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
  • C08F8/00—Chemical modification by after-treatment
• • 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
  • 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
  • C08F220/10—Esters
  • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(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
  • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (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
  • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
  • C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (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
  • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
  • C08F220/36—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate
  • C08F220/365—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate containing oxygen in addition to the carboxy oxygen, e.g. 2-N-morpholinoethyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate containing further carboxylic moieties
• • 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
  • C08F220/40—Esters of unsaturated alcohols, e.g. allyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/71—Monoisocyanates or monoisothiocyanates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/80—Masked polyisocyanates
• • 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
  • G03F7/038—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
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
  • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
• • 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
  • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
  • C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages

Definitions

• the present invention relates to a copolymer, a photosensitive resin composition, a photosensitive coloring composition, a cured resin film, and an image display element.
• photosensitive resin compositions that can be cured by active energy rays such as ultraviolet rays and electron beams have been widely used in fields such as various coatings, printing, paints, and adhesives.
• active energy rays such as ultraviolet rays and electron beams
• photosensitive resin compositions that can be cured by active energy rays are also used in solder resists and color filter resists.
• the properties required for curable photosensitive resin compositions are becoming increasingly diverse and sophisticated, and among them, short-time curing properties that take productivity into consideration and low-temperature curing properties that suppress thermal damage to the components to which they are applied are particularly required.
• a color filter generally consists of a transparent substrate such as a glass substrate, red (R), green (G) and blue (B) pixels formed on the transparent substrate, a black matrix formed at the boundaries of the pixels, and a protective film formed on the pixels and the black matrix.
• a color filter having such a configuration is usually manufactured by sequentially forming the black matrix, pixels and protective film on the transparent substrate.
• Various methods have been proposed for forming the pixels and black matrix (hereinafter, the pixels and black matrix are referred to as "colored patterns").
• the pigment/dye dispersion method which uses a photosensitive resin composition as a resist and creates a colored pattern by a photolithography process that repeats coating, exposure, development and baking, is currently the mainstream because it gives a colored pattern with excellent durability and few defects such as pinholes.
• photosensitive resin compositions used in photolithography contain an alkali-soluble resin, a reactive diluent, a photopolymerization initiator, a colorant, and a solvent. While the pigment/dye dispersion method has the above advantages, it often has problems in that the photosensitive resin composition is required to have high heat resistance because baking is repeated to form the black matrix and R, G, and B patterns, and the types of colorants that can be used are limited to those that can withstand high baking temperatures.
• Patent Document 1 discloses a colored composition having a specific partial structure and a hydroxyl group as a photosensitive resin composition that can give a cured product with excellent solvent resistance even under low-temperature curing conditions and can be suitably used for applications such as color filters.
• the present invention has been made to solve the above problems, and aims to provide a copolymer that contributes to improved developability and gives a cured resin film with excellent solvent resistance, as well as a photosensitive resin composition and a photosensitive coloring composition that use the copolymer.
• Another aim of the present invention is to provide a cured resin film with excellent solvent resistance, and an image display element that includes the copolymer.
• R5 and R6 each independently represent an alkyl group having 1 to 10 carbon atoms
• n1 and n2 each independently represent an integer of 0 to 2
• * represents a linking site with a residue remaining after removing the blocked isocyanato group from the structural unit (d).
• R7 and R8 each independently represent an alkyl group having 1 to 10 carbon atoms
• n3 and n4 each independently represent an integer of 0 to 2
• * represents a linking site with a residue remaining after removing the blocked isocyanato group from the structural unit (d).
• [6] Further having a structural unit (e) other than the structural units (a) to (d), The copolymer according to any one of [1] to [5], wherein the structural unit (e) is a structural unit derived from an alkyl (meth)acrylate having an alkyl group having 1 to 12 carbon atoms.
• a copolymer (A) according to any one of [1] to [9], A reactive diluent (B); A photopolymerization initiator (C); A solvent (D), A photosensitive resin composition comprising: [11] For a total of 100 parts by mass of the copolymer (A) and the reactive diluent (B), The copolymer (A) is contained in an amount of 10 parts by mass to 90 parts by mass, The reactive diluent (B) is contained in an amount of 10 parts by mass to 90 parts by mass, The photopolymerization initiator (C) is contained in an amount of 0.1 to 30 parts by mass, The photosensitive resin composition according to [10], comprising 30 parts by mass to 1,000 parts by mass of the solvent (D).
• a photosensitive coloring composition comprising the photosensitive resin composition according to [10] or [11] and a colorant (E).
• the copolymer (A) is contained in an amount of 10 parts by mass to 90 parts by mass
• the reactive diluent (B) is contained in an amount of 10 parts by mass to 90 parts by mass
• the photopolymerization initiator (C) is contained in an amount of 0.1 to 30 parts by mass
• the solvent (D) is contained in an amount of 30 parts by mass to 1,000 parts by mass
• the colorant (E) is contained in an amount of 3 parts by mass to 80 parts by mass.
