Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/04—Acids; Metal salts or ammonium salts thereof
  • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/12—Esters of monohydric alcohols or phenols
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
  • C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
  • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/36—Amides or imides
  • C08F222/40—Imides, e.g. cyclic imides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
  • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
  • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F267/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00
  • C08F267/10—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00 on to polymers of amides or imides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/12—Polymers provided for in subclasses C08C or C08F
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/10—Esters; Ether-esters
  • C08K5/101—Esters; Ether-esters of monocarboxylic acids
  • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
• • 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
  • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
  • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
• • 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
• • 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
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
  • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
• • G—PHYSICS
  • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
  • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
  • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
  • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements

Definitions

• the present invention relates to polymers and photosensitive resin compositions thereof. More particularly, it relates to a polymer, and a photosensitive resin composition containing a polymer and a polyfunctional monomer.
• Curable resin compositions that can be cured by heat or active energy rays are used in various applications such as color filters, inks, printing plates, printed wiring boards, semiconductor elements, and photoresists used in liquid crystal display devices, solid-state imaging devices, and the like.
• Various applications have been studied for various applications such as optical members and electrical and electronic equipment, and curable resin compositions having excellent properties required for each application have been developed.
• Patent Document 1 discloses a colored resin composition containing (A) a dye, (B) a solvent, and (C) a binder resin. and a colored resin composition further containing (D) a specific antioxidant and (E) a specific ultraviolet absorber.
• a particularly preferred binder resin is a copolymer of an epoxy group-containing (meth)acrylate and another radically polymerizable monomer.
• a resin obtained by adding an acid, or an alkali-soluble resin (C-1) obtained by adding a polybasic acid anhydride to at least part of the hydroxyl groups generated by the addition reaction is described.
• Patent Document 1 it is required that the pattern diameter when the color filter resist is cured be close to the mask diameter during exposure.
• Patent Document 2 discloses a (meth)acrylic acid ester having a hydrocarbon group having 8 to 20 carbon atoms and (meth)acrylic acid. Including a polymer obtained by polymerizing a monomer component containing as a photosensitive A resin composition is described. In Patent Document 2, a resist binder is required to have high curability.
• the present invention provides a polymer that has a high development speed, can form a fine pattern, and can give a cured product having excellent fine line adhesion, and a photosensitive resin composition containing the polymer. intended to provide
• the present inventors have conducted various studies on polymers that can be used for optical members and electric and electronic equipment applications.
• a polymer having a structural unit having a structure and a specific structural unit By using a polymer having a structural unit having a structure and a specific structural unit, the position of the acid group in a specific range, and substantially having no ethylenically unsaturated double bond in the side chain, the development speed It gives a cured product (cured film) that has excellent adhesion (especially adhesion of fine lines) to the formed pattern without thickening or chipping of the pattern, even fine patterns of several ⁇ m level can be formed satisfactorily. I found out.
• the present inventors have found that a photosensitive resin composition containing such a polymer is particularly suitable as a resin composition for forming optical members such as color filters, and have completed the present invention. reached.
• ⁇ 1> A polymer having an acid group, the polymer having a structural unit having a ring structure in its main chain, and a homopolymer represented by the following general formula (1) having a Tg of ⁇ 5° C. or less.
• R 1 represents a hydrogen atom or a methyl group.
• R 2 represents a linear or branched hydrocarbon group having 6 to 20 carbon atoms.
• a polymer having an acid group the polymer having a structural unit having a ring structure in its main chain, and a homopolymer represented by the following general formula (1) having a Tg of ⁇ 5° C. or less. It has a structural unit derived from a monomer, the acid group has a distance of 6 atoms or less from the main chain, and the content ratio of the structural unit represented by the following general formula (2) is A polymer having a content of 5% by mass or less based on 100% by mass of all structural units.
• R 1 represents a hydrogen atom or a methyl group.
• R 2 represents a linear or branched hydrocarbon group having 6 to 20 carbon atoms.
• R 3 and R 4 are the same or different and represent a hydrogen atom or a methyl group.
• Z represents a divalent organic group.
• ⁇ 3> The polymer according to ⁇ 1> or ⁇ 2>, wherein the acid group is a carboxyl group derived from (meth)acrylic acid.
• ⁇ 4> The polymer according to any one of ⁇ 1> to ⁇ 3>, which has a structural unit derived from an N-substituted maleimide monomer. Further, the polymer is preferably a resist polymer.
• a photosensitive resin composition comprising the polymer according to any one of ⁇ 1> to ⁇ 4> and a polyfunctional monomer.
• ⁇ 6> The photosensitive resin composition according to ⁇ 5>, further comprising a photopolymerization initiator and a colorant.
• ⁇ 7> The photosensitive resin composition according to ⁇ 5> or ⁇ 6>, which is a color filter resist.
• ⁇ 8> A cured film obtained by curing the photosensitive resin composition according to any one of ⁇ 5> to ⁇ 7>.
• ⁇ 9> A display device member comprising the cured film according to ⁇ 8>.
• the polymer and photosensitive resin composition of the present invention can provide a cured product having a high development rate and excellent pattern formability and fine line adhesion.
• a polymer and photosensitive resin composition of the present invention can be used in optical members such as color filters, inks, printing plates, printed wiring boards, semiconductor elements, photoresists, etc., and electric machinery, which are used in liquid crystal display devices, solid-state imaging devices, and the like. - It can be suitably used for various applications such as electronic devices.
• the polymer of the present invention has an acid group (preferably has an acid group in a side chain), a structural unit having a ring structure in the main chain, and the following general formula (1),
• the Tg (glass transition temperature) of the homopolymer has a structural unit derived from a monomer of ⁇ 5° C. or less, and substantially does not have an ethylenically unsaturated double bond in the side chain, and the acid group is It is a polymer (also referred to as “polymer-1”) having 6 atoms or less between it and the main chain.
• R 1 represents a hydrogen atom or a methyl group.
• R 2 represents a linear or branched hydrocarbon group having 6 to 20 carbon atoms.
• the polymer of the present invention has an acid group (preferably has an acid group in a side chain), a structural unit having a ring structure in the main chain, and the following general formula (1)
• the homopolymer has a structural unit derived from a monomer whose Tg is ⁇ 5° C. or less, and the acid group has a distance of 6 atoms or less from the main chain, and is represented by the following general formula (2)
• a polymer also referred to as “polymer-2” having a structural unit content of 5% by mass or less with respect to 100% by mass of the total structural units of the polymer.
• R 1 represents a hydrogen atom or a methyl group.
• R 2 represents a linear or branched hydrocarbon group having 6 to 20 carbon atoms.
• R 3 and R 4 are the same or different and represent a hydrogen atom or a methyl group.
• Z represents a divalent organic group.
• the polymer-1 and polymer-2 of the present invention have the above constitution, the development speed is high, a fine pattern can be formed, and a cured product (cured film, fine line pattern) with excellent adhesion is provided. be able to.
• the polymer of the present invention has improved developability, pattern formability, and adhesion, and the position of the acid group in a specific range, that is, the distance between the main chain and the number of atoms is 6 or less. This improves the developability and adhesion, and substantially does not have an ethylenically unsaturated double bond in the side chain, so that curing due to diffracted light can be prevented during UV exposure, and the pattern can be made finer. presumed to have become possible. Details are given below.
• the polymer of the present invention has structural units containing acid groups. Since the polymer has an acid group, it becomes alkali-soluble and exhibits developability.
• the acid group is located at a position where the number of atoms between the acid group and the main chain is 6 or less.
• the presence of the acid group in a specific range of positions close to the main chain improves the developability of the polymer.
• the hydrocarbon group of the structural unit represented by the general formula (1) contained in the polymer has 6 to 20 carbon atoms (low Tg)
• the developing speed is further increased.
• a compound having an acid group or an acid anhydride is reacted with a vinyl monomer to form an acid group at a position distant from the vinyl group.
• a monomer having a group is synthesized and copolymerized using this monomer. For example, by reacting hydroxyethyl (meth)acrylate and maleic anhydride, it is possible to obtain a monomer having an acid group at a position distant from the vinyl group, and the copolymer is produced by copolymerizing this monomer.
• this polymer is used in the production of color filters, water is added during the post-curing process (heating process), and the maleic acid moiety is eliminated.
• the distance between the acid group and the main chain is 6 atoms or less, there is no need to use a compound having an acid group or a monomer obtained by reacting an acid anhydride with a vinyl monomer. Also, there is the advantage that the acid groups do not detach during the manufacturing process of the color filter, and the heat resistance, transparency, etc. of the polymer are less likely to deteriorate.
• the fact that the number of atoms between the main chain is 6 or less means that the number of atoms between the atom of the main chain to which the side chain is bonded and the atom to which the acid group is bonded on the side chain is 6 or less.
• the acid group X has a distance of 4 atoms from the main chain
• the structural unit represented by (a2) below the acid group X is , and the distance from the main chain is 6 atoms.
• the distance between the acid group and the main chain is assumed to be 0 atoms.
