a peak derived from the (200) plane when CuK ⁇ rays are used as an X-ray source and more than 42.6 ° and 43.5 ° or less.
  • a cured film obtained by using a curable composition containing titanium nitride-containing particles having such characteristics can achieve a high OD (optical density) value.
  • TiN has a peak derived from the (200) plane as a strongest peak
  • TiO has a (200 )
  • the diffraction angle 2 ⁇ of the peak derived from the (200) plane of the titanium nitride-containing particle is preferably more than 42.6 ° and less than 43.5 ° from the viewpoint of the stability of the particle over time. From the viewpoint of excellent process margin, 42.7 ° or more and less than 43.5 ° is more preferable, and from the viewpoint of excellent reproducibility of particle performance, it is more preferably 42.7 ° or more and less than 43.4 °.
  • the crystallite size constituting the titanium nitride-containing particles can be determined from the half width of the X-ray diffraction peak, and is calculated using Scherrer's formula.
  • the crystallite size is preferably 20 nm or more, and more preferably 20 to 50 nm.
  • the transmitted light of the cured film exhibits a blue to blue purple color having a peak wavelength of 475 nm or less, and has high light-shielding properties.
  • a black matrix having both ultraviolet sensitivity can be obtained.
  • the crystallite size is 20 nm or more, the proportion of the active particle surface with respect to the volume of the particle is reduced, providing a good balance, and the titanium nitride-containing particles have better heat resistance and / or durability. It becomes.
  • metal nitride-containing particles that are metal nitride-containing particles and contain predetermined atoms A are used as the metal nitride-containing particles. You can also.
  • the metal in the metal nitride-containing particles include Nb, V, Cr, Y, Zr, Nb, Hf, Ta, W, and Re, and Nb or V is more preferable.
  • the atom A include B, Al, Si, Mn, Fe, Ni, and Ag.
  • the content is not particularly limited, but the content of the atoms A in the metal nitride-containing particles is preferably 0.00005 to 10% by mass.
  • the method for producing the metal nitride-containing particles containing the atom A is not particularly limited, and a known method can be used.
  • a gas phase reaction method is usually used, and specific examples include an electric furnace method and a thermal plasma method.
  • the thermal plasma method is preferable because it is less contaminated with impurities, has a uniform particle diameter, and has high productivity.
  • a specific method for producing metal nitride-containing particles by the thermal plasma method for example, a method using a metal fine particle production apparatus (an apparatus similar to a “black composite fine particle production apparatus” described later) can be mentioned.
  • the metal fine particle manufacturing apparatus includes, for example, a plasma torch that generates thermal plasma, a material supply device that supplies metal raw material powder into the plasma torch, a chamber that includes a cooling function, a cyclone that classifies the generated metal fine particles, and metal fine particles It is comprised by the collection
  • the metal fine particles mean particles having a primary particle diameter of 20 nm to 40 ⁇ m containing particles of a metal element.
  • the method for producing metal nitride-containing particles using a metal fine particle production apparatus includes the following steps in that the yield of metal nitride-containing particles having the following predetermined average primary particle diameter is increased. preferable.
  • Step A A step of supplying a thermal plasma flame by supplying an inert gas containing no nitrogen gas as a plasma gas in the plasma torch.
  • Step B A step of supplying a metal raw material powder containing a transition metal to a thermal plasma flame in a plasma torch and evaporating the metal raw material powder to obtain a gas phase raw material metal.
  • Step C Step of cooling the gas phase raw material metal to obtain fine metal particles containing a transition metal.
  • Step D A step of supplying a thermal plasma flame by supplying an inert gas containing nitrogen gas as a plasma gas in the plasma torch.
  • Step E A step of supplying metal fine particles containing a transition metal to a thermal plasma flame in a plasma torch and evaporating the metal fine particles to obtain a gas phase raw material metal.
  • Step F Step of cooling the gas phase raw metal to obtain metal nitride-containing particles.
  • the process for producing metal nitride-containing particles may optionally include the following step G after step C and / or step F.
  • Step G A step of classifying the obtained particles.
  • Step A2 A step of mixing atoms A into a metal raw material powder containing a transition metal. Furthermore, the following steps A3-1 to A3-3 may be included before step A2.
  • Step A3-1 A step of generating a thermal plasma flame by supplying an inert gas containing no nitrogen gas as a plasma gas in the plasma torch.
  • Step A3-2 A step of supplying raw material powder containing atoms A to the thermal plasma flame in the plasma torch and evaporating the raw material powder to obtain gas phase atoms A.
  • Step A3-3 A step of cooling the gas phase atoms A to obtain atomized atoms A.
  • Step G may further be included after step A3-3.
  • the atomized atom A means a particle containing the atom A and having a primary particle diameter of 20 nm to 40 ⁇ m.
  • grains contains the following process H further after the process F (when the process G is included, after the process G after the process F).
  • Step H A step of exposing the metal nitride-containing particles obtained in Step F (or Step G) to a mixed atmosphere of water vapor and nitrogen gas to perform nitriding treatment.
  • the method for producing metal nitride-containing particles may further include a step G after the step H.
  • Process A Step A is a step of generating a thermal plasma flame by supplying an inert gas containing no nitrogen gas as a plasma gas in the plasma torch.
  • the generation method of the thermal plasma flame is not particularly limited, and examples thereof include a direct current arc discharge method, a multiphase arc discharge method, a high frequency plasma method, a hybrid plasma method, and the like. Is preferred.
  • the method of generating a thermal plasma flame by the high frequency plasma method is not particularly limited. For example, a plasma gas is supplied into a plasma torch containing a high frequency oscillation coil and a quartz tube, and a high frequency current is applied to the high frequency oscillation coil. The method of obtaining a thermal plasma flame by doing is mentioned.
  • Examples of the plasma gas in the process A include an inert gas that does not contain nitrogen gas.
  • Examples of the inert gas not containing nitrogen gas include argon gas and hydrogen gas.
  • the inert gas which does not contain nitrogen gas may be used individually by 1 type, or may use 2 or more types together.
  • Step A2 is a step of mixing atoms A into a metal raw material powder containing a transition metal.
  • the method for mixing the raw metal powder and the atom A is not particularly limited, and a known method can be used.
  • the material supply device for supplying the metal raw material powder into the plasma torch may contain a mixing and dispersing function.
  • the material supply apparatus described in Paragraphs 0047 to 0058 of International Publication No. 2010/147098 can be used, the contents of which are incorporated herein.
  • the method for producing metal nitride-containing particles may further include the following steps A3-1 to A3-3 before step A2.
  • Step B is a step of supplying a metal raw material powder containing a transition metal to a thermal plasma flame in the plasma torch and evaporating the metal raw material powder to obtain a gas phase raw material metal.
  • the method for supplying the metal raw material powder to the thermal plasma flame in the plasma torch is not particularly limited, but the obtained gas phase raw material metal may be sprayed using a carrier gas in a more uniform state. preferable.
  • the carrier gas it is preferable to use an inert gas that does not contain nitrogen gas.
  • the aspect of the inert gas not containing nitrogen gas is as described above.
  • the method for producing metal nitride-containing particles includes the above step A2, the metal raw material powder is maintained in a uniform dispersed state until the metal raw material powder is supplied into the plasma torch. Is preferred.
  • Step C is a step of cooling the gas phase raw material metal to obtain fine metal particles containing a transition metal.
  • the cooling method is not particularly limited, but it is preferable to use a chamber containing a cooling function.
  • metal fine particles having the following desired particle diameter can be generated.
  • the generated metal fine particles are recovered by, for example, a recovery unit.
  • the atmosphere in the chamber is preferably an inert gas that does not contain nitrogen gas.
  • the aspect of the inert gas not containing nitrogen gas is as described above.
  • Step D is a step of generating a thermal plasma flame by supplying an inert gas containing nitrogen gas as a plasma gas in the plasma torch.
  • the inert gas containing nitrogen include nitrogen gas and nitrogen gas containing an inert gas.
  • the inert gas include argon gas and hydrogen gas.
  • the nitrogen gas containing the inert gas is not particularly limited, but the nitrogen gas content is usually about 10 to 90 mol%, preferably about 30 to 60 mol%. Other aspects are the same as in step A.
  • Step E is a step of supplying metal fine particles containing a transition metal to the thermal plasma flame in the plasma torch and evaporating the metal fine particles to obtain a gas phase raw material metal.
  • the method for supplying the metal fine particles to the thermal plasma flame in the plasma torch is as described above, but the carrier gas is preferably an inert gas containing nitrogen.
  • the aspect of the inert gas containing nitrogen is as described above.
  • step E the raw material metal that has become fine metal particles in steps A to C is supplied to the thermal plasma flame, so that a vapor phase raw metal is easily obtained, and the state of the vapor phase raw metal is likely to be more uniform.
  • Step F is a step of cooling the gas phase raw material metal to obtain metal nitride-containing particles containing a transition metal nitride.
  • the suitable aspect of the cooling method is as above-mentioned, as the atmosphere in a chamber, the inert gas containing nitrogen gas is preferable.
  • the suitable aspect of the inert gas containing nitrogen gas is as above-mentioned.
  • Step G is a step of classifying the obtained metal fine particles and / or metal nitride-containing particles.
  • the classification method is not particularly limited, and for example, a cyclone can be used.
  • the cyclone has a container on a cone, and generates a swirling flow in the container and has a function of classifying particles using centrifugal force.
  • the classification is preferably performed in an inert gas atmosphere. The aspect of the inert gas is as described above.
  • Process H is a process in which the metal nitride-containing particles are exposed to a mixed atmosphere of water vapor and nitrogen gas to perform nitriding treatment. Through this step, the metal nitride content in the metal nitride-containing particles can be increased.
  • the method for exposing the metal nitride-containing particles to a mixed atmosphere of water vapor and nitrogen gas is not particularly limited. There may be mentioned a method of standing or stirring for a predetermined time, and it is more preferred that the metal nitride-containing particles are allowed to stand for stabilization of the surface and crystal boundaries.
  • the mixing ratio of water vapor and nitrogen gas is preferably such that the relative humidity is 25 to 95% in the atmosphere.
  • the time for standing or stirring is preferably 0.5 to 72 hours, and the temperature at that time is preferably 10 to 40 ° C.
  • Steps A3-1 to A3-3 In steps A3-1 to A3-3, an inert gas not containing nitrogen gas is supplied as a plasma gas in the plasma torch to generate a thermal plasma flame (A3-1), and a thermal plasma flame in the plasma torch is used. Supplying a raw material powder containing atoms A, evaporating the raw material powder to obtain gas phase atoms A (A3-2), and cooling the gas phase atoms A to form fine particles comprising atoms A This is the obtaining step (A3-3).
  • each process is the above-mentioned process A, process B (instead of a metal raw material powder containing a transition metal, using a raw material powder containing an atom A), and process C (substituting metal fine particles containing a transition metal)
  • process A instead of a metal raw material powder containing a transition metal, using a raw material powder containing an atom A
  • process C substituted metal fine particles containing a transition metal
  • a preferred embodiment of a method for producing metal nitride-containing particles containing atom A includes a method having the following steps in order.
  • Step A A step of supplying a thermal plasma flame by supplying an inert gas containing no nitrogen gas as a plasma gas in the plasma torch.
  • Step B A step of supplying a metal raw material powder containing a transition metal to a thermal plasma flame in a plasma torch and evaporating the metal raw material powder to obtain a gas phase raw material metal.
  • Step C Step of cooling the gas phase raw material metal to obtain fine metal particles containing a transition metal.
  • Step G A step of classifying the obtained particles.
  • Step A3-1 A step of generating a thermal plasma flame by supplying an inert gas containing no nitrogen gas as a plasma gas in the plasma torch.
  • Step A3-2 A step of supplying raw material powder containing atoms A to the thermal plasma flame in the plasma torch and evaporating the raw material powder to obtain gas phase atoms A.
  • Step A3-3 A step of cooling the gas phase atoms A to obtain atomized atoms A.
  • Step G A step of classifying the obtained particles.
  • Step A2 A step of mixing atoms A (in this case, atomized atoms A) with a metal raw material powder (in this case, metal fine particles) containing a transition metal.
  • Step D A step of supplying a thermal plasma flame by supplying an inert gas containing nitrogen gas as a plasma gas in the plasma torch.
  • Step E A step of supplying metal fine particles containing a transition metal to a thermal plasma flame in a plasma torch and evaporating the metal fine particles to obtain a gas phase raw material metal.
  • Step F Step of cooling the gas phase raw metal to obtain metal nitride-containing particles.
  • Step G A step of classifying the obtained particles.
  • Step H A step of exposing the metal nitride-containing particles obtained in Step G to a mixed atmosphere of water vapor and nitrogen gas to perform nitriding treatment.
  • the order of steps A to C and steps A3-1 to A3-3 may be changed. That is, steps A to C may be performed after steps A3-1 to A3-3.
  • the metal raw material powder and the metal nitride that can remove impurities contained in the raw material particles and have a desired average primary particle diameter Containing particles can be produced.
  • the reason is that the transition metal and / or atom A is ionized by plasma treatment, and when the ions are cooled, the transition metal, atom A, and impurities are micronized to reflect their melting points. It is guessed. At this time, the atomization with a low melting point is fast, and the atomization with a high melting point is slow.
  • the fine particles (steps B and C and steps A3-2 and A3-3) once plasma-treated are likely to become a single component (single crystal).
  • the impurity particles can be removed depending on the density and / or particle size difference between the transition metal particles and / or the atom A particles and the impurity particles. it can.
  • the classification can be performed, for example, by using a cyclone or the like and appropriately setting the classification conditions.
  • Metal raw material powder containing a transition metal that can be used in the above step B (hereinafter simply referred to as “metal raw material powder”) and raw material powder containing atom A (hereinafter simply referred to as “raw material”)
  • the “powder” is not particularly limited, but is preferably highly purified.
  • the content of the transition metal in the metal raw material powder is not particularly limited, but is preferably 99.99% or more, and more preferably 99.999% or more. The same applies to the content of atom A in the raw material powder.
  • Metal raw material powder and / or raw material powder may contain atoms other than the desired transition metal and / or atom A as impurities.
  • impurities contained in the metal raw material powder include boron, aluminum, silicon, manganese, iron, nickel, and silver.
  • a metal element etc. are mentioned as an impurity contained in raw material powder.
  • the method for producing metal nitride-containing particles may further include the following step A0 before step B (when step A2 is included, before step A2).
  • Step A0 A step of removing impurities from the metal raw material powder and / or the raw material powder.
  • the metal raw material powder and / or the method for removing impurities from the raw material powder are not particularly limited.
  • niobium is described in paragraphs 0013 to 0030 of JP2012-211048.
  • a method similar to this can be used for other metal raw material powders and / or raw material powders.
  • the metal nitride-containing particles may be metal nitride-containing particles coated with an inorganic compound. That is, it may be a coated metal nitride-containing particle having metal nitride-containing particles and a coating layer formed using an inorganic compound that coats the metal nitride-containing particles.
  • a curable composition containing metal nitride-containing particles coated with an inorganic compound has better dispersion stability.
  • the inorganic compound is not particularly limited, and oxides such as SiO 2 , ZrO 2 , TiO 2 , GeO 2 , Al 2 O 3 , Y 2 O 3 , and P 2 O 5 , aluminum hydroxide, and hydroxide Examples thereof include hydroxides such as zirconium. Among these, aluminum hydroxide is preferable in that it can easily form a thinner film and can easily form a film having a higher coverage.
  • the low refractive index film is preferably silicon oxide
  • the high refractive index film is preferably zirconium hydroxide.
  • the method for coating the metal nitride-containing particles with the inorganic compound is not particularly limited, but the method for producing the metal nitride-containing particles preferably includes the following inorganic compound coating step.
  • the inorganic compound coating step is a step of coating the metal nitride-containing particles with an oxide and / or a hydroxide. Although it does not restrict
  • the metal nitride-containing particles are mixed with water to prepare a slurry.
  • a water-soluble compound for example, sodium silicate
  • Alkaline ions are removed by decantation and / or ion exchange resin.
  • the slurry is dried to obtain metal nitride-containing particles coated with an oxide.
  • the above metal nitride-containing particles are mixed with an organic solvent such as alcohol to prepare a slurry.
  • an organometallic compound such as an alkoxide containing at least one selected from the group consisting of Si, Zr, Ti, Ge, Al, Y, and P is generated in the slurry, and the slurry is heated at a high temperature. Bake. When the slurry is fired at a high temperature, a sol-gel reaction proceeds, and metal nitride-containing particles coated with an oxide are obtained.
  • a slurry containing an ionic liquid is prepared using urea and aluminum chloride in the presence of metal nitride-containing particles.
  • the metal nitride-containing particles are taken out from the slurry and dried, and then the metal nitride-containing particles are fired to obtain metal nitride-containing particles coated with a hydroxide containing aluminum hydroxide.
  • Organic pigment examples include, for example, Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 16 7,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,19
  • a pigment may be used individually by 1 type, or may use 2 or more types together.
  • dye examples include, for example, JP-A No. 64-90403, JP-A No. 64-91102, JP-A No. 1-94301, JP-A No. 6-11614, No. 2592207, and US Pat. No. 4,808,501. No. 5,667,920, U.S. Pat. No. 505950, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, etc. Can be used.
  • pyrazole azo compounds When classified by chemical structure, pyrazole azo compounds, pyromethene compounds, anilinoazo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, etc. Can be used.
  • a dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A.
  • a polymerizable dye having polymerizability in the molecule may be used, and examples of commercially available products include RDW series manufactured by Wako Pure Chemical Industries, Ltd.
  • the colorant may further contain an infrared absorber.
  • the infrared absorber means a compound having absorption in the wavelength region in the infrared region (preferably, wavelength 650 to 1,300 nm).
  • the infrared absorber is a compound having a maximum absorption wavelength in a wavelength region of 675 to 900 nm.
  • Examples of colorants having such spectral characteristics include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squarylium compounds, naphthalocyanine compounds, quaterylenes. Compounds, dithiol metal complex compounds, croconium compounds and the like.
  • phthalocyanine compound naphthalocyanine compound, iminium compound, cyanine compound, squalium compound and croconium compound
  • the compounds disclosed in paragraphs 0010 to 0081 of JP-A No. 2010-1111750 may be used.
  • the cyanine compound for example, “functional pigment, Shin Okawara / Ken Matsuoka / Keijiro Kitao / Kensuke Hirashima, written by Kodansha Scientific”, the contents of which are incorporated herein.
  • the compound having a maximum absorption wavelength in the wavelength region of 675 to 900 nm is preferably at least one selected from the group consisting of a cyanine compound, a pyrrolopyrrole compound, a squarylium compound, a phthalocyanine compound, and a naphthalocyanine compound.
  • the infrared absorber is preferably a compound that dissolves 1% by mass or more in 25 ° C. water, and more preferably a compound that dissolves 10% by mass or more in 25 ° C. water. By using such a compound, the solvent resistance is improved.
  • the infrared absorber is preferably at least one selected from the group consisting of compounds represented by the following general formulas 1 to 3.
  • General formula 1 In General Formula 1, A 1 and A 2 each independently represent an aryl group, a heteroaryl group, or a group represented by General Formula 1-A below.
  • the wavy line represents the connecting hand.
  • R 1a and R 1b each independently represent an alkyl group, an aryl group, or a heteroaryl group
  • R 2 to R 5 each independently represents a hydrogen atom or a substituent
  • R 2 and R 3 , R 4 and R 5 may be bonded to each other to form a ring
  • R 6 and R 7 each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, —BR A R B , or a metal atom
  • R A and R B each independently represent a hydrogen atom Represents an atom or substituent
  • R 6 may be covalently or coordinated with R 1a or R 3
  • R 7 may be covalently or coordinated with R 1b or R 5 .
  • Z 1 and Z 2 are each independently a nonmetallic atomic group that forms a 5-membered or 6-membered nitrogen-containing heterocycle that may be condensed
  • R 101 and R 102 each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, or an aryl group
  • L 1 represents a methine chain composed of an odd number of methines
  • a and b are each independently 0 or 1
  • X 1 represents an anion
  • c represents the number necessary for balancing the charge
  • the site represented by Cy in the formula is an anion moiety.
  • X 1 represents a cation
  • c represents a number necessary to balance the charge
  • the curable composition may contain a pigment derivative.
  • the pigment derivative is preferably a compound having a structure in which a part of an organic pigment is substituted with an acidic group, a basic group or a phthalimidomethyl group.
  • a pigment derivative having an acidic group or a basic group is preferable. It is particularly preferable that the pigment derivative has a basic group.
  • the combination of the resin (dispersant) and the pigment derivative described above is preferably a combination in which the dispersant is an acidic dispersant and the pigment derivative has a basic group.
  • organic pigment for constituting the pigment derivative examples include diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments , Isoindoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, metal complex pigments, and the like.
  • an acidic group which a pigment derivative has a sulfonic acid group, a carboxylic acid group, and its salt are preferable, a carboxylic acid group and a sulfonic acid group are more preferable, and a sulfonic acid group is still more preferable.
  • a basic group which a pigment derivative has an amino group is preferable and a tertiary amino group is more preferable.
  • the content of the pigment derivative is preferably 1 to 30% by mass and more preferably 3 to 20% by mass with respect to the mass of the pigment. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination.
  • the curable composition may contain a polymerization inhibitor.
  • a polymerization inhibitor By containing a polymerization inhibitor, the curable composition has better stability over time.
  • the term “stability over time” means that a cured film having an excellent pattern shape can be obtained even when the curable composition is prepared and stored for a predetermined period.
  • the polymerization inhibitor has an action of suppressing the progress of the reaction between the polyfunctional thiol compound and the polymerizable compound in the curable composition being stored, and it is presumed that the above-described effect can be obtained.
  • the content of the polymerization inhibitor is preferably 0.001 to 1% by mass, more preferably 0.005 to 1% by mass, and further 0.05 to 1% by mass based on the total solid content of the curable composition. preferable.
  • the curable composition has more excellent temporal stability.
  • the polymerization inhibitor is not particularly limited, and a known compound used as a polymerization inhibitor can be used.
  • the compound used as the polymerization inhibitor include phenolic compounds, quinone compounds, hindered amine compounds, phenothiazine compounds, and nitrobenzene compounds.
  • the said compound may be used individually by 1 type, or may use 2 or more types together.
  • phenolic compounds include phenol, 4-methoxyphenol, hydroquinone, 2-tert-butylhydroquinone, catechol, 4-tert-butyl-catechol, 2,6-di-tert-butylphenol, 2,6-di- tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, pentaerythritol tetrakis (3,5-di-tert -Butyl-4-hydroxyhydrocinnamate), 4-methoxy-1-naphthol, 1,4-dihydroxynaphthalene and the like.
  • phenolic compound a phenolic compound represented by the formula (IH-1) is preferable.
  • R 1 to R 5 are each independently a hydrogen atom, alkyl group, alkenyl group, hydroxy group, amino group, aryl group, alkoxy group, carboxyl group, alkoxycarbonyl group, or acyl. Represents a group. R 1 to R 5 may be connected to each other to form a ring.
  • R 1 to R 5 in formula (IH-1) are each a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (eg, a methyl group or an ethyl group), or an alkoxy group having 1 to 5 carbon atoms (eg, methoxy A alkenyl group having 2 to 4 carbon atoms (for example, a vinyl group), or a phenyl group.
  • R 1 and R 5 are each independently more preferably a hydrogen atom or a tert-butyl group
  • R 2 and R 4 are more preferably a hydrogen atom
  • R 3 is a hydrogen atom
  • an alkyl having 1 to 5 carbon atoms A group or an alkoxy group having 1 to 5 carbon atoms is more preferable.
  • Examples of the quinone compound include 1,4-benzoquinone, 1,2-benzoquinone, and 1,4-naphthoquinone.
  • Examples of the hindered amine compound include a polymerization inhibitor represented by the following formula (IH-2).
  • R 6 in formula (IH-2) represents a hydrogen atom, a hydroxy group, an amino group, an alkoxy group, an alkoxycarbonyl group, or an acyl group. Of these, a hydrogen atom or a hydroxy group is preferable, and a hydroxy group is more preferable.
  • R 7 to R 10 in formula (IH-2) each independently represent a hydrogen atom or an alkyl group.
  • the alkyl group represented by R 7 to R 10 is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group or an ethyl group.
  • each of the above compounds may be used alone, in combination of two or in combination of three or more.
  • the polymerization inhibitor preferably contains a phenolic compound. Especially, it is more preferable that a polymerization inhibitor contains 2 or more types of phenolic compounds.
  • a curable composition containing a different phenolic compound has a more excellent effect of the present invention.
  • the polymerization inhibitor preferably contains a phenolic compound and a hindered amine compound.
  • the curable composition containing a phenol compound and a hindered amine compound has a more excellent effect of the present invention.
  • the curable composition preferably contains a solvent.
  • the solvent include water and organic solvents.
  • the curable composition preferably contains an organic solvent.
  • the solid content of the curable composition is preferably 10 to 30% by mass.
  • a viscosity is low and applicability
  • paintability will improve.
  • the concentration of the highly reactive compound is lowered, the temporal stability is improved.
  • the solid content of the curable composition is less than or equal to the upper limit value, the viscosity is maintained at a certain level and the applicability is improved.
  • the colorant having a high specific gravity is less likely to settle, and the stability over time is improved.
  • organic solvent When the curable composition contains an organic solvent, the content of the organic solvent is preferably 70 to 90% by mass with respect to the total mass of the curable composition.
  • an organic solvent may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of organic solvents together, it is preferable that the total amount becomes the said range.
  • the organic solvent is not particularly limited.
  • acetone, methyl ethyl ketone, cyclohexane, ethylene dichloride, tetrahydrofuran, toluene ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether.
  • the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, -It is preferably composed of two or more selected from the group consisting of heptanone, cyclohexanone, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.
  • the curable composition may contain water. Water may be intentionally added, or may be inevitably contained in the curable composition by adding each component contained in the curable composition.
  • the water content is preferably 0.01 to 1% by mass relative to the total mass of the curable composition. When the water content is within the above range, the generation of pinholes is suppressed when a cured film is produced, and the moisture resistance of the cured film is further improved.
  • the curable composition preferably contains a dispersant.
  • the dispersant contributes to the improvement of the dispersibility of the colorant.
  • the dispersant and the binder resin described later are different components.
  • the content of the dispersant is preferably 0.05 to 50% by mass, and 0.05 to 30% by mass with respect to the total solid content of the curable composition. More preferred. When the content of the dispersant is 0.05 to 30% by mass with respect to the total solid content of the curable composition, the pattern shape of the cured film obtained by curing the curable composition is more excellent.
  • a dispersing agent may be used individually by 1 type, or may use 2 or more types together. When two or more dispersants are used in combination, the total amount is preferably within the above range.
  • the dispersant for example, a known pigment dispersant can be appropriately selected and used.
  • polymer compounds are preferable.
  • the dispersant include polymer dispersants [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic type Copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, and pigment derivatives.
  • the polymer compounds can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.
  • the polymer compound is adsorbed on the surface of the dispersion of the colorant (for example, inorganic pigment) and acts to prevent reaggregation of the dispersion. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer containing an anchor site to the pigment surface are preferable.
  • the polymer compound preferably contains a structural unit containing a graft chain.
  • structural unit is synonymous with “repeating unit”. Since the polymer compound containing a structural unit containing such a graft chain has an affinity for a solvent due to the graft chain, the dispersibility of a colorant such as a black pigment and the dispersion stability after the lapse of time ( Excellent stability.
  • the polymer compound containing a structural unit containing a graft chain has an affinity for a polymerizable compound or other resin that can be used in combination due to the presence of the graft chain. As a result, it becomes difficult to produce a residue by alkali development.
  • the graft chain When the graft chain becomes longer, the steric repulsion effect becomes higher and the dispersibility of the black pigment and the like is improved. On the other hand, if the graft chain is too long, the adsorptive power to colored pigments such as black pigments is lowered, and the dispersibility of black pigments and the like tends to be lowered. Therefore, the graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2,000 atoms excluding hydrogen atoms, and excluding hydrogen atoms. More preferred are those having 60 to 500 atoms.
  • the graft chain means from the base of the main chain of the copolymer (the atom bonded to the main chain in a group branched from the main chain) to the end of the group branched from the main chain.
  • the graft chain preferably contains a polymer structure.
  • a polymer structure include a poly (meth) acrylate structure (for example, a poly (meth) acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, and a polyamide.
  • examples thereof include a structure and a polyether structure.
  • the graft chain was selected from the group consisting of a polyester structure, a polyether structure and a poly (meth) acrylate structure in order to improve the interaction between the graft chain and the solvent, thereby increasing the dispersibility of the black pigment and the like.
  • a graft chain containing at least one kind is preferred, and a graft chain containing at least one of a polyester structure or a polyether structure is more preferred.
  • the macromonomer containing such a graft chain is not particularly limited, but a macromonomer containing a reactive double bond group can be preferably used.
  • AA-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-10 (trade name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AS-6 (trade name, Toa Gosei Co., Ltd.), AN-6 (trade name, manufactured by Toa Gosei Co., Ltd.), and Bremer PME-4000 (trade name, manufactured by NOF Corporation) are preferred.
  • the dispersant preferably contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyester. More preferably, the dispersant contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and chain polyester. More preferably, the dispersant contains at least one structure selected from the group consisting of a polymethyl acrylate structure, a polymethyl methacrylate structure, a polycaprolactone structure, and a polyvalerolactone structure. The dispersant may contain the above structure alone in one dispersant, or may contain a plurality of these structures in one dispersant.
  • the polycaprolactone structure means a structure containing a ring-opened structure of ⁇ -caprolactone as a repeating unit.
  • the polyvalerolactone structure means a structure containing a ring-opened structure of ⁇ -valerolactone as a repeating unit.
  • Specific examples of the dispersant containing a polycaprolactone structure include those in which j and k are 5 in the following formula (1) and the following formula (2).
  • Specific examples of the dispersant containing a polyvalerolactone structure include those in which j and k in the following formula (1) and the following formula (2) are 4.
  • dispersant containing a polymethyl acrylate structure examples include those in which X 5 in the following formula (4) is a hydrogen atom and R 4 is a methyl group. Further, specific examples of the dispersant containing a polymethyl methacrylate structure include those in which X 5 in the following formula (4) is a methyl group and R 4 is a methyl group.
  • the polymer compound preferably contains a structural unit represented by any of the following formulas (1) to (4) as a structural unit containing a graft chain. It is more preferable to contain a structural unit represented by any one of (1A), the following formula (2A), the following formula (3A), the following formula (3B), and the following (4).
  • W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH.
  • W 1 , W 2 , W 3 , and W 4 are preferably oxygen atoms.
  • X 1 , X 2 , X 3 , X 4 , and X 5 each independently represent a hydrogen atom or a monovalent organic group.
  • X 1 , X 2 , X 3 , X 4 , and X 5 are each independently preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (the number of carbon atoms), from the viewpoint of synthesis constraints, Independently, a hydrogen atom or a methyl group is more preferable, and a methyl group is still more preferable.
  • Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group, and the linking group is not particularly limited in structure.
  • Specific examples of the divalent linking group represented by Y 1 , Y 2 , Y 3 , and Y 4 include the following (Y-1) to (Y-21) linking groups. .
  • a and B each represent a binding site. Of the structures shown below, (Y-2) or (Y-13) is more preferable from the viewpoint of ease of synthesis.
  • Z 1 , Z 2 , Z 3 , and Z 4 each independently represent a monovalent organic group.
  • the structure of the organic group is not particularly limited, and specifically, an alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group Etc.
  • the organic group represented by Z 1 , Z 2 , Z 3 , and Z 4 those containing a steric repulsion effect are particularly preferable from the viewpoint of improving dispersibility, and each independently has 5 carbon atoms.
  • alkyl groups or alkoxy groups are more preferable, and among them, each independently a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms is more preferable.
  • the alkyl group contained in the alkoxy group may be linear, branched, or cyclic.
  • n, m, p, and q are each independently an integer of 1 to 500.
  • j and k each independently represent an integer of 2 to 8.
  • J and k in the formulas (1) and (2) are preferably integers of 4 to 6 and most preferably 5 from the viewpoint of the temporal stability and developability of the curable composition.
  • R 3 represents a branched or straight chain alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R 3 may be the same or different from each other.
  • R 4 represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in terms of structure.
  • R 4 is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and more preferably a hydrogen atom or an alkyl group.
  • R 4 is an alkyl group
  • a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms is preferable, and 1 to 20 carbon atoms is preferable.
  • linear alkyl groups having 1 to 6 carbon atoms are more preferable.
  • q is 2 to 500
  • a plurality of X 5 and R 4 present in the graft copolymer may be the same or different from each other.
  • a high molecular compound can contain the structural unit containing the graft chain from which 2 or more types of structures differ. That is, in the molecule of the polymer compound, structural units represented by the formulas (1) to (4) having different structures from each other may be included. , And q each represent an integer of 2 or more, in Formula (1) and Formula (2), j and k may contain structures different from each other in the side chain, and Formula (3) and Formula ( In 4), a plurality of R 3 , R 4 and X 5 present in the molecule may be the same or different from each other.
  • the structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of temporal stability and developability of the curable composition.
  • the structural unit represented by the formula (2) is more preferably a structural unit represented by the following formula (2A) from the viewpoint of temporal stability and developability of the curable composition.
  • X 1, Y 1, Z 1 and n are as defined X 1, Y 1, Z 1 and n in Formula (1), and preferred ranges are also the same.
  • X 2, Y 2, Z 2 and m are as defined X 2, Y 2, Z 2 and m in the formula (2), and preferred ranges are also the same.
  • the structural unit represented by the formula (3) is more preferably a structural unit represented by the following formula (3A) or the formula (3B) from the viewpoint of temporal stability and developability of the curable composition. .
  • X 3, Y 3, Z 3 and p are as defined X 3, Y 3, Z 3 and p in formula (3), and preferred ranges are also the same.
  • the polymer compound contains a structural unit represented by the formula (1A) as a structural unit containing a graft chain.
  • the structural unit containing a graft chain (for example, the structural unit represented by the above formulas (1) to (4)) is 2 to 90% in terms of mass with respect to the total mass of the polymer compound. Preferably, it is contained in the range of 5 to 30%.
  • the structural unit containing a graft chain is included within this range, the dispersibility of the black pigment is high, and the developability when forming a cured film is good.
  • a high molecular compound contains the hydrophobic structural unit different from the structural unit containing a graft chain (namely, it does not correspond to the structural unit containing a graft chain).
  • a hydrophobic structural unit is a structural unit which does not have an acid group (for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxy group, etc.).
  • the hydrophobic structural unit is preferably a structural unit derived from (corresponding to) a compound (monomer) having a ClogP value of 1.2 or more, more preferably derived from a compound having a ClogP value of 1.2 to 8. A structural unit. Thereby, the effect of this invention can be expressed more reliably.
  • ClogP values can be obtained from Daylight Chemical Information System, Inc. It is a value calculated by the program “CLOGP” available from This program provides the value of “computation logP” calculated by Hansch, Leo's fragment approach (see below). The fragment approach is based on the chemical structure of a compound, which divides the chemical structure into substructures (fragments) and estimates the logP value of the compound by summing the logP contributions assigned to that fragment. Details thereof are described in the following documents. In this specification, ClogP value intends the value calculated by program CLOGP v4.82. A. J. et al. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P.A. G. Sammunens, J. et al. B.
  • logP means the common logarithm of the partition coefficient P (Partition Coefficient), and quantitatively determines how an organic compound is distributed in the equilibrium of a two-phase system of oil (generally 1-octanol) and water. It is a physical property value expressed as a numerical value, and is represented by the following formula.
  • logP log (Coil / Cwater)
  • Coil represents the molar concentration of the compound in the oil phase
  • Cwater represents the molar concentration of the compound in the aqueous phase.
  • the polymer compound preferably contains one or more structural units selected from structural units derived from monomers represented by the following formulas (i) to (iii) as hydrophobic structural units.
  • R 1 , R 2 , and R 3 each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number of 1 to 6 alkyl groups (for example, a methyl group, an ethyl group, a propyl group, etc.).
  • R 1 , R 2 , and R 3 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group.
  • R 2 and R 3 are more preferably a hydrogen atom.
  • X represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
  • L is a single bond or a divalent linking group.
  • a divalent aliphatic group for example, alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, substituted alkynylene group
  • divalent aromatic group for example, arylene group
  • Substituted arylene group divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino group (—NR 31 —, where R 31 Includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (—CO—), and combinations thereof.
  • the divalent aliphatic group may have a cyclic structure or a branched structure.
  • the aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
  • the aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but is preferably a saturated aliphatic group.
  • the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group and a heterocyclic group.
  • the carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.
  • the aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group.
  • the divalent heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as the heterocyclic ring. Another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring.
  • the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 32 , where R 32 is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group, or heterocyclic group.
  • L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure.
  • the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
  • L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures.
  • the polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure.
  • the polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
  • Z is an aliphatic group (eg, alkyl group, substituted alkyl group, unsaturated alkyl group, substituted unsaturated alkyl group), aromatic group (eg, aryl group, substituted aryl group, arylene group, substituted arylene group), A heterocyclic group or a combination thereof can be mentioned. These groups include an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group (—NR 31 —, wherein R 31 is an aliphatic group, an aromatic group Group or heterocyclic group) or a carbonyl group (—CO—) may be contained.
  • the aliphatic group may have a cyclic structure or a branched structure.
  • the aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
  • the aliphatic group further includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. Examples of the ring assembly hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and 4 -A cyclohexylphenyl group and the like are included.
  • bridged cyclic hydrocarbon ring examples include 2 such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.).
  • Tricyclic hydrocarbon rings such as cyclic hydrocarbon rings, homobredan, adamantane, tricyclo [5.2.1.0 2,6 ] decane, and tricyclo [4.3.1.1 2,5 ] undecane rings , And tetracyclo [4.4.0.1 2,5 .
  • bridged cyclic hydrocarbon rings include fused cyclic hydrocarbon rings such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and perhydroindene.
  • a condensed ring formed by condensing a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring is also included.
  • the aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group.
  • the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. However, the aliphatic group does not have an acid group as a substituent.
  • the carbon number of the aromatic group is preferably 6-20, more preferably 6-15, and still more preferably 6-10.
  • the aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group. However, the aromatic group does not have an acid group as a substituent.
  • a heterocyclic group contains a 5-membered ring or a 6-membered ring as a heterocyclic ring.
  • Another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring.
  • the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 32 , where R 32 is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.
  • the heterocyclic group does not have an acid group as a substituent.
  • R 4 , R 5 , and R 6 are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms ( For example, it represents a methyl group, an ethyl group, a propyl group, etc.), Z, or LZ.
  • L and Z are as defined above.
  • R 4 , R 5 and R 6 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
  • R 1 , R 2 , and R 3 are a hydrogen atom or a methyl group, and L is a single bond, an alkylene group, or a divalent linkage containing an oxyalkylene structure
  • a compound in which X is an oxygen atom or an imino group and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferred.
  • R 4 , R 5 , and R 6 are a hydrogen atom or a methyl group and Z is an aliphatic group, a heterocyclic group, or an aromatic group is preferable.
  • Examples of typical compounds represented by formulas (i) to (iii) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, and the like.
  • radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, and the like.
  • representative compounds represented by formulas (i) to (iii) the compounds described in paragraphs 0089 to 0093 of JP2013-249417A can be referred to, and the contents thereof are incorporated in the present specification. It is.
  • the hydrophobic structural unit is preferably contained in a range of 10 to 90%, more preferably in a range of 20 to 80% with respect to the total mass of the polymer compound in terms of mass. When the content is within the above range, good pattern formation can be obtained.
  • the polymer compound can introduce a functional group capable of forming interaction with a colorant such as black pigment.
  • the polymer compound preferably further contains a structural unit containing a functional group capable of forming an interaction with a colorant such as a black pigment.
  • the functional group capable of forming an interaction with the colorant such as the black pigment include an acid group, a basic group, a coordinating group, and a reactive functional group.
  • the polymer compound contains an acid group, a basic group, a coordination group, or a reactive functional group, the structural unit containing an acid group, the structural unit containing a basic group, and a coordination group, respectively.
  • the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as the acid group, developability for pattern formation by alkali development can be imparted to the polymer compound. That is, by introducing an alkali-soluble group into a polymer compound, the polymer compound as a dispersant that contributes to the dispersion of a colorant such as a black pigment in the curable composition contains alkali-solubility.
  • the curable composition containing such a polymer compound has excellent light-shielding properties in the exposed area, and the alkali developability in the unexposed area is improved.
  • the polymer compound When the polymer compound contains a structural unit containing an acid group, the polymer compound tends to become compatible with the solvent and the coating property tends to be improved. This is because the acid group in the structural unit containing an acid group easily interacts with a colorant such as a black pigment, and the polymer compound stably disperses the colorant such as a black pigment, and the colorant such as a black pigment This is probably because the viscosity of the polymer compound in which the polymer is dispersed is lowered, and the polymer compound itself is easily dispersed stably.
  • the structural unit containing an alkali-soluble group as an acid group may be the same structural unit as the structural unit containing the graft chain or a different structural unit. Are different structural units (ie, do not correspond to the hydrophobic structural units described above).
  • the acid group that is a functional group capable of forming an interaction with a colorant such as a black pigment examples include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxy group, a carboxylic acid group, At least one of a sulfonic acid group and a phosphoric acid group is preferable, and a carboxylic acid group is more preferable in terms of good adsorbing power to a colorant such as a black pigment and high dispersibility of the colorant. That is, the polymer compound preferably further contains a structural unit containing at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
  • the polymer compound may have one or more structural units containing an acid group.
  • the polymer compound may or may not contain a structural unit containing an acid group.
  • the content of the structural unit containing an acid group is the total mass of the polymer compound in terms of mass. On the other hand, it is preferably 5 to 80%, and more preferably 10 to 60% from the viewpoint of suppressing damage of image strength due to alkali development.
  • Examples of the basic group that is a functional group capable of interacting with a colorant such as a black pigment include a primary amino group, a secondary amino group, a tertiary amino group, and a heterocyclic ring containing an N atom. And an amide group and the like, and a preferable one is a tertiary amino group in that the adsorbing power to a colorant such as a black pigment is good and the dispersibility of the colorant is high.
  • the polymer compound can contain one or more of these basic groups.
  • the polymer compound may or may not contain a structural unit containing a basic group, but when it is contained, the content of the structural unit containing a basic group is the total amount of the polymer compound in terms of mass. It is preferably 0.01% or more and 50% or less with respect to the mass, and more preferably 0.01% or more and 30% or less from the viewpoint of inhibiting developability inhibition.
  • a coordinating group that is a functional group capable of forming an interaction with a colorant such as a black pigment, and a functional group having reactivity
  • a acetylacetoxy group for example, an acetylacetoxy group, a trialkoxysilyl group, an isocyanate group, an acid anhydride, And acid chloride etc. are mentioned.
  • Preferable one is an acetylacetoxy group from the viewpoint of good adsorbing power to a colorant such as a black pigment and high dispersibility of the colorant.
  • the polymer compound may have one or more of these groups.
  • the polymer compound may or may not contain a structural unit containing a coordinating group or a structural unit containing a reactive functional group, but if it contains, the content of these structural units Is preferably 10% or more and 80% or less in terms of mass, and more preferably 20% or more and 60% or less from the viewpoint of inhibiting developability inhibition.
  • the polymer compound contains a functional group capable of interacting with a colorant such as a black pigment in addition to the graft chain
  • the functional group capable of interacting with a colorant such as the above various black pigments
  • the polymer compound is derived from monomers represented by the following general formulas (iv) to (vi) It is preferable to contain one or more structural units selected from these structural units.
  • R 11 , R 12 , and R 13 each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number of 1 Represents an alkyl group of ⁇ 6 (for example, methyl group, ethyl group, propyl group, etc.).
  • R 11 , R 12 and R 13 are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably each independently Are a hydrogen atom or a methyl group.
  • R 12 and R 13 are each particularly preferably a hydrogen atom.
  • X 1 in the formula (iv) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
  • Y in the formula (v) represents a methine group or a nitrogen atom.
  • L 1 in the formulas (iv) to (v) represents a single bond or a divalent linking group.
  • the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group (for example, , Arylene groups and substituted arylene groups), divalent heterocyclic groups, oxygen atoms (—O—), sulfur atoms (—S—), imino groups (—NH—), substituted imino bonds (—NR 31 ′ —
  • R 31 ′ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (—CO—), and combinations thereof.
  • the divalent aliphatic group may have a cyclic structure or a branched structure.
  • the aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
  • the aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group.
  • the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an aromatic group, and a heterocyclic group.
  • the carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.
  • the aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an aliphatic group, an aromatic group, and a heterocyclic group.
  • the divalent heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as the heterocyclic ring.
  • One or more heterocycles, aliphatic rings or aromatic rings may be condensed with the heterocycle.
  • the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 32 , where R 32 is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.
  • L 1 is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure.
  • the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
  • L 1 may include a polyoxyalkylene structure containing two or more oxyalkylene structures.
  • the polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure.
  • the polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
  • Z 1 represents a functional group capable of forming an interaction with a colorant such as a black pigment in addition to the graft chain, and is a carboxylic acid group or a tertiary amino group. It is preferable that it is a carboxylic acid group.
  • R 14 , R 15 , and R 16 are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.), - Z 1, or an L 1 -Z 1.
  • L 1 and Z 1 are the same meaning as L 1 and Z 1 in the above, it is the preferable examples.
  • R 14 , R 15 and R 16 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
  • R 11 , R 12 and R 13 are each independently a hydrogen atom or a methyl group, and L 1 is an alkylene group or a divalent oxyalkylene structure.
  • a compound in which X 1 is an oxygen atom or imino group and Z 1 is a carboxylic acid group is preferable.
  • R 11 is a hydrogen atom or a methyl group
  • L 1 is an alkylene group
  • Z 1 is a carboxylic acid group
  • Y is a methine group.
  • R 14 , R 15 , and R 16 are each independently a hydrogen atom or a methyl group, L 1 is a single bond or an alkylene group, and Z A compound in which 1 is a carboxylic acid group is preferred.
  • monomers represented by the formulas (iv) to (vi).
  • examples of the monomer include methacrylic acid, crotonic acid, isocrotonic acid, a compound containing an addition polymerizable double bond and a hydroxy group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride.
  • Reaction product reaction product of a compound containing an addition polymerizable double bond and hydroxy group in the molecule and phthalic anhydride, compound containing an addition polymerizable double bond and hydroxy group in the molecule and tetrahydroxyphthalic acid Reaction product with anhydride, reaction product of compound containing addition polymerizable double bond and hydroxy group in the molecule and trimellitic anhydride, compound containing addition polymerizable double bond and hydroxy group in the molecule Reaction product with pyromellitic anhydride, acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid , Vinylphenol, and, and 4-hydroxyphenyl methacrylamide.
  • the content of the structural unit containing a functional group capable of forming an interaction with a colorant such as a black pigment is from the viewpoint of interaction with the colorant such as a black pigment, stability over time, and permeability to a developer.
  • the amount is preferably 0.05% by mass to 90% by mass, more preferably 1.0% by mass to 80% by mass, and still more preferably 10% by mass to 70% by mass based on the total mass of the polymer compound.
  • the polymer compound is a structural unit containing a graft chain, a hydrophobic structural unit, and a black color as long as the effects of the present invention are not impaired for the purpose of improving various performances such as image strength.
  • structural units containing functional groups that can interact with colorants such as pigments other structural units having various functions (for example, functional groups having affinity with the dispersion medium used in the dispersion) And the like may be further included.
  • other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like.
  • the polymer compound may use one or more of these other structural units, and the content is preferably 0% or more and 80% or less based on the total mass of the polymer compound in terms of mass. 10% or more and 60% or less is more preferable. When the content is in the above range, sufficient pattern formability is maintained.
  • the acid value of the polymer compound is preferably in the range of 0 mgKOH / g to 250 mgKOH / g, more preferably in the range of 10 mgKOH / g to 200 mgKOH / g, and in the range of 20 mgKOH / g to 120 mgKOH / g. A range is more preferred. If the acid value of the polymer compound is 160 mgKOH / g or less, pattern peeling during development when forming a cured film can be more effectively suppressed. When the acid value of the polymer compound is 10 mgKOH / g or more, the alkali developability becomes better.
  • the acid value of the polymer compound is 20 mgKOH / g or more, precipitation of a colorant such as a black pigment can be further suppressed, the number of coarse particles can be reduced, and the temporal stability of the curable composition can be reduced. It can be improved.
  • the acid value of the polymer compound can be calculated, for example, from the average content of acid groups in the polymer compound. Moreover, the resin which has a desired acid value can be obtained by changing content of the structural unit containing the acid group which is a structural component of a high molecular compound.
  • the weight average molecular weight of the polymer compound is 4 in terms of polystyrene converted by GPC (Gel Permeation Chromatography) method from the viewpoint of pattern peeling inhibition during development and developability. It is preferably 000 or more and 300,000 or less, more preferably 5,000 or more and 200,000 or less, further preferably 6,000 or more and 100,000 or less, and 10,000 or more and 50,000 or less.
  • the GPC method is based on a method using HLC-8020GPC (manufactured by Tosoh), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh, 4.6 mm ID ⁇ 15 cm) as a column and THF (tetrahydrofuran) as an eluent. .
  • the polymer compound can be synthesized based on a known method, and examples of the solvent used when synthesizing the polymer compound include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, and ethylene glycol monomethyl.
  • Ether ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene,
  • Examples include ethyl acetate, methyl lactate, and ethyl lactate. These solvents may be used alone or in combination of two or more.
  • polymer compound examples include “DA-7301” manufactured by Kashiwagi Kasei Co., Ltd., “Disperbyk-101 (polyamideamine phosphate), 107 (carboxylic acid ester)” manufactured by BYK Chemie, and 110 (copolymers containing acid groups).
  • Acrybase FFS-6752, Acrybase FFS-187, Acrycure-RD-F8, and Cyclomer P can be used.
  • Examples of commercially available amphoteric resins include DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPER10K, 2001-DISPERBY, manufactured by BYK Chemie. DISPERBYK-2012, DISPERBYK-2025, BYK-9076, Ajisper PB821, Azisper PB822, Azisper PB881, etc. manufactured by Ajinomoto Fine Techno Co. These polymer compounds may be used alone or in combination of two or more.
  • polymer compound As specific examples of the polymer compound, the polymer compounds described in paragraphs 0127 to 0129 of JP2013-249417A can be referred to, and the contents thereof are incorporated in the present specification.
  • a graft copolymer described in JP-A 2010-106268, paragraphs 0037 to 0115 (corresponding to paragraphs 0075 to 0133 in US2011 / 0124824) can be used. Can be incorporated and incorporated herein by reference.
  • Polymeric compounds containing components can be used, the contents of which can be incorporated and incorporated herein.
  • the curable composition preferably contains a binder resin.
  • the content of the binder resin is preferably 0.1 to 30% by mass with respect to the total solid content of the curable composition.
  • Binder resin may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of binder resin together, it is preferable that the total amount is in the said range.
  • a linear organic polymer is preferably used.
  • a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to enable water development or weak alkaline water development.
  • alkali-soluble resin (resin containing group which accelerates
  • the binder resin is a linear organic polymer that promotes at least one alkali solubility in the molecule (preferably a molecule having a (meth) acrylic copolymer or styrene copolymer as the main chain).
  • alkali-soluble resins containing a group to be used can be suitably selected from alkali-soluble resins containing a group to be used.
  • polyhydroxystyrene resins, polysiloxane resins, (meth) acrylic resins, (meth) acrylamide resins, (meth) acrylic / (meth) acrylamide copolymer resins, epoxy resins and Polyimide resins are preferred, and (meth) acrylic resins, (meth) acrylamide resins, (meth) acryl / (meth) acrylamide copolymer resins, or polyimide resins are more preferred from the viewpoint of control of developability.
  • Examples of the group that promotes alkali solubility include a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxy group. Especially, what is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution is preferable, and an alkali-soluble resin containing a structural unit derived from (meth) acrylic acid is more preferable. These acid groups may be used alone or in combination of two or more.
  • binder resin examples include a radical polymer containing a carboxylic acid group in the side chain.
  • examples of the radical polymer containing a carboxylic acid group in the side chain include, for example, JP 59-44615, JP-B 54-34327, JP-B 58-12777, JP-B 54-25957, JP-A 54 -92723, JP-A-59-53836, and JP-A-59-71048.
  • a resin obtained by singly or copolymerizing a monomer containing a carboxylic acid group, an acid anhydride obtained by singly or copolymerizing a monomer containing an acid anhydride examples thereof include resins obtained by hydrolysis, half-esterification or half-amidation of units, and epoxy acrylates obtained by modifying epoxy resins with unsaturated monocarboxylic acids and acid anhydrides.
  • the monomer containing a carboxylic acid group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxylstyrene.
  • Examples include acidic cellulose derivatives containing a carboxylic acid group in the side chain.
  • Examples of the monomer containing an acid anhydride include maleic anhydride.
  • those obtained by adding a cyclic acid anhydride to a polymer containing a hydroxy group are useful.
  • Acetal-modified polyvinyl alcohol binder resins containing acid groups are described in European Patent No. 993966, European Patent No. 1204000, and Japanese Patent Application Laid-Open No. 2001-318463.
  • An acetal-modified polyvinyl alcohol-based binder resin containing an acid group is suitable because of its excellent balance between film strength and developability.
  • polyvinyl pyrrolidone or polyethylene oxide is useful as the water-soluble linear organic polymer.
  • alcohol-soluble nylon and polyether which is a reaction product of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful.
  • a polyimide resin described in International Publication No. 2008/123097 is also useful.
  • [benzyl (meth) acrylate / (meth) acrylic acid / other addition-polymerizable vinyl monomer as required] copolymer, and [allyl (meth) acrylate / (meth) acrylic acid / if necessary Other addition-polymerizable vinyl monomers] are preferable because they are excellent in the balance of film strength, sensitivity, and developability.
  • Examples of commercially available products include Acrybase FF-187, FF-426 (manufactured by Fujikura Kasei Co., Ltd.), Acrycure-RD-F8 (Nippon Shokubai), and Daicel Ornex Cyclomer P (ACA) 230AA.
  • a known radical polymerization method can be applied.
  • Those skilled in the art can easily set the polymerization conditions such as temperature, pressure, type and amount of radical initiator, and type of solvent when the binder resin is produced by the radical polymerization method.
  • the binder resin it is also preferable to use a polymer containing a structural unit containing a graft chain and a structural unit containing an acid group (alkali-soluble group).
  • the definition of the structural unit containing the graft chain is synonymous with the structural unit containing the graft chain contained in the dispersant, and the preferred range is also the same.
  • the acid group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxy group, and at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group is preferable.
  • a carboxylic acid group is more preferable.
  • the structural unit containing an acid group preferably contains one or more structural units selected from structural units derived from monomers represented by the following formulas (vii) to (ix).
  • R 21 , R 22 , and R 23 each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number of 1 Represents an alkyl group of ⁇ 6 (for example, methyl group, ethyl group, propyl group, etc.).
  • R 21 , R 22 , and R 23 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each independently a hydrogen atom or More preferred is a methyl group.
  • R 21 and R 23 are each particularly preferably a hydrogen atom.
  • X 2 in the formula (vii) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
  • Y in formula (viii) represents a methine group or a nitrogen atom.
  • L 2 in the formulas (vii) to (ix) represents a single bond or a divalent linking group.
  • the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group (for example, , Arylene group, and substituted arylene group), divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino bond (—NR 41 ′ —
  • R 41 ′ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (—CO—), and combinations thereof.
  • the divalent aliphatic group may have a cyclic structure or a branched structure.
  • the aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
  • the aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group.
  • the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an aromatic group, and a heterocyclic group.
  • the carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.
  • the aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an aliphatic group, an aromatic group, and a heterocyclic group.
  • the divalent heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as the heterocyclic ring.
  • One or more heterocycles, aliphatic rings or aromatic rings may be condensed with the heterocycle.
  • the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 42 , where R 42 represents a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.
  • L 2 is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure.
  • the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
  • L 2 may include a polyoxyalkylene structure containing two or more oxyalkylene structures.
  • the polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure.
  • the polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
  • Z 2 is an acid group, preferably a carboxylic acid group.
  • R 24 , R 25 , and R 26 are each independently a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), an alkyl group having 1 to 6 carbon atoms (eg, methyl group, an ethyl group, a propyl group, etc.), - represents a Z 2, or L 2 -Z 2.
  • L 2 and Z 2 has the same meaning as L 2 and Z 2 in the above, and preferred examples are also the same.
  • R 24 , R 25 and R 26 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
  • R 21 , R 22 , and R 23 are each independently a hydrogen atom or a methyl group, and L 2 is an alkylene group or a divalent oxyalkylene structure.
  • a compound in which X 2 is an oxygen atom or an imino group and Z 2 is a carboxylic acid group is preferable.
  • R 21 is a hydrogen atom or a methyl group
  • L 2 is an alkylene group
  • Z 2 is a carboxylic acid group
  • Y is a methine group.
  • Compounds are preferred.
  • a compound in which R 24 , R 25 and R 26 are each independently a hydrogen atom or a methyl group and Z 2 is a carboxylic acid group is preferable.
  • the binder resin can be synthesized by the same method as the dispersant containing the structural unit containing the graft chain, and the preferred acid value and weight average molecular weight are also the same.
  • the binder resin may have one or more structural units containing an acid group.
  • the content of the structural unit containing an acid group is preferably 5 to 95% in terms of mass with respect to the total mass of the binder resin, and is preferably 10 to 90% from the viewpoint of suppressing damage to the image strength due to alkali development. preferable.
  • the curable composition preferably contains a surfactant.
  • Surfactant contributes to the applicability
  • the content of the surfactant is preferably 0.001 to 2.0% by mass with respect to the total solid content of the curable composition.
  • Surfactant may be used individually by 1 type, or may use 2 or more types together. When two or more surfactants are used in combination, the total amount is preferably within the above range.
  • surfactant examples include fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants.
  • the liquid properties (particularly fluidity) of the curable composition are further improved. That is, in the case of forming a film using a curable composition containing a fluorosurfactant, the wettability to the coated surface is improved by reducing the interfacial tension between the coated surface and the coating liquid. The applicability to the coated surface is improved. For this reason, even when a thin film of about several ⁇ m is formed with a small amount of liquid, it is effective in that a film having a uniform thickness with small thickness unevenness can be more suitably formed.
  • the fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 7 to 25% by mass.
  • a fluorosurfactant having a fluorine content within this range is effective in terms of uniformity in the thickness of the coating film and / or liquid-saving properties, and has good solubility in the curable composition. .
  • fluorosurfactant examples include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 (above DIC Corporation), Florad FC430, FC431, FC171 (Sumitomo 3M Limited), Surflon S-382, SC-101, SC- 103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, K-H-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (made by OMNOVA) etc. are mentioned.
  • a block polymer can also be used as the fluorosurfactant, and specific examples thereof include compounds described in JP-A-2011-89090.
  • the compound (F-1) represented by the following formula is also exemplified as the fluorosurfactant.
  • the structural units represented by formulas (A) and (B) are 62 mol% and 38 mol%, respectively.
  • the weight average molecular weight of the following compound is 15,311, for example.
  • nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1), Rusupasu 20000 (Lubrizol Japan Co., Ltd.), and the like.
  • Pionein D-6112-W manufactured by Takemoto Yushi Co., Ltd., NCW-101 Pionein D
  • cationic surfactant examples include phthalocyanine derivatives (trade name, EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (Yusho Co., Ltd.) and the like.
  • phthalocyanine derivatives trade name, EFKA-745, manufactured by Morishita Sangyo Co., Ltd.
  • organosiloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd.
  • (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 manufactured by Kyoeisha Chemical Co., Ltd.
  • W001 Yusho Co., Ltd.
  • anionic surfactants include W004, W005, W017 (Yusho Co., Ltd.) and the like.
  • silicone surfactant examples include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Tore Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd.
  • a silane coupling agent is a compound containing a hydrolyzable group and other functional groups in the molecule.
  • a hydrolyzable group such as an alkoxy group is bonded to a silicon atom.
  • the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond by a hydrolysis reaction and / or a condensation reaction.
  • Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group.
  • the hydrolyzable group contains a carbon atom, the number of carbon atoms is preferably 6 or less, and more preferably 4 or less.
  • the silane coupling agent contains fluorine atoms and silicon atoms (except for silicon atoms to which hydrolyzable groups are bonded) in order to improve the adhesion between the substrate and the cured film.
  • the silane coupling agent preferably contains a group represented by the following formula (Z). * Represents a bonding position.
  • R Z1 represents a hydrolyzable group, and the definition thereof is as described above.
  • the silane coupling agent preferably contains one or more curable functional groups selected from the group consisting of a (meth) acryloyloxy group, an epoxy group, and an oxetanyl group.
  • the curable functional group may be directly bonded to the silicon atom, or may be bonded to the silicon atom via a linking group.
  • a radically polymerizable group is also mentioned as a suitable aspect of the curable functional group contained in the said silane coupling agent.
  • the molecular weight of the silane coupling agent is not particularly limited, and is often 100 to 1,000 from the viewpoint of handleability, preferably 270 or more, and more preferably 270 to 1,000.
  • silane coupling agent X represented by the formula (W).
  • R z1 represents a hydrolyzable group, and the definition is as described above.
  • R z2 represents a curable functional group, the definition is as described above, and the preferred range is also as described above.
  • Lz represents a single bond or a divalent linking group.
  • Lz represents a divalent linking group
  • the divalent As the linking group an alkylene group optionally substituted with a halogen atom, an arylene group optionally halogen atoms substituted, -NR 12 -, - CONR 12 -, - CO -, - CO 2 -, SO 2 NR 12 -, - O -, - S -, - SO 2 -, or combinations thereof.
  • a group composed of a combination with one kind of group is preferable, an alkylene group which may be substituted by a halogen atom having 2 to 10 carbon atoms, —CO 2 —, —O—, —CO—, —CONR 12 —, or A group consisting of a combination of these groups is more preferred.
  • R 12 represents a hydrogen atom or a methyl group.
  • N- ⁇ -aminoethyl- ⁇ -aminopropyl-methyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-602)
  • N- ⁇ -aminoethyl- ⁇ -aminopropyl-tri Methoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-603)
  • N- ⁇ -aminoethyl- ⁇ -aminopropyl-triethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE-602)
  • ⁇ -aminopropyl- Trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-903)
  • ⁇ -aminopropyl-triethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd
  • a silane coupling agent Y having at least a silicon atom, a nitrogen atom, and a curable functional group in the molecule and containing a hydrolyzable group bonded to the silicon atom.
  • the silane coupling agent Y only needs to have at least one silicon atom in the molecule, and the silicon atom can be bonded to the following atoms and substituents. They may be the same atom, substituent or different.
  • the bondable atom or substituent is a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, an alkyl group and / or an amino group which can be substituted with an aryl group, Examples thereof include a silyl group, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group.
  • substituents further include silyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, aryloxy group, thioalkoxy group, alkyl group and / or aryl group, an amino group, a halogen atom, a sulfonamide group, It may be substituted with an alkoxycarbonyl group, an amide group, a urea group, an ammonium group, an alkylammonium group, a carboxylic acid group, or a salt thereof, a sulfo group, or a salt thereof.
  • at least one hydrolyzable group is bonded to the silicon atom.
  • the definition of the hydrolyzable group is as described above.
  • the silane coupling agent Y may contain a group represented by the formula (Z).
  • the silane coupling agent Y has at least one nitrogen atom in the molecule, and the nitrogen atom is preferably present in the form of a secondary amino group or a tertiary amino group, that is, the nitrogen atom is used as a substituent. It preferably contains at least one organic group.
  • the amino group structure may exist in the molecule in the form of a partial structure of a nitrogen-containing heterocycle, or may exist as a substituted amino group such as aniline.
  • examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof. These may further have a substituent.
  • substituents that can be introduced include a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an amino group, a halogen atom, and a sulfonamide.
  • the nitrogen atom is preferably bonded to the curable functional group via any organic linking group.
  • Preferred examples of the organic linking group include a substituent that can be introduced into the nitrogen atom and the organic group bonded thereto.
  • the definition of the curable functional group contained in the silane coupling agent Y is as described above, and the preferred range is also as described above.
  • the silane coupling agent Y only needs to have at least one curable functional group in one molecule, but it is also possible to contain two or more curable functional groups. From the viewpoint of sensitivity and stability, the curable functional group is preferably contained in the molecule in an amount of 2 to 20, more preferably 4 to 15, and even more preferably 6 to 10.
  • the molecular weights of the silane coupling agent X and the silane coupling agent Y are not particularly limited, but include the above ranges (preferably 270 or more).
  • the content of the silane coupling agent in the curable composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass with respect to the total solid content in the curable composition. More preferably, the content is 0.0 to 6% by mass.
  • the curable composition may contain one type of silane coupling agent or two or more types. When a curable composition contains 2 or more types of silane coupling agents, the sum should just be in the said range.
  • the curable composition may contain an ultraviolet absorber. Thereby, the shape of the pattern of a cured film can be made more excellent (fine).
  • an ultraviolet absorber salicylate, benzophenone, benzotriazole, substituted acrylonitrile, and triazine ultraviolet absorbers can be used.
  • compounds of paragraphs 0137 to 0142 corresponding to paragraphs 0251 to 0254 of US2012 / 0068292 of JP2012-068418A can be used, and the contents thereof can be incorporated and incorporated in the present specification. .
  • a diethylamino-phenylsulfonyl-based ultraviolet absorber (manufactured by Daito Chemical Co., Ltd., trade name: UV-503) is also preferably used.
  • the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP2012-32556A.
  • the content of the ultraviolet absorber is preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, and further preferably 0.1 to 5% by mass with respect to the total solid content of the curable composition. preferable.
  • the curable composition may contain a thermal polymerization initiator.
  • the 1-minute half-life temperature of the thermal polymerization initiator is preferably 120 to 300 ° C, more preferably 150 to 250 ° C, and still more preferably 150 to 230 ° C, from the viewpoint of stability and curability of the photosensitive resin composition. 170 to 200 ° C. is particularly preferable.
  • the half-life temperature for 1 minute of the thermal polymerization initiator is equal to or higher than the above lower limit, the film is not excessively cured when dried and the developability is good. If the 1-minute half-life temperature of a thermal-polymerization initiator is below the said lower limit, sclerosis
  • the molecular weight of the thermal polymerization initiator is preferably 100 or more, more preferably 150 or more, still more preferably 200 or more, and particularly preferably 250 or more.
  • the upper limit is preferably 1,000 or less, and more preferably 500 or less. If the molecular weight of the thermal polymerization initiator is not less than the above lower limit, volatilization of the thermal polymerization initiator during drying of the coating film can be effectively suppressed, and curability is good.
  • thermal polymerization initiator a compound that generates a radical by heat (hereinafter also simply referred to as a thermal radical generator) or a compound that generates an acid by heat (hereinafter also simply referred to as a thermal acid generator) is used. Can do.
  • a thermal radical generator is preferable. Since the thermal radical generator can promote radical polymerization of ethylenically unsaturated groups, when a compound containing a group having an ethylenically unsaturated bond is used as the crosslinking agent, the polymerization reaction of the crosslinking agent is more effective. And can be cured in a shorter time.
  • the reaction in which the polymerization reaction is initiated and accelerated by the thermal acid generator is epoxy ring-opening polymerization. Since ring-opening polymerization of epoxy has a slower polymerization rate than radical polymerization, curability may not be sufficiently promoted.
  • thermal radical generator As the thermal radical generator, a known thermal radical generator can be used.
  • the thermal radical generator is a compound that generates radicals by heat energy and initiates or accelerates the polymerization reaction of the crosslinking agent.
  • Thermal radical generators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon halogens Examples thereof include a compound having a bond and an azo compound. Of these, azo compounds are more preferable.
  • the manufacturing method of a curable composition contains the following mixing and dispersion
  • a mixing and dispersing process is a process of mixing the said component with a well-known mixing method (For example, a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, and a wet disperser), and obtaining a curable composition.
  • a well-known mixing method for example, a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, and a wet disperser
  • each component constituting the curable composition may be mixed at once, or may be sequentially added after each component is dissolved or dispersed in an organic solvent. There are no particular restrictions on the charging sequence and working conditions when blending.
  • the mixing and dispersing step may include a step of producing a dispersion.
  • the step of preparing the dispersion is a step of mixing the colorant, the dispersant, and the solvent, and dispersing the colorant by the above method to prepare the dispersion.
  • a curable composition can be manufactured by mixing other components with the prepared dispersion.
  • the mechanical force used for dispersing the pigment includes compression, squeezing, impact, shearing and cavitation. Specific examples of these processes include a bead mill, a sand mill, a roll mill, a high speed impeller, a sand grinder, a flow jet mixer, high pressure wet atomization, and ultrasonic dispersion.
  • the pigment may be refined by a salt milling step.
  • materials described in JP-A-2015-194521 and JP-A-2012-046629 can be used as materials, equipment and processing conditions used in the salt milling process.
  • the manufacturing method of a curable composition contains the process of obtaining the said coloring agent by a thermal plasma method.
  • the step of obtaining the colorant is performed before mixing the above-described components.
  • the aspect of the specific manufacturing process of the colorant by the thermal plasma method is as described above.
  • the colorant may be subjected to the following standing step before being subjected to the mixing and dispersing step or the step of producing a dispersion.
  • the standing step refers to a predetermined time (preferably 12 to 72 hours, more preferably, in a sealed container in which the colorant obtained by the thermal plasma method is not exposed to the atmosphere after its production and the oxygen concentration is controlled. 12 to 48 hours, more preferably 12 to 24 hours). At this time, it is more preferable that the moisture content in the sealed container is controlled.
  • the oxygen (O 2 ) concentration and the water content in the sealed container are each preferably 100 ppm or less, more preferably 10 ppm or less, and still more preferably 1 ppm or less.
  • the oxygen (O 2 ) concentration and moisture content in the sealed container can be adjusted by adjusting the oxygen concentration and moisture content in the inert gas supplied into the sealed container.
  • the inert gas nitrogen gas and argon gas are preferably used, and among these, it is more preferable to use nitrogen gas.
  • the surface of the colorant and the crystal grain boundary become stable. Thereby, generation
  • a filtration process is a process of filtering the curable composition manufactured by the said mixing and dispersion
  • a filter In the filtration step, foreign substances can be removed from the curable composition and / or defects can be reduced.
  • Any filter can be used without particular limitation as long as it has been conventionally used for filtration.
  • a filter made of a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon, a polyolefin resin such as polyethylene or polypropylene (PP) (containing high density and ultra high molecular weight), and the like.
  • PTFE polytetrafluoroethylene
  • nylon polyamide resin
  • PP polyolefin resin
  • polyethylene or polypropylene (PP) containing high density and ultra high molecular weight
  • polypropylene containing high density and ultra high molecular weight
  • the pore size of the filter is suitably about 0.1 to 7.0 ⁇ m, preferably about 0.2 to 2.5 ⁇ m, more preferably about 0.2 to 1.5 ⁇ m, and about 0.3 to 0.7 ⁇ m. Further preferred. By setting this range, it is possible to reliably remove fine foreign matters such as impurities and aggregates contained in the pigment while suppressing filtration clogging of the pigment.
  • different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more. When filtering two or more times by combining different filters, it is preferable that the second and subsequent pore diameters are the same or larger than the pore diameter of the first filtering. You may combine the 1st filter of a different hole diameter within said range.
  • the pore diameter here can refer to the nominal value of the filter manufacturer.
  • a commercially available filter for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (former Nihon Microlith Co., Ltd.), or Kitz Micro Filter Co., Ltd. .
  • the second filter a filter formed of the same material as the first filter can be used.
  • the pore size of the second filter is suitably about 0.2 to 10.0 ⁇ m, preferably about 0.2 to 7.0 ⁇ m, more preferably about 0.3 to 6.0 ⁇ m.
  • the cured film is obtained by curing the curable composition.
  • the cured film contains a colorant.
  • the cured film is preferably used as a light-shielding film, and specifically used for light-shielding the periphery of the light receiving portion of the image sensor.
  • a case where the cured film is used as a light shielding film around the light receiving portion of the image sensor will be described as an example.
  • the film thickness of the light-shielding film is not particularly limited, but the film thickness after drying is preferably 0.2 ⁇ m or more and 50 ⁇ m or less, and preferably 0.3 ⁇ m or more and 10 ⁇ m or less, in that the light-shielding film has more excellent effects of the present invention. Is more preferably 0.3 ⁇ m or more and 5 ⁇ m or less. Since the curable composition has a high optical density per unit volume (because of its high light-shielding property), the film thickness can be reduced as compared with a curable composition using a conventional black pigment.
  • the size of the light-shielding film (the length of one side of the light-shielding film provided around the sensor light-receiving portion) is preferably 0.001 mm or more and 10 mm or less in that the light-shielding film has more excellent effects of the present invention.
  • 05 mm or more and 7 mm or less are more preferable, and 0.1 mm or more and 3.5 mm or less are still more preferable.
  • the manufacturing method of a cured film contains the following curable composition layer formation process and an exposure process.
  • the method for producing a cured film preferably further includes a development step.
  • Curable composition layer forming step A step of forming a curable composition layer on a support.
  • Exposure process The process of exposing the said curable composition layer.
  • Development step a step of developing the curable composition layer after exposure to form a patterned cured film (light-shielding film).
  • the curable composition is applied to the substrate directly or via another layer to form a curable composition layer (curable composition layer forming step), and a predetermined mask pattern is formed.
  • the cured film can be produced by curing only the coating film portion exposed to light through light (exposure process) and developing with a developer (development process). Hereafter, each said process is demonstrated.
  • the curable composition layer forming step is a step of forming a curable composition layer on a support (hereinafter also referred to as “substrate”). Among them, it is preferable to include a coating step in which a curable composition is applied on a support to form a curable composition layer, and the curable composition is directly applied on the support to form a curable composition layer on the support. It is more preferable to include a coating step of forming a curable composition layer.
  • the substrate examples include alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display devices and the like, and those obtained by attaching a transparent conductive film to these, photoelectric devices used for solid-state imaging devices, and the like.
  • Examples include a conversion element substrate (for example, a silicon substrate), a CCD (Charge Coupled Device) substrate, and a CMOS (Complementary Metal-Oxide Semiconductor) substrate.
  • the support may be provided with an undercoat layer for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the substrate surface (hereinafter also referred to as “support with undercoat layer”).
  • various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing method can be applied.
  • the coating film thickness of the curable composition is preferably 0.35 ⁇ m or more and 1.5 ⁇ m or less from the viewpoint of resolution. More preferably, it is 40 ⁇ m or more and 1.0 ⁇ m or less.
  • the curable composition applied on the substrate is usually dried at 70 ° C. to 110 ° C. for 2 minutes to 4 minutes. Thereby, a curable composition layer can be formed.
  • the exposure step is a step in which the curable composition layer (coating film) formed in the curable composition layer forming step is exposed through a mask and only the coating film portion irradiated with light is cured.
  • the exposure is preferably performed by irradiation with actinic rays or radiation, in particular, ultraviolet rays such as g-line, h-line, and i-line are preferable, and a high-pressure mercury lamp is more preferable.
  • the amount of exposure is not particularly limited, but can be appropriately selected depending on the type of pigment used and / or the mask pattern shape.
  • the lower limit of the amount of exposure is preferably 50 mJ / cm 2 or more, 80 mJ / cm 2 or more is more preferable.
  • Upper limit of the amount of exposure is preferably 1,500 mJ / cm 2 or less, less than 500 mJ / cm 2 is more preferable.
  • the exposure amount is 80 mJ / cm 2 or more and less than 500 mJ / cm 2 , the method for producing a cured film (light-shielding film) has more excellent stability and productivity.
  • the lower limit of the amount of exposure is preferably 50 mJ / cm 2 or more, 80 mJ / cm 2 or more is more preferable.
  • Upper limit of the amount of exposure is preferably 1,500 mJ / cm 2 or less, more preferably less than 500 mJ / cm 2, still more preferably less than 400 mJ / cm 2, less than 300 mJ / cm 2 is particularly preferred.
  • the exposure dose is 80 to less than 300 mJ / cm 2 , the method for producing a cured film has more excellent stability and productivity. From the viewpoint of improving resolution, exposure with an i-line stepper is preferable in forming a light-shielding film for a solid-state imaging device.
  • a development process is a process of developing the exposed curable composition layer.