• a cured resin film comprising a cured product of the photosensitive resin composition according to [10] or [11].
• a resin cured film comprising a cured product of the photosensitive coloring composition according to [12] or [13].
• An image display element comprising the color filter according to [16].
• the present invention can provide a copolymer that contributes to improved developability and gives a cured resin film with excellent solvent resistance, as well as a photosensitive resin composition and a photosensitive coloring composition using the copolymer. It can also provide a cured resin film with excellent solvent resistance obtained by curing the photosensitive resin composition and the photosensitive coloring composition, a color filter, and an image display element equipped with the same.
• (meth)acrylic acid means methacrylic acid or acrylic acid
• (meth)acrylate means acrylate or methacrylate
• (meth)acryloyloxy means acryloyloxy or methacryloyloxy.
• ethylenically unsaturated bond means a double bond formed between carbon atoms other than those forming an aromatic ring
• ethylenically unsaturated group means a group having an ethylenically unsaturated bond
• structural unit means a unit derived from a polymerizable compound used as a monomer or a unit obtained by further modifying a unit derived from a polymerizable compound used as a monomer.
• the copolymer (A) of one embodiment contains a structural unit (a) having an acid group and a structural unit (b) having a group represented by the following formula (1-1) or the following formula (1-2). Since the copolymer (A) has the structural unit (b) having an ethylenically unsaturated group, good photocurability is obtained and low-temperature curability is improved when the copolymer (A) is used in a photosensitive resin composition.
• the copolymer (A) is used together with a reactive diluent (B) described later, the ethylenically unsaturated group of the structural unit (b) reacts with the reactive diluent (B), and good adhesion of the cured film to the substrate is obtained.
• R 1 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
• R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and * represents a linking site with a residue obtained by removing the group of formula (1-1) from structural unit (b).
• R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
• R 4 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
• * represents a linking site with a residue obtained by removing the group of formula (1-2) from the structural unit (b).
• the copolymer (A) may further contain, as necessary, a structural unit (c) having a hydroxy group and a structural unit (d) having a blocked isocyanato group.
• the copolymer (A) may further contain, as necessary, a structural unit (e) other than the structural units (a) to (d).
• the structural unit (a) having an acid group is not particularly limited as long as it is a structural unit having an acid group and does not have an ethylenically unsaturated group.
• the copolymer (A) has the structural unit (a) having an acid group, good alkaline developability can be obtained when the copolymer (A) is used in a photosensitive resin composition.
• the acid group include a carboxy group, a sulfo group, and a phospho group. Among these acid groups, the carboxy group is preferred as the acid group of the structural unit (a) in terms of ease of availability.
• the structural unit (a) having an acid group is preferably a structural unit derived from a monomer (m-a) having an acid group and an ethylenically unsaturated bond (hereinafter also simply referred to as monomer (m-a)).
• monomer (m-a) examples include unsaturated carboxylic acids or anhydrides thereof, such as (meth)acrylic acid, ⁇ -bromo(meth)acrylic acid, ⁇ -furyl(meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, ⁇ -cyanocinnamic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, and citraconic anhydride; unsaturated sulfonic acids, such as 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, and p-styrenesulfonic acid; and unsaturated phosphonic acids, such as vinylphosphonic acid.
• unsaturated carboxylic acids or anhydrides thereof such as (meth)acrylic acid,
• Monomer (m-a) is preferably an unsaturated carboxylic acid or an anhydride thereof, more preferably (meth)acrylic acid or a (meth)acrylate having a carboxylic acid group, and even more preferably (meth)acrylic acid.
• the monomer (m-a) having an acid group and an ethylenically unsaturated bond may be used alone or in combination of two or more kinds.
• the content of structural unit (a) is preferably 5 to 50 mol %, more preferably 8 to 40 mol %, and even more preferably 10 to 30 mol % of all structural units of copolymer (A).
• the content of structural unit (a) is 5 mol % or more, good developability of the photosensitive resin composition using copolymer (A) is obtained.
• the content of structural unit (a) is 50 mol % or less, the content of structural unit (b) can be sufficiently ensured, and therefore the effect attributable to structural unit (b) can be sufficiently ensured.
• the structural unit (b) having a group represented by formula (1-1) or formula (1-2) is a structural unit having a group represented by the following formula (1-1) or formula (1-2):
• R 1 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
• R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
• * represents a linking site with a residue obtained by removing the group of formula (1-1) from structural unit (b).
• R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
• R 4 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
• * represents a linking site with a residue obtained by removing the group of formula (1-2) from the structural unit
• the group represented by formula (1-1) does not have to be of one type.
• R 1 in each structural unit may be different, R 2 in each structural unit may be different, and R 3 in each structural unit may be different.
• R 1 and R 4 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 5 carbon atoms.
• a conversion reaction from the structural unit (pb) described later to the structural unit (b) having a group represented by formula (1-1) or formula (1-2) is likely to occur, so a hydrocarbon group having 1 to 3 carbon atoms is more preferable.