• the number of atoms between the acid group and the main chain is preferably 6 or less, more preferably 5 or less, particularly preferably 3 or less, and most preferably 0.
• the acid group is directly attached to the main chain.
• the acid group examples include functional groups capable of neutralizing reaction with alkaline water, such as carboxyl group, phenolic hydroxyl group, carboxylic acid anhydride group, phosphoric acid group, and sulfonic acid group.
• a carboxyl group or a carboxylic anhydride group is preferable, a carboxyl group is more preferable, and a (meth)acrylic acid group is even more preferable.
• the acid group is preferably a carboxyl group derived from (meth)acrylic acid
• the structural unit containing the acid group is preferably a structural unit derived from (meth)acrylic acid.
• a structural unit derived from methacrylic acid is particularly preferable in that the Tg of the entire resin can be increased and the fine wire adhesion can be improved.
• the combination of the structure represented by the above general formula (1) and a unit with a high Tg such as methacrylic acid improves the followability to the substrate, thereby improving the fine line adhesion. It is considered to be a thing.
• the content ratio of the structural unit containing the acid group is 1 to 50% by mass with respect to 100% by mass of the total structural units of the polymer, considering both developability and adhesion of the polymer. is preferred. It is more preferably 5% by mass or more, more preferably 45% by mass or less, even more preferably 40% by mass or less, and particularly preferably 35% by mass or less, based on 100% by mass of all structural units. That is, the content ratio of the structural unit containing the acid group is preferably 5 to 45% by mass, more preferably 5 to 40% by mass, and still more preferably 5 to 45% by mass, based on 100% by mass of the total structural units of the polymer. 35% by mass.
• the structural unit containing an acid group is preferably introduced by polymerizing an acid group-containing monomer (also referred to as "acid group-containing monomer (s)").
• the acid group-containing monomer (s) include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, cinnamic acid, and vinylbenzoic acid; maleic acid, fumaric acid, itaconic acid, citraconic acid; , unsaturated polycarboxylic acids such as mesaconic acid; maleic anhydride, unsaturated acid anhydrides such as itaconic anhydride; phosphoric acid group-containing unsaturated compounds such as Light Ester P-1M (manufactured by Kyoeisha Chemical); mentioned.
• unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, cinnamic acid, and vinylbenzoic acid
• carboxylic acid-based monomers (unsaturated monocarboxylic acids, unsaturated polyvalent carboxylic acids, unsaturated acid anhydrides) are preferably used from the viewpoint of versatility, availability, and the like. Unsaturated monocarboxylic acids are more preferred, and (meth)acrylic acid is even more preferred from the viewpoint of reactivity, heat-resistant color resistance, and the like.
• Polymer-1 of the present invention has substantially no ethylenically unsaturated double bonds in side chains. As a result, the sensitivity to light is lowered, so line thickening during exposure (formation of a pattern wider than the diameter of the exposure mask) is less likely to occur, and the pattern can be made finer.
• the ethylenically unsaturated double bond means a polymerizable double bond, ie, a carbon-carbon double bond. Having substantially no ethylenically unsaturated double bond in the side chain is a range in which the effect of the present invention is not exhibited. , in the range of 5% by mass or less, preferably 0 to 3% by mass, more preferably 0 to 1% by mass, still more preferably 0 to 0.5% by mass, based on 100% by mass of the total structural units of the polymer Range.
• the double bond equivalent of the polymer is preferably 3000 (g/mol) or more, most preferably 30000 (g/mol) or more. In the actual measurement of the double bond equivalent, it is in the range below the measurement limit value by various analyses, such as NMR and IR, and by the iodine value test method described in JIS K 0070:1992.
• Examples of the ethylenically unsaturated double bond include a (meth)acryloyl group, vinyl group, allyl group, methallyl group, and the like.
• the ethylenically unsaturated double bond is introduced into the polymer by, for example, reacting an epoxy group-containing monomer with the acid group of the polymer in order to increase reactivity. Do not introduce or substantially do not introduce.
• the epoxy group-containing monomer include compounds containing an epoxy group and a polymerizable double bond.
• the polymerizable double bond are the same as the ethylenically unsaturated double bond described above, and include a (meth)acryloyl group, a vinyl group, an allyl group, a methallyl group, and the like.
• an epoxy group includes not only a narrowly defined epoxy group, but also a group in which an oxirane ring is bonded to carbon such as a glycidyl group, an ether bond or an ester bond such as a glycidyl ether group and a glycidyl ester group. containing groups, epoxycyclohexane rings, and the like.
• epoxy group-containing monomer examples include glycidyl (meth)acrylate, ⁇ -methylglycidyl (meth)acrylate, ⁇ -ethylglycidyl (meth)acrylate, vinylbenzyl glycidyl ether, allyl glycidyl ether, (meth) ) (3,4-epoxycyclohexyl)methyl acrylate, vinylcyclohexene oxide and the like.
• Examples of the structural unit containing an ethylenically unsaturated double bond in the side chain include structural units represented by the following general formula (2).
• R 3 and R 4 are the same or different and represent a hydrogen atom or a methyl group.
• Z represents a divalent organic group.
• Various organic groups are exemplified depending on the structure of the epoxy group-containing monomer.
• Z includes, for example, an organic group represented by the following general formula (61) or (62).
• * 1 in the following general formulas (61) and (62) is the position of bonding to the oxygen atom on the main chain side of the polymer
• * 2 is the side chain ethylenically unsaturated double bond side This is the position where the oxygen atom is bonded.
• the content ratio of the structural unit represented by the general formula (2) is 5% by mass or less with respect to 100% by mass of the total structural units of the polymer. It is particularly preferred that the polymer-2 substantially does not contain the structural unit. Specifically, the content ratio of the structural unit represented by the general formula (2) is preferably 3% by mass or less with respect to 100% by mass of the total structural units of the polymer from the viewpoint of pattern refinement. , is more preferably 1% by mass or less, particularly preferably 0.5% by mass or less, and most preferably 0% by mass.
• the content of structural units containing ethylenically unsaturated double bonds in the side chains is the same as that of the entire structure of the polymer. It is preferably 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less, and particularly 0.5% by mass or less with respect to 100% by mass of the unit. Preferably, it is 0% by weight, most preferably.
• Examples of the structural unit containing an ethylenically unsaturated double bond in the side chain of the polymer-2 are the same as those of the polymer-1.
• the polymer of the present invention has a structural unit having a ring structure in its main chain and a structural unit represented by the general formula (1). Each structural unit will be explained.
• a structural unit having a ring structure in its main chain is hereinafter also referred to as "structural unit (A)".
• the heat resistance of the polymer of the present invention can be improved, and the adhesiveness of the cured product can be improved.
• Having a ring structure in the main chain improves the thermal decomposition resistance of the polymer, so it is thought that the fine line adhesion of the cured film is also ensured. Further, it is considered that fine line adhesion is further improved by combining with methacrylic acid as an acid compound.
• Examples of the monomer that gives the structural unit (A) include a monomer having a double bond-containing ring structure in the molecule, and a monomer that forms a polymer having a ring structure in the main chain by cyclopolymerization. etc. 1 type, or 2 or more types are suitable.
• Such monomers include N-substituted maleimide-based monomers, dialkyl-2,2′-(oxydimethylene) diacrylate-based monomers, and ⁇ -(unsaturated alkoxyalkyl) acrylate-based monomers. It is preferred to use at least one selected from the group consisting of mers.
• Such structural units having a ring structure in the main chain include N-substituted maleimide-based monomer units (structural units derived from N-substituted maleimide monomers), dialkyl-2,2′-(oxydimethylene)di At least one selected from the group consisting of acrylate-based monomer units and ⁇ -(unsaturated alkoxyalkyl) acrylate-based monomer units is suitable.
• a polymer containing an N-substituted maleimide-based monomer unit can provide a cured product having improved heat resistance, dispersibility (for example, dispersibility of coloring material), hardness, and the like.
• the polymer containing the above-mentioned monomer unit means a polymer containing a structural unit derived from the monomer by polymerization reaction or crosslinking reaction of the monomer, for example.
• N-substituted maleimide-based monomers examples include N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, Nt-butylmaleimide, and N-dodecylmaleimide.
• N-benzylmaleimide, N-naphthylmaleimide and the like, and one or more of these can be used.
• N-cyclohexylmaleimide, N-phenylmaleimide, and N-benzylmaleimide are preferred, and N-benzylmaleimide is particularly preferred, in view of less coloring and excellent dispersibility.
• N-benzylmaleimide examples include benzylmaleimide; alkyl-substituted benzylmaleimide such as p-methylbenzylmaleimide and p-butylbenzylmaleimide; phenolic hydroxyl group-substituted benzylmaleimide such as p-hydroxybenzylmaleimide; o-chlorobenzylmaleimide. , o-dichlorobenzylmaleimide, p-dichlorobenzylmaleimide and other halogen-substituted benzylmaleimides.