  • a patterned cured film can be obtained by the development step. It is preferable that the manufacturing method of the said cured film contains a image development process and the following washing
  • an alkali development treatment (development process) is performed, and the light non-irradiated part in the exposure process is eluted in an alkaline aqueous solution. Thereby, only the photocured part (the coating film part irradiated with light) remains.
  • the developer when producing a light-shielding color filter containing a black matrix for a solid-state image sensor, an organic alkali developer that does not damage the underlying circuit or the like is preferable.
  • the development temperature is usually preferably 20 to 30 ° C., and the development time is preferably 20 to 90 seconds.
  • Examples of the alkaline aqueous solution include an inorganic developer and an organic developer.
  • As the inorganic developer sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, or sodium metasuccinate having a concentration of 0.001 to 10% by mass, preferably 0.01 to 1 is used.
  • An alkaline aqueous solution dissolved so as to be in mass% can be mentioned.
  • organic developers include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, or 1,8-diazabicyclo- [5.4.0]- Examples thereof include an alkaline aqueous solution in which an alkaline compound such as 7-undecene is dissolved so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An appropriate amount of a water-soluble organic solvent such as methanol and ethanol and / or a surfactant can be added to the alkaline aqueous solution.
  • a developing method for example, a paddle developing method and a shower developing method can be used.
  • the washing step is a step of washing (rinsing) the developed curable composition layer with pure water or the like.
  • the cleaning method is not particularly limited, and a known cleaning method can be used.
  • the manufacturing method of the said cured film may contain the post-baking process which heats a cured film, and / or the hardening process which exposes a cured film whole surface after the said image development process.
  • a color filter containing a cured film is suitable for a solid-state imaging device such as a CCD image sensor and / or a CMOS image sensor. Particularly, it is suitable for a CCD image sensor and / or a CMOS image sensor having a high resolution exceeding 1 million pixels. That is, the color filter containing the cured film is suitable for a solid-state imaging device.
  • the color filter may contain a structure in which a cured film that forms each color pixel is embedded in a space partitioned by a partition, for example, in a lattice shape.
  • the cured film (black matrix) is disposed, for example, between a light receiving portion of each pixel constituting a CCD image sensor and / or a CMOS image sensor and a microlens for condensing light.
  • the solid-state imaging device contains the cured film (black matrix).
  • the solid-state imaging device preferably contains a color filter containing a black matrix and, if necessary, a patterned film composed of pixels of other colors (three colors or four colors).
  • the solid-state imaging device is not particularly limited as long as it contains the above-described black matrix and functions as a solid-state imaging device. Examples include a solid-state imaging device that includes a plurality of photodiodes, a light-receiving element made of polysilicon, and the like, and that includes the black matrix on the surface opposite to the light-receiving element formation surface of the substrate.
  • the color filter may have a structure in which a cured film that forms each color pixel is embedded in a space partitioned by a partition, for example, in a lattice shape.
  • the partition in this case preferably has a low refractive index for each color pixel.
  • the solid-state imaging device containing such a structure include the solid-state imaging devices described in JP2012-227478A and JP2014-179577A.
  • the cured film can be suitably used for an image display device (for example, a liquid crystal display device and an organic electroluminescence display device).
  • an image display device for example, a liquid crystal display device and an organic electroluminescence display device.
  • image display devices For the definition of image display devices and details of each image display device, refer to, for example, “Electronic Display Device (Akio Sasaki, Kogyo Kenkyukai, 1990)” and “Display Device (Junsho Ibuki, Industrial Books ( (Issued in 1989)).
  • the liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 1994)”.
  • the cured film is suitable for, for example, a liquid crystal display device of the method described in the “next generation liquid crystal display technology”.
  • the liquid crystal display device containing the cured film for example, a color filter, a liquid crystal layer, and a liquid crystal driving means (simple matrix driving method and active matrix driving) are provided between a pair of substrates at least one of which is light transmissive And a liquid crystal display device containing at least a method.
  • the liquid crystal display device includes a plurality of pixel groups, and each pixel constituting the pixel group includes a color filter separated from each other by the cured film (black matrix).
  • At least one of the light transmissive substrates contains at least a color filter, a liquid crystal layer, and liquid crystal driving means
  • the liquid crystal driving means is an active element (for example, TFT (Thin Film Transistor)) and a color filter containing the cured film (black matrix) between the active elements.
  • the color filter containing the cured film is suitable for a liquid crystal display device of a color TFT (Thin Film Transistor) type.
  • the color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”.
  • the color filter is a liquid crystal display device with a wide viewing angle, such as a lateral electric field driving method such as IPS (In Plane Switching); a pixel division method such as MVA (Multi-domain Vertical Alignment); and STN (Super-Twist).
  • the color filter is suitable for a bright, high-definition COA (Color-filter On Array) type liquid crystal display device.
  • COA Color-filter On Array
  • the required characteristics for the color filter may require the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the resistance to the peeling solution, in addition to the normal required characteristics.
  • the COA type liquid crystal display device containing the color filter has better resolution or better durability.
  • a resin film may be further included on the color filter layer.
  • the liquid crystal display device includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film.
  • the color filter can be applied to a liquid crystal display device composed of these known members.
  • these materials for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima, CMC 1994)” and “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” "Fuji Chimera Research Institute, Ltd., published in 2003)”.
  • backlights SID meeting Digest 1380 (2005) (A. Konno et.al) and / or Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi) It is described in.
  • the cured film is composed of portable devices such as personal computers, tablets, mobile phones, smartphones, and digital cameras; OA (Office Automation) devices such as printer multifunction devices and scanners; surveillance cameras, bar code readers, and automatic teller machines ( ATM (automated teller machine), industrial equipment such as personal authentication using high-speed camera and face image authentication; in-vehicle camera equipment; medical camera equipment such as endoscope, capsule endoscope and catheter; biosensor, Optical filters used in space devices such as biosensors, military reconnaissance cameras, stereoscopic map cameras, weather and ocean observation cameras, land resource exploration cameras, and exploration cameras for space astronomy and deep space targets Module shading member and shading And further is suitable for anti-reflection member and the antireflection layer.
  • OA Office Automation
  • ATM automatic teller machine
  • industrial equipment such as personal authentication using high-speed camera and face image authentication
  • in-vehicle camera equipment medical camera equipment such as endoscope, capsule endoscope and catheter
  • biosensor Optical filters used in space devices such as biosensors, military
  • the cured film can also be used for applications such as micro LED (Light Emitting Diode) and micro OLED (Organic Light Emitting Diode).
  • the cured film is suitable for members that provide a light shielding function or an antireflection function, in addition to optical filters and optical films used in micro LEDs and micro OLEDs.
  • Examples of the micro LED and the micro OLED include those described in JP-T-2015-500562 and JP-T-2014-533890.
  • the cured film is suitable as an optical and optical film used in quantum dot displays. Moreover, the said cured film is suitable as a member which provides a light-shielding function and an antireflection function.
  • quantum dot displays include US Patent Application Publication No. 2013/0335677, US Patent Application Publication No. 2014/0036536, US Patent Application Publication No. 2014/0036203, and US Patent Application Publication No. 2014/0035960. What has been described.
  • reaction liquid tetrahydrofuran
  • T-1 and T-2 represent the following polyfunctional thiol compounds (polyfunctional thiol compounds having no interactive group).
  • the dye solution 1 was prepared by mixing the following components.
  • Organic solvent cyclohexanone
  • Dye A-1 having the following structure
  • Pigment dispersion P1 was prepared by the following procedure.
  • C. I. Pigment Blue 15: 6 (blue pigment, hereinafter also referred to as “PB15: 6”) 19.4 parts by mass (average primary particle size 55 nm), pigment dispersant DISPERBYK-161 (solid content concentration 30% by mass, manufactured by BYK) 2.95 parts by mass, alkali-soluble resin 1 (benzyl methacrylate / methacrylic acid (47/53 [mass ratio]), 30% by mass propylene glycol monomethyl ether solution, Mw 11,000) 2.95 in terms of solid content
  • a mixed solution consisting of parts by mass (9.93 parts by mass of solution) and 165.3 parts by mass of propylene glycol monomethyl ether was mixed and dispersed for 3 hours by a beads mill (zirconia beads 0.3 mm diameter).
  • the dispersion treatment was further performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism.
  • This dispersion treatment was repeated 10 times to obtain C.I. I. Pigment Blue 15: 6 dispersion was obtained.
  • the average primary particle size of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)) and found to be 24 nm.
  • a curable composition was prepared in the same manner as in Example 1 except that the polyfunctional thiol compound was not added.
  • the curable compositions of each Example and Comparative Example were spin-coated on a glass substrate, and then dried to form a 1.0 ⁇ m-thick coating film (curable composition layer) on the glass substrate. Formed.
  • the spin coating conditions were 300 rpm for 5 seconds, 800 rpm for 20 seconds, and the drying conditions were 100 ° C. for 80 seconds.
  • the obtained coating film (curable composition layer) is a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultrahigh pressure mercury lamp using a test photomask having a line width of 2.0 ⁇ m.
  • the exposure sensitivity was evaluated based on the minimum exposure amount at which the pattern line width after development of the region irradiated with light in the exposure process was 1 ⁇ m or more. The smaller the exposure sensitivity value, the better the exposure sensitivity of the curable composition.
  • the exposure sensitivity is preferably less than 300 mJ / cm 2 practically under the above test conditions. The results are summarized in Table 2.
  • the curable compositions of Examples 1 to 23 (the curable composition containing a coloring colorant) containing the predetermined polyfunctional thiol compound have excellent exposure sensitivity, and It had excellent adhesion to the support.
  • the curable composition of Comparative Example 1 that does not contain a polyfunctional thiol compound, the above effect was not obtained.
  • the polyfunctional thiol compound of Comparative Example 2 and Comparative Example 3 containing a polyfunctional thiol compound having no interactive group the above effect was not obtained.
  • the curable composition of Examples 2, 10, 18, and 21 in which m of the polyfunctional thiol compound represented by the formula (2) is 3 or more is superior to the curable composition of Example 1. Exposure sensitivity.
  • the curable composition of Example 10 has better adhesion to the support compared to the curable composition of Example 18 where m + n is equal and m / n is greater.
  • An interactive group different from the thiol group is a carboxylic acid group or a salt thereof, a hydroxyl group, an amino group, a pyridinyl group, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, or —Si (R X ) p (R Y ) 3-p
  • the curable compositions of Examples 2 to 6, 8 and 9 are compared with Example 7 in which the interactive group is a phenyl group, the resulting cured film is applied to the support. It had better adhesion.
  • Example 55 In the preparation of the curable composition of Example 1, the content of the polyfunctional thiol compound was changed from 0.35 parts by mass to 0.17 parts by mass (Example 55) and 0.70 parts by mass (Example 56). As a result, the same results as in Example 1 were obtained.
  • Example 57 and 58 In the preparation of the curable composition of Example 1, the content of the polymerizable compound was changed from 1.96 parts by mass to 1.5 parts by mass (Example 57) and 3.0 parts by mass (Example 58). As a result, the same results as in Example 1 were obtained.
  • Ti nanoparticles (TC-200, manufactured by Toho Tech Co., Ltd.) were formed into Ti nanoparticles by plasma treatment in Ar gas. The Ti nanoparticles after the plasma treatment were allowed to stand for 24 hours under conditions of an O 2 concentration of 50 ppm or less and 30 ° C. in an Ar gas atmosphere. Then, it was allowed to stand at 30 ° C. for 24 hours in a state where O 2 gas was introduced into the Ar atmosphere so that the O 2 concentration was 100 ppm (pretreatment of Ti particles).
  • the obtained Ti nanoparticles were classified using a TTSP separator manufactured by Hosokawa Micron under the condition of a yield of 10% to obtain a powder of Ti particles.
  • the primary particle size of the obtained powder was 120 nm when the average particle size of 100 particles was determined by arithmetic average by TEM observation.
  • the titanium nitride-containing particles TiN-1 were produced using an apparatus according to the black composite fine particle production apparatus described in FIG. 1 of International Publication No. 2010/147098.
  • a high frequency voltage of about 4 MHz and about 80 kVA is applied to a high frequency oscillation coil of a plasma torch, and argon gas 50 L / min and nitrogen 50 L / min are used as plasma gases from a plasma gas supply source.
  • a mixed gas of min was supplied to generate an argon-nitrogen thermal plasma flame in the plasma torch.
  • a carrier gas of 10 L / min was supplied from the spray gas supply source of the material supply apparatus.
  • This mixture was supplied together with argon gas as a carrier gas into a thermal plasma flame in a plasma torch, evaporated in the thermal plasma flame, and highly dispersed in a gas phase state. Further, nitrogen was used as a gas supplied into the chamber by the gas supply device.
  • the flow rate in the chamber at this time was 5 m / sec, and the supply amount was 1,000 L / min.
  • the pressure in the cyclone was 50 kPa, and the supply rate of each raw material from the chamber to the cyclone was 10 m / s (average value). In this way, titanium nitride-containing particles TiN-1 were obtained.
  • the obtained titanium nitride-containing particles TiN-1 were measured for the content of titanium (Ti) atoms, iron (Fe) atoms, and silicon (Si) atoms by ICP emission spectroscopy.
  • ICP emission spectroscopic analysis an ICP emission spectroscopic analyzer “SPS3000” (trade name) manufactured by Seiko Instruments Inc. was used.
  • the nitrogen atom content was measured using an oxygen / nitrogen analyzer “EMGA-620W / C” (trade name) manufactured by Horiba, Ltd., and was calculated by an inert gas melting-thermal conductivity method.
  • X-ray diffraction of titanium nitride-containing particles TiN-1 was measured by a wide-angle X-ray diffraction method (trade name “RU-200R” manufactured by Rigaku Corporation) with a powder sample placed in an aluminum standard sample holder.
  • the X-ray source is CuK ⁇ ray
  • the output is 50 kV / 200 mA
  • the slit system is 1 ° -1 ° -0.15 mm-0.45 mm
  • the measurement step (2 ⁇ ) is 0.02 °
  • the scan speed is It was 2 ° / min.
  • the diffraction angle of the peak derived from the TiN (200) plane observed in the vicinity of the diffraction angle 2 ⁇ (42.6 °) was measured.
  • the crystallite size constituting the particle was determined using Scherrer's equation. As a result, the peak diffraction angle was 42.62 ° and the crystallite size was 10 nm. Note that no X-ray diffraction peak due to TiO 2 was observed.
  • TiN-2 titanium nitride-containing particles TiN-2
  • Ti-particles titanium nitride-containing particles TiN-2
  • the peak diffraction angle measured by X-ray diffraction was 42.81 °, and the crystallite size was 12 nm.
  • the peak diffraction angle measured by X-ray diffraction was 43.1 °, and the crystallite size was 12 nm.
  • titanium black A-1 100 g of titanium oxide MT-150A (trade name, manufactured by Teika Co., Ltd.) having an average particle diameter of 15 nm and silica particles AEROSIL300 (registered trademark) 300/30 (Evonik) having a BET (Brunauer, Emmett, Teller) specific surface area of 300 m 2 / g 25 g) and Disperbyk190 (trade name, manufactured by Big Chemie) were weighed 100 g, and these were added to 71 g of ion electroexchanged water to obtain a mixture.
  • the mixture was treated at a revolution speed of 1,360 rpm and a rotation speed of 1,047 rpm for 30 minutes using a MURASTAR KK-400W manufactured by KURABO to obtain a uniform aqueous mixture solution.
  • This aqueous mixture was filled in a quartz container and heated to 920 ° C. in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Co., Ltd.). Thereafter, the inside of the small rotary kiln was replaced with nitrogen, and nitriding reduction treatment was performed by flowing ammonia gas at 100 mL / min for 5 hours at the same temperature.
  • the recovered powder was pulverized in a mortar to obtain a powdery titanium black (dispersed material containing titanium black particles and Si atoms) having a powder specific surface area of 73 m 2 / g (hereinafter referred to as “titanium”). Black A-1 ”).
  • Niobium nitride-containing particles containing Fe atoms were produced by the following method. First, niobium (powder) ⁇ 100-325 mesh> manufactured by Mitsuwa Chemicals was prepared as a raw material (hereinafter also referred to as “metal raw material powder”). Next, the metal raw material powder was subjected to plasma treatment in Ar gas to form Nb nanoparticles. The conditions for the plasma treatment were the following plasma treatment (1).
  • Plasma treatment (1) was performed by the following method. Plasma treatment (1) was performed under the following conditions using an apparatus according to the above black composite fine particle production apparatus. ⁇ High frequency voltage applied to the coil for high frequency oscillation: frequency about 4 MHz, voltage about 80 kVA ⁇ Plasma gas: Argon gas (Supply rate: 100 L / min) Carrier gas: Argon gas (Supply amount: 10 L / min) ⁇ Atmosphere in chamber: Argon gas (amount supplied: 1,000 l / min, flow velocity in chamber: 5 m / sec) ⁇ Cyclone atmosphere: Argon gas, internal pressure 50kPa ⁇ Material supply speed from chamber to cyclone: 10 m / s (average value)
  • Fe powder JIP270M, manufactured by JFE Steel Co., Ltd.
  • JFE Steel Co., Ltd. was prepared and subjected to plasma treatment under the conditions of plasma treatment (1) to form Fe nanoparticles.
  • Nb nanoparticles and Fe nanoparticles obtained as described above were mixed to obtain a raw metal powder.
  • This raw metal powder was subjected to plasma treatment in nitrogen gas to obtain niobium nitride-containing particles.
  • the conditions for the plasma treatment were the following plasma treatment (2).
  • Plasma treatment (2) was performed by the following method.
  • the apparatus used was the same as in the plasma treatment (1).
  • Plasma gas Argon gas and nitrogen gas (Supply amount 50L / min each)
  • Carrier gas Nitrogen gas (Supply amount: 10L / min)
  • Atmosphere in the chamber Nitrogen gas (amount supplied: 1,000 L / min, flow velocity in the chamber: 5 m / sec)
  • Cyclone atmosphere Nitrogen gas, internal pressure 50kPa ⁇ Material supply speed from chamber to cyclone: 10 m / s (average value)
  • niobium nitride-containing particles NbN
  • Nitrogen gas was supplied to the separator.
  • the obtained niobium nitride-containing particles were measured for the content of iron (Fe) atoms by ICP emission spectroscopy, and found to be 50 ppm by mass.
  • VN vanadium nitride-containing particles containing Fe atoms
  • Fe atoms were used in the same manner except that the metal vanadium powder VHO manufactured by Taiyo Mining Co. was used instead of Niobium (powder) ⁇ 100-325 mesh> manufactured by Mitsuwa Chemicals.
  • Dispersant A having the following structure was used as the dispersant.
  • the numerical value described in each structural unit intends the mass% of each structural unit with respect to all the structural units.
  • Binder resin As the binder resin, the following resin A was used. The numerical value described in each structural unit intends mol% of each structural unit with respect to the total structural unit. In the formula of resin A, each abbreviation represents the following. BzMA: benzyl methacrylate MMA: methyl methacrylate
  • Polymerizable compound M1 dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name “KAYARAD”, see the following formula)
  • Polymerizable compound M2 PET-30 (pentaerythritol triacrylate, manufactured by Nippon Kayaku Co., Ltd.)
  • OXE-01 Irgacure OXE01 (trade name, manufactured by BASF Japan Ltd., applicable to oxime compounds)
  • OXE-02 Irgacure OXE02 (trade name, manufactured by BASF Japan Ltd., corresponding to oxime compound)
  • PI-3 a photopolymerization initiator having the following structure (corresponding to an oxime compound)
  • NCI-831 (trade name, manufactured by ADEKA, applicable to oxime compounds)
  • IRGACURE 379EG (trade name, manufactured by BASF Japan, not applicable to oxime compounds)
  • the exposed coating film was subjected to paddle development for 30 seconds using a coater developer ACT8 manufactured by Tokyo Electron, using tetramethylammonium hydroxide as a developer. After the development, a shower rinsing process was performed with pure water for 20 seconds. The minimum exposure amount that was maintained without peeling off the pattern after development was evaluated as exposure sensitivity.
  • the exposure sensitivity is preferably less than 500 mJ / cm 2 practically under the above test conditions. The results are summarized in Table 4.
  • the patterned cured film produced in the evaluation of the exposure sensitivity was post-baked (temperature: 220 ° C., time: 300 seconds).
  • the pattern shape of the cured film after post-baking was measured by a length measuring SEM (Scanning Electron Microscope). Specifically, the film thickness at the end of the line pattern and the film thickness at the center were measured, and the ratio (film thickness at the pattern end / film thickness at the center) was calculated and evaluated according to the following criteria. In addition, evaluation "2" or more is a practical range. -7: The ratio is more than 0.98 and less than 1.00, and no difference is observed in the film thickness between the central part and the end part of the pattern by observation with SEM.
  • the ratio is more than 0.96 and not more than 0.98, and there is a slight difference in the film thickness between the central portion and the end portion of the pattern.
  • 5 The ratio is more than 0.94 and not more than 0.96, and there is a difference in film thickness between the pattern center and the edge.
  • -4 The ratio is more than 0.92 and less than 0.94, the film thickness at the end is thin, and it is slightly distorted, but there is no practical problem.
  • -3 The ratio is more than 0.90 and not more than 0.92, and the film thickness at the end is thin and distorted, but there is no practical problem.
  • -2 The ratio is more than 0.80 and 0.90 or less, and the film thickness at the end is thin, but the practical level is possible.
  • -1 The ratio is 0.80 or less, the film thickness at the end is thin, and is not acceptable.
  • the curable compositions of Examples 24 to 54 and 59 containing a predetermined polyfunctional thiol compound have excellent exposure sensitivity. And had excellent adhesion to the support.
  • the curable composition of Comparative Example 4 that did not contain a polyfunctional thiol compound did not have the above effect.
  • the polyfunctional thiol compounds of Comparative Example 5 and Comparative Example 6 containing a polyfunctional thiol compound having no interactive group did not have the above effects.
  • the curable compositions of Examples 25 to 54 and 59 in which m of the polyfunctional thiol compound represented by the formula (2) is 3 or more are more in comparison with the curable composition of Example 24. It had excellent exposure sensitivity.
  • the curable composition in which the interactive group different from the thiol group is a carboxylic acid group (Example 25), a phosphoric acid group (Example 28), or a sulfonic acid group (Example 29) is a thiol group.
  • the up arrow means the same as the column immediately above, and “-” means that the curable composition does not contain the component.
  • a curable composition was prepared and evaluated in the same manner as in Example 33 except that the polymerizable compound M2 was used in place of the polymerizable compound M1, and the same results as in Example 33 were obtained. .
  • the content of the above mixture was the same as the content of the polymerizable compound M1 in Example 33.)
  • a curable composition was prepared and evaluated in the same manner as in Example 33 except that it was used. The same results as in Example 33 were obtained.
  • CB dispersion Preparation of carbon black dispersion (CB dispersion) and evaluation of curable composition
  • the colorant is carbon black (trade name “Color Black S170”, manufactured by Degussa, average primary particle size 17 nm, BET specific surface area 200 m 2 / g, carbon produced by a gas black method.
  • a carbon black dispersion (CB dispersion) was obtained in the same manner except that it was black.
  • chromatic pigment dispersion (PY dispersion) and evaluation of curable composition]
  • PY dispersion A chromatic pigment dispersion was prepared in the same manner as in the preparation of the colorant dispersion, except that Pigment Yellow 150 (trade name: 6150 Pigment Yellow 5GN, manufactured by Hangzhou Star-up Pigment Co., Ltd.) was used as the colorant. (PY dispersion) was obtained.
  • chromatic pigment dispersion (PR dispersion)
  • the colorant is C.I. I.
  • a chromatic pigment dispersion (PR dispersion) was obtained in the same manner except that Pigment Red 254 (manufactured by Ciba Specialty Chemicals) was used.
  • PB dispersion Preparation of chromatic pigment dispersion (PB dispersion)
  • the colorant is C.I. I.
  • a chromatic pigment dispersion (PB dispersion) was obtained in the same manner except that Pigment Blue 15: 6 (manufactured by DIC Corporation) was used.
  • chromatic pigment dispersion (PV dispersion)
  • the colorant is C.I. I.
  • a chromatic pigment dispersion (PV dispersion) was obtained in the same manner except that Pigment Violet 23 (manufactured by Clariant) was used.
  • Example 33 In the preparation of the curable composition of Example 33, instead of the colorant dispersion added so as to contain 58% by mass of titanium nitride-containing particles TiN-1 in the curable composition, the above-mentioned titanium nitride-containing solution was used.
  • the same evaluation including exposure sensitivity and adhesion
  • the above-mentioned titanium nitride-containing solution was used.
  • a curable composition was prepared and evaluated using this. As a result of the evaluation, it was found that the same evaluation (including exposure sensitivity and adhesion) as in Example 33 was obtained, and a film having excellent light shielding properties in the infrared region was obtained.
  • Example 1 Evaluation was conducted in the same manner as in Example 1 except that the surfactant F-1 was not used. As a result of the evaluation, it was found that the same result as in Example 1 was obtained.

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Abstract

Provided are: a curable composition which has excellent light exposure sensitivity and enables the achievement of a cured film that exhibits excellent adhesion to a supporting body; a cured film; a color filter; a light-blocking film; a solid-state imaging element; an image display device; a method for producing a cured film; and a polyfunctional thiol compound. This curable composition contains a polyfunctional thiol compound, a polymerizable compound and a photopolymerization initiator; and the polyfunctional thiol compound comprises two or more thiol groups and an interactive group that is different from the thiol groups.

Description

硬化性組成物、硬化膜、カラーフィルタ、遮光膜、固体撮像素子、画像表示装置、硬化膜の製造方法、及び、多官能チオール化合物Curable composition, cured film, color filter, light shielding film, solid-state imaging device, image display device, method for producing cured film, and polyfunctional thiol compound
　本発明は、硬化性組成物、硬化膜、カラーフィルタ、遮光膜、固体撮像素子、画像表示装置、硬化膜の製造方法、及び、多官能チオール化合物に関する。 The present invention relates to a curable composition, a cured film, a color filter, a light shielding film, a solid-state imaging device, an image display device, a method for producing a cured film, and a polyfunctional thiol compound.
　画像表示装置に用いられるカラーフィルタには着色画素間の光を遮蔽し、コントラストを向上させる等の目的で、ブラックマトリクスと呼ばれる遮光膜が備えられている。
　また、固体撮像素子においてもノイズ発生防止、及び、画質の向上等を目的として遮光膜が設けられている。現在、携帯電話及びＰＤＡ（Ｐｅｒｓｏｎａｌ　Ｄｉｇｉｔａｌ　Ａｓｓｉｓｔａｎｔ）等の電子機器の携帯端末には、小型で薄型な撮像ユニットが搭載されている。このような撮像ユニットは、一般に、ＣＣＤ（Ｃｈａｒｇｅ　Ｃｏｕｐｌｅｄ　Ｄｅｖｉｃｅ）イメージセンサ及びＣＭＯＳ（Ｃｏｍｐｌｅｍｅｎｔａｒｙ　Ｍｅｔａｌ－Ｏｘｉｄｅ　Ｓｅｍｉｃｏｎｄｕｃｔｏｒ）イメージセンサ等の固体撮像素子と、固体撮像素子上に被写体像を形成するためのレンズと、を備えている。 A color filter used in an image display device is provided with a light shielding film called a black matrix for the purpose of shielding light between colored pixels and improving contrast.
In the solid-state image sensor, a light shielding film is provided for the purpose of preventing noise and improving image quality. Currently, portable terminals of electronic devices such as mobile phones and PDAs (Personal Digital Assistants) are equipped with small and thin imaging units. Such an imaging unit generally includes a solid-state imaging device such as a CCD (Charge Coupled Device) image sensor and a CMOS (Complementary Metal-Oxide Semiconductor) image sensor, a lens for forming a subject image on the solid-state imaging device, It has.
　特許文献１には、「画像表示装置における、画素を分離する隔壁を形成するための感光性樹脂組成物であって、感光性樹脂組成物が、（Ａ）成分として分子内にカルボキシル基を有するバインダーポリマーと、（Ｂ）成分として光重合性化合物と、（Ｃ）成分として光重合開始剤と、（Ｄ）成分としてメルカプト基を有する化合物と、（Ｅ）成分として黒色顔料とを含有する感光性樹脂組成物。」が記載されている。 Patent Document 1 discloses that “a photosensitive resin composition for forming a partition for separating pixels in an image display device, wherein the photosensitive resin composition has a carboxyl group in the molecule as the component (A). Photosensitizer containing a binder polymer, a photopolymerizable compound as component (B), a photopolymerization initiator as component (C), a compound having a mercapto group as component (D), and a black pigment as component (E) Resin composition ".
特開２０１４－４１１８８号公報JP 2014-41188 A
　本発明者は、特許文献１に記載された感光性樹脂組成物を支持体上に塗布し、得られた感光性樹脂組成物層を露光して硬化膜を作製したところ、露光感度にさらなる改善の余地があることを知見した。具体的には、特許文献１に記載された感光性樹脂組成物は、より微細なパターン形状を得ようとすると、露光に必要なエネルギーが大きくなるという問題があることを知見した。
　また、本発明者は、上記の方法により得られた硬化膜について検討したところ、支持体（以下「基板」ともいう。）との密着性にさらなる改善の余地があることもまた知見した。 The present inventor applied the photosensitive resin composition described in Patent Document 1 onto a support and exposed the obtained photosensitive resin composition layer to produce a cured film. As a result, the exposure sensitivity was further improved. I found out that there is room for it. Specifically, it has been found that the photosensitive resin composition described in Patent Document 1 has a problem that the energy required for exposure increases when trying to obtain a finer pattern shape.
Moreover, when this inventor examined the cured film obtained by said method, it also discovered that there was room for the further improvement in adhesiveness with a support body (henceforth a "board | substrate").
　そこで、本発明は、優れた露光感度を有し、かつ支持体との優れた密着性を有する硬化膜を得ることができる、硬化性組成物を提供することを課題とする。
　また、本発明は、硬化膜、カラーフィルタ、遮光膜、固体撮像素子、画像表示装置、硬化膜の製造方法、及び、多官能チオール化合物を提供することを課題とする。 Then, this invention makes it a subject to provide the curable composition which can obtain the cured film which has the outstanding exposure sensitivity and has the outstanding adhesiveness with a support body.
Moreover, this invention makes it a subject to provide the manufacturing method of a cured film, a color filter, a light shielding film, a solid-state image sensor, an image display apparatus, a cured film, and a polyfunctional thiol compound.
　本発明者は、上記課題を達成すべく鋭意検討した結果、所定の多官能チオール化合物を含有する硬化性組成物が上記課題を解決することができることを見出し、本発明を完成させた。
　すなわち、以下の構成により上記課題を達成することができることを見出した。 As a result of intensive studies to achieve the above problems, the present inventor has found that a curable composition containing a predetermined polyfunctional thiol compound can solve the above problems, and has completed the present invention.
That is, it has been found that the above-described problem can be achieved by the following configuration.
　［１］　多官能チオール化合物と、重合性化合物と、光重合開始剤とを含有する硬化性組成物であって、多官能チオール化合物が、２個以上のチオール基と、チオール基とは異なる相互作用性基とを含有する硬化性組成物。
　［２］　多官能チオール化合物が、式（１）で表される化合物である、［１］に記載の硬化性組成物。
　［３］　多官能チオール化合物が、式（２）で表される化合物である、［１］又は［２］に記載の硬化性組成物。
　［４］　ｍが３～１４の整数である、［２］又は［３］に記載の硬化性組成物。
　［５］　チオール基とは異なる相互作用性基が、ヒドロキシル基、アミノ基、ピリジニル基、ピリジニウム基、アンモニウム基、ホスホニウム基、カルボン酸基又はその塩、リン酸基又はその塩、スルホン酸基又はその塩、アリール基、－Ｓｉ（ＲＸ）ｐ（ＲＹ）３－ｐ、及び、－（ＯＲＡ）ｑ－ＲＺからなる群から選択される少なくとも１種である、［１］～［４］のいずれかに記載の硬化性組成物。
　なお、ｐは１～３の整数を表し、ＲＸは加水分解性基を表し、ＲＹは、加水分解性基を除く１価の有機基を表し、ｐ個のＲＸ、及び３－ｐ個のＲＹは、それぞれ、同一でも、異なってもよい。また、ＲＺは水素原子、アルキル基、又はアルコキシ基を表し、ｑは１～４の整数を表し、ＲＡは炭素数１～１５のアルキレン基を表す。
　［６］　チオール基とは異なる相互作用性基が、ヒドロキシル基、アミノ基、ピリジニル基、ピリジニウム基、アンモニウム基、ホスホニウム基、カルボン酸基又はその塩、リン酸基又はその塩、及びスルホン酸基又はその塩からなる群から選択される少なくとも１種である、［１］～［５］のいずれかに記載の硬化性組成物。
　［７］　チオール基とは異なる相互作用性基が、ヒドロキシル基、アミノ基、ピリジニル基、カルボン酸基又はその塩、リン酸基又はその塩、及びスルホン酸基又はその塩からなる群から選択される少なくとも１種である、［１］～［６］のいずれかに記載の硬化性組成物。
　［８］　更に着色剤を含有する、［１］～［７］のいずれかに記載の硬化性組成物。
　［９］　着色剤が黒色顔料を含有する、［８］に記載の硬化性組成物。
　［１０］　光重合開始剤がオキシム化合物である［１］～［９］のいずれかに記載の硬化性組成物。
　［１１］　［１］～［１０］のいずれかに記載の硬化性組成物を硬化して得られる、硬化膜。
　［１２］　［１１］に記載の硬化膜を含有する、カラーフィルタ。
　［１３］　［１１］に記載の硬化膜を含有する、遮光膜。
　［１４］　［１１］に記載の硬化膜を含有する、固体撮像素子。
　［１５］　［１１］に記載の硬化膜を含有する、画像表示装置。
　［１６］　［１］～［１０］のいずれかに記載の硬化性組成物を用いて支持体上に硬化性組成物層を形成する、硬化性組成物層形成工程と、硬化性組成物層を露光する、露光工程とを含有する硬化膜の製造方法。
　［１７］　硬化性組成物層形成工程が、支持体上に硬化性組成物を直接塗布して、支持体上に硬化性組成物層を形成する工程を含む、［１６］に記載の硬化膜の製造方法。
　［１８］　更に、露光された硬化性組成物層を現像する、現像工程と、現像した硬化性組成物層を洗浄する、洗浄工程とを含有する、［１６］又は［１７］に記載の硬化膜の製造方法。
　［１９］　２個以上のチオール基と、チオール基とは異なる相互作用性基とを含有する、多官能チオール化合物。
　［２０］　式（１）で表される化合物である、［１９］に記載の多官能チオール化合物。
　［２１］　式（２）で表される化合物である、［１９］又は［２０］に記載の多官能チオール化合物。
　［２２］　ｍが３～１４の整数である、［２０］又は［２１］に記載の多官能チオール化合物。
　［２３］　チオール基とは異なる相互作用性基が、ヒドロキシル基、アミノ基、ピリジニル基、ピリジニウム基、アンモニウム基、ホスホニウム基、カルボン酸基又はその塩、リン酸基又はその塩、スルホン酸基又はその塩、アリール基、－Ｓｉ（ＲＸ）ｐ（ＲＹ）３－ｐ、及び、－（ＯＲＡ）ｑ－ＲＺからなる群から選択される少なくとも１種である、［１９］～［２２］のいずれかに記載の多官能チオール化合物。
　なお、ｐは１～３の整数を表し、ＲＸは加水分解性基を表し、ＲＹは、加水分解性基を除く１価の有機基を表し、ｐ個のＲＸ、及び３－ｐ個のＲＹは、それぞれ、同一でも、異なってもよい。また、ＲＺは水素原子、アルキル基、又は、アルコキシ基を表し、ｑは１～４の整数を表し、ＲＡは炭素数１～１５のアルキレン基を表す。
　［２４］　チオール基とは異なる相互作用性基が、ヒドロキシル基、アミノ基、ピリジニル基、ピリジニウム基、アンモニウム基、ホスホニウム基、カルボン酸基又はその塩、リン酸基又はその塩、及びスルホン酸基又はその塩からなる群から選択される少なくとも１種である、［１９］～［２３］のいずれかに記載の多官能チオール化合物。 [1] A curable composition containing a polyfunctional thiol compound, a polymerizable compound, and a photopolymerization initiator, wherein the polyfunctional thiol compound is different from two or more thiol groups and thiol groups. A curable composition containing an active group.
[2] The curable composition according to [1], wherein the polyfunctional thiol compound is a compound represented by the formula (1).
[3] The curable composition according to [1] or [2], wherein the polyfunctional thiol compound is a compound represented by the formula (2).
[4] The curable composition according to [2] or [3], wherein m is an integer of 3 to 14.
[5] The interactive group different from the thiol group is a hydroxyl group, amino group, pyridinyl group, pyridinium group, ammonium group, phosphonium group, carboxylic acid group or salt thereof, phosphoric acid group or salt thereof, sulfonic acid group or [1] to [1] which are at least one selected from the group consisting of a salt, an aryl group, —Si (R X ) p (R Y ) 3-p , and — (OR A ) q —R Z 4]. The curable composition according to any one of [4].
P represents an integer of 1 to 3, R X represents a hydrolyzable group, R Y represents a monovalent organic group excluding the hydrolyzable group, p R X , and 3-p Each R Y may be the same or different. R Z represents a hydrogen atom, an alkyl group, or an alkoxy group, q represents an integer of 1 to 4, and R A represents an alkylene group having 1 to 15 carbon atoms.
[6] The interactive group different from the thiol group is a hydroxyl group, amino group, pyridinyl group, pyridinium group, ammonium group, phosphonium group, carboxylic acid group or salt thereof, phosphoric acid group or salt thereof, and sulfonic acid group Alternatively, the curable composition according to any one of [1] to [5], which is at least one selected from the group consisting of salts thereof.
[7] The interactive group different from the thiol group is selected from the group consisting of hydroxyl group, amino group, pyridinyl group, carboxylic acid group or salt thereof, phosphoric acid group or salt thereof, and sulfonic acid group or salt thereof. The curable composition according to any one of [1] to [6], which is at least one kind.
[8] The curable composition according to any one of [1] to [7], further containing a colorant.
[9] The curable composition according to [8], wherein the colorant contains a black pigment.
[10] The curable composition according to any one of [1] to [9], wherein the photopolymerization initiator is an oxime compound.
[11] A cured film obtained by curing the curable composition according to any one of [1] to [10].
[12] A color filter containing the cured film according to [11].
[13] A light shielding film containing the cured film according to [11].
[14] A solid-state imaging device containing the cured film according to [11].
[15] An image display device comprising the cured film according to [11].
[16] A curable composition layer forming step of forming a curable composition layer on a support using the curable composition according to any one of [1] to [10], and a curable composition layer The manufacturing method of the cured film containing the exposure process which exposes.
[17] The cured film according to [16], wherein the curable composition layer forming step includes a step of directly applying the curable composition on the support to form a curable composition layer on the support. Manufacturing method.
[18] The curing according to [16] or [17], further comprising: a developing step for developing the exposed curable composition layer; and a washing step for washing the developed curable composition layer. A method for producing a membrane.
[19] A polyfunctional thiol compound containing two or more thiol groups and an interactive group different from the thiol group.
[20] The polyfunctional thiol compound according to [19], which is a compound represented by the formula (1).
[21] The polyfunctional thiol compound according to [19] or [20], which is a compound represented by the formula (2).
[22] The polyfunctional thiol compound according to [20] or [21], wherein m is an integer of 3 to 14.
[23] The interactive group different from the thiol group is a hydroxyl group, amino group, pyridinyl group, pyridinium group, ammonium group, phosphonium group, carboxylic acid group or salt thereof, phosphoric acid group or salt thereof, sulfonic acid group or [19] to [19], which is at least one selected from the group consisting of a salt thereof, an aryl group, —Si (R X ) p (R Y ) 3-p , and — (OR A ) q —R Z. 22]. The polyfunctional thiol compound according to any one of [22].
P represents an integer of 1 to 3, R X represents a hydrolyzable group, R Y represents a monovalent organic group excluding the hydrolyzable group, p R X , and 3-p Each R Y may be the same or different. R Z represents a hydrogen atom, an alkyl group, or an alkoxy group, q represents an integer of 1 to 4, and R A represents an alkylene group having 1 to 15 carbon atoms.
[24] The interactive group different from the thiol group is a hydroxyl group, amino group, pyridinyl group, pyridinium group, ammonium group, phosphonium group, carboxylic acid group or salt thereof, phosphoric acid group or salt thereof, and sulfonic acid group Alternatively, the polyfunctional thiol compound according to any one of [19] to [23], which is at least one selected from the group consisting of salts thereof.
　本発明によれば、優れた露光感度を有し、かつ支持体との優れた密着性を有する硬化膜を得ることができる、硬化性組成物を提供することができる。
　また、本発明は、硬化膜、カラーフィルタ、遮光膜、固体撮像素子、画像表示装置、硬化膜の製造方法、及び、多官能チオール化合物を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the curable composition which has the outstanding exposure sensitivity and can obtain the cured film which has the outstanding adhesiveness with a support body can be provided.
In addition, the present invention can provide a cured film, a color filter, a light shielding film, a solid-state imaging device, an image display device, a method for producing a cured film, and a polyfunctional thiol compound.
　以下、本発明について詳細に説明する。
　以下の説明は、本発明の代表的な実施態様に基づいてなされることがあるが、本発明はそのような実施態様に限定されない。
　本明細書において、「～」を用いて表される数値範囲は、「～」の前後に記載される数値を下限値及び上限値として含む範囲を意味する。
　本明細書における基（原子団）の表記において、置換及び無置換を記していない表記は、置換基を含有しないものと共に置換基を含有するものをも包含する。例えば、「アルキル基」とは、置換基を含有しないアルキル基（無置換アルキル基）のみならず、置換基を含有するアルキル基（置換アルキル基）をも包含する。
　本明細書中における「活性光線」又は「放射線」とは、例えば、水銀灯の輝線スペクトル、及びエキシマレーザーに代表される遠紫外線、極紫外線（ＥＵＶ：Extreme ultraviolet lithography光）、Ｘ線、並びに電子線等を意味する。また本明細書において「光」とは、活性光線及び放射線を意味する。本明細書中における「露光」とは、特に断らない限り、水銀灯の輝線スペクトル、及びエキシマレーザーに代表される遠紫外線、Ｘ線、並びにＥＵＶ光等による露光のみならず、電子線及びイオンビーム等の粒子線による描画も包含する。
　本明細書において、「（メタ）アクリレート」はアクリレート及びメタアクリレートを表す。本明細書において、「（メタ）アクリル」はアクリル及びメタアクリルを表す。本明細書において、「（メタ）アクリロイル」は、アクリロイル及びメタクリロイルを表す。本明細書において、「（メタ）アクリルアミド」は、アクリルアミド及びメタアクリルアミドを表す。
本明細書中において、「単量体」と「モノマー」とは同義である。単量体は、オリゴマー及びポリマーと区別され、重量平均分子量が２，０００以下の化合物をいう。本明細書中において、重合性化合物とは、重合性基を含有する化合物のことをいい、単量体であっても、ポリマーであってもよい。重合性基とは、重合反応に関与する基をいう。 Hereinafter, the present invention will be described in detail.
The following description may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In the notation of group (atomic group) in this specification, the notation which does not describe substitution and unsubstitution includes what does not contain a substituent and what contains a substituent. For example, the “alkyl group” includes not only an alkyl group not containing a substituent (unsubstituted alkyl group) but also an alkyl group containing a substituent (substituted alkyl group).
In the present specification, “active light” or “radiation” means, for example, the emission line spectrum of a mercury lamp, deep ultraviolet light represented by an excimer laser, extreme ultraviolet lithography (EUV), X-ray, and electron beam. Etc. In this specification, “light” means actinic rays and radiation. Unless otherwise specified, “exposure” in the present specification includes not only exposure with an emission line spectrum of a mercury lamp and far ultraviolet rays such as an excimer laser, X-rays and EUV light, but also an electron beam and an ion beam, etc. Also includes drawing with particle beams.
In the present specification, “(meth) acrylate” represents acrylate and methacrylate. In the present specification, “(meth) acryl” represents acryl and methacryl. In this specification, “(meth) acryloyl” represents acryloyl and methacryloyl. In this specification, “(meth) acrylamide” represents acrylamide and methacrylamide.
In the present specification, “monomer” and “monomer” are synonymous. A monomer is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound means a compound containing a polymerizable group, and may be a monomer or a polymer. The polymerizable group refers to a group that participates in a polymerization reaction.
［硬化性組成物］
　硬化性組成物は、多官能チオール化合物と、重合性化合物と、光重合開始剤とを含有する硬化性組成物であって、多官能チオール化合物が、２個以上のチオール基と、チオール基とは異なる相互作用性基とを含有する。 [Curable composition]
The curable composition is a curable composition containing a polyfunctional thiol compound, a polymerizable compound, and a photopolymerization initiator, and the polyfunctional thiol compound includes two or more thiol groups, a thiol group, Contains different interactive groups.
　本発明者は、特許文献１に記載された、チオール化合物を含有する硬化性組成物を用いて支持体上に硬化性組成物層を形成し、この硬化性組成物層を露光して、微細なパターン形状を有する硬化膜を作製しようとすると、露光量を多くしなければならないという問題を知見した。
　これは、パターン形状を微細化しようとすると、フォトマスクの開口部が狭くなり、結果として硬化性組成物層に照射される光量がより減少するためであると推測される。すなわち、硬化性組成物の底部に達する光量が少なくなるため、硬化性組成物層の底部が硬化しにくくなるものと推測される。
　このような場合、露光量を多くすることにより、硬化性組成物層の底部まで到達する光量を増大させることができる。
　一方で、露光量を多くすると、マスク開口部において回折した光、いわゆる「漏れ光」も多くなりやすく、硬化性組成物層の上部（すなわち、フォトマスクにより近い部分）において、本来マスクされるべき部分が露光され、パターン形状の悪化を招くことがあった。 The inventor forms a curable composition layer on a support using the curable composition containing a thiol compound described in Patent Document 1, and exposes the curable composition layer to fine It has been found that the amount of exposure must be increased when trying to produce a cured film having a simple pattern shape.
It is presumed that this is because when the pattern shape is made finer, the opening of the photomask becomes narrower, and as a result, the amount of light applied to the curable composition layer is further reduced. That is, since the amount of light reaching the bottom of the curable composition is reduced, it is estimated that the bottom of the curable composition layer is difficult to cure.
In such a case, the amount of light reaching the bottom of the curable composition layer can be increased by increasing the exposure amount.
On the other hand, when the exposure amount is increased, the light diffracted at the mask opening, so-called “leakage light”, tends to increase, and the mask should be originally masked on the upper part of the curable composition layer (that is, the portion closer to the photomask). The part was exposed and the pattern shape might be deteriorated.
　一般に、光重合開始剤を含有する硬化性組成物を用いて支持体上に硬化性組成物層を形成し、この硬化性組成物層を露光すると、光重合開始剤によりラジカル反応が開始される。このとき、光重合開始剤により生じたラジカルと硬化性組成物層内の酸素が発生し、ペルオキシラジカルが発生することがある。ペルオキシラジカルは反応を進行する作用を有しないため、そこで重合反応が停止してしまうことがある。 Generally, when a curable composition layer is formed on a support using a curable composition containing a photopolymerization initiator and the curable composition layer is exposed, a radical reaction is initiated by the photopolymerization initiator. . At this time, radicals generated by the photopolymerization initiator and oxygen in the curable composition layer may be generated, and peroxy radicals may be generated. Since peroxy radicals do not have an action to advance the reaction, the polymerization reaction may stop there.
　本発明の一態様において、硬化性組成物は、２個以上のチオール基を含有する多官能チオール化合物を含有する。チオール基は、ペルオキシラジカルに水素を供与することにより重合失活を受けにくいチイルラジカルを生成するため、重合反応が継続する。
　更に、多官能チオール化合物はチオール基とは異なる相互作用性基を含有する。相互作用性基は、支持体と（又は、支持体が上塗り層を備える場合には、上塗り層を構成する分子と）相互作用する。従って、多官能チオール化合物は、上記硬化性組成物を用いて形成された硬化性組成物層において、支持体により近い部分（すなわち、底部）に偏在しやすいものと推測される。上記硬化性組成物層において、露光時に到達する光量が相対的に少ない硬化性組成物層の底部に、多官能チオール化合物が偏在すると、上記チオール基の作用がより効果的に発揮されるものと推測される。
　すなわち、より少ない露光量であると、硬化性組成物層の底部に到達する光量が少ないものの、多官能チオール化合物は底部に偏在しやすいため、硬化性組成物層の底部でチイルラジカルが生成しやすく、少ない光量でも底部まで十分に硬化すると推測される。
　更に、硬化膜においては、支持体により近い部分（すなわち、底部）に相互作用性基が偏在するため、支持体との相互作用がより強くなり、支持体との優れた密着性を有するものと推測される。
　以下では本発明の一態様に係る硬化性組成物に含有される成分を説明する。 In one embodiment of the present invention, the curable composition contains a polyfunctional thiol compound containing two or more thiol groups. Since the thiol group generates a thiyl radical that is less susceptible to polymerization deactivation by donating hydrogen to the peroxy radical, the polymerization reaction continues.
Furthermore, the polyfunctional thiol compound contains an interactive group different from the thiol group. The interactive group interacts with the support (or with the molecules constituting the overcoat layer if the support comprises an overcoat layer). Therefore, it is estimated that the polyfunctional thiol compound is likely to be unevenly distributed in a portion closer to the support (that is, the bottom portion) in the curable composition layer formed using the curable composition. In the curable composition layer, when the polyfunctional thiol compound is unevenly distributed at the bottom of the curable composition layer in which the amount of light reaching the exposure is relatively small, the action of the thiol group is more effectively exhibited. Guessed.
That is, when the exposure amount is smaller, the amount of light reaching the bottom of the curable composition layer is small, but the polyfunctional thiol compound is likely to be unevenly distributed at the bottom, so that thiyl radicals are easily generated at the bottom of the curable composition layer. It is estimated that even the small amount of light is sufficiently cured to the bottom.
Furthermore, in the cured film, the interaction group is unevenly distributed in a portion closer to the support (that is, the bottom), so that the interaction with the support becomes stronger and has excellent adhesion to the support. Guessed.
Hereinafter, components contained in the curable composition according to one embodiment of the present invention will be described.
〔多官能チオール化合物〕
　硬化性組成物は、所定の多官能チオール化合物を含有する。
　多官能チオール化合物は、２個以上のチオール基（－ＳＨで表される基）と、チオール基とは異なる相互作用性基と、を含有していれば特に制限されず、公知の多官能チオール化合物を用いることができる。 [Polyfunctional thiol compound]
The curable composition contains a predetermined polyfunctional thiol compound.
The polyfunctional thiol compound is not particularly limited as long as it contains two or more thiol groups (a group represented by —SH) and an interactive group different from the thiol group. Compounds can be used.
　多官能チオール化合物が含有するチオール基の数は２個以上であり、３個以上が好ましく、４個以上がより好ましい。
　多官能チオール化合物が含有するチオール基の数の上限は特に制限されないが、一般に３０個以下が好ましく、２０個以下がより好ましく、１４個以下が更に好ましい。 The number of thiol groups contained in the polyfunctional thiol compound is 2 or more, preferably 3 or more, and more preferably 4 or more.
The upper limit of the number of thiol groups contained in the polyfunctional thiol compound is not particularly limited, but is generally preferably 30 or less, more preferably 20 or less, and still more preferably 14 or less.
　多官能チオール化合物が含有する、チオール基とは異なる相互作用性基の数は１個以上であり、２個以上が好ましい。
　多官能チオール化合物が含有する、チオール基とは異なる相互作用性基の上限は特に制限されないが、一般に３０個以下が好ましく、２０個以下がより好ましく、１５個以下が更に好ましい。 The number of interactive groups different from the thiol group contained in the polyfunctional thiol compound is 1 or more, and preferably 2 or more.
The upper limit of the interactive group different from the thiol group contained in the polyfunctional thiol compound is not particularly limited, but is generally preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less.
　なお、本明細書において、相互作用性基とは、他の分子と相互作用し得る基を意図する。相互作用は、分子間力、分子会合、静電的引力、イオン結合、及び／又は水素結合等の任意の態様で相互作用し得る基が挙げられる。
　なかでも、相互作用性基としては、後述する支持体、及び／又は下塗り層を形成する分子と相互作用し得る基が好ましい。相互作用性基の具体例は、後段で詳述する。 In the present specification, the interactive group means a group capable of interacting with other molecules. The interaction includes groups capable of interacting in any manner such as intermolecular force, molecular association, electrostatic attraction, ionic bond, and / or hydrogen bond.
Especially, as an interactive group, the group | base which can interact with the molecule | numerator which forms the support body and / or undercoat which are mentioned later is preferable. Specific examples of the interactive group will be described in detail later.
　多官能チオール化合物の含有量としては、硬化性組成物の全固形分に対して、０．５～１０質量％が好ましい。
　多官能チオール化合物の含有量が、０．５～１０質量％であることにより、露光感度がより優れる。
　多官能チオール化合物は、１種を単独で用いても、２種以上を併用してもよい。多官能チオール化合物を２種以上併用する場合には、その合計量が上記範囲内であることが好ましい。 The content of the polyfunctional thiol compound is preferably 0.5 to 10% by mass with respect to the total solid content of the curable composition.
When the content of the polyfunctional thiol compound is 0.5 to 10% by mass, the exposure sensitivity is more excellent.
A polyfunctional thiol compound may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of polyfunctional thiol compounds together, it is preferable that the total amount is in the said range.
＜多官能チオール化合物の好適態様１＞
　多官能チオール化合物としては、以下の式（１）で表される化合物が好ましい。
Figure JPOXMLDOC01-appb-C000005
 <Preferred embodiment 1 of polyfunctional thiol compound>
As the polyfunctional thiol compound, a compound represented by the following formula (1) is preferable.
Figure JPOXMLDOC01-appb-C000005
　式（１）中、Ｌ１、及びＬ２はそれぞれ独立に２価の連結基を表す。ｍは２～１４の整数を表し、３～１４の整数が好ましく、３～６がより好ましい。ｍが３以上の整数だと、硬化性組成物はより優れた露光感度を有する。ｎは１～１５の整数を表す。Ｌ３はｍ＋ｎ価の連結基を表し、Ｒ１はチオール基とは異なる相互作用性基を表す。
　なお、Ｌ１、及び、Ｌ２は、互いに、同一でも、異なってもよく、ｍ個のＬ１、ｎ個のＬ２、及び、ｎ個のＲ１は、それぞれ、同一でも、異なってもよい。 In formula (1), L 1 and L 2 each independently represent a divalent linking group. m represents an integer of 2 to 14, preferably an integer of 3 to 14, and more preferably 3 to 6. When m is an integer of 3 or more, the curable composition has more excellent exposure sensitivity. n represents an integer of 1 to 15. L 3 represents an m + n-valent linking group, and R 1 represents an interactive group different from the thiol group.
Note that L 1 and L 2 may be the same as or different from each other, and m L 1 , n L 2 , and n R 1 may be the same or different. Good.
　Ｌ１の２価の連結基としては、例えば、２価の脂肪族炭化水素基（好ましくは炭素数１～８）、２価の芳香族炭化水素基（好ましくは炭素数６～１２）、－Ｏ－、－Ｓ－、－Ｎ（Ｒ４）－（Ｒ４：１価の有機基）、－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｃ（＝Ｏ）－Ｏ－、－Ｃ（＝Ｏ）－ＮＨ－、－Ｏ－Ｃ（＝Ｏ）－ＮＨ－、－Ｓ（＝Ｏ）－、－Ｓ（＝Ｏ）－Ｏ－、－Ｓ（＝Ｏ）2－、－Ｓ（＝Ｏ）2－Ｏ－、－ＣＨ＝Ｎ－、－Ｎ(Ｒ)－（Ｒ：アルキル基）、又は、これらを組み合わせた基（例えば、アルキレンオキシ基、アルキレンオキシカルボニル基、及びアルキレンカルボニルオキシ基等）等が挙げられる。 Examples of the divalent linking group for L 1 include a divalent aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms), a divalent aromatic hydrocarbon group (preferably having 6 to 12 carbon atoms),- O—, —S—, —N (R 4 ) — (R 4 : monovalent organic group), —C (═O) —, —C (═O) —O—, —O—C (═O ) —O—, —C (═O) —NH—, —O—C (═O) —NH—, —S (═O) —, —S (═O) —O—, —S (═O ) 2 —, —S (═O) 2 —O—, —CH═N—, —N (R) — (R: alkyl group), or a combination thereof (eg, alkyleneoxy group, alkyleneoxy group) Carbonyl group, alkylenecarbonyloxy group and the like).
　Ｌ２の２価の連結基としては、上記Ｌ１の態様と同様である。なお、Ｌ１、及びＬ２は、互いに、同一でも、異なってもよい。また、多官能チオール化合物の１分子内のｍ個のＬ１、及び、ｎ個のＬ２は、それぞれ、同一でも、異なってもよい。 The divalent linking group of L 2 is the same as the above aspect of L 1 . Note that L 1 and L 2 may be the same as or different from each other. Further, m L 1 and n L 2 in one molecule of the polyfunctional thiol compound may be the same or different.
　Ｌ３のｍ＋ｎ価の連結基としては、例えばトリメチロールプロパン残基、－（ＣＨ2）ｋ－（ｋは例えば、２～６の整数を表す。）を３個有するイソシアヌール環等の３価の連結基、ペンタエリスリトール残基等の４価の連結基又は５価の連結基、ジペンタエリスリトール残基等の６価の連結基、及び、これらの組み合わせ等が挙げられる。
　ｍ＋ｎは３以上であり、４以上が好ましい。
　ｍ＋ｎは２９以下であり、１０以下が好ましい。 Examples of the m + n-valent linking group of L 3 include a trimethylolpropane residue and a trivalent group such as an isocyanur ring having three — (CH 2 ) k — (k represents an integer of 2 to 6, for example). , A tetravalent linking group such as a pentaerythritol residue, a pentavalent linking group, a hexavalent linking group such as a dipentaerythritol residue, and combinations thereof.
m + n is 3 or more, preferably 4 or more.
m + n is 29 or less, and preferably 10 or less.
　Ｌ３のｍ＋ｎ価の連結基としては、例えば、以下の式（Ａ）～（Ｄ）のいずれかで表される基、又は、これらを組み合わせた基が挙げられる。
Figure JPOXMLDOC01-appb-C000006
 Examples of the m + n-valent linking group of L 3 include a group represented by any of the following formulas (A) to (D), or a group obtained by combining these groups.
Figure JPOXMLDOC01-appb-C000006
　式（Ａ）～（Ｄ）中、
　Ｌ４は３価の基を表す。Ｔ３は単結合又は２価の連結基を表し、３個のＴ３は互いに同一であっても異なっていてもよい。
　Ｌ５は４価の基を表す。Ｔ４は単結合又は２価の連結基を表し、４個のＴ４は互いに同一であっても異なっていてもよい。
　Ｌ６は５価の基を表す。Ｔ５は単結合又は２価の連結基を表し、５個のＴ５は互いに同一であっても異なっていてもよい。
　Ｌ７は６価の基を表す。Ｔ６は単結合又は２価の連結基を表し、６個のＴ６は互いに同一であっても異なっていてもよい。
　なお、Ｔ３、Ｔ４、Ｔ５及びＴ６で表される２価の連結基の定義は、上述したＬ１で表される２価の連結基の定義と同義である。 In formulas (A) to (D),
L 4 represents a trivalent group. T 3 represents a single bond or a divalent linking group, and three T 3 s may be the same as or different from each other.
L 5 represents a tetravalent group. T 4 represents a single bond or a divalent linking group, and the four T 4 s may be the same as or different from each other.
L 6 represents a pentavalent group. T 5 represents a single bond or a divalent linking group, and the five T 5 s may be the same as or different from each other.
L 7 represents a hexavalent group. T 6 represents a single bond or a divalent linking group, and the six T 6 s may be the same as or different from each other.
The definition of the divalent linking group represented by T 3, T 4, T 5 and T 6 are the same as those defined divalent linking group represented by L 1 described above.
　Ｌ３のｍ＋ｎ価の連結基としては、例えば、以下の式（Ｅ）～（Ｊ）で表される基、又は、これらを組み合わせた基が好ましい。
Figure JPOXMLDOC01-appb-C000007
 As the m + n-valent linking group of L 3 , for example, groups represented by the following formulas (E) to (J), or a group obtained by combining these are preferable.
Figure JPOXMLDOC01-appb-C000007
　式（Ｅ）～（Ｊ）中、
　Ｒは水素原子、又は、１価の有機基を表す。１価の有機基としては、アルキル基が好ましい。＊は結合位置を示す。ｔは２～１１の整数を表す。 In formulas (E) to (J),
R represents a hydrogen atom or a monovalent organic group. As the monovalent organic group, an alkyl group is preferable. * Indicates a binding position. t represents an integer of 2 to 11.
　Ｌ３は以下の式（Ｋ）～（Ｏ）で表される基、又は、これらを組み合わせた基であってもよい。式中、＊は結合位置を表す。
Figure JPOXMLDOC01-appb-C000008
 L 3 may be a group represented by the following formulas (K) to (O), or a group obtained by combining these. In the formula, * represents a bonding position.
Figure JPOXMLDOC01-appb-C000008
　式（１）中、Ｒ１は、すでに説明したチオール基とは異なる相互作用性基の態様と同様である。
　なかでも、硬化膜が、支持体とのより優れた密着性を有する点で、チオール基とは異なる相互作用性基としては、ヒドロキシル基、アミノ基、ピリジニル基、ピリジニウム基、アンモニウム基、ホスホニウム基、カルボン酸基又はその塩、リン酸基又はその塩、スルホン酸基又はその塩、アリール基、－Ｓｉ（ＲＸ）ｐ（ＲＹ）３－ｐ（以下、本明細書において「Ｓｉ基」ともいう。）、及び、－（ＯＲＡ）ｑ－ＲＺからなる群から選択される少なくとも１種が好ましく、ヒドロキシル基、アミノ基、ピリジニル基、ピリジニウム基、アンモニウム基、ホスホニウム基、カルボン酸基又はその塩、リン酸基又はその塩、及びスルホン酸基又はその塩からなる群から選択される少なくとも１種がより好ましく、ヒドロキシル基、アミノ基、ピリジニル基、カルボン酸基又はその塩、リン酸基又はその塩、及び、スルホン酸基又はその塩からなる群から選択される少なくとも１種が更に好ましい。
　チオール基とは異なる相互作用性基が、上記の官能基であることによって、硬化膜が支持体とのより優れた密着性を有する機序は必ずしも明らかではないが、本発明者は以下のとおり推測している。すなわち、相互作用（非結合性の分子間力）は、ファンデルワールス相互作用、π－πスタッキング、水素－π結合、静電相互作用、又は、水素結合と大きく分類され、概ねこの順に強くなると推測され、「水素結合」が最も強く、次いで「静電相互作用」が強い。ここで、例えば、フェニル基のπ電子とＯ－Ｈの水素の結合である水素－π結合は、上記の２つと比べると弱いと考えられ、上記の効果が得られたものと推測される。なお、本発明の効果が得られる機序は上記推測に限られない。
　なお、上記アミノ基には、第１級アミノ基（ＮＨ２－）、第２級アミノ基（ＮＲａＨ－）、及び、第３級アミノ基（ＮＲａＲａ－）が含まれる。第２級アミノ基及び第３級アミノ基に含まれるＲａは、１価の有機基であれば特に制限されないが、例えば、炭化水素基（例えば、アルキル基）が挙げられる。 In formula (1), R 1 is the same as the embodiment of the interactive group different from the thiol group already described.
Among them, the hydroxyl group, the amino group, the pyridinyl group, the pyridinium group, the ammonium group, and the phosphonium group are examples of the interactive group different from the thiol group in that the cured film has better adhesion to the support. , A carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, an aryl group, —Si (R X ) p (R Y ) 3-p (hereinafter referred to as “Si group” in the present specification) And at least one selected from the group consisting of — (OR A ) q —R Z and is preferably a hydroxyl group, an amino group, a pyridinyl group, a pyridinium group, an ammonium group, a phosphonium group, or a carboxylic acid group. Or at least one selected from the group consisting of a salt thereof, a phosphoric acid group or a salt thereof, and a sulfonic acid group or a salt thereof. More preferred is at least one selected from the group consisting of a group, a pyridinyl group, a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and a sulfonic acid group or a salt thereof.
Although the interaction group different from the thiol group is the functional group described above, the mechanism by which the cured film has better adhesion to the support is not necessarily clear. I guess. In other words, the interaction (non-bonding intermolecular force) is broadly classified as van der Waals interaction, π-π stacking, hydrogen-π bond, electrostatic interaction, or hydrogen bond. It is speculated that “hydrogen bonding” is the strongest, followed by “electrostatic interaction”. Here, for example, the hydrogen-π bond, which is a bond between the π electron of the phenyl group and the O—H hydrogen, is considered to be weaker than the above two, and it is presumed that the above-described effect was obtained. In addition, the mechanism by which the effect of this invention is acquired is not restricted to the said estimation.
The amino group includes a primary amino group (NH 2 —), a secondary amino group (NR a H—), and a tertiary amino group (NR a R a —). Although Ra contained in a secondary amino group and a tertiary amino group will not be restrict | limited especially if it is a monovalent organic group, For example, a hydrocarbon group (for example, alkyl group) is mentioned.
　上記－Ｓｉ（ＲＸ）ｐ（ＲＹ）３－ｐにおいてＲＸは加水分解性基を表す。
　本明細書において加水分解性基とは、ケイ素原子（Ｓｉ）に直結し、加水分解反応を進行し得る基を意図し、例えば、アルコキシ基、ハロゲン原子、アシルオキシ基、アルケニルオキシ基、及び、イソシアネート基等が挙げられる。 In the above -Si (R X ) p (R Y ) 3-p , R X represents a hydrolyzable group.
In the present specification, the hydrolyzable group means a group that is directly bonded to a silicon atom (Si) and can proceed with a hydrolysis reaction. For example, an alkoxy group, a halogen atom, an acyloxy group, an alkenyloxy group, and an isocyanate Groups and the like.
　ＲＹは、１価の有機基を表す。ただし、上記有機基から、上記加水分解性基は除く。
　上記１価の有機基としては、加水分解性基以外の有機基であればよく、例えば、アルキル基、アルケニル基、アリール基、アルキルカルボニル基、シクロアルキルカルボニル基、アリールカルボニル基、アルキルオキシカルボニル基、シクロアルキルオキシカルボニル基、アリールオキシカルボニル基、アルキルアミノカルボニル基、シクロアルキルアミノカルボニル基、アリールアミノカルボニル基、及び、これらを組み合わせた基等が挙げられる。なかでも、アルキル基、アリール基、アルケニル基、又はこれらを組み合わせた基が好ましい。 R Y represents a monovalent organic group. However, the hydrolyzable group is excluded from the organic group.
The monovalent organic group may be any organic group other than a hydrolyzable group, such as an alkyl group, alkenyl group, aryl group, alkylcarbonyl group, cycloalkylcarbonyl group, arylcarbonyl group, alkyloxycarbonyl group. , A cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, a cycloalkylaminocarbonyl group, an arylaminocarbonyl group, and a group obtained by combining these. Of these, an alkyl group, an aryl group, an alkenyl group, or a combination of these is preferable.
　上記アルキル基中に含まれる炭素数は１～６が好ましく、直鎖状、分岐鎖状、及び、環状のいずれであってもよい。また、上記アリール基中に含まれる炭素数は６～１０が好ましい。また、上記アルケニル基中に含まれる炭素数は２～１２が好ましい。 The number of carbon atoms contained in the alkyl group is preferably 1 to 6, and may be any of linear, branched, and cyclic. The number of carbon atoms contained in the aryl group is preferably 6-10. The number of carbon atoms contained in the alkenyl group is preferably 2-12.
　ｐは１～３の整数である。なかでも、硬化膜が、支持体とのより優れた密着性を有する点で、ｐは３が好ましい。
　また、ｐ個のＲＸ、及び、３－ｐ個のＲＹは、それぞれ、同一でも、異なってもよい。 p is an integer of 1 to 3. Among these, p is preferably 3 in that the cured film has better adhesion to the support.
In addition, p R X and 3-p R Y may be the same or different.
　上記－（ＯＲＡ）ｑ－ＲＺにおいて、ＲＺは水素原子、アルキル基、又は、アルコキシ基を表し、アルキル基、及び、アルコキシ基中のアルキル基の炭素数は１～６が好ましく、直鎖状、分岐状、又は、環状のいずれであってもよい。 In the above — (OR A ) q —R Z , R Z represents a hydrogen atom, an alkyl group, or an alkoxy group, and the alkyl group and the alkyl group in the alkoxy group preferably have 1 to 6 carbon atoms. It may be any of a chain, a branch, or a ring.
　ＲＡは炭素数１～１５のアルキレン基を表し、炭素数１～１０のアルキレン基がより好ましく、炭素数１～６のアルキレン基が更に好ましい。ｑは１～４の整数を表し、２～４の整数がより好ましく、３～４の整数が更に好ましい。 R A represents an alkylene group having 1 to 15 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and still more preferably an alkylene group having 1 to 6 carbon atoms. q represents an integer of 1 to 4, more preferably an integer of 2 to 4, and still more preferably an integer of 3 to 4.
＜多官能チオール化合物の好適態様２＞
　上記多官能チオール化合物としては、以下の式（２）で表される化合物がより好ましい。
Figure JPOXMLDOC01-appb-C000009
 <Preferred embodiment 2 of polyfunctional thiol compound>
As the polyfunctional thiol compound, a compound represented by the following formula (2) is more preferable.
Figure JPOXMLDOC01-appb-C000009
　式（２）中、Ｒ２、及びＲ３はそれぞれ独立に炭素数１以上の２価の連結基を表す。
　炭素数１以上の２価の連結基としては特に制限されず、例えば、２価の脂肪族炭化水素基（好ましくは炭素数１～８）、２価の芳香族炭化水素基（好ましくは炭素数６～１２）、－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｃ（＝Ｏ）－Ｏ－、－Ｃ（＝Ｏ）－ＮＨ－、－Ｏ－Ｃ（＝Ｏ）、－ＣＨ＝Ｎ－、－Ｎ(Ｒ)－（Ｒ：アルキル基）、又はこれらと、上記式（１）中のＬ１として説明した基等を組み合わせた基等が挙げられる。
　なお、Ｒ２、及びＲ３は、互いに、同一でも、異なってもよく、ｍ個のＲ２、ｎ個のＲ２、及び、ｎ個のＲ３は、それぞれ、同一でも、異なってもよい。 In formula (2), R 2 and R 3 each independently represent a divalent linking group having 1 or more carbon atoms.
The divalent linking group having 1 or more carbon atoms is not particularly limited. For example, a divalent aliphatic hydrocarbon group (preferably having 1 to 8 carbon atoms), a divalent aromatic hydrocarbon group (preferably having a carbon number) 6-12), —C (═O) —, —C (═O) —O—, —O—C (═O) —O—, —C (═O) —NH—, —O—C ( ═O), —CH═N—, —N (R) — (R: alkyl group), or a combination of these and the group described as L 1 in the above formula (1).
R 2 and R 3 may be the same as or different from each other, and m R 2 , n R 2 , and n R 3 may be the same or different from each other. .
　式（２）中、ｍは２～１４の整数を表し、３～１４の整数が好ましく、３～６がより好ましい。ｍが３以上の整数だと、硬化性組成物はより優れた露光感度を有する。
　ｎは１～１５の整数を表し、１～４が好ましい。
　ｎに対するｍの値（ｍ／ｎ）は特に制限されないが、０．１３～１４が好ましく、１～５がより好ましく、２～５が更に好ましい。
　ｍ／ｎが１～５の範囲内だと、硬化性組成物を用いて支持体上に形成した硬化膜と、支持体との密着性がより優れる。
　ｍ＋ｎが同じ場合、ｍ／ｎがより小さい多官能チオール化合物ほど、硬化性組成物を硬化して得られるパターン形状がより優れるとともに、硬化性組成物を用いて支持体上に形成した硬化膜と、支持体との密着性がより優れる。 In the formula (2), m represents an integer of 2 to 14, preferably an integer of 3 to 14, and more preferably 3 to 6. When m is an integer of 3 or more, the curable composition has more excellent exposure sensitivity.
n represents an integer of 1 to 15, and preferably 1 to 4.
The value of m with respect to n (m / n) is not particularly limited, but is preferably 0.13 to 14, more preferably 1 to 5, and still more preferably 2 to 5.
When m / n is in the range of 1 to 5, the adhesion between the cured film formed on the support using the curable composition and the support is more excellent.
When m + n is the same, the polyfunctional thiol compound having a smaller m / n has a more excellent pattern shape obtained by curing the curable composition, and a cured film formed on the support using the curable composition; The adhesion with the support is more excellent.
　上記式（２）中、Ｍ１は、それぞれ独立に、単結合、－Ｏ－、－Ｓ－、－Ｎ（Ｒ４）－（Ｒ４：１価の有機基）、－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｃ（＝Ｏ）－Ｏ－、－Ｃ（＝Ｏ）－ＮＨ－、－Ｏ－Ｃ（＝Ｏ）－ＮＨ－、－Ｓ（＝Ｏ）－、－Ｓ（＝Ｏ）－Ｏ－、－Ｓ（＝Ｏ）2－、－Ｓ（＝Ｏ）2－Ｏ－、又は－ＣＨ＝Ｎ－を表す。
　なお、ｍ個のＭ１、及び、ｎ個のＭ１は、それぞれ同一でも、異なってもよい。 In the above formula (2), M 1 each independently represents a single bond, —O—, —S—, —N (R 4 ) — (R 4 : a monovalent organic group), —C (═O). —, —C (═O) —O—, —O—C (═O) —O—, —C (═O) —NH—, —O—C (═O) —NH—, —S (= O) —, —S (═O) —O—, —S (═O) 2 —, —S (═O) 2 —O—, or —CH═N— is represented.
Note that m pieces of M 1 and n pieces of M 1 may be the same or different.
　Ｌ３はｍ＋ｎ価の連結基を表しその態様は既に説明したとおりである。また、Ｒ１はチオール基とは異なる相互作用性基を表し、その態様は上述した式（１）中のものと同様のものが挙げられる。
　なお、ｎ個のＲ１はそれぞれ同一でも、異なってもよい。 L 3 represents an m + n-valent linking group, and the aspect thereof is as described above. R 1 represents an interactive group different from the thiol group, and the mode thereof is the same as that in formula (1) described above.
The n R 1 s may be the same or different.
　多官能チオール化合物の合成方法は特に制限されず、公知の方法を組み合わせることにより合成することができる。
　例えば、チオール基を複数有する原料化合物と、所定の相互作用性基を有し、上記チオール基と反応可能な基を有する化合物とを反応させることにより、所望の多官能チオール化合物を合成することができる。なお、チオール基と反応可能な基としては、炭素－炭素二重結合基、炭素－炭素三重結合基、エポキシ基、カルボキシル基、ハロゲン原子、アルキルスルホネート基、アリールスルホネート基などが挙げられる。
　より具体的には、チオール基を複数有する原料化合物に対して、所定の相互作用性基を有する（メタ）アクリレート化合物をマイケル付加により反応させ、所望の多官能チオール化合物を合成することができる。 The synthesis method of the polyfunctional thiol compound is not particularly limited, and can be synthesized by combining known methods.
For example, a desired polyfunctional thiol compound can be synthesized by reacting a raw material compound having a plurality of thiol groups with a compound having a predetermined interactive group and having a group capable of reacting with the thiol group. it can. Examples of groups capable of reacting with thiol groups include carbon-carbon double bond groups, carbon-carbon triple bond groups, epoxy groups, carboxyl groups, halogen atoms, alkyl sulfonate groups, and aryl sulfonate groups.
More specifically, a desired polyfunctional thiol compound can be synthesized by reacting a raw material compound having a plurality of thiol groups with a (meth) acrylate compound having a predetermined interactive group by Michael addition.
　多官能チオール化合物の具体的な例を以下の表１に示す。但し、多官能チオール化合物はこれらに限定されない。 Specific examples of polyfunctional thiol compounds are shown in Table 1 below. However, the polyfunctional thiol compound is not limited to these.