• R 1 and R 4 are preferably an alkyl group having 1 to 5 carbon atoms, preferably a methyl group or an ethyl group, and particularly preferably an ethyl group.
• R 1 and R 4 may be the same or different.
• R 1 and R 4 are preferably the same, so that a monomer (m-pb) described later can be easily produced.
• R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms.
• a hydrogen atom or a methyl group is more preferable, and a hydrogen atom is particularly preferable.
• R 2 and R 3 may be the same or different. Since a monomer (m-pb) described later can be easily produced, it is preferable that R 2 and R 3 are the same.
• the structural unit (b) can be obtained by carrying out a dealcoholization reaction and a decarboxylation reaction of a structural unit (pb) (also simply referred to as "structural unit (pb)”) having a group represented by the following formula (1) in a solvent (PD) using a basic catalyst.
• a structural unit (pb) also simply referred to as "structural unit (pb)" having a group represented by the following formula (1) in a solvent (PD) using a basic catalyst.
• R1 and R4 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
• R2 and R3 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
• * represents a linking site with a residue remaining after removing the group of formula (1) from the structural unit (pb).
• the structural unit (pb) is a structural unit derived from a monomer (m-pb) (also simply referred to as "monomer (m-pb)”) having a group represented by the above formula (1).
• the structural unit (pb) may be used alone or in combination of two or more kinds.
• the monomer (m-pb) is a monomer having an ethylenically unsaturated bond and a group represented by the formula (1).
• R 1 , R 2 , R 3 and R 4 are the same as defined above.
• Examples of the monomer (m-pb) include a compound obtained by a urethane reaction between an isocyanato group in an isocyanate compound having an ethylenically unsaturated group such as a vinyl group or a (meth)acryloyloxy group in the molecule and a hydroxy group in a hydroxy group-containing compound represented by the following formula (4).
• R 1 , R 2 , R 3 and R 4 are the same as R 1 , R 2 , R 3 and R 4 in formula (1).
• a conventional method can be used to carry out the urethane reaction between the isocyanate compound having an ethylenically unsaturated group and the hydroxyl group-containing compound represented by formula (4).
• the above urethane reaction can be carried out regardless of the presence or absence of a solvent.
• the solvent used should be a solvent that is inactive to the isocyanato group, and any known solvent can be used.
• the above urethane reaction is generally preferably carried out at a temperature of -10°C or higher and 90°C or lower, more preferably at a temperature of 5°C or higher and 70°C or lower, and even more preferably at a temperature of 10°C or higher and 40°C or lower.
• a urethanization catalyst such as dibutyltin dilaurate and a polymerization inhibitor such as phenothiazine, hydroquinone monomethyl ether, or 2,6-di-tert-butyl-4-methylphenol (BHT) may be used as necessary.
• an isocyanate compound having an ethylenically unsaturated group used as a raw material for the monomer (m-pb)
• an isocyanate compound represented by the following formula (5) R 9 represents a hydrogen atom or a methyl group
• R 10 represents -CO-, -COOR 11 - (wherein R 11 is an alkylene group having 1 to 6 carbon atoms), or -COO-R 12 O-CONH-R 13 - (wherein R 12 is an alkylene group having 2 to 6 carbon atoms, and R 13 is an alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms which may have a substituent).
• R 10 is preferably —COOR 11 — in terms of ease of preparation of the isocyanate compound, and R 11 is more preferably an alkylene group having 1 to 4 carbon atoms.
• isocyanate compounds represented by the above formula (5) include 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, and methacryloyl isocyanate.
• the alkyl group of the hydroxyalkyl (meth)acrylate is preferably an ethyl group or an n-propyl group, more preferably an ethyl group, in view of the ease of preparation of the isocyanate compound and the simplicity of the reaction.
• diisocyanate compound examples include hexamethylene diisocyanate, 2,4- (or 2,6-) tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 3,5,5-trimethyl-3-isocyanatomethylcyclohexyl isocyanate (IPDI), m- (or p-) xylene diisocyanate, 1,3- (or 1,4-) bis (isocyanatomethyl) cyclohexane, lysine diisocyanate, etc.
• TDI 2,4- (or 2,6-) tolylene diisocyanate
• MDI 4,4'-diphenylmethane diisocyanate
• IPDI 3,5,5-trimethyl-3-isocyanatomethylcyclohexyl isocyanate
• m- (or p-) xylene diisocyanate 1,3- (or 1,4-) bis (isocyanatomethyl
• isocyanate compounds used as raw materials for the monomer (m-pb) include 1,1-bis(methacryloyloxymethyl)methyl isocyanate, 1,1-bis(methacryloyloxymethyl)ethyl isocyanate, 1,1-bis(acryloyloxymethyl)methyl isocyanate, and 1,1-bis(acryloyloxymethyl)ethyl isocyanate.