• N-phenylmaleimide examples include phenylmaleimide; alkyl-substituted phenylmaleimide such as p-methylphenylmaleimide and p-butylphenylmaleimide; phenolic hydroxyl group-substituted phenylmaleimide such as p-hydroxyphenylmaleimide; o-chlorophenylmaleimide; Halogen-substituted phenylmaleimides such as o-dichlorophenylmaleimide and p-dichlorophenylmaleimide are included.
• dialkyl-2,2'-(oxydimethylene) diacrylate-based monomer from the viewpoint of less coloring, dispersibility, and ease of industrial availability, for example, dimethyl-2,2'-[ Oxybis(methylene)]bis-2-propenoate and the like are preferably used.
• Examples of the ⁇ -(unsaturated alkoxyalkyl) acrylate monomers include ⁇ -allyloxymethyl acrylic acid, methyl ⁇ -allyloxymethyl acrylate, ethyl ⁇ -allyloxymethyl acrylate, ⁇ -allyloxymethyl n-propyl acrylate, i-propyl ⁇ -allyloxymethyl acrylate, n-butyl ⁇ -allyloxymethyl acrylate, s-butyl ⁇ -allyloxymethyl acrylate, t-butyl ⁇ -allyloxymethyl acrylate, ⁇ -Allyloxymethyl acrylate n-amyl, ⁇ -Allyloxymethyl acrylate s-amyl, ⁇ -Allyloxymethyl acrylate t-amyl, ⁇ -Allyloxymethyl acrylate neopentyl acrylate, ⁇ -Allyloxymethyl acrylate n -hexyl, s-hexyl ⁇ -
• alkyl-( ⁇ -methallyloxymethyl) acrylate monomers are also preferred.
• methyl ⁇ -allyloxymethyl acrylate also referred to as ⁇ -(allyloxymethyl)methyl acrylate
• ⁇ -(allyloxymethyl)methyl acrylate is particularly preferred.
• the ⁇ -(unsaturated alkoxyalkyl) acrylate-based monomer can be produced, for example, by the production method disclosed in WO 2010/114077 pamphlet.
• the polymer may have only one type of the structural unit (A), or may have two or more types of the structural unit (A).
• the content of the structural unit (A) is 0.5 to 50% by mass with respect to 100% by mass of the total structural units of the polymer, considering both developability and adhesion of the polymer. is preferred.
• the content of the structural unit (A) is more preferably 1% by mass or more, still more preferably 2% by mass or more, and more preferably 45% by mass with respect to 100% by mass of the total structural units of the polymer. 40% by mass or less, more preferably 40% by mass or less. That is, the content of the structural unit (A) is more preferably 1 to 45% by mass, still more preferably 2 to 40% by mass, based on 100% by mass of all structural units in the polymer.
• the structural unit represented by the following general formula (1) is hereinafter also referred to as "structural unit (B)".
• the structural unit (B) is preferably a structural unit derived from a monomer having a homopolymer Tg (Tg as a homopolymer) of ⁇ 5° C. or less.
• the polymer of the present invention has a structural unit (B) derived from a monomer having a homopolymer Tg of ⁇ 5° C. or less, so that the developing solution during development can easily permeate and the development speed can be increased. can. In addition, miniaturization of patterns can be achieved.
• the Tg of the homopolymer is preferably ⁇ 10° C. or lower, more preferably ⁇ 20° C.
• Tg of the above homopolymer is -60°C.
• a Tg of ⁇ 60° C. or lower is not suitable because the developability is so improved that a pattern smaller than the mask diameter is formed. That is, by setting the range of Tg as described above, a pattern diameter close to the mask diameter can be obtained.
• R 1 represents a hydrogen atom or a methyl group. From the viewpoint of development speed, R 1 is preferably a hydrogen atom.
• R 2 represents a linear or branched hydrocarbon group having 6 to 20 carbon atoms.
• the linear or branched hydrocarbon group having 6 to 20 carbon atoms include 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,2,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group, 1-ethyl-2-methylpropyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecy
• the linear or branched hydrocarbon group having 6 to 20 carbon atoms is preferably a linear or branched hydrocarbon group having 6 to 18 carbon atoms, and a linear or branched hydrocarbon group having 6 to 14 carbon atoms. or a branched hydrocarbon group is more preferred, and a branched hydrocarbon group having 7 to 12 carbon atoms is particularly preferred. If the number of carbon atoms is selected within the above range, adhesion to the substrate is improved. The reason is due to the hydrophobic interactions of the carbon chains. If the number of carbon atoms is less than 6, the hydrophobic interaction is weak and adhesion is reduced. On the other hand, if the number of carbon atoms is 21 or more, the hydrophobic interaction is improved and the adhesion is improved. be.
• R 2 above include preferably n-octyl group, n-dodecyl group, 2-ethylhexyl group, 2-ethylbutyl group and n-stearyl group, and more preferably 2-ethylhexyl group. be done.
• a branched chain of R2 is more likely to effectively express a hydrophobic interaction than a straight chain, and is excellent in fine wire adhesiveness.
• a polymer having the structural unit (B) can be obtained by polymerizing a monomer component containing such a monomer compound. Examples of R 1 and R 2 in general formula (1-1) are the same as R 1 and R 2 in general formula (1) above.
• the monomers that provide the structural unit (B) are preferably n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-ethylbutyl (meth)acrylate, (meth) ) n-dodecyl acrylate, n-octadecyl (meth)acrylate and the like, and more preferably 2-ethylhexyl (meth)acrylate.
• the polymer may have only one type of structural unit (B), or may have two or more types of structural units (B).
• the content of the structural unit (B) is 10% by mass or more with respect to 100% by mass of the total structural units of the polymer, in consideration of compatibility between developability, pattern formability, and adhesion of the polymer. is preferred.
• the content of the structural unit (B) is more preferably 15% by mass or more, still more preferably 20% by mass or more, and preferably 80% by mass or less, relative to 100% by mass of all the structural units.
• it is 70% by mass or less. That is, the content of the structural unit (B) is preferably 10 to 80% by mass, more preferably 15 to 70% by mass, still more preferably 20 to 70% by mass, relative to 100% by mass of the total structural units of the polymer. % by mass.
• the polymer of the present invention may also have a ring structure in its side chain. That is, the polymer may have a structural unit having a ring structure in its side chain (hereinafter also referred to as "structural unit (C)").
• structural unit (C) structural unit having a ring structure in its side chain
• the hydrophobicity of the polymer can be improved, and for example, the solvent resistance can be improved.
• the ring structure examples include an aromatic ring structure such as benzene, or an alicyclic structure such as a cyclohexane skeleton, an adamantane skeleton, and a norbornene skeleton.
• an aromatic ring structure such as benzene
• an alicyclic structure such as a cyclohexane skeleton, an adamantane skeleton, and a norbornene skeleton.
• aromatic hydrocarbon group examples include aryl groups such as benzyl, tolyl, naphthyl and biphenyl.
• the above alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms.
• Specific examples of the alicyclic hydrocarbon group include monocyclic hydrocarbon groups such as cyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, cycloheptyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl; Examples include polycyclic hydrocarbon groups such as pentanyl, dicyclopentenyl, tricyclodecanyl, adamantyl, and isobornyl. These may have a substituent.
• Examples of the polymerizable double bond are the same as the ethylenically unsaturated double bond described above, and include a (meth)acryloyl group, a vinyl group, an allyl group, a methallyl group, and the like. Among them, a (meth)acryloyl group is preferred in terms of reactivity.
• monomers that provide the structural unit (C) include cyclohexyl (meth)acrylate, cyclohexylmethyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, (3 , 4-epoxycyclohexyl)methyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, tricyclodecanyl (meth)acrylate, dimethylol- Alicyclic hydrocarbon group-containing monomers such as tricyclodecane di(meth)acrylate, pentacyclopentadecanedimethanol di(meth)acrylate, cyclohexanedimethanol di(meth)acrylate, norbornanedimethanol di(meth)acrylate; Aromatic hydrocarbon group-containing monomers such as benzyl (meth)acrylate and
• the content of the structural unit (C) is preferably 1 to 60% by mass, more preferably 5 to 50% by mass, relative to 100% by mass of the total structural units of the polymer. It is more preferably 40% by mass.
• the polymer may have only one type of the structural unit (C), or may have two or more types of the structural unit (C).
• the above polymer may further have other structural units (D) as necessary.
• the other structural unit (D) for example, a (meth)acrylic acid ester-based monomer other than the monomer that provides the structural unit (B), a hydroxyl group-containing monomer, or other copolymerizable and structural units derived from such monomers.
• Examples of the (meth)acrylic acid ester-based monomer other than the monomer giving the structural unit (B) include methyl (meth)acrylate, ethyl (meth)acrylate, and n-propyl (meth)acrylate.
• hydroxyl group-containing monomers examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 2-hydroxybutyl (meth)acrylate. , 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and 2,3-hydroxypropyl (meth)acrylate.
• Examples of other copolymerizable monomers include one or more of the following compounds.