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015
　表１－１～１－６中、「Ｍｅ」はメチル基（－ＣＨ３）を意図する。「ＯＴｓ」はトシル基を表す。
　表１－１～１－６中、Ｒ１～Ｒ３、Ｌ３、及びＭ１は、式（２）における各部に対応する基であり、ｍ及びｎは式（２）におけるｍ及びｎに対応する数である。 In Tables 1-1 to 1-6, “Me” intends a methyl group (—CH 3 ). “OTs” represents a tosyl group.
In Tables 1-1 to 1-6, R 1 to R 3 , L 3 , and M 1 are groups corresponding to the respective parts in the formula (2), and m and n are the same as m and n in the formula (2). The corresponding number.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　表１－１～１－６中の記号は、以下の内容を意図する。
＊：Ｌ３とＭ１の連結箇所を示す。
●：Ｍ１、及びＲ２の列においては、Ｍ１とＲ２の連結箇所を示す。また、Ｒ３の列においては、Ｒ３と－Ｓ－基との連結箇所を示す。
○：チオール（－ＳＨ）基、又は－Ｓ－基との連結箇所を示す。
Ｒ３、Ｒ１の波線：Ｒ３とＲ１との連結箇所を示す。
上矢印：直上の欄と同じという意味を示す。 The symbols in Tables 1-1 to 1-6 are intended as follows.
*: Shows the connection location of L 3 and M 1 .
●: M 1, and in the column of R 2, showing the coupling portion of the M 1 and R 2. Further, in the column of R 3, showing the connection portion between R 3 and -S- group.
◯: A thiol (—SH) group or a connection site with an —S— group is shown.
R 3, R 1 of the wavy line: indicates the connection points of R 3 and R 1.
Up arrow: Indicates the same meaning as the column immediately above.
〔光重合開始剤〕
　硬化性組成物は、光重合開始剤を含有する。
　光重合開始剤としては、重合性化合物の重合を開始することができれば特に制限されず、公知の光重合開始剤を用いることができる。光重合開始剤としては、例えば、紫外線領域から可視光線領域に対して感光性を有するものが好ましい。光重合開始剤は、光励起された増感剤と何らかの作用を生じ、活性ラジカルを生成する活性剤であってもよく、重合性化合物の種類に応じてカチオン重合を開始させるような開始剤であってもよい。
　光重合開始剤は、約３００ｎｍ～８００ｎｍ（３３０ｎｍ～５００ｎｍがより好ましい。）の波長領域に少なくとも約５０のモル吸光係数を有する化合物を、少なくとも１種含有していることが好ましい。 (Photopolymerization initiator)
The curable composition contains a photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as the polymerization of the polymerizable compound can be initiated, and a known photopolymerization initiator can be used. As the photopolymerization initiator, for example, those having photosensitivity from the ultraviolet region to the visible light region are preferable. The photopolymerization initiator may be an activator that generates an active radical by generating some action with the photoexcited sensitizer, and is an initiator that initiates cationic polymerization according to the type of the polymerizable compound. May be.
The photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 in the wavelength region of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).
　光重合開始剤の含有量としては、硬化性組成物の全固形分に対して、１～９質量％が好ましい。
　光重合開始剤の含有量が、硬化性組成物の全固形分に対して、１～９質量％だと、硬化性組成物を硬化して得られる硬化膜のパターン形状がより優れる。
　光重合開始剤は、１種を単独で用いても、２種以上を併用してもよい。光重合開始剤を２種以上併用する場合には、その合計量が上記範囲内であることが好ましい。 The content of the photopolymerization initiator is preferably 1 to 9% by mass with respect to the total solid content of the curable composition.
When the content of the photopolymerization initiator is 1 to 9% by mass with respect to the total solid content of the curable composition, the pattern shape of the cured film obtained by curing the curable composition is more excellent.
A photoinitiator may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of photoinitiators together, it is preferable that the total amount is in the said range.
　光重合開始剤としては、例えば、ハロゲン化炭化水素誘導体（例えば、トリアジン骨格を含有するもの、オキサジアゾール骨格を含有するもの、等）、アシルホスフィンオキサイド等のアシルホスフィン化合物、ヘキサアリールビイミダゾール、オキシム誘導体等のオキシム化合物、有機過酸化物、チオ化合物、ケトン化合物、芳香族オニウム塩、ケトオキシムエーテル、アミノアセトフェノン化合物、及び、ヒドロキシアセトフェノン等が挙げられる。
　上記トリアジン骨格を含有するハロゲン化炭化水素化合物としては、例えば、若林ら著、Ｂｕｌｌ．Ｃｈｅｍ．Ｓｏｃ．Ｊａｐａｎ，４２、２９２４（１９６９）記載の化合物、英国特許１３８８４９２号明細書記載の化合物、特開昭５３－１３３４２８号公報記載の化合物、独国特許３３３７０２４号明細書記載の化合物、Ｆ．Ｃ．Ｓｃｈａｅｆｅｒ等によるＪ．Ｏｒｇ．Ｃｈｅｍ．；２９、１５２７（１９６４）記載の化合物、特開昭６２－５８２４１号公報記載の化合物、特開平５－２８１７２８号公報記載の化合物、特開平５－３４９２０号公報記載の化合物、米国特許第４２１２９７６号明細書記載の化合物、等が挙げられる。 Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those containing a triazine skeleton, those containing an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, Examples include oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones.
Examples of the halogenated hydrocarbon compound containing the triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent No. 1388492, a compound described in JP-A-53-133428, a compound described in German Patent No. 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Pat. No. 4,221,976 And compounds described in the specification.
　露光感度の観点から、トリハロメチルトリアジン化合物、ベンジルジメチルケタール化合物、α－ヒドロキシケトン化合物、α－アミノケトン化合物、アシルホスフィン化合物、フォスフィンオキサイド化合物、メタロセン化合物、オキシム化合物、トリアリルイミダゾールダイマー、オニウム化合物、ベンゾチアゾール化合物、ベンゾフェノン化合物、アセトフェノン化合物及びその誘導体、シクロペンタジエン－ベンゼン－鉄錯体及びその塩、ハロメチルオキサジアゾール化合物、並びに３－アリール置換クマリン化合物からなる群より選択される化合物が好ましい。 From the viewpoint of exposure sensitivity, trihalomethyltriazine compound, benzyldimethyl ketal compound, α-hydroxyketone compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, metallocene compound, oxime compound, triallylimidazole dimer, onium compound, Preferred are compounds selected from the group consisting of benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl-substituted coumarin compounds.
　なかでも、トリハロメチルトリアジン化合物、α－アミノケトン化合物、アシルホスフィン化合物、フォスフィンオキサイド化合物、オキシム化合物、トリアリルイミダゾールダイマー、オニウム化合物、ベンゾフェノン化合物、又はアセトフェノン化合物がより好ましく、トリハロメチルトリアジン化合物、α－アミノケトン化合物、オキシム化合物、トリアリルイミダゾールダイマー、及びベンゾフェノン化合物からなる群より選ばれる少なくとも１種の化合物が更に好ましい。 Among these, trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, or acetophenone compounds are more preferable, trihalomethyltriazine compounds, α- More preferred is at least one compound selected from the group consisting of an aminoketone compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound.
　特に、硬化性組成物を遮光膜の作製に使用する場合には、微細なパターンをシャープな形状で形成する必要があるため、硬化性と共に未露光部に残渣がなく現像されることが重要である。このような観点からは、光重合開始剤としてはオキシム化合物を使用することが特に好ましい。特に、微細なパターンを形成する場合、硬化用露光にステッパー露光を用いるが、この露光機はハロゲンにより損傷される場合があり、光重合開始剤の添加量も低く抑える必要がある。これらの点を考慮すれば、微細パターンを形成するには、光重合開始剤としては、オキシム化合物を用いるのが特に好ましい。
　光重合開始剤の具体例としては、例えば、特開２０１３－２９７６０号公報の段落０２６５～０２６８を参酌することができ、この内容は本明細書に組み込まれる。 In particular, when a curable composition is used for the production of a light-shielding film, it is necessary to form a fine pattern with a sharp shape. is there. From such a viewpoint, it is particularly preferable to use an oxime compound as the photopolymerization initiator. In particular, when a fine pattern is formed, stepper exposure is used for exposure for curing, but this exposure machine may be damaged by halogen, and the amount of photopolymerization initiator added must be kept low. Considering these points, it is particularly preferable to use an oxime compound as a photopolymerization initiator in order to form a fine pattern.
As specific examples of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
　光重合開始剤としては、ヒドロキシアセトフェノン化合物、アミノアセトフェノン化合物、及び、アシルホスフィン化合物も好適に用いることができる。より具体的には、例えば、特開平１０－２９１９６９号公報に記載のアミノアセトフェノン系開始剤、及び特許第４２２５８９８号公報に記載のアシルホスフィン系開始剤も用いることができる。
　ヒドロキシアセトフェノン化合物としては、ＩＲＧＡＣＵＲＥ－１８４、ＤＡＲＯＣＵＲ－１１７３、ＩＲＧＡＣＵＲＥ－５００、ＩＲＧＡＣＵＲＥ－２９５９、及びＩＲＧＡＣＵＲＥ－１２７（商品名、いずれもＢＡＳＦ社製）が挙げられる。
　アミノアセトフェノン化合物としては、市販品であるＩＲＧＡＣＵＲＥ－９０７、ＩＲＧＡＣＵＲＥ－３６９、及びＩＲＧＡＣＵＲＥ－３７９ＥＧ（商品名、いずれもＢＡＳＦ社製）が挙げられる。アミノアセトフェノン化合物としては、３６５ｎｍ又は４０５ｎｍ等の長波光源に吸収波長がマッチングされた特開２００９－１９１１７９公報に記載の化合物も挙げられる。
　アシルホスフィン化合物としては、市販品であるＩＲＧＡＣＵＲＥ－８１９、及びＤＡＲＯＣＵＲ－ＴＰＯ（商品名、いずれもＢＡＳＦ社製）が挙げられる。 As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine initiator described in Japanese Patent No. 4225898 can also be used.
Examples of the hydroxyacetophenone compound include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names, all manufactured by BASF).
Examples of aminoacetophenone compounds include commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (trade names, all manufactured by BASF). Examples of the aminoacetophenone compound include compounds described in JP-A-2009-191179 in which an absorption wavelength is matched with a long wave light source such as 365 nm or 405 nm.
Examples of the acylphosphine compound include IRGACURE-819 and DAROCUR-TPO (trade names, both manufactured by BASF), which are commercially available products.
＜オキシム化合物＞
　光重合開始剤として、より好ましくはオキシム化合物（オキシム系開始剤）が挙げられる。
　光重合開始剤がオキシム化合物である、上記硬化性組成物は、より優れた露光感度を有する。また、オキシム化合物は高感度で重合効率が高く、着色剤濃度によらず硬化性組成物層を硬化でき、着色剤の濃度を高く設計しやすいため好ましい。
　オキシム化合物の具体例としては、特開２００１－２３３８４２号公報記載の化合物、特開２０００－８００６８号公報記載の化合物、及び特開２００６－３４２１６６号公報記載の化合物が挙げられる。
　オキシム化合物としては、３－ベンゾイロキシイミノブタン－２－オン、３－アセトキシイミノブタン－２－オン、３－プロピオニルオキシイミノブタン－２－オン、２－アセトキシイミノペンタン－３－オン、２－アセトキシイミノ－１－フェニルプロパン－１－オン、２－ベンゾイロキシイミノ－１－フェニルプロパン－１－オン、３－（４－トルエンスルホニルオキシ）イミノブタン－２－オン、及び２－エトキシカルボニルオキシイミノ－１－フェニルプロパン－１－オン等が挙げられる。
　また、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ ＩＩ（１９７９年）ｐｐ．１６５３－１６６０）、Ｊ．Ｃ．Ｓ．Ｐｅｒｋｉｎ ＩＩ（１９７９年）ｐｐ.１５６－１６２、Ｊｏｕｒｎａｌ ｏｆ Ｐｈｏｔｏｐｏｌｙｍｅｒ Ｓｃｉｅｎｃｅ ａｎｄ Ｔｅｃｈｎｏｌｏｇｙ（１９９５年）ｐｐ．２０２－２３２に記載の化合物、特開２０００－６６３８５号公報記載の化合物、特開２０００－８００６８号公報、特表２００４－５３４７９７号公報、及び特開２００６－３４２１６６号公報の各公報に記載の化合物等も挙げられる。
　市販品ではＩＲＧＡＣＵＲＥ－ＯＸＥ０１（ＢＡＳＦ社製）、ＩＲＧＡＣＵＲＥ－ＯＸＥ０２（ＢＡＳＦ社製）、ＩＲＧＡＣＵＲＥ－ＯＸＥ０３（ＢＡＳＦ社製）、又はＩＲＧＡＣＵＲＥ－ＯＸＥ０４（ＢＡＳＦ社製）も好適に用いられる。また、ＴＲ－ＰＢＧ－３０４（常州強力電子新材料有限公司製）、アデカアークルズＮＣＩ－８３１及びアデカアークルズＮＣＩ－９３０（ＡＤＥＫＡ社製）、又はＮ－１９１９（カルバゾール・オキシムエステル骨格含有光開始剤（ＡＤＥＫＡ社製））も用いることができる。 <Oxime compound>
More preferred examples of the photopolymerization initiator include oxime compounds (oxime initiators).
The said curable composition whose photoinitiator is an oxime compound has more excellent exposure sensitivity. Oxime compounds are preferred because they are highly sensitive, have high polymerization efficiency, can cure the curable composition layer regardless of the colorant concentration, and are easy to design with a high colorant concentration.
Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
Examples of oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2- Acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxycarbonyloxyimino -1-phenylpropan-1-one and the like.
In addition, J.H. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. Compounds described in 202-232, compounds described in JP-A-2000-66385, compounds described in JP-A-2000-80068, JP-T 2004-534797, and JP-A-2006-342166 And so on.
IRGACURE-OXE01 (manufactured by BASF), IRGACURE-OXE02 (manufactured by BASF), IRGACURE-OXE03 (manufactured by BASF), or IRGACURE-OXE04 (manufactured by BASF) are also suitably used as commercial products. Also, TR-PBG-304 (manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.), Adeka Arcles NCI-831 and Adeka Arcles NCI-930 (manufactured by ADEKA), or N-1919 (carbazole / oxime ester skeleton-containing photoinitiator) An agent (manufactured by ADEKA)) can also be used.
　上記記載以外のオキシム化合物として、カルバゾールＮ位にオキシムが連結した特表２００９－５１９９０４号公報に記載の化合物；ベンゾフェノン部位にヘテロ置換基が導入された米国特許第７６２６９５７号公報に記載の化合物；色素部位にニトロ基が導入された特開２０１０－１５０２５号公報及び米国特許公開２００９－２９２０３９号に記載の化合物；国際公開特許２００９－１３１１８９号公報に記載のケトオキシム化合物；トリアジン骨格とオキシム骨格を同一分子内に含有する米国特許７５５６９１０号公報に記載の化合物；４０５ｎｍに吸収極大を有しｇ線光源に対して良好な感度を有する特開２００９－２２１１１４号公報に記載の化合物；等を用いてもよい。
　好ましくは、例えば、特開２０１３－２９７６０号公報の段落０２７４～０２７５を参酌することができ、この内容は本明細書に組み込まれる。
　具体的には、オキシム化合物としては、下記式（ＯＸ－１）で表される化合物が好ましい。なお、オキシム化合物のＮ－Ｏ結合が（Ｅ）体のオキシム化合物であっても、（Ｚ）体のオキシム化合物であっても、（Ｅ）体と（Ｚ）体との混合物であってもよい。 As oxime compounds other than those described above, compounds described in JP-T-2009-519904 in which an oxime is linked to the carbazole N-position; compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety; dyes Compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced; Ketooxime compounds described in International Patent Publication No. 2009-131189; Triazine skeleton and oxime skeleton are the same molecule A compound described in US Pat. No. 7,556,910 contained therein; a compound described in JP-A-2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source; .
Preferably, for example, paragraphs 0274 to 0275 of JP 2013-29760 A can be referred to, the contents of which are incorporated herein.
Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). The N—O bond of the oxime compound may be an (E) oxime compound, a (Z) oxime compound, a mixture of (E) isomer and (Z) isomer. Good.
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　式（ＯＸ－１）中、Ｒ及びＢは各々独立に１価の置換基を表し、Ａは２価の有機基を表し、Ａｒはアリール基を表す。
　式（ＯＸ－１）中、Ｒで表される１価の置換基としては、１価の非金属原子団であることが好ましい。
　１価の非金属原子団としては、アルキル基、アリール基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、複素環基、アルキルチオカルボニル基、及び、アリールチオカルボニル基等が挙げられる。これらの基は、１以上の置換基を有していてもよい。また、前述した置換基は、更に他の置換基で置換されていてもよい。
　置換基としてはハロゲン原子、アリールオキシ基、アルコキシカルボニル基又はアリールオキシカルボニル基、アシルオキシ基、アシル基、アルキル基、及び、アリール基等が挙げられる。
　式（ＯＸ－１）中、Ｂで表される１価の置換基としては、アリール基、複素環基、アリールカルボニル基、又は、複素環カルボニル基が好ましい。これらの基は１以上の置換基を有していてもよい。置換基としては、前述した置換基が挙げられる。
　式（ＯＸ－１）中、Ａで表される２価の有機基としては、炭素数１～１２のアルキレン基、シクロアルキレン基、又は、アルキニレン基が好ましい。これらの基は１以上の置換基を有していてもよい。置換基としては、前述した置換基が挙げられる。 In formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
In the formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. These groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
In the formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the substituents described above.
In the formula (OX-1), the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the substituents described above.
　光重合開始剤として、フッ素原子を含有するオキシム化合物を用いることもできる。フッ素原子を含有するオキシム化合物の具体例としては、特開２０１０－２６２０２８号公報記載の化合物；特表２０１４－５００８５２号公報記載の化合物２４、３６～４０；特開２０１３－１６４４７１号公報記載の化合物（Ｃ－３）；等が挙げられる。この内容は本明細書に組み込まれる。 An oxime compound containing a fluorine atom can also be used as a photopolymerization initiator. Specific examples of the oxime compound containing a fluorine atom include compounds described in JP2010-262028; compounds 24 and 36 to 40 described in JP2014-500852; compounds described in JP2013-164471A (C-3); and the like. This content is incorporated herein.
　光重合開始剤として、下記一般式（１）～（４）で表される化合物を用いることもできる。 As the photopolymerization initiator, compounds represented by the following general formulas (1) to (4) can also be used.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　式（１）において、Ｒ１及びＲ２は、それぞれ独立に、炭素数１～２０のアルキル基、炭素数４～２０の脂環式炭化水素基、炭素数６～３０のアリール基、又は、炭素数７～３０のアリールアルキル基を表し、Ｒ１及びＲ２がフェニル基の場合、フェニル基同士が結合してフルオレン基を形成してもよく、Ｒ３及びＲ４は、それぞれ独立に、水素原子、炭素数１～２０のアルキル基、炭素数６～３０のアリール基、炭素数７～３０のアリールアルキル基又は炭素数４～２０の複素環基を表し、Ｘは、直接結合又はカルボニル基を示す。 In Formula (1), R 1 and R 2 are each independently an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or Represents an arylalkyl group having 7 to 30 carbon atoms, and when R 1 and R 2 are phenyl groups, the phenyl groups may be bonded to each other to form a fluorene group, and R 3 and R 4 are each independently Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or carbonyl Indicates a group.
　式（２）において、Ｒ１、Ｒ２、Ｒ３及びＲ４は、式（１）におけるＲ１、Ｒ２、Ｒ３及びＲ４と同義であり、Ｒ５は、－Ｒ６、－ＯＲ６、－ＳＲ６、－ＣＯＲ６、－ＣＯＮＲ６Ｒ６、－ＮＲ６ＣＯＲ６、－ＯＣＯＲ６、－ＣＯＯＲ６、－ＳＣＯＲ６、－ＯＣＳＲ６、－ＣＯＳＲ６、－ＣＳＯＲ６、－ＣＮ、ハロゲン原子又はヒドロキシ基を表し、Ｒ６は、炭素数１～２０のアルキル基、炭素数６～３０のアリール基、炭素数７～３０のアリールアルキル基又は炭素数４～２０の複素環基を表し、Ｘは、直接結合又はカルボニル基を表し、ａは０～４の整数を表す。 In the formula (2), R 1, R 2, R 3 and R 4 have the same meanings as R 1, R 2, R 3 and R 4 in Formula (1), R 5 is -R 6, -OR 6 , —SR 6 , —COR 6 , —CONR 6 R 6 , —NR 6 COR 6 , —OCOR 6 , —COOR 6 , —SCOR 6 , —OCSR 6 , —COSR 6 , —CSOR 6 , —CN, halogen R 6 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms. , X represents a direct bond or a carbonyl group, and a represents an integer of 0-4.
　式（３）において、Ｒ１は、炭素数１～２０のアルキル基、炭素数４～２０の脂環式炭化水素基、炭素数６～３０のアリール基、又は、炭素数７～３０のアリールアルキル基を表し、Ｒ３及びＲ４は、それぞれ独立に、水素原子、炭素数１～２０のアルキル基、炭素数６～３０のアリール基、炭素数７～３０のアリールアルキル基又は炭素数４～２０の複素環基を表し、Ｘは、直接結合又はカルボニル基を示す。 In Formula (3), R 1 represents an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aryl group having 7 to 30 carbon atoms. R 3 and R 4 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a carbon number of 4 Represents a heterocyclic group of ˜20, and X represents a direct bond or a carbonyl group.
　式（４）において、Ｒ１、Ｒ３及びＲ４は、式（３）におけるＲ１、Ｒ３及びＲ４と同義であり、Ｒ５は、－Ｒ６、－ＯＲ６、－ＳＲ６、－ＣＯＲ６、－ＣＯＮＲ６Ｒ６、－ＮＲ６ＣＯＲ６、－ＯＣＯＲ６、－ＣＯＯＲ６、－ＳＣＯＲ６、－ＯＣＳＲ６、－ＣＯＳＲ６、－ＣＳＯＲ６、－ＣＮ、ハロゲン原子又はヒドロキシ基を表し、Ｒ６は、炭素数１～２０のアルキル基、炭素数６～３０のアリール基、炭素数７～３０のアリールアルキル基又は炭素数４～２０の複素環基を表し、Ｘは、直接結合又はカルボニル基を表し、ａは０～４の整数を表す。 In the formula (4), R 1, R 3 and R 4 have the same meanings as R 1, R 3 and R 4 in the formula (3), R 5 is, -R 6, -OR 6, -SR 6, Represents —COR 6 , —CONR 6 R 6 , —NR 6 COR 6 , —OCOR 6 , —COOR 6 , —SCOR 6 , —OCSR 6 , —COSR 6 , —CSOR 6 , —CN, a halogen atom or a hydroxy group; , R 6 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms, and X is a direct bond Or a carbonyl group, and a represents an integer of 0 to 4.
　上記式（１）及び式（２）において、Ｒ１及びＲ２は、それぞれ独立に、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、シクロヘキシル基又はフェニル基が好ましい。Ｒ３はメチル基、エチル基、フェニル基、トリル基又はキシリル基が好ましい。Ｒ４は炭素数１～６のアルキル基又はフェニル基が好ましい。Ｒ５はメチル基、エチル基、フェニル基、トリル基又はナフチル基が好ましい。Ｘは直接結合が好ましい。
　上記式（３）及び（４）において、Ｒ１は、それぞれ独立に、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基、シクロヘキシル基又はフェニル基が好ましい。Ｒ３はメチル基、エチル基、フェニル基、トリル基又はキシリル基が好ましい。Ｒ４は炭素数１～６のアルキル基又はフェニル基が好ましい。Ｒ５はメチル基、エチル基、フェニル基、トリル基又はナフチル基が好ましい。Ｘは直接結合が好ましい。
　式（１）及び式（２）で表される化合物の具体例としては、例えば、特開２０１４－１３７４６６号公報の段落番号００７６～００７９に記載された化合物が挙げられる。この内容は本明細書に組み込まれることとする。 In the above formulas (1) and (2), R 1 and R 2 are preferably each independently a methyl group, ethyl group, n-propyl group, i-propyl group, cyclohexyl group or phenyl group. R 3 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group. R 4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R 5 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. X is preferably a direct bond.
In the above formulas (3) and (4), R 1 is preferably each independently a methyl group, ethyl group, n-propyl group, i-propyl group, cyclohexyl group or phenyl group. R 3 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group. R 4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. R 5 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. X is preferably a direct bond.
Specific examples of the compounds represented by formula (1) and formula (2) include, for example, compounds described in paragraph numbers 0076 to 0079 of JP-A No. 2014-137466. This content is incorporated herein.
　硬化性組成物に好ましく使用されるオキシム化合物の具体例を以下に示す。 Specific examples of oxime compounds preferably used in the curable composition are shown below.
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　オキシム化合物は、３５０ｎｍ～５００ｎｍの波長領域に極大吸収波長を有するものが好ましく、３６０ｎｍ～４８０ｎｍの波長領域に極大吸収波長を有するものがより好ましく、３６５ｎｍ及び４０５ｎｍの吸光度が高いものが更に好ましい。
　オキシム化合物の３６５ｎｍ又は４０５ｎｍにおけるモル吸光係数は、感度の観点から、１,０００～３００，０００であることが好ましく、２,０００～３００，０００であることがより好ましく、５,０００～２００，０００であることが更に好ましい。
　化合物のモル吸光係数は、公知の方法を用いることができるが、例えば、紫外可視分光光度計（Ｖａｒｉａｎ社製Ｃａｒｙ－５ ｓｐｃｔｒｏｐｈｏｔｏｍｅｔｅｒ）にて、酢酸エチル溶媒を用い、０．０１ｇ／Ｌの濃度で測定することが好ましい。
　光重合開始剤は、必要に応じて２種以上を組み合わせて使用してもよい。 The oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably has a maximum absorption wavelength in the wavelength region of 360 nm to 480 nm, and more preferably has a high absorbance at 365 nm and 405 nm.
The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, from the viewpoint of sensitivity, and from 5,000 to 200,000. More preferably, it is 000.
For the molar extinction coefficient of the compound, a known method can be used. For example, in a UV-visible spectrophotometer (Cary-5 spctrophotometer manufactured by Varian), an ethyl acetate solvent is used at a concentration of 0.01 g / L. It is preferable to measure.
You may use a photoinitiator in combination of 2 or more type as needed.
〔重合性化合物〕
　硬化性組成物は、重合性化合物を含有する。
　重合性化合物の含有量は、硬化性組成物の全固形分に対して、１～４０質量％が好ましく、１０～４０質量％がより好ましい。
　重合性化合物の含有量が、硬化性組成物の全固形分に対して１０～４０質量％だと、硬化性組成物はより優れた露光感度を有する。なお、重合性化合物は、１種を単独で用いても、２種以上を併用してもよい。２種以上の重合性化合物を併用する場合は、その合計量が上記範囲内であることが好ましい。 (Polymerizable compound)
The curable composition contains a polymerizable compound.
The content of the polymerizable compound is preferably 1 to 40% by mass and more preferably 10 to 40% by mass with respect to the total solid content of the curable composition.
When the content of the polymerizable compound is 10 to 40% by mass with respect to the total solid content of the curable composition, the curable composition has better exposure sensitivity. In addition, a polymeric compound may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of polymeric compounds together, it is preferable that the total amount is in the said range.
　重合性化合物は、エチレン性不飽和結合を含有する基を１個以上含有する化合物が好ましく、２個以上含有する化合物がより好ましく、３個以上含有することが更に好ましく、５個以上含有することが特に好ましい。上限は、たとえば、１５個以下である。エチレン性不飽和結合を含有する基としては、例えば、ビニル基、（メタ）アリル基、及び、（メタ）アクリロイル基等が挙げられる。 The polymerizable compound is preferably a compound containing at least one group containing an ethylenically unsaturated bond, more preferably a compound containing 2 or more, further preferably containing 3 or more, and containing 5 or more. Is particularly preferred. The upper limit is 15 or less, for example. Examples of the group containing an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
　重合性化合物は、例えば、モノマー、プレポリマー、オリゴマー、及び、これらの混合物、並びに、これらの多量体等の化学的形態のいずれであってもよく、モノマーが好ましい。
　重合性化合物の分子量は、１００～３，０００が好ましく、２５０～１，５００がより好ましい。
　重合性化合物は、３～１５官能の（メタ）アクリレート化合物であることが好ましく、３～６官能の（メタ）アクリレート化合物であることがより好ましい。
　モノマー、プレポリマーの例としては、不飽和カルボン酸（例えば、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、イソクロトン酸、マレイン酸等）又はそのエステル類、アミド類、並びにこれらの多量体が挙げられ、好ましくは、不飽和カルボン酸と脂肪族多価アルコール化合物とのエステル、及び不飽和カルボン酸と脂肪族多価アミン化合物とのアミド類、並びにこれらの多量体である。また、ヒドロキシ基、アミノ基、メルカプト基等の求核性置換基を含有する不飽和カルボン酸エステル又はアミド類と、単官能若しくは多官能イソシアネート類又はエポキシ類との付加反応物、及び、上記不飽和カルボン酸エステル又はアミド類と、単官能若しくは多官能のカルボン酸との脱水縮合反応物等も好適に使用される。また、イソシアネート基、エポキシ基等の親電子性置換基を含有する不飽和カルボン酸エステル又はアミド類と、単官能若しくは多官能のアルコール類、アミン類、又は、チオール類との反応物、ハロゲン基又はトシルオキシ基等の脱離性置換基を含有する不飽和カルボン酸エステル又はアミド類と、単官能若しくは多官能のアルコール類、アミン類、又は、チオール類との反応物も好適である。また、上記の不飽和カルボン酸の代わりに、不飽和ホスホン酸、スチレン等のビニルベンゼン誘導体、ビニルエーテル、アリルエーテル等に置き換えた化合物群を使用することも可能である。
　これらの具体的な化合物としては、特開２００９－２８８７０５号公報の段落００９５～０１０８に記載の化合物を本発明においても好適に用いることができる。 The polymerizable compound may be in any of chemical forms such as a monomer, a prepolymer, an oligomer, a mixture thereof, and a multimer thereof, and is preferably a monomer.
The molecular weight of the polymerizable compound is preferably 100 to 3,000, more preferably 250 to 1,500.
The polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, more preferably a 3 to 6 functional (meth) acrylate compound.
Examples of monomers and prepolymers include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters thereof, amides, and multimers thereof. Preferred are esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds, and multimers thereof. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide containing a nucleophilic substituent such as a hydroxy group, an amino group, or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and A dehydration condensation reaction product of a saturated carboxylic acid ester or amide with a monofunctional or polyfunctional carboxylic acid is also preferably used. In addition, a reaction product of an unsaturated carboxylic acid ester or amide containing an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group A reaction product of an unsaturated carboxylic acid ester or amide containing a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. Moreover, it is also possible to use a compound group in which the unsaturated carboxylic acid is replaced with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, vinyl ether, allyl ether or the like.
As these specific compounds, the compounds described in paragraphs 0095 to 0108 of JP-A-2009-288705 can also be suitably used in the present invention.
　重合性化合物は、エチレン性不飽和結合を含有する基を１個以上含有する、常圧下で１００℃以上の沸点を持つ化合物も好ましい。例えば、特開２０１３－２９７６０号公報の段落０２２７、特開２００８－２９２９７０号公報の段落０２５４～０２５７に記載の化合物を参酌でき、この内容は本明細書に組み込まれる。 The polymerizable compound is also preferably a compound having one or more groups containing an ethylenically unsaturated bond and having a boiling point of 100 ° C. or higher under normal pressure. For example, compounds described in JP-A-2013-29760, paragraph 0227, and JP-A-2008-292970, paragraphs 0254 to 0257 can be referred to, the contents of which are incorporated herein.
　重合性化合物は、ジペンタエリスリトールトリアクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３３０、ＰＥＴ－３０、日本化薬社製）、ジペンタエリスリトールテトラアクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３２０、日本化薬社製）、ジペンタエリスリトールペンタ（メタ）アクリレート（市販品としてはＫＡＹＡＲＡＤ　Ｄ－３１０、日本化薬社製）、ジペンタエリスリトールヘキサ（メタ）アクリレート（市販品としてはＫＡＹＡＲＡＤ　ＤＰＨＡ、日本化薬社製、Ａ－ＤＰＨ－１２Ｅ、新中村化学社製）、及びこれらの（メタ）アクリロイル基がエチレングリコール残基又はプロピレングリコール残基を介している構造（例えば、サートマー社から市販されている、ＳＲ４５４、ＳＲ４９９）が好ましい。これらのオリゴマータイプも使用できる。また、ＮＫエステルＡ－ＴＭＭＴ（ペンタエリスリトールテトラアクリレート、新中村化学社製）、及び、ＫＡＹＡＲＡＤ　ＲＰ－１０４０（日本化薬社製）等を使用することもできる。
　以下に好ましい重合性化合物の態様を示す。 Polymerizable compounds are dipentaerythritol triacrylate (KAYARAD D-330, PET-30, manufactured by Nippon Kayaku Co., Ltd. as a commercial product), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product, Nippon Kayaku Co., Ltd.) Dipentaerythritol penta (meth) acrylate (commercially available product: KAYARAD D-310, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available product: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which these (meth) acryloyl groups are mediated by ethylene glycol or propylene glycol residues (eg, commercially available from Sartomer, SR454, SR499) ) Is preferred. These oligomer types can also be used. Further, NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and the like can also be used.
Preferred embodiments of the polymerizable compound are shown below.
　重合性化合物は、カルボン酸基、スルホン酸基、又は、リン酸基等の酸基を有していてもよい。酸基を含有する重合性化合物としては、脂肪族ポリヒドロキシ化合物と不飽和カルボン酸とのエステルが好ましく、脂肪族ポリヒドロキシ化合物の未反応のヒドロキシ基に非芳香族カルボン酸無水物を反応させて酸基を持たせた重合性化合物がより好ましく、このエステルにおいて、脂肪族ポリヒドロキシ化合物がペンタエリスリトール及び／又はジペンタエリスリトールであるものが更に好ましい。市販品としては、例えば、東亞合成社製の、アロニックスＴＯ－２３４９、Ｍ－３０５、Ｍ－５１０、及び、Ｍ－５２０等が挙げられる。 The polymerizable compound may have an acid group such as a carboxylic acid group, a sulfonic acid group, or a phosphoric acid group. As the polymerizable compound containing an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxy group of the aliphatic polyhydroxy compound. A polymerizable compound having an acid group is more preferable, and in this ester, the aliphatic polyhydroxy compound is more preferably pentaerythritol and / or dipentaerythritol. Examples of commercially available products include Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd.
　酸基を含有する重合性化合物の好ましい酸価としては、０．１～４０ｍｇＫＯＨ／ｇであり、より好ましくは５～３０ｍｇＫＯＨ／ｇである。重合性化合物の酸価が、０．１ｍｇＫＯＨ／ｇ以上であれば現像溶解特性が良好であり、４０ｍｇＫＯＨ／ｇ以下であれば製造及び／又は取扱い上有利である。更には、上記範囲であることにより光重合性能が良好で、硬化性に優れる。 The preferred acid value of the polymerizable compound containing an acid group is 0.1 to 40 mgKOH / g, more preferably 5 to 30 mgKOH / g. When the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the development dissolution properties are good, and when it is 40 mgKOH / g or less, it is advantageous in production and / or handling. Furthermore, by being in the above range, the photopolymerization performance is good and the curability is excellent.
　重合性化合物は、カプロラクトン構造を含有する化合物も好ましい態様である。
　カプロラクトン構造を含有する化合物としては、分子内にカプロラクトン構造を含有する限り特に限定されるものではないが、例えば、トリメチロールエタン、ジトリメチロールエタン、トリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、グリセリン、ジグリセロール、トリメチロールメラミン等の多価アルコールと、（メタ）アクリル酸及びε－カプロラクトンとをエステル化することにより得られる、ε－カプロラクトン変性多官能（メタ）アクリレートを挙げることができる。なかでも下記式（Ｚ－１）で表されるカプロラクトン構造を含有する化合物が好ましい。 The polymerizable compound is also preferably a compound containing a caprolactone structure.
The compound containing a caprolactone structure is not particularly limited as long as it contains a caprolactone structure in the molecule. For example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipenta Ε-caprolactone-modified polyfunctional (meth) acrylate obtained by esterifying polyhydric alcohol such as erythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ε-caprolactone Can be mentioned. Of these, compounds containing a caprolactone structure represented by the following formula (Z-1) are preferred.
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　式（Ｚ－１）中、６個のＲは全てが下記式（Ｚ－２）で表される基であるか、又は６個のＲのうち１～５個が下記式（Ｚ－２）で表される基であり、残余が下記式（Ｚ－３）で表される基である。 In the formula (Z-1), all six R are groups represented by the following formula (Z-2), or 1 to 5 of the six R are represented by the following formula (Z-2) And the remainder is a group represented by the following formula (Z-3).
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　式（Ｚ－２）中、Ｒ1は水素原子又はメチル基を示し、ｍは１又は２の数を示し、＊は結合手を示す。 In formula (Z-2), R 1 represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and * represents a bond.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　式（Ｚ－３）中、Ｒ1は水素原子又はメチル基を示し、＊は結合手を示す。 In formula (Z-3), R 1 represents a hydrogen atom or a methyl group, and * represents a bond.
　カプロラクトン構造を含有する重合性化合物は、例えば、日本化薬からＫＡＹＡＲＡＤ　ＤＰＣＡシリーズとして市販されており、ＤＰＣＡ－２０（式（Ｚ－１）～（Ｚ－３）においてｍが１、式（Ｚ－２）で表される基の数が２、Ｒ1が全て水素原子である化合物）、ＤＰＣＡ－３０（同式において、ｍが１、式（Ｚ－２）で表される基の数が３、Ｒ1が全て水素原子である化合物）、ＤＰＣＡ－６０（同式において、ｍが１、式（Ｚ－２）で表される基の数が６、Ｒ1が全て水素原子である化合物）、ＤＰＣＡ－１２０（同式においてｍが２、式（Ｚ－２）で表される基の数が６、Ｒ1が全て水素原子である化合物）等が挙げられる。 Polymerizable compounds containing a caprolactone structure are commercially available from Nippon Kayaku, for example, as the KAYARAD DPCA series. 2) the number of groups represented by 2 and R 1 are all hydrogen atoms), DPCA-30 (wherein m is 1 and the number of groups represented by formula (Z-2) is 3). , Compounds in which R 1 is all hydrogen atoms), DPCA-60 (a compound in which m is 1, the number of groups represented by formula (Z-2) is 6, and R 1 is all hydrogen atoms) DPCA-120 (a compound in which m is 2, the number of groups represented by formula (Z-2) is 6, and all R 1 are hydrogen atoms).
　重合性化合物は、下記式（Ｚ－４）又は（Ｚ－５）で表される化合物を用いることもできる。 As the polymerizable compound, a compound represented by the following formula (Z-4) or (Z-5) can also be used.
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
　式（Ｚ－４）及び（Ｚ－５）中、Ｅは、各々独立に、－（（ＣＨ2）yＣＨ2Ｏ）－、又は（（ＣＨ2）yＣＨ（ＣＨ3）Ｏ）－を表し、ｙは、各々独立に０～１０の整数を表し、
Ｘは、各々独立に、（メタ）アクリロイル基、水素原子、又はカルボン酸基を表す。
　式（Ｚ－４）中、（メタ）アクリロイル基の合計は３個又は４個であり、ｍは各々独立に０～１０の整数を表し、各ｍの合計は０～４０の整数である。
　式（Ｚ－５）中、（メタ）アクリロイル基の合計は５個又は６個であり、ｎは各々独立に０～１０の整数を表し、各ｎの合計は０～６０の整数である。 In formulas (Z-4) and (Z-5), each E independently represents-((CH 2 ) y CH 2 O)-or ((CH 2 ) y CH (CH 3 ) O)-. Y represents an integer of 0 to 10 each independently,
X each independently represents a (meth) acryloyl group, a hydrogen atom, or a carboxylic acid group.
In the formula (Z-4), the total number of (meth) acryloyl groups is 3 or 4, each m independently represents an integer of 0 to 10, and the total of each m is an integer of 0 to 40.
In formula (Z-5), the total number of (meth) acryloyl groups is 5 or 6, each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.
　式（Ｚ－４）中、ｍは、０～６の整数が好ましく、０～４の整数がより好ましい。
　各ｍの合計は、２～４０の整数が好ましく、２～１６の整数がより好ましく、４～８の整数が更に好ましい。
　式（Ｚ－５）中、ｎは、０～６の整数が好ましく、０～４の整数がより好ましい。
　各ｎの合計は、３～６０の整数が好ましく、３～２４の整数がより好ましく、６～１２の整数が更に好ましい。
　式（Ｚ－４）又は式（Ｚ－５）中の－（（ＣＨ2）yＣＨ2Ｏ）－又は（（ＣＨ2）yＣＨ（ＣＨ3）Ｏ）－は、酸素原子側の末端がＸに結合する形態が好ましい。 In the formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and still more preferably an integer of 4 to 8.
In the formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
The total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and still more preferably an integer of 6 to 12.
-((CH 2 ) y CH 2 O)-or ((CH 2 ) y CH (CH 3 ) O)-in formula (Z-4) or formula (Z-5) is A form bonded to X is preferred.
　式（Ｚ－４）又は式（Ｚ－５）で表される化合物は１種単独で用いてもよいし、２種以上併用してもよい。特に、式（Ｚ－５）において、６個のＸ全てがアクリロイル基である形態、式（Ｚ－５）において、６個のＸ全てがアクリロイル基である化合物と、６個のＸのうち、少なくとも１個が水素原子ある化合物との混合物である態様が好ましい。このような構成とすることにより、現像性をより向上できる。 The compounds represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more. In particular, in formula (Z-5), all six Xs are acryloyl groups, in formula (Z-5), all six Xs are acryloyl groups, and among six Xs, An embodiment which is a mixture with a compound having at least one hydrogen atom is preferred. With such a configuration, the developability can be further improved.
　式（Ｚ－４）又は式（Ｚ－５）で表される化合物の重合性化合物中における全含有量は、２０質量％以上が好ましく、５０質量％以上がより好ましい。 The total content of the compound represented by the formula (Z-4) or the formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.
　式（Ｚ－４）又は式（Ｚ－５）で表される化合物は、従来公知の工程である、ペンタエリスリト－ル又はジペンタエリスリト－ルにエチレンオキシド又はプロピレンオキシドを開環付加反応により開環骨格を結合する工程と、開環骨格の末端ヒドロキシ基に、例えば（メタ）アクリロイルクロライドを反応させて（メタ）アクリロイル基を導入する工程と、から合成することができる。各工程はよく知られた工程であり、当業者は容易に一般式（Ｚ－４）又は（Ｚ－５）で表される化合物を合成することができる。 The compound represented by the formula (Z-4) or the formula (Z-5) is a conventionally known process, which is a pentaerythritol or dipentaerythritol by a ring-opening addition reaction with ethylene oxide or propylene oxide. It can be synthesized from the step of bonding a ring-opening skeleton and the step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with the terminal hydroxy group of the ring-opening skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (Z-4) or (Z-5).
　式（Ｚ－４）又は式（Ｚ－５）で表される化合物の中でも、ペンタエリスリトール誘導体及び／又はジペンタエリスリトール誘導体がより好ましい。
　具体的には、下記式（ａ）～（ｆ）で表される化合物（以下、「例示化合物（ａ）～（ｆ）」とも称する。）が挙げられ、中でも、例示化合物（ａ）、（ｂ）、（ｅ）、（ｆ）が好ましい。 Among the compounds represented by formula (Z-4) or formula (Z-5), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.
Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”). Among them, exemplary compounds (a), (f) b), (e) and (f) are preferred.
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
　式（Ｚ－４）及び（Ｚ－５）で表される重合性化合物の市販品としては、例えばサートマー社製のエチレンオキシ鎖を４個含有する４官能アクリレートであるＳＲ－４９４、日本化薬社製のペンチレンオキシ鎖を６個含有する６官能アクリレートであるＤＰＣＡ－６０、イソブチレンオキシ鎖を３個含有する３官能アクリレートであるＴＰＡ－３３０等が挙げられる。 Examples of commercially available polymerizable compounds represented by the formulas (Z-4) and (Z-5) include SR-494, a tetrafunctional acrylate containing four ethyleneoxy chains manufactured by Sartomer, Nippon Kayaku Examples thereof include DPCA-60, which is a hexafunctional acrylate containing six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate containing three isobutyleneoxy chains.
　重合性化合物としては、特公昭４８－４１７０８号公報、特開昭５１－３７１９３号公報、特公平２－３２２９３号公報、特公平２－１６７６５号公報に記載されたウレタンアクリレート類；特公昭５８－４９８６０号公報、特公昭５６－１７６５４号公報、特公昭６２－３９４１７号公報、及び特公昭６２－３９４１８号公報に記載されたエチレンオキサイド系骨格を含有するウレタン化合物類；も好適である。また、特開昭６３－２７７６５３号公報、特開昭６３－２６０９０９号公報、及び特開平１－１０５２３８号公報に記載された、分子内にアミノ構造及び／又はスルフィド構造を含有する付加重合性化合物類を用いることによって、非常に感光スピードに優れた硬化性組成物を得ることができる。
　市販品としては、ウレタンオリゴマーＵＡＳ－１０、ＵＡＢ－１４０（山陽国策パルプ社製）、ＵＡ－７２００（新中村化学社製）、ＤＰＨＡ－４０Ｈ（日本化薬社製）、ＵＡ－３０６Ｈ、ＵＡ－３０６Ｔ、ＵＡ－３０６Ｉ、ＡＨ－６００、Ｔ－６００、及び、ＡＩ－６００（共栄社製）等が挙げられる。 Examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765; Urethane compounds containing an ethylene oxide skeleton described in JP-A-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Further, addition-polymerizable compounds containing an amino structure and / or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 By using a curable composition, it is possible to obtain a curable composition having an extremely excellent photosensitive speed.
Commercially available products include urethane oligomers UAS-10, UAB-140 (Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (Shin Nakamura Chemical Co., Ltd.), DPHA-40H (Nippon Kayaku Co., Ltd.), UA-306H, UA- 306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.
　重合性化合物は、ＳＰ（Solubility Parameter：溶解パラメータ）値が、９．５０以上であることが好ましく、１０．４０以上であることがより好ましく、１０．６０以上が更に好ましい。
　本明細書においてＳＰ値は、特に断らない限り、Ｈｏｙ法によって求める（Ｈ．Ｌ．Ｈｏｙ Ｊｏｕｒｎａｌ ｏｆ Ｐａｉｎｔｉｎｇ，１９７０，Ｖｏｌ．４２，７６－１１８）。ＳＰ値については単位を省略して示しているが、その単位はｃａｌ１／２ｃｍ－３／２である。 The polymerizable compound preferably has an SP (Solubility Parameter) value of 9.50 or more, more preferably 10.40 or more, and still more preferably 10.60 or more.
In this specification, unless otherwise specified, the SP value is obtained by the Hoy method (HL Hoy Journal of Paining, 1970, Vol. 42, 76-118). The SP value is shown with the unit omitted, but the unit is cal 1/2 cm −3/2 .
　硬化性組成物は、現像残渣改善の観点から、カルド骨格を含有する重合性化合物を含有することも好ましい。
　カルド骨格を含有する重合性化合物としては、９，９－ビスアリールフルオレン骨格を含有する重合性化合物が好ましく、下記式（Ｑ３）で表される化合物がより好ましい。 It is also preferable that the curable composition contains a polymerizable compound containing a cardo skeleton from the viewpoint of improving the development residue.
As the polymerizable compound containing a cardo skeleton, a polymerizable compound containing a 9,9-bisarylfluorene skeleton is preferable, and a compound represented by the following formula (Q3) is more preferable.
式（Ｑ３）
Figure JPOXMLDOC01-appb-C000027
 Formula (Q3)
Figure JPOXMLDOC01-appb-C000027
　上記式（Ｑ３）中、Ａｒ１１～Ａｒ１４はそれぞれ独立に破線で囲まれたベンゼン環を含有するアリール基を表す。Ｘ１～Ｘ４はそれぞれ独立に重合性基を含有する置換基を表し、上記置換基中の炭素原子はヘテロ原子によって置換されていてもよい。ａ及びｂはそれぞれ独立に１～５の整数を表し、ｃ及びｄはそれぞれ独立に０～５の整数を表す。Ｒ１～Ｒ４はそれぞれ独立に置換基を表し、ｅ、ｆ、ｇ及びｈはそれぞれ独立に０以上の整数を表し、ｅ、ｆ、ｇ及びｈの上限値はそれぞれＡｒ１１～Ａｒ１４が含有することができる置換基の数からａ、ｂ、ｃ又はｄをそれぞれ減じた値である。但し、Ａｒ１１～Ａｒ１４がそれぞれ独立に破線で囲まれたベンゼン環を縮合環のひとつとして含有する多環芳香族炭化水素基である場合は、Ｘ１～Ｘ４及びＲ１～Ｒ４はそれぞれ独立に破線で囲まれたベンゼン環に置換していても、破線で囲まれたベンゼン環以外の環に置換していてもよい。 In the above formula (Q3), Ar 11 to Ar 14 each independently represents an aryl group containing a benzene ring surrounded by a broken line. X 1 to X 4 each independently represents a substituent containing a polymerizable group, and the carbon atom in the substituent may be substituted with a hetero atom. a and b each independently represents an integer of 1 to 5, and c and d each independently represents an integer of 0 to 5. R 1 to R 4 each independently represents a substituent, e, f, g and h each independently represents an integer of 0 or more, and the upper limit values of e, f, g and h are Ar 11 to Ar 14 respectively. It is a value obtained by subtracting a, b, c, or d from the number of substituents that can be contained. However, when Ar 11 to Ar 14 are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, X 1 to X 4 and R 1 to R 4 are Each may be independently substituted with a benzene ring surrounded by a broken line, or may be substituted with a ring other than the benzene ring surrounded by a broken line.
　式（Ｑ３）中、Ａｒ１１～Ａｒ１４が表す破線で囲まれたベンゼン環を含有するアリール基は、炭素数６～１４のアリール基であることが好ましく、炭素数６～１０のアリール基（例えば、フェニル基、ナフチル基）であることがより好ましく、フェニル基（破線で囲まれたベンゼン環のみ）であることが更に好ましい。 In formula (Q3), the aryl group containing a benzene ring surrounded by a broken line represented by Ar 11 to Ar 14 is preferably an aryl group having 6 to 14 carbon atoms, and an aryl group having 6 to 10 carbon atoms ( For example, a phenyl group or a naphthyl group is more preferable, and a phenyl group (only a benzene ring surrounded by a broken line) is more preferable.
　式（Ｑ３）中、Ｘ１～Ｘ４はそれぞれ独立に重合性基を含有する置換基を表し、上記置換基中の炭素原子はヘテロ原子によって置換されていてもよい。Ｘ１～Ｘ４が表す重合性基を含有する置換基としては特に制限はないが、重合性基を含有する脂肪族基であることが好ましい。
　Ｘ１～Ｘ４が表す重合性基を含有する脂肪族基としては、特に制限はないが、重合性基以外における炭素数が１～１２のアルキレン基であることが好ましく、炭素数２～１０のアルキレン基であることがより好ましく、炭素数２～５のアルキレン基であることが更に好ましい。
　Ｘ１～Ｘ４が表す重合性基を含有する脂肪族基において、上記脂肪族基がヘテロ原子によって置換される場合は、－ＮＲ－（Ｒは置換基）、酸素原子、硫黄原子によって置換されていることが好ましく、上記脂肪族基中の隣り合わない－ＣＨ２－が酸素原子又は硫黄原子で置換されていることがより好ましく、上記脂肪族基中の隣り合わない－ＣＨ２－が酸素原子で置換されていることが更に好ましい。Ｘ１～Ｘ４が表す重合性基を含有する脂肪族基は、ヘテロ原子によって１～２箇所置換されていることが好ましく、ヘテロ原子によって１箇所置換されていることがより好ましく、Ａｒ１１～Ａｒ１４が表す破線で囲まれたベンゼン環を含有するアリール基に隣接する１箇所がヘテロ原子によって置換されていることが更に好ましい。
　Ｘ１～Ｘ４が表す重合性基を含有する脂肪族基に含まれる重合性基としては、ラジカル重合又はカチオン重合可能な重合性基（以下、それぞれラジカル重合性基及びカチオン重合性基とも言う）が好ましい。
　ラジカル重合性基としては、一般に知られているラジカル重合性基を用いることができ、好適なものとしてラジカル重合可能なエチレン性不飽和結合を含有する重合性基を挙げることができ、具体的にはビニル基、（メタ）アクリロイルオキシ基等を挙げることができる。中でも、（メタ）アクリロイルオキシ基が好ましく、アクリロイルオキシ基がより好ましい。
　カチオン重合性基としては、一般に知られているカチオン重合性を用いることができ、具体的には、脂環式エーテル基、環状アセタール基、環状ラクトン基、環状チオエーテル基、スピロオルソエステル基、ビニルオキシ基等を挙げることができる。中でも、脂環式エーテル基、ビニルオキシ基が好適であり、エポキシ基、オキセタニル基、ビニルオキシ基が特に好ましい。
　Ａｒ１１～Ａｒ１４が含有する置換基が含有する上記重合性基は、ラジカル重合性基であることが好ましい。
　Ａｒ１１～Ａｒ１４のうち２つ以上は重合性基を含有する置換基を含み、Ａｒ１１～Ａｒ１４のうち２～４個が重合性基を含有する置換基を含有することが好ましく、Ａｒ１１～Ａｒ１４のうち２又は３個が重合性基を含有する置換基を含有することがより好ましく、Ａｒ１１～Ａｒ１４のうち２個が重合性基を含有する置換基を含有することが更に好ましい。
　Ａｒ１１～Ａｒ１４がそれぞれ独立に破線で囲まれたベンゼン環を縮合環のひとつとして含有する多環芳香族炭化水素基である場合は、Ｘ１～Ｘ４はそれぞれ独立に破線で囲まれたベンゼン環に置換していても、破線で囲まれたベンゼン環以外の環に置換していてもよい。 In formula (Q3), X 1 to X 4 each independently represents a substituent containing a polymerizable group, and the carbon atom in the substituent may be substituted with a hetero atom. The substituent containing a polymerizable group represented by X 1 to X 4 is not particularly limited, but is preferably an aliphatic group containing a polymerizable group.
The aliphatic group containing a polymerizable group represented by X 1 to X 4 is not particularly limited, but is preferably an alkylene group having 1 to 12 carbon atoms other than the polymerizable group, and 2 to 10 carbon atoms. And more preferably an alkylene group having 2 to 5 carbon atoms.
In the aliphatic group containing a polymerizable group represented by X 1 to X 4 , when the aliphatic group is substituted with a heteroatom, it is substituted with —NR— (R is a substituent), an oxygen atom, or a sulfur atom. The non-adjacent —CH 2 — in the aliphatic group is preferably substituted with an oxygen atom or a sulfur atom, and the non-adjacent —CH 2 — in the aliphatic group is oxygen More preferably, it is substituted with an atom. The aliphatic group containing a polymerizable group represented by X 1 to X 4 is preferably substituted at one or two positions with a hetero atom, more preferably at one position with a hetero atom, and Ar 11 to More preferably, one position adjacent to the aryl group containing a benzene ring surrounded by a broken line represented by Ar 14 is substituted with a hetero atom.
The polymerizable group contained in the aliphatic group containing the polymerizable group represented by X 1 to X 4 is a radically polymerizable or cationically polymerizable group (hereinafter also referred to as a radically polymerizable group and a cationically polymerizable group, respectively). ) Is preferred.
As the radically polymerizable group, generally known radically polymerizable groups can be used, and preferable examples thereof include a polymerizable group containing an ethylenically unsaturated bond capable of radical polymerization, Can include a vinyl group, a (meth) acryloyloxy group, and the like. Among these, a (meth) acryloyloxy group is preferable, and an acryloyloxy group is more preferable.
As the cationic polymerizable group, generally known cationic polymerizable groups can be used. Specifically, alicyclic ether group, cyclic acetal group, cyclic lactone group, cyclic thioether group, spiro orthoester group, vinyloxy group Groups and the like. Of these, alicyclic ether groups and vinyloxy groups are preferable, and epoxy groups, oxetanyl groups, and vinyloxy groups are particularly preferable.
The polymerizable group contained in the substituent contained in Ar 11 to Ar 14 is preferably a radical polymerizable group.
Two or more of Ar 11 ~ Ar 14 comprises a substituent containing a polymerizable group, preferably contains a substituent 2-4 of Ar 11 ~ Ar 14 contains a polymerizable group, Ar More preferably, 2 or 3 of 11 to Ar 14 contain a substituent containing a polymerizable group, and two of Ar 11 to Ar 14 contain a substituent containing a polymerizable group. Further preferred.
When Ar 11 to Ar 14 are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, X 1 to X 4 are each independently surrounded by a broken line Even if it is substituted with a benzene ring, it may be substituted with a ring other than the benzene ring surrounded by a broken line.
　式（Ｑ３）中、ａ及びｂはそれぞれ独立に１～５の整数を表し、１又は２であることが好ましく、ａ及びｂがいずれも１であることがより好ましい。
　式（Ｑ３）中、ｃ及びｄはそれぞれ独立に０～５の整数を表し、０又は１であることが好ましく、ｃ及びｄがいずれも０であることがより好ましい。 In formula (Q3), a and b each independently represent an integer of 1 to 5, preferably 1 or 2, and more preferably a and b are all 1.
In formula (Q3), c and d each independently represent an integer of 0 to 5, preferably 0 or 1, and more preferably c and d are both 0.
　式（Ｑ３）中、Ｒ１～Ｒ４はそれぞれ独立に置換基を表す。Ｒ１～Ｒ４が表す置換基としては特に制限はないが、例えば、ハロゲン原子、ハロゲン化アルキル基、アルキル基、アルケニル基、アシル基、ヒドロキシ基、ヒドロキシアルキル基、アルコキシ基、アリール基、ヘテロアリール基、及び、脂環基等を挙げることができる。Ｒ１～Ｒ４が表す置換基はアルキル基、アルコキシ基又はアリール基であることが好ましく、炭素数１～５のアルキル基、炭素数１～５のアルコキシ基又はフェニル基であることがより好ましく、メチル基、メトキシ基又はフェニル基であることが更に好ましい。
　式（Ｑ３）中、Ａｒ１１～Ａｒ１４がそれぞれ独立に破線で囲まれたベンゼン環を縮合環のひとつとして含有する多環芳香族炭化水素基である場合は、Ｒ１～Ｒ４はそれぞれ独立に破線で囲まれたベンゼン環に置換していても、破線で囲まれたベンゼン環以外の環に置換していてもよい。 In formula (Q3), R 1 to R 4 each independently represents a substituent. The substituent represented by R 1 to R 4 is not particularly limited, and examples thereof include halogen atoms, halogenated alkyl groups, alkyl groups, alkenyl groups, acyl groups, hydroxy groups, hydroxyalkyl groups, alkoxy groups, aryl groups, hetero groups. An aryl group, an alicyclic group, etc. can be mentioned. The substituent represented by R 1 to R 4 is preferably an alkyl group, an alkoxy group or an aryl group, more preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a phenyl group. And more preferably a methyl group, a methoxy group or a phenyl group.
In the formula (Q3), when Ar 11 to Ar 14 are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, R 1 to R 4 are each independently May be substituted with a benzene ring surrounded by a broken line, or may be substituted with a ring other than the benzene ring surrounded by a broken line.
　式（Ｑ３）中、ｅ、ｆ、ｇ及びｈはそれぞれ独立に０以上の整数を表し、ｅ、ｆ、ｇ及びｈの上限値はそれぞれＡｒ１１～Ａｒ１４が含有することができる置換基の数からａ、ｂ、ｃ又はｄをそれぞれ減じた値である。
　ｅ、ｆ、ｇ及びｈはそれぞれ独立に０～８であることが好ましく、０～２であることがより好ましく、０であることが更に好ましい。
　Ａｒ１１～Ａｒ１４がそれぞれ独立に破線で囲まれたベンゼン環を縮合環のひとつとして含有する多環芳香族炭化水素基である場合、ｅ、ｆ、ｇ及びｈは０又は１であることが好ましく、０であることがより好ましい。 In formula (Q3), e, f, g and h each independently represent an integer of 0 or more, and the upper limit values of e, f, g and h are the substituents that Ar 11 to Ar 14 can contain, respectively. It is a value obtained by subtracting a, b, c or d from the number.
e, f, g and h are each independently preferably 0 to 8, more preferably 0 to 2, and still more preferably 0.
When Ar 11 to Ar 14 are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, e, f, g and h may be 0 or 1 Preferably, it is 0.
　式（Ｑ３）で表される化合物としては、例えば、９，９－ビス［４－（２－アクリロイルオキシエトキシ）フェニル］フルオレン等が挙げられる。９，９－ビスアリールフルオレン骨格を含有する重合性化合物としては、特開２０１０-２５４７３２号公報に記載の化合物類も好適に用いることができる。 Examples of the compound represented by the formula (Q3) include 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene. As the polymerizable compound containing a 9,9-bisarylfluorene skeleton, compounds described in JP 2010-254732 A can also be suitably used.
　このようなカルド骨格を含有する重合性化合物としては、限定されないが、例えば、オンコートＥＸシリーズ（長瀬産業社製）及びオグソール（大阪ガスケミカル社製）等が挙げられる。 Examples of the polymerizable compound containing a cardo skeleton include, but are not limited to, on-coat EX series (manufactured by Nagase Sangyo Co., Ltd.) and Ogsol (manufactured by Osaka Gas Chemical Co., Ltd.).
〔任意成分〕
＜着色剤＞
　硬化性組成物は着色剤を含有することが好ましい。着色剤は、顔料、及び、染料からなる群から選択される少なくとも１種であり、有彩色着色剤でも、黒色着色剤でもよいが、黒色顔料を含有することが好ましい。
　硬化性組成物における着色剤の含有量は、特に制限されないが、上記硬化性組成物により得られる硬化膜を遮光膜として用いる場合、より優れた遮光性が得られる点で、硬化性組成物の全固形分に対して、５０質量％以上が好ましい。
　着色剤の含有量の上限値は特に制限されないが、一般に、硬化性組成物の全固形分に対して、７０質量％以下が好ましい。着色剤の含有量が上限値以下だと、硬化性組成物はより優れた塗布性を有する。 [Optional ingredients]
<Colorant>
The curable composition preferably contains a colorant. The colorant is at least one selected from the group consisting of pigments and dyes, and may be a chromatic colorant or a black colorant, but preferably contains a black pigment.
The content of the colorant in the curable composition is not particularly limited, but when a cured film obtained from the above curable composition is used as a light-shielding film, a more excellent light-shielding property can be obtained. 50 mass% or more is preferable with respect to the total solid.
The upper limit of the content of the colorant is not particularly limited, but generally 70% by mass or less is preferable with respect to the total solid content of the curable composition. When the content of the colorant is not more than the upper limit value, the curable composition has more excellent coatability.
（顔料）
　顔料としては、特に制限されず、公知の無機顔料及び／又は有機顔料を用いることができる。 (Pigment)
The pigment is not particularly limited, and a known inorganic pigment and / or organic pigment can be used.
・無機顔料
　上記無機顔料としては、特に制限されず、公知の無機顔料を用いることができる。
　無機顔料としては、例えば、亜鉛華、鉛白、リトポン、酸化チタン、酸化クロム、酸化鉄、沈降性硫酸バリウム及びバライト粉、鉛丹、酸化鉄赤、黄鉛、亜鉛黄（亜鉛黄１種、亜鉛黄２種）、ウルトラマリン青、プロシア青（フェロシアン化鉄カリ）ジルコングレー、プラセオジムイエロー、クロムチタンイエロー、クロムグリーン、ピーコック、ビクトリアグリーン、紺青（プルシアンブルーとは無関係）、バナジウムジルコニウム青、クロム錫ピンク、陶試紅、並びにサーモンピンク等が挙げられる。また、黒色の無機顔料としては、Ｃｏ、Ｃｒ、Ｃｕ、Ｍｎ，Ｒｕ、Ｆｅ、Ｎｉ、Ｓｎ、Ｔｉ、及びＡｇからなる群より選ばれた１種又は２種以上の金属元素を含む金属酸化物、金属窒素物、及び金属酸窒化物等が挙げられる。 -Inorganic pigment It does not restrict | limit especially as said inorganic pigment, A well-known inorganic pigment can be used.
Examples of inorganic pigments include zinc white, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, red lead, iron oxide red, yellow lead, zinc yellow (one zinc yellow, 2 types of zinc yellow), ultramarine blue, prussian blue (potassium ferrocyanide) zircon gray, praseodymium yellow, chrome titanium yellow, chrome green, peacock, Victoria green, bitumen (unrelated to Prussian blue), vanadium zirconium blue, Examples include chrome tin pink, ceramic red, and salmon pink. The black inorganic pigment includes a metal oxide containing one or more metal elements selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. , Metal nitrides, metal oxynitrides, and the like.
　無機顔料としては、含有量が少なくとも、高い光学濃度を有する硬化膜を形成することができる硬化性組成物が得られる点で、カーボンブラック、チタンブラック、及び金属顔料等（以下、「黒色顔料」ともいう。）が好ましい。金属顔料としては、例えば、Ｎｂ、Ｖ、Ｃｏ、Ｃｒ、Ｃｕ、Ｍｎ、Ｒｕ、Ｆｅ、Ｎｉ、Ｓｎ、Ｔｉ、及びＡｇからなる群より選ばれる１種又は２種以上の金属元素を含む金属酸化物及び金属窒素物が挙げられる。
　無機顔料としては、窒化チタン、酸窒化チタン、窒化ニオブ、窒化バナジウム、銀、又は錫を含有する金属顔料、並びに銀、及び錫を含有する金属顔料からなる群から選択される少なくとも１種を含有することが好ましく、窒化チタン、酸窒化チタン、窒化ニオブ、及び窒化バナジウムからなる群から選択される少なくとも１種を含有することがより好ましい。窒化ニオブ、及び窒化バナジウムは、酸窒化ニオブ、及び酸窒化バナジウムでもよい。
　なお、無機顔料としては、カーボンブラックを用いることもできる。カーボンブラックの具体例としては、市販品である、Ｃ．Ｉ．ピグメントブラック　１等の有機顔料Ｃ．Ｉ．ピグメントブラック　７等の無機顔料が挙げられるがこれらに限定されない。 As the inorganic pigment, carbon black, titanium black, metal pigment, etc. (hereinafter referred to as “black pigment”) in that a curable composition capable of forming a cured film having at least a high optical density is obtained. Also referred to). Examples of the metal pigment include a metal oxide containing one or more metal elements selected from the group consisting of Nb, V, Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag. And metal nitrides.
The inorganic pigment contains at least one selected from the group consisting of titanium nitride, titanium oxynitride, niobium nitride, vanadium nitride, silver, or tin-containing metal pigments, and silver and tin-containing metal pigments. It is preferable to contain at least one selected from the group consisting of titanium nitride, titanium oxynitride, niobium nitride, and vanadium nitride. Niobium nitride and vanadium nitride may be niobium oxynitride and vanadium oxynitride.
Carbon black can also be used as the inorganic pigment. Specific examples of carbon black are commercially available C.I. I. Pigment Black 1 and other organic pigments C.I. I. Examples thereof include inorganic pigments such as CI Pigment Black 7, but are not limited thereto.
　硬化性組成物には、黒色顔料として記載した顔料以外で赤外線吸収性を有する顔料を用いることもできる。
　赤外線吸収性を有する顔料としては、タングステン化合物、及び金属ホウ化物等が好ましく、なかでも、赤外領域の波長における遮光性に優れる点から、タングステン化合物が好ましい。特に露光による硬化効率に関わる光重合開始剤の光吸収波長領域と、可視光領域の透光性に優れる観点からタングステン化合物が好ましい。 For the curable composition, pigments having infrared absorptivity other than the pigments described as black pigments can also be used.
As the pigment having infrared absorptivity, a tungsten compound, a metal boride, and the like are preferable, and among them, a tungsten compound is preferable from the viewpoint of excellent light-shielding properties at wavelengths in the infrared region. In particular, a tungsten compound is preferable from the viewpoint of excellent light absorption wavelength region of a photopolymerization initiator related to curing efficiency by exposure and transparency of visible light region.
　これらの顔料は、２種以上併用してもよく、また、後述する染料と併用してもよい。色味を調整するため、及び、所望の波長領域の遮光性を高めるため、例えば、黒色顔料、又は赤外線遮光性を有する顔料に、赤色、緑色、黄色、オレンジ色、紫色、及びブルーなどの有彩色顔料若しくは後述する染料を混ぜる態様が挙げられる。黒色顔料、又は赤外線遮光性を有する顔料に、赤色顔料若しくは染料、又は、紫色顔料若しくは染料を混合することが好ましく、黒色顔料、又は赤外線遮光性を有する顔料に赤色顔料を混合することがより好ましい。
　更に、後述する近赤外線吸収剤、赤外線吸収剤を加えても良い。 Two or more of these pigments may be used in combination, or may be used in combination with a dye described later. In order to adjust the color tone and enhance the light-shielding property in a desired wavelength region, for example, a black pigment or an infrared light-shielding pigment has red, green, yellow, orange, purple, blue, or the like. The aspect which mixes a coloring pigment or dye mentioned later is mentioned. It is preferable to mix a red pigment or dye, or a purple pigment or dye with a black pigment or a pigment having infrared light shielding properties, and it is more preferable to mix a red pigment with a black pigment or a pigment having infrared light shielding properties. .
Furthermore, you may add the near-infrared absorber and infrared absorber which are mentioned later.
　黒色顔料は、チタンブラック及び／又は酸窒化ニオブを含有することが好ましい。チタンブラックとは、チタン原子を含有する黒色粒子である。好ましくは低次酸化チタン、酸窒化チタン又は窒化チタン等である。チタンブラック粒子は、分散性向上、凝集性抑制などの目的で必要に応じ、表面を修飾することが可能である。酸化珪素、酸化チタン、酸化ゲルマニウム、酸化アルミニウム、酸化マグネシウム、又は、酸化ジルコニウムで被覆することが可能であり、また、特開２００７－３０２８３６号公報に表されるような撥水性物質での処理も可能である。
　チタンブラックは、典型的には、チタンブラック粒子であり、個々の粒子の一次粒子径及び平均一次粒子径のいずれもが小さいものであることが好ましい。酸窒化ニオブも同様である。
　具体的には、平均一次粒子径で１０ｎｍ～４５ｎｍの範囲のものが好ましい。 The black pigment preferably contains titanium black and / or niobium oxynitride. Titanium black is black particles containing titanium atoms. Preferred are low-order titanium oxide, titanium oxynitride, titanium nitride, and the like. The surface of titanium black particles can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation. It can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide, and treatment with a water-repellent substance as disclosed in JP-A-2007-302836 is also possible. Is possible.
Titanium black is typically titanium black particles, and it is preferable that both the primary particle diameter and the average primary particle diameter of each particle are small. The same applies to niobium oxynitride.
Specifically, an average primary particle diameter in the range of 10 nm to 45 nm is preferable.
　なお、顔料の平均一次粒子径は、透過型電子顕微鏡（Ｔｒａｎｓｍｉｓｓｉｏｎ Ｅｌｅｃｔｒｏｎ Ｍｉｃｒｏｓｃｏｐｅ、ＴＥＭ）を用いて測定できる。透過型電子顕微鏡としては、例えば、日立ハイテクノロジーズ社製の透過型顕微鏡ＨＴ７７００を用いることができる。
　本明細書において、顔料の平均一次粒子径は、透過型電子顕微鏡を用いて得た粒子像の最大長（Ｄｍａｘ：粒子画像の輪郭上の２点における最大長さ）、及び最大長垂直長（ＤＶ－ｍａｘ：最大長に平行な２本の直線で画像を挟んだ時、２直線間を垂直に結ぶ最短の長さ）を測長し、その相乗平均値（Ｄｍａｘ×ＤＶ－ｍａｘ）１／２を粒子径とした。顔料の平均一次粒子径は、この方法で１００個の粒子の粒子径を測定し、その算術平均値を意図する。 In addition, the average primary particle diameter of a pigment can be measured using a transmission electron microscope (Transmission Electron Microscope, TEM). As the transmission electron microscope, for example, a transmission microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used.
In the present specification, the average primary particle diameter of the pigment is the maximum length of a particle image obtained using a transmission electron microscope (Dmax: the maximum length at two points on the contour of the particle image), and the maximum vertical length ( DV-max: When an image is sandwiched between two straight lines parallel to the maximum length, the shortest length connecting the two straight lines vertically is measured, and the geometric mean value (Dmax × DV-max) 1 / 2 was the particle size. The average primary particle diameter of the pigment is determined by measuring the particle diameter of 100 particles by this method and intending the arithmetic average value thereof.
チタンブラック及び酸窒化ニオブの比表面積は特に制限されないが、チタンブラック及び酸窒化ニオブを撥水化剤で表面処理した後の撥水性が所定の性能となるために、ＢＥＴ（Ｂｒｕｎａｕｅｒ，　Ｅｍｍｅｔｔ，　Ｔｅｌｌｅｒ）法にて測定した値が５ｍ2／ｇ以上１５０ｍ2／ｇ以下であることが好ましく、２０ｍ2／ｇ以上１２０ｍ2／ｇ以下であることがより好ましい。
　チタンブラックの市販品の例としては、チタンブラック１０Ｓ、１２Ｓ、１３Ｒ、１３Ｍ、１３Ｍ－Ｃ、１３Ｒ、１３Ｒ－Ｎ、１３Ｍ－Ｔ（商品名、三菱マテリアル（株）製）、ティラック（Ｔｉｌａｃｋ）Ｄ（商品名、赤穂化成（株）製）、窒化チタン５０ｎｍ（商品名、和光純薬（株）製）などが挙げられる。 The specific surface area of titanium black and niobium oxynitride is not particularly limited. However, since the water repellency after surface treatment of titanium black and niobium oxynitride with a water repellent becomes a predetermined performance, BET (Brunauer, Emmett, Teller) The value measured by the method is preferably 5 m 2 / g or more and 150 m 2 / g or less, more preferably 20 m 2 / g or more and 120 m 2 / g or less.
Examples of commercially available titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade name, manufactured by Mitsubishi Materials Corporation), Tilack D (trade name, manufactured by Ako Kasei Co., Ltd.), titanium nitride 50 nm (trade name, manufactured by Wako Pure Chemical Industries, Ltd.), and the like.
　着色剤として、酸窒化チタン、窒化チタン又は酸窒化ニオブを使用することが好ましく、得られる硬化膜の耐湿性がより優れるという理由から、窒化チタン又は酸窒化ニオブがより好ましく、酸窒化ニオブが更に好ましい。これは、これらの着色剤が疎水性であるためと考えられる。 Titanium oxynitride, titanium nitride, or niobium oxynitride is preferably used as the colorant, and titanium nitride or niobium oxynitride is more preferable, and niobium oxynitride is more preferable because the resulting cured film has better moisture resistance. preferable. This is presumably because these colorants are hydrophobic.
　更に、チタンブラックを、チタンブラック及びＳｉ原子を含む被分散体として含有することも好ましい。
　この形態において、チタンブラックは、硬化性組成物中において被分散体として含有されるものであり、被分散体中のＳｉ原子とＴｉ原子との含有比（Ｓｉ／Ｔｉ）が質量換算で０．０５以上が好ましく、０．０５～０．５がより好ましく、０．０７～０．４が更に好ましい。
　ここで、上記被分散体は、チタンブラックが一次粒子の状態であるもの、凝集体（二次粒子）の状態であるものの双方を包含する。
　被分散体の含有比（Ｓｉ／Ｔｉ）を変更する（例えば、０．０５以上とする）ためには、以下のような手段を用いることができる。
　先ず、酸化チタンとシリカ粒子とを分散機を用いて分散することにより分散物を得て、この分散物を高温（例えば、８５０～１，０００℃）にて還元処理することにより、チタンブラック粒子を主成分とし、ＳｉとＴｉとを含有する被分散体を得ることができる。上記還元処理は、アンモニアなどの還元性ガスの雰囲気下で行うこともできる。
　酸化チタンとしては、ＴＴＯ－５１Ｎ（商品名、石原産業製）などが挙げられる。
　シリカ粒子の市販品としては、ＡＥＲＯＳＩＬ（登録商標）９０、１３０、１５０、２００、２５５、３００、３８０（商品名、エボニック製）などが挙げられる。
　酸化チタンとシリカ粒子との分散は、分散剤を用いてもよい。分散剤としては、後述する分散剤の欄で説明するものが挙げられる。
　上記の分散は溶剤中で行ってもよい。溶剤としては、水、有機溶剤が挙げられる。後述する有機溶剤の欄で説明するものが挙げられる。
　含有比（Ｓｉ／Ｔｉ）が、例えば、０．０５以上等に調整されたチタンブラックは、例えば、特開２００８－２６６０４５公報の段落番号〔０００５〕及び段落番号〔００１６〕～〔００２１〕に記載の方法により作製することができる。 Furthermore, it is also preferable to contain titanium black as a dispersion containing titanium black and Si atoms.