• an isocyanato group-containing (meth)acrylate is preferred, 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 1,1-bis(methacryloyloxymethyl)ethyl isocyanate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate and methacryloyl isocyanate are more preferred, and 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate and 1,1-bis(methacryloyloxymethyl)ethyl isocyanate are more preferred, and 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl
• Hydroxy group-containing compounds represented by formula (4) that are used as raw materials for the monomer (m-pb) include malic acid esters, 2-methylmalic acid esters, 3-methylmalic acid esters, and 2,3-dimethylmalic acid esters.
• malic acid esters are preferred from the viewpoints of ease of conversion reaction to structural unit (b) having a group represented by formula (1-1) or formula (1-2) and ease of availability.
• the number of carbon atoms in the two ester moieties contained in the hydroxy group-containing compound represented by formula (4) is each 1 to 20, preferably 1 to 5, and more preferably 1 to 3.
• the hydroxyl group-containing compound represented by formula (4) is particularly preferably diethyl malate from the viewpoint of ease of availability.
• the monomer (m-pb) include one or more selected from 2-[(diethyl malate)carbonylamino]ethyl acrylate, [(diethyl malate)carbonylamino]methyl acrylate, 2-[(diethyl malate)carbonylamino]propyl acrylate, and 2-[(diethyl malate)carbonylamino]butyl acrylate. From the viewpoint of ease of production, 2-[(diethyl malate)carbonylamino]ethyl acrylate is particularly preferred.
• the content of the structural unit (b) is preferably 3 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, of the total structural units of the copolymer (A).
• the content of the structural unit (b) is preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less, of the total structural units of the copolymer (A). Any combination of these lower and upper limits may be used.
• the content of the structural unit (b) is preferably 3 to 40 mol%, more preferably 5 to 35 mol%, and even more preferably 10 to 30 mol% of the total structural units of the copolymer (A).
• the photosensitive resin composition using the copolymer (A) has good low-temperature curing properties and developability.
• the content of the structural unit (b) is 40 mol% or less, the content of the structural unit (a) can be sufficiently secured, and sufficient developability can be obtained.
• the content of the structural unit (b) is a value calculated from the charge ratio of the monomer (m-pb) used in producing the resin precursor (PA) described below to all the monomers used in producing the resin precursor (PA). In other words, the content of the structural unit (b) also includes the content of the structural unit (pb).
• the structural unit (c) having a hydroxyl group (also simply referred to as “structural unit (c)") is not limited as long as it is a structural unit having a hydroxyl group and does not have an acid group, an ethylenically unsaturated group, or a blocked isocyanato group.
• structural unit (c) When the copolymer (A) has the structural unit (c) having a hydroxyl group, crosslinking with the structural unit (d) having a blocked isocyanato group described below progresses upon heating. As a result, when the copolymer (A) is used in a photosensitive resin composition, good solvent resistance of the cured product can be obtained even in heat curing under low temperature conditions.
• the structural unit (c) having a hydroxy group is preferably a structural unit derived from a monomer (m-c) having a hydroxy group and an ethylenically unsaturated group (hereinafter also simply referred to as monomer (m-c)).
• monomer (m-c) examples include (meth)acrylic acid ester derivatives having a hydroxy group, specifically hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; 2-hydroxy-3-phenoxypropyl (meth)acrylate, and the like.
• hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; 2-hydroxy-3-phenoxypropyl (meth)acrylate, and the like.
• hydroxyalkyl (meth)acrylates are preferred from the viewpoints of reactivity in synthesizing copolymer (A), low-temperature curing properties of the photosensitive resin composition containing copolymer (A), and ease of availability.
• hydroxyalkyl (meth)acrylate 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate are preferred, and from the viewpoint of reducing the glass transition temperature of the copolymer (A), 4-hydroxybutyl (meth)acrylate is more preferred.
• the monomer (m-c) having a hydroxy group and an ethylenically unsaturated group may be used alone or in combination of two or more kinds.
• the content of the structural unit (c) is preferably 3 to 40 mol %, more preferably 5 to 30 mol %, and even more preferably 8 to 25 mol % of the total structural units of the copolymer (A).
• the content of the structural unit (c) is 3 mol % or more, the amount of crosslinking between the hydroxyl group of the structural unit (c) and the blocked isocyanato group of the structural unit (d) can be sufficiently ensured. As a result, the low-temperature curing property of the photosensitive resin composition using the copolymer (A) is improved.
• the content of the structural unit (c) is 40 mol % or less, the contents of the structural units (a) and (b) can be sufficiently ensured, and therefore sufficient developability of the cured product can be obtained.
• the content of the structural unit (d) can be sufficiently ensured, and therefore the amount of crosslinking with the structural unit (c) can be sufficiently ensured.
• the structural unit (d) having a blocked isocyanato group (also simply referred to as “structural unit (d)") is not particularly limited as long as it is a structural unit having no acid group and no ethylenically unsaturated group, does not fall under the structural unit (pb), and has a blocked isocyanato group.