• (Meth)acrylamides such as N,N-dimethyl (meth)acrylamide and N-methylol (meth)acrylamide; polystyrene, polymethyl (meth)acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone, polycaprolactam and the like; Macromonomers having a (meth)acryloyl group at one end of the combined molecular chain; Conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate Class; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl
• the content of the structural unit (D) is preferably 0 to 60% by mass, more preferably 0.5 to 50% by mass, and still more preferably 1 ⁇ 40% by mass.
• the weight average molecular weight of the polymer is preferably 3,000 to 50,000. When the weight-average molecular weight is within the above range, the viscosity can be adjusted to an appropriate range, the handleability is good, and the adhesion and developability are further improved.
• the weight average molecular weight is more preferably 4,000 to 30,000, even more preferably 5,000 to 20,000, and particularly preferably 5,000 to 15,000. In the present specification, the weight average molecular weight can be determined by the method described in Examples below.
• the acid value of the polymer is preferably 50-200 mgKOH/g.
• the acid value is more preferably 60 to 150 mgKOH/g, even more preferably 70 to 150 mgKOH/g.
• the acid value can be determined by the method described in Examples below.
• the glass transition temperature (Tg) of the polymer is preferably 100° C. or lower. When the glass transition temperature is within the above range, the developability and adhesion are excellent.
• the glass transition temperature is preferably 90° C. or lower, more preferably 80° C. or lower, and even more preferably 70° C. or lower. From the viewpoint of heat resistance, the glass transition temperature is preferably ⁇ 20° C. or higher, more preferably 0° C. or higher, and particularly preferably 20° C. or higher. That is, the glass transition temperature (Tg) of the polymer is preferably -20 to 100°C, more preferably 0 to 90°C, still more preferably 20 to 80°C, and particularly preferably 20 to 70°C. In the present specification, the glass transition temperature can be determined by the method described in Examples below.
• the method for obtaining the polymer is not particularly limited, but for example, the monomer (a) that gives the structural unit (A) described above, the monomer (b) that gives the structural unit (B) described above, and the above It is preferably a polymer obtained by polymerizing a monomer component containing at least the acid group-containing monomer (s). The synthesis method will be described below.
• the monomer component used for polymerization is a monomer component containing at least the above monomer (a), the above monomer (b), and the above acid group-containing monomer (s).
• the ratio of each monomer shown in the monomer component is not particularly limited as long as a polymer having excellent developability and adhesiveness to a cured product can be obtained.
• the monomers (a) and (b) , (s) content is 0.5 to 50% by mass of the monomer (a) and 15 to 80% of the monomer (b) with respect to 100% by mass of the total amount of the monomer components that give the polymer. mass%, the monomer (s) is preferably 1 to 50 mass%, the monomer (a) 1 to 40 mass%, the monomer (b) 20 to 70 mass%, the monomer More preferably, the body (s) is 5 to 35% by mass.
• the monomer component that gives the polymer is the monomer (a), the monomer (b), the monomer (s), and the monomer that gives the structural unit (C)
• the content of each monomer is 0.5 to 50% by mass of the monomer (a) with respect to 100% by mass of the total amount of monomer components that give the polymer, and the above monomer
• the body (b) is 15 to 80% by mass
• the monomer (s) is 1 to 50% by mass
• the monomer (c) is 1 to 60% by mass. 40% by mass, 20 to 70% by mass of the monomer (b), 5 to 35% by mass of the monomer (s), and 5 to 40% by mass of the monomer (c).
• the monomer components that give the polymer are the monomer (a), the monomer (b), the monomer (s), the monomer (c), and the structural unit described above.
• the content ratio of each monomer is 0.5 for the monomer (a) with respect to the total amount of 100% by mass of the monomer components that give the polymer ⁇ 50% by mass, the monomer (b) 15 to 80% by mass, the monomer (s) 1 to 50% by mass, the monomer (c) 1 to 60% by mass, the monomer (d ) is preferably 1 to 60 mass%, the monomer (a) 1 to 40 mass%, the monomer (b) 20 to 70 mass%, the monomer (s) 5 to 35 mass% , 5 to 40% by mass of the monomer (c) and 1 to 40% by mass of the monomer (d).
• the method for polymerizing the above monomer component is not particularly limited, and commonly-used techniques such as bulk polymerization, solution polymerization, and emulsion polymerization can be used, and can be appropriately selected according to the purpose and application. Among them, solution polymerization is industrially advantageous, and structural adjustment such as molecular weight is easy, and therefore, it is preferable.
• a polymerization method based on a mechanism such as radical polymerization, anionic polymerization, cationic polymerization, or coordination polymerization can be used. is also advantageous, so it is preferable.
• Preferred forms of the polymerization reaction are as described in [0062] to [0072] of JP-A-2016-29151.
• the polymerization initiation method in the above polymerization reaction may be performed by supplying energy necessary for polymerization initiation from an active energy source such as heat, electromagnetic waves (e.g., infrared rays, ultraviolet rays, X-rays, etc.), electron beams, etc. to the monomer components.
• an active energy source such as heat, electromagnetic waves (e.g., infrared rays, ultraviolet rays, X-rays, etc.), electron beams, etc.
• an initiator is preferable because the energy required for polymerization initiation can be greatly reduced and the reaction can be easily controlled.
• the molecular weight of the polymer obtained by polymerizing the above monomer components can be controlled by adjusting the amount and type of the polymerization initiator, the polymerization temperature, the type and amount of the chain transfer agent, and the like.
• Examples of the polymerization initiator include peroxides and azo compounds that are commonly used as polymerization initiators.
• Examples of the chain transfer agent include compounds having a mercapto group, such as alkylmercaptans, mercaptocarboxylic acids, and mercaptocarboxylic acid esters, which are commonly used as chain transfer agents. These may be used individually by 1 type, or may be used in combination of 2 or more type. Moreover, the amount of these additives can be appropriately set by a known method.
• solvents used in the polymerization include alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether; ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; Ketones such as acetone and methyl ethyl ketone; Esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate and 3-methoxybutyl acetate; Aromatic hydrocarbons such as toluene, xylene and ethylbenzene; Chloroform; etc. These solvents may be used alone or in combination of two or more.
• an epoxy group-containing monomer may be added to a part of the acid groups contained in the polymer as long as the effect of the present invention is not impaired.
• the reaction method is not particularly limited, and a known method may be appropriately employed.
• the reaction temperature is preferably 60 to 140°C.
• Amine compounds such as triethylamine and dimethylbenzylamine; ammonium salts such as tetraethylammonium chloride; phosphonium salts such as tetraphenylphosphonium bromide; and amide compounds such as dimethylformamide.
• the amount of the epoxy group-containing monomer used is such that the content ratio of the structural unit represented by the general formula (2) is 5% by mass or less with respect to 100% by mass of the total structural units of the polymer. 3% by mass or less is more preferable, 0.5% by mass or less is particularly preferable, and 0% by mass is most preferable. For example, it is preferably 0 to 5 parts by mass, more preferably 0 to 3 parts by mass, and more preferably 0 to 1 part by mass with respect to 100 parts by mass of the total amount of monomer components that give the polymer. It is particularly preferable and most preferably 0 to 0.5 parts by mass (a range in which it is substantially absent). As a result, fine line adhesion is further improved, and pattern miniaturization becomes possible.
• the final solid content concentration of the polymer solution is 10 to 70% by mass.
• the final solid content is more preferably 20 to 65% by mass, more preferably 25 to 60% by mass.
• the polymer of the present invention is excellent in developability and can give a cured product (cured film, fine pattern) excellent in pattern formability and fine line adhesion. Therefore, it is useful as a resist polymer and an alkali-developable negative resist material for producing colored pixels of color filters, black matrices, black column spacers, overcoats, photospacers, optical waveguides, and the like. Moreover, since it has good colorant dispersibility, it is also useful for a colored photosensitive resin composition for color filters.
• the above polymer is particularly preferably used as an alkali-soluble resin or the like for binder resins for color resists, and the above polymer is extremely useful as a component of a photosensitive resin composition.
• Photosensitive resin composition The polymer described above can be made into a photosensitive resin composition further containing a polyfunctional monomer. Moreover, it can be made into the photosensitive resin composition containing a photoinitiator and a coloring material as needed. Since the photosensitive resin composition contains the polymer, the development speed is high, and a cured product having excellent pattern formability and fine line adhesion can be obtained. In addition, by further including a polyfunctional monomer, it is possible to give a cured product excellent in various physical properties such as curability of the resin composition, adhesion to substrates, mechanical strength and heat resistance. A photosensitive resin composition containing such a polymer and a polyfunctional monomer is also one aspect of the present invention. Although the application is not limited, it is suitably used as a material for forming a protective film for colored pixels of color filters, color filters, liquid crystal display elements, integrated circuit elements, solid-state imaging elements, and the like.
• the content of the polymer is preferably 5% by mass or more and 70% by mass or less with respect to 100% by mass of the total solid content of the photosensitive resin composition.