In this embodiment, titanium black is contained as a dispersion in the curable composition, and the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.00 on a mass basis. 05 or more is preferable, 0.05 to 0.5 is more preferable, and 0.07 to 0.4 is still more preferable.
Here, the to-be-dispersed bodies include both those in which titanium black is in the state of primary particles and those in the state of aggregates (secondary particles).
In order to change the content ratio (Si / Ti) of the object to be dispersed (for example, 0.05 or more), the following means can be used.
First, titanium black particles and silica particles are dispersed by using a disperser to obtain a dispersion, and the dispersion is subjected to reduction treatment at a high temperature (for example, 850 to 1,000 ° C.) to thereby obtain titanium black particles. It is possible to obtain a to-be-dispersed body containing Si and Ti as a main component. The reduction treatment can also be performed in an atmosphere of a reducing gas such as ammonia.
Examples of titanium oxide include TTO-51N (trade name, manufactured by Ishihara Sangyo).
Examples of commercially available silica particles include AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, 380 (trade name, manufactured by Evonik).
A dispersing agent may be used for the dispersion of titanium oxide and silica particles. Examples of the dispersant include those described in the section of the dispersant described later.
The dispersion may be performed in a solvent. Examples of the solvent include water and organic solvents. What is demonstrated in the column of the organic solvent mentioned later is mentioned.
Titanium black whose content ratio (Si / Ti) is adjusted to, for example, 0.05 or more is described, for example, in paragraph numbers [0005] and paragraphs [0016] to [0021] of JP-A-2008-266045. It can produce by the method of.
　チタンブラック及びＳｉ原子を含む被分散体中のＳｉ原子とＴｉ原子との含有比（Ｓｉ／Ｔｉ）を好適な範囲（例えば０．０５以上）に調整することで、この被分散体を含む硬化性組成物を用いて硬化膜を形成した際に、硬化膜の形成領域外における硬化性組成物由来の残渣物が低減される。なお、残渣物は、チタンブラック粒子、樹脂成分等の硬化性組成物に由来する成分を含むものである。
　残渣物が低減される理由は未だ明確ではないが、上記のような被分散体は粒子径が小さくなる傾向があり（例えば、粒子径３０ｎｍ以下）、更に、この被分散体のＳｉ原子が含まれる成分が増すことにより、膜全体の下地との吸着性が低減される。これが、硬化膜の形成における未硬化の硬化性組成物（特に、チタンブラック）の現像除去性の向上に寄与すると推測される。
　チタンブラックは、紫外光から赤外光までの広範囲に亘る波長領域の光に対する遮光性に優れることから、上記したチタンブラック及びＳｉ原子を含む被分散体（好ましくは含有比（Ｓｉ／Ｔｉ）が質量換算で０．０５以上であるもの）を用いて形成された硬化膜は優れた遮光性を発揮する。
　なお、被分散体中のＳｉ原子とＴｉ原子との含有比（Ｓｉ／Ｔｉ）は、例えば、特開２０１３－２４９４１７号公報の段落００３３に記載の方法（１－１）又は方法（１－２）を用いて測定できる。
　硬化性組成物を硬化して得られた硬化膜に含有される被分散体について、その被分散体中のＳｉ原子とＴｉ原子との含有比（Ｓｉ／Ｔｉ）が０．０５以上か否かを判断するには、特開２０１３－２４９４１７号公報の段落００３５に記載の方法（２）を用いることができる。 Curing including this dispersion by adjusting the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion including titanium black and Si atoms to a suitable range (for example, 0.05 or more). When a cured film is formed using the curable composition, residues derived from the curable composition outside the region where the cured film is formed are reduced. The residue includes components derived from a curable composition such as titanium black particles and a resin component.
The reason why the residue is reduced is not yet clear, but the above-described dispersion tends to have a small particle diameter (for example, a particle diameter of 30 nm or less), and further contains Si atoms of the dispersion. By increasing the amount of components to be absorbed, the adsorptivity with the entire film is reduced. This is presumed to contribute to the improvement of the development removability of an uncured curable composition (particularly titanium black) in the formation of a cured film.
Titanium black is excellent in light-shielding property for light in a wide wavelength range from ultraviolet light to infrared light. A cured film formed using a material having a mass conversion of 0.05 or more exhibits excellent light shielding properties.
The content ratio (Si / Ti) of Si atoms to Ti atoms in the dispersion is, for example, the method (1-1) or the method (1-2) described in paragraph 0033 of JP2013-249417A ).
Whether the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.05 or more with respect to the dispersion to be contained in the cured film obtained by curing the curable composition Can be determined by the method (2) described in paragraph 0035 of JP2013-249417A.
　チタンブラック及びＳｉ原子を含む被分散体において、チタンブラックは、上記したものを使用できる。
　この被分散体においては、チタンブラックと共に、分散性、着色性等を調整する目的で、Ｃｕ、Ｆｅ、Ｍｎ、Ｖ、Ｎｉ等の複合酸化物、酸化コバルト、酸化鉄、カーボンブラック、アニリンブラック等からなる黒色顔料を、１種又は２種以上組み合わせて用いてもよい。この場合、全被分散体中の５０質量％以上をチタンブラックからなる被分散体が占めることが好ましい。
　この被分散体においては、遮光性の調整等を目的として、本発明の効果を損なわない限りにおいて、チタンブラックと共に、他の着色剤（有機顔料及び／又は染料など）を所望により併用してもよい。
　以下、被分散体にＳｉ原子を導入する際に用いられる材料について述べる。被分散体にＳｉ原子を導入する際には、シリカなどのＳｉ含有物質を用いればよい。
　用いうるシリカとしては、沈降シリカ、フュームドシリカ、コロイダルシリカ、合成シリカなどを挙げることができ、これらを適宜選択して使用すればよい。
　更に、シリカ粒子の粒子径が硬化膜を形成した際の膜厚よりも小さい粒子径であると遮光性がより優れるため、微粒子タイプのシリカを用いることが好ましい。なお、微粒子タイプのシリカの例としては、例えば、特開２０１３－２４９４１７号公報の段落００３９に記載のシリカが挙げられ、これらの内容は本明細書に組み込まれる。 In the dispersion containing titanium black and Si atoms, the above-described titanium black can be used.
In this dispersion, for the purpose of adjusting dispersibility, colorability, etc. together with titanium black, complex oxides such as Cu, Fe, Mn, V, Ni, cobalt oxide, iron oxide, carbon black, aniline black, etc. You may use the black pigment which consists of 1 type (s) or 2 or more types in combination. In this case, it is preferable that 50% by mass or more of the total dispersion is occupied by the dispersion made of titanium black.
In this dispersion, other colorants (such as organic pigments and / or dyes) may be used in combination with titanium black, if desired, for the purpose of adjusting the light shielding property and the like, as long as the effects of the present invention are not impaired. Good.
Hereinafter, materials used for introducing Si atoms into the dispersion will be described. When Si atoms are introduced into the dispersion, a Si-containing material such as silica may be used.
Examples of silica that can be used include precipitated silica, fumed silica, colloidal silica, and synthetic silica. These may be appropriately selected and used.
Furthermore, if the particle diameter of the silica particles is smaller than the film thickness when the cured film is formed, the light-shielding property is more excellent, so it is preferable to use fine particle type silica. Examples of the fine particle type silica include silica described in paragraph 0039 of JP2013-249417A, and the contents thereof are incorporated in the present specification.
　
　硬化性組成物は、顔料としてタングステン化合物、及び／又は金属ホウ化物を使用できる。
　タングステン化合物、及び金属ホウ化物は、赤外線（波長が約８００～１，２００ｎｍの光）に対しては吸収が高く（すなわち、赤外線に対する遮光性（遮蔽性）が高く）、可視光に対しては吸収が低い赤外線遮蔽材である。このため、硬化性組成物は、タングステン化合物、及び／又は金属ホウ化物を含有することで、赤外領域における遮光性が高く、可視光領域における透光性が高いパターンを形成できる。
　タングステン化合物、及び金属ホウ化物は、画像形成に用いられる、高圧水銀灯、ＫｒＦ、ＡｒＦなどの露光に用いられる可視域より短波の光に対しても吸収が小さい。このため、前述の重合性化合物、光重合開始剤、及び後述のアルカリ可溶性樹脂と組み合わされることにより、優れたパターンが得られるとともに、パターン形成において、現像残渣をより抑制できる。
The curable composition can use a tungsten compound and / or a metal boride as a pigment.
Tungsten compounds and metal borides have high absorption with respect to infrared rays (light having a wavelength of about 800 to 1,200 nm) (that is, they have high light shielding properties (shielding properties) with respect to infrared rays), and with respect to visible light. Infrared shielding material with low absorption. For this reason, a curable composition can form a pattern with high light-shielding property in an infrared region, and high translucency in a visible light region by containing a tungsten compound and / or a metal boride.
Tungsten compounds and metal borides have low absorption even for light shorter than the visible range used for exposure of high pressure mercury lamps, KrF, ArF and the like used for image formation. For this reason, by combining with the above-mentioned polymerizable compound, photopolymerization initiator, and alkali-soluble resin described later, an excellent pattern can be obtained, and development residue can be further suppressed in pattern formation.
　タングステン化合物としては、酸化タングステン系化合物、ホウ化タングステン系化合物、硫化タングステン系化合物などを挙げることができ、下記一般式（組成式）（Ｉ）で表される酸化タングステン系化合物が好ましい。
ＭｘＷｙＯｚ・・・（Ｉ）
　Ｍは金属、Ｗはタングステン、Ｏは酸素を表す。
　０．００１≦ｘ／ｙ≦１．１
　２．２≦ｚ／ｙ≦３．０ Examples of the tungsten compound include a tungsten oxide compound, a tungsten boride compound, a tungsten sulfide compound, and the like, and a tungsten oxide compound represented by the following general formula (composition formula) (I) is preferable.
M x W y O z (I)
M represents a metal, W represents tungsten, and O represents oxygen.
0.001 ≦ x / y ≦ 1.1
2.2 ≦ z / y ≦ 3.0
　Ｍの金属としては、例えば、アルカリ金属、アルカリ土類金属、Ｍｇ、Ｚｒ、Ｃｒ、Ｍｎ、Ｆｅ、Ｒｕ、Ｃｏ、Ｒｈ、Ｉｒ、Ｎｉ、Ｐｄ、Ｐｔ、Ｃｕ、Ａｇ、Ａｕ、Ｚｎ、Ｃｄ、Ａｌ、Ｇａ、Ｉｎ、Ｔｌ、Ｓｎ、Ｐｂ、Ｔｉ、Ｎｂ、Ｖ、Ｍｏ、Ｔａ、Ｒｅ、Ｂｅ、Ｈｆ、Ｏｓ、Ｂｉ、Ｒｂ、Ｃｓなどが挙げられるが、アルカリ金属が好ましい。Ｍの金属は１種でも２種以上でもよい。 As the metal of M, for example, alkali metal, alkaline earth metal, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, Rb, Cs and the like can be mentioned, and alkali metals are preferable. 1 type or 2 types or more may be sufficient as the metal of M.
　Ｍはアルカリ金属であることが好ましく、Ｒｂ又はＣｓがより好ましく、Ｃｓが更に好ましい。 M is preferably an alkali metal, more preferably Rb or Cs, and even more preferably Cs.
　ｘ／ｙが０．００１以上であることにより、赤外線を十分に遮蔽することができ、１．１以下であることにより、タングステン化合物中に不純物相が生成されることをより確実に回避することできる。
　ｚ／ｙが２．２以上であることにより、材料としての化学的安定性をより向上させることができ、３．０以下であることにより赤外線を十分に遮蔽することができる。 When x / y is 0.001 or more, infrared rays can be sufficiently shielded, and when it is 1.1 or less, generation of an impurity phase in the tungsten compound can be more reliably avoided. it can.
When z / y is 2.2 or more, chemical stability as a material can be further improved, and when it is 3.0 or less, infrared rays can be sufficiently shielded.
　一般式（Ｉ）で表される酸化タングステン系化合物の具体例としては、Ｃｓ０．３３ＷＯ３、Ｒｂ０．３３ＷＯ３、Ｋ０．３３ＷＯ３、Ｂａ０．３３ＷＯ３などを挙げることができ、Ｃｓ０．３３ＷＯ３又はＲｂ０．３３ＷＯ３が好ましく、Ｃｓ０．３３ＷＯ３がより好ましい。 Specific examples of the tungsten oxide compound represented by the general formula (I) include Cs 0.33 WO 3 , Rb 0.33 WO 3 , K 0.33 WO 3 , Ba 0.33 WO 3 and the like. Cs 0.33 WO 3 or Rb 0.33 WO 3 is preferable, and Cs 0.33 WO 3 is more preferable.
　タングステン化合物は微粒子であることが好ましい。タングステン微粒子の平均一次粒子径は、８００ｎｍ以下であることが好ましく、４００ｎｍ以下であることがより好ましく、２００ｎｍ以下であることが更に好ましい。平均一次粒子径がこのような範囲であることによって、タングステン微粒子が光散乱によって可視光を遮断しにくくなることから、可視光領域における透光性をより確実にすることができる。光散乱を回避する観点からは、平均一次粒子径は小さいほど好ましいが、製造時における取り扱い容易性などの理由から、タングステン微粒子の平均一次粒子径は、通常、１ｎｍ以上である。 The tungsten compound is preferably fine particles. The average primary particle diameter of the tungsten fine particles is preferably 800 nm or less, more preferably 400 nm or less, and even more preferably 200 nm or less. When the average primary particle diameter is in such a range, it becomes difficult for the tungsten fine particles to block visible light by light scattering, and thus the translucency in the visible light region can be further ensured. From the viewpoint of avoiding light scattering, the average primary particle size is preferably as small as possible. However, for reasons such as ease of handling during production, the average primary particle size of the tungsten fine particles is usually 1 nm or more.
　タングステン化合物は２種以上を使用することが可能である。 Two or more tungsten compounds can be used.
　タングステン化合物は市販品として入手可能である。タングステン化合物が、例えば酸化タングステン系化合物である場合、酸化タングステン系化合物は、タングステン化合物を不活性ガス雰囲気又は還元性ガス雰囲気中で熱処理する方法により得ることができる（特許第４０９６２０５号公報を参照）。
　酸化タングステン系化合物は、例えば、住友金属鉱山株式会社製のＹＭＦ－０２などのタングステン微粒子の分散物としても入手可能である。 Tungsten compounds are commercially available. When the tungsten compound is, for example, a tungsten oxide compound, the tungsten oxide compound can be obtained by a method of heat-treating the tungsten compound in an inert gas atmosphere or a reducing gas atmosphere (see Japanese Patent No. 4096205). .
The tungsten oxide compound is also available as a dispersion of tungsten fine particles such as YMF-02 manufactured by Sumitomo Metal Mining Co., Ltd.
　金属ホウ化物としては、ホウ化ランタン（ＬａＢ６）、ホウ化プラセオジウム（ＰｒＢ６）、ホウ化ネオジウム（ＮｄＢ６）、ホウ化セリウム（ＣｅＢ６）、ホウ化イットリウム（ＹＢ６）、ホウ化チタン（ＴｉＢ２）、ホウ化ジルコニウム（ＺｒＢ２）、ホウ化ハフニウム（ＨｆＢ２）、ホウ化バナジウム（ＶＢ２）、ホウ化タンタル（ＴａＢ２）、ホウ化クロム（ＣｒＢ、ＣｒＢ２）、ホウ化モリブデン（ＭｏＢ２、Ｍｏ２Ｂ５、ＭｏＢ）、ホウ化タングステン（Ｗ２Ｂ５）などの１種又は２種以上を挙げることができ、ホウ化ランタン（ＬａＢ６）が好ましい。 As the metal boride, lanthanum boride (LaB 6 ), praseodymium boride (PrB 6 ), neodymium boride (NdB 6 ), cerium boride (CeB 6 ), yttrium boride (YB 6 ), titanium boride ( TiB 2 ), zirconium boride (ZrB 2 ), hafnium boride (HfB 2 ), vanadium boride (VB 2 ), tantalum boride (TaB 2 ), chromium boride (CrB, CrB 2 ), molybdenum boride ( One or more of MoB 2 , Mo 2 B 5 , MoB), tungsten boride (W 2 B 5 ) and the like can be mentioned, and lanthanum boride (LaB 6 ) is preferable.
　金属ホウ化物は微粒子であることが好ましい。金属ホウ化物微粒子の平均一次粒子径は、８００ｎｍ以下であることが好ましく、３００ｎｍ以下であることがより好ましく、１００ｎｍ以下であることが更に好ましい。平均一次粒子径がこのような範囲であることによって、金属ホウ化物微粒子が光散乱によって可視光を遮断しにくくなることから、可視光領域における透光性をより確実にすることができる。光散乱を回避する観点からは、平均一次粒子径は小さいほど好ましいが、製造時における取り扱い容易性などの理由から、金属ホウ化物微粒子の平均一次粒子径は、通常、１ｎｍ以上である。 The metal boride is preferably fine particles. The average primary particle diameter of the metal boride fine particles is preferably 800 nm or less, more preferably 300 nm or less, and further preferably 100 nm or less. When the average primary particle diameter is in such a range, the metal boride fine particles are less likely to block visible light by light scattering, and thus the translucency in the visible light region can be further ensured. From the viewpoint of avoiding light scattering, the average primary particle size is preferably as small as possible. However, for reasons such as ease of handling during production, the average primary particle size of the metal boride fine particles is usually 1 nm or more.
　金属ホウ化物は２種以上を使用してもよい。 Two or more metal borides may be used.
　金属ホウ化物は市販品として入手可能であり、例えば、住友金属鉱山株式会社製のＫＨＦ－７等の金属ホウ化物微粒子の分散物としても、入手可能である。 The metal boride is available as a commercial product, for example, as a dispersion of metal boride fine particles such as KHF-7 manufactured by Sumitomo Metal Mining Co., Ltd.
・・チタン窒化物含有粒子
　無機顔料としては、Ｆｅ原子を含むチタン窒化物含有粒子を用いることもできる。チタン窒化物含有粒子の製造には、通常、気相反応法が用いられ、具体的には電気炉法及び熱プラズマ法等が挙げられる。これらの製法の中でも、不純物の混入が少ない点、粒子径が揃いやすい点、及び、生産性が高い点などの理由から、熱プラズマ法が好ましい。
　熱プラズマの発生方法としては、直流アーク放電、多相アーク放電、高周波（ＲＦ）プラズマ、及び、ハイブリッドプラズマ等が挙げられ、電極からの不純物の混入が少ない高周波プラズマが好ましい。熱プラズマ法によるチタン窒化物含有微粒子の具体的な製造方法としては、例えば、チタン粉末を高周波熱プラズマにより蒸発させ、窒素をキャリアガスとして装置内に導入し、冷却過程にてチタン粉末を窒化させ、チタン窒化物含有粒子を合成する方法等が挙げられる。なお、熱プラズマ法は、上記に限定されない。 .. Titanium nitride-containing particles As the inorganic pigment, titanium nitride-containing particles containing Fe atoms can also be used. For production of titanium nitride-containing particles, a gas phase reaction method is usually used, and specific examples include an electric furnace method and a thermal plasma method. Among these production methods, the thermal plasma method is preferable because it is less contaminated with impurities, easily has a uniform particle diameter, and has high productivity.
Examples of the method for generating thermal plasma include direct current arc discharge, multiphase arc discharge, radio frequency (RF) plasma, hybrid plasma, and the like, and high frequency plasma with less impurities from the electrodes is preferable. As a specific method for producing titanium nitride-containing fine particles by the thermal plasma method, for example, titanium powder is evaporated by high-frequency thermal plasma, nitrogen is introduced into the apparatus as a carrier gas, and titanium powder is nitrided in the cooling process. And a method of synthesizing titanium nitride-containing particles. The thermal plasma method is not limited to the above.
　チタン窒化物含有粒子の製造方法としては、特に限定されないが、国際公開第２０１０／１４７０９８号の段落＜００３７＞～＜００８９＞に記載の製造方法を参照することができる。例えば、国際公開第２０１０／１４７０９８号のＡｇ粉末に代えて、後述するＦｅを含む成分及び／又はＳｉを含む成分を用いて、これとチタン粉末材料（チタン粒子）とを混合したものを原料として、本発明の硬化性組成物に含まれるチタン窒化物含有粒子を製造することができる。 The method for producing titanium nitride-containing particles is not particularly limited, but the production methods described in paragraphs <0037> to <0089> of International Publication No. 2010/147098 can be referred to. For example, instead of the Ag powder of International Publication No. 2010/147098, using a component containing Fe and / or a component containing Si, which will be described later, and a mixture of this and a titanium powder material (titanium particles) as a raw material The titanium nitride-containing particles contained in the curable composition of the present invention can be produced.
　チタン窒化物含有粒子の製造に使用するチタン粉末材料（チタン粒子）は、高純度のものであることが好ましい。チタン粉末材料は、特に限定されないが、チタン元素の純度が９９．９９％以上であるものが好ましく、９９．９９９％以上のものがより好ましく用いられる。 The titanium powder material (titanium particles) used for the production of titanium nitride-containing particles is preferably of high purity. The titanium powder material is not particularly limited, but a titanium element having a purity of 99.99% or more is preferable, and a material having 99.999% or more is more preferably used.
　チタン窒化物含有粒子の製造に使用するチタン粉末材料（チタン粒子）は、チタン原子以外の原子を含有する場合がある。チタン粉末材料に含まれ得る他の原子としては、例えばＦｅ原子及びＳｉ原子などが挙げられる。
　チタン粉末材料がＦｅ原子を含有する場合には、Ｆｅ原子の含有量は、チタン粉末材料の全質量に対して、０．００１質量％超であることが好ましい。
　チタン粉末材料がＳｉ原子を含有する場合には、Ｓｉ原子の含有量が、チタン粉末材料全質量に対して、０．００２質量％超０．３質量％未満であることが好ましく、０．０１～０．１５質量％であることがより好ましく、０．０２～０．１質量％であることが更に好ましい。Ｓｉ原子の含有量が０．００２質量％超であることで、硬化膜のパターニング性がより向上する。Ｓｉ原子の含有量が０．３質量％未満であることで、得られるチタン窒化物含有粒子の最表層の極性がより安定化する。これにより、チタン窒化物含有粒子を分散させる際にチタン窒化物含有粒子への分散剤の吸着性が良化して、チタン窒化物含有粒子の未分散物が低減し、パーティクル発生を抑制できると考えられる。
　チタン窒化物含有粒子の製造に使用するチタン粉末材料（チタン粒子）中の水分は、チタン粉末材料の全質量に対して、１質量％未満であることが好ましく、０．１質量％未満であることがより好ましく、実質的に含まないことが更に好ましい。 The titanium powder material (titanium particles) used for the production of titanium nitride-containing particles may contain atoms other than titanium atoms. Examples of other atoms that can be contained in the titanium powder material include Fe atoms and Si atoms.
When the titanium powder material contains Fe atoms, the content of Fe atoms is preferably more than 0.001% by mass with respect to the total mass of the titanium powder material.
When the titanium powder material contains Si atoms, the content of Si atoms is preferably more than 0.002% by mass and less than 0.3% by mass with respect to the total mass of the titanium powder material. The content is more preferably from 0.15% by mass, and even more preferably from 0.02 to 0.1% by mass. When the content of Si atoms is more than 0.002% by mass, the patterning property of the cured film is further improved. When the content of Si atoms is less than 0.3% by mass, the polarity of the outermost layer of the obtained titanium nitride-containing particles is further stabilized. As a result, when the titanium nitride-containing particles are dispersed, the adsorptivity of the dispersant to the titanium nitride-containing particles is improved, the undispersed titanium nitride-containing particles are reduced, and the generation of particles can be suppressed. It is done.
The water content in the titanium powder material (titanium particles) used for the production of titanium nitride-containing particles is preferably less than 1% by mass and less than 0.1% by mass with respect to the total mass of the titanium powder material. It is more preferable that it is not substantially contained.
　チタン窒化物含有粒子は、熱プラズマ法を用いて得ることにより、ＣｕＫα線をＸ線源とした場合の（２００）面に由来するピークの回折角２θ（詳細は後述する）を、４２．６°超４３．５°以下の範囲に調整することが容易になる。 The titanium nitride-containing particles are obtained by using a thermal plasma method, whereby a diffraction angle 2θ of a peak derived from the (200) plane when CuKα rays are used as an X-ray source (details will be described later) is 42.6. It becomes easy to adjust to a range of more than 4 ° to 43.5 °.
　チタン窒化物含有粒子にＦｅ原子を含有させる方法としては、特に限定されず、例えば、上述したチタン窒化物含有粒子の原料として用いられるチタン粒子（チタン粉末）を得る段階において、Ｆｅ原子を導入する方法などが挙げられる。より詳細には、クロール法などによりチタンを製造する際に、反応容器としてステンレス鋼などのＦｅ原子を含有する材料から構成されるものを用いたり、チタンを破砕する際のプレス機及び粉砕機の材料としてＦｅ原子を含有するものを用いたりすることによって、チタン粒子の表面にＦｅ原子を付着させることができる。
　チタン窒化物含有粒子の製造に熱プラズマ法を用いる場合には、原料であるチタン粒子の他に、Ｆｅ粒子、Ｆｅ酸化物などの成分を添加して、これらを熱プラズマ法によって窒化することによって、チタン窒化物含有粒子にＦｅ原子を含有させることができる。
　チタン窒化物含有粒子中に含まれるＦｅ原子は、イオン、金属化合物（錯化合物も含む）、金属間化合物、合金、酸化物、複合酸化物、窒化物、酸窒化物、硫化物及び酸硫化物など、いずれの形態で含まれていてもよい。チタン窒化物含有粒子中に含まれているＦｅ原子は、結晶格子間位置の不純物として存在していてもよいし、結晶粒界にアモルファス状態で不純物として存在していてもよい。 The method for causing the titanium nitride-containing particles to contain Fe atoms is not particularly limited. For example, in the stage of obtaining titanium particles (titanium powder) used as a raw material for the above-described titanium nitride-containing particles, Fe atoms are introduced. The method etc. are mentioned. More specifically, when titanium is produced by the crawl method or the like, a reaction vessel made of a material containing Fe atoms such as stainless steel is used, or a press machine and a crusher for crushing titanium are used. By using a material containing Fe atoms as a material, Fe atoms can be attached to the surface of the titanium particles.
When the thermal plasma method is used for the production of titanium nitride-containing particles, in addition to the titanium particles as raw materials, components such as Fe particles and Fe oxide are added, and these are nitrided by the thermal plasma method. The titanium nitride-containing particles can contain Fe atoms.
Fe atoms contained in titanium nitride-containing particles are ions, metal compounds (including complex compounds), intermetallic compounds, alloys, oxides, composite oxides, nitrides, oxynitrides, sulfides, and oxysulfides. And may be included in any form. The Fe atom contained in the titanium nitride-containing particle may exist as an impurity at a position between crystal lattices, or may exist as an impurity in an amorphous state at a crystal grain boundary.
本発明者は、鋭意検討の結果、チタン窒化物含有粒子中のＦｅ原子の含有量が、パターニング性及び電極の防食性に関連することを知見した。チタン窒化物含有粒子中に含まれるＦｅ原子は、電極及び基板に対する密着性に優れており、チタン窒化物含有粒子中のチタン窒化物は、Ｆｅ原子を介して電極及び基板に付着すると考えられる。現像処理などの硬化膜のパターニング後、Ｆｅ原子は電極及び基板上に残留し、チタン窒化物は除去されやすいと考えられる。そのため、チタン窒化物含有粒子中のＦｅ原子の含有量を所定量以上にすることで、硬化膜のパターニング性が向上すると推測される。一方で、チタン窒化物含有粒子中に含まれるＦｅ原子の含有量が多すぎると、電極及び基板上に残留するＦｅ原子の量が増加し、電極の腐食の原因になると考えられる。そのため、チタン窒化物含有粒子中のＦｅ原子の含有量を所定量以下にすることで、電極の防食性が向上すると推測される。
　チタン窒化物含有粒子中におけるＦｅ原子の含有量は、チタン窒化物含有粒子全質量に対して、０．００１質量％超０．４質量％未満であることが好ましい。なかでも、０．０１～０．２質量％であることがより好ましく、０．０２～０．１質量％であることが更に好ましい。Ｆｅ原子の含有量が０．００１質量％超であることで、硬化膜のパターニング性がより向上する。Ｆｅ原子の含有量が０．４質量％未満であることで、硬化膜による電極の防食性がより向上する（硬化膜が電極を腐食することを抑制できる）。すなわち、チタン窒化物含有粒子中におけるＦｅ原子の含有量が上記範囲内にあることで、優れた硬化膜のパターニング性及び電極の防食性を得ることができる。
チタン窒化物含有粒子中におけるＦｅ原子の含有量は、ＩＣＰ（Inductively Coupled Plasma；高周波誘導結合プラズマ）発光分光分析法により測定することができる。 As a result of intensive studies, the present inventor has found that the content of Fe atoms in the titanium nitride-containing particles is related to the patterning property and the corrosion resistance of the electrode. The Fe atoms contained in the titanium nitride-containing particles are excellent in adhesion to the electrode and the substrate, and the titanium nitride in the titanium nitride-containing particles is considered to adhere to the electrode and the substrate through the Fe atoms. After patterning of the cured film such as development, Fe atoms remain on the electrode and the substrate, and titanium nitride is considered to be easily removed. Therefore, it is presumed that the patterning property of the cured film is improved by setting the content of Fe atoms in the titanium nitride-containing particles to a predetermined amount or more. On the other hand, if the content of Fe atoms contained in the titanium nitride-containing particles is too large, the amount of Fe atoms remaining on the electrode and the substrate increases, which is considered to cause corrosion of the electrode. Therefore, it is estimated that the corrosion resistance of the electrode is improved by setting the content of Fe atoms in the titanium nitride-containing particles to a predetermined amount or less.
The content of Fe atoms in the titanium nitride-containing particles is preferably more than 0.001% by mass and less than 0.4% by mass with respect to the total mass of the titanium nitride-containing particles. Of these, 0.01 to 0.2% by mass is more preferable, and 0.02 to 0.1% by mass is even more preferable. When the content of Fe atoms is more than 0.001% by mass, the patterning property of the cured film is further improved. When the content of Fe atoms is less than 0.4% by mass, the corrosion resistance of the electrode by the cured film is further improved (the cured film can be inhibited from corroding the electrode). That is, when the content of Fe atoms in the titanium nitride-containing particles is within the above range, excellent patterning properties of the cured film and anticorrosion properties of the electrodes can be obtained.
The content of Fe atoms in the titanium nitride-containing particles can be measured by ICP (Inductively Coupled Plasma) emission spectroscopy.
　チタン窒化物含有粒子は、更にＳｉ原子（ケイ素原子）を含有することが好ましい。これにより、硬化膜のパターニング性がより向上する。Ｓｉ原子を含有することによりパターニング性が向上する理由としては、上述したＦｅ原子と同様と考えられる。
　チタン窒化物含有粒子中におけるＳｉ原子の含有量は、チタン窒化物含有粒子全質量に対して、０．００２質量％超０．３質量％未満であることが好ましく、０．０１～０．１５質量％であることがより好ましく、０．０２～０．１質量％であることが更に好ましい。Ｓｉ原子の含有量が０．００２質量％超であることで、硬化膜のパターニング性がより向上する。Ｓｉ原子の含有量が０．３質量％未満であることで、チタン窒化物含有粒子の最表層の極性がより安定化する。これにより、チタン窒化物含有粒子を分散させる際にチタン窒化物含有粒子への分散剤の吸着性が良化して、チタン窒化物含有粒子の未分散物が低減し、パーティクル発生を抑制できると考えられる。
チタン窒化物含有粒子中におけるＳｉ原子の含有量は、上述したＦｅ原子と同様の方法によって測定することができる。 The titanium nitride-containing particles preferably further contain Si atoms (silicon atoms). Thereby, the patterning property of a cured film improves more. The reason why the patterning property is improved by containing Si atoms is considered to be the same as the above-described Fe atoms.
The content of Si atoms in the titanium nitride-containing particles is preferably more than 0.002% by mass and less than 0.3% by mass with respect to the total mass of the titanium nitride-containing particles, and 0.01 to 0.15 The mass is more preferably 0.02 to 0.1% by mass. When the content of Si atoms is more than 0.002% by mass, the patterning property of the cured film is further improved. When the Si atom content is less than 0.3% by mass, the polarity of the outermost layer of the titanium nitride-containing particles is further stabilized. As a result, when the titanium nitride-containing particles are dispersed, the adsorptivity of the dispersant to the titanium nitride-containing particles is improved, the undispersed titanium nitride-containing particles are reduced, and the generation of particles can be suppressed. It is done.
The content of Si atoms in the titanium nitride-containing particles can be measured by the same method as that for Fe atoms.
　チタン窒化物含有粒子にＳｉ原子を含有させる方法としては、特に限定されず、例えば、上述したチタン窒化物含有粒子の原料として用いられるチタン粒子（チタン粉末）を得る段階において、Ｓｉ原子を導入する方法などが挙げられる。より詳細には、クロール法などによりチタンを製造する際に、反応容器としてＳｉ原子を含有する材料から構成されるものを用いたり、チタンを破砕する際のプレス機及び粉砕機の材料としてＳｉ原子を含有するものを用いたりすることによって、チタン粒子の表面にＳｉ原子を付着させることができる。
　チタン窒化物含有粒子の製造に熱プラズマ法を用いる場合には、原料であるチタン粒子の他に、Ｓｉ粒子、Ｓｉ酸化物などの成分を添加して、これらを熱プラズマ法によって窒化することによって、チタン窒化物含有粒子にＳｉ原子を含有させることができる。
　チタン窒化物含有粒子中に含まれるＳｉ原子は、イオン、金属化合物（錯化合物も含む）、金属間化合物、合金、酸化物、複合酸化物、窒化物、酸窒化物、硫化物及び酸硫化物など、いずれの形態で含まれていてもよい。チタン窒化物含有粒子中に含まれるＳｉ原子は、結晶格子間位置の不純物として存在していてもよいし、結晶粒界にアモルファス状態で不純物として存在していてもよい。 The method for incorporating Si atoms into the titanium nitride-containing particles is not particularly limited. For example, Si atoms are introduced at the stage of obtaining titanium particles (titanium powder) used as a raw material for the above-described titanium nitride-containing particles. The method etc. are mentioned. More specifically, when titanium is produced by a crawl method or the like, a reaction vessel made of a material containing Si atoms is used, or Si atom is used as a material for a press machine and a crusher when crushing titanium. Si atoms can be attached to the surface of the titanium particles.
When the thermal plasma method is used to manufacture titanium nitride-containing particles, in addition to the titanium particles that are raw materials, components such as Si particles and Si oxide are added, and these are nitrided by the thermal plasma method. The titanium nitride-containing particles can contain Si atoms.
Si atoms contained in titanium nitride-containing particles are ions, metal compounds (including complex compounds), intermetallic compounds, alloys, oxides, complex oxides, nitrides, oxynitrides, sulfides, and oxysulfides. And may be included in any form. Si atoms contained in the titanium nitride-containing particles may be present as impurities at the position between the crystal lattices, or may be present as impurities in the amorphous state at the crystal grain boundaries.
　チタン窒化物含有粒子中のチタン原子（Ｔｉ原子）の含有量は、チタン窒化物含有粒子の全質量に対して、１０～８５質量％であることが好ましく、１５～７５質量％であることがより好ましく、２０～７０質量％であることが更に好ましい。チタン窒化物含有粒子中のＴｉ原子の含有量は、ＩＣＰ発光分光分析法により測定できる。
　チタン窒化物含有粒子中の窒素原子（Ｎ原子）の含有量は、チタン窒化物含有粒子の全質量に対して、３～６０質量％であることが好ましく、５～５０質量％であることがより好ましく、１０～４０質量％であることが更に好ましい。窒素原子の含有量は不活性ガス融解－熱伝導度法により分析することができる。
　チタン窒化物含有粒子は、主成分としてチタン窒化物（ＴｉＮ）を含み、通常、その合成時に酸素が混入する場合、及び、粒子径が小さい場合などに顕著になるが、粒子表面の酸化などにより、一部酸素原子を含有してもよい。
　チタン窒化物含有粒子中の酸素原子の含有量は、チタン窒化物含有粒子の全質量に対して、１～４０質量％であることが好ましく、１～３５質量％であることがより好ましく、５～３０質量％であることが更に好ましい。酸素原子の含有量は、不活性ガス融解－赤外線吸収法により分析することができる。 The content of titanium atoms (Ti atoms) in the titanium nitride-containing particles is preferably 10 to 85% by mass and preferably 15 to 75% by mass with respect to the total mass of the titanium nitride-containing particles. More preferred is 20 to 70% by mass. The content of Ti atoms in the titanium nitride-containing particles can be measured by ICP emission spectroscopy.
The content of nitrogen atoms (N atoms) in the titanium nitride-containing particles is preferably 3 to 60% by mass and preferably 5 to 50% by mass with respect to the total mass of the titanium nitride-containing particles. More preferably, it is 10 to 40% by mass. The nitrogen atom content can be analyzed by an inert gas melting-thermal conductivity method.
Titanium nitride-containing particles contain titanium nitride (TiN) as a main component, and are usually noticeable when oxygen is mixed during the synthesis and when the particle size is small. , A part of oxygen atoms may be contained.
The content of oxygen atoms in the titanium nitride-containing particles is preferably 1 to 40% by mass, more preferably 1 to 35% by mass with respect to the total mass of the titanium nitride-containing particles. More preferably, it is ˜30% by mass. The oxygen atom content can be analyzed by an inert gas melting-infrared absorption method.
　分散安定性及び遮光性の観点から、チタン窒化物含有粒子の比表面積は５ｍ２／ｇ以上１００ｍ２／ｇ以下が好ましく、１０ｍ２／ｇ以上６０ｍ２／ｇ以下がより好ましい。比表面積はＢＥＴ（Brunauer，Emmett，Teller）法により求めることができる。 From the viewpoint of dispersion stability and light-shielding property, the specific surface area is preferably 5 m 2 / g or more 100 m 2 / g or less of titanium nitride-containing particles, 10 m 2 / g or more 60 m 2 / g or less is more preferable. The specific surface area can be determined by the BET (Brunauer, Emmett, Teller) method.
　チタン窒化物含有粒子は、チタン窒化物粒子と金属微粒子からなる複合微粒子であってもよい。
　複合微粒子とは、チタン窒化物粒子と金属微粒子が複合化しているか、高度に分散した状態にある粒子のことをいう。ここで、「複合化している」とは、チタン窒化物と金属の両成分によって粒子が構成されていることを意味し、「高度に分散した状態」とは、チタン窒化物粒子と金属粒子がそれぞれ個別で存在し、かつ少量成分の粒子が凝集せず均一、一様に分散していることを意味する。
　金属微粒子としては特に限定されず、例えば、銅、銀、金、白金、パラジウム、ニッケル、錫、コバルト、ロジウム、イリジウム、ルテニウム、オスミウム、マンガン、モリブデン、タングステン、ニオブ、タンタル、カルシウム、チタン、ビスマス、アンチモン及び鉛、並びにこれらの合金、から選ばれる少なくとも１種が挙げられる。中でも、銅、銀、金、白金、パラジウム、ニッケル、錫、コバルト、ロジウム及びイリジウム、並びにこれらの合金から選ばれる少なくとも１種であることが好ましく、銅、銀、金、白金及び錫、並びにこれらの合金から選ばれる少なくとも１種であることがより好ましい。耐湿性により優れる観点から、銀であることが好ましい。
　チタン窒化物含有粒子における金属微粒子の含有量としては、チタン窒化物含有粒子の全質量に対して５質量％以上５０質量％以下であることが好ましく、１０質量％以上３０質量％以下であることがより好ましい。 The titanium nitride-containing particles may be composite fine particles composed of titanium nitride particles and metal fine particles.
Composite fine particles refer to particles in which titanium nitride particles and metal fine particles are complexed or in a highly dispersed state. Here, “composite” means that the particles are composed of both titanium nitride and metal components, and “highly dispersed” means that the titanium nitride particles and metal particles are It means that the particles exist individually and the small amount of particles are not aggregated and are uniformly and uniformly dispersed.
The metal fine particles are not particularly limited. For example, copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, calcium, titanium, bismuth. , Antimony and lead, and alloys thereof, at least one selected from these. Among these, at least one selected from copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium and iridium, and alloys thereof is preferable, and copper, silver, gold, platinum and tin, and these More preferably, it is at least one selected from these alloys. From the viewpoint of better moisture resistance, silver is preferred.
The content of the metal fine particles in the titanium nitride-containing particles is preferably 5% by mass or more and 50% by mass or less, and preferably 10% by mass or more and 30% by mass or less with respect to the total mass of the titanium nitride-containing particles. Is more preferable.
　チタン窒化物含有粒子は、ＣｕＫα線をＸ線源とした場合の（２００）面に由来するピークの回折角２θが４２．６°超４３．５°以下であることが好ましい。このような特徴をもつチタン窒化物含有粒子を含有する硬化性組成物を用いて得られる硬化膜（例えば、ブラックマトリクスなど）は、高いＯＤ（optical density）値を達成することが可能となる。 The titanium nitride-containing particles preferably have a diffraction angle 2θ of a peak derived from the (200) plane when CuKα rays are used as an X-ray source and more than 42.6 ° and 43.5 ° or less. A cured film (for example, a black matrix) obtained by using a curable composition containing titanium nitride-containing particles having such characteristics can achieve a high OD (optical density) value.
　ＣｕＫα線をＸ線源としてチタン化合物のＸ線回折スペクトルを測定した場合において、最も強度の強いピークとしてＴｉＮは（２００）面に由来するピークが２θ＝４２．５°近傍に、ＴｉＯは（２００）面に由来するピークが２θ＝４３．４°近傍にみられる。一方、最も強度の強いピークではないがアナターゼ型ＴｉＯ２は（２００）面に由来するピークは２θ＝４８．１°近傍に、ルチル型ＴｉＯ２は（２００）面に由来するピークは２θ＝３９．２°近傍に観測される。よって、酸素原子を多く含有する結晶状態であるほどピーク位置は４２．５°に対して高角度側にシフトする。 When an X-ray diffraction spectrum of a titanium compound is measured using CuKα rays as an X-ray source, TiN has a peak derived from the (200) plane as a strongest peak, and TiO has a (200 ) A peak derived from the surface is seen in the vicinity of 2θ = 43.4 °. On the other hand, although not the strongest peak, the peak derived from the (200) plane of anatase TiO 2 is in the vicinity of 2θ = 48.1 °, and the peak derived from the (200) plane of rutile TiO 2 is 2θ = 39. Observed around 2 °. Therefore, the peak position shifts to the higher angle side with respect to 42.5 ° as the crystal state contains more oxygen atoms.
　チタン窒化物含有粒子の（２００）面に由来するピークの回折角２θは、粒子の経時安定性の観点から、４２．６°超４３．５°未満であることが好ましく、更に、製造時のプロセスマージンが優れる観点から、４２．７°以上４３．５°未満がより好ましく、更に、粒子性能の再現性が優れる観点から、４２．７°以上４３．４°未満が更に好ましい。副成分として酸化チタンＴｉＯ２を含有する場合、最も強度の強いピークとしてアナターゼ型ＴｉＯ２（１０１）に由来するピークが２θ＝２５．３°近傍に、ルチル型ＴｉＯ２（１１０）に由来するピークが２θ＝２７．４°近傍に見られる。しかし、ＴｉＯ２は白色でありブラックマトリクスの遮光性を低下させる要因となるため、ピークとして観察されない程度に低減されていることが好ましい。 The diffraction angle 2θ of the peak derived from the (200) plane of the titanium nitride-containing particle is preferably more than 42.6 ° and less than 43.5 ° from the viewpoint of the stability of the particle over time. From the viewpoint of excellent process margin, 42.7 ° or more and less than 43.5 ° is more preferable, and from the viewpoint of excellent reproducibility of particle performance, it is more preferably 42.7 ° or more and less than 43.4 °. When titanium oxide TiO 2 is contained as an accessory component, the peak derived from anatase TiO 2 (101) as the strongest peak is in the vicinity of 2θ = 25.3 °, and the peak derived from rutile TiO 2 (110). Is seen around 2θ = 27.4 °. However, since TiO 2 is white and causes a reduction in the light shielding properties of the black matrix, it is preferably reduced to such an extent that it is not observed as a peak.
　Ｘ線回折ピークの半値幅よりチタン窒化物含有粒子を構成する結晶子サイズを求めることができ、シェラーの式を用いて算出される。 The crystallite size constituting the titanium nitride-containing particles can be determined from the half width of the X-ray diffraction peak, and is calculated using Scherrer's formula.
　結晶子サイズは、２０ｎｍ以上であることが好ましく、２０～５０ｎｍであることがより好ましい。結晶子サイズが２０ｎｍ以上のチタン窒化物含有粒子を用いてブラックマトリクスを形成することにより、硬化膜の透過光はそのピーク波長が４７５ｎｍ以下であるような青色から青紫色を呈し、高い遮光性と紫外線感度を併せ持つブラックマトリクスを得ることができる。結晶子サイズが２０ｎｍ以上であることで、活性の有する粒子表面が粒子体積に対して占める割合が小さくなり良好なバランスとなり、チタン窒化物含有粒子の耐熱性及び／又は耐久性がより優れたものとなる。 The crystallite size is preferably 20 nm or more, and more preferably 20 to 50 nm. By forming a black matrix using titanium nitride-containing particles having a crystallite size of 20 nm or more, the transmitted light of the cured film exhibits a blue to blue purple color having a peak wavelength of 475 nm or less, and has high light-shielding properties. A black matrix having both ultraviolet sensitivity can be obtained. When the crystallite size is 20 nm or more, the proportion of the active particle surface with respect to the volume of the particle is reduced, providing a good balance, and the titanium nitride-containing particles have better heat resistance and / or durability. It becomes.
・・原子Ａを含有する金属窒化物含有粒子
　また、無機顔料としては、金属窒化物含有粒子であって、上記金属窒化物含有粒子に所定の原子Ａを含有する金属窒化物含有粒子を用いることもできる。
　金属窒化物含有粒子中の金属としては、例えばＮｂ、Ｖ、Ｃｒ、Ｙ、Ｚｒ、Ｎｂ、Ｈｆ、Ｔａ、Ｗ、及びＲｅ等が挙げられ、Ｎｂ、又はＶがより好ましい。
　上記原子Ａとしては、例えば、Ｂ、Ａｌ、Ｓｉ、Ｍｎ、Ｆｅ、Ｎｉ、及びＡｇ等が挙げられる。
　金属窒化物含有粒子が、上記原子Ａを含有する場合、その含有量としては特に制限されないが、金属窒化物含有粒子中における原子Ａの含有量が、０．００００５～１０質量％が好ましい。 ..Metal nitride-containing particles containing atom A Further, as the inorganic pigment, metal nitride-containing particles that are metal nitride-containing particles and contain predetermined atoms A are used as the metal nitride-containing particles. You can also.
Examples of the metal in the metal nitride-containing particles include Nb, V, Cr, Y, Zr, Nb, Hf, Ta, W, and Re, and Nb or V is more preferable.
Examples of the atom A include B, Al, Si, Mn, Fe, Ni, and Ag.
When the metal nitride-containing particles contain the atom A, the content is not particularly limited, but the content of the atoms A in the metal nitride-containing particles is preferably 0.00005 to 10% by mass.
　上記原子Ａを含有する金属窒化物含有粒子の製造方法としては、特に制限されず、公知の方法を用いることができる。
　金属窒化物含有粒子の製造には、通常、気相反応法が用いられ、具体的には電気炉法及び熱プラズマ法等が挙げられる。これらの製法の中でも、不純物の混入が少ない点、粒子径が揃いやすい点、及び、生産性が高い点等の理由から、熱プラズマ法が好ましい。
　熱プラズマ法による金属窒化物含有粒子の具体的な製造方法としては、例えば、金属微粒子製造装置（後述する「黒色複合微粒子製造装置」と同様の装置）を用いるものが挙げられる。金属微粒子製造装置は、例えば、熱プラズマを発生させるプラズマトーチ、金属原料粉末をプラズマトーチ内へ供給する材料供給装置、冷却機能を含有するチャンバ、生成された金属微粒子を分級するサイクロン、及び金属微粒子を回収する回収部によって構成される。
　本明細書において、金属微粒子とは、金属元素を含有する粒子の一次粒子径が２０ｎｍ～４０μｍの粒子を意図する。 The method for producing the metal nitride-containing particles containing the atom A is not particularly limited, and a known method can be used.
For the production of metal nitride-containing particles, a gas phase reaction method is usually used, and specific examples include an electric furnace method and a thermal plasma method. Among these production methods, the thermal plasma method is preferable because it is less contaminated with impurities, has a uniform particle diameter, and has high productivity.
As a specific method for producing metal nitride-containing particles by the thermal plasma method, for example, a method using a metal fine particle production apparatus (an apparatus similar to a “black composite fine particle production apparatus” described later) can be mentioned. The metal fine particle manufacturing apparatus includes, for example, a plasma torch that generates thermal plasma, a material supply device that supplies metal raw material powder into the plasma torch, a chamber that includes a cooling function, a cyclone that classifies the generated metal fine particles, and metal fine particles It is comprised by the collection | recovery part which collect | recovers.
In the present specification, the metal fine particles mean particles having a primary particle diameter of 20 nm to 40 μm containing particles of a metal element.
　金属微粒子製造装置を用いた金属窒化物含有粒子の製造方法としては、特に限定されず、公知の方法を用いることができる。中でも、下記の所定の平均一次粒子径の金属窒化物含有粒子の収率が高まる点で、金属微粒子製造装置を用いて金属窒化物含有粒子を製造する方法は以下に示す工程を含有することが好ましい。
工程Ａ：プラズマトーチ内に窒素ガスを含有しない不活性ガスをプラズマガスとして供給し、熱プラズマ炎を発生する工程。
工程Ｂ：プラズマトーチ内の熱プラズマ炎に、遷移金属を含有する金属原料粉末を供給し、上記金属原料粉末を蒸発させ、気相の原料金属を得る工程。
工程Ｃ：上記気相の原料金属を冷却し、遷移金属を含有する金属微粒子を得る工程。
工程Ｄ：プラズマトーチ内に窒素ガスを含有する不活性ガスをプラズマガスとして供給し、熱プラズマ炎を発生する工程。
工程Ｅ：プラズマトーチ内の熱プラズマ炎に、遷移金属を含有する金属微粒子を供給し、上記金属微粒子を蒸発させ、気相の原料金属を得る工程。
工程Ｆ：上記気相の原料金属を冷却し、金属窒化物含有粒子を得る工程。
　金属窒化物含有粒子の製造方法は、工程Ｃ及び／又は工程Ｆの後に、所望により下記の工程Ｇを含有してもよい。
工程Ｇ：得られた粒子を分級する工程。
　更に、工程Ａの前、工程Ａと工程Ｂとの間、工程Ｃと工程Ｄとの間、又は工程Ｄと工程Ｅとの間に、以下の工程Ａ２を含有してもよい。
工程Ａ２：遷移金属を含有する金属原料粉末に、原子Ａを混合する工程。
　更に、工程Ａ２の前に、以下の工程Ａ３－１～Ａ３－３を含有してもよい。
工程Ａ３－１：プラズマトーチ内に窒素ガスを含有しない不活性ガスをプラズマガスとして供給し、熱プラズマ炎を発生する工程。
工程Ａ３－２：プラズマトーチ内の熱プラズマ炎に、原子Ａを含有する原料粉末を供給し、上記原料粉末を蒸発させ、気相の原子Ａを得る工程。
工程Ａ３－３：上記気相の原子Ａを冷却し、微粒子化された原子Ａを得る工程。
　工程Ａ３－３の後に更に、工程Ｇを含有してもよい。
　本明細書において、微粒子化された原子Ａとは、原子Ａを含有する一次粒子径が２０ｎｍ～４０μｍの粒子を意図する。 It does not specifically limit as a manufacturing method of metal nitride containing particle | grains using a metal microparticle manufacturing apparatus, A well-known method can be used. Among them, the method for producing metal nitride-containing particles using a metal fine particle production apparatus includes the following steps in that the yield of metal nitride-containing particles having the following predetermined average primary particle diameter is increased. preferable.
Step A: A step of supplying a thermal plasma flame by supplying an inert gas containing no nitrogen gas as a plasma gas in the plasma torch.
Step B: A step of supplying a metal raw material powder containing a transition metal to a thermal plasma flame in a plasma torch and evaporating the metal raw material powder to obtain a gas phase raw material metal.
Step C: Step of cooling the gas phase raw material metal to obtain fine metal particles containing a transition metal.
Step D: A step of supplying a thermal plasma flame by supplying an inert gas containing nitrogen gas as a plasma gas in the plasma torch.
Step E: A step of supplying metal fine particles containing a transition metal to a thermal plasma flame in a plasma torch and evaporating the metal fine particles to obtain a gas phase raw material metal.
Step F: Step of cooling the gas phase raw metal to obtain metal nitride-containing particles.
The process for producing metal nitride-containing particles may optionally include the following step G after step C and / or step F.
Step G: A step of classifying the obtained particles.
Further, before step A, between step A and step B, between step C and step D, or between step D and step E, the following step A2 may be included.
Step A2: A step of mixing atoms A into a metal raw material powder containing a transition metal.
Furthermore, the following steps A3-1 to A3-3 may be included before step A2.
Step A3-1: A step of generating a thermal plasma flame by supplying an inert gas containing no nitrogen gas as a plasma gas in the plasma torch.
Step A3-2: A step of supplying raw material powder containing atoms A to the thermal plasma flame in the plasma torch and evaporating the raw material powder to obtain gas phase atoms A.
Step A3-3: A step of cooling the gas phase atoms A to obtain atomized atoms A.
Step G may further be included after step A3-3.
In the present specification, the atomized atom A means a particle containing the atom A and having a primary particle diameter of 20 nm to 40 μm.
　更に、上記金属窒化物含有粒子の製造方法は、工程Ｆの後（工程Ｇを含有する場合は、工程Ｆの後の工程Ｇの後）に更に下記の工程Ｈを含有することが好ましい。
工程Ｈ：工程Ｆ（又は工程Ｇ）において得られた金属窒化物含有粒子を、水蒸気及び窒素ガスの混合雰囲気に曝露し、窒化処理する工程。
　所望により、上記金属窒化物含有粒子の製造方法は、工程Ｈの後に更に工程Ｇを含有してもよい。以下では、各工程の好適態様について詳述する。 Furthermore, it is preferable that the manufacturing method of the said metal nitride containing particle | grains contains the following process H further after the process F (when the process G is included, after the process G after the process F).
Step H: A step of exposing the metal nitride-containing particles obtained in Step F (or Step G) to a mixed atmosphere of water vapor and nitrogen gas to perform nitriding treatment.
If desired, the method for producing metal nitride-containing particles may further include a step G after the step H. Below, the suitable aspect of each process is explained in full detail.
工程Ａ
　工程Ａはプラズマトーチ内に窒素ガスを含有しない不活性ガスをプラズマガスとして供給し、熱プラズマ炎を発生する工程である。熱プラズマ炎の発生方法としては、特に限定されないが、直流アーク放電法、多相アーク放電法、高周波プラズマ法、及び、ハイブリッドプラズマ法等が挙げられ、電極からの不純物の混入が少ない高周波プラズマ法が好ましい。
　高周波プラズマ法による熱プラズマ炎の発生方法としては、特に制限されず、例えば、高周波発振用コイルと石英管を含有するプラズマトーチ内にプラズマガスを供給し、上記高周波発振用コイルに高周波電流を印加することにより熱プラズマ炎を得る方法が挙げられる。
　工程Ａにおけるプラズマガスとしては、窒素ガスを含有しない不活性ガスが挙げられる。窒素ガスを含有しない不活性ガスとしては、アルゴンガス、及び水素ガス等が挙げられる。窒素ガスを含有しない不活性ガスは、１種を単独で用いても、２種以上を併用してもよい。 Process A
Step A is a step of generating a thermal plasma flame by supplying an inert gas containing no nitrogen gas as a plasma gas in the plasma torch. The generation method of the thermal plasma flame is not particularly limited, and examples thereof include a direct current arc discharge method, a multiphase arc discharge method, a high frequency plasma method, a hybrid plasma method, and the like. Is preferred.
The method of generating a thermal plasma flame by the high frequency plasma method is not particularly limited. For example, a plasma gas is supplied into a plasma torch containing a high frequency oscillation coil and a quartz tube, and a high frequency current is applied to the high frequency oscillation coil. The method of obtaining a thermal plasma flame by doing is mentioned.
Examples of the plasma gas in the process A include an inert gas that does not contain nitrogen gas. Examples of the inert gas not containing nitrogen gas include argon gas and hydrogen gas. The inert gas which does not contain nitrogen gas may be used individually by 1 type, or may use 2 or more types together.
工程Ａ２
　工程Ａ２は遷移金属を含有する金属原料粉末に、原子Ａを混合する工程である。原料金属粉末及び原子Ａの混合方法としては特に制限されず、公知の方法を用いることができる。例えば、金属原料粉末をプラズマトーチ内へ供給する上記材料供給装置が、混合及び分散機能を含有してもよい。具体的には、国際公開第２０１０／１４７０９８号公報の段落００４７～００５８に記載された材料供給装置を用いることができ、この内容は本明細書に組み込まれる。金属窒化物含有粒子の製造方法は、工程Ａ２の前に、以下の工程Ａ３－１～Ａ３－３を更に含有してもよい。 Process A2
Step A2 is a step of mixing atoms A into a metal raw material powder containing a transition metal. The method for mixing the raw metal powder and the atom A is not particularly limited, and a known method can be used. For example, the material supply device for supplying the metal raw material powder into the plasma torch may contain a mixing and dispersing function. Specifically, the material supply apparatus described in Paragraphs 0047 to 0058 of International Publication No. 2010/147098 can be used, the contents of which are incorporated herein. The method for producing metal nitride-containing particles may further include the following steps A3-1 to A3-3 before step A2.
工程Ｂ
　工程Ｂは、プラズマトーチ内の熱プラズマ炎に、遷移金属を含有する金属原料粉末を供給し、上記金属原料粉末を蒸発させ、気相の原料金属を得る工程である。プラズマトーチ内の熱プラズマ炎に金属原料粉末を供給する方法としては特に制限されないが、得られる気相の原料金属が、より均一な状態となる点で、キャリアガスを用いて噴霧されることが好ましい。キャリアガスとしては、窒素ガスを含有しない不活性ガスを用いることが好ましい。窒素ガスを含有しない不活性ガスの態様は上記のとおりである。
　金属窒化物含有粒子を製造する方法が、上記工程Ａ２を含有する場合、金属原料粉末のプラズマトーチ内への供給に至るまでの間、金属原料粉末は、均一な分散状態が維持されていることが好ましい。 Process B
Step B is a step of supplying a metal raw material powder containing a transition metal to a thermal plasma flame in the plasma torch and evaporating the metal raw material powder to obtain a gas phase raw material metal. The method for supplying the metal raw material powder to the thermal plasma flame in the plasma torch is not particularly limited, but the obtained gas phase raw material metal may be sprayed using a carrier gas in a more uniform state. preferable. As the carrier gas, it is preferable to use an inert gas that does not contain nitrogen gas. The aspect of the inert gas not containing nitrogen gas is as described above.
When the method for producing metal nitride-containing particles includes the above step A2, the metal raw material powder is maintained in a uniform dispersed state until the metal raw material powder is supplied into the plasma torch. Is preferred.
工程Ｃ
　工程Ｃは、気相の原料金属を冷却し、遷移金属を含有する金属微粒子を得る工程である。冷却方法としては特に制限されないが、冷却機能を含有するチャンバを用いることが好ましい。工程Ｂにおいて得られた気相の原料金属を、上記冷却機能を含有するチャンバに導入し、チャンバ内で急冷することにより、下記の所望の粒子径の金属微粒子を生成することができる。生成した金属微粒子は、例えば、回収部により回収される。チャンバ内の雰囲気としては、窒素ガスを含有しない不活性ガスが好ましい。窒素ガスを含有しない不活性ガスの態様は上記のとおりである。
　なお、上記工程Ａ～Ｃを経ることにより、遷移金属を含有する金属微粒子が得られる。遷移金属を含有する金属微粒子は、工程Ｅにおいて蒸発しやすい。金属原料粉末が不純物を含有する場合にも、上記工程Ａ～Ｃを経ることにより、上記不純物を除去することができる。 Process C
Step C is a step of cooling the gas phase raw material metal to obtain fine metal particles containing a transition metal. The cooling method is not particularly limited, but it is preferable to use a chamber containing a cooling function. By introducing the gas phase raw material metal obtained in the step B into the chamber containing the cooling function and quenching in the chamber, metal fine particles having the following desired particle diameter can be generated. The generated metal fine particles are recovered by, for example, a recovery unit. The atmosphere in the chamber is preferably an inert gas that does not contain nitrogen gas. The aspect of the inert gas not containing nitrogen gas is as described above.
By passing through the above steps A to C, metal fine particles containing a transition metal can be obtained. The metal fine particles containing the transition metal are likely to evaporate in the process E. Even when the metal raw material powder contains impurities, the impurities can be removed by performing the steps A to C.
工程Ｄ
　工程Ｄは、プラズマトーチ内に窒素ガスを含有する不活性ガスをプラズマガスとして供給し、熱プラズマ炎を発生する工程である。窒素を含有する不活性ガスとしては、窒素ガス、及び不活性ガスを含有する窒素ガスが挙げられる。不活性ガスとしては、アルゴンガス、及び水素ガス等が挙げられる。不活性ガスを含有する窒素ガスは、特に制限されないが、窒素ガスの含有量は、通常、１０～９０モル％程度であり、３０～６０モル％程度が好ましい。その他の態様は工程Ａと同様である。 Process D
Step D is a step of generating a thermal plasma flame by supplying an inert gas containing nitrogen gas as a plasma gas in the plasma torch. Examples of the inert gas containing nitrogen include nitrogen gas and nitrogen gas containing an inert gas. Examples of the inert gas include argon gas and hydrogen gas. The nitrogen gas containing the inert gas is not particularly limited, but the nitrogen gas content is usually about 10 to 90 mol%, preferably about 30 to 60 mol%. Other aspects are the same as in step A.
工程Ｅ
　工程Ｅは、プラズマトーチ内の熱プラズマ炎に、遷移金属を含有する金属微粒子を供給し、上記金属微粒子を蒸発させ、気相の原料金属を得る工程である。プラズマトーチ内の熱プラズマ炎に金属微粒子を供給する方法としては上記のとおりであるが、キャリアガスとしては、窒素を含有する不活性ガスが好ましい。窒素を含有する不活性ガスの態様は上記のとおりである。
　工程Ｅでは、工程Ａ～工程Ｃによって金属微粒子となった原料金属を熱プラズマ炎に供給するため、気相の原料金属が得られやすく、気相の原料金属の状態もより均一になりやすい。 Process E
Step E is a step of supplying metal fine particles containing a transition metal to the thermal plasma flame in the plasma torch and evaporating the metal fine particles to obtain a gas phase raw material metal. The method for supplying the metal fine particles to the thermal plasma flame in the plasma torch is as described above, but the carrier gas is preferably an inert gas containing nitrogen. The aspect of the inert gas containing nitrogen is as described above.
In step E, the raw material metal that has become fine metal particles in steps A to C is supplied to the thermal plasma flame, so that a vapor phase raw metal is easily obtained, and the state of the vapor phase raw metal is likely to be more uniform.
工程Ｆ
　工程Ｆは、気相の原料金属を冷却し、遷移金属の窒化物を含有する金属窒化物含有粒子を得る工程である。冷却方法の好適態様は上記のとおりであるが、チャンバ内の雰囲気としては、窒素ガスを含有する不活性ガスが好ましい。窒素ガスを含有する不活性ガスの好適態様は上記のとおりである。 Process F
Step F is a step of cooling the gas phase raw material metal to obtain metal nitride-containing particles containing a transition metal nitride. Although the suitable aspect of the cooling method is as above-mentioned, as the atmosphere in a chamber, the inert gas containing nitrogen gas is preferable. The suitable aspect of the inert gas containing nitrogen gas is as above-mentioned.
工程Ｇ
　工程Ｇは、得られた金属微粒子及び／又は金属窒化物含有粒子を分級する工程である。分級の方法としては特に制限されないが、例えば、サイクロンを用いることができる。サイクロンは、円錐上の容器を有し、容器内に旋回流を発生して、遠心力を利用して粒子を分級する機能を有する。分級は、不活性ガスの雰囲気下で行うことが好ましい。不活性ガスの態様は上記のとおりである。 Process G
Step G is a step of classifying the obtained metal fine particles and / or metal nitride-containing particles. The classification method is not particularly limited, and for example, a cyclone can be used. The cyclone has a container on a cone, and generates a swirling flow in the container and has a function of classifying particles using centrifugal force. The classification is preferably performed in an inert gas atmosphere. The aspect of the inert gas is as described above.
工程Ｈ
　工程Ｈは金属窒化物含有粒子を、水蒸気及び窒素ガスの混合雰囲気に曝露し、窒化処理する工程である。この工程を経ることにより、金属窒化物含有粒子における金属窒化物の含有量をより多くすることができる。金属窒化物含有粒子を、水蒸気及び窒素ガスの混合雰囲気に曝露する方法については特に制限されないが、例えば、金属窒化物含有粒子を水蒸気及び窒素ガスを混合したガスで満たされた恒温槽に導入し、所定時間静置又は攪拌する方法が挙げられ、金属窒化物含有粒子の表面及び結晶境界がより安定化する点で静置することがより好ましい。
　水蒸気及び窒素ガスの混合比率は、大気中であれば相対湿度が２５～９５％となる条件が好ましい。静置又は攪拌する時間は０．５～７２時間が好ましく、その際の温度は１０～４０℃が好ましい。 Process H
Process H is a process in which the metal nitride-containing particles are exposed to a mixed atmosphere of water vapor and nitrogen gas to perform nitriding treatment. Through this step, the metal nitride content in the metal nitride-containing particles can be increased. The method for exposing the metal nitride-containing particles to a mixed atmosphere of water vapor and nitrogen gas is not particularly limited. There may be mentioned a method of standing or stirring for a predetermined time, and it is more preferred that the metal nitride-containing particles are allowed to stand for stabilization of the surface and crystal boundaries.
The mixing ratio of water vapor and nitrogen gas is preferably such that the relative humidity is 25 to 95% in the atmosphere. The time for standing or stirring is preferably 0.5 to 72 hours, and the temperature at that time is preferably 10 to 40 ° C.
工程Ａ３－１～Ａ３－３
　工程Ａ３－１～Ａ３－３は、プラズマトーチ内に窒素ガスを含有しない不活性ガスをプラズマガスとして供給し、熱プラズマ炎を発生する工程（Ａ３－１）、プラズマトーチ内の熱プラズマ炎に、原子Ａを含有する原料粉末を供給し、上記原料粉末を蒸発させ、気相の原子Ａを得る工程（Ａ３－２）、及び上記気相の原子Ａを冷却し、原子Ａからなる微粒子を得る工程（Ａ３－３）である。それぞれの工程における態様は、上記工程Ａ、工程Ｂ（遷移金属を含有する金属原料粉末に代えて、原子Ａを含有する原料粉末を用いる）、及び工程Ｃ（遷移金属を含有する金属微粒子に代えて、微粒子化された原子Ａを得る。）で説明したとおりである。
　上記工程を経ることにより、原子Ａが微粒子化され、工程Ｅにおいて原子Ａが蒸発し易くなる。また、上記工程を経ることにより、原子Ａを含有する原料粉末が含有する不純物（原子Ａ以外の金属成分等）を除去することができる。 Steps A3-1 to A3-3
In steps A3-1 to A3-3, an inert gas not containing nitrogen gas is supplied as a plasma gas in the plasma torch to generate a thermal plasma flame (A3-1), and a thermal plasma flame in the plasma torch is used. Supplying a raw material powder containing atoms A, evaporating the raw material powder to obtain gas phase atoms A (A3-2), and cooling the gas phase atoms A to form fine particles comprising atoms A This is the obtaining step (A3-3). The aspect in each process is the above-mentioned process A, process B (instead of a metal raw material powder containing a transition metal, using a raw material powder containing an atom A), and process C (substituting metal fine particles containing a transition metal) Thus, atomized atom A is obtained.
Through the above steps, the atom A is atomized and the atom A is easily evaporated in the step E. Moreover, the impurities (metal components other than the atom A) contained in the raw material powder containing the atom A can be removed through the above steps.
原子Ａを含有する金属窒化物含有粒子の製造方法の好適態様
　原子Ａを含有する金属窒化物含有粒子の製造方法の好適態様としては、以下の工程を順に有する方法が挙げられる。
工程Ａ：プラズマトーチ内に窒素ガスを含有しない不活性ガスをプラズマガスとして供給し、熱プラズマ炎を発生する工程。
工程Ｂ：プラズマトーチ内の熱プラズマ炎に、遷移金属を含有する金属原料粉末を供給し、上記金属原料粉末を蒸発させ、気相の原料金属を得る工程。
工程Ｃ：上記気相の原料金属を冷却し、遷移金属を含有する金属微粒子を得る工程。
工程Ｇ：得られた粒子を分級する工程。
工程Ａ３－１：プラズマトーチ内に窒素ガスを含有しない不活性ガスをプラズマガスとして供給し、熱プラズマ炎を発生する工程。
工程Ａ３－２：プラズマトーチ内の熱プラズマ炎に、原子Ａを含有する原料粉末を供給し、上記原料粉末を蒸発させ、気相の原子Ａを得る工程。
工程Ａ３－３：上記気相の原子Ａを冷却し、微粒子化された原子Ａを得る工程。
工程Ｇ：得られた粒子を分級する工程。
工程Ａ２：遷移金属を含有する金属原料粉末（この場合、金属微粒子）に、原子Ａ（この場合、微粒子化された原子Ａ）を混合する工程。
工程Ｄ：プラズマトーチ内に窒素ガスを含有する不活性ガスをプラズマガスとして供給し、熱プラズマ炎を発生する工程。
工程Ｅ：プラズマトーチ内の熱プラズマ炎に、遷移金属を含有する金属微粒子を供給し、上記金属微粒子を蒸発させ、気相の原料金属を得る工程。
工程Ｆ：上記気相の原料金属を冷却し、金属窒化物含有粒子を得る工程。
工程Ｇ：得られた粒子を分級する工程。
工程Ｈ：工程Ｇにおいて得られた金属窒化物含有粒子を、水蒸気及び窒素ガスの混合雰囲気に曝露し、窒化処理する工程。
　上記一連の工程において、工程Ａ～Ｃ、及び工程Ａ３－１～Ａ３－３の順序を入れ替えてもよい。すなわち、工程Ａ３－１～Ａ３－３の後、工程Ａ～Ｃを実施してもよい。 Preferred Embodiment of Method for Producing Metal Nitride-Containing Particles Containing Atom A preferred embodiment of a method for producing metal nitride-containing particles containing atom A includes a method having the following steps in order.
Step A: A step of supplying a thermal plasma flame by supplying an inert gas containing no nitrogen gas as a plasma gas in the plasma torch.
Step B: A step of supplying a metal raw material powder containing a transition metal to a thermal plasma flame in a plasma torch and evaporating the metal raw material powder to obtain a gas phase raw material metal.
Step C: Step of cooling the gas phase raw material metal to obtain fine metal particles containing a transition metal.
Step G: A step of classifying the obtained particles.
Step A3-1: A step of generating a thermal plasma flame by supplying an inert gas containing no nitrogen gas as a plasma gas in the plasma torch.
Step A3-2: A step of supplying raw material powder containing atoms A to the thermal plasma flame in the plasma torch and evaporating the raw material powder to obtain gas phase atoms A.
Step A3-3: A step of cooling the gas phase atoms A to obtain atomized atoms A.
Step G: A step of classifying the obtained particles.
Step A2: A step of mixing atoms A (in this case, atomized atoms A) with a metal raw material powder (in this case, metal fine particles) containing a transition metal.
Step D: A step of supplying a thermal plasma flame by supplying an inert gas containing nitrogen gas as a plasma gas in the plasma torch.
Step E: A step of supplying metal fine particles containing a transition metal to a thermal plasma flame in a plasma torch and evaporating the metal fine particles to obtain a gas phase raw material metal.
Step F: Step of cooling the gas phase raw metal to obtain metal nitride-containing particles.
Step G: A step of classifying the obtained particles.
Step H: A step of exposing the metal nitride-containing particles obtained in Step G to a mixed atmosphere of water vapor and nitrogen gas to perform nitriding treatment.
In the above series of steps, the order of steps A to C and steps A3-1 to A3-3 may be changed. That is, steps A to C may be performed after steps A3-1 to A3-3.
　上記の原子Ａを含有する金属窒化物含有粒子の製造方法の好適態様によれば、金属原料粉末、及び原料粒子が含有する不純物を除去でき、かつ、所望の平均一次粒子径を有する金属窒化物含有粒子を製造することができる。その理由としては、遷移金属及び／又は原子Ａはプラズマ処理によりイオン化され、上記イオンが冷却される際には、遷移金属、原子Ａ及び不純物は、それぞれの融点を反映して微粒子化されるものと推測される。このとき、融点が低い原子は粒子化が速く、融点が高い原子は粒子化が遅くなる。そのため、上記のとおり、一度プラズマ処理された微粒子（工程Ｂ及びＣ、並びに工程Ａ３－２及びＡ３－３）は単一成分（単一結晶）になりやすいものと推測される。上記により得られた単一成分の粒子を分級すれば、遷移金属の粒子及び／又は原子Ａの粒子と、不純物の粒子の密度及び／又は粒径の違いにより、不純物の粒子を除去することができる。上記分級は、例えばサイクロン等を用い、分級条件を適宜設定することで行うことができる。 According to the preferred embodiment of the method for producing the metal nitride-containing particles containing the atom A, the metal raw material powder and the metal nitride that can remove impurities contained in the raw material particles and have a desired average primary particle diameter Containing particles can be produced. The reason is that the transition metal and / or atom A is ionized by plasma treatment, and when the ions are cooled, the transition metal, atom A, and impurities are micronized to reflect their melting points. It is guessed. At this time, the atomization with a low melting point is fast, and the atomization with a high melting point is slow. Therefore, as described above, it is presumed that the fine particles (steps B and C and steps A3-2 and A3-3) once plasma-treated are likely to become a single component (single crystal). If the single-component particles obtained as described above are classified, the impurity particles can be removed depending on the density and / or particle size difference between the transition metal particles and / or the atom A particles and the impurity particles. it can. The classification can be performed, for example, by using a cyclone or the like and appropriately setting the classification conditions.
金属原料粉末及び原料粉末の精製
　上記工程Ｂにおいて用いることのできる遷移金属を含有する金属原料粉末（以下、単に「金属原料粉末」という。）及び原子Ａを含有する原料粉末（以下、単に「原料粉末」という。）としては、特に制限されないが、高純度のものであることが好ましい。金属原料粉末における遷移金属の含有量は、特に限定されないが、９９．９９％以上が好ましく、９９．９９９％以上がより好ましい。原料粉末における原子Ａの含有量も同様である。 Purification of metal raw material powder and raw material powder Metal raw material powder containing a transition metal that can be used in the above step B (hereinafter simply referred to as “metal raw material powder”) and raw material powder containing atom A (hereinafter simply referred to as “raw material”) The “powder” is not particularly limited, but is preferably highly purified. The content of the transition metal in the metal raw material powder is not particularly limited, but is preferably 99.99% or more, and more preferably 99.999% or more. The same applies to the content of atom A in the raw material powder.