• structural unit (d) also simply referred to as "structural unit (d)”
• crosslinking with the structural unit (c) having a hydroxyl group proceeds upon heating.
• the crosslinking is formed, for example, by the reaction between the isocyanato group generated by dissociation of the blocking agent and the hydroxyl group.
• the blocking agent is a compound having a carboxylic acid alkyl ester structure
• crosslinking can be formed by transesterification between the carboxylic acid alkyl ester structure and the hydroxyl group, as described below, even if the blocking agent does not dissociate.
• the copolymer (A) is used in a photosensitive resin composition, good solvent resistance of the cured product can be obtained even in heat curing under low temperature conditions.
• the structural unit (d) having a blocked isocyanato group has a structure in which the isocyanato group is blocked with a blocking agent.
• the reaction between the isocyanato group and the blocking agent can be carried out regardless of the presence or absence of a solvent. If a solvent is used, it is necessary to use a solvent that is inactive to the isocyanato group.
• an organic metal salt such as tin, zinc, or lead, or a tertiary amine may be used as a catalyst.
• the blocking reaction can generally be carried out at -20 to 150°C, but is preferably carried out at 0 to 100°C.
• Blocking agents that block isocyanato groups include, for example, lactam compounds such as ⁇ -caprolactam, ⁇ -valerolactam, ⁇ -butyrolactam, and ⁇ -propiolactam; alcohol compounds such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol, and cyclohexanol; phenol compounds such as phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, o-isopropylphenol, and butylphenols such as p-tert-butylphenol, p-tert-octylphenol, nonylphenol, dinonylphenol, styrenated phenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, th
• active methylene compounds such as diphenyl mercaptan, thiophenol, tert-dodecyl mercaptan, and the like; amine compounds such as diphenylamine, phenylnaphthylamine, aniline, carbazole, and the like; acid amide compounds such as acetanilide, acetanisidide, acetate amide, benzamide, and the like; imide compounds such as succinimide, maleimide, and the like; imidazole compounds such as imidazole, 2-methylimidazole, 2-ethylimidazole, and the like; pyrazole, 3,5- These include pyrazole compounds such as dimethylpyrazole; urea compounds such as urea, thiourea, and ethyleneurea; carbamic acid compounds such as N-phenylcarbamate phenyl and 2-oxazolidone; imine compounds such as ethyleneimine and polyethyleneimine; oxime compounds
• the blocking agents may be used alone or in combination of two or more.
• the blocking agent is preferably one that has a dissociation rate of blocked isocyanato groups of 5 to 99 mass% when heated at 100°C for 30 minutes, more preferably one or more selected from the group consisting of 3,5-dimethylpyrazole, methyl ethyl ketoxime, methyl 4-hydroxybenzoate, methyl 2-hydroxybenzoate, and 3,5-xylenol, and even more preferably 3,5-dimethylpyrazole.
• the dissociation rate of the blocked isocyanato group is defined as the value obtained by preparing an n-octanol solution containing a blocked isocyanato group-containing compound at a concentration of 20% by mass, adding 1% by mass of dibutyltin laurate and 3% by mass of phenothiazine (polymerization inhibitor) to the solution, and then heating at 100°C for 30 minutes, and measuring the mass loss rate of the blocked isocyanato group-containing compound by HPLC analysis.
• the blocked isocyanato group-containing compound a compound in which the isocyanato group of 2-isocyanatoethyl acrylate is blocked with the blocking agent to be measured is used.
• the stability of the copolymer (A) during synthesis can be sufficiently ensured, the baking temperature during the production of the cured film can be set sufficiently low, and the solvent resistance of the cured film can be sufficiently ensured.
• a blocking agent having a carboxylic acid alkyl ester structure is also preferred.
• the structural unit (d) having a blocked isocyanato group has a carboxylic acid alkyl ester structure.
• the carboxylic acid alkyl ester structure means a structure having an alkyloxycarbonyl group, and a structure having an alkyloxycarbonyl group with 1 to 10 carbon atoms in the alkyl group is preferred.
• the alkyloxycarbonyl group undergoes ester exchange with the hydroxy group of the structural unit (c) to form a crosslinked structure by heating the photosensitive resin composition containing the copolymer (A).
• a photosensitive resin composition using the copolymer (A) containing a structural unit having a carboxylic acid alkyl ester structure can provide a cured film with excellent solvent resistance even when cured at a low temperature of 50°C to 150°C.
• the structural unit having a carboxylate alkyl ester structure is more preferably a structural unit having a group represented by the following formula (2) or a group represented by the following formula (3).
• R5 and R6 each independently represent an alkyl group having 1 to 10 carbon atoms
• n1 and n2 each independently represent an integer of 0 to 2
• * represents a linking site with a residue remaining after removing the blocked isocyanato group from the structural unit (d).
• R7 and R8 each independently represent an alkyl group having 1 to 10 carbon atoms
• n3 and n4 each independently represent an integer of 0 to 2
• * represents a linking site with a residue remaining after removing the blocked isocyanato group from the structural unit (d).