• the effects of the present invention can be exhibited more remarkably. More preferably 10 to 65% by mass, still more preferably 10 to 50% by mass, particularly preferably 10 to 40% by mass, still more preferably 10 to 35% by mass, most preferably 15 to 35% by mass.
• total solid content means the total amount of components forming the cured product (excluding the solvent and the like that volatilize during the formation of the cured product).
• the polyfunctional monomer can be polymerized by irradiation with free radicals, electromagnetic waves (e.g., infrared rays, ultraviolet rays, X-rays, etc.), active energy rays such as electron beams, etc., polymerizable unsaturated bonds (polymerization It is a low-molecular-weight compound having a polyunsaturated group). Examples thereof include polyfunctional compounds having two or more polymerizable unsaturated groups in the molecule. Although the molecular weight of the polyfunctional monomer is not particularly limited, it is preferably 3,000 or less, more preferably 2,000 or less, from the viewpoint of handling.
• a bifunctional or higher polyfunctional (meth)acrylate compound (hereinafter also simply referred to as “polyfunctional (meth)acrylate compound”) is particularly preferred. It is a compound having two or more (meth)acryloyl groups in one molecule. By containing such a compound, the photosensitive resin composition becomes excellent in photosensitivity and curability, and it becomes possible to obtain a cured film (fine pattern) with high hardness and high adhesion.
• the functionality of the polyfunctional (meth)acrylate compound is preferably 3 or more, more preferably 4 or more, still more preferably 5 or more.
• the functional number is preferably 10 or less, more preferably 8 or less, and still more preferably 6 or less. That is, the functional number of the polyfunctional (meth)acrylate compound is preferably 3-10, more preferably 4-8, still more preferably 5-6.
• polyfunctional monomer examples include (di)ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol di(meth) ) acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta Polyfunctional (meth)acrylates such as (meth)acrylate, dipentaerythritol hexa(meth)acrylate, tris(hydroxyethyl)isocyanurate tri(meth)acrylate, and the like.
• trimethylolpropane tri(meth)acrylate pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-added dipentaerythritol hexa(meth)acrylate, propylene oxide-added trimethylolpropane tri(meth)acrylate, ) acrylate, propylene oxide-added ditrimethylolpropane tetra(meth)acrylate, propylene oxide-added pentaerythritol tetra(meth)acrylate, propylene oxide-added dipentaerythritol hexa(meth)acrylate, ⁇ -caprolactone-added trimethylolpropane tri(meth)acrylate , ⁇ -caprolactone-added ditrimethylolpropane tetra(meth)acrylate, ⁇ -caprolactone
• the content of the polyfunctional monomer may be appropriately set according to the type of the polyfunctional monomer and the polymer used, as well as the purpose and application. It is preferably 2% by mass or more and preferably 85% by mass or less with respect to 100% by mass of the total solid content of the photosensitive resin composition.
• the lower limit is more preferably 5% by mass or more, still more preferably 10% by mass or more, particularly preferably 15% by mass or more, and the upper limit is more preferably 75% by mass or less, still more preferably 60% by mass or less, and particularly preferably. is 50 mass % or less, most preferably 40 mass % or less.
• the content of the polyfunctional monomer is more preferably 5 to 75% by mass, still more preferably 10 to 60% by mass, particularly preferably 15 to 50% by mass, relative to 100% by mass of the total solid content of the photosensitive resin composition. % by weight, most preferably 15 to 40% by weight.
• content of the said polyfunctional monomer is 50 to 500 mass parts with respect to 100 mass parts of polymers.
• content of the polyfunctional monomer is within this range, a cured film having a higher surface hardness can be obtained, and the developability is further improved, coupled with the preferable weight-average molecular weight of the polymer being 3000 or more.
• it is more preferably 400 parts by mass or less. More preferably 300 parts by mass or less, particularly preferably 200 parts by mass or less, and most preferably 150 parts by mass or less.
• the content of the polyfunctional monomer is more preferably 80 to 400 parts by mass, more preferably 100 to 300 parts by mass, particularly preferably 120 to 200 parts by mass, most preferably 120 parts by mass, relative to 100 parts by mass of the polymer. ⁇ 150 parts by mass.
• photopolymerization initiators include alkylphenone-based compounds, aminoketone-based compounds, benzophenone-based compounds, benzoin-based compounds, thioxanthone-based compounds, halomethylated triazine-based compounds, halomethylated oxadiazole-based compounds, biimidazole-based compounds, and oximes.
• photopolymerization initiators such as ester-based compounds, oxime ether-based compounds, titanocene-based compounds, benzoic acid ester-based compounds, and acridine-based compounds can be used.
• the photopolymerization initiator it is preferable to use an alkylphenone compound, an aminoketone compound, an oxime ester compound, an oxime ether compound, and 2-methyl-1-[4-(methylthio)phenyl]- 2-morpholinopropan-1-one (“IRGACURE907”, manufactured by BASF), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (“IRGACURE369”, manufactured by BASF), etc.
• Alkylphenone compounds 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime) ("OXE01", manufactured by BASF), ethanone, 1-[9- Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime) (“OXE02”, manufactured by BASF), 1,2-octanedione, 1-[4 -(phenylthio)-,2-,(O-benzoyloxime)], ethanone ("OXE03", manufactured by BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3- It is more preferable to use an oxime ester compound such as yl]-,1-(O-acetyloxime) (“OXE04”, manufactured by BASF).
• the photopolymerization initiators may be used singly or in combination of two
• the photosensitive resin composition preferably further contains an aminoketone-based polymerization initiator. As a result, the hardness and adhesion are further improved.
• the content of the photopolymerization initiator may be appropriately set according to the purpose, application, etc., and is not particularly limited. It is preferable to have Thereby, a cured film having excellent adhesion can be obtained. It is more preferably 1 part by mass or more, still more preferably 1.5 parts by mass or more. Further, considering the influence of the decomposed product of the photopolymerization initiator and the balance with economic efficiency, etc., it is preferably 30 parts by mass or less. It is more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less.
• the content of the photopolymerization initiator is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, more preferably 1 part by mass with respect to 100 parts by mass of the total solid content of the photosensitive resin composition. .5 to 10 parts by mass.
• photosensitizers and photoradical polymerization accelerators that may be used in combination with the photopolymerization initiator include dye compounds such as xanthene dyes, coumarin dyes, 3-ketocoumarin compounds, and pyrromethene dyes; dialkylaminobenzene-based compounds such as ethyl dimethylaminobenzoate and 2-ethylhexyl 4-dimethylaminobenzoate; mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole and 2-mercaptobenzimidazole; be done.
• dye compounds such as xanthene dyes, coumarin dyes, 3-ketocoumarin compounds, and pyrromethene dyes
• dialkylaminobenzene-based compounds such as ethyl dimethylaminobenzoate and 2-ethylhexyl 4-dimethylaminobenzoate
• mercaptan-based hydrogen donors such as
• the photosensitive resin composition (preferably negative photosensitive resin composition) of the present invention preferably contains a colorant.
• the coloring material include pigments and dyes.
• the coloring material either a pigment or a dye may be used, or a combination of the pigment and the dye may be used.
• a pigment or a dye may be used, or a combination of the pigment and the dye may be used.
• a black coloring material when forming red, blue, and green pixels of a color filter, it is preferable to use a known technique that achieves desired color characteristics by appropriately combining color materials such as blue and purple, green and yellow, and the like.
• a black matrix or a black column spacer it is preferable to use a black coloring material.
• pigments are preferred from the standpoint of durability, and dyes are preferred from the standpoint of improving the luminance of panels and the like. These can be appropriately selected according to the properties required.
• a pigment is preferable because the heat-resistant coloring resistance of the cured product can be further improved.
• Pigments similar to those described in JP-A-2015-157909 can be used.
• the above pigments are not particularly limited, but examples include azo pigments, phthalocyanine pigments, polycyclic pigments (quinacridone-based, perylene-based, perinone-based, isoindolinone-based, isoindoline-based, dioxazine-based, thioindigo-based, and anthraquinone-based pigments).
• organic pigments such as dye lake-based pigments; white and extender pigments (titanium oxide, zinc oxide, zinc sulfide, clay, talc, barium sulfate, calcium carbonate, etc.) , Chromatic pigments (yellow, cadmium, chrome vermilion, nickel titanium, chrome titanium, yellow iron oxide, red iron oxide, zinc chromate, red lead, ultramarine blue, Prussian blue, cobalt blue, chrome green, chromium oxide, bismuth vanadate, etc.) ), black pigments (carbon black, bone black, graphite, iron black, titanium black, etc.), luster pigments (pearl pigments, aluminum pigments, bronze pigments, etc.), fluorescent pigments (zinc sulfide, strontium sulfide, strontium aluminate, etc.) inorganic pigments such as;
• the dye examples include organic dyes described in JP-A-2010-9033, JP-A-2010-211198, JP-A-2009-51896, and JP-A-2008-50599. can. Among them, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes and the like are preferable. These colorants may be used singly or in combination of two or more.