　金属原料粉末及び／又は原料粉末は、所望の遷移金属及び／又は原子Ａ以外の原子を不純物として含有する場合がある。金属原料粉末に含有される不純物としては、ホウ素、アルミニウム、ケイ素、マンガン、鉄、ニッケル及び銀等が挙げられる。また、原料粉末に含有される不純物としては、金属元素等が挙げられる。 Metal raw material powder and / or raw material powder may contain atoms other than the desired transition metal and / or atom A as impurities. Examples of impurities contained in the metal raw material powder include boron, aluminum, silicon, manganese, iron, nickel, and silver. Moreover, a metal element etc. are mentioned as an impurity contained in raw material powder.
　金属窒化物含有粒子の製造方法は、工程Ｂの前（工程Ａ２を含有する場合は、工程Ａ２の前）に、以下の工程Ａ０を更に含有してもよい。
工程Ａ０：金属原料粉末及び／又は原料粉末から不純物を除去する工程。 The method for producing metal nitride-containing particles may further include the following step A0 before step B (when step A2 is included, before step A2).
Step A0: A step of removing impurities from the metal raw material powder and / or the raw material powder.
工程Ａ０
　工程Ａ０において、金属原料粉末及び／又は原料粉末から不純物を除去する方法（分離精製方法）としては特に限定されないが、例えば、ニオブについて特開２０１２－２１１０４８号公報の段落００１３～００３０に記載された方法を用いることができ、その他の金属原料粉末及び／又は原料粉末についてもこれに準じた方法を用いることができる。 Process A0
In step A0, the metal raw material powder and / or the method for removing impurities from the raw material powder (separation and purification method) are not particularly limited. For example, niobium is described in paragraphs 0013 to 0030 of JP2012-211048. A method similar to this can be used for other metal raw material powders and / or raw material powders.
金属窒化物含有粒子の被覆
　金属窒化物含有粒子は、無機化合物で被覆された金属窒化物含有粒子であってもよい。つまり、金属窒化物含有粒子と、金属窒化物含有粒子を被覆する、無機化合物を用いて形成される被覆層とを有する、被覆金属窒化物含有粒子であってもよい。無機化合物で被覆された金属窒化物含有粒子を含有する硬化性組成物は、より優れた分散安定性を有する。
　無機化合物としては特に限定されず、ＳｉＯ２、ＺｒＯ２、ＴｉＯ２、ＧｅＯ２、Ａｌ２Ｏ３、Ｙ２Ｏ３、及びＰ２Ｏ５等の酸化物、並びに、水酸化アルミニウム、及び水酸化ジルコニウム等の水酸化物が挙げられる。なかでも、より薄い被膜を形成しやすく、かつ、より被覆率の高い被膜を形成しやすい点で、水酸化アルミニウムが好ましい。
　金属窒化物含有粒子の屈折率を制御することを意図した場合には、低屈折率被膜としては酸化ケイ素が好ましく、高屈折率被膜としては水酸化ジルコニウムが好ましい。
　金属窒化物含有粒子を無機化合物で被覆する方法については特に制限されないが、金属窒化物含有粒子の製造方法が、下記の無機化合物被覆工程を含有することが好ましい。 Coating of metal nitride-containing particles The metal nitride-containing particles may be metal nitride-containing particles coated with an inorganic compound. That is, it may be a coated metal nitride-containing particle having metal nitride-containing particles and a coating layer formed using an inorganic compound that coats the metal nitride-containing particles. A curable composition containing metal nitride-containing particles coated with an inorganic compound has better dispersion stability.
The inorganic compound is not particularly limited, and oxides such as SiO 2 , ZrO 2 , TiO 2 , GeO 2 , Al 2 O 3 , Y 2 O 3 , and P 2 O 5 , aluminum hydroxide, and hydroxide Examples thereof include hydroxides such as zirconium. Among these, aluminum hydroxide is preferable in that it can easily form a thinner film and can easily form a film having a higher coverage.
When it is intended to control the refractive index of the metal nitride-containing particles, the low refractive index film is preferably silicon oxide, and the high refractive index film is preferably zirconium hydroxide.
The method for coating the metal nitride-containing particles with the inorganic compound is not particularly limited, but the method for producing the metal nitride-containing particles preferably includes the following inorganic compound coating step.
無機化合物被覆工程
　無機化合物被覆工程は上記の金属窒化物含有粒子を酸化物及び／又は水酸化物により被覆する工程である。被覆する方法としては、特に制限されないが、例えば以下の湿式コーティング法等が挙げられる。 Inorganic compound coating step The inorganic compound coating step is a step of coating the metal nitride-containing particles with an oxide and / or a hydroxide. Although it does not restrict | limit especially as a method to coat | cover, For example, the following wet coating methods etc. are mentioned.
　第一の湿式コーティング法としては、まず、上記の金属窒化物含有粒子を水と混合してスラリーを作製する。次に上記スラリーに、Ｓｉ，Ｚｒ，Ｔｉ，Ｇｅ，Ａｌ，Ｙ，及び、Ｐからなる群から選択される少なくとも１種を含有する水溶性化合物（例えば珪ケイ酸ナトリウム）を反応させ、余分なアルカリイオンをデカンテーション及び／又はイオン交換樹脂等で除去する。その後、上記スラリーを乾燥させ、酸化物で被覆された金属窒化物含有粒子を得る。 As the first wet coating method, first, the metal nitride-containing particles are mixed with water to prepare a slurry. Next, the slurry is reacted with a water-soluble compound (for example, sodium silicate) containing at least one selected from the group consisting of Si, Zr, Ti, Ge, Al, Y, and P, and an excess amount. Alkaline ions are removed by decantation and / or ion exchange resin. Thereafter, the slurry is dried to obtain metal nitride-containing particles coated with an oxide.
　第二の湿式コーティング法としては、まず、上記の金属窒化物含有粒子をアルコール等の有機溶剤と混合してスラリーを作製する。次に、上記スラリー中でＳｉ，Ｚｒ，Ｔｉ，Ｇｅ，Ａｌ，Ｙ，及び、Ｐからなる群から選択される少なくとも１種を含有するアルコキシド等の有機金属化合物を生成し、上記スラリーを高温で焼成する。上記スラリーを高温で焼成するとゾルゲル反応が進行し、酸化物で被覆された金属窒化物含有粒子が得られる。 As the second wet coating method, first, the above metal nitride-containing particles are mixed with an organic solvent such as alcohol to prepare a slurry. Next, an organometallic compound such as an alkoxide containing at least one selected from the group consisting of Si, Zr, Ti, Ge, Al, Y, and P is generated in the slurry, and the slurry is heated at a high temperature. Bake. When the slurry is fired at a high temperature, a sol-gel reaction proceeds, and metal nitride-containing particles coated with an oxide are obtained.
　第三の湿式コーティング法としては、金属窒化物含有粒子の存在下で、尿素と塩化アルミニウムを用いて、イオン液体を含有するスラリーを作製する。このスラリーから金属窒化物含有粒子を取り出し、乾燥させ、その後、上記金属窒化物含有粒子を焼成することにより、水酸化アルミニウムを含有する水酸化物により被覆された金属窒化物含有粒子が得られる。 As a third wet coating method, a slurry containing an ionic liquid is prepared using urea and aluminum chloride in the presence of metal nitride-containing particles. The metal nitride-containing particles are taken out from the slurry and dried, and then the metal nitride-containing particles are fired to obtain metal nitride-containing particles coated with a hydroxide containing aluminum hydroxide.
・有機顔料
　有機顔料としては、例えば、カラーインデックス（Ｃ．Ｉ．）ピグメントイエロー１，２，３，４，５，６，１０，１１，１２，１３，１４，１５，１６，１７，１８，２０，２４，３１，３２，３４，３５，３５：１，３６，３６：１，３７，３７：１，４０，４２，４３，５３，５５，６０，６１，６２，６３，６５，７３，７４，７７，８１，８３，８６，９３，９４，９５，９７，９８，１００，１０１，１０４，１０６，１０８，１０９，１１０，１１３，１１４，１１５，１１６，１１７，１１８，１１９，１２０，１２３，１２５，１２６，１２７，１２８，１２９，１３７，１３８，１３９，１４７，１４８，１５０，１５１，１５２，１５３，１５４，１５５，１５６，１６１，１６２，１６４，１６６，１６７，１６８，１６９，１７０，１７１，１７２，１７３，１７４，１７５，１７６，１７７，１７９，１８０，１８１，１８２，１８５，１８７，１８８，１９３，１９４，１９９，２１３，２１４等；
　Ｃ．Ｉ．ピグメントオレンジ　２，５，１３，１６，１７：１，３１，３４，３６，３８，４３，４６，４８，４９，５１，５２，５５，５９，６０，６１，６２，６４，７１，７３等；
　Ｃ．Ｉ．ピグメントレッド　１，２，３，４，５，６，７，９，１０，１４，１７，２２，２３，３１，３８，４１，４８：１，４８：２，４８：３，４８：４，４９，４９：１，４９：２，５２：１，５２：２，５３：１，５７：１，６０：１，６３：１，６６，６７，８１：１，８１：２，８１：３，８３，８８，９０，１０５，１１２，１１９，１２２，１２３，１４４，１４６，１４９，１５０，１５５，１６６，１６８，１６９，１７０，１７１，１７２，１７５，１７６，１７７，１７８，１７９，１８４，１８５，１８７，１８８，１９０，２００，２０２，２０６，２０７，２０８，２０９，２１０，２１６，２２０，２２４，２２６，２４２，２４６，２５４，２５５，２６４，２７０，２７２，２７９等；
　Ｃ．Ｉ．ピグメントグリーン　７，１０，３６，３７，５８，５９等；
　Ｃ．Ｉ．ピグメントバイオレット　１，１９，２３，２７，３２，３７，４２等；及び
　Ｃ．Ｉ．ピグメントブルー　１，２，１５，１５：１，１５：２，１５：３，１５：４，１５：６，１６，２２，６０，６４，６６，７９，８０等；
が挙げられる。なお、顔料は１種を単独で用いても、２種以上を併用してもよい。 Organic pigment Examples of the organic pigment include, for example, Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 16 7,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214, etc .;
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. ;
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, etc .;
C. I. Pigment green 7, 10, 36, 37, 58, 59, etc .;
C. I. Pigment violet 1, 19, 23, 27, 32, 37, 42, etc .; and C.I. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, etc .;
Is mentioned. In addition, a pigment may be used individually by 1 type, or may use 2 or more types together.
（染料）
　染料としては、例えば特開昭６４－９０４０３号公報、特開昭６４－９１１０２号公報、特開平１－９４３０１号公報、特開平６－１１６１４号公報、特登２５９２２０７号、米国特許４８０８５０１号明細書、米国特許５６６７９２０号明細書、米国特許５０５９５０号明細書、特開平５－３３３２０７号公報、特開平６－３５１８３号公報、特開平６－５１１１５号公報、特開平６－１９４８２８号公報等に開示されている色素を使用できる。化学構造で区分すると、ピラゾールアゾ化合物、ピロメテン化合物、アニリノアゾ化合物、トリフェニルメタン化合物、アントラキノン化合物、ベンジリデン化合物、オキソノール化合物、ピラゾロトリアゾールアゾ化合物、ピリドンアゾ化合物、シアニン化合物、フェノチアジン化合物、ピロロピラゾールアゾメチン化合物等を使用できる。染料としては色素多量体を用いてもよい。色素多量体としては、特開２０１１－２１３９２５号公報、特開２０１３－０４１０９７号公報に記載されている化合物が挙げられる。分子内に重合性を有する重合性染料を用いてもよく、市販品としては、例えば、和光純薬株式会社製ＲＤＷシリーズが挙げられる。 (dye)
Examples of the dye include, for example, JP-A No. 64-90403, JP-A No. 64-91102, JP-A No. 1-94301, JP-A No. 6-11614, No. 2592207, and US Pat. No. 4,808,501. No. 5,667,920, U.S. Pat. No. 505950, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, etc. Can be used. When classified by chemical structure, pyrazole azo compounds, pyromethene compounds, anilinoazo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, etc. Can be used. A dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A. A polymerizable dye having polymerizability in the molecule may be used, and examples of commercially available products include RDW series manufactured by Wako Pure Chemical Industries, Ltd.
（赤外線吸収剤）
　着色剤は、更に赤外線吸収剤を含有してもよい。
　赤外線吸収剤は、赤外領域（好ましくは、波長６５０～１，３００ｎｍ）の波長領域に吸収を有する化合物を意味する。好ましくは、赤外線吸収剤は、波長６７５～９００ｎｍの波長領域に極大吸収波長を有する化合物が好ましい。
　このような分光特性を有する着色剤としては、例えば、ピロロピロール化合物、銅化合物、シアニン化合物、フタロシアニン化合物、イミニウム化合物、チオール錯体系化合物、遷移金属酸化物系化合物、スクアリリウム化合物、ナフタロシアニン化合物、クオテリレン化合物、ジチオール金属錯体系化合物、クロコニウム化合物等が挙げられる。
　フタロシアニン化合物、ナフタロシアニン化合物、イミニウム化合物、シアニン化合物、スクアリウム化合物及びクロコニウム化合物は、特開２０１０－１１１７５０号公報の段落００１０～００８１に開示の化合物を使用してもよく、この内容は本明細書に組み込まれる。シアニン化合物は、例えば、「機能性色素、大河原信／松岡賢／北尾悌次郎／平嶋恒亮・著、講談社サイエンティフィック」を参酌することができ、この内容は本明細書に組み込まれる。 (Infrared absorber)
The colorant may further contain an infrared absorber.
The infrared absorber means a compound having absorption in the wavelength region in the infrared region (preferably, wavelength 650 to 1,300 nm). Preferably, the infrared absorber is a compound having a maximum absorption wavelength in a wavelength region of 675 to 900 nm.
Examples of colorants having such spectral characteristics include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, iminium compounds, thiol complex compounds, transition metal oxide compounds, squarylium compounds, naphthalocyanine compounds, quaterylenes. Compounds, dithiol metal complex compounds, croconium compounds and the like.
As the phthalocyanine compound, naphthalocyanine compound, iminium compound, cyanine compound, squalium compound and croconium compound, the compounds disclosed in paragraphs 0010 to 0081 of JP-A No. 2010-1111750 may be used. Incorporated. As the cyanine compound, for example, “functional pigment, Shin Okawara / Ken Matsuoka / Keijiro Kitao / Kensuke Hirashima, written by Kodansha Scientific”, the contents of which are incorporated herein.
　上記分光特性を有する着色剤として、特開平０７－１６４７２９号公報の段落０００４～００１６に開示の化合物及び／又は特開２００２－１４６２５４号公報の段落００２７～００６２に開示の化合物、特開２０１１－１６４５８３号公報の段落００３４～００６７に開示のＣｕ及び／又はＰを含む酸化物の結晶子からなり数平均凝集粒子径が５～２００ｎｍである近赤外線吸収粒子を使用することもできる。 As the colorant having the above-mentioned spectral characteristics, compounds disclosed in paragraphs 0004 to 0016 of JP-A-07-164729 and / or compounds disclosed in paragraphs 0027 to 0062 of JP-A-2002-146254, JP-A-2011-16483 It is also possible to use near-infrared absorbing particles comprising a crystallite of an oxide containing Cu and / or P disclosed in paragraphs 0034 to 0067 of the publication and having a number average aggregate particle diameter of 5 to 200 nm.
　波長６７５～９００ｎｍの波長領域に極大吸収波長を有する化合物としては、シアニン化合物、ピロロピロール化合物、スクアリリウム化合物、フタロシアニン化合物、及びナフタロシアニン化合物からなる群から選択される少なくとも１種が好ましい。
　赤外線吸収剤は、２５℃の水に１質量％以上溶解する化合物であることが好ましく、２５℃の水に１０質量％以上溶解する化合物がより好ましい。このような化合物を用いることで、耐溶剤性が良化する。
　ピロロピロール化合物は、特開２０１０－２２２５５７号公報の段落番号００４９～００６２を参酌でき、この内容は本明細書に組み込まれることとする。シアニン化合物及びスクアリリウム化合物は、国際公開２０１４／０８８０６３号公報の段落番号００２２～００６３、国際公開２０１４／０３０６２８号公報の段落番号００５３～０１１８、特開２０１４－５９５５０号公報の段落番号００２８～００７４、国際公開２０１２／１６９４４７号公報の段落番号００１３～００９１、特開２０１５－１７６０４６号公報の段落番号００１９～００３３、特開２０１４－６３１４４号公報の段落番号００５３～００９９、特開２０１４－５２４３１号公報の段落番号００８５～０１５０、特開２０１４－４４３０１号公報の段落番号００７６～０１２４、特開２０１２－８５３２号公報の段落番号００４５～００７８、特開２０１５－１７２１０２号公報の段落番号００２７～００６７、特開２０１５－１７２００４号公報の段落番号００２９～００６７、特開２０１５－４０８９５号公報の段落番号００２９～００８５、特開２０１４－１２６６４２号公報の段落番号００２２～００３６、特開２０１４－１４８５６７号公報の段落番号００１１～００１７、特開２０１５－１５７８９３号公報の段落番号００１０～００２５、特開２０１４－０９５００７号公報の段落番号００１３～００２６、特開２０１４－８０４８７号公報の段落番号００１３～００４７、及び特開２０１３－２２７４０３号公報の段落番号０００７～００２８等を参酌でき、この内容は本明細書に組み込まれる。 The compound having a maximum absorption wavelength in the wavelength region of 675 to 900 nm is preferably at least one selected from the group consisting of a cyanine compound, a pyrrolopyrrole compound, a squarylium compound, a phthalocyanine compound, and a naphthalocyanine compound.
The infrared absorber is preferably a compound that dissolves 1% by mass or more in 25 ° C. water, and more preferably a compound that dissolves 10% by mass or more in 25 ° C. water. By using such a compound, the solvent resistance is improved.
As for the pyrrolopyrrole compound, paragraph numbers 0049 to 0062 of JP 2010-222557 A can be referred to, and the contents thereof are incorporated in the present specification. Cyanine compounds and squarylium compounds are disclosed in International Publication No. 2014/088063, Paragraph Nos. 0022 to 0063, International Publication No. 2014/030628, Paragraph Nos. 0053 to 0118, Japanese Patent Application Laid-Open No. 2014-59550, Paragraph Nos. 0028 to 0074, Paragraph Nos. 0013 to 0091 of Japanese Unexamined Patent Publication No. 2012/169447, Paragraph Nos. 0019 to 0033 of Japanese Unexamined Patent Publication No. 2015-176046, Paragraph Nos. 0053 to 00099 of Japanese Unexamined Patent Publication No. 2014-63144, Paragraphs of Japanese Unexamined Patent Publication No. 2014-52431 Nos. 0085 to 0150, paragraph numbers 0076 to 0124 of Japanese Patent Application Laid-Open No. 2014-44301, paragraph numbers 0045 to 0078 of Japanese Patent Application Laid-Open No. 2012-8532, paragraph numbers 0027 to 0067 of Japanese Patent Application Laid-Open No. 2015-172102, Paragraph numbers 0029 to 0067 of JP015-172004, paragraph numbers 0029 to 0085 of JP2015-40895, paragraph numbers 0022 to 0036 of JP2014-126642, paragraph numbers of JP2014-148567. 0011 to 0017, paragraph numbers 0010 to 0025 of JP-A-2015-157893, paragraph numbers 0013 to 0026 of JP-A-2014-095007, paragraph numbers 0013 to 0047 of JP-A-2014-80487, and JP-A 2013. No. 227403, paragraph numbers 0007 to 0028, etc. can be referred to, the contents of which are incorporated herein.
　赤外線吸収剤は、下記一般式１～３で表される化合物からなる群から選択される少なくとも１種が好ましい。
一般式１
Figure JPOXMLDOC01-appb-C000028
　一般式１中、Ａ1及びＡ2は、それぞれ独立に、アリール基、ヘテロアリール基又は下記一般式１－Ａで表される基を表す。
一般式１－Ａ
Figure JPOXMLDOC01-appb-C000029
　一般式１－Ａ中、Ｚ1Aは、含窒素複素環を形成する非金属原子団を表し、Ｒ2Aは、アルキル基、アルケニル基、又はアラルキル基を表し、ｄは、０、又は１を表し、波線は連結手を表す。
一般式２
Figure JPOXMLDOC01-appb-C000030
　一般式２中、Ｒ1a及びＲ1bは、それぞれ独立に、アルキル基、アリール基、又はヘテロアリール基を表し、
　Ｒ2～Ｒ5は、それぞれ独立に、水素原子、又は置換基を表し、Ｒ2とＲ3、Ｒ4とＲ5は、それぞれ結合して環を形成していてもよく、
　Ｒ6、及びＲ7は、それぞれ独立に、水素原子、アルキル基、アリール基、ヘテロアリール基、－ＢＲAＲB、又は金属原子を表し、ＲA、及びＲBは、それぞれ独立に、水素原子、又は置換基を表し、
　Ｒ6は、Ｒ1a、又はＲ3と、共有結合、又は配位結合していてもよく、Ｒ7は、Ｒ1b、又はＲ5と、共有結合、又は配位結合していてもよい。
一般式３
Figure JPOXMLDOC01-appb-C000031
　一般式３中、Ｚ1、及びＺ2は、それぞれ独立に、縮環してもよい５員、又は６員の含窒素複素環を形成する非金属原子団であり、
　Ｒ101、及びＲ102は、それぞれ独立に、アルキル基、アルケニル基、アルキニル基、アラルキル基、又はアリール基を表し、
　Ｌ1は、奇数個のメチンからなるメチン鎖を表し、
　ａ、及びｂは、それぞれ独立に、０、又は１であり、
　ａが０の場合は、炭素原子と窒素原子とが二重結合で結合し、ｂが０の場合は、炭素原子と窒素原子とが単結合で結合し、
　式中のＣｙで表される部位がカチオン部である場合、Ｘ1はアニオンを表し、ｃは電荷のバランスを取るために必要な数を表し、式中のＣｙで表される部位がアニオン部である場合、Ｘ1はカチオンを表し、ｃは電荷のバランスを取るために必要な数を表し、式中のＣｙで表される部位の電荷が分子内で中和されている場合、ｃは０である。 The infrared absorber is preferably at least one selected from the group consisting of compounds represented by the following general formulas 1 to 3.
General formula 1
Figure JPOXMLDOC01-appb-C000028
In General Formula 1, A 1 and A 2 each independently represent an aryl group, a heteroaryl group, or a group represented by General Formula 1-A below.
Formula 1-A
Figure JPOXMLDOC01-appb-C000029
In General Formula 1-A, Z 1A represents a nonmetallic atomic group that forms a nitrogen-containing heterocycle, R 2A represents an alkyl group, an alkenyl group, or an aralkyl group, and d represents 0 or 1 The wavy line represents the connecting hand.
General formula 2
Figure JPOXMLDOC01-appb-C000030
In General Formula 2, R 1a and R 1b each independently represent an alkyl group, an aryl group, or a heteroaryl group,
R 2 to R 5 each independently represents a hydrogen atom or a substituent, and R 2 and R 3 , R 4 and R 5 may be bonded to each other to form a ring,
R 6 and R 7 each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, —BR A R B , or a metal atom, and R A and R B each independently represent a hydrogen atom Represents an atom or substituent,
R 6 may be covalently or coordinated with R 1a or R 3, and R 7 may be covalently or coordinated with R 1b or R 5 .
General formula 3
Figure JPOXMLDOC01-appb-C000031
In General Formula 3, Z 1 and Z 2 are each independently a nonmetallic atomic group that forms a 5-membered or 6-membered nitrogen-containing heterocycle that may be condensed,
R 101 and R 102 each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, or an aryl group,
L 1 represents a methine chain composed of an odd number of methines;
a and b are each independently 0 or 1,
When a is 0, a carbon atom and a nitrogen atom are bonded by a double bond, and when b is 0, a carbon atom and a nitrogen atom are bonded by a single bond,
When the site represented by Cy in the formula is a cation moiety, X 1 represents an anion, c represents the number necessary for balancing the charge, and the site represented by Cy in the formula is an anion moiety. X 1 represents a cation, c represents a number necessary to balance the charge, and when the charge at the site represented by Cy in the formula is neutralized in the molecule, c is 0.
（顔料誘導体）
　硬化性組成物は、顔料誘導体を含有してもよい。顔料誘導体は、有機顔料の一部分を、酸性基、塩基性基又はフタルイミドメチル基で置換した構造を有する化合物が好ましい。顔料誘導体としては、着色剤Ａの分散性及び分散安定性の観点から、酸性基又は塩基性基を有する顔料誘導体が好ましい。顔料誘導体は、塩基性基を有することが特に好ましい。上述した樹脂（分散剤）と、顔料誘導体との組み合わせは、分散剤が酸性分散剤で、顔料誘導体が塩基性基を有する組み合わせが好ましい。 (Pigment derivative)
The curable composition may contain a pigment derivative. The pigment derivative is preferably a compound having a structure in which a part of an organic pigment is substituted with an acidic group, a basic group or a phthalimidomethyl group. As the pigment derivative, from the viewpoint of dispersibility and dispersion stability of the colorant A, a pigment derivative having an acidic group or a basic group is preferable. It is particularly preferable that the pigment derivative has a basic group. The combination of the resin (dispersant) and the pigment derivative described above is preferably a combination in which the dispersant is an acidic dispersant and the pigment derivative has a basic group.
　顔料誘導体を構成するための有機顔料としては、ジケトピロロピロール系顔料、アゾ系顔料、フタロシアニン系顔料、アントラキノン系顔料、キナクリドン系顔料、ジオキサジン系顔料、ペリノン系顔料、ペリレン系顔料、チオインジゴ系顔料、イソインドリン系顔料、イソインドリノン系顔料、キノフタロン系顔料、スレン系顔料、金属錯体系顔料等が挙げられる。
　顔料誘導体が有する酸性基としては、スルホン酸基、カルボン酸基及びその塩が好ましく、カルボン酸基及びスルホン酸基がより好ましく、スルホン酸基が更に好ましい。顔料誘導体が有する塩基性基としては、アミノ基が好ましく、三級アミノ基がより好ましい。 Examples of the organic pigment for constituting the pigment derivative include diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments , Isoindoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, metal complex pigments, and the like.
As an acidic group which a pigment derivative has, a sulfonic acid group, a carboxylic acid group, and its salt are preferable, a carboxylic acid group and a sulfonic acid group are more preferable, and a sulfonic acid group is still more preferable. As a basic group which a pigment derivative has, an amino group is preferable and a tertiary amino group is more preferable.
　硬化性組成物が顔料誘導体を含有する場合、顔料誘導体の含有量は、顔料の質量に対し、１～３０質量％が好ましく、３～２０質量％がより好ましい。顔料誘導体は、１種のみを用いてもよいし、２種以上を併用してもよい。 When the curable composition contains a pigment derivative, the content of the pigment derivative is preferably 1 to 30% by mass and more preferably 3 to 20% by mass with respect to the mass of the pigment. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination.
＜重合禁止剤＞
　硬化性組成物は、重合禁止剤を含有してもよい。重合禁止剤を含有することにより硬化性組成物はより優れた経時安定性を有する。なお、本明細書において経時安定性とは、硬化性組成物を調製後、所定期間保管した場合であっても、優れたパターン形状を有する硬化膜を得ることができることを意図する。
　重合禁止剤は、保管中の硬化性組成物中において、多官能チオール化合物と重合性化合物との反応が進行するのを抑制する作用を有し、上記効果が得られるものと推測される。
　重合禁止剤の含有量は、硬化性組成物の全固形分に対して、０．００１～１質量％が好ましく、０．００５～１質量％がより好ましく、０．０５～１質量％が更に好ましい。
　重合禁止剤の含有量が上記範囲内だと硬化性組成物はより優れた経時安定性を有する。 <Polymerization inhibitor>
The curable composition may contain a polymerization inhibitor. By containing a polymerization inhibitor, the curable composition has better stability over time. In the present specification, the term “stability over time” means that a cured film having an excellent pattern shape can be obtained even when the curable composition is prepared and stored for a predetermined period.
The polymerization inhibitor has an action of suppressing the progress of the reaction between the polyfunctional thiol compound and the polymerizable compound in the curable composition being stored, and it is presumed that the above-described effect can be obtained.
The content of the polymerization inhibitor is preferably 0.001 to 1% by mass, more preferably 0.005 to 1% by mass, and further 0.05 to 1% by mass based on the total solid content of the curable composition. preferable.
When the content of the polymerization inhibitor is within the above range, the curable composition has more excellent temporal stability.
　重合禁止剤としては、特に制限されず、重合禁止剤として用いられる公知の化合物を用いることができる。重合禁止剤として用いられる化合物としては、例えば、フェノール系化合物、キノン系化合物、ヒンダードアミン系化合物、フェノチアジン系化合物、及びニトロベンゼン系化合物等が挙げられる。上記化合物は１種を単独で用いても、２種以上を併用してもよい。 The polymerization inhibitor is not particularly limited, and a known compound used as a polymerization inhibitor can be used. Examples of the compound used as the polymerization inhibitor include phenolic compounds, quinone compounds, hindered amine compounds, phenothiazine compounds, and nitrobenzene compounds. The said compound may be used individually by 1 type, or may use 2 or more types together.
　フェノール系化合物としては、例えば、フェノール、４－メトキシフェノール、ヒドロキノン、２－ｔｅｒｔ－ブチルヒドロキノン、カテコール、４－ｔｅｒｔ－ブチル－カテコール、２，６－ジ－ｔｅｒｔ－ブチルフェノール、２，６－ジ－ｔｅｒｔ－ブチル－４－メチルフェノール、２，６－ジ－ｔｅｒｔ－ブチル－４－エチルフェノール、４－ヒドロキシメチル－２，６－ジ－ｔｅｒｔ－ブチルフェノール、ペンタエリスリトールテトラキス（３，５－ジ－ｔｅｒｔ－ブチル－４－ヒドロキシヒドロシンナメート）、４－メトキシ－１－ナフトール、及び１，４－ジヒドロキシナフタレン等が挙げられる。 Examples of phenolic compounds include phenol, 4-methoxyphenol, hydroquinone, 2-tert-butylhydroquinone, catechol, 4-tert-butyl-catechol, 2,6-di-tert-butylphenol, 2,6-di- tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, pentaerythritol tetrakis (3,5-di-tert -Butyl-4-hydroxyhydrocinnamate), 4-methoxy-1-naphthol, 1,4-dihydroxynaphthalene and the like.
　フェノール系化合物としては、式（ＩＨ－１）で示されるフェノール系化合物が好ましい。 As the phenolic compound, a phenolic compound represented by the formula (IH-1) is preferable.
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
　式（ＩＨ－１）中、Ｒ１～Ｒ５は、それぞれ独立して、水素原子、アルキル基、アルケニル基、ヒドロキシ基、アミノ基、アリール基、アルコキシ基、カルボキシル基、アルコキシカルボニル基、又はアシル基を表す。Ｒ１～Ｒ５はそれぞれ連結して環を形成してもよい。 In formula (IH-1), R 1 to R 5 are each independently a hydrogen atom, alkyl group, alkenyl group, hydroxy group, amino group, aryl group, alkoxy group, carboxyl group, alkoxycarbonyl group, or acyl. Represents a group. R 1 to R 5 may be connected to each other to form a ring.
　式（ＩＨ－１）中のＲ１～Ｒ５としては、水素原子、炭素数１～５のアルキル基（例えば、メチル基及びエチル基等）、炭素数１～５のアルコキシ基（例えば、メトキシ基及びエトキシ基等）、炭素数２～４のアルケニル基（例えば、ビニル基等）、又はフェニル基が好ましい。
　なかでも、Ｒ１及びＲ５はそれぞれ独立して、水素原子又はｔｅｒｔ－ブチル基がより好ましく、Ｒ２及びＲ４は水素原子がより好ましく、Ｒ３は水素原子、炭素数１～５のアルキル基又は炭素数１～５のアルコキシ基がより好ましい。 R 1 to R 5 in formula (IH-1) are each a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (eg, a methyl group or an ethyl group), or an alkoxy group having 1 to 5 carbon atoms (eg, methoxy A alkenyl group having 2 to 4 carbon atoms (for example, a vinyl group), or a phenyl group.
Among them, R 1 and R 5 are each independently more preferably a hydrogen atom or a tert-butyl group, R 2 and R 4 are more preferably a hydrogen atom, R 3 is a hydrogen atom, and an alkyl having 1 to 5 carbon atoms. A group or an alkoxy group having 1 to 5 carbon atoms is more preferable.
　キノン系化合物としては、例えば、１，４－ベンゾキノン、１，２－ベンゾキノン、及び１，４－ナフトキノン等が挙げられる。 Examples of the quinone compound include 1,4-benzoquinone, 1,2-benzoquinone, and 1,4-naphthoquinone.
　ヒンダードアミン系化合物としては、例えば、下記式（ＩＨ－２）で表わされる重合禁止剤が挙げられる。 Examples of the hindered amine compound include a polymerization inhibitor represented by the following formula (IH-2).
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
　式（ＩＨ－２）中のＲ６は、水素原子、ヒドロキシ基、アミノ基、アルコキシ基、アルコキシカルボニル基、又はアシル基を表す。なかでも、水素原子又はヒドロキシ基が好ましく、ヒドロキシ基がより好ましい。
　式（ＩＨ－２）中のＲ７～Ｒ１０は、それぞれ独立して、水素原子又はアルキル基を表す。Ｒ７～Ｒ１０が表すアルキル基としては、炭素数１～５のアルキル基が好ましく、メチル基又はエチル基がより好ましい。 R 6 in formula (IH-2) represents a hydrogen atom, a hydroxy group, an amino group, an alkoxy group, an alkoxycarbonyl group, or an acyl group. Of these, a hydrogen atom or a hydroxy group is preferable, and a hydroxy group is more preferable.
R 7 to R 10 in formula (IH-2) each independently represent a hydrogen atom or an alkyl group. The alkyl group represented by R 7 to R 10 is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group or an ethyl group.
　重合禁止剤としては、上記の各化合物を１種単独で用いても、２種を併用してもよく、３種以上を併用してもよい。
　重合禁止剤は、フェノール系化合物を含有することが好ましい。なかでも、重合禁止剤は２種以上のフェノール系化合物を含有することがより好ましい。異なるフェノール系化合物を含有する硬化性組成物はより優れた本発明の効果を有する。
　重合禁止剤は、フェノール系化合物と、ヒンダードアミン系化合物とを含有することが好ましい。フェノール系化合物とヒンダードアミン系化合物とを含有する硬化性組成物はより優れた本発明の効果を有する。 As a polymerization inhibitor, each of the above compounds may be used alone, in combination of two or in combination of three or more.
The polymerization inhibitor preferably contains a phenolic compound. Especially, it is more preferable that a polymerization inhibitor contains 2 or more types of phenolic compounds. A curable composition containing a different phenolic compound has a more excellent effect of the present invention.
The polymerization inhibitor preferably contains a phenolic compound and a hindered amine compound. The curable composition containing a phenol compound and a hindered amine compound has a more excellent effect of the present invention.
＜溶剤＞
　硬化性組成物は、溶剤を含有することが好ましい。溶剤としては、水、及び有機溶剤が挙げられる。硬化性組成物は有機溶剤を含有することが好ましい。
　硬化性組成物が溶剤を含有する場合、硬化性組成物の固形分は１０～３０質量％が好ましい。硬化性組成物の固形分が下限値以上だと、粘度が低く塗布性が良化する。更に、反応性の高い化合物の濃度が低くなることから経時安定性が良化する。硬化性組成物の固形分が上限値以下だと、粘度が程度に保たれ塗布性が良化する。更に、比重の重い着色剤が沈降しにくくなり、経時安定性が良化する。 <Solvent>
The curable composition preferably contains a solvent. Examples of the solvent include water and organic solvents. The curable composition preferably contains an organic solvent.
When the curable composition contains a solvent, the solid content of the curable composition is preferably 10 to 30% by mass. When solid content of a curable composition is more than a lower limit, a viscosity is low and applicability | paintability will improve. Furthermore, since the concentration of the highly reactive compound is lowered, the temporal stability is improved. When the solid content of the curable composition is less than or equal to the upper limit value, the viscosity is maintained at a certain level and the applicability is improved. Furthermore, the colorant having a high specific gravity is less likely to settle, and the stability over time is improved.
（有機溶剤）
　硬化性組成物が有機溶剤を含有する場合、有機溶剤の含有量としては、硬化性組成物の全質量に対し、７０～９０質量％が好ましい。
　なお、有機溶剤は１種を単独で用いても、２種以上を併用してもよい。２種以上の有機溶剤を併用する場合には、その合計量が上記範囲となることが好ましい。 (Organic solvent)
When the curable composition contains an organic solvent, the content of the organic solvent is preferably 70 to 90% by mass with respect to the total mass of the curable composition.
In addition, an organic solvent may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of organic solvents together, it is preferable that the total amount becomes the said range.
　有機溶剤としては、特に制限されないが、例えば、アセトン、メチルエチルケトン、シクロヘキサン、エチレンジクロライド、テトラヒドロフラン、トルエン、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、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、アセチルアセトン、シクロヘキサノン、シクロペンタノン、ジアセトンアルコール、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エチルエーテルアセテート、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテルアセテート、３－メトキシプロパノール、メトキシメトキシエタノール、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、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、３－メトキシプロピルアセテート、Ｎ，Ｎ－ジメチルホルムアミド、ジメチルスルホキシド、γ－ブチロラクトン、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、エチルセロソルブアセテート、３－メトキシプロピオン酸メチル、２－ヘプタノン、エチルカルビトールアセテート、ブチルカルビトールアセテート、酢酸エチル、酢酸ブチル、乳酸メチル、及び乳酸エチル等が挙げられる。 The organic solvent is not particularly limited. For example, acetone, methyl ethyl ketone, cyclohexane, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether. , Acetylacetone, cyclohexanone, cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol Monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, methyl 3-methoxypropionate, 2-heptanone, ethyl carbitol acetate, butyl carbitol acetate, ethyl acetate, butyl acetate, methyl lactate, and lactic acid And ethyl.
　２種以上の有機溶剤を含有する場合には、上記の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、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、３－メトキシプロピオン酸メチル、２－ヘプタノン、シクロヘキサノン、シクロペンタノン、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテル、及びプロピレングリコールモノメチルエーテルアセテートからなる群から選択される２種以上で構成されることが好ましい。 When two or more organic solvents are contained, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, -It is preferably composed of two or more selected from the group consisting of heptanone, cyclohexanone, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.
（水）
　硬化性組成物は、水を含有してもよい。水は、意図的に添加されるものであってもよいし、硬化性組成物に含まれる各成分を添加することで不可避的に硬化性組成物中に含有されるものであってもよい。
　水の含有量は、硬化性組成物の全質量に対して、０．０１～１質量％が好ましい。水の含有量が上記範囲内にあると、硬化膜を作製した際にピンホールの発生が抑制され、更に、硬化膜の耐湿性が向上する。 (water)
The curable composition may contain water. Water may be intentionally added, or may be inevitably contained in the curable composition by adding each component contained in the curable composition.
The water content is preferably 0.01 to 1% by mass relative to the total mass of the curable composition. When the water content is within the above range, the generation of pinholes is suppressed when a cured film is produced, and the moisture resistance of the cured film is further improved.
＜分散剤＞
　硬化性組成物は、分散剤を含有することが好ましい。分散剤は、着色剤の分散性向上に寄与する。本明細書において、分散剤と、後述するバインダー樹脂とは、異なる成分である。 <Dispersant>
The curable composition preferably contains a dispersant. The dispersant contributes to the improvement of the dispersibility of the colorant. In the present specification, the dispersant and the binder resin described later are different components.
　硬化性組成物が、分散剤を含有する場合、分散剤の含有量は、硬化性組成物の全固形分に対して、０．０５～５０質量％が好ましく、０．０５～３０質量％がより好ましい。
　分散剤の含有量が、硬化性組成物の全固形分に対して０．０５～３０質量％であると、硬化性組成物を硬化して得られる硬化膜のパターン形状がより優れる。
　分散剤は、１種を単独で用いても、２種以上を併用してもよい。分散剤を２種以上併用する場合は、合計量が上記範囲内であることが好ましい。 When the curable composition contains a dispersant, the content of the dispersant is preferably 0.05 to 50% by mass, and 0.05 to 30% by mass with respect to the total solid content of the curable composition. More preferred.
When the content of the dispersant is 0.05 to 30% by mass with respect to the total solid content of the curable composition, the pattern shape of the cured film obtained by curing the curable composition is more excellent.
A dispersing agent may be used individually by 1 type, or may use 2 or more types together. When two or more dispersants are used in combination, the total amount is preferably within the above range.
　分散剤としては、例えば、公知の顔料分散剤を適宜選択して用いることができる。なかでも、高分子化合物が好ましい。
　分散剤としては、高分子分散剤〔例えば、ポリアミドアミンとその塩、ポリカルボン酸とその塩、高分子量不飽和酸エステル、変性ポリウレタン、変性ポリエステル、変性ポリ（メタ）アクリレート、（メタ）アクリル系共重合体、ナフタレンスルホン酸ホルマリン縮合物〕、ポリオキシエチレンアルキルリン酸エステル、ポリオキシエチレンアルキルアミン、及び、顔料誘導体等を挙げることができる。
　高分子化合物は、その構造から更に直鎖状高分子、末端変性型高分子、グラフト型高分子、及びブロック型高分子に分類することができる。 As the dispersant, for example, a known pigment dispersant can be appropriately selected and used. Of these, polymer compounds are preferable.
Examples of the dispersant include polymer dispersants [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) acrylic type Copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, and pigment derivatives.
The polymer compounds can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.
（高分子化合物）
　高分子化合物は、着色剤（例えば、無機顔料）の被分散体の表面に吸着し、被分散体の再凝集を防止するように作用する。そのため、顔料表面へのアンカー部位を含有する、末端変性型高分子、グラフト型高分子、及び、ブロック型高分子が好ましい。 (Polymer compound)
The polymer compound is adsorbed on the surface of the dispersion of the colorant (for example, inorganic pigment) and acts to prevent reaggregation of the dispersion. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer containing an anchor site to the pigment surface are preferable.
　高分子化合物は、グラフト鎖を含有する構造単位を含有することが好ましい。本明細書において、「構造単位」とは「繰り返し単位」と同義である。
　このようなグラフト鎖を含有する構造単位を含有する高分子化合物は、グラフト鎖によって溶剤との親和性を有するため、黒色顔料等の着色剤の分散性、及び、経時後の分散安定性（経時安定性）に優れる。グラフト鎖を含有する構造単位を含有する高分子化合物は、グラフト鎖の存在により、重合性化合物又はその他の併用可能な樹脂等との親和性を有する。結果として、アルカリ現像で残渣を生じにくくなる。
　グラフト鎖が長くなると立体反発効果が高くなり黒色顔料等の分散性は向上する。一方、グラフト鎖が長すぎると黒色顔料等の着色顔料への吸着力が低下して、黒色顔料等の分散性は低下する傾向となる。このため、グラフト鎖は、水素原子を除いた原子数が４０～１０，０００であるものが好ましく、水素原子を除いた原子数が５０～２，０００であるものがより好ましく、水素原子を除いた原子数が６０～５００であるものが更に好ましい。
　ここで、グラフト鎖とは、共重合体の主鎖の根元（主鎖から枝分かれしている基において主鎖に結合する原子）から、主鎖から枝分かれしている基の末端までを示す。 The polymer compound preferably contains a structural unit containing a graft chain. In this specification, “structural unit” is synonymous with “repeating unit”.
Since the polymer compound containing a structural unit containing such a graft chain has an affinity for a solvent due to the graft chain, the dispersibility of a colorant such as a black pigment and the dispersion stability after the lapse of time ( Excellent stability. The polymer compound containing a structural unit containing a graft chain has an affinity for a polymerizable compound or other resin that can be used in combination due to the presence of the graft chain. As a result, it becomes difficult to produce a residue by alkali development.
When the graft chain becomes longer, the steric repulsion effect becomes higher and the dispersibility of the black pigment and the like is improved. On the other hand, if the graft chain is too long, the adsorptive power to colored pigments such as black pigments is lowered, and the dispersibility of black pigments and the like tends to be lowered. Therefore, the graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2,000 atoms excluding hydrogen atoms, and excluding hydrogen atoms. More preferred are those having 60 to 500 atoms.
Here, the graft chain means from the base of the main chain of the copolymer (the atom bonded to the main chain in a group branched from the main chain) to the end of the group branched from the main chain.
　グラフト鎖は、ポリマー構造を含有することが好ましく、このようなポリマー構造としては、例えば、ポリ（メタ）アクリレート構造（例えば、ポリ（メタ）アクリル構造）、ポリエステル構造、ポリウレタン構造、ポリウレア構造、ポリアミド構造、及び、ポリエーテル構造等を挙げることができる。
　グラフト鎖と溶剤との相互作用性を向上させ、それにより黒色顔料等の分散性を高めるために、グラフト鎖は、ポリエステル構造、ポリエーテル構造及びポリ（メタ）アクリレート構造からなる群から選ばれた少なくとも１種を含有するグラフト鎖であることが好ましく、ポリエステル構造又はポリエーテル構造の少なくともいずれかを含有するグラフト鎖であることがより好ましい。 The graft chain preferably contains a polymer structure. Examples of such a polymer structure include a poly (meth) acrylate structure (for example, a poly (meth) acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, and a polyamide. Examples thereof include a structure and a polyether structure.
The graft chain was selected from the group consisting of a polyester structure, a polyether structure and a poly (meth) acrylate structure in order to improve the interaction between the graft chain and the solvent, thereby increasing the dispersibility of the black pigment and the like. A graft chain containing at least one kind is preferred, and a graft chain containing at least one of a polyester structure or a polyether structure is more preferred.
　このようなグラフト鎖を含有するマクロモノマーとしては、特に限定されないが、反応性二重結合性基を含有するマクロモノマーを好適に使用することができる。 The macromonomer containing such a graft chain is not particularly limited, but a macromonomer containing a reactive double bond group can be preferably used.
　高分子化合物が含有するグラフト鎖を含有する構造単位に対応し、高分子化合物の合成に好適に用いられる市販のマクロモノマーとしては、ＡＡ－６（商品名、東亜合成社製）、ＡＡ－１０（商品名、東亜合成社製）、ＡＢ－６（商品名、東亜合成社製）、ＡＳ－６（商品名、東亜合成社製）、ＡＮ－６（商品名、東亜合成社製）、ＡＷ－６（商品名、東亜合成社製）、ＡＡ－７１４（商品名、東亜合成社製）、ＡＹ－７０７（商品名、東亜合成社製）、ＡＹ－７１４（商品名、東亜合成社製）、ＡＫ－５（商品名、東亜合成社製）、ＡＫ－３０（商品名、東亜合成社製）、ＡＫ－３２（商品名、東亜合成社製）、ブレンマーＰＰ－１００（商品名、日油社製）、ブレンマーＰＰ－５００（商品名、日油社製）、ブレンマーＰＰ－８００（商品名、日油社製）、ブレンマーＰＰ－１０００（商品名、日油社製）、ブレンマー５５－ＰＥＴ－８００（商品名、日油社製）、ブレンマーＰＭＥ－４０００（商品名、日油社製）、ブレンマーＰＳＥ－４００（商品名、日油社製）、ブレンマーＰＳＥ－１３００（商品名、日油社製）、ブレンマー４３ＰＡＰＥ－６００Ｂ（商品名、日油社製）等が挙げられる。このなかでも、ＡＡ－６（商品名、東亜合成社製）、ＡＡ－１０（商品名、東亜合成社製）、ＡＢ－６（商品名、東亜合成社製）、ＡＳ－６（商品名、東亜合成社製）、ＡＮ－６（商品名、東亜合成社製）、及び、ブレンマーＰＭＥ－４０００（商品名、日油社製）等が好ましい。 Corresponding to the structural unit containing a graft chain contained in the polymer compound, commercially available macromonomers suitably used for the synthesis of the polymer compound include AA-6 (trade name, manufactured by Toagosei Co., Ltd.), AA-10. (Trade name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AS-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AN-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AW -6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-714 (trade name, manufactured by Toa Gosei Co., Ltd.), AY-707 (trade name, manufactured by Toa Gosei Co., Ltd.), AY-714 (trade name, manufactured by Toa Gosei Co., Ltd.) AK-5 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-30 (trade name, manufactured by Toa Gosei Co., Ltd.), AK-32 (trade name, manufactured by Toa Gosei Co., Ltd.), Blemmer PP-100 (trade name, NOF Corporation) Blemmer PP-500 (trade name, manufactured by NOF Corporation), Blemmer PP-800 ( Product name, manufactured by NOF Corporation), BLEMMER PP-1000 (trade name, manufactured by NOF CORPORATION), BLEMMER 55-PET-800 (trade name, manufactured by NOF CORPORATION), BLEMMER PME-4000 (trade name, manufactured by NOF Corporation) ), BLEMMER PSE-400 (trade name, manufactured by NOF Corporation), BLEMMER PSE-1300 (trade name, manufactured by NOF Corporation), BLEMMER 43PAPE-600B (trade name, manufactured by NOF Corporation) and the like. Among these, AA-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AA-10 (trade name, manufactured by Toa Gosei Co., Ltd.), AB-6 (trade name, manufactured by Toa Gosei Co., Ltd.), AS-6 (trade name, Toa Gosei Co., Ltd.), AN-6 (trade name, manufactured by Toa Gosei Co., Ltd.), and Bremer PME-4000 (trade name, manufactured by NOF Corporation) are preferred.
　分散剤は、ポリアクリル酸メチル、ポリメタクリル酸メチル、及び環状又は鎖状のポリエステルからなる群より選択される少なくとも１種の構造を含有することが好ましい。分散剤は、ポリアクリル酸メチル、ポリメタクリル酸メチル、及び鎖状のポリエステルからなる群より選択される少なくとも１種の構造を含有することがより好ましい。分散剤は、ポリアクリル酸メチル構造、ポリメタクリル酸メチル構造、ポリカプロラクトン構造、及びポリバレロラクトン構造からなる群より選択される少なくとも１種の構造を含有することが更に好ましい。分散剤は、１つの分散剤中に上記構造を単独で含有するものであってもよいし、１つの分散剤中にこれらの構造を複数含有するものであってもよい。
　ここで、ポリカプロラクトン構造とは、ε－カプロラクトンを開環した構造を繰り返し単位として含有するものをいう。ポリバレロラクトン構造とは、δ－バレロラクトンを開環した構造を繰り返し単位として含有するものをいう。
　ポリカプロラクトン構造を含有する分散剤の具体例としては、下記式（１）及び下記式（２）におけるｊ及びｋが５であるものが挙げられる。また、ポリバレロラクトン構造を含有する分散剤の具体例としては、下記式（１）及び下記式（２）におけるｊ及びｋが４であるものが挙げられる。
　ポリアクリル酸メチル構造を含有する分散剤の具体例としては、下記式（４）におけるＸ５が水素原子であり、Ｒ４がメチル基であるものが挙げられる。また、ポリメタクリル酸メチル構造を含有する分散剤の具体例としては、下記式（４）におけるＸ５がメチル基であり、Ｒ４がメチル基であるものが挙げられる。 The dispersant preferably contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyester. More preferably, the dispersant contains at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and chain polyester. More preferably, the dispersant contains at least one structure selected from the group consisting of a polymethyl acrylate structure, a polymethyl methacrylate structure, a polycaprolactone structure, and a polyvalerolactone structure. The dispersant may contain the above structure alone in one dispersant, or may contain a plurality of these structures in one dispersant.
Here, the polycaprolactone structure means a structure containing a ring-opened structure of ε-caprolactone as a repeating unit. The polyvalerolactone structure means a structure containing a ring-opened structure of δ-valerolactone as a repeating unit.
Specific examples of the dispersant containing a polycaprolactone structure include those in which j and k are 5 in the following formula (1) and the following formula (2). Specific examples of the dispersant containing a polyvalerolactone structure include those in which j and k in the following formula (1) and the following formula (2) are 4.
Specific examples of the dispersant containing a polymethyl acrylate structure include those in which X 5 in the following formula (4) is a hydrogen atom and R 4 is a methyl group. Further, specific examples of the dispersant containing a polymethyl methacrylate structure include those in which X 5 in the following formula (4) is a methyl group and R 4 is a methyl group.
・グラフト鎖を含有する構造単位
　高分子化合物は、グラフト鎖を含有する構造単位として、下記式（１）～式（４）のいずれかで表される構造単位を含有することが好ましく、下記式（１Ａ）、下記式（２Ａ）、下記式（３Ａ）、下記式（３Ｂ）、及び下記（４）のいずれかで表される構造単位を含有することがより好ましい。 Structural unit containing a graft chain The polymer compound preferably contains a structural unit represented by any of the following formulas (1) to (4) as a structural unit containing a graft chain. It is more preferable to contain a structural unit represented by any one of (1A), the following formula (2A), the following formula (3A), the following formula (3B), and the following (4).
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
　式（１）～式（４）において、Ｗ１、Ｗ２、Ｗ３、及びＷ４はそれぞれ独立に酸素原子又はＮＨを表す。Ｗ１、Ｗ２、Ｗ３、及びＷ４は酸素原子であることが好ましい。
　式（１）～式（４）において、Ｘ１、Ｘ２、Ｘ３、Ｘ４、及びＸ５は、それぞれ独立に、水素原子又は１価の有機基を表す。Ｘ１、Ｘ２、Ｘ３、Ｘ４、及びＸ５は、合成上の制約の観点からは、それぞれ独立に、水素原子又は炭素数（炭素原子数）１～１２のアルキル基が好ましく、それぞれ独立に、水素原子又はメチル基がより好ましく、メチル基が更に好ましい。 In the formulas (1) to (4), W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH. W 1 , W 2 , W 3 , and W 4 are preferably oxygen atoms.
In the formulas (1) to (4), X 1 , X 2 , X 3 , X 4 , and X 5 each independently represent a hydrogen atom or a monovalent organic group. X 1 , X 2 , X 3 , X 4 , and X 5 are each independently preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (the number of carbon atoms), from the viewpoint of synthesis constraints, Independently, a hydrogen atom or a methyl group is more preferable, and a methyl group is still more preferable.
　式（１）～式（４）において、Ｙ１、Ｙ２、Ｙ３、及びＹ４は、それぞれ独立に、２価の連結基を表し、連結基は特に構造上制約されない。Ｙ１、Ｙ２、Ｙ３、及びＹ４で表される２価の連結基として、具体的には、下記の（Ｙ－１）～（Ｙ－２１）の連結基等が例として挙げられる。下記に示した構造において、Ａ、Ｂはそれぞれ結合部位を意味する。下記に示した構造のうち、合成の簡便性から、(Ｙ－２)又は（Ｙ－１３）であることがより好ましい。 In the formulas (1) to (4), Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group, and the linking group is not particularly limited in structure. Specific examples of the divalent linking group represented by Y 1 , Y 2 , Y 3 , and Y 4 include the following (Y-1) to (Y-21) linking groups. . In the structure shown below, A and B each represent a binding site. Of the structures shown below, (Y-2) or (Y-13) is more preferable from the viewpoint of ease of synthesis.
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
　式（１）～式（４）において、Ｚ１、Ｚ２、Ｚ３、及びＺ４は、それぞれ独立に１価の有機基を表す。有機基の構造は、特に限定されないが、具体的には、アルキル基、ヒドロキシ基、アルコキシ基、アリールオキシ基、ヘテロアリールオキシ基、アルキルチオエーテル基、アリールチオエーテル基、ヘテロアリールチオエーテル基、及びアミノ基等が挙げられる。これらの中でも、Ｚ１、Ｚ２、Ｚ３、及びＺ４で表される有機基としては、特に分散性向上の観点から、立体反発効果を含有するものが好ましく、各々独立に炭素数５から２４のアルキル基又はアルコキシ基がより好ましく、その中でも、各々独立に炭素数５から２４の分岐アルキル基、炭素数５から２４の環状アルキル基、又は、炭素数５から２４のアルコキシ基が更に好ましい。アルコキシ基中に含まれるアルキル基は、直鎖状、分岐鎖状、及び、環状のいずれでもよい。 In the formulas (1) to (4), Z 1 , Z 2 , Z 3 , and Z 4 each independently represent a monovalent organic group. The structure of the organic group is not particularly limited, and specifically, an alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an amino group Etc. Among these, as the organic group represented by Z 1 , Z 2 , Z 3 , and Z 4 , those containing a steric repulsion effect are particularly preferable from the viewpoint of improving dispersibility, and each independently has 5 carbon atoms. 24 alkyl groups or alkoxy groups are more preferable, and among them, each independently a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms is more preferable. . The alkyl group contained in the alkoxy group may be linear, branched, or cyclic.
　式（１）～式（４）において、ｎ、ｍ、ｐ、及びｑは、それぞれ独立に、１から５００の整数である。
　式（１）及び式（２）において、ｊ及びｋは、それぞれ独立に、２～８の整数を表す。式（１）及び式（２）におけるｊ及びｋは、硬化性組成物の経時安定性及び現像性の観点から、４～６の整数が好ましく、５が最も好ましい。 In the formulas (1) to (4), n, m, p, and q are each independently an integer of 1 to 500.
In Formula (1) and Formula (2), j and k each independently represent an integer of 2 to 8. J and k in the formulas (1) and (2) are preferably integers of 4 to 6 and most preferably 5 from the viewpoint of the temporal stability and developability of the curable composition.
　式（３）中、Ｒ３は分岐又は直鎖のアルキレン基を表し、炭素数１～１０のアルキレン基が好ましく、炭素数２又は３のアルキレン基がより好ましい。ｐが２～５００のとき、複数存在するＲ３は互いに同じであっても異なっていてもよい。
　式（４）中、Ｒ４は水素原子又は１価の有機基を表し、この１価の有機基としては特に構造上限定はされない。Ｒ４は、水素原子、アルキル基、アリール基、又は、ヘテロアリール基が好ましく、水素原子、又はアルキル基がより好ましい。Ｒ４がアルキル基である場合、炭素数１～２０の直鎖状アルキル基、炭素数３～２０の分岐状アルキル基、又は炭素数５～２０の環状アルキル基が好ましく、炭素数１～２０の直鎖状アルキル基がより好ましく、炭素数１～６の直鎖状アルキル基が更に好ましい。式（４）において、ｑが２～５００のとき、グラフト共重合体中に複数存在するＸ５及びＲ４は互いに同じであっても異なっていてもよい。 In formula (3), R 3 represents a branched or straight chain alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, a plurality of R 3 may be the same or different from each other.
In the formula (4), R 4 represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in terms of structure. R 4 is preferably a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, and more preferably a hydrogen atom or an alkyl group. When R 4 is an alkyl group, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms is preferable, and 1 to 20 carbon atoms is preferable. Are more preferable, and linear alkyl groups having 1 to 6 carbon atoms are more preferable. In the formula (4), when q is 2 to 500, a plurality of X 5 and R 4 present in the graft copolymer may be the same or different from each other.
　高分子化合物は、２種以上の構造が異なる、グラフト鎖を含有する構造単位を含有することができる。即ち、高分子化合物の分子中に、互いに構造の異なる式（１）～式（４）で示される構造単位を含んでいてもよく、式（１）～式（４）においてｎ、ｍ、ｐ、及びｑがそれぞれ２以上の整数を表す場合、式（１）及び式（２）においては、側鎖中にｊ及びｋが互いに異なる構造を含んでいてもよく、式（３）及び式（４）においては、分子内に複数存在するＲ３、Ｒ４及びＸ５は互いに同じであっても異なっていてもよい。 A high molecular compound can contain the structural unit containing the graft chain from which 2 or more types of structures differ. That is, in the molecule of the polymer compound, structural units represented by the formulas (1) to (4) having different structures from each other may be included. , And q each represent an integer of 2 or more, in Formula (1) and Formula (2), j and k may contain structures different from each other in the side chain, and Formula (3) and Formula ( In 4), a plurality of R 3 , R 4 and X 5 present in the molecule may be the same or different from each other.
　式（１）で表される構造単位としては、硬化性組成物の経時安定性及び現像性の観点から、下記式（１Ａ）で表される構造単位であることがより好ましい。
　式（２）で表される構造単位としては、硬化性組成物の経時安定性及び現像性の観点から、下記式（２Ａ）で表される構造単位であることがより好ましい。 The structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of temporal stability and developability of the curable composition.
The structural unit represented by the formula (2) is more preferably a structural unit represented by the following formula (2A) from the viewpoint of temporal stability and developability of the curable composition.
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
　式（１Ａ）中、Ｘ１、Ｙ１、Ｚ１及びｎは、式（１）におけるＸ１、Ｙ１、Ｚ１及びｎと同義であり、好ましい範囲も同様である。式（２Ａ）中、Ｘ２、Ｙ２、Ｚ２及びｍは、式（２）におけるＸ２、Ｙ２、Ｚ２及びｍと同義であり、好ましい範囲も同様である。 Wherein (1A), X 1, Y 1, Z 1 and n are as defined X 1, Y 1, Z 1 and n in Formula (1), and preferred ranges are also the same. Wherein (2A), X 2, Y 2, Z 2 and m are as defined X 2, Y 2, Z 2 and m in the formula (2), and preferred ranges are also the same.
　式（３）で表される構造単位としては、硬化性組成物の経時安定性及び現像性の観点から、下記式（３Ａ）又は式（３Ｂ）で表される構造単位であることがより好ましい。 The structural unit represented by the formula (3) is more preferably a structural unit represented by the following formula (3A) or the formula (3B) from the viewpoint of temporal stability and developability of the curable composition. .
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
　式（３Ａ）又は（３Ｂ）中、Ｘ３、Ｙ３、Ｚ３及びｐは、式（３）におけるＸ３、Ｙ３、Ｚ３及びｐと同義であり、好ましい範囲も同様である。 Wherein (3A) or (3B), X 3, Y 3, Z 3 and p are as defined X 3, Y 3, Z 3 and p in formula (3), and preferred ranges are also the same.
　高分子化合物は、グラフト鎖を含有する構造単位として、式（１Ａ）で表される構造単位を含有することがより好ましい。 More preferably, the polymer compound contains a structural unit represented by the formula (1A) as a structural unit containing a graft chain.
　高分子化合物において、グラフト鎖を含有する構造単位（例えば、上記式（１）～式（４）で表される構造単位）は、質量換算で、高分子化合物の総質量に対し２～９０％の範囲で含まれることが好ましく、５～３０％の範囲で含まれることがより好ましい。グラフト鎖を含有する構造単位がこの範囲内で含まれると、黒色顔料の分散性が高く、硬化膜を形成する際の現像性が良好である。 In the polymer compound, the structural unit containing a graft chain (for example, the structural unit represented by the above formulas (1) to (4)) is 2 to 90% in terms of mass with respect to the total mass of the polymer compound. Preferably, it is contained in the range of 5 to 30%. When the structural unit containing a graft chain is included within this range, the dispersibility of the black pigment is high, and the developability when forming a cured film is good.
・疎水性構造単位
　高分子化合物は、グラフト鎖を含有する構造単位とは異なる（すなわち、グラフト鎖を含有する構造単位には相当しない）疎水性構造単位を含有することが好ましい。ただし、本明細書において、疎水性構造単位は、酸基（例えば、カルボン酸基、スルホン酸基、リン酸基、フェノール性ヒドロキシ基等）を有さない構造単位である。 -Hydrophobic structural unit It is preferable that a high molecular compound contains the hydrophobic structural unit different from the structural unit containing a graft chain (namely, it does not correspond to the structural unit containing a graft chain). However, in this specification, a hydrophobic structural unit is a structural unit which does not have an acid group (for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, a phenolic hydroxy group, etc.).
　疎水性構造単位は、好ましくは、ＣｌｏｇＰ値が１．２以上の化合物（モノマー）に由来する（対応する）構造単位であり、より好ましくは、ＣｌｏｇＰ値が１．２～８の化合物に由来する構造単位である。これにより、本発明の効果をより確実に発現することができる。 The hydrophobic structural unit is preferably a structural unit derived from (corresponding to) a compound (monomer) having a ClogP value of 1.2 or more, more preferably derived from a compound having a ClogP value of 1.2 to 8. A structural unit. Thereby, the effect of this invention can be expressed more reliably.
　ＣｌｏｇＰ値は、Ｄａｙｌｉｇｈｔ　Ｃｈｅｍｉｃａｌ　Ｉｎｆｏｒｍａｔｉｏｎ　Ｓｙｓｔｅｍ，　Ｉｎｃ．から入手できるプログラム“ＣＬＯＧＰ”で計算される値である。このプログラムは、Ｈａｎｓｃｈ，　Ｌｅｏのフラグメントアプローチ（下記文献参照）により算出される“計算ｌｏｇＰ”の値を提供する。フラグメントアプローチは化合物の化学構造に基づいており、化学構造を部分構造（フラグメント）に分割し、そのフラグメントに対して割り当てられたｌｏｇＰ寄与分を合計することにより化合物のｌｏｇＰ値を推算している。その詳細は以下の文献に記載されている。本明細書では、ＣｌｏｇＰ値は、プログラムＣＬＯＧＰ　ｖ４．８２により計算した値を意図する。
　Ａ．　Ｊ．　Ｌｅｏ，　Ｃｏｍｐｒｅｈｅｎｓｉｖｅ　Ｍｅｄｉｃｉｎａｌ　Ｃｈｅｍｉｓｔｒｙ，　Ｖｏｌ．４，　Ｃ．　Ｈａｎｓｃｈ，　Ｐ．　Ｇ．　Ｓａｍｍｎｅｎｓ，　Ｊ．　Ｂ．　Ｔａｙｌｏｒ　ａｎｄ　Ｃ．　Ａ．　Ｒａｍｓｄｅｎ，　Ｅｄｓ．，　ｐ．２９５，　Ｐｅｒｇａｍｏｎ　Ｐｒｅｓｓ，　１９９０　Ｃ．　Ｈａｎｓｃｈ　＆　Ａ．　Ｊ．　Ｌｅｏ．　ＳＵｂｓｔｉｔｕｅｎｔ　Ｃｏｎｓｔａｎｔｓ　Ｆｏｒ　Ｃｏｒｒｅｌａｔｉｏｎ　Ａｎａｌｙｓｉｓ　ｉｎ　Ｃｈｅｍｉｓｔｒｙ　ａｎｄ　Ｂｉｏｌｏｇｙ．　Ｊｏｈｎ　Ｗｉｌｅｙ　＆　Ｓｏｎｓ．　Ａ．Ｊ．　Ｌｅｏ．　Ｃａｌｃｕｌａｔｉｎｇ　ｌｏｇＰｏｃｔ　ｆｒｏｍ　ｓｔｒｕｃｔｕｒｅ．　Ｃｈｅｍ．　Ｒｅｖ．，　９３，　１２８１－１３０６，　１９９３． ClogP values can be obtained from Daylight Chemical Information System, Inc. It is a value calculated by the program “CLOGP” available from This program provides the value of “computation logP” calculated by Hansch, Leo's fragment approach (see below). The fragment approach is based on the chemical structure of a compound, which divides the chemical structure into substructures (fragments) and estimates the logP value of the compound by summing the logP contributions assigned to that fragment. Details thereof are described in the following documents. In this specification, ClogP value intends the value calculated by program CLOGP v4.82.
A. J. et al. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P.A. G. Sammunens, J. et al. B. Taylor and C.M. A. Ramsden, Eds. , P. 295, Pergamon Press, 1990 C.I. Hansch & A. J. et al. Leo. Substituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A. J. et al. Leo. Calculating logPoch from structure. Chem. Rev. , 93, 1281-1306, 1993.
　ｌｏｇＰは、分配係数Ｐ（Ｐａｒｔｉｔｉｏｎ　Ｃｏｅｆｆｉｃｉｅｎｔ）の常用対数を意味し、ある有機化合物が油（一般的には１－オクタノール）と水の２相系の平衡でどのように分配されるかを定量的な数値として表す物性値であり、以下の式で示される。
　　ｌｏｇＰ＝ｌｏｇ（Ｃｏｉｌ／Ｃｗａｔｅｒ）
　式中、Ｃｏｉｌは油相中の化合物のモル濃度を、Ｃｗａｔｅｒは水相中の化合物のモル濃度を表す。
　ｌｏｇＰの値が０をはさんでプラスに大きくなると油溶性が増し、マイナスで絶対値が大きくなると水溶性が増すことを意味し、有機化合物の水溶性と負の相関があり、有機化合物の親疎水性を見積るパラメータとして広く利用されている。 logP means the common logarithm of the partition coefficient P (Partition Coefficient), and quantitatively determines how an organic compound is distributed in the equilibrium of a two-phase system of oil (generally 1-octanol) and water. It is a physical property value expressed as a numerical value, and is represented by the following formula.
logP = log (Coil / Cwater)
In the formula, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the aqueous phase.
When the logP value increases to a positive value across 0, the oil solubility increases. When the logP value increases to a negative value, the water solubility increases. There is a negative correlation with the water solubility of the organic compound. It is widely used as a parameter for estimating aqueous properties.
　高分子化合物は、疎水性構造単位として、下記式（ｉ）～（ｉｉｉ）で表される単量体に由来の構造単位から選択された１種以上の構造単位を含有することが好ましい。 The polymer compound preferably contains one or more structural units selected from structural units derived from monomers represented by the following formulas (i) to (iii) as hydrophobic structural units.
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
　式（ｉ）～（ｉｉｉ）中、Ｒ１、Ｒ２、及びＲ３は、それぞれ独立に、水素原子、ハロゲン原子（例えば、フッ素原子、塩素原子、臭素原子等）、又は炭素数が１～６のアルキル基（例えば、メチル基、エチル基、プロピル基等）を表す。
　Ｒ１、Ｒ２、及びＲ３は、好ましくは水素原子、又は炭素数が１～３のアルキル基であり、より好ましくは水素原子又はメチル基である。Ｒ２及びＲ３は、水素原子であることが更に好ましい。
　Ｘは、酸素原子（－Ｏ－）又はイミノ基（－ＮＨ－）を表し、酸素原子であることが好ましい。 In formulas (i) to (iii), R 1 , R 2 , and R 3 each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number of 1 to 6 alkyl groups (for example, a methyl group, an ethyl group, a propyl group, etc.).
R 1 , R 2 , and R 3 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom or a methyl group. R 2 and R 3 are more preferably a hydrogen atom.
X represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
　Ｌは、単結合又は２価の連結基である。２価の連結基としては、２価の脂肪族基（例えば、アルキレン基、置換アルキレン基、アルケニレン基、置換アルケニレン基、アルキニレン基、置換アルキニレン基）、２価の芳香族基（例えば、アリーレン基、置換アリーレン基）、２価の複素環基、酸素原子（－Ｏ－）、硫黄原子（－Ｓ－）、イミノ基（－ＮＨ－）、置換イミノ基（－ＮＲ３１－、ここでＲ３１は脂肪族基、芳香族基又は複素環基）、カルボニル基（－ＣＯ－）、及び、これらの組合せ等が挙げられる。 L is a single bond or a divalent linking group. As the divalent linking group, a divalent aliphatic group (for example, alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, substituted alkynylene group), divalent aromatic group (for example, arylene group) , Substituted arylene group), divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino group (—NR 31 —, where R 31 Includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (—CO—), and combinations thereof.
　２価の脂肪族基は、環状構造又は分岐構造を有していてもよい。脂肪族基の炭素数は、１～２０が好ましく、１～１５がより好ましく、１～１０が更に好ましい。脂肪族基は不飽和脂肪族基であっても飽和脂肪族基であってもよいが、飽和脂肪族基であることが好ましい。脂肪族基は、置換基を有していてもよい。置換基の例は、ハロゲン原子、芳香族基及び複素環基等が挙げられる。 The divalent aliphatic group may have a cyclic structure or a branched structure. The aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. The aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but is preferably a saturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group and a heterocyclic group.
　２価の芳香族基の炭素数は、６～２０が好ましく、６～１５がより好ましく、６～１０が更に好ましい。芳香族基は置換基を有していてもよい。置換基の例は、ハロゲン原子、脂肪族基、芳香族基及び複素環基等が挙げられる。 The carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group.
　２価の複素環基は、複素環として５員環又は６員環を含有することが好ましい。複素環に他の複素環、脂肪族環又は芳香族環が縮合していてもよい。複素環基は置換基を有していてもよい。置換基の例としては、ハロゲン原子、ヒドロキシ基、オキソ基（＝Ｏ）、チオキソ基（＝Ｓ）、イミノ基（＝ＮＨ）、置換イミノ基（＝Ｎ－Ｒ３２、ここでＲ３２は脂肪族基、芳香族基又は複素環基）、脂肪族基、芳香族基、又は、複素環基が挙げられる。 The divalent heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as the heterocyclic ring. Another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring. The heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R 32 , where R 32 is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group, or heterocyclic group.
　Ｌは、単結合、アルキレン基又はオキシアルキレン構造を含有する２価の連結基であることが好ましい。オキシアルキレン構造は、オキシエチレン構造又はオキシプロピレン構造であることがより好ましい。Ｌは、オキシアルキレン構造を２以上繰り返して含有するポリオキシアルキレン構造を含んでいてもよい。ポリオキシアルキレン構造としては、ポリオキシエチレン構造又はポリオキシプロピレン構造が好ましい。ポリオキシエチレン構造は、－（ＯＣＨ２ＣＨ２）ｎ－で表され、ｎは、２以上の整数が好ましく、２～１０の整数であることがより好ましい。 L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
　Ｚは、脂肪族基（例えば、アルキル基、置換アルキル基、不飽和アルキル基、置換不飽和アルキル基、）、芳香族基（例えば、アリール基、置換アリール基、アリーレン基、置換アリーレン基）、複素環基、又は、これらの組み合わせが挙げられる。これらの基には、酸素原子（－Ｏ－）、硫黄原子（－Ｓ－）、イミノ基（－ＮＨ－）、置換イミノ基（－ＮＲ３１－、ここでＲ３１は脂肪族基、芳香族基又は複素環基）、又は、カルボニル基（－ＣＯ－）が含まれていてもよい。 Z is an aliphatic group (eg, alkyl group, substituted alkyl group, unsaturated alkyl group, substituted unsaturated alkyl group), aromatic group (eg, aryl group, substituted aryl group, arylene group, substituted arylene group), A heterocyclic group or a combination thereof can be mentioned. These groups include an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group (—NR 31 —, wherein R 31 is an aliphatic group, an aromatic group Group or heterocyclic group) or a carbonyl group (—CO—) may be contained.
　脂肪族基は、環状構造又は分岐構造を有していてもよい。脂肪族基の炭素数は、１～２０が好ましく、１～１５がより好ましく、１～１０が更に好ましい。脂肪族基には、更に環集合炭化水素基、架橋環式炭化水素基が含まれ、環集合炭化水素基の例としては、ビシクロヘキシル基、パーヒドロナフタレニル基、ビフェニル基、及び、４－シクロヘキシルフェニル基等が含まれる。架橋環式炭化水素環として、例えば、ピナン、ボルナン、ノルピナン、ノルボルナン、ビシクロオクタン環（ビシクロ［２．２．２］オクタン環、及び、ビシクロ［３．２．１］オクタン環等）等の２環式炭化水素環、ホモブレダン、アダマンタン、トリシクロ［５．２．１．０２，６］デカン、及び、トリシクロ［４．３．１．１２，５］ウンデカン環等の３環式炭化水素環、並びに、テトラシクロ［４．４．０．１２，５．１７，１０］ドデカン、及び、パーヒドロ－１，４－メタノ－５，８－メタノナフタレン環等の４環式炭化水素環等が挙げられる。架橋環式炭化水素環には、縮合環式炭化水素環、例えば、パーヒドロナフタレン（デカリン）、パーヒドロアントラセン、パーヒドロフェナントレン、パーヒドロアセナフテン、パーヒドロフルオレン、パーヒドロインデン、及び、パーヒドロフェナレン環等の５～８員シクロアルカン環が複数個縮合した縮合環も含まれる。
　脂肪族基は不飽和脂肪族基よりも飽和脂肪族基の方が好ましい。脂肪族基は、置換基を有していてもよい。置換基の例は、ハロゲン原子、芳香族基及び複素環基が挙げられる。ただし、脂肪族基は、置換基として酸基を有さない。 The aliphatic group may have a cyclic structure or a branched structure. The aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. The aliphatic group further includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. Examples of the ring assembly hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and 4 -A cyclohexylphenyl group and the like are included. Examples of the bridged cyclic hydrocarbon ring include 2 such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.). Tricyclic hydrocarbon rings such as cyclic hydrocarbon rings, homobredan, adamantane, tricyclo [5.2.1.0 2,6 ] decane, and tricyclo [4.3.1.1 2,5 ] undecane rings , And tetracyclo [4.4.0.1 2,5 . 1 7, 10 ] dodecane, and tetracyclic hydrocarbon rings such as perhydro-1,4-methano-5,8-methanonaphthalene ring. Bridged cyclic hydrocarbon rings include fused cyclic hydrocarbon rings such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and perhydroindene. A condensed ring formed by condensing a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring is also included.