• the group represented by formula (2) may not be of one type.
• R5 of each structural unit may be different, R6 of each structural unit may be different, n1 of each structural unit may be different, and n2 of each structural unit may be different.
• R5 and R6 are each independently an alkyl group having 1 to 10 carbon atoms.
• R5 and R6 are each independently preferably an alkyl group having 2 to 6 carbon atoms, more preferably an alkyl group having 2 to 3 carbon atoms, and most preferably both R5 and R6 are an ethyl group.
• R5 and R6 are ethyl groups
• R5 and R6 undergo ester exchange with the hydroxy group of the structural unit (c) to generate ethanol when the photosensitive resin composition containing the copolymer (A) is thermally cured.
• This is preferable because the ethanol generated during thermal curing of the photosensitive resin composition is easily evaporated and removed by heating for thermally curing the photosensitive resin composition.
• n1 and n2 each independently represent an integer from 0 to 2. It is preferable that n1 and n2 each independently represent 0 or 1, and it is more preferable that both are 0.
• R7 and R8 in the above formula (3) are each independently an alkyl group having 1 to 10 carbon atoms.
• R7 is preferably an alkyl group having 2 to 6 carbon atoms, more preferably an alkyl group having 2 to 3 carbon atoms, and even more preferably an ethyl group.
• R7 When R7 is an ethyl group, R7 undergoes ester exchange with the hydroxy group of the structural unit (c) to generate ethanol when the photosensitive resin composition containing the copolymer (A) is thermally cured. This is preferable because the ethanol generated during thermal curing of the photosensitive resin composition is easily evaporated and removed by heating for thermally curing the photosensitive resin composition.
• R 8 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group.
• n3 and n4 each independently represent an integer from 0 to 2. It is preferable that n3 and n4 each independently represent 0 or 1, and it is more preferable that both are 0.
• structural unit (d) has a group represented by formula (2).
• the structural unit (d) having a blocked isocyanato group is preferably a structural unit derived from a monomer (m-d) (also simply referred to as monomer (m-d)) having a blocked isocyanato group and an ethylenically unsaturated bond.
• the monomer (m-d) may be used alone or in combination of two or more kinds.
• Specific examples of groups having an ethylenically unsaturated bond include a vinyl group, a (meth)acryloyloxy group, etc.
• An example of the monomer (m-d) is a reaction product of an isocyanate compound having an ethylenically unsaturated group with a blocking agent.
• the isocyanate compound having an ethylenically unsaturated group may be the same as the isocyanate compound used as a raw material for the above-mentioned monomer (m-pb).
• the structural unit having a group represented by formula (2) or (3) is preferably a structural unit derived from a monomer having a group represented by formula (2) or (3) and an ethylenically unsaturated bond.
• Specific examples of the group having an ethylenically unsaturated bond include a vinyl group and a (meth)acryloyloxy group.
• Examples of monomers having a group represented by formula (2) or (3) and an ethylenically unsaturated bond include the reaction products of an isocyanate compound having an ethylenically unsaturated group with a malonic acid diester or an acetoacetic acid ester.
• an isocyanate compound having an ethylenically unsaturated group As an isocyanate compound having an ethylenically unsaturated group, the same isocyanate compound used as a raw material for the above-mentioned monomer (m-pb) can be used.
• malonic acid diesters examples include dimethyl malonate, diethyl malonate, di(n-propyl) malonate, and di(i-propyl) malonate. From the standpoints of availability, cost, and quality, diethyl malonate and dimethyl malonate are preferred.
• acetoacetic esters examples include methyl acetoacetate and ethyl acetoacetate.
• monomers having a group represented by formula (2) and an ethylenically unsaturated bond include Karenz (trademark) MOI-DEM (manufactured by Showa Denko K.K.) and Karenz (trademark) AOI-DEM (manufactured by Showa Denko K.K.).
• the reaction between an isocyanate compound having an ethylenically unsaturated group and a malonic acid diester or an acetoacetate ester can be carried out regardless of the presence or absence of a solvent.
• a solvent that is inactive to the isocyanato group is used.
• organic metal salts such as tin, zinc, and lead, and tertiary amines may be used as catalysts.
• the content of the structural unit (d) is preferably 5 to 45 mol %, more preferably 10 to 40 mol %, and even more preferably 15 to 35 mol % of the total structural units of the copolymer (A).
• the content of the structural unit (d) is 5 mol % or more, the amount of crosslinking between the blocked isocyanato group of the structural unit (d) and the hydroxyl group of the structural unit (c) can be sufficiently ensured. As a result, the low-temperature curing property of the photosensitive resin composition using the copolymer (A) is improved.
• the content of the structural unit (d) is 45 mol % or less, the contents of the structural units (a) and (b) can be sufficiently ensured, and therefore sufficient developability of the cured product can be obtained.
• the content of the structural unit (c) can be sufficiently ensured, and the amount of crosslinking with the structural unit (d) can be sufficiently ensured.