• the content ratio of the coloring material is not particularly limited, and can be appropriately set according to the purpose and application. 80 mass %, more preferably 5 to 70 mass %, still more preferably 10 to 60 mass %. By controlling within these ranges, it is possible to fully meet the recent demands for higher color purity and higher luminance.
• the photosensitive resin composition of the present invention contains the coloring material, it preferably further contains a dispersant.
• the dispersant has a site for interaction with the colorant and a site for interaction with the dispersion medium (for example, solvent or binder resin), and has the function of stabilizing the dispersion of the colorant in the dispersion medium.
• resin-type dispersants eg, polymer dispersants
• surfactants eg, low-molecular-weight dispersants
• pigment derivatives may be used individually by 1 type, and may be used in combination of 2 or more type.
• resin-type dispersant examples include polyurethanes, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, and polysiloxanes.
• long-chain polyaminoamide phosphates hydrogen group-containing polycarboxylic acid esters, amides and salts thereof formed by the reaction of poly(lower alkyleneimine) with polyesters having free carboxyl groups, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide/polypropylene oxide adducts, etc. mentioned.
• Commercially available products of the resin-type dispersant include those described in JP-A-2015-157909.
• surfactant examples include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, Anionic surfactants such as sodium stearate and sodium lauryl sulfate; nonions such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate cationic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic acid betaine and alkylimidazoline;
• the dye derivative is a compound having a structure in which a functional group is introduced into the dye.
• the functional group include a sulfonic acid group, a sulfonamide group and quaternary salts thereof, a dialkylamino group, a hydroxyl group, a carboxyl group, and an amide group. , a phthalimide group, and the like.
• the structure of the base dye include azo, anthraquinone, quinophthalone, phthalocyanine, quinacridone, benzimidazolone, isoindoline, dioxazine, indanthrene, perylene, and diketopyrrolopyrroles. system and the like.
• the content of the dispersant may be appropriately set according to the purpose and application. It is preferably 0.01 to 60% by mass with respect to 100% by mass of the total solid content of the resin composition. More preferably 0.1 to 50% by mass, still more preferably 0.3 to 40% by mass.
• the method for preparing the photosensitive resin composition is not particularly limited, and a known method may be used. For example, a method of mixing and dispersing each of the above-described components using various mixers or dispersers may be mentioned. be done.
• the mixing/dispersing step is not particularly limited, and may be performed by a known method. In addition, other steps that are normally performed may be further included.
• the photosensitive resin composition contains a coloring material, it is preferably prepared through a coloring material dispersion treatment step.
• a colorant preferably an organic pigment
• a dispersant preferably an organic pigment
• a solvent preferably an organic pigment
• a disperser preferably an organic pigment
• Methods of obtaining dispersions also referred to as "millbases”
• the dispersing machine include paint conditioners, bead mills, roll mills, ball mills, jet mills, homogenizers, kneaders and blenders.
• the dispersion treatment step preferably, after kneading and dispersing with a roll mill, a kneader, a blender, etc., fine dispersion treatment is performed with a media mill such as a bead mill filled with beads of 0.01 to 1 mm. .
• a composition preferably a transparent liquid
• the obtained photosensitive resin composition is preferably filtered using a filter or the like to remove fine dust.
• the photosensitive resin composition (preferably negative photosensitive resin composition) of the present invention preferably contains a solvent as a diluent, if necessary.
• the solvent is not particularly limited as long as it uniformly dissolves the components such as the polymer, the polyfunctional monomer, the photopolymerization initiator and the coloring material.
• ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3- Esters such as methoxybutyl acetate; Alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether; Aromatic hydrocarbons such as toluene, xylene, ethylbenzene; Chloroform, dimethyl sulfoxide; etc.
• ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone
• the content of the solvent may be appropriately set according to the optimum viscosity when using the photosensitive resin composition. For example, it is 1000 parts by mass or less, more preferably 700 parts by mass or less with respect to 100 parts by mass of the polymer.
• a preferred lower limit is 30 parts by mass or more, more preferably 60 parts by mass or more, relative to 100 parts by mass of the polymer.
• the solvent content is preferably 30 to 1000 parts by mass, more preferably 60 to 700 parts by mass, per 100 parts by mass of the polymer.
• the viscosity of the photosensitive resin composition can be appropriately set according to the desired thickness of the cured film.
• the viscosity of the photosensitive resin composition can be adjusted by adding a solvent.
• the upper limit of the viscosity of the photosensitive resin composition in which a solvent is added to adjust the solid content (non-volatile content) to 40% is, for example, preferably 30 mPa s or less, more preferably 20 mPa s or less, and 15 mPa s or less. is particularly preferred.
• the lower limit of the viscosity is preferably, for example, 1 mPa ⁇ s or more, more preferably 5 mPa ⁇ s or more, depending on the desired thickness of the cured film.
• the photosensitive resin composition of the present invention includes fillers such as aluminum hydroxide, talc, clay, and barium sulfate, quantum dot particles, and antifoaming, as long as the effects of the present invention are not impaired.
• agents, coupling agents, leveling agents, sensitizers, release agents, lubricants, plasticizers, antioxidants, UV absorbers, light stabilizers, flame retardants, polymerization inhibitors, polymerization retarders, polymerization accelerators It may contain known additives such as viscosity agents, dispersants and surfactants.
• the present invention also provides a cured film obtained by curing the polymer and/or the photosensitive resin composition.
• a cured film can be obtained by coating the photosensitive resin composition on a substrate and curing the composition.
• materials used as substrates to be coated include transparent materials such as glass, acrylic resins, polycarbonate resins, polyester resins such as PET, polystyrene resins, and metal materials such as aluminum, copper, iron, and stainless steel.
• the cured film preferably has a film thickness (thickness) of 0.1 to 20 ⁇ m. As a result, it is possible to satisfactorily meet the demand for reduction in the height of members, display devices, and the like using the cured film. More preferably 0.5 to 10 ⁇ m, still more preferably 0.5 to 8 ⁇ m.
• the above cured film is used, for example, in liquid crystal/organic EL/quantum dot/micro LED liquid crystal display devices, solid-state imaging devices, touch panel display devices, color filters, black matrices, photospacers, black column spacers, inks, and printing plates. , printed wiring boards, semiconductor elements, photoresists, insulating films, films, organic protective films, and various other optical members and structural members of electrical and electronic equipment. Among them, it is preferably used for color filter applications.
• a color filter using the above photosensitive resin composition that is, specifically, a color filter and a color filter having a cured product (cured film) formed from the above photosensitive resin composition on a substrate.
• a manufacturing method is one of the preferred embodiments of the present invention.
• Color filter As an example of an embodiment having the above cured product (cured film), there is a color filter having the above cured film on a substrate. This manufacturing method will be described in detail below.
• the members constituting the color filter specifically include three primary color (RGB) pixels, a resin black matrix, a protective film, a columnar spacer, etc. At least one of these members constituting the color filter is It is preferable to have a cured film formed from the photosensitive resin composition of the invention.
• the resin composition of the present invention contains three primary colors of red, green, and blue coloring materials, and when forming a resin black matrix, it contains a black coloring material.
• the color filter can be produced, for example, as follows. 1) A substrate is coated with a photosensitive resin composition by a known coating method and dried to form a coating film.
• the substrate is preferably a transparent substrate, and specific examples thereof include glass (preferably non-alkali glass), transparent plastic, and the like. If necessary, the substrate may be subjected to corona discharge treatment, ozone treatment, chemical treatment using a silane coupling agent or the like.
• Known coating methods include a spin coating method, a spray method, and the like, and the spin coating method is preferred.
• the drying temperature is preferably room temperature to 120°C, more preferably 60 to 100°C.
• the drying time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 10 minutes. Moreover, it is preferable to heat-dry under normal pressure or a vacuum.
• a photomask (patterning film) provided with openings corresponding to a desired pattern shape is placed on the coating film obtained in 1) in a contact state or a non-contact state, and light is irradiated. , to harden.
• Light means not only visible light but also radiation such as ultraviolet rays, X-rays and electron beams, with ultraviolet rays being the most preferred.
• a high-pressure mercury lamp is generally preferably used as the ultraviolet light source.
• the alkaline component in the alkaline aqueous solution is not particularly limited, potassium hydroxide, sodium hydroxide and/or sodium carbonate are preferred.
• the concentration of the alkaline component is preferably 0.01 to 5% by mass in 100% by mass of the alkaline aqueous solution. When the concentration of the alkali component is within this range, the solubility of the alkali-soluble polymer is further improved, and the developability (development speed) can be further increased. More preferably 0.05 to 3% by mass, still more preferably 0.1 to 1% by mass.
• a surfactant may be added to the alkaline aqueous solution.
• the coloring material of the photosensitive resin composition is sequentially changed to red (R), green (G), and blue (B), and the above steps 1) to 3) are repeated to obtain R, G, B are formed to produce RGB pixels.
• a protective film is formed as necessary.