The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. However, the aliphatic group does not have an acid group as a substituent.
　芳香族基の炭素数は、６～２０が好ましく、６～１５がより好ましく、６～１０が更に好ましい。芳香族基は置換基を有していてもよい。置換基の例は、ハロゲン原子、脂肪族基、芳香族基及び複素環基が挙げられる。ただし、芳香族基は、置換基として酸基を有さない。 The carbon number of the aromatic group is preferably 6-20, more preferably 6-15, and still more preferably 6-10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group. However, the aromatic group does not have an acid group as a substituent.
　複素環基は、複素環として５員環又は６員環を含有することが好ましい。複素環に他の複素環、脂肪族環又は芳香族環が縮合していてもよい。複素環基は置換基を有していてもよい。置換基の例としては、ハロゲン原子、ヒドロキシ基、オキソ基（＝Ｏ）、チオキソ基（＝Ｓ）、イミノ基（＝ＮＨ）、置換イミノ基（＝Ｎ－Ｒ３２、ここでＲ３２は脂肪族基、芳香族基又は複素環基）、脂肪族基、芳香族基及び複素環基が挙げられる。ただし、複素環基は、置換基として酸基を有さない。 It is preferable that a heterocyclic group contains a 5-membered ring or a 6-membered ring as a heterocyclic ring. Another heterocyclic ring, an aliphatic ring or an aromatic ring may be condensed with the heterocyclic ring. The heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R 32 , where R 32 is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group. However, the heterocyclic group does not have an acid group as a substituent.
　式（ｉｉｉ）中、Ｒ４、Ｒ５、及びＲ６は、それぞれ独立に、水素原子、ハロゲン原子（例えば、フッ素原子、塩素原子、臭素原子等）、炭素数が１～６のアルキル基（例えば、メチル基、エチル基、プロピル基等）、Ｚ、又はＬ－Ｚを表す。ここでＬ及びＺは、上記におけるものと同義である。Ｒ４、Ｒ５、及びＲ６としては、水素原子、又は炭素数が１～３のアルキル基が好ましく、水素原子がより好ましい。 In formula (iii), R 4 , R 5 , and R 6 are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms ( For example, it represents a methyl group, an ethyl group, a propyl group, etc.), Z, or LZ. Here, L and Z are as defined above. R 4 , R 5 and R 6 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
　式（ｉ）で表される単量体として、Ｒ１、Ｒ２、及びＲ３が水素原子又はメチル基であって、Ｌが単結合又はアルキレン基もしくはオキシアルキレン構造を含有する２価の連結基であって、Ｘが酸素原子又はイミノ基であって、Ｚが脂肪族基、複素環基又は芳香族基である化合物が好ましい。
　式（ｉｉ）で表される単量体として、Ｒ１が水素原子又はメチル基であって、Ｌがアルキレン基であって、Ｚが脂肪族基、複素環基又は芳香族基である化合物が好ましい。
式（ｉｉｉ）で表される単量体として、Ｒ４、Ｒ５、及びＲ６が水素原子又はメチル基であって、Ｚが脂肪族基、複素環基又は芳香族基である化合物が好ましい。 As the monomer represented by formula (i), R 1 , R 2 , and R 3 are a hydrogen atom or a methyl group, and L is a single bond, an alkylene group, or a divalent linkage containing an oxyalkylene structure A compound in which X is an oxygen atom or an imino group and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferred.
As the monomer represented by the formula (ii), a compound in which R 1 is a hydrogen atom or a methyl group, L is an alkylene group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. preferable.
As the monomer represented by the formula (iii), a compound in which R 4 , R 5 , and R 6 are a hydrogen atom or a methyl group and Z is an aliphatic group, a heterocyclic group, or an aromatic group is preferable. .
　式（ｉ）～（ｉｉｉ）で表される代表的な化合物の例としては、アクリル酸エステル類、メタクリル酸エステル類、及び、スチレン類等から選ばれるラジカル重合性化合物が挙げられる。
　式（ｉ）～（ｉｉｉ）で表される代表的な化合物の例としては、特開２０１３－２４９４１７号公報の段落００８９～００９３に記載の化合物を参照でき、これらの内容は本明細書に組み込まれる。 Examples of typical compounds represented by formulas (i) to (iii) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, and the like.
As examples of representative compounds represented by formulas (i) to (iii), the compounds described in paragraphs 0089 to 0093 of JP2013-249417A can be referred to, and the contents thereof are incorporated in the present specification. It is.
　高分子化合物において、疎水性構造単位は、質量換算で、高分子化合物の総質量に対し１０～９０％の範囲で含まれることが好ましく、２０～８０％の範囲で含まれることがより好ましい。含有量が上記範囲であることにより良好なパターン形成が得られる。 In the polymer compound, the hydrophobic structural unit is preferably contained in a range of 10 to 90%, more preferably in a range of 20 to 80% with respect to the total mass of the polymer compound in terms of mass. When the content is within the above range, good pattern formation can be obtained.
・黒色顔料等の着色剤と相互作用を形成しうる官能基
　高分子化合物は、黒色顔料等の着色剤と相互作用を形成しうる官能基を導入することができる。ここで、高分子化合物は、黒色顔料等の着色剤と相互作用を形成しうる官能基を含有する構造単位を更に含有することが好ましい。
　この黒色顔料等の着色剤と相互作用を形成しうる官能基としては、例えば、酸基、塩基性基、配位性基、及び、反応性を有する官能基等が挙げられる。
　高分子化合物が、酸基、塩基性基、配位性基、又は、反応性を有する官能基を含有する場合、それぞれ、酸基を含有する構造単位、塩基性基を含有する構造単位、配位性基を含有する構造単位、又は、反応性を有する構造単位を含有することが好ましい。
　特に、高分子化合物が、更に、酸基として、カルボン酸基等のアルカリ可溶性基を含有することで、高分子化合物に、アルカリ現像によるパターン形成のための現像性を付与することができる。
　すなわち、高分子化合物にアルカリ可溶性基を導入することで、硬化性組成物は、黒色顔料等の着色剤の分散に寄与する分散剤としての高分子化合物がアルカリ可溶性を含有することになる。このような高分子化合物を含有する硬化性組成物は、露光部の遮光性に優れたものとなり、且つ、未露光部のアルカリ現像性が向上される。
　高分子化合物が酸基を含有する構造単位を含有することにより、高分子化合物が溶剤となじみやすくなり、塗布性も向上する傾向となる。
　これは、酸基を含有する構造単位における酸基が黒色顔料等の着色剤と相互作用しやすく、高分子化合物が黒色顔料等の着色剤を安定的に分散すると共に、黒色顔料等の着色剤を分散する高分子化合物の粘度が低くなり、高分子化合物自体も安定的に分散されやすいためであると推測される。 -Functional group capable of forming interaction with colorant such as black pigment The polymer compound can introduce a functional group capable of forming interaction with a colorant such as black pigment. Here, the polymer compound preferably further contains a structural unit containing a functional group capable of forming an interaction with a colorant such as a black pigment.
Examples of the functional group capable of forming an interaction with the colorant such as the black pigment include an acid group, a basic group, a coordinating group, and a reactive functional group.
When the polymer compound contains an acid group, a basic group, a coordination group, or a reactive functional group, the structural unit containing an acid group, the structural unit containing a basic group, and a coordination group, respectively. It is preferable to contain a structural unit containing a coordinate group or a structural unit having reactivity.
In particular, when the polymer compound further contains an alkali-soluble group such as a carboxylic acid group as the acid group, developability for pattern formation by alkali development can be imparted to the polymer compound.
That is, by introducing an alkali-soluble group into a polymer compound, the polymer compound as a dispersant that contributes to the dispersion of a colorant such as a black pigment in the curable composition contains alkali-solubility. The curable composition containing such a polymer compound has excellent light-shielding properties in the exposed area, and the alkali developability in the unexposed area is improved.
When the polymer compound contains a structural unit containing an acid group, the polymer compound tends to become compatible with the solvent and the coating property tends to be improved.
This is because the acid group in the structural unit containing an acid group easily interacts with a colorant such as a black pigment, and the polymer compound stably disperses the colorant such as a black pigment, and the colorant such as a black pigment This is probably because the viscosity of the polymer compound in which the polymer is dispersed is lowered, and the polymer compound itself is easily dispersed stably.
　酸基としてのアルカリ可溶性基を含有する構造単位は、上記のグラフト鎖を含有する構造単位と同一の構造単位であっても、異なる構造単位であってもよいが、上記の疎水性構造単位とは異なる構造単位である（すなわち、上記の疎水性構造単位には相当しない）。 The structural unit containing an alkali-soluble group as an acid group may be the same structural unit as the structural unit containing the graft chain or a different structural unit. Are different structural units (ie, do not correspond to the hydrophobic structural units described above).
　黒色顔料等の着色剤と相互作用を形成しうる官能基である酸基としては、例えば、カルボン酸基、スルホン酸基、リン酸基、又は、フェノール性ヒドロキシ基等があり、カルボン酸基、スルホン酸基、及び、リン酸基のうち少なくとも１種が好ましく、黒色顔料等の着色剤への吸着力が良好で、且つ、着色剤の分散性が高い点で、カルボン酸基がより好ましい。
　すなわち、高分子化合物は、カルボン酸基、スルホン酸基、及び、リン酸基のうち少なくとも１種を含有する構造単位を更に含有することが好ましい。 Examples of the acid group that is a functional group capable of forming an interaction with a colorant such as a black pigment include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxy group, a carboxylic acid group, At least one of a sulfonic acid group and a phosphoric acid group is preferable, and a carboxylic acid group is more preferable in terms of good adsorbing power to a colorant such as a black pigment and high dispersibility of the colorant.
That is, the polymer compound preferably further contains a structural unit containing at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
　高分子化合物は、酸基を含有する構造単位を１種又は２種以上有してもよい。
　高分子化合物は、酸基を含有する構造単位を含有してもしなくてもよいが、含有する場合、酸基を含有する構造単位の含有量は、質量換算で、高分子化合物の総質量に対して、好ましくは５～８０％であり、より好ましくは、アルカリ現像による画像強度のダメージ抑制という観点から、１０～６０％である。 The polymer compound may have one or more structural units containing an acid group.
The polymer compound may or may not contain a structural unit containing an acid group. However, when it is contained, the content of the structural unit containing an acid group is the total mass of the polymer compound in terms of mass. On the other hand, it is preferably 5 to 80%, and more preferably 10 to 60% from the viewpoint of suppressing damage of image strength due to alkali development.
　黒色顔料等の着色剤と相互作用を形成しうる官能基である塩基性基としては、例えば、第１級アミノ基、第２級アミノ基、第３級アミノ基、Ｎ原子を含有するヘテロ環、及び、アミド基等があり、好ましいものは、黒色顔料等の着色剤への吸着力が良好で、且つ、着色剤の分散性が高い点で、第３級アミノ基である。高分子化合物は、これらの塩基性基を１種又は２種以上、含有することができる。
　高分子化合物は、塩基性基を含有する構造単位を含有してもしなくてもよいが、含有する場合、塩基性基を含有する構造単位の含有量は、質量換算で、高分子化合物の総質量に対して、０．０１％以上５０％以下が好ましく、現像性阻害抑制という観点から、０．０１％以上３０％以下がより好ましい。 Examples of the basic group that is a functional group capable of interacting with a colorant such as a black pigment include a primary amino group, a secondary amino group, a tertiary amino group, and a heterocyclic ring containing an N atom. And an amide group and the like, and a preferable one is a tertiary amino group in that the adsorbing power to a colorant such as a black pigment is good and the dispersibility of the colorant is high. The polymer compound can contain one or more of these basic groups.
The polymer compound may or may not contain a structural unit containing a basic group, but when it is contained, the content of the structural unit containing a basic group is the total amount of the polymer compound in terms of mass. It is preferably 0.01% or more and 50% or less with respect to the mass, and more preferably 0.01% or more and 30% or less from the viewpoint of inhibiting developability inhibition.
　黒色顔料等の着色剤と相互作用を形成しうる官能基である配位性基、及び反応性を有する官能基としては、例えば、アセチルアセトキシ基、トリアルコキシシリル基、イソシアネート基、酸無水物、及び、酸塩化物等が挙げられる。好ましいものは、黒色顔料等の着色剤への吸着力が良好で、着色剤の分散性が高い点で、アセチルアセトキシ基である。高分子化合物は、これらの基を１種又は２種以上有してもよい。
　高分子化合物は、配位性基を含有する構造単位、又は、反応性を有する官能基を含有する構造単位を含有してもしなくてもよいが、含有する場合、これらの構造単位の含有量は、質量換算で、高分子化合物の総質量に対して、１０％以上８０％以下が好ましく、現像性阻害抑制という観点から、２０％以上６０％以下がより好ましい。 As a coordinating group that is a functional group capable of forming an interaction with a colorant such as a black pigment, and a functional group having reactivity, for example, an acetylacetoxy group, a trialkoxysilyl group, an isocyanate group, an acid anhydride, And acid chloride etc. are mentioned. Preferable one is an acetylacetoxy group from the viewpoint of good adsorbing power to a colorant such as a black pigment and high dispersibility of the colorant. The polymer compound may have one or more of these groups.
The polymer compound may or may not contain a structural unit containing a coordinating group or a structural unit containing a reactive functional group, but if it contains, the content of these structural units Is preferably 10% or more and 80% or less in terms of mass, and more preferably 20% or more and 60% or less from the viewpoint of inhibiting developability inhibition.
　高分子化合物が、グラフト鎖以外に、黒色顔料等の着色剤と相互作用を形成しうる官能基を含有する場合、上記の各種の黒色顔料等の着色剤と相互作用を形成しうる官能基を含有していればよく、これらの官能基がどのように導入されているかは特に限定はされないが、高分子化合物は、下記一般式（ｉｖ）～（ｖｉ）で表される単量体に由来の構造単位から選択された１種以上の構造単位を含有することが好ましい。 When the polymer compound contains a functional group capable of interacting with a colorant such as a black pigment in addition to the graft chain, the functional group capable of interacting with a colorant such as the above various black pigments There is no particular limitation on how these functional groups are introduced as long as they are contained, but the polymer compound is derived from monomers represented by the following general formulas (iv) to (vi) It is preferable to contain one or more structural units selected from these structural units.
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
　式（ｉｖ）～式（ｖｉ）中、Ｒ１１、Ｒ１２、及びＲ１３は、それぞれ独立に、水素原子、ハロゲン原子（例えば、フッ素原子、塩素原子、臭素原子等）、又は炭素数が１～６のアルキル基（例えば、メチル基、エチル基、プロピル基等）を表す。
　式（ｉｖ）～式（ｖｉ）中、Ｒ１１、Ｒ１２、及びＲ１３は、好ましくは、それぞれ独立に水素原子、又は炭素数が１～３のアルキル基であり、より好ましくは、それぞれ独立に水素原子又はメチル基である。一般式（ｉｖ）中、Ｒ１２及びＲ１３は、それぞれ水素原子であることが特に好ましい。 In formulas (iv) to (vi), R 11 , R 12 , and R 13 each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number of 1 Represents an alkyl group of ˜6 (for example, methyl group, ethyl group, propyl group, etc.).
In the formulas (iv) to (vi), R 11 , R 12 and R 13 are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably each independently Are a hydrogen atom or a methyl group. In general formula (iv), R 12 and R 13 are each particularly preferably a hydrogen atom.
　式（ｉｖ）中のＸ１は、酸素原子（－Ｏ－）又はイミノ基（－ＮＨ－）を表し、酸素原子であることが好ましい。
　式（ｖ）中のＹは、メチン基又は窒素原子を表す。 X 1 in the formula (iv) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
Y in the formula (v) represents a methine group or a nitrogen atom.
　式（ｉｖ）～式（ｖ）中のＬ１は、単結合又は２価の連結基を表す。２価の連結基の例としては、２価の脂肪族基（例えば、アルキレン基、置換アルキレン基、アルケニレン基、置換アルケニレン基、アルキニレン基、及び置換アルキニレン基）、２価の芳香族基（例えば、アリーレン基、及び置換アリーレン基）、２価の複素環基、酸素原子（－Ｏ－）、硫黄原子（－Ｓ－）、イミノ基（－ＮＨ－）、置換イミノ結合（－ＮＲ３１’－、ここでＲ３１’は脂肪族基、芳香族基又は複素環基）、カルボニル結合（－ＣＯ－）、及び、これらの組合せ等が挙げられる。 L 1 in the formulas (iv) to (v) represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group (for example, , Arylene groups and substituted arylene groups), divalent heterocyclic groups, oxygen atoms (—O—), sulfur atoms (—S—), imino groups (—NH—), substituted imino bonds (—NR 31 ′ — Here, R 31 ′ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (—CO—), and combinations thereof.
　２価の脂肪族基は、環状構造又は分岐構造を有していてもよい。脂肪族基の炭素数は、１～２０が好ましく、１～１５がより好ましく、１～１０が更に好ましい。脂肪族基は不飽和脂肪族基よりも飽和脂肪族基の方が好ましい。脂肪族基は、置換基を有していてもよい。置換基の例としては、ハロゲン原子、ヒドロキシ基、芳香族基及び複素環基が挙げられる。 The divalent aliphatic group may have a cyclic structure or a branched structure. The aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an aromatic group, and a heterocyclic group.
　２価の芳香族基の炭素数は、６～２０が好ましく、６～１５がより好ましく、６～１０が更に好ましい。芳香族基は置換基を有していてもよい。置換基の例は、ハロゲン原子、ヒドロキシ基、脂肪族基、芳香族基及び複素環基が挙げられる。 The carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an aliphatic group, an aromatic group, and a heterocyclic group.
　２価の複素環基は、複素環として５員環又は６員環を含有することが好ましい。複素環に他の複素環、脂肪族環又は芳香族環のうち１つ以上が縮合していてもよい。複素環基は置換基を有していてもよい。置換基の例としては、ハロゲン原子、ヒドロキシ基、オキソ基（＝Ｏ）、チオキソ基（＝Ｓ）、イミノ基（＝ＮＨ）、置換イミノ基（＝Ｎ－Ｒ３２、ここでＲ３２は脂肪族基、芳香族基又は複素環基）、脂肪族基、芳香族基及び複素環基が挙げられる。 The divalent heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as the heterocyclic ring. One or more heterocycles, aliphatic rings or aromatic rings may be condensed with the heterocycle. The heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R 32 , where R 32 is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.
　Ｌ１は、単結合、アルキレン基又はオキシアルキレン構造を含有する２価の連結基であることが好ましい。オキシアルキレン構造は、オキシエチレン構造又はオキシプロピレン構造であることがより好ましい。Ｌ１は、オキシアルキレン構造を２以上繰り返して含有するポリオキシアルキレン構造を含んでいてもよい。ポリオキシアルキレン構造としては、ポリオキシエチレン構造又はポリオキシプロピレン構造が好ましい。ポリオキシエチレン構造は、－（ＯＣＨ２ＣＨ２）ｎ－で表され、ｎは、２以上の整数が好ましく、２～１０の整数であることがより好ましい。 L 1 is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L 1 may include a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
　式（ｉｖ）～式（ｖｉ）中、Ｚ１は、グラフト鎖以外に黒色顔料等の着色剤と相互作用を形成しうる官能基を表し、カルボン酸基、及び、第三級アミノ基であることが好ましく、カルボン酸基であることがより好ましい。 In the formulas (iv) to (vi), Z 1 represents a functional group capable of forming an interaction with a colorant such as a black pigment in addition to the graft chain, and is a carboxylic acid group or a tertiary amino group. It is preferable that it is a carboxylic acid group.
　式（ｖｉ）中、Ｒ１４、Ｒ１５、及びＲ１６は、それぞれ独立に、水素原子、ハロゲン原子（例えば、フッ素原子、塩素原子、臭素原子等）、炭素数が１～６のアルキル基（例えば、メチル基、エチル基、プロピル基等）、－Ｚ１、又はＬ１－Ｚ１を表す。ここでＬ１及びＺ１は、上記におけるＬ１及びＺ１と同義であり、好ましい例も同様である。Ｒ１４、Ｒ１５、及びＲ１６としては、それぞれ独立に水素原子、又は炭素数が１～３のアルキル基が好ましく、水素原子がより好ましい。 In the formula (vi), R 14 , R 15 , and R 16 are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group having 1 to 6 carbon atoms ( for example, a methyl group, an ethyl group, a propyl group, etc.), - Z 1, or an L 1 -Z 1. Wherein L 1 and Z 1 are the same meaning as L 1 and Z 1 in the above, it is the preferable examples. R 14 , R 15 and R 16 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
　式（ｉｖ）で表される単量体として、Ｒ１１、Ｒ１２、及びＲ１３がそれぞれ独立に水素原子又はメチル基であって、Ｌ１がアルキレン基又はオキシアルキレン構造を含有する２価の連結基であって、Ｘ１が酸素原子又はイミノ基であって、Ｚ１がカルボン酸基である化合物が好ましい。
　式（ｖ）で表される単量体として、Ｒ１１が水素原子又はメチル基であって、Ｌ１がアルキレン基であって、Ｚ１がカルボン酸基であって、Ｙがメチン基である化合物が好ましい。
　更に、式（ｖｉ）で表される単量体として、Ｒ１４、Ｒ１５、及びＲ１６がそれぞれ独立に水素原子又はメチル基であって、Ｌ１が単結合又はアルキレン基であって、Ｚ１がカルボン酸基である化合物が好ましい。 As the monomer represented by the formula (iv), R 11 , R 12 and R 13 are each independently a hydrogen atom or a methyl group, and L 1 is an alkylene group or a divalent oxyalkylene structure. A compound in which X 1 is an oxygen atom or imino group and Z 1 is a carboxylic acid group is preferable.
As the monomer represented by the formula (v), R 11 is a hydrogen atom or a methyl group, L 1 is an alkylene group, Z 1 is a carboxylic acid group, and Y is a methine group. Compounds are preferred.
Furthermore, as a monomer represented by the formula (vi), R 14 , R 15 , and R 16 are each independently a hydrogen atom or a methyl group, L 1 is a single bond or an alkylene group, and Z A compound in which 1 is a carboxylic acid group is preferred.
　以下に、式（ｉｖ）～式（ｖｉ）で表される単量体（化合物）の代表的な例を示す。
　単量体の例としては、メタクリル酸、クロトン酸、イソクロトン酸、分子内に付加重合性二重結合及びヒドロキシ基を含有する化合物（例えば、メタクリル酸２－ヒドロキシエチル）とコハク酸無水物との反応物、分子内に付加重合性二重結合及びヒドロキシ基を含有する化合物とフタル酸無水物との反応物、分子内に付加重合性二重結合及びヒドロキシ基を含有する化合物とテトラヒドロキシフタル酸無水物との反応物、分子内に付加重合性二重結合及びヒドロキシ基を含有する化合物と無水トリメリット酸との反応物、分子内に付加重合性二重結合及びヒドロキシ基を含有する化合物とピロメリット酸無水物との反応物、アクリル酸、アクリル酸ダイマー、アクリル酸オリゴマー、マレイン酸、イタコン酸、フマル酸、４－ビニル安息香酸、ビニルフェノール、及び、４－ヒドロキシフェニルメタクリルアミド等が挙げられる。 The following are typical examples of monomers (compounds) represented by the formulas (iv) to (vi).
Examples of the monomer include methacrylic acid, crotonic acid, isocrotonic acid, a compound containing an addition polymerizable double bond and a hydroxy group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride. Reaction product, reaction product of a compound containing an addition polymerizable double bond and hydroxy group in the molecule and phthalic anhydride, compound containing an addition polymerizable double bond and hydroxy group in the molecule and tetrahydroxyphthalic acid Reaction product with anhydride, reaction product of compound containing addition polymerizable double bond and hydroxy group in the molecule and trimellitic anhydride, compound containing addition polymerizable double bond and hydroxy group in the molecule Reaction product with pyromellitic anhydride, acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid , Vinylphenol, and, and 4-hydroxyphenyl methacrylamide.
　黒色顔料等の着色剤と相互作用を形成しうる官能基を含有する構造単位の含有量は、黒色顔料等の着色剤との相互作用、経時安定性、及び現像液への浸透性の観点から、高分子化合物の全質量に対して、０．０５質量％～９０質量％が好ましく、１．０質量％～８０質量％がより好ましく、１０質量％～７０質量％が更に好ましい。 The content of the structural unit containing a functional group capable of forming an interaction with a colorant such as a black pigment is from the viewpoint of interaction with the colorant such as a black pigment, stability over time, and permeability to a developer. The amount is preferably 0.05% by mass to 90% by mass, more preferably 1.0% by mass to 80% by mass, and still more preferably 10% by mass to 70% by mass based on the total mass of the polymer compound.
・その他の構造単位
　更に、高分子化合物は、画像強度等の諸性能を向上する目的で、本発明の効果を損なわない限りにおいて、グラフト鎖を含有する構造単位、疎水性構造単位、及び、黒色顔料等の着色剤と相互作用を形成しうる官能基を含有する構造単位とは異なる、種々の機能を有する他の構造単位（例えば、分散物に用いられる分散媒との親和性を有する官能基等を含有する構造単位）を更に有していてもよい。
　このような、他の構造単位としては、例えば、アクリロニトリル類、及び、メタクリロニトリル類等から選ばれるラジカル重合性化合物に由来の構造単位が挙げられる。
　高分子化合物は、これらの他の構造単位を１種又は２種以上用いることができ、その含有量は、質量換算で、高分子化合物の総質量に対して、０％以上８０％以下が好ましく、１０％以上６０％以下がより好ましい。含有量が上記範囲において、十分なパターン形成性が維持される。 Other structural units Furthermore, the polymer compound is a structural unit containing a graft chain, a hydrophobic structural unit, and a black color as long as the effects of the present invention are not impaired for the purpose of improving various performances such as image strength. Different from structural units containing functional groups that can interact with colorants such as pigments, other structural units having various functions (for example, functional groups having affinity with the dispersion medium used in the dispersion) And the like may be further included.
Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles, methacrylonitriles, and the like.
The polymer compound may use one or more of these other structural units, and the content is preferably 0% or more and 80% or less based on the total mass of the polymer compound in terms of mass. 10% or more and 60% or less is more preferable. When the content is in the above range, sufficient pattern formability is maintained.
・高分子化合物の物性
　高分子化合物の酸価は、０ｍｇＫＯＨ／ｇ以上２５０ｍｇＫＯＨ／ｇ以下の範囲が好ましく、１０ｍｇＫＯＨ／ｇ以上２００ｍｇＫＯＨ／ｇ以下の範囲がより好ましく、２０ｍｇＫＯＨ／ｇ以上１２０ｍｇＫＯＨ／ｇ以下の範囲が更に好ましい。
　高分子化合物の酸価が１６０ｍｇＫＯＨ／ｇ以下であれば、硬化膜を形成する際の現像時におけるパターン剥離がより効果的に抑えられる。高分子化合物の酸価が１０ｍｇＫＯＨ／ｇ以上であればアルカリ現像性がより良好となる。また、高分子化合物の酸価が２０ｍｇＫＯＨ／ｇ以上であれば、黒色顔料等の着色剤の沈降をより抑制でき、粗大粒子数をより少なくすることができ、硬化性組成物の経時安定性をより向上できる。 -Physical properties of polymer compound The acid value of the polymer compound is preferably in the range of 0 mgKOH / g to 250 mgKOH / g, more preferably in the range of 10 mgKOH / g to 200 mgKOH / g, and in the range of 20 mgKOH / g to 120 mgKOH / g. A range is more preferred.
If the acid value of the polymer compound is 160 mgKOH / g or less, pattern peeling during development when forming a cured film can be more effectively suppressed. When the acid value of the polymer compound is 10 mgKOH / g or more, the alkali developability becomes better. Moreover, if the acid value of the polymer compound is 20 mgKOH / g or more, precipitation of a colorant such as a black pigment can be further suppressed, the number of coarse particles can be reduced, and the temporal stability of the curable composition can be reduced. It can be improved.
　高分子化合物の酸価は、例えば、高分子化合物中における酸基の平均含有量から算出することができる。また、高分子化合物の構成成分である酸基を含有する構造単位の含有量を変化させることで所望の酸価を有する樹脂を得ることができる。 The acid value of the polymer compound can be calculated, for example, from the average content of acid groups in the polymer compound. Moreover, the resin which has a desired acid value can be obtained by changing content of the structural unit containing the acid group which is a structural component of a high molecular compound.
　高分子化合物の重量平均分子量は、硬化膜を形成する際において、現像時のパターン剥離抑制と現像性の観点から、ＧＰＣ（Gel Permeation Chromatography：ゲル浸透クロマトグラフィー）法によるポリスチレン換算値として、４，０００以上３００，０００以下であることが好ましく、５，０００以上２００，０００以下であることがより好ましく、６，０００以上１００，０００以下であることが更に好ましく、１０，０００以上５０，０００以下であることが特に好ましい。
　ＧＰＣ法は、ＨＬＣ－８０２０ＧＰＣ（東ソー製）を用い、カラムとしてＴＳＫｇｅｌ　ＳｕｐｅｒＨＺＭ－Ｈ、ＴＳＫｇｅｌ　ＳｕｐｅｒＨＺ４０００、ＴＳＫｇｅｌ　ＳｕｐｅｒＨＺ２０００（東ソー製、４．６ｍｍＩＤ×１５ｃｍ）を、溶離液としてＴＨＦ（テトラヒドロフラン）を用いる方法に基づく。 When forming a cured film, the weight average molecular weight of the polymer compound is 4 in terms of polystyrene converted by GPC (Gel Permeation Chromatography) method from the viewpoint of pattern peeling inhibition during development and developability. It is preferably 000 or more and 300,000 or less, more preferably 5,000 or more and 200,000 or less, further preferably 6,000 or more and 100,000 or less, and 10,000 or more and 50,000 or less. It is particularly preferred that
The GPC method is based on a method using HLC-8020GPC (manufactured by Tosoh), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh, 4.6 mm ID × 15 cm) as a column and THF (tetrahydrofuran) as an eluent. .
　高分子化合物は、公知の方法に基づいて合成でき、高分子化合物を合成する際に用いられる溶剤としては、例えば、エチレンジクロリド、シクロヘキサノン、メチルエチルケトン、アセトン、メタノール、エタノール、プロパノール、ブタノール、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、２－メトキシエチルアセテート、１－メトキシ－２－プロパノール、１－メトキシ－２－プロピルアセテート、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、ジメチルスルホキシド、トルエン、酢酸エチル、乳酸メチル、及び、乳酸エチル等が挙げられる。これらの溶剤は単独で用いても２種以上混合して用いてもよい。 The polymer compound can be synthesized based on a known method, and examples of the solvent used when synthesizing the polymer compound include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, and ethylene glycol monomethyl. Ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, Examples include ethyl acetate, methyl lactate, and ethyl lactate. These solvents may be used alone or in combination of two or more.
　高分子化合物の具体例としては、楠木化成社製「ＤＡ－７３０１」、ＢＹＫＣｈｅｍｉｅ社製「Ｄｉｓｐｅｒｂｙｋ－１０１（ポリアミドアミン燐酸塩）、１０７（カルボン酸エステル）、１１０（酸基を含有する共重合物）、１１１（リン酸系分散剤）、１３０（ポリアミド）、１６１、１６２、１６３、１６４、１６５、１６６、１７０、１９０（高分子共重合物）」、「ＢＹＫ－Ｐ１０４、Ｐ１０５（高分子量不飽和ポリカルボン酸）」、ＥＦＫＡ社製「ＥＦＫＡ４０４７、４０５０～４０１０～４１６５（ポリウレタン系）、ＥＦＫＡ４３３０～４３４０（ブロック共重合体）、４４００～４４０２（変性ポリアクリレート）、５０１０（ポリエステルアミド）、５７６５（高分子量ポリカルボン酸塩）、６２２０（脂肪酸ポリエステル）、６７４５（フタロシアニン誘導体）、６７５０（アゾ顔料誘導体）」、味の素ファインテクノ社製「アジスパーＰＢ８２１、ＰＢ８２２、ＰＢ８８０、ＰＢ８８１」、共栄社化学社製「フローレンＴＧ－７１０（ウレタンオリゴマー）」、「ポリフローＮｏ．５０Ｅ、Ｎｏ．３００（アクリル系共重合体）」、楠本化成社製「ディスパロンＫＳ－８６０、８７３ＳＮ、８７４、＃２１５０（脂肪族多価カルボン酸）、＃７００４（ポリエーテルエステル）、ＤＡ－７０３－５０、ＤＡ－７０５、ＤＡ－７２５」、花王社製「デモールＲＮ、Ｎ（ナフタレンスルホン酸ホルマリン重縮合物）、ＭＳ、Ｃ、ＳＮ－Ｂ（芳香族スルホン酸ホルマリン重縮合物）」、「ホモゲノールＬ－１８（高分子ポリカルボン酸）」、「エマルゲン９２０、９３０、９３５、９８５（ポリオキシエチレンノニルフェニルエーテル）」、「アセタミン８６（ステアリルアミンアセテート）」、日本ルーブリゾール製「ソルスパース５０００（フタロシアニン誘導体）、２２０００（アゾ顔料誘導体）、１３２４０（ポリエステルアミン）、３０００、１２０００、１７０００、２００００、２７０００（末端部に機能部を含有する高分子）、２４０００、２８０００、３２０００、３８５００（グラフト共重合体）」、日光ケミカルズ社製「ニッコールＴ１０６（ポリオキシエチレンソルビタンモノオレアート）、ＭＹＳ－ＩＥＸ（ポリオキシエチレンモノステアレート）」、川研ファインケミカル製 ヒノアクトＴ－８０００Ｅ等、信越化学工業製、オルガノシロキサンポリマーＫＰ３４１、裕商「Ｗ００１：カチオン系界面活性剤」、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ソルビタン脂肪酸エステル等のノニオン系界面活性剤、「Ｗ００４、Ｗ００５、Ｗ０１７」等のアニオン系界面活性剤、森下産業製「ＥＦＫＡ－４６、ＥＦＫＡ－４７、ＥＦＫＡ－４７ＥＡ、ＥＦＫＡポリマー１００、ＥＦＫＡポリマー４００、ＥＦＫＡポリマー４０１、ＥＦＫＡポリマー４５０」、サンノプコ製「ディスパースエイド６、ディスパースエイド８、ディスパースエイド１５、ディスパースエイド９１００」等の高分子分散剤、ＡＤＥＫＡ製「アデカプルロニックＬ３１、Ｆ３８、Ｌ４２、Ｌ４４、Ｌ６１、Ｌ６４、Ｆ６８、Ｌ７２、Ｐ９５、Ｆ７７、Ｐ８４、Ｆ８７、Ｐ９４、Ｌ１０１、Ｐ１０３、Ｆ１０８、Ｌ１２１、Ｐ－１２３」、及び三洋化成製「イオネット（商品名）Ｓ－２０」等が挙げられる。また、アクリベースＦＦＳ－６７５２、アクリベースＦＦＳ－１８７、アクリキュア－ＲＤ－Ｆ８、及び、サイクロマーＰを用いることもできる。
　両性樹脂の市販品としては、例えば、ビックケミー社製のＤＩＳＰＥＲＢＹＫ－１３０、ＤＩＳＰＥＲＢＹＫ－１４０、ＤＩＳＰＥＲＢＹＫ－１４２、ＤＩＳＰＥＲＢＹＫ－１４５、ＤＩＳＰＥＲＢＹＫ－１８０、ＤＩＳＰＥＲＢＹＫ－１８７、ＤＩＳＰＥＲＢＹＫ－１９１、ＤＩＳＰＥＲＢＹＫ－２００１、ＤＩＳＰＥＲＢＹＫ－２０１０、ＤＩＳＰＥＲＢＹＫ－２０１２、ＤＩＳＰＥＲＢＹＫ－２０２５、ＢＹＫ－９０７６、味の素ファインテクノ社製のアジスパーＰＢ８２１、アジスパーＰＢ８２２、及び、アジスパーＰＢ８８１等が挙げられる。
　これらの高分子化合物は、１種を単独で用いても、２種以上を併用してもよい。 Specific examples of the polymer compound include “DA-7301” manufactured by Kashiwagi Kasei Co., Ltd., “Disperbyk-101 (polyamideamine phosphate), 107 (carboxylic acid ester)” manufactured by BYK Chemie, and 110 (copolymers containing acid groups). ), 111 (phosphate dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymer) ”,“ BYK-P104, P105 (non-high molecular weight) Saturated polycarboxylic acid) ”,“ EFKA 4047, 4050 to 4010 to 4165 (polyurethane) ”, EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (polyester), manufactured by EFKA High molecular weight polycarboxylate), 6220 (fatty acid polyester) ), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative), “Ajisper PB821, PB822, PB880, PB881” manufactured by Ajinomoto Fine Techno Co., Ltd., “Floren TG-710 (urethane oligomer)” manufactured by Kyoeisha Chemical Co., Ltd., “Polyflow” No. 50E, No. 300 (acrylic copolymer) ”,“ Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyether ester), DA, manufactured by Enomoto Kasei Co., Ltd. -703-50, DA-705, DA-725 "," Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) "manufactured by Kao Corporation "Homogenol L-18 (polymeric polycarboxylic acid)", "Emulgen 920" 930, 935, 985 (polyoxyethylene nonylphenyl ether) ”,“ acetamine 86 (stearylamine acetate) ”,“ Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), manufactured by Nippon Lubrizol, 3000, 12000, 17000, 20000, 27000 (polymers containing a functional part at the end), 24000, 28000, 32000, 38500 (graft copolymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan mono) manufactured by Nikko Chemicals Oleart), MYS-IEX (polyoxyethylene monostearate), Kawano Fine Chemical's Hinoact T-8000E, Shin-Etsu Chemical Co., Ltd., organosiloxane polymer KP341, Yusho W001: Cationic surfactant ", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate Nonionic surfactants such as sorbitan fatty acid esters, anionic surfactants such as “W004, W005, W017”, “EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400 manufactured by Morishita Sangyo , EFKA Polymer 401, EFKA Polymer 450 ", Sannopco" Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disper Polymer dispersants such as Suede 9100, manufactured by ADEKA "Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P -123 ", Sanyo Kasei" Ionet (trade name) S-20 ", and the like. Also, Acrybase FFS-6752, Acrybase FFS-187, Acrycure-RD-F8, and Cyclomer P can be used.
Examples of commercially available amphoteric resins include DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPER10K, 2001-DISPERBY, manufactured by BYK Chemie. DISPERBYK-2012, DISPERBYK-2025, BYK-9076, Ajisper PB821, Azisper PB822, Azisper PB881, etc. manufactured by Ajinomoto Fine Techno Co.
These polymer compounds may be used alone or in combination of two or more.
　高分子化合物の具体例としては、特開２０１３－２４９４１７号公報の段落０１２７～０１２９に記載の高分子化合物を参照でき、これらの内容は本明細書に組み込まれる。 As specific examples of the polymer compound, the polymer compounds described in paragraphs 0127 to 0129 of JP2013-249417A can be referred to, and the contents thereof are incorporated in the present specification.
　分散剤としては、上記の高分子化合物以外に、特開２０１０－１０６２６８号公報の段落００３７～０１１５（対応するＵＳ２０１１／０１２４８２４の段落００７５～０１３３欄）のグラフト共重合体が使用でき、これらの内容は援用でき、本明細書に組み込まれる。
　上記以外にも、特開２０１１－１５３２８３号公報の段落００２８～００８４（対応するＵＳ２０１１／０２７９７５９の段落００７５～０１３３欄）の酸性基が連結基を介して結合してなる側鎖構造を含有する構成成分を含有する高分子化合物が使用でき、これらの内容は援用でき、本明細書に組み込まれる。 As the dispersant, in addition to the above-described polymer compound, a graft copolymer described in JP-A 2010-106268, paragraphs 0037 to 0115 (corresponding to paragraphs 0075 to 0133 in US2011 / 0124824) can be used. Can be incorporated and incorporated herein by reference.
In addition to the above, a structure containing a side chain structure in which acidic groups in paragraphs 0028 to 0084 of JP 2011-153283 A (corresponding to columns 0075 to 0133 of US2011 / 0279759) are bonded via a linking group Polymeric compounds containing components can be used, the contents of which can be incorporated and incorporated herein.
＜バインダー樹脂＞
　硬化性組成物は、バインダー樹脂を含有することが好ましい。
　バインダー樹脂の含有量は、硬化性組成物の全固形分に対して、０．１～３０質量％が好ましい。
　バインダー樹脂の含有量が、硬化性組成物の全固形分に対して、０．３～２５質量％以上だと、硬化性組成物を硬化して得られる硬化膜のパターン形状がより優れる。
　バインダー樹脂は、１種を単独で用いても、２種以上を併用してもよい。バインダー樹脂を２種以上併用する場合は、その合計量が上記範囲内であることが好ましい。 <Binder resin>
The curable composition preferably contains a binder resin.
The content of the binder resin is preferably 0.1 to 30% by mass with respect to the total solid content of the curable composition.
When the content of the binder resin is 0.3 to 25% by mass or more based on the total solid content of the curable composition, the pattern shape of the cured film obtained by curing the curable composition is more excellent.
Binder resin may be used individually by 1 type, or may use 2 or more types together. When using 2 or more types of binder resin together, it is preferable that the total amount is in the said range.
　バインダー樹脂としては、線状有機ポリマーを用いることが好ましい。このような線状有機ポリマーとしては、公知のものを任意に使用することができる。好ましくは、水現像又は弱アルカリ水現像を可能とするために、水又は弱アルカリ水に可溶性又は膨潤性である線状有機ポリマーが選択される。なかでも、バインダー樹脂としては、アルカリ可溶性樹脂（アルカリ可溶性を促進する基を含有する樹脂）が特に好ましい。
　バインダー樹脂としては、線状有機ポリマーであって、分子（好ましくは、(メタ)アクリル系共重合体、又は、スチレン系共重合体を主鎖とする分子）中に少なくとも１つのアルカリ可溶性を促進する基を含有するアルカリ可溶性樹脂の中から適宜選択することができる。耐熱性の観点からは、ポリヒドロキシスチレン系樹脂、ポリシロキサン系樹脂、（メタ）アクリル系樹脂、（メタ）アクリルアミド系樹脂、（メタ）アクリル／（メタ）アクリルアミド共重合体樹脂、エポキシ系樹脂及びポリイミド系樹脂が好ましく、現像性制御の観点からは、（メタ）アクリル系樹脂、(メタ)アクリルアミド系樹脂、(メタ)アクリル／（メタ）アクリルアミド共重合体樹脂又はポリイミド系樹脂がより好ましい。
　アルカリ可溶性を促進する基（以下、酸基ともいう）としては、例えば、カルボン酸基、リン酸基、スルホン酸基、及び、フェノール性ヒドロキシ基等が挙げられる。なかでも、有機溶剤に可溶で弱アルカリ水溶液により現像可能なものが好ましく、（メタ）アクリル酸由来の構造単位を含有するアルカリ可溶性樹脂がより好ましいものとして挙げられる。これら酸基は、１種のみであってもよいし、２種以上であってもよい。 As the binder resin, a linear organic polymer is preferably used. As such a linear organic polymer, a well-known thing can be used arbitrarily. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to enable water development or weak alkaline water development. Especially, as binder resin, alkali-soluble resin (resin containing group which accelerates | stimulates alkali solubility) is especially preferable.
The binder resin is a linear organic polymer that promotes at least one alkali solubility in the molecule (preferably a molecule having a (meth) acrylic copolymer or styrene copolymer as the main chain). It can be suitably selected from alkali-soluble resins containing a group to be used. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, (meth) acrylic resins, (meth) acrylamide resins, (meth) acrylic / (meth) acrylamide copolymer resins, epoxy resins and Polyimide resins are preferred, and (meth) acrylic resins, (meth) acrylamide resins, (meth) acryl / (meth) acrylamide copolymer resins, or polyimide resins are more preferred from the viewpoint of control of developability.
Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxy group. Especially, what is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution is preferable, and an alkali-soluble resin containing a structural unit derived from (meth) acrylic acid is more preferable. These acid groups may be used alone or in combination of two or more.
　バインダー樹脂としては、例えば、側鎖にカルボン酸基を含有するラジカル重合体が挙げられる。側鎖にカルボン酸基を含有するラジカル重合体としては、例えば、特開昭５９－４４６１５号、特公昭５４－３４３２７号、特公昭５８－１２５７７号、特公昭５４－２５９５７号、特開昭５４－９２７２３号、特開昭５９－５３８３６号、及び、特開昭５９－７１０４８号に記載されているものが挙げられる。側鎖にカルボン酸基を含有するラジカル重合体としては、カルボン酸基を含有するモノマーを単独又は共重合させた樹脂、酸無水物を含有するモノマーを単独又は共重合させて得た酸無水物ユニットを、加水分解、ハーフエステル化又はハーフアミド化させた樹脂、及び、エポキシ樹脂を不飽和モノカルボン酸及び酸無水物で変性させたエポキシアクリレート等が挙げられる。
　カルボン酸基を含有するモノマーとしては、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、マレイン酸、フマル酸、及び、４－カルボキシルスチレン等が挙げられる。側鎖にカルボン酸基を含有する酸性セルロース誘導体も例として挙げられる。
　酸無水物を含有するモノマーとしては、無水マレイン酸等が挙げられる。この他にヒドロキシ基を含有する重合体に環状酸無水物を付加させたもの等が有用である。
　酸基を含有するアセタール変性ポリビニルアルコール系バインダー樹脂が、欧州特許第９９３９６６号、欧州特許第１２０４０００号、及び、特開２００１－３１８４６３号等の各公報に記載されている。酸基を含有するアセタール変性ポリビニルアルコール系バインダー樹脂は、膜強度、及び、現像性のバランスに優れており、好適である。
　更に、水溶性線状有機ポリマーとして、ポリビニルピロリドン、又はポリエチレンオキサイド等が有用である。また、硬化皮膜の強度を上げるために、アルコール可溶性ナイロン、及び、２，２－ビス－（４－ヒドロキシフェニル）－プロパンとエピクロロヒドリンとの反応物であるポリエーテル等も有用である。
　国際公開第２００８／１２３０９７号に記載のポリイミド樹脂も有用である。 Examples of the binder resin include a radical polymer containing a carboxylic acid group in the side chain. Examples of the radical polymer containing a carboxylic acid group in the side chain include, for example, JP 59-44615, JP-B 54-34327, JP-B 58-12777, JP-B 54-25957, JP-A 54 -92723, JP-A-59-53836, and JP-A-59-71048. As a radical polymer containing a carboxylic acid group in the side chain, a resin obtained by singly or copolymerizing a monomer containing a carboxylic acid group, an acid anhydride obtained by singly or copolymerizing a monomer containing an acid anhydride Examples thereof include resins obtained by hydrolysis, half-esterification or half-amidation of units, and epoxy acrylates obtained by modifying epoxy resins with unsaturated monocarboxylic acids and acid anhydrides.
Examples of the monomer containing a carboxylic acid group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxylstyrene. Examples include acidic cellulose derivatives containing a carboxylic acid group in the side chain.
Examples of the monomer containing an acid anhydride include maleic anhydride. In addition, those obtained by adding a cyclic acid anhydride to a polymer containing a hydroxy group are useful.
Acetal-modified polyvinyl alcohol binder resins containing acid groups are described in European Patent No. 993966, European Patent No. 1204000, and Japanese Patent Application Laid-Open No. 2001-318463. An acetal-modified polyvinyl alcohol-based binder resin containing an acid group is suitable because of its excellent balance between film strength and developability.
Furthermore, polyvinyl pyrrolidone or polyethylene oxide is useful as the water-soluble linear organic polymer. In addition, in order to increase the strength of the cured film, alcohol-soluble nylon and polyether which is a reaction product of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful.
A polyimide resin described in International Publication No. 2008/123097 is also useful.
　これらの中でも、〔ベンジル（メタ）アクリレート／（メタ）アクリル酸／必要に応じてその他の付加重合性ビニルモノマー〕共重合体、及び〔アリル（メタ）アクリレート／（メタ）アクリル酸／必要に応じてその他の付加重合性ビニルモノマー〕共重合体は、膜強度、感度、及び、現像性のバランスに優れており、好適である。
　市販品としては、例えばアクリベースＦＦ－１８７、ＦＦ－４２６（藤倉化成社製）、アクリキュア－ＲＤ－Ｆ８（日本触媒）、及び、ダイセルオルネクス製サイクロマーＰ（ＡＣＡ）２３０ＡＡ等が挙げられる。 Among these, [benzyl (meth) acrylate / (meth) acrylic acid / other addition-polymerizable vinyl monomer as required] copolymer, and [allyl (meth) acrylate / (meth) acrylic acid / if necessary Other addition-polymerizable vinyl monomers] are preferable because they are excellent in the balance of film strength, sensitivity, and developability.
Examples of commercially available products include Acrybase FF-187, FF-426 (manufactured by Fujikura Kasei Co., Ltd.), Acrycure-RD-F8 (Nippon Shokubai), and Daicel Ornex Cyclomer P (ACA) 230AA.
　バインダー樹脂の製造には、例えば、公知のラジカル重合法による方法を適用することができる。ラジカル重合法でバインダー樹脂を製造する際の温度、圧力、ラジカル開始剤の種類及びその量、並びに、溶剤の種類等々の重合条件は、当業者において容易に設定可能である。 For the production of the binder resin, for example, a known radical polymerization method can be applied. Those skilled in the art can easily set the polymerization conditions such as temperature, pressure, type and amount of radical initiator, and type of solvent when the binder resin is produced by the radical polymerization method.
　バインダー樹脂として、グラフト鎖を含有する構造単位と、酸基（アルカリ可溶性基）を含有する構造単位と、を含有するポリマーを使用することも好ましい。
　グラフト鎖を含有する構造単位の定義は、上記の分散剤が含有するグラフト鎖を含有する構造単位と同義であり、また好適範囲も同様である。
　酸基としては、例えば、カルボン酸基、スルホン酸基、リン酸基、又は、フェノール性ヒドロキシ基等が挙げられ、カルボン酸基、スルホン酸基、及び、リン酸基のうち少なくとも１種が好ましく、カルボン酸基がより好ましい。 As the binder resin, it is also preferable to use a polymer containing a structural unit containing a graft chain and a structural unit containing an acid group (alkali-soluble group).
The definition of the structural unit containing the graft chain is synonymous with the structural unit containing the graft chain contained in the dispersant, and the preferred range is also the same.
Examples of the acid group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxy group, and at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group is preferable. A carboxylic acid group is more preferable.
（酸基を含有する構造単位）
　酸基を含有する構造単位としては、下記式（ｖｉｉ）～式（ｉｘ）で表される単量体に由来の構造単位から選択された１種以上の構造単位を含有することが好ましい。 (Structural unit containing acid group)
The structural unit containing an acid group preferably contains one or more structural units selected from structural units derived from monomers represented by the following formulas (vii) to (ix).
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
　式（ｖｉｉ）～式（ｉｘ）中、Ｒ２１、Ｒ２２、及びＲ２３は、それぞれ独立に、水素原子、ハロゲン原子（例えば、フッ素原子、塩素原子、臭素原子等）、又は炭素数が１～６のアルキル基（例えば、メチル基、エチル基、プロピル基等）を表す。
　式（ｖｉｉ）～式（ｉｘ）中、Ｒ２１、Ｒ２２、及びＲ２３は、それぞれ独立に水素原子、又は炭素数が１～３のアルキル基であることが好ましく、それぞれ独立に水素原子又はメチル基であることがより好ましい。式（ｖｉｉ）中、Ｒ２１及びＲ２３は、それぞれ水素原子であることが特に好ましい。 In formulas (vii) to (ix), R 21 , R 22 , and R 23 each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number of 1 Represents an alkyl group of ˜6 (for example, methyl group, ethyl group, propyl group, etc.).
In formulas (vii) to (ix), R 21 , R 22 , and R 23 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and each independently a hydrogen atom or More preferred is a methyl group. In formula (vii), R 21 and R 23 are each particularly preferably a hydrogen atom.
　式（ｖｉｉ）中のＸ２は、酸素原子（－Ｏ－）又はイミノ基（－ＮＨ－）を表し、酸素原子であることが好ましい。
　また、式（ｖｉｉｉ）中のＹは、メチン基又は窒素原子を表す。 X 2 in the formula (vii) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
Y in formula (viii) represents a methine group or a nitrogen atom.
　式（ｖｉｉ）～式（ｉｘ）中のＬ２は、単結合又は２価の連結基を表す。２価の連結基の例としては、２価の脂肪族基（例えば、アルキレン基、置換アルキレン基、アルケニレン基、置換アルケニレン基、アルキニレン基、及び置換アルキニレン基）、２価の芳香族基（例えば、アリーレン基、及び置換アリーレン基）、２価の複素環基、酸素原子（－Ｏ－）、硫黄原子（－Ｓ－）、イミノ基（－ＮＨ－）、置換イミノ結合（－ＮＲ４１’－、ここでＲ４１’は脂肪族基、芳香族基又は複素環基）、カルボニル結合（－ＣＯ－）、及び、これらの組合せ等が挙げられる。 L 2 in the formulas (vii) to (ix) represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group (for example, , Arylene group, and substituted arylene group), divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino bond (—NR 41 ′ — Here, R 41 ′ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (—CO—), and combinations thereof.
　２価の脂肪族基は、環状構造又は分岐構造を有していてもよい。脂肪族基の炭素数は、１～２０が好ましく、１～１５がより好ましく、１～１０が更に好ましい。脂肪族基は不飽和脂肪族基よりも飽和脂肪族基の方が好ましい。脂肪族基は、置換基を有していてもよい。置換基の例としては、ハロゲン原子、ヒドロキシ基、芳香族基及び複素環基が挙げられる。 The divalent aliphatic group may have a cyclic structure or a branched structure. The aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. The aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. The aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an aromatic group, and a heterocyclic group.
　２価の芳香族基の炭素数は、６～２０が好ましく、６～１５がより好ましく、６～１０が更に好ましい。芳香族基は置換基を有していてもよい。置換基の例は、ハロゲン原子、ヒドロキシ基、脂肪族基、芳香族基及び複素環基が挙げられる。 The carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10. The aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, an aliphatic group, an aromatic group, and a heterocyclic group.
　２価の複素環基は、複素環として５員環又は６員環を含有することが好ましい。複素環に他の複素環、脂肪族環又は芳香族環のうち１つ以上が縮合していてもよい。複素環基は置換基を有していてもよい。置換基の例としては、ハロゲン原子、ヒドロキシ基、オキソ基（＝Ｏ）、チオキソ基（＝Ｓ）、イミノ基（＝ＮＨ）、置換イミノ基（＝Ｎ－Ｒ４２、ここでＲ４２は脂肪族基、芳香族基又は複素環基）、脂肪族基、芳香族基及び複素環基が挙げられる。 The divalent heterocyclic group preferably contains a 5-membered ring or a 6-membered ring as the heterocyclic ring. One or more heterocycles, aliphatic rings or aromatic rings may be condensed with the heterocycle. The heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups (═O), thioxo groups (═S), imino groups (═NH), substituted imino groups (═N—R 42 , where R 42 represents a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.
　Ｌ２は、単結合、アルキレン基又はオキシアルキレン構造を含有する２価の連結基であることが好ましい。オキシアルキレン構造は、オキシエチレン構造又はオキシプロピレン構造であることがより好ましい。Ｌ２は、オキシアルキレン構造を２以上繰り返して含有するポリオキシアルキレン構造を含んでいてもよい。ポリオキシアルキレン構造としては、ポリオキシエチレン構造又はポリオキシプロピレン構造が好ましい。ポリオキシエチレン構造は、－（ＯＣＨ２ＣＨ２）ｎ－で表され、ｎは、２以上の整数が好ましく、２～１０の整数であることがより好ましい。 L 2 is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. L 2 may include a polyoxyalkylene structure containing two or more oxyalkylene structures. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
　式（ｖｉｉ）～式（ｉｘ）中、Ｚ２は、酸基であり、カルボン酸基であることが好ましい。 In the formulas (vii) to (ix), Z 2 is an acid group, preferably a carboxylic acid group.
　式（ｉｘ）中、Ｒ２４、Ｒ２５、及びＲ２６は、それぞれ独立に、水素原子、ハロゲン原子（例えば、フッ素、塩素、臭素等）、炭素数が１～６のアルキル基（例えば、メチル基、エチル基、プロピル基等）、－Ｚ２、又はＬ２－Ｚ２を表す。ここでＬ２及びＺ２は、上記におけるＬ２及びＺ２と同義であり、好ましい例も同様である。Ｒ２４、Ｒ２５、及びＲ２６としては、それぞれ独立に水素原子、又は炭素数が１～３のアルキル基が好ましく、水素原子がより好ましい。 In the formula (ix), R 24 , R 25 , and R 26 are each independently a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), an alkyl group having 1 to 6 carbon atoms (eg, methyl group, an ethyl group, a propyl group, etc.), - represents a Z 2, or L 2 -Z 2. Here L 2 and Z 2 has the same meaning as L 2 and Z 2 in the above, and preferred examples are also the same. R 24 , R 25 and R 26 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
　式（ｖｉｉ）で表される単量体として、Ｒ２１、Ｒ２２、及びＲ２３がそれぞれ独立に水素原子又はメチル基であって、Ｌ２がアルキレン基又はオキシアルキレン構造を含有する２価の連結基であって、Ｘ２が酸素原子又はイミノ基であって、Ｚ２がカルボン酸基である化合物が好ましい。
　式（ｖｉｉ）で表される単量体として、Ｒ２１が水素原子又はメチル基であって、Ｌ２がアルキレン基であって、Ｚ２がカルボン酸基であって、Ｙがメチン基である化合物が好ましい。
　更に、式（ｉｘ）で表される単量体として、Ｒ２４、Ｒ２５、及びＲ２６がそれぞれ独立に水素原子又はメチル基であって、Ｚ２がカルボン酸基である化合物が好ましい。 As the monomer represented by the formula (vii), R 21 , R 22 , and R 23 are each independently a hydrogen atom or a methyl group, and L 2 is an alkylene group or a divalent oxyalkylene structure. A compound in which X 2 is an oxygen atom or an imino group and Z 2 is a carboxylic acid group is preferable.
As the monomer represented by the formula (vii), R 21 is a hydrogen atom or a methyl group, L 2 is an alkylene group, Z 2 is a carboxylic acid group, and Y is a methine group. Compounds are preferred.
Furthermore, as the monomer represented by the formula (ix), a compound in which R 24 , R 25 and R 26 are each independently a hydrogen atom or a methyl group and Z 2 is a carboxylic acid group is preferable.
　バインダー樹脂は、上記のグラフト鎖を含有する構造単位を含有する分散剤と同様の方法により合成することができ、その好ましい酸価、重量平均分子量も同様である。 The binder resin can be synthesized by the same method as the dispersant containing the structural unit containing the graft chain, and the preferred acid value and weight average molecular weight are also the same.
　バインダー樹脂は、酸基を含有する構造単位を１種又は２種以上有してもよい。
　酸基を含有する構造単位の含有量は、質量換算で、バインダー樹脂の総質量に対して、５～９５％が好ましく、アルカリ現像による画像強度のダメージ抑制という観点から、１０～９０％がより好ましい。 The binder resin may have one or more structural units containing an acid group.
The content of the structural unit containing an acid group is preferably 5 to 95% in terms of mass with respect to the total mass of the binder resin, and is preferably 10 to 90% from the viewpoint of suppressing damage to the image strength due to alkali development. preferable.
＜界面活性剤＞
　硬化性組成物は、界面活性剤を含有することが好ましい。界面活性剤は、硬化性組成物の塗布性向上に寄与する。 <Surfactant>
The curable composition preferably contains a surfactant. Surfactant contributes to the applicability | paintability improvement of a curable composition.
　硬化性組成物が、界面活性剤を含有する場合、界面活性剤の含有量としては、硬化性組成物の全固形分に対して、０．００１～２．０質量％が好ましい。
　界面活性剤は、１種を単独で用いても、２種以上を併用してもよい。界面活性剤を２種以上併用する場合は、合計量が上記範囲内であることが好ましい。 When the curable composition contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass with respect to the total solid content of the curable composition.
Surfactant may be used individually by 1 type, or may use 2 or more types together. When two or more surfactants are used in combination, the total amount is preferably within the above range.
　界面活性剤としては、例えば、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、及びシリコーン系界面活性剤等が挙げられる。 Examples of the surfactant include fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants.
　例えば、硬化性組成物がフッ素系界面活性剤を含有することで、硬化性組成物の液特性（特に、流動性）がより向上する。即ち、フッ素系界面活性剤を含有する硬化性組成物を用いて膜形成する場合においては、被塗布面と塗布液との界面張力を低下させることにより、被塗布面への濡れ性が改善され、被塗布面への塗布性が向上する。このため、少量の液量で数μｍ程度の薄膜を形成した場合であっても、厚さムラの小さい均一厚の膜形成をより好適に行える点で有効である。 For example, when the curable composition contains a fluorosurfactant, the liquid properties (particularly fluidity) of the curable composition are further improved. That is, in the case of forming a film using a curable composition containing a fluorosurfactant, the wettability to the coated surface is improved by reducing the interfacial tension between the coated surface and the coating liquid. The applicability to the coated surface is improved. For this reason, even when a thin film of about several μm is formed with a small amount of liquid, it is effective in that a film having a uniform thickness with small thickness unevenness can be more suitably formed.
　フッ素系界面活性剤中のフッ素含有率は、３～４０質量％が好適であり、５～３０質量％がより好ましく、７～２５質量％が更に好ましい。フッ素含有率がこの範囲内であるフッ素系界面活性剤は、塗布膜の厚さの均一性及び／又は省液性の点で効果的であり、硬化性組成物中における溶解性も良好である。 The fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 7 to 25% by mass. A fluorosurfactant having a fluorine content within this range is effective in terms of uniformity in the thickness of the coating film and / or liquid-saving properties, and has good solubility in the curable composition. .
　フッ素系界面活性剤としては、例えば、メガファックＦ１７１、同Ｆ１７２、同Ｆ１７３、同Ｆ１７６、同Ｆ１７７、同Ｆ１４１、同Ｆ１４２、同Ｆ１４３、同Ｆ１４４、同Ｒ３０、同Ｆ４３７、同Ｆ４７５、同Ｆ４７９、同Ｆ４８２、同Ｆ５５４、同Ｆ７８０（以上、ＤＩＣ（株）製）、フロラードＦＣ４３０、同ＦＣ４３１、同ＦＣ１７１（以上、住友スリーエム（株）製）、サーフロンＳ－３８２、同ＳＣ－１０１、同ＳＣ－１０３、同ＳＣ－１０４、同ＳＣ－１０５、同ＳＣ－１０６８、同ＳＣ－３８１、同ＳＣ－３８３、同Ｓ－３９３、同ＫＨ－４０（以上、旭硝子（株）製）、ＰＦ６３６、ＰＦ６５６、ＰＦ６３２０、ＰＦ６５２０、ＰＦ７００２（ＯＭＮＯＶＡ社製）等が挙げられる。
　フッ素系界面活性剤としてブロックポリマーを用いることもでき、具体例としては、例えば特開２０１１－８９０９０号公報に記載の化合物が挙げられる。下記式で表される化合物（Ｆ－１）もフッ素系界面活性剤として挙げられる。化合物（Ｆ－１）において、式中（Ａ）及び（Ｂ）で表される構造単位はそれぞれ６２モル％、３８モル％である。式（Ｂ）で表される構造単位中、ａ、ｂ、ｃは、それぞれ、ａ＋ｃ＝１４、ｂ＝１７の関係を満たす。なお、下記化合物の重量平均分子量は、例えば１５，３１１である。 Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780 (above DIC Corporation), Florad FC430, FC431, FC171 (Sumitomo 3M Limited), Surflon S-382, SC-101, SC- 103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, K-H-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (made by OMNOVA) etc. are mentioned.
A block polymer can also be used as the fluorosurfactant, and specific examples thereof include compounds described in JP-A-2011-89090. The compound (F-1) represented by the following formula is also exemplified as the fluorosurfactant. In the compound (F-1), the structural units represented by formulas (A) and (B) are 62 mol% and 38 mol%, respectively. In the structural unit represented by the formula (B), a, b, and c satisfy the relationship of a + c = 14 and b = 17, respectively. In addition, the weight average molecular weight of the following compound is 15,311, for example.
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
　ノニオン系界面活性剤として具体的には、グリセロール、トリメチロールプロパン、トリメチロールエタン並びにそれらのエトキシレート及びプロポキシレート（例えば、グリセロールプロポキシレート、グリセリンエトキシレート等）、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテル、ポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールジラウレート、ポリエチレングリコールジステアレート、ソルビタン脂肪酸エステル（ＢＡＳＦ社製のプルロニックＬ１０、Ｌ３１、Ｌ６１、Ｌ６２、１０Ｒ５、１７Ｒ２、２５Ｒ２、テトロニック３０４、７０１、７０４、９０１、９０４、１５０Ｒ１）、ソルスパース２００００（日本ルーブリゾール（株））等が挙げられる。また、竹本油脂（株）製のパイオニンＤ－６１１２－Ｗ、和光純薬工業社製の、ＮＣＷ－１０１、ＮＣＷ－１００１、ＮＣＷ－１００２を使用することもできる。 Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1), Rusupasu 20000 (Lubrizol Japan Co., Ltd.), and the like. Alternatively, Pionein D-6112-W manufactured by Takemoto Yushi Co., Ltd., NCW-101, NCW-1001, NCW-1002 manufactured by Wako Pure Chemical Industries, Ltd. may be used.
　カチオン系界面活性剤として具体的には、フタロシアニン誘導体（商品名、ＥＦＫＡ－７４５、森下産業（株）製）、オルガノシロキサンポリマーＫＰ３４１（信越化学工業（株）製）、（メタ）アクリル酸系（共）重合体ポリフローＮｏ．７５、Ｎｏ．９０、Ｎｏ．９５（共栄社化学（株）製）、Ｗ００１（裕商（株））等が挙げられる。 Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name, EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (Yusho Co., Ltd.) and the like.
　アニオン系界面活性剤として具体的には、Ｗ００４、Ｗ００５、Ｗ０１７（裕商（株））等が挙げられる。 Specific examples of anionic surfactants include W004, W005, W017 (Yusho Co., Ltd.) and the like.
　シリコーン系界面活性剤としては、例えば、東レ・ダウコーニング（株）製「トーレシリコーンＤＣ３ＰＡ」、「トーレシリコーンＳＨ７ＰＡ」、「トーレシリコーンＤＣ１１ＰＡ」，「トーレシリコーンＳＨ２１ＰＡ」，「トーレシリコーンＳＨ２８ＰＡ」、「トーレシリコーンＳＨ２９ＰＡ」、「トーレシリコーンＳＨ３０ＰＡ」、「トーレシリコーンＳＨ８４００」、モメンティブ・パフォーマンス・マテリアルズ社製「ＴＳＦ－４４４０」、「ＴＳＦ－４３００」、「ＴＳＦ－４４４５」、「ＴＳＦ－４４６０」、「ＴＳＦ－４４５２」、信越シリコーン株式会社製「ＫＰ３４１」、「ＫＦ６００１」、「ＫＦ６００２」、ビックケミー社製「ＢＹＫ３０７」、「ＢＹＫ３２３」、「ＢＹＫ３３０」等が挙げられる。 Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Tore Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400, Momentive Performance Materials TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by BYK Chemie.
＜シランカップリング剤＞
　シランカップリング剤とは、分子中に加水分解性基とそれ以外の官能基とを含有する化合物である。なお、アルコキシ基等の加水分解性基は、珪素原子に結合している。
　加水分解性基とは、珪素原子に直結し、加水分解反応及び／又は縮合反応によってシロキサン結合を生じ得る置換基をいう。加水分解性基としては、例えば、ハロゲン原子、アルコキシ基、アシルオキシ基、及びアルケニルオキシ基が挙げられる。加水分解性基が炭素原子を含有する場合、その炭素数は６以下であることが好ましく、４以下であることがより好ましい。特に、炭素数４以下のアルコキシ基又は炭素数４以下のアルケニルオキシ基が好ましい。
　基板上に硬化膜を形成する場合、シランカップリング剤は基板と硬化膜間の密着性を向上させるため、フッ素原子及び珪素原子（ただし、加水分解性基が結合した珪素原子は除く）を含まないことが好ましく、フッ素原子、珪素原子（ただし、加水分解性基が結合した珪素原子は除く）、珪素原子で置換されたアルキレン基、炭素数８以上の直鎖アルキル基、及び、炭素数３以上の分鎖アルキル基は含まないことが望ましい。 <Silane coupling agent>
A silane coupling agent is a compound containing a hydrolyzable group and other functional groups in the molecule. Note that a hydrolyzable group such as an alkoxy group is bonded to a silicon atom.
The hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond by a hydrolysis reaction and / or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group. When the hydrolyzable group contains a carbon atom, the number of carbon atoms is preferably 6 or less, and more preferably 4 or less. In particular, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable.
When a cured film is formed on a substrate, the silane coupling agent contains fluorine atoms and silicon atoms (except for silicon atoms to which hydrolyzable groups are bonded) in order to improve the adhesion between the substrate and the cured film. Preferably a fluorine atom, a silicon atom (excluding a silicon atom to which a hydrolyzable group is bonded), an alkylene group substituted with a silicon atom, a linear alkyl group having 8 or more carbon atoms, and a carbon number of 3 It is desirable not to include the above branched alkyl groups.
　シランカップリング剤は、以下の式（Ｚ）で表される基を含有することが好ましい。＊は結合位置を表す。
　式（Ｚ）　＊－Ｓｉ－（ＲＺ１）３
　式（Ｚ）中、ＲＺ１は加水分解性基を表し、その定義は上記のとおりである。 The silane coupling agent preferably contains a group represented by the following formula (Z). * Represents a bonding position.
Formula (Z) * -Si- (R Z1 ) 3
In formula (Z), R Z1 represents a hydrolyzable group, and the definition thereof is as described above.
　シランカップリング剤は、（メタ）アクリロイルオキシ基、エポキシ基、及び、オキセタニル基からなる群から選択される１種以上の硬化性官能基を含有することが好ましい。硬化性官能基は、直接、珪素原子に結合してもよく、連結基を介して珪素原子に結合していてもよい。
　なお、上記シランカップリング剤に含まれる硬化性官能基の好適態様としては、ラジカル重合性基も挙げられる。 The silane coupling agent preferably contains one or more curable functional groups selected from the group consisting of a (meth) acryloyloxy group, an epoxy group, and an oxetanyl group. The curable functional group may be directly bonded to the silicon atom, or may be bonded to the silicon atom via a linking group.
In addition, a radically polymerizable group is also mentioned as a suitable aspect of the curable functional group contained in the said silane coupling agent.
　シランカップリング剤の分子量は特に制限されず、取り扱い性の点から、１００～１，０００の場合が多く、２７０以上が好ましく、２７０～１，０００がより好ましい。 The molecular weight of the silane coupling agent is not particularly limited, and is often 100 to 1,000 from the viewpoint of handleability, preferably 270 or more, and more preferably 270 to 1,000.
　シランカップリング剤の好適態様の１つとしては、式（Ｗ）で表されるシランカップリング剤Ｘが挙げられる。
　式（Ｗ）　　　ＲＺ２－Ｌｚ－Ｓｉ－（ＲＺ１）３
　Ｒｚ１は、加水分解性基を表し、定義は上記のとおりである。
　Ｒｚ２は、硬化性官能基を表し、定義は上記のとおりであり、好適範囲も上記のとおりである。
　Ｌｚは、単結合又は２価の連結基を表す。Ｌｚが２価の連結基を表す場合、２価の連結基としては、ハロゲン原子が置換していてもよいアルキレン基、ハロゲン原子が置換していてもよいアリーレン基、－ＮＲ１２－、－ＣＯＮＲ１２－、－ＣＯ－、－ＣＯ２－、ＳＯ２ＮＲ１２－、－Ｏ－、－Ｓ－、－ＳＯ２－、又は、これらの組み合わせが挙げられる。なかでも、炭素数２～１０のハロゲン原子が置換していてもよいアルキレン基及び炭素数６～１２のハロゲン原子が置換していてもよいアリーレン基からなる群から選択される少なくとも１種、又は、これらの基と－ＮＲ１２－、－ＣＯＮＲ１２－、－ＣＯ－、－ＣＯ２－、ＳＯ２ＮＲ１２－、－Ｏ－、－Ｓ－、及びＳＯ２－からなる群から選択される少なくとも１種の基との組み合わせからなる基が好ましく、炭素数２～１０のハロゲン原子が置換していてもよいアルキレン基、－ＣＯ２－、－Ｏ－、－ＣＯ－、－ＣＯＮＲ１２－、又は、これらの基の組み合わせからなる基がより好ましい。ここで、上記Ｒ１２は、水素原子又はメチル基を表す。 One preferred embodiment of the silane coupling agent is a silane coupling agent X represented by the formula (W).
Formula (W) R Z2 -Lz-Si- (R Z1 ) 3
R z1 represents a hydrolyzable group, and the definition is as described above.
R z2 represents a curable functional group, the definition is as described above, and the preferred range is also as described above.
Lz represents a single bond or a divalent linking group. If Lz represents a divalent linking group, the divalent As the linking group, an alkylene group optionally substituted with a halogen atom, an arylene group optionally halogen atoms substituted, -NR 12 -, - CONR 12 -, - CO -, - CO 2 -, SO 2 NR 12 -, - O -, - S -, - SO 2 -, or combinations thereof. Among them, at least one selected from the group consisting of an alkylene group which may be substituted with a halogen atom having 2 to 10 carbon atoms and an arylene group which may be substituted with a halogen atom having 6 to 12 carbon atoms, or At least selected from the group consisting of these groups and —NR 12 —, —CONR 12 —, —CO—, —CO 2 —, SO 2 NR 12 —, —O—, —S—, and SO 2 —. A group composed of a combination with one kind of group is preferable, an alkylene group which may be substituted by a halogen atom having 2 to 10 carbon atoms, —CO 2 —, —O—, —CO—, —CONR 12 —, or A group consisting of a combination of these groups is more preferred. Here, R 12 represents a hydrogen atom or a methyl group.
　シランカップリング剤Ｘとしては、Ｎ－β－アミノエチル－γ－アミノプロピル－メチルジメトキシシラン（信越化学工業社製、商品名　ＫＢＭ－６０２）、Ｎ－β－アミノエチル－γ－アミノプロピル－トリメトキシシラン（信越化学工業社製、商品名　ＫＢＭ－６０３）、Ｎ－β－アミノエチル－γ－アミノプロピル－トリエトキシシラン（信越化学工業社製、商品名　ＫＢＥ－６０２）、γ－アミノプロピル－トリメトキシシラン（信越化学工業社製、商品名　ＫＢＭ－９０３）、γ－アミノプロピル－トリエトキシシラン（信越化学工業社製、商品名　ＫＢＥ－９０３）、３－メタクリロキシプロピルトリメトキシシラン（信越化学工業社製、商品名　ＫＢＭ－５０３）、及び、グリシドキシオクチルトリメトキシシラン（信越化学工業社製、商品名　ＫＢＭ－４８０３）等が挙げられる。 As the silane coupling agent X, N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-602), N-β-aminoethyl-γ-aminopropyl-tri Methoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-603), N-β-aminoethyl-γ-aminopropyl-triethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE-602), γ-aminopropyl- Trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-903), γ-aminopropyl-triethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBE-903), 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical) Manufactured by Kogyo Co., Ltd., trade name KBM-503), and glycidoxyoctyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) And a trade name KBM-4803) manufactured by the company.