• Copolymer (A) may contain, as necessary, a structural unit (e) other than the structural units (a) to (d) (also simply referred to as "structural unit (e)"). That is, a structural unit derived from a monomer other than the monomers (m-a), (m-pb), (m-c), and (m-d).
• the structural unit (e) is a structural unit other than the structural units (a) to (d) and the structural unit (pb) that does not have an acid group, an ethylenically unsaturated group, a hydroxy group, or a blocked isocyanato group.
• copolymer (A) contains the structural unit (e), it is possible to impart additionally required functions.
• aromatic vinyl compounds include aromatic vinyl compounds, cyclic olefins having a norbornene structure, dienes, (meth)acrylic acid esters, (meth)acrylic acid amides, vinyl compounds, unsaturated dicarboxylic acid diesters, monomaleimides, glycidyl (meth)acrylate, (meth)acrylic acid anilide, (meth)acrylonitrile, acrolein, etc.
• Aromatic vinyl compounds include styrene, ⁇ -methylstyrene, o-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, methoxystyrene, p-nitrostyrene, p-cyanostyrene, and p-acetylaminostyrene.
• cyclic olefins having a norbornene structure examples include norbornene (bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, tetracyclo[4.4.0.1 2,5 . 1 7,10 ]dodec-3-ene, 8-ethyltetracyclo[4.4.0.1 2,5 .
• Dienes include butadiene, isoprene, and chloroprene.
• (Meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, benzyl (meth)acrylate, isoamyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, rosin (meth)acrylate, norbornyl (meth)acrylate, 5-ethylnorbornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyloxyethyl acrylate, isobornyl (meth)acrylate, adamanty
• Examples of (meth)acrylic acid amides include (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diisopropylamide, (meth)acrylic acid anthracenylamide, etc.
• Vinyl compounds include vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, vinyltoluene, etc.
• Unsaturated dicarboxylic acid diesters include diethyl citraconate, diethyl maleate, diethyl fumarate, and diethyl itaconate.
• monomaleimides examples include N-phenylmaleimide, N-cyclohexylmaleimide, and N-laurylmaleimide.
• aromatic vinyl compounds, aromatic group-containing (meth)acrylates, and alkyl (meth)acrylates in which the alkyl group has 1 to 12 carbon atoms are preferred, with styrene, benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and methyl (meth)acrylate being more preferred, and 2-ethylhexyl (meth)acrylate and methyl (meth)acrylate being even more preferred.
• the monomers (m-e) may be used alone or in combination of two or more.
• copolymer (A) contains structural unit (e), its content is preferably 1 to 50 mol %, more preferably 3 to 45 mol %, and even more preferably 5 to 40 mol %, of all structural units in copolymer (A).
• structural unit (e) By setting the content of structural unit (e) within the above range, it is possible to impart additional functions by structural unit (e) while fully securing the functions of structural units (a) to (d), or to adjust the functions obtained from structural units (a) to (d) to an appropriate range.
• the ethylenically unsaturated group equivalent of the copolymer (A) is preferably 300 g/mol or more, more preferably 500 g/mol or more, and even more preferably 1000 g/mol or more.
• the ethylenically unsaturated group equivalent of the copolymer (A) is preferably 8000 g/mol or less, more preferably 7000 g/mol or less, and even more preferably 5000 g/mol or less. Any combination of these lower limit values and upper limit values may be used.
• the ethylenically unsaturated group equivalent of the copolymer (A) is preferably 300 to 8000 g/mol, more preferably 500 to 7000 g/mol, and even more preferably 1000 to 5000 g/mol.
• it is 300 g/mol or more, the storage stability as a photosensitive resin composition is good.
• it is 8000 g/mol or less, the solvent resistance of the cured product is good even when cured at a low temperature.
• the "ethylenically unsaturated group equivalent” is the mass of a polymer per 1 mol of ethylenically unsaturated groups.
• the ethylenically unsaturated group equivalent (g/mol) of copolymer (A) is determined by dividing the mass of copolymer (A) by the number of moles of ethylenically unsaturated groups contained in copolymer (A).
• the ethylenically unsaturated group equivalent is a value calculated from the conversion rate of structural unit (pb) to structural unit (b), which is calculated from the area ratio of an NMR spectrum obtained under the following conditions using an NMR device (e.g., Bruker ULTRA SHIELD PLUS 400 (400 MHz), Bruker Corporation), and the amounts of monomers (m-a), (m-pb), and (m-c) to (m-e) used in producing a resin precursor (PA) described later.
• an NMR device e.g., Bruker ULTRA SHIELD PLUS 400 (400 MHz), Bruker Corporation
• Example Preparation Method 20 mg of the dried copolymer is precisely weighed, dissolved in 20 mL of sample bottle with the addition of CDCl 3 (1 mL), shaken for 5 minutes in an ultrasonic cleaner, and then sealed in a 5 mm ⁇ NMR sample tube. NMR measurement is performed immediately after sampling.