• the columnar spacers can be produced by applying a photosensitive resin composition to the surface on which the spacers are to be formed in such a thickness that the spacers have the desired height, and then performing the above steps 1) to 3).
• the temperature for post-baking is preferably 120 to 300.degree.
• the temperature is set at this temperature, deterioration of smoothness of the coating film due to coloring of pixels and thermal decomposition can be more sufficiently suppressed, and further curing proceeds to further increase the strength of the coating film. Therefore, it becomes possible to further increase the hardness and adhesion of the patterned cured film. It is more preferably 150 to 250°C, still more preferably 180 to 230°C.
• Post-baking may be performed after development in the formation of each member (after the above 3) in the formation of each member), or may be performed after all the members are formed.
• the polymer of the present invention can give a cured product with excellent developability and excellent adhesion.
• the photosensitive resin composition containing the polymer of the present invention and a polyfunctional monomer can provide a cured product having a high developing speed and excellent adhesion to substrates, heat resistance, and the like.
• Such a polymer and photosensitive resin composition of the present invention can be used for applications such as resist materials (preferably color filter resists), various coating agents, and paints. Since it has a group, it can be suitably used as an alkali-developable negative resist material for producing colored pixels of a color filter, a black matrix, an overcoat, a photospacer, an optical waveguide, and the like.
• Display device member and display device The display device member and display device of the present invention have the above cured film, and may further have one or more other constituent members. In recent years, with the advancement of technology such as display devices, there is a strong demand for even higher performance for each member used, but if the photosensitive resin composition of the present invention is used, such needs can be met. It is possible to sufficiently improve the reliability of the display quality and imaging quality of various display devices to the extent that it is possible to sufficiently cope with .
• the display device is not particularly limited, for example, a liquid crystal display device, a solid-state imaging device, a touch panel display device, and the like are suitable. As the touch panel type display device, a capacitive type display device is particularly preferable.
• the display device member may be a film-like single-layer or multi-layer member composed of the cured film, or a member in which the single-layer or multi-layer member is further combined with another layer. Alternatively, it may be a member (for example, a color filter, etc.) containing the cured film.
• Acid value 1.5 g of the polymer solutions prepared in Examples and Comparative Examples were precisely weighed, dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and titrated with a 0.1N KOH aqueous solution. Titration was performed using an automatic titrator (trade name: COM-1700A, manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value per 1 g of polymer was obtained from the solid content concentration (mgKOH/g).
• Tg Glass transition temperature
• the Tg of the homopolymer of the monomer used in the FOX formula is, for example, described in "POLYMER HANDBOOK THIRD EDITION" (J. BRANDRUP, E. H.
• Tg polymer Tg (w 1 , w 2 , ...: weight fractions of monomers 1, 2, ... in the polymer Tg 1 , Tg 2 , ...: monomers 1, 2 constituting the polymer , homopolymer Tg)
• the polymer solution was applied to a 5 cm square glass substrate, spin-coated onto the glass substrate, and dried at room temperature under reduced pressure for 4 hours to form a thin film with a film mass of 30 mg or less. Volatile components are removed to obtain a solid content. Regarding the solid content, it is confirmed by quantification by gas chromatography that the residual solvent is 0.1 wt % or less.
• the obtained solid content is measured using a DSC (differential scanning calorimeter method, measuring instrument: Netsch DSC3500) under a nitrogen stream at a heating rate of 10° C./min according to JIS-K7121.
• DSC differential scanning calorimeter method, measuring instrument: Netsch DSC3500
• Double bond equivalent (g/mol) It was obtained by dividing the mass (g) of the polymer solid content by the double bond amount (mol) of the polymer.
• the temperature was raised to 90°C by On the other hand, as a dropping tank (A), 210 g of N-benzylmaleimide (BzMI), 134 g of methacrylic acid (MAA), 8 g of cyclohexyl methacrylate (CHMA), 8 g of methyl methacrylate (MMA), 2-ethylhexyl acrylate (2EHA) were placed in a beaker. ) 479 g, propylene glycol monomethyl ether acetate (PGMEA) 147 g, propylene glycol monomethyl ether (PGME) 63 g, t-butyl peroxy-2-ethylhexanoate (NOF Co., Ltd.
• PzMI N-benzylmaleimide
• MAA methacrylic acid
• CHMA cyclohexyl methacrylate
• MMA methyl methacrylate
• 2EHA 2-ethylhexyl acrylate
• Example 2 978 g of propylene glycol monomethyl ether acetate (PGMEA) was introduced into a reactor equipped with a thermometer, a stirrer, a gas inlet pipe, a cooling pipe and a dropping tank inlet port, and after purging with nitrogen, the temperature was raised to 90°C.
• a dropping tank (A) 120 g of N-benzylmaleimide (BzMI), 72 g of methacrylic acid (MAA), 80 g of cyclohexyl methacrylate (CHMA), 248 g of methyl methacrylate (MMA), and 2-ethylhexyl acrylate (2EHA) were placed in a beaker.
• BzMI N-benzylmaleimide
• MAA methacrylic acid
• CHMA cyclohexyl methacrylate
• MMA methyl methacrylate
• 2EHA 2-ethylhexyl acrylate
• Example 3 A reaction tank equipped with a thermometer, a stirrer, a gas inlet pipe, a cooling pipe and a dropping tank inlet was charged with 572 g of propylene glycol monomethyl ether acetate (PGMEA) and 276 g of propylene glycol monomethyl ether (PGME), replaced with nitrogen, and then heated.
• PGMEA propylene glycol monomethyl ether acetate
• PGME propylene glycol monomethyl ether
• the temperature was raised to 90°C by On the other hand, as a dropping tank (A), 240 g of N-benzylmaleimide (BzMI), 172 g of methacrylic acid (MAA), 160 g of cyclohexyl methacrylate (CHMA), 68 g of methyl methacrylate (MMA), and 2-ethylhexyl acrylate (2EHA) were placed in a beaker. ) 160 g, propylene glycol monomethyl ether acetate (PGMEA) 168 g, propylene glycol monomethyl ether (PGME) 72 g, t-butyl peroxy-2-ethylhexanoate (NOF Co., Ltd.
• PzMI N-benzylmaleimide
• MAA methacrylic acid
• CHMA cyclohexyl methacrylate
• MMA methyl methacrylate
• 2EHA 2-ethylhexyl acrylate
• Example 4 A reaction tank equipped with a thermometer, a stirrer, a gas inlet pipe, a cooling pipe, and a dropping tank inlet was charged with 586 g of propylene glycol monomethyl ether acetate (PGMEA) and 283 g of propylene glycol monomethyl ether (PGME), purged with nitrogen, and then heated.
• PGMEA propylene glycol monomethyl ether acetate
• PGME propylene glycol monomethyl ether
• the temperature was raised to 90°C by On the other hand, as a dropping tank (A), 40 g of N-benzylmaleimide (BzMI), 128 g of acrylic acid (AA), 64 g of cyclohexyl methacrylate (CHMA), 8 g of methyl methacrylate (MMA), 2-ethylhexyl acrylate (2EHA) were placed in a beaker. ) 560 g, propylene glycol monomethyl ether acetate (PGMEA) 159 g, propylene glycol monomethyl ether (PGME) 68 g, t-butyl peroxy-2-ethylhexanoate (NOF Co., Ltd.
• PzMI N-benzylmaleimide
• AA acrylic acid
• CHMA cyclohexyl methacrylate
• MMA methyl methacrylate
• 2EHA 2-ethylhexyl acrylate
• Example 5 A reaction vessel equipped with a thermometer, a stirrer, a gas inlet tube, a cooling tube, and a dropping tank inlet was charged with 620 g of propylene glycol monomethyl ether acetate (PGMEA) and 294 g of propylene glycol monomethyl ether (PGME), purged with nitrogen, and then heated.
• PGMEA propylene glycol monomethyl ether acetate
• PGME propylene glycol monomethyl ether
• the temperature was raised to 90°C by On the other hand, as a dropping tank (A), 80 g of N-benzylmaleimide (BzMI), 112 g of methacrylic acid (MAA), 208 g of cyclohexyl methacrylate (CHMA), 400 g of 2-ethylbutyl acrylate (2EBA), and propylene glycol monomethyl ether acetate were placed in a beaker.
• BzMI N-benzylmaleimide
• MAA methacrylic acid
• CHMA 208 g of cyclohexyl methacrylate
• 2EBA 2-ethylbutyl acrylate
• propylene glycol monomethyl ether acetate propylene glycol monomethyl ether acetate
• PMEA propylene glycol monomethyl ether
• PGME propylene glycol monomethyl ether
• PERBUTYL (registered trademark) O t-butyl peroxy-2-ethylhexanoate
• nDM n-dodecyl mercaptan
• PGMEA propylene glycol monomethyl ether acetate
• GMA glycidyl methacrylate
• TEA triethylamine
• Antage W-400 manufactured by Kawaguchi Kagaku Kogyo Co., Ltd.