　シランカップリング剤の他の好適態様としては、分子内に少なくとも珪素原子と窒素原子と硬化性官能基とを有し、かつ、珪素原子に結合した加水分解性基を含有するシランカップリング剤Ｙが挙げられる。
　このシランカップリング剤Ｙは、分子内に少なくとも１つの珪素原子を有すればよく、珪素原子は、以下の原子、置換基と結合できる。それらは同じ原子、置換基であっても異なっていてもよい。結合しうる原子、置換基は、水素原子、ハロゲン原子、ヒドロキシ基、炭素数１から２０のアルキル基、アルケニル基、アルキニル基、アリール基、アルキル基及び／又はアリール基で置換可能なアミノ基、シリル基、炭素数１から２０のアルコキシ基、アリーロキシ基等が挙げられる。これらの置換基は更に、シリル基、アルケニル基、アルキニル基、アリール基、アルコキシ基、アリーロキシ基、チオアルコキシ基、アルキル基及び／又はアリール基で置換可能なアミノ基、ハロゲン原子、スルホンアミド基、アルコキシカルボニル基、アミド基、ウレア基、アンモニウム基、アルキルアンモニウム基、カルボン酸基、又はその塩、スルホ基、又はその塩等で置換されていてもよい。
　なお、珪素原子には少なくとも１つの加水分解性基が結合している。加水分解性基の定義は、上記のとおりである。
　シランカップリング剤Ｙには、式（Ｚ）で表される基が含まれていてもよい。 As another preferred embodiment of the silane coupling agent, a silane coupling agent Y having at least a silicon atom, a nitrogen atom, and a curable functional group in the molecule and containing a hydrolyzable group bonded to the silicon atom. Is mentioned.
The silane coupling agent Y only needs to have at least one silicon atom in the molecule, and the silicon atom can be bonded to the following atoms and substituents. They may be the same atom, substituent or different. The bondable atom or substituent is a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, an alkyl group and / or an amino group which can be substituted with an aryl group, Examples thereof include a silyl group, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group. These substituents further include silyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, aryloxy group, thioalkoxy group, alkyl group and / or aryl group, an amino group, a halogen atom, a sulfonamide group, It may be substituted with an alkoxycarbonyl group, an amide group, a urea group, an ammonium group, an alkylammonium group, a carboxylic acid group, or a salt thereof, a sulfo group, or a salt thereof.
Note that at least one hydrolyzable group is bonded to the silicon atom. The definition of the hydrolyzable group is as described above.
The silane coupling agent Y may contain a group represented by the formula (Z).
　シランカップリング剤Ｙは、分子内に窒素原子を少なくとも１つ以上有し、窒素原子は、２級アミノ基又は３級アミノ基の形態で存在することが好ましく、即ち、窒素原子は置換基として少なくとも１つの有機基を含有することが好ましい。なお、アミノ基の構造としては、含窒素ヘテロ環の部分構造の形態で分子内に存在してもよく、アニリン等の置換アミノ基として存在していてもよい。
　ここで、有機基としては、アルキル基、アルケニル基、アルキニル基、アリール基、又は、これらの組み合わせ等が挙げられる。これらは更に置換基を有してもよく、導入可能な置換基としては、シリル基、アルケニル基、アルキニル基、アリール基、アルコキシ基、アリーロキシ基、チオアルコキシ基、アミノ基、ハロゲン原子、スルホンアミド基、アルコキシカルボニル基、カルボニルオキシ基、アミド基、ウレア基、アルキレンオキシ基アンモニウム基、アルキルアンモニウム基、カルボン酸基、又はその塩、スルホ基等が挙げられる。
　窒素原子は、任意の有機連結基を介して硬化性官能基と結合していることが好ましい。好ましい有機連結基としては、上記の窒素原子及びそれに結合する有機基に導入可能な置換基を挙げることができる。 The silane coupling agent Y has at least one nitrogen atom in the molecule, and the nitrogen atom is preferably present in the form of a secondary amino group or a tertiary amino group, that is, the nitrogen atom is used as a substituent. It preferably contains at least one organic group. The amino group structure may exist in the molecule in the form of a partial structure of a nitrogen-containing heterocycle, or may exist as a substituted amino group such as aniline.
Here, examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof. These may further have a substituent. Examples of the substituent that can be introduced include a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an amino group, a halogen atom, and a sulfonamide. Group, alkoxycarbonyl group, carbonyloxy group, amide group, urea group, alkyleneoxy group ammonium group, alkylammonium group, carboxylic acid group, or a salt thereof, sulfo group and the like.
The nitrogen atom is preferably bonded to the curable functional group via any organic linking group. Preferred examples of the organic linking group include a substituent that can be introduced into the nitrogen atom and the organic group bonded thereto.
　シランカップリング剤Ｙに含まれる硬化性官能基の定義は、上記のとおりであり、好適範囲も上記のとおりである。
　シランカップリング剤Ｙは、硬化性官能基を１分子中に少なくとも１つ以上有していればよいが、硬化性官能基を２以上含有することも可能である。感度、安定性の観点からは、硬化性官能基を分子内に２～２０含有することが好ましく、４～１５含有することがより好ましく、６～１０含有することが更に好ましい。 The definition of the curable functional group contained in the silane coupling agent Y is as described above, and the preferred range is also as described above.
The silane coupling agent Y only needs to have at least one curable functional group in one molecule, but it is also possible to contain two or more curable functional groups. From the viewpoint of sensitivity and stability, the curable functional group is preferably contained in the molecule in an amount of 2 to 20, more preferably 4 to 15, and even more preferably 6 to 10.
　シランカップリング剤Ｘ及びシランカップリング剤Ｙの分子量は特に制限されないが、上記の範囲（２７０以上が好ましい）が挙げられる。 The molecular weights of the silane coupling agent X and the silane coupling agent Y are not particularly limited, but include the above ranges (preferably 270 or more).
　硬化性組成物中におけるシランカップリング剤の含有量は、硬化性組成物中の全固形分に対して、０．１～１０質量％が好ましく、０．５～８質量％がより好ましく、１．０～６質量％が更に好ましい。 The content of the silane coupling agent in the curable composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass with respect to the total solid content in the curable composition. More preferably, the content is 0.0 to 6% by mass.
　硬化性組成物は、シランカップリング剤を１種単独で含んでいてもよく、２種以上を含んでいてもよい。硬化性組成物がシランカップリング剤を２種以上含有する場合は、その合計が上記範囲内であればよい。 The curable composition may contain one type of silane coupling agent or two or more types. When a curable composition contains 2 or more types of silane coupling agents, the sum should just be in the said range.
＜紫外線吸収剤＞
　硬化性組成物は、紫外線吸収剤を含有してもよい。これにより、硬化膜のパターンの形状をより優れた（精細な）ものにすることができる。
　紫外線吸収剤としては、サリシレート系、ベンゾフェノン系、ベンゾトリアゾール系、置換アクリロニトリル系、及びトリアジン系の紫外線吸収剤を使用することができる。これらの具体例としては、特開２０１２－０６８４１８号公報の段落０１３７～０１４２（対応するＵＳ２０１２／００６８２９２の段落０２５１～０２５４）の化合物が使用でき、これらの内容が援用でき、本明細書に組み込まれる。
　他にジエチルアミノ－フェニルスルホニル系紫外線吸収剤（大東化学社製、商品名：ＵＶ－５０３）なども好適に用いられる。
　紫外線吸収剤としては、特開２０１２－３２５５６号公報の段落０１３４～０１４８に例示される化合物が挙げられる。
　紫外線吸収剤の含有量は、硬化性組成物の全固形分に対して、０．００１～１５質量％が好ましく、０．０１～１０質量％がより好ましく、０．１～５質量％が更に好ましい。 <Ultraviolet absorber>
The curable composition may contain an ultraviolet absorber. Thereby, the shape of the pattern of a cured film can be made more excellent (fine).
As the ultraviolet absorber, salicylate, benzophenone, benzotriazole, substituted acrylonitrile, and triazine ultraviolet absorbers can be used. As specific examples of these, compounds of paragraphs 0137 to 0142 (corresponding to paragraphs 0251 to 0254 of US2012 / 0068292) of JP2012-068418A can be used, and the contents thereof can be incorporated and incorporated in the present specification. .
In addition, a diethylamino-phenylsulfonyl-based ultraviolet absorber (manufactured by Daito Chemical Co., Ltd., trade name: UV-503) is also preferably used.
Examples of the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP2012-32556A.
The content of the ultraviolet absorber is preferably 0.001 to 15% by mass, more preferably 0.01 to 10% by mass, and further preferably 0.1 to 5% by mass with respect to the total solid content of the curable composition. preferable.
＜熱重合開始剤＞
　硬化性組成物は熱重合開始剤を含有してもよい。
　熱重合開始剤の１分間半減期温度は、感光性樹脂組成物の安定性及び硬化性の観点から、１２０～３００℃が好ましく、１５０～２５０℃がより好ましく、１５０～２３０℃が更に好ましく、１７０～２００℃が特に好ましい。熱重合開始剤の１分間半減期温度が、上記下限値以上であれば、塗膜の乾燥時に硬化しすぎず、現像性が良好である。熱重合開始剤の１分間半減期温度が、上記下限値以下であれば、硬化性が良好である。
　熱重合開始剤の分子量は、揮発性の観点から、１００以上が好ましく、１５０以上がより好ましく、２００以上が更に好ましく、２５０以上が特に好ましい。上限は、例えば、１，０００以下が好ましく、５００以下がより好ましい。熱重合開始剤の分子量が上記下限値以上であれば、塗膜の乾燥時における熱重合開始剤の揮散を効果的に抑制でき、硬化性が良好である。 <Thermal polymerization initiator>
The curable composition may contain a thermal polymerization initiator.
The 1-minute half-life temperature of the thermal polymerization initiator is preferably 120 to 300 ° C, more preferably 150 to 250 ° C, and still more preferably 150 to 230 ° C, from the viewpoint of stability and curability of the photosensitive resin composition. 170 to 200 ° C. is particularly preferable. When the half-life temperature for 1 minute of the thermal polymerization initiator is equal to or higher than the above lower limit, the film is not excessively cured when dried and the developability is good. If the 1-minute half-life temperature of a thermal-polymerization initiator is below the said lower limit, sclerosis | hardenability is favorable.
From the viewpoint of volatility, the molecular weight of the thermal polymerization initiator is preferably 100 or more, more preferably 150 or more, still more preferably 200 or more, and particularly preferably 250 or more. For example, the upper limit is preferably 1,000 or less, and more preferably 500 or less. If the molecular weight of the thermal polymerization initiator is not less than the above lower limit, volatilization of the thermal polymerization initiator during drying of the coating film can be effectively suppressed, and curability is good.
　熱重合開始剤は、熱によりラジカルを発生する化合物（以下、単に、熱ラジカル発生剤とも言う）、又は、熱により酸を発生する化合物（以下、単に、熱酸発生剤とも言う）を用いることができる。特に、熱ラジカル発生剤が好ましい。熱ラジカル発生剤は、エチレン性不飽和基のラジカル重合を促進できるので、架橋剤として、エチレン性不飽和結合を有する基を含有する化合物を用いた場合において、架橋剤の重合反応をより効果的に促進でき、より短時間で硬化させることができる。なお、熱酸発生剤によって重合反応が開始及び促進される反応は、エポキシの開環重合である。エポキシの開環重合は、ラジカル重合に比べて重合速度が遅いため、硬化性を十分に促進できないことがある。 As the thermal polymerization initiator, a compound that generates a radical by heat (hereinafter also simply referred to as a thermal radical generator) or a compound that generates an acid by heat (hereinafter also simply referred to as a thermal acid generator) is used. Can do. In particular, a thermal radical generator is preferable. Since the thermal radical generator can promote radical polymerization of ethylenically unsaturated groups, when a compound containing a group having an ethylenically unsaturated bond is used as the crosslinking agent, the polymerization reaction of the crosslinking agent is more effective. And can be cured in a shorter time. The reaction in which the polymerization reaction is initiated and accelerated by the thermal acid generator is epoxy ring-opening polymerization. Since ring-opening polymerization of epoxy has a slower polymerization rate than radical polymerization, curability may not be sufficiently promoted.
（熱ラジカル発生剤）
　熱ラジカル発生剤としては、公知の熱ラジカル発生剤を用いることができる。熱ラジカル発生剤は、熱のエネルギーによってラジカルを発生し、架橋剤の重合反応を開始又は促進させる化合物である。
　熱ラジカル発生剤としては、芳香族ケトン類、オニウム塩化合物、有機過酸化物、チオ化合物、ヘキサアリールビイミダゾール化合物、ケトオキシムエステル化合物、ボレート化合物、アジニウム化合物、メタロセン化合物、活性エステル化合物、炭素ハロゲン結合を有する化合物、及びアゾ系化合物等が挙げられる。中でも、アゾ系化合物がより好ましい。 (Thermal radical generator)
As the thermal radical generator, a known thermal radical generator can be used. The thermal radical generator is a compound that generates radicals by heat energy and initiates or accelerates the polymerization reaction of the crosslinking agent.
Thermal radical generators include aromatic ketones, onium salt compounds, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, carbon halogens Examples thereof include a compound having a bond and an azo compound. Of these, azo compounds are more preferable.
［硬化性組成物の製造方法］
　硬化性組成物の製造方法は以下の混合及び分散工程を含有する。静置工程及び／又はろ過工程を含有することが好ましい。以下では、各工程について好適態様を詳述する。 [Method for producing curable composition]
The manufacturing method of a curable composition contains the following mixing and dispersion | distribution processes. It is preferable to contain a stationary process and / or a filtration process. Below, a suitable aspect is explained in full detail about each process.
〔混合及び分散工程〕
　混合及び分散工程は、上記成分を公知の混合方法（例えば、攪拌機、ホモジナイザー、高圧乳化装置、湿式粉砕機、及び湿式分散機）により混合し、硬化性組成物を得る工程である。混合及び分散工程においては、硬化性組成物を構成する各成分を一括配合してもよいし、各成分を有機溶剤に溶解又は分散した後に逐次配合してもよい。配合する際の投入順序及び作業条件は、特に制限されない。混合及び分散工程は、分散液を作製する工程を含有してもよい。 [Mixing and dispersing process]
A mixing and dispersion | distribution process is a process of mixing the said component with a well-known mixing method (For example, a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, and a wet disperser), and obtaining a curable composition. In the mixing and dispersing step, each component constituting the curable composition may be mixed at once, or may be sequentially added after each component is dissolved or dispersed in an organic solvent. There are no particular restrictions on the charging sequence and working conditions when blending. The mixing and dispersing step may include a step of producing a dispersion.
（分散液を作製する工程）
　分散液を作製する工程は、着色剤と、分散剤と、溶剤とを混合し、着色剤を上記の方法により分散させて、分散液を作製する工程である。作製した分散液に、その他の成分を混合し、硬化性組成物を製造することができる。
　分散液を作製する工程において、顔料の分散に用いる機械力としては、圧縮、圧搾、衝撃、剪断及びキャビテーションなどが挙げられる。これらプロセスの具体例としては、ビーズミル、サンドミル、ロールミル、高速インペラー、サンドグラインダー、フロージェットミキサー、高圧湿式微粒化及び超音波分散などが挙げられる。また、「分散技術大全、株式会社情報機構発行、２００５年７月１５日」及び「サスペンション（固／液分散系）を中心とした分散技術と工業的応用の実際　総合資料集、経営開発センター出版部発行、１９７８年１０月１０日」に記載のプロセス及び分散機を好適に使用することができる。
　分散液を作製する工程においては、ソルトミリング工程による顔料の微細化処理を行ってもよい。ソルトミリング工程に用いられる素材、機器及び処理条件等は、例えば、特開２０１５－１９４５２１号及び特開２０１２－０４６６２９号に記載のものを使用することができる。
　硬化性組成物の製造方法は、熱プラズマ法によって上記着色剤を得る工程を含有することが好ましい。着色剤を得る工程は、上記の各成分を混合する前に実施される。熱プラズマ法による着色剤の具体的な製造工程の態様は上記のとおりである。 (Process for producing dispersion)
The step of preparing the dispersion is a step of mixing the colorant, the dispersant, and the solvent, and dispersing the colorant by the above method to prepare the dispersion. A curable composition can be manufactured by mixing other components with the prepared dispersion.
In the step of producing the dispersion, the mechanical force used for dispersing the pigment includes compression, squeezing, impact, shearing and cavitation. Specific examples of these processes include a bead mill, a sand mill, a roll mill, a high speed impeller, a sand grinder, a flow jet mixer, high pressure wet atomization, and ultrasonic dispersion. In addition, “Dispersion Technology Encyclopedia, Issued by Information Technology Corporation, July 15, 2005” and “Distribution technology and industrial application centered on suspension (solid / liquid dispersion system) and comprehensive application data collection, Management Development Center publication. The process and the dispersing machine described in “Issuance of the Department, October 10, 1978” can be preferably used.
In the step of preparing the dispersion, the pigment may be refined by a salt milling step. For example, materials described in JP-A-2015-194521 and JP-A-2012-046629 can be used as materials, equipment and processing conditions used in the salt milling process.
It is preferable that the manufacturing method of a curable composition contains the process of obtaining the said coloring agent by a thermal plasma method. The step of obtaining the colorant is performed before mixing the above-described components. The aspect of the specific manufacturing process of the colorant by the thermal plasma method is as described above.
＜静置工程＞
　着色剤は、混合及び分散工程、又は分散液を作製する工程に供される前に、以下の静置工程を経てもよい。
　静置工程とは、熱プラズマ法によって得られた着色剤を、その製造後に大気に曝露せず、酸素濃度が制御された密閉容器内において、所定時間（好ましくは１２～７２時間、より好ましくは１２～４８時間、更に好ましくは１２～２４時間）静置する工程である。この際、密閉容器内における水分の含有量が制御されているとより好ましい。 <Standing process>
The colorant may be subjected to the following standing step before being subjected to the mixing and dispersing step or the step of producing a dispersion.
The standing step refers to a predetermined time (preferably 12 to 72 hours, more preferably, in a sealed container in which the colorant obtained by the thermal plasma method is not exposed to the atmosphere after its production and the oxygen concentration is controlled. 12 to 48 hours, more preferably 12 to 24 hours). At this time, it is more preferable that the moisture content in the sealed container is controlled.
　この際、密閉容器内における酸素（Ｏ２）濃度及び水分の含有量は、それぞれ１００ｐｐｍ以下であることが好ましく、１０ｐｐｍ以下であることがより好ましく、１ｐｐｍ以下であることが更に好ましい。
　密閉容器内における酸素（Ｏ２）濃度及び水分の含有量は、密閉容器内に供給する不活性ガス中の酸素濃度及び水分量を調整することによって行うことができる。不活性ガスとしては、窒素ガス及びアルゴンガスが好ましく用いられ、この中でも窒素ガスを用いることがより好ましい。
　上記静置工程を経ると、着色剤の表面及び結晶粒界が安定となる。これにより、硬化性組成物を硬化して得られる硬化膜のピンホールの発生を抑制できる。
　なお、上記静置工程は、着色剤の製造方法において説明した工程Ｈで代えることが可能であり、硬化性組成物がより優れた本発明の効果を有する点で、工程Ｈで代えることが好ましい。 At this time, the oxygen (O 2 ) concentration and the water content in the sealed container are each preferably 100 ppm or less, more preferably 10 ppm or less, and still more preferably 1 ppm or less.
The oxygen (O 2 ) concentration and moisture content in the sealed container can be adjusted by adjusting the oxygen concentration and moisture content in the inert gas supplied into the sealed container. As the inert gas, nitrogen gas and argon gas are preferably used, and among these, it is more preferable to use nitrogen gas.
After the standing step, the surface of the colorant and the crystal grain boundary become stable. Thereby, generation | occurrence | production of the pinhole of the cured film obtained by hardening | curing a curable composition can be suppressed.
In addition, it is preferable to replace the said stationary process with the process H at the point which can replace with the process H demonstrated in the manufacturing method of a coloring agent, and the curable composition has the effect of this invention which was more excellent. .
＜ろ過工程＞
　ろ過工程は、上記混合及び分散工程により製造された硬化性組成物をフィルタでろ過する工程である。ろ過工程では、硬化性組成物から異物を除去及び／又は欠陥を低減することができる。
　フィルタとしては、従来からろ過用途等に用いられているものであれば特に限定されることなく用いることができる。例えば、ＰＴＦＥ（polytetrafluoroethylene：ポリテトラフルオロエチレン）等のフッ素樹脂、ナイロン等のポリアミド系樹脂、ポリエチレン、ポリプロピレン（ＰＰ）等のポリオレフィン樹脂（高密度、超高分子量を含有する）等によるフィルタが挙げられる。これら素材の中でもポリプロピレン（高密度ポリプロピレンを含有する）、ナイロンが好ましい。
　フィルタの孔径は、０．１～７．０μｍ程度が適しており、０．２～２．５μｍ程度が好ましく、０．２～１．５μｍ程度がより好ましく、０．３～０．７μｍ程度が更に好ましい。この範囲とすることにより、顔料のろ過詰まりを抑えつつ、顔料に含まれる不純物及び凝集物など、微細な異物を確実に除去することが可能となる。
　フィルタを使用する際、異なるフィルタを組み合わせてもよい。その際、第１のフィルタでのフィルタリングは、１回のみでもよいし、２回以上行ってもよい。異なるフィルタを組み合わせて２回以上フィルタリングを行う場合は１回目のフィルタリングの孔径より２回目以降の孔径が同じ、又は、大きい方が好ましい。上記の範囲内で異なる孔径の第１のフィルタを組み合わせてもよい。ここでの孔径は、フィルタメーカーの公称値を参照することができる。市販のフィルタとしては、例えば、日本ポール株式会社、アドバンテック東洋株式会社、日本インテグリス株式会社（旧日本マイクロリス株式会社）又は株式会社キッツマイクロフィルタ等が提供する各種フィルタの中から選択することができる。
　第２のフィルタは、上記の第１のフィルタと同様の材料等で形成されたものを使用することができる。第２のフィルタの孔径は、０．２～１０．０μｍ程度が適しており、０．２～７．０μｍ程度が好ましく、０．３～６．０μｍ程度がより好ましい。 <Filtration process>
A filtration process is a process of filtering the curable composition manufactured by the said mixing and dispersion | distribution process with a filter. In the filtration step, foreign substances can be removed from the curable composition and / or defects can be reduced.
Any filter can be used without particular limitation as long as it has been conventionally used for filtration. For example, a filter made of a fluororesin such as PTFE (polytetrafluoroethylene), a polyamide resin such as nylon, a polyolefin resin such as polyethylene or polypropylene (PP) (containing high density and ultra high molecular weight), and the like. . Among these materials, polypropylene (containing high density polypropylene) and nylon are preferable.
The pore size of the filter is suitably about 0.1 to 7.0 μm, preferably about 0.2 to 2.5 μm, more preferably about 0.2 to 1.5 μm, and about 0.3 to 0.7 μm. Further preferred. By setting this range, it is possible to reliably remove fine foreign matters such as impurities and aggregates contained in the pigment while suppressing filtration clogging of the pigment.
When using filters, different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more. When filtering two or more times by combining different filters, it is preferable that the second and subsequent pore diameters are the same or larger than the pore diameter of the first filtering. You may combine the 1st filter of a different hole diameter within said range. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (former Nihon Microlith Co., Ltd.), or Kitz Micro Filter Co., Ltd. .
As the second filter, a filter formed of the same material as the first filter can be used. The pore size of the second filter is suitably about 0.2 to 10.0 μm, preferably about 0.2 to 7.0 μm, more preferably about 0.3 to 6.0 μm.
［硬化膜（遮光膜）］
　硬化膜は、上記硬化性組成物を硬化して得られる。硬化膜には、着色剤が含まれる。硬化膜は、遮光膜として好適に用いられ、具体的にはイメージセンサの受光部周辺部分の遮光に好適に用いられる。
　以下、硬化膜がイメージセンサの受光部周辺部分の遮光膜として使用された場合を一例として説明する。 [Curing film (light-shielding film)]
The cured film is obtained by curing the curable composition. The cured film contains a colorant. The cured film is preferably used as a light-shielding film, and specifically used for light-shielding the periphery of the light receiving portion of the image sensor.
Hereinafter, a case where the cured film is used as a light shielding film around the light receiving portion of the image sensor will be described as an example.
　遮光膜の膜厚としては特に限定はないが、遮光膜がより優れた本発明の効果を有する点で、乾燥後の膜厚で、０．２μｍ以上５０μｍ以下が好ましく、０．３μｍ以上１０μｍ以下がより好ましく、０．３μｍ以上５μｍ以下が更に好ましい。上記硬化性組成物は単位体積あたりの光学濃度が高いため（遮光性が高いため）、従来の黒色顔料を使用した硬化性組成物より膜厚を減らすことも可能である。
　遮光膜のサイズ（センサー受光部周辺に設けられた遮光膜の一辺の長さ）としては、遮光膜がより優れた本発明の効果を有する点で、０．００１ｍｍ以上１０ｍｍ以下が好ましく、０．０５ｍｍ以上７ｍｍ以下がより好ましく、０．１ｍｍ以上３．５ｍｍ以下が更に好ましい。 The film thickness of the light-shielding film is not particularly limited, but the film thickness after drying is preferably 0.2 μm or more and 50 μm or less, and preferably 0.3 μm or more and 10 μm or less, in that the light-shielding film has more excellent effects of the present invention. Is more preferably 0.3 μm or more and 5 μm or less. Since the curable composition has a high optical density per unit volume (because of its high light-shielding property), the film thickness can be reduced as compared with a curable composition using a conventional black pigment.
The size of the light-shielding film (the length of one side of the light-shielding film provided around the sensor light-receiving portion) is preferably 0.001 mm or more and 10 mm or less in that the light-shielding film has more excellent effects of the present invention. 05 mm or more and 7 mm or less are more preferable, and 0.1 mm or more and 3.5 mm or less are still more preferable.
〔硬化膜の製造方法〕
　次に、硬化膜（遮光膜）の製造方法について説明する。
　以下、製造方法を工程ごとに詳述する。 [Method for producing cured film]
Next, a method for producing a cured film (light-shielding film) will be described.
Hereinafter, a manufacturing method is explained in full detail for every process.
　硬化膜の製造方法は、以下の硬化性組成物層形成工程及び露光工程を含有する。硬化膜の製造方法は、更に現像工程を含有することが好ましい。
硬化性組成物層形成工程：支持体上に、硬化性組成物層を形成する工程。
露光工程：上記硬化性組成物層を、露光する工程。
現像工程：露光後の硬化性組成物層を現像してパターン状の硬化膜（遮光膜）を形成する工程。 The manufacturing method of a cured film contains the following curable composition layer formation process and an exposure process. The method for producing a cured film preferably further includes a development step.
Curable composition layer forming step: A step of forming a curable composition layer on a support.
Exposure process: The process of exposing the said curable composition layer.
Development step: a step of developing the curable composition layer after exposure to form a patterned cured film (light-shielding film).
　具体的には、上記硬化性組成物を、直接又は他の層を介して基板上に塗布して、硬化性組成物層を形成し（硬化性組成物層形成工程）、所定のマスクパターンを介して露光し、光照射された塗布膜部分だけを硬化させ（露光工程）、現像液で現像することによって（現像工程）、上記硬化膜を製造することができる。
　以下、上記各工程について説明する。 Specifically, the curable composition is applied to the substrate directly or via another layer to form a curable composition layer (curable composition layer forming step), and a predetermined mask pattern is formed. The cured film can be produced by curing only the coating film portion exposed to light through light (exposure process) and developing with a developer (development process).
Hereafter, each said process is demonstrated.
＜硬化性組成物層形成工程＞
　硬化性組成物層形成工程は、支持体（以下「基板」ともいう。）上に、硬化性組成物層を形成する工程である。なかでも、支持体上に、硬化性組成物を塗布して、硬化性組成物層を形成する塗布工程を含むことが好ましく、支持体上に硬化性組成物を直接塗布して、支持体上に硬化性組成物層を形成する塗布工程を含むことがより好ましい。
　基板としては、例えば、液晶表示装置等に用いられる無アルカリガラス、ソーダガラス、パイレックス（登録商標）ガラス、石英ガラス、及びこれらに透明導電膜を付着させたもの、固体撮像素子等に用いられる光電変換素子基板（例えば、シリコン基板等）、ＣＣＤ（Ｃｈａｒｇｅ　Ｃｏｕｐｌｅｄ　Ｄｅｖｉｃｅ）基板、並びに、ＣＭＯＳ（Ｃｏｍｐｌｅｍｅｎｔａｒｙ　Ｍｅｔａｌ－Ｏｘｉｄｅ　Ｓｅｍｉｃｏｎｄｕｃｔｏｒ）基板等が挙げられる。
　支持体は、上部の層との密着改良、物質の拡散防止又は基板表面の平坦化のために下塗り層を備えていてもよい（以下、「下塗り層付き支持体」ともいう。）。 <Curable composition layer forming step>
The curable composition layer forming step is a step of forming a curable composition layer on a support (hereinafter also referred to as “substrate”). Among them, it is preferable to include a coating step in which a curable composition is applied on a support to form a curable composition layer, and the curable composition is directly applied on the support to form a curable composition layer on the support. It is more preferable to include a coating step of forming a curable composition layer.
Examples of the substrate include alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display devices and the like, and those obtained by attaching a transparent conductive film to these, photoelectric devices used for solid-state imaging devices, and the like. Examples include a conversion element substrate (for example, a silicon substrate), a CCD (Charge Coupled Device) substrate, and a CMOS (Complementary Metal-Oxide Semiconductor) substrate.
The support may be provided with an undercoat layer for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the substrate surface (hereinafter also referred to as “support with undercoat layer”).
　基板上への硬化性組成物の塗布方法としては、スリット塗布、インクジェット法、回転塗布、流延塗布、ロール塗布、及びスクリーン印刷法等の各種の塗布方法を適用することができる。 As the coating method of the curable composition on the substrate, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing method can be applied.
　固体撮像素子用のブラックマトリクスを含有するカラーフィルタを製造する際には、硬化性組成物の塗布膜厚としては、解像性の観点から、０．３５μｍ以上１．５μｍ以下が好ましく、０．４０μｍ以上１．０μｍ以下がより好ましい。 When manufacturing a color filter containing a black matrix for a solid-state imaging device, the coating film thickness of the curable composition is preferably 0.35 μm or more and 1.5 μm or less from the viewpoint of resolution. More preferably, it is 40 μm or more and 1.0 μm or less.
　基板上に塗布された硬化性組成物は、通常、７０℃以上１１０℃以下で２分間以上４分間以下程度の条件下で乾燥する。これにより、硬化性組成物層を形成できる。 The curable composition applied on the substrate is usually dried at 70 ° C. to 110 ° C. for 2 minutes to 4 minutes. Thereby, a curable composition layer can be formed.
＜露光工程＞
　露光工程は、硬化性組成物層形成工程において形成された硬化性組成物層（塗布膜）を、マスクを介して露光し、光照射された塗布膜部分だけを硬化させる工程である。
　露光は、活性光線又は放射線の照射により行うことが好ましく、特に、ｇ線、ｈ線、及びｉ線等の紫外線が好ましく、高圧水銀灯がより好ましい。露光量は特に制限されないが、使用する顔料の種類及び／又はマスクパターン形状により適宜選択できる。例えば、実施例に記載した黒色顔料を含有する硬化性組成物により形成した塗布膜に対しては、露光量の下限値は５０ｍＪ／ｃｍ２以上が好ましく、８０ｍＪ／ｃｍ２以上がより好ましい。露光量の上限値は、１，５００ｍＪ／ｃｍ２以下が好ましく、５００ｍＪ／ｃｍ２未満がより好ましい。露光量が８０ｍＪ／ｃｍ２以上５００ｍＪ／ｃｍ２未満であると、硬化膜（遮光膜）の製造方法は、より優れた安定性及び生産性を有する。
　また、実施例に記載した有彩色顔料を含有する硬化性組成物により形成した塗布膜に対しては、露光量の下限値は５０ｍＪ／ｃｍ２以上が好ましく、８０ｍＪ／ｃｍ２以上がより好ましい。露光量の上限値は、１，５００ｍＪ／ｃｍ２以下が好ましく、５００ｍＪ／ｃｍ２未満がより好ましく、４００ｍＪ／ｃｍ２未満が更に好ましく、３００ｍＪ／ｃｍ２未満が特に好ましい。露光量が８０～３００ｍＪ／ｃｍ２未満であると、硬化膜の製造方法は、より優れた安定性及び生産性を有する。
　解像性向上の観点から固体撮像素子用の遮光膜形成では、i線ステッパーによる露光が好ましい。 <Exposure process>
The exposure step is a step in which the curable composition layer (coating film) formed in the curable composition layer forming step is exposed through a mask and only the coating film portion irradiated with light is cured.
The exposure is preferably performed by irradiation with actinic rays or radiation, in particular, ultraviolet rays such as g-line, h-line, and i-line are preferable, and a high-pressure mercury lamp is more preferable. The amount of exposure is not particularly limited, but can be appropriately selected depending on the type of pigment used and / or the mask pattern shape. For example, for a coating film formed by the curable composition containing a black pigment described in Example, the lower limit of the amount of exposure is preferably 50 mJ / cm 2 or more, 80 mJ / cm 2 or more is more preferable. Upper limit of the amount of exposure is preferably 1,500 mJ / cm 2 or less, less than 500 mJ / cm 2 is more preferable. When the exposure amount is 80 mJ / cm 2 or more and less than 500 mJ / cm 2 , the method for producing a cured film (light-shielding film) has more excellent stability and productivity.
Further, with respect to the coating film formed by the curable composition containing a chromatic pigment as described in Example, the lower limit of the amount of exposure is preferably 50 mJ / cm 2 or more, 80 mJ / cm 2 or more is more preferable. Upper limit of the amount of exposure is preferably 1,500 mJ / cm 2 or less, more preferably less than 500 mJ / cm 2, still more preferably less than 400 mJ / cm 2, less than 300 mJ / cm 2 is particularly preferred. When the exposure dose is 80 to less than 300 mJ / cm 2 , the method for producing a cured film has more excellent stability and productivity.
From the viewpoint of improving resolution, exposure with an i-line stepper is preferable in forming a light-shielding film for a solid-state imaging device.
＜現像工程＞
　現像工程は、露光された硬化性組成物層を現像する工程である。現像工程によって、パターン状の硬化膜を得ることができる。
　上記硬化膜の製造方法は、現像工程と、下記の洗浄工程とを含有することが好ましい。現像工程においては、アルカリ現像処理（現像工程）を行い、露光工程における光未照射部分をアルカリ水溶液に溶出させる。これにより、光硬化した部分（光照射された塗布膜部分）だけが残る。
　現像液としては、固体撮像素子用のブラックマトリクスを含有する遮光性カラーフィルタを作製する場合には、下地の回路などにダメージを起さない、有機アルカリ現像液が好ましい。現像温度は通常２０～３０℃が好ましく、現像時間は２０～９０秒が好ましい。 <Development process>
A development process is a process of developing the exposed curable composition layer. A patterned cured film can be obtained by the development step.
It is preferable that the manufacturing method of the said cured film contains a image development process and the following washing | cleaning process. In the development process, an alkali development treatment (development process) is performed, and the light non-irradiated part in the exposure process is eluted in an alkaline aqueous solution. Thereby, only the photocured part (the coating film part irradiated with light) remains.
As the developer, when producing a light-shielding color filter containing a black matrix for a solid-state image sensor, an organic alkali developer that does not damage the underlying circuit or the like is preferable. The development temperature is usually preferably 20 to 30 ° C., and the development time is preferably 20 to 90 seconds.
　アルカリ性の水溶液としては、例えば、無機系現像液及び有機系現像液が挙げられる。無機系現像液としては、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、硅酸ナトリウム、又はメタ硅酸ナトリウムを、濃度が０．００１～１０質量％、好ましくは０．０１～１質量％となるように溶解したアルカリ性水溶液が挙げられる。有機系現像液としては、アンモニア水、エチルアミン、ジエチルアミン、ジメチルエタノールアミン、テトラメチルアンモニウムヒドロキシド、テトラエチルアンモニウムヒドロキシド、コリン、ピロール、ピペリジン、又は１，８－ジアザビシクロ－［５．４．０］－７－ウンデセン等のアルカリ性化合物を、濃度が０．００１～１０質量％、好ましくは０．０１～１質量％となるように溶解したアルカリ性水溶液が挙げられる。アルカリ性水溶液には、例えばメタノール、及びエタノール等の水溶性有機溶剤及び／又は界面活性剤等を適量添加することもできる。なお、現像方法としては、例えば、パドル現像方法及びシャワー現像方法などを用いることができる。 Examples of the alkaline aqueous solution include an inorganic developer and an organic developer. As the inorganic developer, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, or sodium metasuccinate having a concentration of 0.001 to 10% by mass, preferably 0.01 to 1 is used. An alkaline aqueous solution dissolved so as to be in mass% can be mentioned. Examples of organic developers include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, or 1,8-diazabicyclo- [5.4.0]- Examples thereof include an alkaline aqueous solution in which an alkaline compound such as 7-undecene is dissolved so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An appropriate amount of a water-soluble organic solvent such as methanol and ethanol and / or a surfactant can be added to the alkaline aqueous solution. As a developing method, for example, a paddle developing method and a shower developing method can be used.
＜洗浄工程＞
　洗浄工程は、現像された硬化性組成物層を純水等によって洗浄（リンス）する工程である。洗浄方法としては特に制限されず、公知の洗浄方法を用いることができる。 <Washing process>
The washing step is a step of washing (rinsing) the developed curable composition layer with pure water or the like. The cleaning method is not particularly limited, and a known cleaning method can be used.
　なお、上記硬化膜の製造方法は、上記現像工程の後に、硬化膜を加熱するポストベーク工程及び／又は硬化膜を全面露光する硬化工程を含有してもよい。 In addition, the manufacturing method of the said cured film may contain the post-baking process which heats a cured film, and / or the hardening process which exposes a cured film whole surface after the said image development process.
　硬化膜（ブラックマトリクス）を含有するカラーフィルタは、ＣＣＤイメージセンサ及び／又はＣＭＯＳイメージセンサ等の固体撮像素子に好適である。特に１００万画素を超えるような高解像度のＣＣＤイメージセンサ及び／又はＣＭＯＳイメージセンサ等に好適である。すなわち、上記硬化膜を含有するカラーフィルタは、固体撮像素子に好適である。カラーフィルタは、隔壁により例えば格子状に仕切られた空間に、各色画素を形成する硬化膜が埋め込まれた構造を含有してもよい。
　上記硬化膜（ブラックマトリクス）は、例えば、ＣＣＤイメージセンサ及び／又はＣＭＯＳイメージセンサ等を構成する各画素の受光部と、集光するためのマイクロレンズと、の間に配置される。 A color filter containing a cured film (black matrix) is suitable for a solid-state imaging device such as a CCD image sensor and / or a CMOS image sensor. Particularly, it is suitable for a CCD image sensor and / or a CMOS image sensor having a high resolution exceeding 1 million pixels. That is, the color filter containing the cured film is suitable for a solid-state imaging device. The color filter may contain a structure in which a cured film that forms each color pixel is embedded in a space partitioned by a partition, for example, in a lattice shape.
The cured film (black matrix) is disposed, for example, between a light receiving portion of each pixel constituting a CCD image sensor and / or a CMOS image sensor and a microlens for condensing light.
［固体撮像素子］
　固体撮像素子は、上記硬化膜（ブラックマトリクス）を含有する。固体撮像素子は、ブラックマトリクスを含有し、更に、必要により、他の色（３色あるいは４色）の画素からなるパターン状皮膜とを含有する、カラーフィルタを含有することが好ましい。
　固体撮像素子は、上記ブラックマトリクスを含有し、固体撮像素子として機能すれば特に制限されず、例えば、基板上に、固体撮像素子（ＣＣＤイメージセンサ、及びＣＭＯＳイメージセンサ等）の受光エリアを構成する複数のフォトダイオード及びポリシリコン等からなる受光素子を含有し、基板の受光素子形成面の反対側の面に上記ブラックマトリクスを含有する固体撮像素子が挙げられる。
　カラーフィルタは、隔壁により例えば格子状に仕切られた空間に、各色画素を形成する硬化膜が埋め込まれた構造を有していてもよい。この場合の隔壁は各色画素に対して低屈折率であることが好ましい。このような構造を含有する固体撮像素子の例としては、特開２０１２－２２７４７８号公報及び特開２０１４－１７９５７７号公報に記載の固体撮像素子が挙げられる。 [Solid-state imaging device]
The solid-state imaging device contains the cured film (black matrix). The solid-state imaging device preferably contains a color filter containing a black matrix and, if necessary, a patterned film composed of pixels of other colors (three colors or four colors).
The solid-state imaging device is not particularly limited as long as it contains the above-described black matrix and functions as a solid-state imaging device. Examples include a solid-state imaging device that includes a plurality of photodiodes, a light-receiving element made of polysilicon, and the like, and that includes the black matrix on the surface opposite to the light-receiving element formation surface of the substrate.
The color filter may have a structure in which a cured film that forms each color pixel is embedded in a space partitioned by a partition, for example, in a lattice shape. The partition in this case preferably has a low refractive index for each color pixel. Examples of the solid-state imaging device containing such a structure include the solid-state imaging devices described in JP2012-227478A and JP2014-179577A.
［画像表示装置］
　上記硬化膜は、画像表示装置（例えば液晶表示装置及び有機エレクトロルミネッセンス表示装置等）に好適に用いることができる。 [Image display device]
The cured film can be suitably used for an image display device (for example, a liquid crystal display device and an organic electroluminescence display device).
　画像表示装置の定義及び各画像表示装置の詳細については、例えば「電子ディスプレイデバイス（佐々木　昭夫著、（株）工業調査会　１９９０年発行）」、及び「ディスプレイデバイス（伊吹　順章著、産業図書（株）平成元年発行）」などに記載される。液晶表示装置については、例えば「次世代液晶ディスプレイ技術（内田　龍男編集、（株）工業調査会　１９９４年発行）」に記載されている。上記硬化膜は、例えば、上記の「次世代液晶ディスプレイ技術」に記載されている方式の液晶表示装置に好適である。 For the definition of image display devices and details of each image display device, refer to, for example, “Electronic Display Device (Akio Sasaki, Kogyo Kenkyukai, 1990)” and “Display Device (Junsho Ibuki, Industrial Books ( (Issued in 1989)). The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 1994)”. The cured film is suitable for, for example, a liquid crystal display device of the method described in the “next generation liquid crystal display technology”.
　上記硬化膜を含有する液晶表示装置の一態様としては、例えば、少なくとも１つが光透過性の１対の基板の間にカラーフィルタ、液晶層及び液晶駆動手段（単純マトリックス駆動方式、及びアクティブマトリックス駆動方式を含有する）を少なくとも含有する液晶表示装置が挙げられる。上記液晶表示装置は、複数の画素群を含有し、この画素群を構成する各画素が、互いに上記硬化膜（ブラックマトリクス）により離画されているカラーフィルタを含有する。 As one mode of the liquid crystal display device containing the cured film, for example, a color filter, a liquid crystal layer, and a liquid crystal driving means (simple matrix driving method and active matrix driving) are provided between a pair of substrates at least one of which is light transmissive And a liquid crystal display device containing at least a method. The liquid crystal display device includes a plurality of pixel groups, and each pixel constituting the pixel group includes a color filter separated from each other by the cured film (black matrix).
　液晶表示装置の別の態様としては、少なくとも１つが光透過性の１対の基板の間に、カラーフィルタ、液晶層及び液晶駆動手段を少なくも含有し、液晶駆動手段がアクティブ素子（例えばＴＦＴ（Ｔｈｉｎ　Ｆｉｌｍ　Ｔｒａｎｓｉｓｔｏｒ））を含有し、かつ各アクティブ素子の間に上記硬化膜（ブラックマトリクス）を含有するカラーフィルタを含有する。 As another embodiment of the liquid crystal display device, at least one of the light transmissive substrates contains at least a color filter, a liquid crystal layer, and liquid crystal driving means, and the liquid crystal driving means is an active element (for example, TFT ( (Thin Film Transistor)) and a color filter containing the cured film (black matrix) between the active elements.
　上記硬化膜を含有するカラーフィルタは、カラーＴＦＴ（Ｔｈｉｎ　Ｆｉｌｍ　Ｔｒａｎｓｉｓｔｏｒ）方式の液晶表示装置に好適である。カラーＴＦＴ方式の液晶表示装置については、例えば「カラーＴＦＴ液晶ディスプレイ（共立出版（株）１９９６年発行）」に記載されている。更に、上記カラーフィルタはＩＰＳ（Ｉｎ　Ｐｌａｎｅ　Ｓｗｉｔｃｈｉｎｇ）などの横電界駆動方式；ＭＶＡ（Ｍｕｌｔｉ－ｄｏｍａｉｎ　Ｖｅｒｔｉｃａｌ　Ａｌｉｇｎｍｅｎｔ）などの画素分割方式；等の視野角が拡大された液晶表示装置、ＳＴＮ（Ｓｕｐｅｒ－Ｔｗｉｓｔ　Ｎｅｍａｔｉｃ）、ＴＮ（Ｔｗｉｓｔｅｄ　Ｎｅｍａｔｉｃ）、ＶＡ（Ｖｅｒｔｉｃａｌ　Ａｌｉｇｎｍｅｎｔ）、ＯＣＳ（ｏｎ－ｃｈｉｐ　ｓｐａｃｅｒ）、ＦＦＳ（ｆｒｉｎｇｅ　ｆｉｅｌｄ　ｓｗｉｔｃｈｉｎｇ）、及び、Ｒ－ＯＣＢ（Ｒｅｆｌｅｃｔｉｖｅ　Ｏｐｔｉｃａｌｌｙ　Ｃｏｍｐｅｎｓａｔｅｄ　Ｂｅｎｄ）等にも好適である。 The color filter containing the cured film is suitable for a liquid crystal display device of a color TFT (Thin Film Transistor) type. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Further, the color filter is a liquid crystal display device with a wide viewing angle, such as a lateral electric field driving method such as IPS (In Plane Switching); a pixel division method such as MVA (Multi-domain Vertical Alignment); and STN (Super-Twist). Nematic), TN (Twisted Nematic), VA (Vertical Alignment), OCS (on-chip spacer), FFS (fringe field switching), and R-OCB (Reflective Optics).
　上記カラーフィルタは、明るく高精細なＣＯＡ（Ｃｏｌｏｒ－ｆｉｌｔｅｒ　Ｏｎ　Ａｒｒａｙ）方式の液晶表示装置に好適である。ＣＯＡ方式の液晶表示装置にあっては、カラーフィルタに対する要求特性は、通常の要求特性に加えて、層間絶縁膜に対する要求特性、すなわち低誘電率及び剥離液耐性が必要とされることがある。上記カラーフィルタを含有するＣＯＡ方式の液晶表示装置は、より優れた解像度を有し、又はより優れた耐久性を有する。なお、低誘電率の要求特性を満足するためには、カラーフィルタ層の上に樹脂被膜を更に含有してもよい。 The color filter is suitable for a bright, high-definition COA (Color-filter On Array) type liquid crystal display device. In the COA type liquid crystal display device, the required characteristics for the color filter may require the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the resistance to the peeling solution, in addition to the normal required characteristics. The COA type liquid crystal display device containing the color filter has better resolution or better durability. In order to satisfy the required characteristics of a low dielectric constant, a resin film may be further included on the color filter layer.
　これらの画像表示方式については、例えば、「ＥＬ、ＰＤＰ、ＬＣＤディスプレイ－技術と市場の最新動向－（東レリサーチセンター調査研究部門　２００１年発行）」の４３ページなどに記載されている。なお、上記において、ＥＬとはElectroluminescence、ＰＤＰとはPlasma Display Panel、ＬＣＤとはliquid crystal displayの略を表す。 These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-latest technology and market trends-(Toray Research Center Research Division, issued in 2001)". In the above, EL stands for Electroluminescence, PDP stands for PlasmaPDisplay Panel, and LCD stands for liquid crystal display.
　上記液晶表示装置は、上記カラーフィルタ以外に、電極基板、偏光フィルム、位相差フィルム、バックライト、スペーサ、及び、視野角保障フィルムなど様々な部材から構成される。上記カラーフィルタは、これらの公知の部材で構成される液晶表示装置に適用することができる。これらの部材については、例えば、「’９４液晶ディスプレイ周辺材料・ケミカルズの市場（島　健太郎　（株）シーエムシー　１９９４年発行）」、及び「２００３液晶関連市場の現状と将来展望（下巻）（表良吉（株）富士キメラ総研、２００３年発行）」に記載されている。
　バックライトに関しては、ＳＩＤ　ｍｅｅｔｉｎｇ　Ｄｉｇｅｓｔ　１３８０（２００５）（Ａ．Ｋｏｎｎｏ　ｅｔ．ａｌ）、及び／又は月刊ディスプレイ　２００５年１２月号の１８～２４ページ（島　康裕）、同２５～３０ページ（八木隆明）などに記載されている。 In addition to the color filter, the liquid crystal display device includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film. The color filter can be applied to a liquid crystal display device composed of these known members. Regarding these materials, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima, CMC 1994)” and “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” "Fuji Chimera Research Institute, Ltd., published in 2003)".
Regarding backlights, SID meeting Digest 1380 (2005) (A. Konno et.al) and / or Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi) It is described in.
　上記硬化膜は、パーソナルコンピュータ、タブレット、携帯電話、スマートフォン及びデジタルカメラなどのポータブル機器；プリンタ複合機及びスキャナなどのＯＡ（Ｏｆｆｉｃｅ　Ａｕｔｏｍａｔｉｏｎ）機器；監視カメラ、バーコードリーダ、及び現金自動預け払い機（ＡＴＭ：automated teller machine）、ハイスピードカメラ及び顔画像認証を使用した本人認証などの産業用機器；車載用カメラ機器；内視鏡、カプセル内視鏡及びカテーテルなどの医療用カメラ機器；生体センサー、バイオセンサー、軍事偵察用カメラ、立体地図用カメラ、気象及び海洋観測カメラ、陸地資源探査カメラ、並びに、宇宙の天文及び深宇宙ターゲット用の探査カメラなどの宇宙用機器などに使用される光学フィルター及びモジュールの遮光部材及び遮光層、更には反射防止部材及び反射防止層に好適である。 The cured film is composed of portable devices such as personal computers, tablets, mobile phones, smartphones, and digital cameras; OA (Office Automation) devices such as printer multifunction devices and scanners; surveillance cameras, bar code readers, and automatic teller machines ( ATM (automated teller machine), industrial equipment such as personal authentication using high-speed camera and face image authentication; in-vehicle camera equipment; medical camera equipment such as endoscope, capsule endoscope and catheter; biosensor, Optical filters used in space devices such as biosensors, military reconnaissance cameras, stereoscopic map cameras, weather and ocean observation cameras, land resource exploration cameras, and exploration cameras for space astronomy and deep space targets Module shading member and shading And further is suitable for anti-reflection member and the antireflection layer.
　上記硬化膜は、マイクロＬＥＤ（Ｌｉｇｈｔ　Ｅｍｉｔｔｉｎｇ　Ｄｉｏｄｅ）及びマイクロＯＬＥＤ（Ｏｒｇａｎｉｃ　Ｌｉｇｈｔ　Ｅｍｉｔｔｉｎｇ　Ｄｉｏｄｅ）などの用途にも用いることができる。上記硬化膜は、マイクロＬＥＤ及びマイクロＯＬＥＤに使用される光学フィルタ及び光学フィルムのほか、遮光機能又は反射防止機能を付与する部材に対して好適である。
　マイクロＬＥＤ及びマイクロＯＬＥＤの例としては、特表２０１５－５００５６２号及び特表２０１４－５３３８９０に記載されたものが挙げられる。 The cured film can also be used for applications such as micro LED (Light Emitting Diode) and micro OLED (Organic Light Emitting Diode). The cured film is suitable for members that provide a light shielding function or an antireflection function, in addition to optical filters and optical films used in micro LEDs and micro OLEDs.
Examples of the micro LED and the micro OLED include those described in JP-T-2015-500562 and JP-T-2014-533890.
　上記硬化膜は、量子ドットディスプレイに使用される光学及び光学フィルムとして好適である。また、上記硬化膜は、遮光機能及び反射防止機能を付与する部材として好適である。
　量子ドットディスプレイの例としては、米国特許出願公開第２０１３／０３３５６７７号、米国特許出願公開第２０１４／００３６５３６号、米国特許出願公開第２０１４／００３６２０３号、及び、米国特許出願公開第２０１４／００３５９６０号に記載されたものが挙げられる。 The cured film is suitable as an optical and optical film used in quantum dot displays. Moreover, the said cured film is suitable as a member which provides a light-shielding function and an antireflection function.
Examples of quantum dot displays include US Patent Application Publication No. 2013/0335677, US Patent Application Publication No. 2014/0036536, US Patent Application Publication No. 2014/0036203, and US Patent Application Publication No. 2014/0035960. What has been described.
　以下に実施例に基づいて本発明を更に詳細に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り適宜変更することができる。従って、本発明の範囲は以下に示す実施例により限定的に解釈されない。 Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limitedly interpreted by the following examples.
［多官能チオール化合物Ｓ－１５の合成］
　以下の式で表される多官能チオール化合物Ｓ－１５は、次の方法により合成した。
Figure JPOXMLDOC01-appb-C000042
なお、上記式中、「Ｅｔ」はエチル基（－ＣＨ２ＣＨ３）を表し、以下同様である。 [Synthesis of Multifunctional Thiol Compound S-15]
Polyfunctional thiol compound S-15 represented by the following formula was synthesized by the following method.
Figure JPOXMLDOC01-appb-C000042
In the above formula, “Et” represents an ethyl group (—CH 2 CH 3 ), and so on.
　窒素雰囲気下、ペンタエリトリトールテトラ（３－メルカプトプロピオネート）（ＴＣＩ社製）（２．００ｇ）と、アクリル酸（０．２９５ｇ）とを、テトラヒドロフラン（ＴＨＦ）（１０．０ｇ）に溶解させた（得られた液を、以下「反応液」という。）。次に上記反応液の内温を５℃以下に冷却した。冷却後の反応液に、トリエチルアミン（０．４５０ｇ）を添加した。その後、反応液の液温を５０℃まで昇温した。昇温後、反応液を３時間攪拌した。攪拌後の反応液に対して、酢酸エチル（５０ｇ）と、１規定塩酸（５０ｇ）とを添加した。その後、反応液を水相と、有機相とに分液した。続いて、有機相を水（５０ｇ）で洗浄し、得られた有機相に硫酸ナトリウムを加えた後、有機相から固形物をろ別し、得られたろ液を減圧濃縮することで、Ｓ－１５（２．０１ｇ）（収率８７．６％）を得た。得られたＳ－１５の構造は、１Ｈ－ＮＭＲ（nuclear magnetic resonance）により同定した。同定結果を以下に示す。 Under a nitrogen atmosphere, pentaerythritol tetra (3-mercaptopropionate) (manufactured by TCI) (2.00 g) and acrylic acid (0.295 g) were dissolved in tetrahydrofuran (THF) (10.0 g). (The obtained liquid is hereinafter referred to as “reaction liquid”). Next, the internal temperature of the reaction solution was cooled to 5 ° C. or lower. Triethylamine (0.450 g) was added to the reaction solution after cooling. Thereafter, the temperature of the reaction solution was raised to 50 ° C. After raising the temperature, the reaction solution was stirred for 3 hours. Ethyl acetate (50 g) and 1N hydrochloric acid (50 g) were added to the reaction solution after stirring. Thereafter, the reaction solution was separated into an aqueous phase and an organic phase. Subsequently, the organic phase was washed with water (50 g), sodium sulfate was added to the obtained organic phase, solids were filtered off from the organic phase, and the obtained filtrate was concentrated under reduced pressure to obtain S- 15 (2.01 g) (yield 87.6%) was obtained. The structure of S-15 thus obtained was identified by 1 H-NMR (nuclear magnetic resonance). The identification results are shown below.
（１Ｈ－ＮＭＲ　３００ＭＨｚ　重クロロホルム）：１．３５（ｔ、３Ｈ）、２．５３（ｔ、２Ｈ）、２．６６－２．７１（ｍ、８Ｈ）、２．７３－２．８０（ｍ、１０Ｈ）、４．０９（ｓ、８Ｈ）。 ( 1 H-NMR 300 MHz deuterated chloroform): 1.35 (t, 3H), 2.53 (t, 2H), 2.66-2.71 (m, 8H), 2.73-2.80 (m 10H), 4.09 (s, 8H).
［多官能チオール化合物Ｓ－１６の合成］
　以下の式で表される多官能チオール化合物Ｓ－１６は、次の方法により合成した。
Figure JPOXMLDOC01-appb-C000043
 [Synthesis of Multifunctional Thiol Compound S-16]
Polyfunctional thiol compound S-16 represented by the following formula was synthesized by the following method.
Figure JPOXMLDOC01-appb-C000043
　窒素雰囲気下、ペンタエリトリトールテトラ（３－メルカプトプロピオネート）（ＴＣＩ社製）（２．００ｇ）と、アクリル酸２－ヒドロキシエチル（０．４７５ｇ）とを、テトラヒドロフラン（１０．０ｇ）に溶解させて、反応液を得た。次に上記反応液の内温を５℃以下に冷却した。冷却後の反応液に、トリエチルアミン（０．４５０ｇ）を添加した。その後、反応液の液温を５０℃まで昇温した。昇温後、反応液を３時間攪拌した。その後、反応液に対してヘキサン（５０ｇ）を添加し、ヘキサン添加後の反応液の上澄み成分を除去した。上澄み成分除去後の反応液に対して、再度、ヘキサン（５０ｇ）を添加し、ヘキサン再添加後の反応液の上澄み成分を除去した。その後、反応液に残留する溶媒を減圧留去を用いて除去し、Ｓ－１６（２．０１ｇ）（収率８８．８％）を得た。得られたＳ－１６の構造は、１Ｈ－ＮＭＲにより同定した。同定結果を以下に示す。 Under a nitrogen atmosphere, pentaerythritol tetra (3-mercaptopropionate) (manufactured by TCI) (2.00 g) and 2-hydroxyethyl acrylate (0.475 g) were dissolved in tetrahydrofuran (10.0 g). Thus, a reaction solution was obtained. Next, the internal temperature of the reaction solution was cooled to 5 ° C. or lower. Triethylamine (0.450 g) was added to the reaction solution after cooling. Thereafter, the temperature of the reaction solution was raised to 50 ° C. After raising the temperature, the reaction solution was stirred for 3 hours. Then, hexane (50g) was added with respect to the reaction liquid, and the supernatant component of the reaction liquid after hexane addition was removed. Hexane (50 g) was added again to the reaction solution after removal of the supernatant component, and the supernatant component of the reaction solution after hexane re-addition was removed. Thereafter, the solvent remaining in the reaction solution was removed by distillation under reduced pressure to obtain S-16 (2.01 g) (yield 88.8%). The structure of S-16 obtained was identified by 1 H-NMR. The identification results are shown below.
（１Ｈ－ＮＭＲ　３００ＭＨｚ　重クロロホルム）：１．３５（ｔ、３Ｈ）、２．６４－２．７１（ｍ、１０Ｈ）、２．７３－２．８２（ｍ、１０Ｈ）、３．７９－３．８７（ｍ、２Ｈ）、４．０９（ｓ、８Ｈ）、４．２２－４．２９（ｍ、２Ｈ）。 ( 1 H-NMR 300 MHz deuterated chloroform): 1.35 (t, 3H), 2.64-2.71 (m, 10H), 2.73-2.82 (m, 10H), 3.79-3 .87 (m, 2H), 4.09 (s, 8H), 4.22-4.29 (m, 2H).
［多官能チオール化合物Ｓ－１７の合成］
　以下の式で表される多官能チオール化合物Ｓ－１７は、次の方法により合成した。
Figure JPOXMLDOC01-appb-C000044
　なお、上記式において「Ｍｅ」はメチル基（－ＣＨ３）を意図し、以下同様である。 [Synthesis of Multifunctional Thiol Compound S-17]
Polyfunctional thiol compound S-17 represented by the following formula was synthesized by the following method.
Figure JPOXMLDOC01-appb-C000044
In the above formula, “Me” intends a methyl group (—CH 3 ), and so on.
　窒素雰囲気下、ペンタエリトリトールテトラ（３－メルカプトプロピオネート）（ＴＣＩ社製）（２．００ｇ）と、アクリル酸２－（ジメチルアミノ）エチル（０．５８６ｇ）とを、テトラヒドロフラン（１０．０ｇ）に溶解させて、反応液を得た。次に、上記反応液の内温を５℃以下に冷却した。冷却後の反応液に、トリエチルアミン（０．４５０ｇ）を添加した。その後、反応液の液温を５０℃まで昇温した。昇温後、反応液を３時間攪拌した。その後、反応液に対してヘキサン（５０ｇ）を添加し、ヘキサン添加後の反応液の上澄み成分を除去した。上澄み成分除去後の反応液に対して、再度、ヘキサン（５０ｇ）を添加し、ヘキサン再添加後の反応液の上澄み成分を除去した。その後、反応液に残留する溶媒を減圧留去を用いて除去し、Ｓ－１７（２．１５ｇ）（収率８３．１％）を得た。得られたＳ－１７の構造は、１Ｈ－ＮＭＲにより同定した。同定結果を以下に示す。 Under a nitrogen atmosphere, pentaerythritol tetra (3-mercaptopropionate) (manufactured by TCI) (2.00 g), 2- (dimethylamino) ethyl acrylate (0.586 g), and tetrahydrofuran (10.0 g) To obtain a reaction solution. Next, the internal temperature of the reaction solution was cooled to 5 ° C. or lower. Triethylamine (0.450 g) was added to the reaction solution after cooling. Thereafter, the temperature of the reaction solution was raised to 50 ° C. After raising the temperature, the reaction solution was stirred for 3 hours. Then, hexane (50g) was added with respect to the reaction liquid, and the supernatant component of the reaction liquid after hexane addition was removed. Hexane (50 g) was added again to the reaction solution after removal of the supernatant component, and the supernatant component of the reaction solution after hexane re-addition was removed. Thereafter, the solvent remaining in the reaction solution was removed by distillation under reduced pressure to obtain S-17 (2.15 g) (yield 83.1%). The structure of S-17 obtained was identified by 1 H-NMR. The identification results are shown below.
（１Ｈ－ＮＭＲ　３００ＭＨｚ　重クロロホルム）：　０．６２－０．７１１（ｍ、２Ｈ）、１．７０－１．８５（ｍ、２Ｈ）、１．３６（ｔ、３Ｈ）、２．５７（ｔ、２Ｈ）、２．６２－２．７０（ｍ、１０Ｈ）、２．７３－２．８５（ｍ、１０Ｈ）、３．７９－３．８７（ｍ、２Ｈ）、４．０８（ｓ、８Ｈ）、４．１９（ｔ、２Ｈ）。 ( 1 H-NMR 300 MHz deuterated chloroform): 0.62-0.711 (m, 2H), 1.70-1.85 (m, 2H), 1.36 (t, 3H), 2.57 (t 2H), 2.62-2.70 (m, 10H), 2.73-2.85 (m, 10H), 3.79-3.87 (m, 2H), 4.08 (s, 8H) ), 4.19 (t, 2H).
［多官能チオール化合物Ｓ－２６の合成］
　以下の式で表される多官能チオール化合物Ｓ－２６は、次の方法により合成した。
Figure JPOXMLDOC01-appb-C000045
 [Synthesis of Multifunctional Thiol Compound S-26]
Polyfunctional thiol compound S-26 represented by the following formula was synthesized by the following method.
Figure JPOXMLDOC01-appb-C000045
　窒素雰囲気下、ペンタエリトリトールテトラ（３－メルカプトプロピオネート）（ＴＣＩ社製）（２．００ｇ）と、アクリル酸３－（トリメトキシシリル）プロピル（１．９２ｇ）とを、テトラヒドロフラン（１０．０ｇ）に溶解させて、反応液を得た。次に、上記反応液の内温を５℃以下に冷却した。冷却後の反応液に、トリエチルアミン（０．４５０ｇ）を添加した。その後、反応液の液温を５０℃まで昇温した。昇温後、反応液を３時間攪拌した。その後、反応液に対してヘキサン（５０ｇ）を添加し、ヘキサン添加後の反応液の上澄み成分を除去した。上澄み成分除去後の反応液に対して、再度、ヘキサン（５０ｇ）を添加し、ヘキサン再添加後の反応液の上澄み成分を除去した。その後、反応液に残留する溶媒を減圧留去を用いて除去し、Ｓ－２６（２．２３ｇ）（収率７５．４％）を得た。得られたＳ－２６の構造は、１Ｈ－ＮＭＲにより同定した。同定結果を以下に示す。 Under a nitrogen atmosphere, pentaerythritol tetra (3-mercaptopropionate) (manufactured by TCI) (2.00 g) and 3- (trimethoxysilyl) propyl acrylate (1.92 g) were added to tetrahydrofuran (10.0 g). To obtain a reaction solution. Next, the internal temperature of the reaction solution was cooled to 5 ° C. or lower. Triethylamine (0.450 g) was added to the reaction solution after cooling. Thereafter, the temperature of the reaction solution was raised to 50 ° C. After raising the temperature, the reaction solution was stirred for 3 hours. Then, hexane (50g) was added with respect to the reaction liquid, and the supernatant component of the reaction liquid after hexane addition was removed. Hexane (50 g) was added again to the reaction solution after removal of the supernatant component, and the supernatant component of the reaction solution after hexane re-addition was removed. Thereafter, the solvent remaining in the reaction solution was removed by distillation under reduced pressure to obtain S-26 (2.23 g) (yield 75.4%). The structure of S-26 obtained was identified by 1 H-NMR. The identification results are shown below.
（１Ｈ－ＮＭＲ　３００ＭＨｚ　重クロロホルム）：１．３５（ｔ、３Ｈ）、２．５９（ｔ、２Ｈ）、２．６４－２．７１（ｍ、８Ｈ）、２．７３－２．８２（ｍ、１０Ｈ）、３．５８（ｓ、９Ｈ）、４．０２－４．１１（ｓ、１０Ｈ）。 ( 1 H-NMR 300 MHz deuterated chloroform): 1.35 (t, 3H), 2.59 (t, 2H), 2.64-2.71 (m, 8H), 2.73-2.82 (m 10H), 3.58 (s, 9H), 4.02-4.11 (s, 10H).
［多官能チオール化合物Ｓ－８、２０、２２、２４、２５、６４～６６、６９、７１、７３～７５、８８～９０、及び１１２～１１４の合成］
　原料を適宜変更した以外は上記と同様の方法により、多官能チオール化合物Ｓ－８、２０、２２、２４、２５、６４～６６、６９、７１、７３～７５、８８～９０、及び１１２～１１４を合成した。
　なお、１Ｈ－ＮＭＲで同定した各多官能チオール化合物の構造は、表１－１～１－６に示したとおりである。 [Synthesis of Multifunctional Thiol Compound S-8, 20, 22, 24, 25, 64-66, 69, 71, 73-75, 88-90, and 112-114]
A polyfunctional thiol compound S-8, 20, 22, 24, 25, 64 to 66, 69, 71, 73 to 75, 88 to 90, and 112 to 114 is produced in the same manner as described above except that the raw materials are appropriately changed. Was synthesized.
The structures of the polyfunctional thiol compounds identified by 1 H-NMR are as shown in Tables 1-1 to 1-6.
［実施例１～２３、及び比較例２、３の硬化性組成物の調製］
　表２の各欄に示した多官能チオール化合物と、以下の各成分を混合して、実施例１～２３、及び比較例２、３の硬化性組成物を調製した。 [Preparation of curable compositions of Examples 1 to 23 and Comparative Examples 2 and 3]
The polyfunctional thiol compound shown in each column of Table 2 and the following components were mixed to prepare curable compositions of Examples 1 to 23 and Comparative Examples 2 and 3.
＜組成＞
有機溶剤１（シクロヘキサノン）・・・１７．１２質量部
アルカリ可溶性樹脂１（メタクリル酸ベンジル／メタクリル酸（４７／５３［質量比］）、３０質量％プロピレングリコールモノメチルエーテル溶液、Ｍｗ＝１１，０００）・・・１．２３質量部
アルカリ可溶性樹脂２（アクリキュアーＲＤ－Ｆ８（日本触媒製））　　０．２３質量部重合性化合物（ラジカル重合性化合物、新中村化学工業（株）製、ＮＫエステルＡ－ＤＰＨ－１２Ｅ）・・・１．９６質量部
重合禁止剤（パラメトキシフェノール）・・・０．０００７質量部
光重合開始剤（ＩＲＧＡＣＵＲＥ　ＯＸＥ０２）・・・０．９７５質量部
多官能チオール化合物（下記表２に記載の多官能チオール化合物）・・・０．３５質量部
フッ素系界面活性剤（ＤＩＣ製、商品名：メガファックＦ－４７５、１質量％プロピレングリコールモノメチルエーテルアセテート溶液）・・・２．５０質量部
有彩色着色剤１：染料溶液１（下記の方法で調製した染料溶液）・・・２４．５７質量部
有彩色着色剤２：顔料分散液Ｐ１（下記の方法で調製したＣ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１５：６分散液、固形分濃度１１．８質量％）・・・５１．４０質量部 <Composition>
Organic solvent 1 (cyclohexanone) 17.17 parts by mass Alkali-soluble resin 1 (benzyl methacrylate / methacrylic acid (47/53 [mass ratio]), 30% by mass propylene glycol monomethyl ether solution, Mw = 11,000) ... 1.23 parts by mass alkali-soluble resin 2 (Acryl RD-F8 (manufactured by Nippon Shokubai)) 0.23 parts by mass polymerizable compound (radical polymerizable compound, manufactured by Shin-Nakamura Chemical Co., Ltd., NK Ester A -DPH-12E) ... 1.96 parts by weight polymerization inhibitor (paramethoxyphenol) ... 0.0007 parts by weight photopolymerization initiator (IRGACURE OXE02) ... 0.975 parts by weight polyfunctional thiol compound ( Polyfunctional thiol compounds listed in Table 2 below: 0.35 parts by mass fluorinated surfactant (manufactured by DIC, trade name: Megafu) F-475, 1% by mass propylene glycol monomethyl ether acetate solution) ... 2.50 parts by mass chromatic colorant 1: dye solution 1 (dye solution prepared by the following method) ... 24.57 mass Part chromatic colorant 2: Pigment dispersion P1 (CI Pigment Blue 15: 6 dispersion prepared by the following method, solid content concentration 11.8% by mass) ... 51.40 parts by mass
　なお、表２中、Ｔ－１及びＴ－２は、以下の多官能チオール化合物（相互作用性基を有しない多官能チオール化合物）を示す。 In Table 2, T-1 and T-2 represent the following polyfunctional thiol compounds (polyfunctional thiol compounds having no interactive group).
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000046
〔染料溶液１の調製〕
　染料溶液１は、下記の各成分を混合して調製した。
有機溶剤（シクロヘキサノン）・・・２１．５５質量部
染料（下記構造のＡ－１）・・・３．０２質量部
Figure JPOXMLDOC01-appb-C000047
 [Preparation of dye solution 1]
The dye solution 1 was prepared by mixing the following components.
Organic solvent (cyclohexanone) ... 21.55 parts by mass Dye (A-1 having the following structure) ... 3.02 parts by mass
Figure JPOXMLDOC01-appb-C000047
〔顔料分散液Ｐ１の調製〕
　以下の手順で顔料分散液Ｐ１を調製した。
　Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ１５：６（青色顔料、以下、「ＰＢ１５：６」とも称する）を１９．４質量部（平均一次粒径５５ｎｍ）、顔料分散剤ＤＩＳＰＥＲＢＹＫ－１６１（固形分濃度３０質量％、ＢＹＫ製）を２．９５質量部、アルカリ可溶性樹脂１（メタクリル酸ベンジル／メタクリル酸（４７／５３［質量比］）、３０質量％プロピレングリコールモノメチルエーテル溶液、Ｍｗ＝１１，０００）を固形分換算で２．９５質量部（溶液９．９３質量部）、プロピレングリコールモノメチルエーテル１６５．３質量部からなる混合液を、ビーズミル（ｂｅａｄｓ　ｍｉｌｌ）（ジルコニアビーズ０．３ｍｍ径）により３時間混合し、分散した。その後、更に、減圧機構付き高圧分散機ＮＡＮＯ－３０００－１０（日本ビーイーイー製）を用いて、２０００ｋｇ／ｃｍ３の圧力下で流量５００ｇ／分として分散処理を行った。この分散処理を１０回繰り返し、顔料分散液Ｐ１である、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ１５：６分散液を得た。得られた顔料分散液Ｐ１について、顔料の平均一次粒径を動的光散乱法（Ｍｉｃｒｏｔｒａｃ　Ｎａｎｏｔｒａｃ　ＵＰＡ－ＥＸ１５０（日機装社（Ｎｉｋｋｉｓｏ　Ｃｏ．，ｌｔｄ．製））により測定したところ、２４ｎｍであった。 [Preparation of Pigment Dispersion P1]
Pigment dispersion P1 was prepared by the following procedure.
C. I. Pigment Blue 15: 6 (blue pigment, hereinafter also referred to as “PB15: 6”) 19.4 parts by mass (average primary particle size 55 nm), pigment dispersant DISPERBYK-161 (solid content concentration 30% by mass, manufactured by BYK) 2.95 parts by mass, alkali-soluble resin 1 (benzyl methacrylate / methacrylic acid (47/53 [mass ratio]), 30% by mass propylene glycol monomethyl ether solution, Mw = 11,000) 2.95 in terms of solid content A mixed solution consisting of parts by mass (9.93 parts by mass of solution) and 165.3 parts by mass of propylene glycol monomethyl ether was mixed and dispersed for 3 hours by a beads mill (zirconia beads 0.3 mm diameter). Thereafter, the dispersion treatment was further performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism. This dispersion treatment was repeated 10 times to obtain C.I. I. Pigment Blue 15: 6 dispersion was obtained. With respect to the obtained pigment dispersion P1, the average primary particle size of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)) and found to be 24 nm.
［比較例１の硬化性組成物の調製］
　多官能チオール化合物を添加しないこと以外は実施例１と同様方法で硬化性組成物を調製した。 [Preparation of Curable Composition of Comparative Example 1]
A curable composition was prepared in the same manner as in Example 1 except that the polyfunctional thiol compound was not added.
［性能評価］
　各実施例、及び比較例の硬化性組成物について、下記の方法により露光感度を評価した。また、上記の硬化性組成物を用いて、ガラス基材上に下記の方法により形成したパターンのガラス基材への密着性について、下記の方法で評価した。評価結果をまとめて下記表２に示した。 [Performance evaluation]
About the curable composition of each Example and the comparative example, the exposure sensitivity was evaluated by the following method. Moreover, the following method evaluated the adhesiveness to the glass base material of the pattern formed by the following method on the glass base material using said curable composition. The evaluation results are summarized in Table 2 below.
〔露光感度〕
　各実施例、及び比較例の硬化性組成物を、ガラス基材上にスピンコート塗布し、その後、乾燥して膜厚１．０μｍの塗膜（硬化性組成物層）をガラス基材上に形成した。スピンコート条件は、３００ｒｐｍで５秒間の後、８００ｒｐｍで２０秒間とし、乾燥条件は１００℃で８０秒間とした。次に、得られた塗膜（硬化性組成物層）を、線幅２．０μｍのテスト用のフォトマスクを用い、超高圧水銀灯を有するプロキシミティー型露光機（日立ハイテク電子エンジニアリング（株）製）により、１０ｍＪ／ｃｍ２～２，０００ｍＪ／ｃｍ２の様々な露光量で露光して、硬化性組成物層をパターン状に硬化させた。次に、６０質量％ＣＤ－２０００（富士フイルムエレクトロニクスマテリアルズ（株）製）現像液を使用して、露光後の硬化膜を、２５℃、６０秒間の条件で現像し、パターン状の硬化膜を得た。その後、得られたパターン状の硬化膜を流水で２０秒間リンスした後、エアー乾燥した。
　露光感度は、露光工程において光が照射された領域の現像後のパターン線幅が１μｍ以上となる最小の露光量により評価した。露光感度の値が小さいほど、硬化性組成物の露光感度は良好である。なお、露光感度としては、上記の試験条件下においては、実用上３００ｍＪ／ｃｍ２未満が好ましい。結果は表２にまとめて示した。 [Exposure sensitivity]
The curable compositions of each Example and Comparative Example were spin-coated on a glass substrate, and then dried to form a 1.0 μm-thick coating film (curable composition layer) on the glass substrate. Formed. The spin coating conditions were 300 rpm for 5 seconds, 800 rpm for 20 seconds, and the drying conditions were 100 ° C. for 80 seconds. Next, the obtained coating film (curable composition layer) is a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultrahigh pressure mercury lamp using a test photomask having a line width of 2.0 μm. ) by, and exposed at various exposure amounts of 10mJ / cm 2 ~ 2,000mJ / cm 2, to cure the curable composition layer in a pattern. Next, the cured film after exposure was developed using a developer of 60% by mass CD-2000 (manufactured by FUJIFILM Electronics Materials Co., Ltd.) at 25 ° C. for 60 seconds to obtain a patterned cured film. Got. Thereafter, the obtained patterned cured film was rinsed with running water for 20 seconds and then air-dried.