• Example 7 A polymer solution A-7 was obtained in the same manner as in Example 1, except that N-phenylmaleimide (PMI) was used instead of N-benzylmaleimide.
• PMI N-phenylmaleimide
• Example 8 In [Example 1], 210 g of N-benzylmaleimide (BzMI) was replaced with 252 g of dimethyl-2,2′-[oxybis(methylene)]bis-2-propenoate (MD), and 2-ethylhexyl acrylate (2EHA ) was changed to 437 g instead of 479 g, in the same manner as in Example 1 to obtain a polymer solution A-8.
• BzMI N-benzylmaleimide
• MD dimethyl-2,2′-[oxybis(methylene)]bis-2-propenoate
• 2EHA 2-ethylhexyl acrylate
• Example 9 A polymer solution A-9 was obtained in the same manner as in Example 5, except that octyl acrylate (OA) was used instead of 2-ethylbutyl acrylate.
• OA octyl acrylate
• Example 10 A polymer solution A-10 was obtained in the same manner as in Example 5, except that stearyl methacrylate (STMA) was used instead of 2-ethylbutyl acrylate.
• STMA stearyl methacrylate
• a polymer solution A-11 was obtained in the same manner as in Example 5, except that lauryl acrylate (LA) was used instead of 2-ethylbutyl acrylate.
• LA lauryl acrylate
• a polymer solution A-12 was obtained in the same manner as in Example 5, except that ethyl methacrylate (EMA) was used instead of 2-ethylbutyl acrylate.
• EMA ethyl methacrylate
• the temperature was raised to 90°C by On the other hand, as a dropping tank (A), 70 g of N-benzylmaleimide (BzMI), 98 g of methacrylic acid (MAA), 182 g of cyclohexyl methacrylate (CHMA), 350 g of 2-ethylbutyl acrylate (2EBA), and propylene glycol monomethyl ether acetate were placed in a beaker.
• BzMI N-benzylmaleimide
• MAA methacrylic acid
• CHMA cyclohexyl methacrylate
• 2EBA 2-ethylbutyl acrylate
• propylene glycol monomethyl ether acetate propylene glycol monomethyl ether acetate
• PMEA propylene glycol monomethyl ether
• PGME propylene glycol monomethyl ether
• PERBUTYL (registered trademark) O t-butyl peroxy-2-ethylhexanoate
• nDM n-dodecyl mercaptan
• PGMEA propylene glycol monomethyl ether acetate
• the temperature was raised to 90°C by On the other hand, as a dropping tank (A), 88 g of methacrylic acid (MAA), 183 g of cyclohexyl methacrylate (CHMA), 132 g of methyl methacrylate (MMA), 330 g of 2-ethylhexyl acrylate (2EHA), propylene glycol monomethyl ether acetate ( PGMEA) 92 g, propylene glycol monomethyl ether (PGME) 40 g, t-butyl peroxy-2-ethylhexanoate (NOF Co., Ltd. "PERBUTYL (registered trademark) O”) 15 g were mixed with stirring, and added dropwise.
• MAA methacrylic acid
• CHMA 183 g of cyclohexyl methacrylate
• MMA methyl methacrylate
• EHA 2-ethylhexyl acrylate
• PGMEA propylene glycol monomethyl ether
• nDM n-dodecyl mercaptan
• PMEA propylene glycol monomethyl ether acetate
• a polymer solution A-15 was obtained in the same manner as in Example 1, except that butyl acrylate (BA) was used instead of 2-ethylhexyl acrylate (2EHA).
• BA butyl acrylate
• 2EHA 2-ethylhexyl acrylate
• a polymer solution A-16 was obtained in the same manner as in Example 1, except that 2-acryloyloxyethylsuccinic acid (HOA-MS) was used instead of methacrylic acid.
• HOA-MS 2-acryloyloxyethylsuccinic acid
• Table 1 shows the compositions and physical properties of the polymer solutions A-1 to A-10 (Examples 1 to 10) and A-11 to A-16 (Comparative Examples 1 to 6).
• Pigment dispersion 1 12.9 parts of propylene glycol monomethyl ether acetate (PGMEA), 0.4 parts of Disparlon DA-7301 as a dispersant, and C.I. I. Pigment Green 58 at 2.25 parts and C.I. I. Pigment Yellow 138 was mixed with 1.5 parts and dispersed for 3 hours using a paint shaker to obtain Pigment Dispersion 1 (solid content: 22% by mass).
• PMEA propylene glycol monomethyl ether acetate
• Disparlon DA-7301 Disparlon DA-7301
• photosensitive resin composition 8.4 g of the polymer solution A-1 as a binder resin (total solid content: 3.5 g), 3.5 g of dipentaerythritol hexaacrylate (DPHA) as a polyfunctional monomer, and 39.8 g of pigment dispersion 1 (solid content: total amount 8.75 g) and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one as a photopolymerization initiator (trade name “IRGACURE (registered trademark) 907”, BASF Japan) (hereinafter referred to as Irg907) was added and diluted with PGMEA so that the non-volatile content concentration was 20% by weight to prepare a photosensitive resin composition B1.
• photosensitive resin compositions B2 to B16 were prepared using the above polymer solutions (A-2 to A-16) as binder resins. The composition is shown in Table 2.
• a photosensitive resin composition was applied onto a 10 cm square glass substrate with a spin coater and dried in an oven at 90° C. for 3 minutes. After drying, a photomask having a line and space of 1 to 100 ⁇ m is placed at a distance of 100 ⁇ m from the coating film, and a UV aligner (trade name “TME-150RNS”, TOPCON Co., Ltd.) equipped with a 2.0 kW ultra-high pressure mercury lamp. (manufacturer) at an intensity of 100 mJ/cm 2 (converted to illuminance at 365 nm).
• a 0.05% by mass potassium hydroxide aqueous solution is sprinkled on the coating film using a spin developing machine to dissolve and remove the unexposed areas, and the remaining exposed areas are washed with pure water for 10 seconds for development. to form a line-and-space pattern.
• the time required for dissolving and removing the unexposed portion was measured, and this was defined as development time (seconds), and was evaluated according to the following criteria. Table 2 shows the results.
• [Minimum adhesion pattern] A line-and-space pattern was formed in the same manner as in the development speed test, except that the time for spraying the aqueous potassium hydroxide solution was changed to twice the development time obtained in the development speed test. The size of the minimum pattern formable was observed with an optical microscope and determined as the minimum adhesion pattern. Table 2 shows the results. It was judged that the closer the minimum adhesion pattern is to 1, the better.
• Irg907 IRGACURE® 907, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one
• DPHA dipentaerythritol hexaacrylate
• Example 14 The development time was as short as 9 seconds, and the minimum adhesion pattern was good although inferior to Examples 11-13 and 15-18.
• Example 15 The development time was as short as 12 seconds, and the minimum contact pattern was good although inferior to Examples 11-13 and 16-18.
• the pattern diameter was also good at 21 ⁇ m.
• Example 19 and 20 The development time was as fast as 10 seconds or less. The difference between the pattern system and the mask system was also small compared to Comparative Examples 7-9. The minimum adhesion pattern tended to deteriorate compared to Examples 11-18, but was better than Comparative Examples 8-12.
• Comparative Example 8 The development time was as slow as 25 seconds, the pattern diameter was as large as 26 ⁇ m, and the minimum adhesion pattern was as large as 8 ⁇ m, which is worse than in Examples 11-20.
• the EMA in the polymer of Comparative Example 8 is a monomer having a polymer Tg of about 65°C.
• Comparative Example 9 The development time was as fast as 9 seconds. On the other hand, the pattern diameter was 28 ⁇ m, and the minimum adhesion pattern was as large as 8 ⁇ m.
• the polymer of Comparative Example 9 is a polymer having an ethylenically unsaturated double bond in its side chain.
• the pattern diameter is good at 22 ⁇ m.
• the development time was as slow as 13 seconds, and the minimum adhesion pattern was as large as 8-10 ⁇ m, which was worse than in Examples 11-20.
• the polymer of Comparative Example 10 is a polymer having no structural unit (A), and the BA in the polymer of Comparative Example 11 is a monomer having a butyl group and a polymer Tg of about -54°C. be.
• HOA-MS in Comparative Example 12 is an acid group-containing monomeric compound, and the acid group is 8 atoms apart from the main chain.
• photosensitive resin compositions C1 to C3 were prepared by diluting with PGMEA so that the concentration of non-volatile matter was 20% by weight with the composition shown in Table 3. was evaluated for heat resistance. Table 3 shows the results.
• Example 21 is a value superior to Comparative Examples 13 and 14. became.
• the polymer of Comparative Example 13 is a polymer having no structural unit (A)
• HOA-MS in Comparative Example 14 is an acid group-containing monomeric compound, and the distance between the main chain and the acid group is 8 atoms. is.
• the radically polymerizable polymer and photosensitive resin composition of the present invention can be applied, for example, to resist materials, and can be suitably used in the fields of optics, electrical machinery and electronics.

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