The exposure sensitivity was evaluated based on the minimum exposure amount at which the pattern line width after development of the region irradiated with light in the exposure process was 1 μm or more. The smaller the exposure sensitivity value, the better the exposure sensitivity of the curable composition. The exposure sensitivity is preferably less than 300 mJ / cm 2 practically under the above test conditions. The results are summarized in Table 2.
〔密着性〕
　上記露光感度の試験で作製したパターン状の硬化膜において、パターン欠損が発生しているか否かをＳＥＭ（Ｓｃａｎｎｉｎｇ　Ｅｌｅｃｔｒｏｎ　Ｍｉｃｒｏｓｃｏｐｅ）で観察し、下記基準に基づいて評価した。結果は表２にまとめて示した。 [Adhesion]
In the patterned cured film prepared by the above-described exposure sensitivity test, whether or not a pattern defect occurred was observed by SEM (Scanning Electron Microscope) and evaluated based on the following criteria. The results are summarized in Table 2.
－評価基準－
　Ａ：パターン欠損がまったく観察されなかった。
　Ｂ：パターン欠損がパターン１．０μｍ四方あたり１～３個だった。
　Ｃ：パターン欠損がパターン１．０μｍ四方あたり４個以上１０個以下だった。
　Ｄ：パターン欠損がパターン１．０μｍ四方あたり１１個以上だった。
　なお、評価「Ｂ」以上が実用範囲である。 -Evaluation criteria-
A: No pattern defect was observed.
B: There were 1 to 3 pattern defects per 1.0 μm square pattern.
C: The number of pattern defects was 4 or more and 10 or less per 1.0 μm square pattern.
D: There were 11 or more pattern defects per 1.0 μm square pattern.
In addition, evaluation "B" or more is a practical range.
Figure JPOXMLDOC01-appb-T000048
Figure JPOXMLDOC01-appb-T000048
　表２に示した結果から、所定の多官能チオール化合物を含有する実施例１～２３の硬化性組成物（彩色着色剤を含有する硬化性組成物）は、優れた露光感度を有し、かつ支持体との優れた密着性を有していた。
　一方、多官能チオール化合物を含有しない比較例１の硬化性組成物では、上記効果が得られなかった。相互作用性基を有しない多官能チオール化合物を含有する比較例２及び比較例３の多官能チオール化合物では、上記効果が得られなかった。
　式（２）で表される多官能チオール化合物のｍが３以上である、実施例２、１０、１８、２１の硬化性組成物は、実施例１の硬化性組成物と比較してより優れた露光感度を有していた。
　実施例１０の硬化性組成物は、ｍ＋ｎが等しく、かつｍ／ｎがより大きい実施例１８の硬化性組成物と比較して、得られる硬化膜が支持体へのより優れた密着性を有していた。
　チオール基とは異なる相互作用性基がカルボン酸基若しくはその塩、ヒドロキシル基、アミノ基、ピリジニル基、リン酸基若しくはその塩、スルホン酸基若しくはその塩、又は－Ｓｉ（ＲＸ）ｐ（ＲＹ）３－ｐである、実施例２～６、８及び９の硬化性組成物は、相互作用性基がフェニル基である実施例７と比較して、得られる硬化膜が支持体へのより優れた密着性を有していた。 From the results shown in Table 2, the curable compositions of Examples 1 to 23 (the curable composition containing a coloring colorant) containing the predetermined polyfunctional thiol compound have excellent exposure sensitivity, and It had excellent adhesion to the support.
On the other hand, in the curable composition of Comparative Example 1 that does not contain a polyfunctional thiol compound, the above effect was not obtained. In the polyfunctional thiol compound of Comparative Example 2 and Comparative Example 3 containing a polyfunctional thiol compound having no interactive group, the above effect was not obtained.
The curable composition of Examples 2, 10, 18, and 21 in which m of the polyfunctional thiol compound represented by the formula (2) is 3 or more is superior to the curable composition of Example 1. Exposure sensitivity.
The curable composition of Example 10 has better adhesion to the support compared to the curable composition of Example 18 where m + n is equal and m / n is greater. Was.
An interactive group different from the thiol group is a carboxylic acid group or a salt thereof, a hydroxyl group, an amino group, a pyridinyl group, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, or —Si (R X ) p (R Y ) 3-p , the curable compositions of Examples 2 to 6, 8 and 9 are compared with Example 7 in which the interactive group is a phenyl group, the resulting cured film is applied to the support. It had better adhesion.
［実施例５５及び５６］
　実施例１の硬化性組成物の調製において、多官能チオール化合物の含有量を０．３５質量部から０．１７質量部（実施例５５）、及び０．７０質量部（実施例５６）に変更し、上記と同様に評価したところ、実施例１と同様の結果が得られた。 [Examples 55 and 56]
In the preparation of the curable composition of Example 1, the content of the polyfunctional thiol compound was changed from 0.35 parts by mass to 0.17 parts by mass (Example 55) and 0.70 parts by mass (Example 56). As a result, the same results as in Example 1 were obtained.
［実施例５７及び５８］
　実施例１の硬化性組成物の調製において、重合性化合物の含有量を１．９６質量部から、１．５質量部（実施例５７）、及び３．０質量部（実施例５８）に変更し、上記と同様に評価したところ、実施例１と同様の結果が得られた。 [Examples 57 and 58]
In the preparation of the curable composition of Example 1, the content of the polymerizable compound was changed from 1.96 parts by mass to 1.5 parts by mass (Example 57) and 3.0 parts by mass (Example 58). As a result, the same results as in Example 1 were obtained.
［実施例２４～５４、５９、及び比較例４～６の硬化性組成物の調製］
　表４の各欄に示した多官能チオール化合物と、各成分を表３に記載の組成で混合して、実施例２４～５４、５９、及び比較例５、６の硬化性組成物を調製した。多官能チオール化合物を加えなかったこと以外は実施例２４と同様にして比較例４の硬化性組成物を調製した。
　各硬化性組成物の最終的な固形分は、２８質量％になるよう、有機溶剤で調整した。また、有機溶剤は、各硬化性組成物における質量比がＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート）／酢酸ブチル／シクロヘキサノン＝２７／１８／２７になるよう、併用した。 [Preparation of Curable Compositions of Examples 24 to 54, 59 and Comparative Examples 4 to 6]
The curable compositions of Examples 24 to 54 and 59 and Comparative Examples 5 and 6 were prepared by mixing the polyfunctional thiol compound shown in each column of Table 4 and each component with the composition described in Table 3. . A curable composition of Comparative Example 4 was prepared in the same manner as in Example 24 except that the polyfunctional thiol compound was not added.
The final solid content of each curable composition was adjusted with an organic solvent so that it might become 28 mass%. Moreover, the organic solvent was used together so that the mass ratio in each curable composition might be PGMEA (propylene glycol monomethyl ether acetate) / butyl acetate / cyclohexanone = 27/18/27.
Figure JPOXMLDOC01-appb-T000049
Figure JPOXMLDOC01-appb-T000049
＜着色剤＞
　以下の方法により各着色剤を作製した。 <Colorant>
Each colorant was produced by the following method.
（チタン窒化物含有粒子（ＴｉＮ－１））
　まず、Ｔｉ粒子（ＴＣ－２００、トーホーテック社製）をＡｒガス中においてプラズマ処理することにより、Ｔｉナノ粒子化した。プラズマ処理後のＴｉナノ粒子を、Ａｒガス雰囲気下でＯ２濃度５０ｐｐｍ以下、３０℃の条件で２４時間静置した。その後、Ｏ２濃度が１００ｐｐｍとなるようにＡｒ雰囲気にＯ２ガスを導入した状態において３０℃、２４時間静置した（Ｔｉ粒子の前処理）。
　その後、得られたＴｉナノ粒子をホソカワミクロン製ＴＴＳＰセパレータを用いて収率１０％となる条件で分級を行い、Ｔｉ粒子の粉末を得た。得られた粉末の一次粒子径は、ＴＥＭ観察によって１００個の粒子の平均粒子径を算術平均により求めたところ、１２０ｎｍであった。
　チタン窒化物含有粒子ＴｉＮ－１は、国際公開第２０１０／１４７０９８の図１に記載の黒色複合微粒子製造装置に準ずる装置を用いて製造した。
　具体的には、黒色複合微粒子製造装置において、プラズマトーチの高周波発振用コイルに、約４ＭＨｚ及び約８０ｋＶＡの高周波電圧を印加し、プラズマガス供給源からプラズマガスとしてアルゴンガス５０Ｌ／ｍｉｎ及び窒素５０Ｌ／ｍｉｎの混合ガスを供給し、プラズマトーチ内にアルゴン－窒素熱プラズマ炎を発生させた。材料供給装置の噴霧ガス供給源から１０Ｌ／ｍｉｎのキャリアガスを供給した。
　上記のようにして得られたＴｉ粒子に対して、Ｆｅ粉（ＪＩＰ２７０Ｍ、ＪＦＥスチール社製）、及びＳｉ粉（Ｓｉｌｉｃｏｎ　ｐｏｗｄｅｒ　ＳＩ００６０３１）を、それぞれの質量比がＴｉ／Ｆｅ／Ｓｉ＝残分／０．０５／０．０５となるよう混合した。この混合物をキャリアガスであるアルゴンガスと共に、プラズマトーチ内の熱プラズマ炎中に供給し、熱プラズマ炎中で蒸発させ、気相状態で高度に分散させた。
　また、気体供給装置によって、チャンバ内に供給する気体としては、窒素を使用した。このときのチャンバ内の流速は５ｍ／ｓｅｃとして、供給量は１，０００Ｌ／ｍｉｎとした。また、サイクロン内の圧力は５０ｋＰａとし、また、チャンバからサイクロンへの各原料の供給速度は、１０ｍ／ｓ（平均値）とした。
　このようにして、チタン窒化物含有粒子ＴｉＮ－１を得た。 (Titanium nitride-containing particles (TiN-1))
First, Ti nanoparticles (TC-200, manufactured by Toho Tech Co., Ltd.) were formed into Ti nanoparticles by plasma treatment in Ar gas. The Ti nanoparticles after the plasma treatment were allowed to stand for 24 hours under conditions of an O 2 concentration of 50 ppm or less and 30 ° C. in an Ar gas atmosphere. Then, it was allowed to stand at 30 ° C. for 24 hours in a state where O 2 gas was introduced into the Ar atmosphere so that the O 2 concentration was 100 ppm (pretreatment of Ti particles).
Thereafter, the obtained Ti nanoparticles were classified using a TTSP separator manufactured by Hosokawa Micron under the condition of a yield of 10% to obtain a powder of Ti particles. The primary particle size of the obtained powder was 120 nm when the average particle size of 100 particles was determined by arithmetic average by TEM observation.
The titanium nitride-containing particles TiN-1 were produced using an apparatus according to the black composite fine particle production apparatus described in FIG. 1 of International Publication No. 2010/147098.
Specifically, in the black composite particle manufacturing apparatus, a high frequency voltage of about 4 MHz and about 80 kVA is applied to a high frequency oscillation coil of a plasma torch, and argon gas 50 L / min and nitrogen 50 L / min are used as plasma gases from a plasma gas supply source. A mixed gas of min was supplied to generate an argon-nitrogen thermal plasma flame in the plasma torch. A carrier gas of 10 L / min was supplied from the spray gas supply source of the material supply apparatus.
For the Ti particles obtained as described above, Fe powder (JIP270M, manufactured by JFE Steel) and Si powder (Silicon powder SI006031) have a mass ratio of Ti / Fe / Si = residue / 0. .05 / 0.05 was mixed. This mixture was supplied together with argon gas as a carrier gas into a thermal plasma flame in a plasma torch, evaporated in the thermal plasma flame, and highly dispersed in a gas phase state.
Further, nitrogen was used as a gas supplied into the chamber by the gas supply device. The flow rate in the chamber at this time was 5 m / sec, and the supply amount was 1,000 L / min. The pressure in the cyclone was 50 kPa, and the supply rate of each raw material from the chamber to the cyclone was 10 m / s (average value).
In this way, titanium nitride-containing particles TiN-1 were obtained.
　得られたチタン窒化物含有粒子ＴｉＮ－１について、ＩＣＰ発光分光分析法によって、チタン（Ｔｉ）原子、鉄（Ｆｅ）原子及びケイ素（Ｓｉ）原子の含有量を測定した。なお、ＩＣＰ発光分光分析法には、セイコーインスツルメンツ社製のＩＣＰ発光分光分析装置「ＳＰＳ３０００」（商品名）を用いた。
　窒素原子の含有量は、堀場製作所製の酸素・窒素分析装置「ＥＭＧＡ－６２０Ｗ／Ｃ」（商品名）を用いて測定し、不活性ガス融解－熱伝導度法により算出した。上記の結果、チタン窒化物含有粒子ＴｉＮに含まれる各原子の質量比は、Ｔｉ／Ｎ／Ｆｅ／Ｓｉ＝５７／３４／０．００３０／０．００２０であった。 The obtained titanium nitride-containing particles TiN-1 were measured for the content of titanium (Ti) atoms, iron (Fe) atoms, and silicon (Si) atoms by ICP emission spectroscopy. For the ICP emission spectroscopic analysis, an ICP emission spectroscopic analyzer “SPS3000” (trade name) manufactured by Seiko Instruments Inc. was used.
The nitrogen atom content was measured using an oxygen / nitrogen analyzer “EMGA-620W / C” (trade name) manufactured by Horiba, Ltd., and was calculated by an inert gas melting-thermal conductivity method. As a result, the mass ratio of each atom contained in the titanium nitride-containing particle TiN was Ti / N / Fe / Si = 57/34 / 0.0030 / 0.0020.
　チタン窒化物含有粒子ＴｉＮ－１のＸ線回折は、粉末試料をアルミ製標準試料ホルダーに詰め、広角Ｘ線回折法（理学電機社製、商品名「ＲＵ－２００Ｒ」）により測定した。測定条件としては、Ｘ線源はＣｕＫα線とし、出力は５０ｋＶ／２００ｍＡ、スリット系は１°－１°－０．１５ｍｍ－０．４５ｍｍ、測定ステップ（２θ）は０．０２°、スキャン速度は２°／分とした。
　そして、回折角２θ（４２．６°）付近に観察されるＴｉＮ（２００）面に由来するピークの回折角を測定した。更に、この（２００）面に由来するピークの半値幅より、シェラーの式を用いて、粒子を構成する結晶子サイズを求めた。その結果、ピークの回折角は４２．６２°、結晶子サイズは１０ｎｍだった。なお、ＴｉＯ２に起因するＸ線回折ピークは全く見られなかった。 X-ray diffraction of titanium nitride-containing particles TiN-1 was measured by a wide-angle X-ray diffraction method (trade name “RU-200R” manufactured by Rigaku Corporation) with a powder sample placed in an aluminum standard sample holder. As measurement conditions, the X-ray source is CuKα ray, the output is 50 kV / 200 mA, the slit system is 1 ° -1 ° -0.15 mm-0.45 mm, the measurement step (2θ) is 0.02 °, and the scan speed is It was 2 ° / min.
And the diffraction angle of the peak derived from the TiN (200) plane observed in the vicinity of the diffraction angle 2θ (42.6 °) was measured. Furthermore, from the half width of the peak derived from the (200) plane, the crystallite size constituting the particle was determined using Scherrer's equation. As a result, the peak diffraction angle was 42.62 ° and the crystallite size was 10 nm. Note that no X-ray diffraction peak due to TiO 2 was observed.
（チタン窒化物含有粒子ＴｉＮ－２）
　Ｔｉ粒子として、トーホーテック社製「ＴＣ－２００」に代えて、シグマアルドリッチ社製「５７８３４７」を使用し、Ｆｅ粉、及びＳｉ粉を、それぞれの質量比がＴｉ／Ｆｅ／Ｓｉ＝残分／０．５／１となるよう混合した以外はＴｉＮ－１と同様にして、チタン窒化物含有粒子ＴｉＮ－２を得た。
　なお、Ｘ線回折により測定したピークの回折角は４２．８１°、結晶子サイズは１２ｎｍだった。 (Titanium nitride-containing particles TiN-2)
Instead of “TC-200” manufactured by Toho Tech Co., as “Ti-particles”, “578347” manufactured by Sigma-Aldrich Co. is used, and the Fe and Si powders have a mass ratio of Ti / Fe / Si = residue / Titanium nitride-containing particles TiN-2 were obtained in the same manner as TiN-1, except that the mixture was mixed to 0.5 / 1.
The peak diffraction angle measured by X-ray diffraction was 42.81 °, and the crystallite size was 12 nm.
（チタン窒化物含有粒子ＴｉＮ－３）
　Ｆｅ粉、及びＳｉ粉を、それぞれの質量比がＴｉ／Ｆｅ／Ｓｉ＝残分／１／２となるよう混合した以外はＴｉＮ－１と同様にして、チタン窒化物含有粒子ＴｉＮ－３を得た。
　なお、Ｘ線回折により測定したピークの回折角は４３．１°、結晶子サイズは１２ｎｍだった。 (Titanium nitride-containing particles TiN-3)
Titanium nitride-containing particles TiN-3 are obtained in the same manner as TiN-1, except that Fe powder and Si powder are mixed so that the respective mass ratios are Ti / Fe / Si = residue / 1/2. It was.
The peak diffraction angle measured by X-ray diffraction was 43.1 °, and the crystallite size was 12 nm.
（チタンブラックＡ－１の作製）
　平均粒径１５ｎｍの酸化チタンＭＴ－１５０Ａ（商品名、テイカ（株）製）を１００ｇ、ＢＥＴ（Brunauer，Emmett，Teller）比表面積３００ｍ２／ｇのシリカ粒子ＡＥＲＯＳＩＬ３００（登録商標）３００／３０（エボニック社製）を２５ｇ、及び、Ｄｉｓｐｅｒｂｙｋ１９０（商品名、ビックケミー社製）を１００ｇ秤量し、これらをイオン電気交換水７１ｇに加えて、混合物を得た。その後、ＫＵＲＡＢＯ製ＭＡＺＥＲＳＴＡＲ　ＫＫ－４００Ｗを使用して、公転回転数１，３６０ｒｐｍ、自転回転数１，０４７ｒｐｍにて混合物を３０分間処理することにより均一な混合物水溶液を得た。この混合物水溶液を石英容器に充填し、小型ロータリーキルン（株式会社モトヤマ製）を用いて酸素雰囲気中で９２０℃に加熱した。その後、小型ロータリーキルン内を窒素で置換し、同温度でアンモニアガスを１００ｍＬ／ｍｉｎで５時間流すことにより窒化還元処理を実施した。終了後回収した粉末を乳鉢で粉砕し、Ｓｉ原子を含み、粉末状の比表面積７３ｍ2／ｇのチタンブラック〔チタンブラック粒子及びＳｉ原子を含む被分散体〕を得た（以下では、「チタンブラックＡ－１」と表記する）。 (Preparation of titanium black A-1)
100 g of titanium oxide MT-150A (trade name, manufactured by Teika Co., Ltd.) having an average particle diameter of 15 nm and silica particles AEROSIL300 (registered trademark) 300/30 (Evonik) having a BET (Brunauer, Emmett, Teller) specific surface area of 300 m 2 / g 25 g) and Disperbyk190 (trade name, manufactured by Big Chemie) were weighed 100 g, and these were added to 71 g of ion electroexchanged water to obtain a mixture. Thereafter, the mixture was treated at a revolution speed of 1,360 rpm and a rotation speed of 1,047 rpm for 30 minutes using a MURASTAR KK-400W manufactured by KURABO to obtain a uniform aqueous mixture solution. This aqueous mixture was filled in a quartz container and heated to 920 ° C. in an oxygen atmosphere using a small rotary kiln (manufactured by Motoyama Co., Ltd.). Thereafter, the inside of the small rotary kiln was replaced with nitrogen, and nitriding reduction treatment was performed by flowing ammonia gas at 100 mL / min for 5 hours at the same temperature. After the completion, the recovered powder was pulverized in a mortar to obtain a powdery titanium black (dispersed material containing titanium black particles and Si atoms) having a powder specific surface area of 73 m 2 / g (hereinafter referred to as “titanium”). Black A-1 ”).
（Ｆｅ原子を含有する窒化ニオブ含有粒子（ＮｂＮ）の作製）
　以下の方法によりＦｅ原子を含有する窒化ニオブ含有粒子を作製した。
　まず、三津和化学薬品製ニオブ（粉末）＜１００－３２５ｍｅｓｈ＞を原料（以下、「金属原料粉末」ともいう。）として準備した。
　次に、上記金属原料粉末を、Ａｒガス中においてプラズマ処理することにより、Ｎｂナノ粒子化した。上記プラズマ処理の条件は、下記のプラズマ処理（１）に従った。 (Preparation of niobium nitride-containing particles containing Fe atoms (NbN))
Niobium nitride-containing particles containing Fe atoms were produced by the following method.
First, niobium (powder) <100-325 mesh> manufactured by Mitsuwa Chemicals was prepared as a raw material (hereinafter also referred to as “metal raw material powder”).
Next, the metal raw material powder was subjected to plasma treatment in Ar gas to form Nb nanoparticles. The conditions for the plasma treatment were the following plasma treatment (1).
・プラズマ処理（１）
　プラズマ処理（１）は以下の方法により行った。上記の黒色複合微粒子製造装置に準ずる装置を用い、以下の条件によりプラズマ処理（１）した。
・高周波発振用コイルに印加した高周波電圧：周波数　約４ＭＨｚ、電圧　約８０ｋＶＡ
・プラズマガス：アルゴンガス（供給量　１００Ｌ／ｍｉｎ）
・キャリアガス：アルゴンガス（供給量　１０Ｌ／ｍｉｎ）
・チャンバ内雰囲気：アルゴンガス（供給量　１，０００ｌ／ｍｉｎ、チャンバ内流速　５ｍ／ｓｅｃ）
・サイクロン内雰囲気：アルゴンガス、内圧　５０ｋＰａ
・チャンバからサイクロンへの材料供給速度：１０ｍ／ｓ（平均値） ・ Plasma treatment (1)
Plasma treatment (1) was performed by the following method. Plasma treatment (1) was performed under the following conditions using an apparatus according to the above black composite fine particle production apparatus.
・ High frequency voltage applied to the coil for high frequency oscillation: frequency about 4 MHz, voltage about 80 kVA
・ Plasma gas: Argon gas (Supply rate: 100 L / min)
Carrier gas: Argon gas (Supply amount: 10 L / min)
・ Atmosphere in chamber: Argon gas (amount supplied: 1,000 l / min, flow velocity in chamber: 5 m / sec)
・ Cyclone atmosphere: Argon gas, internal pressure 50kPa
・ Material supply speed from chamber to cyclone: 10 m / s (average value)
　次に、Ｆｅ粉（ＪＩＰ２７０Ｍ、ＪＦＥスチール社製）を準備し、プラズマ処理（１）の条件によりプラズマ処理を行い、Ｆｅナノ粒子化した。 Next, Fe powder (JIP270M, manufactured by JFE Steel Co., Ltd.) was prepared and subjected to plasma treatment under the conditions of plasma treatment (1) to form Fe nanoparticles.
　次に、上記により得られたＮｂナノ粒子、及びＦｅナノ粒子を混合し、原料金属粉末を得た。この原料金属粉末について、窒素ガス中においてプラズマ処理することにより、窒化ニオブ含有粒子を得た。上記プラズマ処理の条件は、下記のプラズマ処理（２）に従った。 Next, the Nb nanoparticles and Fe nanoparticles obtained as described above were mixed to obtain a raw metal powder. This raw metal powder was subjected to plasma treatment in nitrogen gas to obtain niobium nitride-containing particles. The conditions for the plasma treatment were the following plasma treatment (2).
・プラズマ処理（２）
　プラズマ処理（２）は以下の方法により行った。なお、装置はプラズマ処理（１）と同様のものを用いた。
・高周波発振用コイルに印加した高周波電圧：周波数　約４ＭＨｚ、電圧　約８０ｋＶＡ
・プラズマガス：アルゴンガス及び窒素ガス（供給量　それぞれ５０Ｌ／ｍｉｎ）
・キャリアガス：窒素ガス（供給量　１０Ｌ／ｍｉｎ）
・チャンバ内雰囲気：窒素ガス（供給量　１，０００Ｌ／ｍｉｎ、チャンバ内流速　５ｍ／ｓｅｃ）
・サイクロン内雰囲気：窒素ガス、内圧　５０ｋＰａ
・チャンバからサイクロンへの材料供給速度：１０ｍ／ｓ（平均値） ・ Plasma treatment (2)
Plasma treatment (2) was performed by the following method. The apparatus used was the same as in the plasma treatment (1).
・ High frequency voltage applied to the coil for high frequency oscillation: frequency about 4 MHz, voltage about 80 kVA
・ Plasma gas: Argon gas and nitrogen gas (Supply amount 50L / min each)
・ Carrier gas: Nitrogen gas (Supply amount: 10L / min)
・ Atmosphere in the chamber: Nitrogen gas (amount supplied: 1,000 L / min, flow velocity in the chamber: 5 m / sec)
・ Cyclone atmosphere: Nitrogen gas, internal pressure 50kPa
・ Material supply speed from chamber to cyclone: 10 m / s (average value)
　プラズマ処理（２）終了後の粒子を、Ａｒガスを用いて日本シンテック社製分流型湿度供給装置ＳＲＨにより大気中であれば相対湿度９５％となる条件で２０℃の窒素ガスを導入し、２４時間静置した。その後、得られた粒子をホソカワミクロン製ＴＴＳＰセパレータを用いて収率１０％となる条件で分級を行い、窒化ニオブ含有粒子（ＮｂＮ）を得た。なお、セパレータへは窒素ガスを供給した。
　得られた窒化ニオブ含有粒子について、ＩＣＰ発光分光分析法によって、鉄（Ｆｅ）原子の含有量を測定したところ、５０質量ｐｐｍだった。 After completion of the plasma treatment (2), nitrogen gas at 20 ° C. is introduced under the condition that the relative humidity is 95% in the atmosphere by using a shunt type humidity supply device SRH manufactured by Nippon Shintec Co., Ltd. using Ar gas. Let stand for hours. Thereafter, the obtained particles were classified using a TTSP separator manufactured by Hosokawa Micron under the condition of a yield of 10% to obtain niobium nitride-containing particles (NbN). Nitrogen gas was supplied to the separator.
The obtained niobium nitride-containing particles were measured for the content of iron (Fe) atoms by ICP emission spectroscopy, and found to be 50 ppm by mass.
（Ｆｅ原子を含有する窒化バナジウム含有粒子（ＶＮ）の作製）
　Ｆｅ原子を含有する窒化ニオブ含有粒子の作製において、三津和化学薬品製ニオブ（粉末）＜１００－３２５ｍｅｓｈ＞に代えて太陽鉱工製金属バナジウム粉末ＶＨＯを用いたこと以外は同様にして、Ｆｅ原子を含有する窒化バナジウム含有粒子（ＶＮ）を作製した。得られた窒化バナジウム含有粒子について、ＩＣＰ発光分光分析法によって、鉄（Ｆｅ）原子の含有量を測定したところ、５０質量ｐｐｍだった。 (Production of vanadium nitride-containing particles (VN) containing Fe atoms)
In the production of niobium nitride-containing particles containing Fe atoms, Fe atoms were used in the same manner except that the metal vanadium powder VHO manufactured by Taiyo Mining Co. was used instead of Niobium (powder) <100-325 mesh> manufactured by Mitsuwa Chemicals. Vanadium nitride-containing particles (VN) containing About the obtained vanadium nitride containing particle | grains, when content of an iron (Fe) atom was measured by ICP emission spectroscopy analysis, it was 50 mass ppm.
＜分散剤＞
　分散剤として、以下の構造の分散剤Ａを用いた。各構造単位に記載の数値は、全構造単位に対する、各構造単位の質量％を意図する。 <Dispersant>
Dispersant A having the following structure was used as the dispersant. The numerical value described in each structural unit intends the mass% of each structural unit with respect to all the structural units.
・分散剤Ａ
Figure JPOXMLDOC01-appb-C000050
 ・ Dispersant A
Figure JPOXMLDOC01-appb-C000050
＜バインダー樹脂＞
　バインダー樹脂としては、以下の樹脂Ａを用いた。各構造単位に記載の数値は、全構造単位に対する、各構造単位のモル％を意図する。なお、樹脂Ａの式中、各略号は以下を表す。
　ＢｚＭＡ：メタクリル酸ベンジル
　ＭＭＡ：メタクリル酸メチル <Binder resin>
As the binder resin, the following resin A was used. The numerical value described in each structural unit intends mol% of each structural unit with respect to the total structural unit. In the formula of resin A, each abbreviation represents the following.
BzMA: benzyl methacrylate MMA: methyl methacrylate
・樹脂Ａ
Figure JPOXMLDOC01-appb-I000051
・ Resin A
Figure JPOXMLDOC01-appb-I000051
＜重合性化合物＞
・重合性化合物Ｍ１：ジペンタエリスリトールヘキサアクリレート（日本化薬社製、商品名「ＫＡＹＡＲＡＤ」、下記式参照）
Figure JPOXMLDOC01-appb-C000052
・重合性化合物Ｍ２：ＰＥＴ－３０（ペンタエリスリトールトリアクリレート、日本化薬社製） <Polymerizable compound>
Polymerizable compound M1: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name “KAYARAD”, see the following formula)
Figure JPOXMLDOC01-appb-C000052
Polymerizable compound M2: PET-30 (pentaerythritol triacrylate, manufactured by Nippon Kayaku Co., Ltd.)
＜光重合開始剤＞
・ＯＸＥ－０１：Ｉｒｇａｃｕｒｅ　ＯＸＥ０１（商品名、ＢＡＳＦジャパン社製、オキシム化合物に該当する。）
Figure JPOXMLDOC01-appb-C000053
 <Photopolymerization initiator>
OXE-01: Irgacure OXE01 (trade name, manufactured by BASF Japan Ltd., applicable to oxime compounds)
Figure JPOXMLDOC01-appb-C000053
・ＯＸＥ－０２：Ｉｒｇａｃｕｒｅ　ＯＸＥ０２（商品名、ＢＡＳＦジャパン社製、オキシム化合物に該当する。）
Figure JPOXMLDOC01-appb-C000054
 OXE-02: Irgacure OXE02 (trade name, manufactured by BASF Japan Ltd., corresponding to oxime compound)
Figure JPOXMLDOC01-appb-C000054
・ＰＩ－３：下記の構造を有する光重合開始剤（オキシム化合物に該当する。） PI-3: a photopolymerization initiator having the following structure (corresponding to an oxime compound)
Figure JPOXMLDOC01-appb-C000055
Figure JPOXMLDOC01-appb-C000055
・ＮＣＩ－８３１（商品名、ＡＤＥＫＡ社製、オキシム化合物に該当する。）
Figure JPOXMLDOC01-appb-C000056
 NCI-831 (trade name, manufactured by ADEKA, applicable to oxime compounds)
Figure JPOXMLDOC01-appb-C000056
・ＩＲＧ－３７９：ＩＲＧＡＣＵＲＥ　３７９ＥＧ（商品名、ＢＡＳＦジャパン社製、オキシム化合物には該当しない。）
Figure JPOXMLDOC01-appb-C000057
 -IRG-379: IRGACURE 379EG (trade name, manufactured by BASF Japan, not applicable to oxime compounds)
Figure JPOXMLDOC01-appb-C000057
＜界面活性剤＞
・Ｆ－１：下記式で表される化合物（重量平均分子量（Ｍｗ）＝１５，３１１）
　ただし、下記式において、式（Ａ）及び（Ｂ）で表される構造単位はそれぞれ６２モル％、３８モル％である。式（Ｂ）で表される構造単位中、ａ、ｂ、ｃは、それぞれ、ａ＋ｃ＝１４、ｂ＝１７の関係を満たす。 <Surfactant>
F-1: Compound represented by the following formula (weight average molecular weight (Mw) = 15,311)
However, in the following formula, the structural units represented by the formulas (A) and (B) are 62 mol% and 38 mol%, respectively. In the structural unit represented by the formula (B), a, b, and c satisfy the relationship of a + c = 14 and b = 17, respectively.
Figure JPOXMLDOC01-appb-C000058
Figure JPOXMLDOC01-appb-C000058
＜有機溶剤＞
・ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート
・シクロペンタノン
・酢酸ブチル <Organic solvent>
・ PGMEA: Propylene glycol monomethyl ether acetate ・ Cyclopentanone ・ Butyl acetate
〔着色剤分散液の調製〕
　まず、着色剤、分散剤及び有機溶剤を、攪拌機（ＩＫＡ社製ＥＵＲＯＳＴＡＲ）によって１５分間混合し、上記成分の混合液を得た。次に、得られた混合液に対して、シンマルエンタープライゼス製のＮＰＭ－Ｐｉｌｏｔを使用して下記条件にて分散処理を行い、着色剤分散液を得た。 (Preparation of colorant dispersion)
First, a colorant, a dispersant, and an organic solvent were mixed for 15 minutes with a stirrer (EUKA STAR manufactured by IKA) to obtain a mixed solution of the above components. Next, the obtained mixture was subjected to a dispersion treatment under the following conditions using NPM-Pilot made by Shinmaru Enterprises to obtain a colorant dispersion.
＜分散条件＞
・ビーズ径：φ０．０５ｍｍ、（ニッカトー製ジルコニアビーズ、ＹＴＺ）
・ビーズ充填率：６５体積％
・ミル周速：１０ｍ／ｓｅｃ
・セパレータ周速：１３ｍ／ｓ
・分散処理する混合液量：１５ｋｇ
・循環流量（ポンプ供給量）：９０ｋｇ／ｈｏｕｒ
・処理液温度：１９～２１℃
・冷却水：水
・処理時間：２２時間程度 <Distribution conditions>
・ Bead diameter: 0.05mm, (Nikkato zirconia beads, YTZ)
・ Bead filling rate: 65% by volume
・ Mill peripheral speed: 10m / sec
・ Separator peripheral speed: 13m / s
・ Amount of liquid mixture to be dispersed: 15 kg
・ Circulating flow rate (pump supply amount): 90 kg / hour
・ Processing liquid temperature: 19-21 ℃
・ Cooling water: Water ・ Processing time: About 22 hours
［性能評価］
〔露光感度〕
　表面をＳｉＯ２処理したＳｉ基板上に、各硬化性組成物を用いて、膜厚１．５μｍの硬化膜が得られるように回転数を調整して、スピンコートにより塗膜（硬化性組成物層）を形成した。形成した塗膜を、ホットプレート上で１００℃、２分間の熱処理（プリベーク）により乾燥させた。上記プリベーク後の塗膜（硬化性組成物層）付き基板に対してｉ線ステッパー（キヤノン製ＦＰＡ３０００ｉ５＋）を用い、長さ２００μｍ×幅２０μｍラインパターンが形成されたフォトマスクを通して、上記塗膜を露光した。露光後の塗膜を、東京エレクトロン製コーターデベロッパーＡＣＴ８により、現像液として水酸化テトラメチルアンモニウムを用いて、３０秒間パドル現像をした。現像後は純水により２０秒間シャワーリンス処理を行った。現像後パターンが剥がれずに維持された最低露光量を露光感度として評価した。なお、露光感度としては、上記の試験条件下においては、実用上５００ｍＪ／ｃｍ２未満が好ましい。結果は表４にまとめて示した。 [Performance evaluation]
[Exposure sensitivity]
Using a curable composition on a Si substrate whose surface is treated with SiO 2, the number of revolutions is adjusted so that a cured film having a thickness of 1.5 μm is obtained, and a coating film (curable composition) is formed by spin coating. Layer). The formed coating film was dried by heat treatment (prebaking) at 100 ° C. for 2 minutes on a hot plate. Using an i-line stepper (Canon FPA3000i5 +) to the substrate with the pre-baked coating film (curable composition layer), the coating film is exposed through a photomask having a line pattern of length 200 μm × width 20 μm. did. The exposed coating film was subjected to paddle development for 30 seconds using a coater developer ACT8 manufactured by Tokyo Electron, using tetramethylammonium hydroxide as a developer. After the development, a shower rinsing process was performed with pure water for 20 seconds. The minimum exposure amount that was maintained without peeling off the pattern after development was evaluated as exposure sensitivity. The exposure sensitivity is preferably less than 500 mJ / cm 2 practically under the above test conditions. The results are summarized in Table 4.
〔密着性〕
　上記露光感度の試験で作製したパターン状の硬化膜において、パターン欠損が発生しているか否かをＳＥＭ（Ｓｃａｎｎｉｎｇ　Ｅｌｅｃｔｒｏｎ　Ｍｉｃｒｏｓｃｏｐｅ）で観察し、下記基準に基づいて評価した。結果は表４にまとめて示した。 [Adhesion]
In the patterned cured film prepared by the above-described exposure sensitivity test, whether or not a pattern defect occurred was observed by SEM (Scanning Electron Microscope) and evaluated based on the following criteria. The results are summarized in Table 4.
－評価基準－
　Ａ：パターン欠損がまったく観察されなかった。
　Ｂ：パターン欠損がパターン１．０μｍ四方あたり１～３個だった。
　Ｃ：パターン欠損がパターン１．０μｍ四方あたり４個以上１０個以下だった。
　Ｄ：パターン欠損がパターン１．０μｍ四方あたり１１個以上だった。
　なお、評価「Ｂ」以上が実用範囲である。 -Evaluation criteria-
A: No pattern defect was observed.
B: There were 1 to 3 pattern defects per 1.0 μm square pattern.
C: The number of pattern defects was 4 or more and 10 or less per 1.0 μm square pattern.
D: There were 11 or more pattern defects per 1.0 μm square pattern.
In addition, evaluation "B" or more is a practical range.
〔パターン形状〕
　上記露光感度の評価において作製した、パターン状の硬化膜をポストベーク（温度：２２０℃、時間：３００秒）した。ポストベーク後の硬化膜のパターン形状を測長ＳＥＭ（Ｓｃａｎｎｉｎｇ　Ｅｌｅｃｔｒｏｎ　Ｍｉｃｒｏｓｃｏｐｅ）により測定した。具体的には、ラインパターン端部の膜厚と中央部の膜厚を測定し、比（パターン端部の膜厚／中央部の膜厚）を計算し、以下の基準により評価した。なお、評価「２」以上が実用範囲である。
・７：比が０．９８超１．００以下であり、ＳＥＭによる観察でパターン中央部と端部の膜厚に差は見られない。
・６：比が、０．９６超０．９８以下であり、パターン中央部と端部の膜厚にわずかに差がみられる。
・５：比が、０．９４超０．９６以下であり、パターン中央部と端部の膜厚に差がみられる。
・４：比が０．９２超０．９４以下であり、端部の膜厚が薄く、わずかに歪んでいるが実用上問題ないレベル。
・３：比が０．９０超０．９２以下であり、端部の膜厚が薄く、歪んでいるが実用上問題ないレベル。
・２：比が０．８０超０．９０以下であり、端部の膜厚が薄いが、実用は可能なレベル。
・１：比が０．８０以下であり、端部の膜厚が薄く、許容外。 [Pattern shape]
The patterned cured film produced in the evaluation of the exposure sensitivity was post-baked (temperature: 220 ° C., time: 300 seconds). The pattern shape of the cured film after post-baking was measured by a length measuring SEM (Scanning Electron Microscope). Specifically, the film thickness at the end of the line pattern and the film thickness at the center were measured, and the ratio (film thickness at the pattern end / film thickness at the center) was calculated and evaluated according to the following criteria. In addition, evaluation "2" or more is a practical range.
-7: The ratio is more than 0.98 and less than 1.00, and no difference is observed in the film thickness between the central part and the end part of the pattern by observation with SEM.
6: The ratio is more than 0.96 and not more than 0.98, and there is a slight difference in the film thickness between the central portion and the end portion of the pattern.
5: The ratio is more than 0.94 and not more than 0.96, and there is a difference in film thickness between the pattern center and the edge.
-4: The ratio is more than 0.92 and less than 0.94, the film thickness at the end is thin, and it is slightly distorted, but there is no practical problem.
-3: The ratio is more than 0.90 and not more than 0.92, and the film thickness at the end is thin and distorted, but there is no practical problem.
-2: The ratio is more than 0.80 and 0.90 or less, and the film thickness at the end is thin, but the practical level is possible.
-1: The ratio is 0.80 or less, the film thickness at the end is thin, and is not acceptable.
〔現像性〕
　上記露光感度の評価において作製した、パターン状の硬化膜において、露光した際、フォトマスクにより遮蔽されて、光が照射されなかった領域（未露光部）における残渣の有無をＳＥＭ（倍率：２０，０００倍）にて観察し、現像性を評価した。評価基準は以下の通りであり、結果は表４にまとめて示した。 [Developability]
In the patterned cured film prepared in the above-described evaluation of exposure sensitivity, the presence or absence of residue in a region (unexposed portion) that was shielded by a photomask and was not irradiated with light when exposed was determined by SEM (magnification: 20, 000 times), and developability was evaluated. The evaluation criteria are as follows, and the results are summarized in Table 4.
－評価基準－
Ａ：未露光部には、残渣が全く観察されない
Ｂ：未露光部１．０μｍ四方に残渣が１個以上３個以下観察された。
Ｃ：未露光部１．０μｍ四方に残渣が４個以上、１０個以下観察された
Ｄ：未露光部１．０μｍ四方に残渣が１１個以上観察された。
　実用上「Ｃ」以上が好ましく、「Ａ」及び「Ｂ」は優れた性能を有すると評価する。 -Evaluation criteria-
A: No residue is observed at all in the unexposed area. B: 1 or more and 3 or less residues are observed in the 1.0 μm square of the unexposed area.
C: 4 or more and 10 or less residues were observed in the 1.0 μm square of the unexposed area. D: 11 or more residues were observed in the 1.0 μm square of the unexposed area.
Practically, “C” or more is preferable, and “A” and “B” are evaluated as having excellent performance.
Figure JPOXMLDOC01-appb-T000059
Figure JPOXMLDOC01-appb-T000059
　表４に示した結果から、所定の多官能チオール化合物を含有する実施例２４～５４、及び、５９の硬化性組成物（黒色顔料を含有する硬化性組成物）は、優れた露光感度を有し、かつ支持体との優れた密着性を有していた。
　一方、多官能チオール化合物を含有しない比較例４の硬化性組成物は、上記効果を有していなかった。相互作用性基を有しない多官能チオール化合物を含有する比較例５及び比較例６の多官能チオール化合物は、上記効果を有していなかった。
　式（２）で表される多官能チオール化合物のｍが３以上である、実施例２５～５４、及び、５９の硬化性組成物は、実施例２４の硬化性組成物と比較して、より優れた露光感度を有していた。
　チオール基とは異なる相互作用性基がヒドロキシ基（実施例２６）、アミノ基（実施例２７）、又はピリジニル基（実施例３１）である硬化性組成物は、チオール基とは異なる相互作用性基がフェニル基（実施例３０）、又はＳｉ基（実施例３２）である、硬化性組成物と比較してより優れた現像性を有していた。
　チオール基とは異なる相互作用性基が、カルボン酸基（実施例２５）、リン酸基（実施例２８）、又はスルホン酸基（実施例２９）である硬化性組成物は、チオール基とは異なる相互作用性基がヒドロキシ基（実施例２６）、アミノ基（実施例２７）、又はピリジニル基（実施例３１）である硬化性組成物と比較して、更に優れた現像性を有していた。これは、チオール基とは異なる相互作用性基の違いに起因する未露光部の溶解性の違いによるものと推測される。
　実施例３３の硬化性組成物は、ｍ＋ｎが等しく、かつｍ／ｎがより大きい実施例４１の硬化性組成物と比較して、より優れたパターン形状を有しており、かつ支持体へのより優れた密着性を有していた。
　光重合開始剤がオキシム化合物である実施例３３、４７、４８、４９、及び、５０の硬化性組成物は、実施例５９の硬化性組成物と比較して、より優れた露光感度を有していた。 From the results shown in Table 4, the curable compositions of Examples 24 to 54 and 59 containing a predetermined polyfunctional thiol compound (curable composition containing a black pigment) have excellent exposure sensitivity. And had excellent adhesion to the support.
On the other hand, the curable composition of Comparative Example 4 that did not contain a polyfunctional thiol compound did not have the above effect. The polyfunctional thiol compounds of Comparative Example 5 and Comparative Example 6 containing a polyfunctional thiol compound having no interactive group did not have the above effects.
The curable compositions of Examples 25 to 54 and 59 in which m of the polyfunctional thiol compound represented by the formula (2) is 3 or more are more in comparison with the curable composition of Example 24. It had excellent exposure sensitivity.
The curable composition in which the interactive group different from the thiol group is a hydroxy group (Example 26), an amino group (Example 27), or a pyridinyl group (Example 31) is different from the thiol group. Compared with the curable composition whose group is a phenyl group (Example 30) or a Si group (Example 32), it had better developability.
The curable composition in which the interactive group different from the thiol group is a carboxylic acid group (Example 25), a phosphoric acid group (Example 28), or a sulfonic acid group (Example 29) is a thiol group. Compared with a curable composition in which the different interactive group is a hydroxy group (Example 26), an amino group (Example 27), or a pyridinyl group (Example 31), it has further excellent developability. It was. This is presumed to be due to the difference in solubility in the unexposed area due to the difference in the interactive group different from the thiol group.
The curable composition of Example 33 has a better pattern shape as compared to the curable composition of Example 41 where m + n is equal and m / n is greater, and It had better adhesion.
The curable compositions of Examples 33, 47, 48, 49, and 50, in which the photopolymerization initiator is an oxime compound, have superior exposure sensitivity compared to the curable composition of Example 59. It was.
　なお、表４中、上矢印は、直上の欄と同一であることを意味し、「－」は硬化性組成物がその成分を含有しないことを意味する。 In Table 4, the up arrow means the same as the column immediately above, and “-” means that the curable composition does not contain the component.
　重合性化合物Ｍ１に代えて、重合性化合物Ｍ２を用いた以外は、実施例３３と同様にして硬化性組成物を作製し、評価を行ったところ、実施例３３と同様の結果が得られた。 A curable composition was prepared and evaluated in the same manner as in Example 33 except that the polymerizable compound M2 was used in place of the polymerizable compound M1, and the same results as in Example 33 were obtained. .
　重合性化合物Ｍ１に代えて、重合性化合物Ｍ１及びＭ２の混合物（混合物におけるＭ１及びＭ２の含有質量比は、Ｍ１の含有質量：Ｍ２の含有質量＝１：１であり、硬化性組成物全体に対する上記混合物の含有量は、実施例３３における重合性化合物Ｍ１の含有量と同様である。）を用いた以外は、実施例３３と同様にして硬化性組成物を作製し、評価を行ったところ、実施例３３と同様の結果が得られた。 Instead of the polymerizable compound M1, a mixture of the polymerizable compounds M1 and M2 (the content mass ratio of M1 and M2 in the mixture is M1 content mass: M2 content mass = 1: 1, and is based on the entire curable composition) The content of the above mixture was the same as the content of the polymerizable compound M1 in Example 33.) A curable composition was prepared and evaluated in the same manner as in Example 33 except that it was used. The same results as in Example 33 were obtained.
［カーボンブラック分散物（ＣＢ分散液）の調製及び硬化性組成物の評価］
　上記の着色剤分散液の調製において、着色剤をカーボンブラック（商品名「カラーブラック　Ｓ１７０」、デグサ社製、平均一次粒子径１７ｎｍ、ＢＥＴ比表面積２００ｍ2／ｇ、ガスブラック方式により製造されたカーボンブラック）とした以外は同様の方法により、カーボンブラック分散物（ＣＢ分散液）を得た。 [Preparation of carbon black dispersion (CB dispersion) and evaluation of curable composition]
In the preparation of the above colorant dispersion, the colorant is carbon black (trade name “Color Black S170”, manufactured by Degussa, average primary particle size 17 nm, BET specific surface area 200 m 2 / g, carbon produced by a gas black method. A carbon black dispersion (CB dispersion) was obtained in the same manner except that it was black.
　実施例３３の硬化性組成物の調製において、硬化性組成物中でチタン窒化物含有粒子ＴｉＮ－１を５８質量％含有するように添加した着色剤分散液に代えて、チタン窒化物含有粒子ＴｉＮ－１を含有する着色剤分散液と上記ＣＢ分散液との混合物（硬化性組成物中のチタン窒化物含有粒子ＴｉＮ－１：硬化性組成物中のカーボンブラック＝４５：１３（質量比）、上記硬化性組成物中のチタン窒化物含有粒子ＴｉＮ－１とカーボンブラックとの合計含有量は５８質量％である。）を用いた他は同様にして硬化性組成物を調製し、これを用いて評価を行った。評価の結果、実施例３３と同様の評価（露光感度と、密着性を含む）が得られることが分かった。 In the preparation of the curable composition of Example 33, instead of the colorant dispersion added so as to contain 58% by mass of titanium nitride-containing particles TiN-1 in the curable composition, titanium nitride-containing particles TiN were added. -1 and a mixture of the above CB dispersion (titanium nitride-containing particles TiN-1 in the curable composition: carbon black in the curable composition = 45: 13 (mass ratio)) A curable composition was prepared in the same manner except that the total content of titanium nitride-containing particles TiN-1 and carbon black in the curable composition was 58% by mass. And evaluated. As a result of evaluation, it was found that the same evaluation (including exposure sensitivity and adhesion) as in Example 33 was obtained.
［有彩色顔料分散物（ＰＹ分散液）の調製と硬化性組成物の評価］
　上記の着色剤分散液の調製において、着色剤をピグメントイエロー１５０（Hangzhou Star-up Pigment Co., Ltd.製、商品名６１５０顔料黄５ＧＮ）とした以外は同様の方法により、有彩色顔料分散物（ＰＹ分散液）を得た。 [Preparation of chromatic pigment dispersion (PY dispersion) and evaluation of curable composition]
A chromatic pigment dispersion was prepared in the same manner as in the preparation of the colorant dispersion, except that Pigment Yellow 150 (trade name: 6150 Pigment Yellow 5GN, manufactured by Hangzhou Star-up Pigment Co., Ltd.) was used as the colorant. (PY dispersion) was obtained.
　実施例３３の硬化性組成物の調製において、硬化性組成物中でチタン窒化物含有粒子ＴｉＮ－１を５８質量％含有するように添加した着色剤分散液に代えて、チタン窒化物含有粒子ＴｉＮ－１を含有する着色剤分散液と上記ＰＹ分散液との混合物（硬化性組成物中のチタン窒化物含有粒子ＴｉＮ－１：硬化性組成中のピグメントイエロー１５０＝４５：１３（質量比）、硬化性組成物中のチタン窒化物含有粒子ＴｉＮ－１とピグメントイエロー１５０との合計含有量は５８質量％である。）を用いた他は同様にして硬化性組成物を調製し、これを用いて評価を行った。評価の結果、実施例３３と同様の評価（露光感度と、密着性を含む）が得られた。なお、硬化膜としては、更に黒味の濃い膜となった。 In the preparation of the curable composition of Example 33, instead of the colorant dispersion added so as to contain 58% by mass of titanium nitride-containing particles TiN-1 in the curable composition, titanium nitride-containing particles TiN were added. -1-containing colorant dispersion and the above PY dispersion (titanium nitride-containing particles TiN-1 in the curable composition: Pigment Yellow 150 in the curable composition = 45: 13 (mass ratio)) The total content of titanium nitride-containing particles TiN-1 and Pigment Yellow 150 in the curable composition is 58% by mass), and a curable composition was prepared in the same manner. And evaluated. As a result of the evaluation, the same evaluation (including exposure sensitivity and adhesion) as in Example 33 was obtained. The cured film was a darker film.
［有彩色顔料分散物（ＰＲ分散液）の調製］
　上記の着色剤分散液の調製において、着色剤をＣ．Ｉ．Ｐｉｇｍｅｎｔ　Ｒｅｄ　２５４（チバ・スペシャリティー・ケミカルズ社製）とした以外は同様の方法により、有彩色顔料分散物（ＰＲ分散液）を得た。 [Preparation of chromatic pigment dispersion (PR dispersion)]
In the preparation of the colorant dispersion, the colorant is C.I. I. A chromatic pigment dispersion (PR dispersion) was obtained in the same manner except that Pigment Red 254 (manufactured by Ciba Specialty Chemicals) was used.
［有彩色顔料分散物（ＰＢ分散液）の調製］
　上記の着色剤分散液の調製において、着色剤をＣ．Ｉ．Ｐｉｇｍｅｎｔ　Ｂｌｕｅ　１５：６（ＤＩＣ株式会社製）とした以外は同様の方法により、有彩色顔料分散物（ＰＢ分散液）を得た。 [Preparation of chromatic pigment dispersion (PB dispersion)]
In the preparation of the colorant dispersion, the colorant is C.I. I. A chromatic pigment dispersion (PB dispersion) was obtained in the same manner except that Pigment Blue 15: 6 (manufactured by DIC Corporation) was used.
［有彩色顔料分散物（ＰＶ分散液）の調製］
　上記の着色剤分散液の調製において、着色剤をＣ．Ｉ．Ｐｉｇｍｅｎｔ　Ｖｉｏｌｅｔ　２３（クラリアント社製）とした以外は同様の方法により、有彩色顔料分散物（ＰＶ分散液）を得た。 [Preparation of chromatic pigment dispersion (PV dispersion)]
In the preparation of the colorant dispersion, the colorant is C.I. I. A chromatic pigment dispersion (PV dispersion) was obtained in the same manner except that Pigment Violet 23 (manufactured by Clariant) was used.
　実施例３３の硬化性組成物の調製において、硬化性組成物中でチタン窒化物含有粒子ＴｉＮ－１を５８質量％含有するように添加した着色剤分散液に代えて、上記のチタン窒化物含有粒子ＴｉＮ－１、ＰＹ、ＰＲ、ＰＢ、及びＰＶ分散液の混合物（硬化性組成物中のチタン窒化物含有粒子ＴｉＮ－１、ＰＹ、ＰＲ、ＰＢ、及びＰＶの比；チタン窒化物含有粒子ＴｉＮ－１：ＰＹ：ＰＲ：ＰＢ：ＰＶ＝７０：１７：３７：３６：１０（質量比）、硬化性組成物中のチタン窒化物含有粒子ＴｉＮ－１、ＰＹ、ＰＲ、ＰＢ、及びＰＶの合計含有量は５８質量％である。）を用いた他は同様にして硬化性組成物を調製し、これを用いて評価を行った。評価の結果、実施例３３と同様の評価（露光感度と、密着性を含む）が得られ、更に、赤外領域の遮光性が優れる膜が得られることが分かった。 In the preparation of the curable composition of Example 33, instead of the colorant dispersion added so as to contain 58% by mass of titanium nitride-containing particles TiN-1 in the curable composition, the above-mentioned titanium nitride-containing solution was used. Mixture of particles TiN-1, PY, PR, PB, and PV dispersion (ratio of titanium nitride-containing particles TiN-1, PY, PR, PB, and PV in the curable composition; titanium nitride-containing particles TiN −1: PY: PR: PB: PV = 70: 17: 37: 36: 10 (mass ratio), the total of titanium nitride-containing particles TiN-1, PY, PR, PB, and PV in the curable composition A curable composition was prepared in the same manner except that the content was 58% by mass.) And evaluated using this. As a result of the evaluation, it was found that the same evaluation (including exposure sensitivity and adhesion) as in Example 33 was obtained, and a film having excellent light shielding properties in the infrared region was obtained.
　実施例３３の硬化性組成物の調製において、硬化性組成物中でチタン窒化物含有粒子ＴｉＮ－１を５８質量％含有するように添加した着色剤分散液に代えて、上記のチタン窒化物含有粒子ＴｉＮ－１と以下に示す化合物ＳＱ－２３との混合物（硬化性組成物中のチタン窒化物含有粒子ＴｉＮ－１、及び化合物ＳＱ－２３の比；チタン窒化物含有粒子ＴｉＮ－１：化合物ＳＱ－２３＝５０：８（質量比）、硬化性組成物中のチタン窒化物含有粒子ＴｉＮ－１、及び化合物ＳＱ－２３の合計含有量は５８質量％である。）を用いた他は同様にして硬化性組成物を調製し、これを用いて評価を行った。評価の結果、実施例３３と同様の評価（露光感度と、密着性を含む）が得られ、更に、赤外領域の遮光性が優れる膜が得られることが分かった。 In the preparation of the curable composition of Example 33, instead of the colorant dispersion added so as to contain 58% by mass of titanium nitride-containing particles TiN-1 in the curable composition, the above-mentioned titanium nitride-containing solution was used. Mixture of particle TiN-1 and compound SQ-23 shown below (ratio of titanium nitride-containing particle TiN-1 and compound SQ-23 in the curable composition; titanium nitride-containing particle TiN-1: compound SQ −23 = 50: 8 (mass ratio), and the total content of titanium nitride-containing particles TiN-1 and compound SQ-23 in the curable composition is 58% by mass). A curable composition was prepared and evaluated using this. As a result of the evaluation, it was found that the same evaluation (including exposure sensitivity and adhesion) as in Example 33 was obtained, and a film having excellent light shielding properties in the infrared region was obtained.
　実施例３３の硬化性組成物の調製において、硬化性組成物中でチタン窒化物含有粒子ＴｉＮ－１を５８質量％含有するように添加した着色剤分散液に代えて、上記のチタン窒化物含有粒子ＴｉＮ－１と下記化合物Ａ－５２との混合物（硬化性組成物中のチタン窒化物含有粒子ＴｉＮ－１、及び化合物Ａ－５２の比；チタン窒化物含有粒子ＴｉＮ－１：化合物Ａ－５２＝５０：８（質量比）、硬化性組成物中のチタン窒化物含有粒子ＴｉＮ－１、及び化合物Ａ－５２との合計含有量は５８質量％である。）を用いた他は同様にして硬化性組成物を調製し、これを用いて評価を行った。評価の結果、実施例３３と同様の評価（露光感度と、密着性を含む）が得られ、更に、赤外領域の遮光性が優れる膜が得られることが分かった。 In the preparation of the curable composition of Example 33, instead of the colorant dispersion added so as to contain 58% by mass of titanium nitride-containing particles TiN-1 in the curable composition, the above-mentioned titanium nitride-containing solution was used. Mixture of particles TiN-1 and the following compound A-52 (ratio of titanium nitride-containing particles TiN-1 and compound A-52 in the curable composition; titanium nitride-containing particles TiN-1: compound A-52 = 50: 8 (mass ratio), and the total content of titanium nitride-containing particles TiN-1 and compound A-52 in the curable composition is 58% by mass). A curable composition was prepared and evaluated using this. As a result of the evaluation, it was found that the same evaluation (including exposure sensitivity and adhesion) as in Example 33 was obtained, and a film having excellent light shielding properties in the infrared region was obtained.
・化合物ＳＱ－２３
Figure JPOXMLDOC01-appb-C000060
 Compound SQ-23
Figure JPOXMLDOC01-appb-C000060
・化合物Ａ－５２（なお、下記式においてＰｈはフェニル基を表す。）
Figure JPOXMLDOC01-appb-C000061
 Compound A-52 (in the following formula, Ph represents a phenyl group)
Figure JPOXMLDOC01-appb-C000061
　実施例１において、界面活性剤Ｆ－１を用いなかった他は同様にして評価を行った。評価の結果、実施例１と同様の結果が得られることが分かった。
  Evaluation was conducted in the same manner as in Example 1 except that the surfactant F-1 was not used. As a result of the evaluation, it was found that the same result as in Example 1 was obtained.

Claims (24)

  1. 　多官能チオール化合物と、重合性化合物と、光重合開始剤とを含有する硬化性組成物であって、
    　前記多官能チオール化合物が、２個以上のチオール基と、チオール基とは異なる相互作用性基とを含有する硬化性組成物。     A curable composition containing a polyfunctional thiol compound, a polymerizable compound, and a photopolymerization initiator,
    The curable composition in which the polyfunctional thiol compound contains two or more thiol groups and an interactive group different from the thiol group.
  2. 　前記多官能チオール化合物が、式（１）で表される化合物である、請求項１に記載の硬化性組成物。
    Figure JPOXMLDOC01-appb-C000001
    　式中、Ｌ１、及び、Ｌ２はそれぞれ独立に２価の連結基を表し、ｍは２～１４の整数を表し、ｎは１～１５の整数を表し、Ｌ３はｍ＋ｎ価の連結基を表し、Ｒ１は前記チオール基とは異なる相互作用性基を表す。
    　なお、Ｌ１、及び、Ｌ２は、互いに、同一でも、異なってもよく、ｍ個のＬ１、ｎ個のＬ２、及び、ｎ個のＲ１は、それぞれ、同一でも、異なってもよい。     The curable composition of Claim 1 whose said polyfunctional thiol compound is a compound represented by Formula (1).
    Figure JPOXMLDOC01-appb-C000001
    In the formula, L 1 and L 2 each independently represent a divalent linking group, m represents an integer of 2 to 14, n represents an integer of 1 to 15, and L 3 represents an m + n valent linking group. R 1 represents an interactive group different from the thiol group.
    Note that L 1 and L 2 may be the same as or different from each other, and m L 1 , n L 2 , and n R 1 may be the same or different. Good.
  3. 　前記多官能チオール化合物が、式（２）で表される化合物である、請求項１又は２に記載の硬化性組成物。
    Figure JPOXMLDOC01-appb-C000002
    　式中、Ｒ２、及び、Ｒ３は、それぞれ独立に炭素数１以上の２価の連結基を表し、ｍは２～１４の整数を表し、ｎは１～１５の整数を表し、Ｍ１は、それぞれ独立に、単結合、－Ｏ－、－Ｓ－、－Ｎ（Ｒ４）－、－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｃ（＝Ｏ）－Ｏ－、－Ｃ（＝Ｏ）－ＮＨ－、－Ｏ－Ｃ（＝Ｏ）－ＮＨ－、－Ｓ（＝Ｏ）－、－Ｓ（＝Ｏ）－Ｏ－、－Ｓ（＝Ｏ）2－、－Ｓ（＝Ｏ）2－Ｏ－、又は－ＣＨ＝Ｎ－を表し、Ｒ４は１価の有機基を表し、Ｌ３はｍ＋ｎ価の連結基を表し、Ｒ１は前記チオール基とは異なる相互作用性基を表す。
    　なお、Ｒ２、及び、Ｒ３は、互いに、同一でも、異なってもよく、ｎ個のＲ１、ｍ個のＲ２、ｎ個のＲ２、ｎ個のＲ３、ｍ個のＭ１、及び、ｎ個のＭ１は、それぞれ、同一でも、異なってもよい。     The curable composition of Claim 1 or 2 whose said polyfunctional thiol compound is a compound represented by Formula (2).
    Figure JPOXMLDOC01-appb-C000002
    In the formula, R 2 and R 3 each independently represent a divalent linking group having 1 or more carbon atoms, m represents an integer of 2 to 14, n represents an integer of 1 to 15, and M 1 Each independently represents a single bond, —O—, —S—, —N (R 4 ) —, —C (═O) —, —C (═O) —O—, —O—C (═O ) —O—, —C (═O) —NH—, —O—C (═O) —NH—, —S (═O) —, —S (═O) —O—, —S (═O ) 2 —, —S (═O) 2 —O—, or —CH═N—, R 4 represents a monovalent organic group, L 3 represents an m + n valent linking group, and R 1 represents the above-mentioned It represents an interactive group different from a thiol group.
    R 2 and R 3 may be the same as or different from each other, and n R 1 , m R 2 , n R 2 , n R 3 , and m M 1. , And n M 1 s may be the same or different.
  4. 　前記ｍが３～１４の整数である、請求項２又は３に記載の硬化性組成物。 The curable composition according to claim 2 or 3, wherein m is an integer of 3 to 14.
  5. 　前記チオール基とは異なる相互作用性基が、ヒドロキシル基、アミノ基、ピリジニル基、ピリジニウム基、アンモニウム基、ホスホニウム基、カルボン酸基又はその塩、リン酸基又はその塩、スルホン酸基又はその塩、アリール基、－Ｓｉ（ＲＸ）ｐ（ＲＹ）３－ｐ、及び、－（ＯＲＡ）ｑ－ＲＺからなる群から選択される少なくとも１種である、請求項１～４のいずれか一項に記載の硬化性組成物。
    　なお、ｐは１～３の整数を表し、ＲＸは加水分解性基を表し、ＲＹは、加水分解性基を除く１価の有機基を表し、ｐ個のＲＸ、及び３－ｐ個のＲＹは、それぞれ、同一でも、異なってもよい。また、ＲＺは水素原子、アルキル基、又は、アルコキシ基を表し、ｑは１～４の整数を表し、ＲＡは炭素数１～１５のアルキレン基を表す。     The interactive group different from the thiol group is a hydroxyl group, amino group, pyridinyl group, pyridinium group, ammonium group, phosphonium group, carboxylic acid group or salt thereof, phosphoric acid group or salt thereof, sulfonic acid group or salt thereof The aryl group, —Si (R X ) p (R Y ) 3-p , and — (OR A ) q —R Z are at least one selected from the group consisting of The curable composition as described in any one.
    P represents an integer of 1 to 3, R X represents a hydrolyzable group, R Y represents a monovalent organic group excluding the hydrolyzable group, p R X , and 3-p Each R Y may be the same or different. R Z represents a hydrogen atom, an alkyl group, or an alkoxy group, q represents an integer of 1 to 4, and R A represents an alkylene group having 1 to 15 carbon atoms.
  6. 　前記チオール基とは異なる相互作用性基が、ヒドロキシル基、アミノ基、ピリジニル基、ピリジニウム基、アンモニウム基、ホスホニウム基、カルボン酸基又はその塩、リン酸基又はその塩、及びスルホン酸基又はその塩からなる群から選択される少なくとも１種である、請求項１～５のいずれか一項に記載の硬化性組成物。 An interactive group different from the thiol group is a hydroxyl group, amino group, pyridinyl group, pyridinium group, ammonium group, phosphonium group, carboxylic acid group or salt thereof, phosphoric acid group or salt thereof, and sulfonic acid group or salt thereof. The curable composition according to any one of claims 1 to 5, which is at least one selected from the group consisting of salts.
  7. 　前記チオール基とは異なる相互作用性基が、ヒドロキシル基、アミノ基、ピリジニル基、カルボン酸基又はその塩、リン酸基又はその塩、及び、スルホン酸基又はその塩からなる群から選択される少なくとも１種である、請求項１～６のいずれか一項に記載の硬化性組成物。 The interactive group different from the thiol group is selected from the group consisting of a hydroxyl group, an amino group, a pyridinyl group, a carboxylic acid group or a salt thereof, a phosphoric acid group or a salt thereof, and a sulfonic acid group or a salt thereof. The curable composition according to any one of claims 1 to 6, which is at least one kind.
  8. 　更に着色剤を含有する、請求項１～７のいずれか一項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 7, further comprising a colorant.
  9. 　前記着色剤が黒色顔料を含有する、請求項８に記載の硬化性組成物。 The curable composition according to claim 8, wherein the colorant contains a black pigment.
  10. 　前記光重合開始剤がオキシム化合物である請求項１～９のいずれか一項に記載の硬化性組成物。 The curable composition according to any one of claims 1 to 9, wherein the photopolymerization initiator is an oxime compound.
  11. 　請求項１～１０のいずれか一項に記載の硬化性組成物を硬化して得られる、硬化膜。 A cured film obtained by curing the curable composition according to any one of claims 1 to 10.
  12. 　請求項１１に記載の硬化膜を含有する、カラーフィルタ。 A color filter comprising the cured film according to claim 11.
  13. 　請求項１１に記載の硬化膜を含有する、遮光膜。 A light-shielding film containing the cured film according to claim 11.
  14. 　請求項１１に記載の硬化膜を含有する、固体撮像素子。 A solid-state imaging device containing the cured film according to claim 11.
  15. 　請求項１１に記載の硬化膜を含有する、画像表示装置。 An image display device comprising the cured film according to claim 11.
  16. 　請求項１～１０のいずれか一項に記載の硬化性組成物を用いて支持体上に硬化性組成物層を形成する、硬化性組成物層形成工程と、
    　前記硬化性組成物層を露光する、露光工程とを含有する硬化膜の製造方法。     A curable composition layer forming step of forming a curable composition layer on a support using the curable composition according to any one of claims 1 to 10;
    The manufacturing method of the cured film containing the exposure process which exposes the said curable composition layer.
  17. 　前記硬化性組成物層形成工程が、前記支持体上に前記硬化性組成物を塗布して、前記支持体上に前記硬化性組成物層を形成する工程を含む、請求項１６に記載の硬化膜の製造方法。 The said curable composition layer formation process includes the process of apply | coating the said curable composition on the said support body, and forming the said curable composition layer on the said support body. A method for producing a membrane.
  18. 　更に、露光された前記硬化性組成物層を現像する、現像工程と、
    　現像した前記硬化性組成物層を洗浄する、洗浄工程とを含有する、請求項１６又は１７に記載の硬化膜の製造方法。     And developing the exposed curable composition layer; and
    The manufacturing method of the cured film of Claim 16 or 17 containing the washing | cleaning process of wash | cleaning the developed said curable composition layer.
  19. 　２個以上のチオール基と、チオール基とは異なる相互作用性基とを含有する、多官能チオール化合物。 A polyfunctional thiol compound containing two or more thiol groups and an interactive group different from the thiol group.
  20. 　式（１）で表される化合物である、請求項１９に記載の多官能チオール化合物。
    Figure JPOXMLDOC01-appb-C000003
    　式中、Ｌ１、及びＬ２はそれぞれ独立に２価の連結基を表し、ｍは２～１４の整数を表し、ｎは１～１５の整数を表し、Ｌ３はｍ＋ｎ価の連結基を表し、Ｒ１は前記チオール基とは異なる相互作用性基を表す。
    　なお、Ｌ１、及び、Ｌ２は、互いに、同一でも、異なってもよく、ｍ個のＬ１、ｎ個のＬ２、及びｎ個のＲ１は、それぞれ、同一でも、異なってもよい。     The polyfunctional thiol compound of Claim 19 which is a compound represented by Formula (1).
    Figure JPOXMLDOC01-appb-C000003
    In the formula, L 1 and L 2 each independently represent a divalent linking group, m represents an integer of 2 to 14, n represents an integer of 1 to 15, and L 3 represents an m + n valent linking group. R 1 represents an interactive group different from the thiol group.
    Note that L 1 and L 2 may be the same as or different from each other, and m L 1 , n L 2 , and n R 1 may be the same or different. .
  21. 　式（２）で表される化合物である、請求項１９又は２０に記載の多官能チオール化合物。
    Figure JPOXMLDOC01-appb-C000004
    　式中、Ｒ２、及び、Ｒ３は、それぞれ独立に炭素数１以上の２価の連結基を表し、ｍは２～１４の整数を表し、ｎは１～１５の整数を表し、Ｍ１は、それぞれ独立に、単結合、－Ｏ－、－Ｓ－、－Ｎ（Ｒ４）－、－Ｃ（＝Ｏ）－、－Ｃ（＝Ｏ）－Ｏ－、－Ｏ－Ｃ（＝Ｏ）－Ｏ－、－Ｃ（＝Ｏ）－ＮＨ－、－Ｏ－Ｃ（＝Ｏ）－ＮＨ－、－Ｓ（＝Ｏ）－、－Ｓ（＝Ｏ）－Ｏ－、－Ｓ（＝Ｏ）2－、－Ｓ（＝Ｏ）2－Ｏ－、又は－ＣＨ＝Ｎ－を表し、Ｒ４は１価の有機基を表し、Ｌ３はｍ＋ｎ価の連結基を表し、Ｒ１は前記チオール基とは異なる相互作用性基を表す。
    　なお、Ｒ２、及び、Ｒ３は、互いに、同一でも、異なってもよく、ｎ個のＲ１、ｍ個のＲ２、ｎ個のＲ２、ｎ個のＲ３、ｍ個のＭ１、及び、ｎ個のＭ１は、それぞれ、同一でも、異なってもよい。     The polyfunctional thiol compound according to claim 19 or 20, which is a compound represented by the formula (2).
    Figure JPOXMLDOC01-appb-C000004
    In the formula, R 2 and R 3 each independently represent a divalent linking group having 1 or more carbon atoms, m represents an integer of 2 to 14, n represents an integer of 1 to 15, and M 1 Each independently represents a single bond, —O—, —S—, —N (R 4 ) —, —C (═O) —, —C (═O) —O—, —O—C (═O ) —O—, —C (═O) —NH—, —O—C (═O) —NH—, —S (═O) —, —S (═O) —O—, —S (═O ) 2 —, —S (═O) 2 —O—, or —CH═N—, R 4 represents a monovalent organic group, L 3 represents an m + n valent linking group, and R 1 represents the above-mentioned It represents an interactive group different from a thiol group.
    Incidentally, R 2 and,, R 3 are each, same with or may be different, n pieces of R 1, m pieces of R 2, n number of R 2, n number of R 3, m number of M 1 , And n M 1 s may be the same or different.
  22. 　前記ｍが３～１４の整数である、請求項２０又は２１に記載の多官能チオール化合物。 The polyfunctional thiol compound according to claim 20 or 21, wherein m is an integer of 3 to 14.
  23. 　前記チオール基とは異なる相互作用性基が、ヒドロキシル基、アミノ基、ピリジニル基、ピリジニウム基、アンモニウム基、ホスホニウム基、カルボン酸基又はその塩、リン酸基又はその塩、スルホン酸基又はその塩、アリール基、－Ｓｉ（ＲＸ）ｐ（ＲＹ）３－ｐ、及び、－（ＯＲＡ）ｑ－ＲＺからなる群から選択される少なくとも１種である、請求項１９～２２のいずれか一項に記載の多官能チオール化合物。
    　なお、ｐは１～３の整数を表し、ＲＸは加水分解性基を表し、ＲＹは、加水分解性基を除く１価の有機基を表し、ｐ個のＲＸ、及び３－ｐ個のＲＹは、それぞれ、同一でも、異なってもよい。また、ＲＺは水素原子、アルキル基、又は、アルコキシ基を表し、ｑは１～４の整数を表し、ＲＡは炭素数１～１５のアルキレン基を表す。     The interactive group different from the thiol group is a hydroxyl group, amino group, pyridinyl group, pyridinium group, ammonium group, phosphonium group, carboxylic acid group or salt thereof, phosphoric acid group or salt thereof, sulfonic acid group or salt thereof The aryl group, -Si (R X ) p (R Y ) 3-p , and-(OR A ) q -R Z are at least one selected from the group consisting of The polyfunctional thiol compound according to claim 1.
    P represents an integer of 1 to 3, R X represents a hydrolyzable group, R Y represents a monovalent organic group excluding the hydrolyzable group, p R X , and 3-p Each R Y may be the same or different. R Z represents a hydrogen atom, an alkyl group, or an alkoxy group, q represents an integer of 1 to 4, and R A represents an alkylene group having 1 to 15 carbon atoms.
  24. 　前記チオール基とは異なる相互作用性基が、ヒドロキシル基、アミノ基、ピリジニル基、ピリジニウム基、アンモニウム基、ホスホニウム基、カルボン酸基又はその塩、リン酸基又はその塩、及びスルホン酸基又はその塩からなる群から選択される少なくとも１種である、請求項１９～２３のいずれか一項に記載の多官能チオール化合物。
    　　　　　　　　　　　　　　　　　      An interactive group different from the thiol group is a hydroxyl group, amino group, pyridinyl group, pyridinium group, ammonium group, phosphonium group, carboxylic acid group or salt thereof, phosphoric acid group or salt thereof, and sulfonic acid group or salt thereof. The polyfunctional thiol compound according to any one of claims 19 to 23, which is at least one selected from the group consisting of salts.
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