• the ethylenically unsaturated group equivalent is a value calculated from the amount of halogen bonded to the copolymer.
• the amount of halogen bonded to the copolymer is evaluated as follows in accordance with JIS K 0070:1992.
• the dried copolymer is dissolved in chloroform, an appropriate amount of Wies's solution is added, and the mixture is stirred. The mixture is then sealed and left in a dark place at 23°C for 1 hour. Potassium iodide solution and water are added to this solution and the mixture is stirred, and the resulting solution is titrated with sodium thiosulfate solution. When the solution turns slightly yellow, a few drops of starch solution are added and the titration is continued until the blue color disappears. The ethylenically unsaturated bonds in the copolymer react with halogen molecules in a 1:1 ratio. Therefore, the ethylenically unsaturated group equivalent of the copolymer can be calculated by dividing the mass (g) of the copolymer used in the measurement by the amount of halogen molecules bonded to the copolymer determined by this measurement.
• the acid value of the copolymer (A) is preferably 10 KOHmg/g or more, more preferably 15 KOHmg/g or more, and even more preferably 20 KOHmg/g or more.
• the acid value of the copolymer (A) is preferably 300 KOHmg/g or less, more preferably 200 KOHmg/g or less, and even more preferably 150 KOHmg/g or less.
• the combination of these lower limit values and upper limit values may be any combination.
• the acid value of the copolymer (A) is preferably 10 to 300 KOHmg/g, more preferably 15 to 200 KOHmg/g, and even more preferably 20 to 150 KOHmg/g. When it is 10 KOHmg/g or more, the developability is good. When it is 300 KOHmg/g or less, the storage stability is good.
• Acid value refers to the acid value of the curable polymer measured in accordance with JIS K6901:2008 5.3.
• the acid value refers to the number of milligrams of potassium hydroxide required to neutralize the acidic components contained in 1 g of copolymer.
• the weight average molecular weight of the copolymer (A) is preferably 1000 or more, more preferably 3000 or more, and even more preferably 5000 or more.
• the weight average molecular weight of the copolymer (A) is preferably 50000 or less, more preferably 40000 or less, and even more preferably 30000 or less. Any combination of these lower limit values and upper limit values may be used.
• the weight average molecular weight of the copolymer (A) is preferably 1000 to 50000, more preferably 3000 to 40000, and even more preferably 5000 to 30000.
• the weight average molecular weight is 1000 or more, when the copolymer (A) is used as a raw material for a photosensitive resin composition, defects such as chipping are unlikely to occur in the cured resin film after development.
• the weight average molecular weight is 50000 or less, the photosensitive resin composition containing the copolymer (A) has a sufficiently short development time and is excellent in practical use.
• the weight average molecular weight refers to a weight average molecular weight calculated as standard polystyrene using gel permeation chromatography (GPC) under the following conditions.
• GPC gel permeation chromatography
• the blocked isocyanato group equivalent of the copolymer (A) is preferably 100 to 2000 g/mol, more preferably 200 to 1500 g/mol, and even more preferably 300 to 1300 g/mol. When it is 100 g/mol or more, the photosensitive resin composition containing the copolymer (A) has better developability. When it is 2000 g/mol or less, the photosensitive resin composition containing the copolymer (A) can form a resin cured film having superior hardness.
• the "block isocyanato group equivalent” is the mass of a polymer per 1 mol of the blocked isocyanato group.
• the blocked isocyanato group equivalent (g/mol) of a copolymer is determined by dividing the mass of the copolymer by the number of moles of the blocked isocyanato groups contained in the copolymer.
• the “block isocyanato group equivalent” is a theoretical value calculated from the amount of monomer charged when producing the copolymer.
• the hydroxyl group equivalent of the copolymer (A) is preferably 200 to 5000 g/mol, more preferably 400 to 4000 g/mol, and even more preferably 800 to 3000 g/mol.
• the photosensitive resin composition containing the copolymer (A) has better developability.
• the photosensitive resin composition containing the copolymer (A) can form a resin cured film having superior hardness.
• the "hydroxy group equivalent” is the mass of a polymer per 1 mol of hydroxy groups in the polymer.
• the hydroxy group equivalent (g/mol) of a copolymer is determined by dividing the mass of the copolymer by the number of moles of hydroxy groups contained in the copolymer.
• the "hydroxy group equivalent” is a theoretical value calculated from the amount of monomer charged when producing the copolymer.
• the resin precursor (PA) can be produced by copolymerizing monomers (m-a) and (m-pb) corresponding to the structural units (a) and (pb) contained in the resin precursor (PA).
• the proportions of the structural units (a) and (pb) contained in the resin precursor (PA) are equal to the proportions of the monomers (m-a) and (m-pb) in the total of all monomers (hereinafter sometimes referred to as "raw material monomers") used as raw materials for the resin precursor (PA).
• the proportions of the monomers (m-a) and (m-pb) in the raw material monomers used as raw materials for the resin precursor (PA) are preferably 5-50 mol% (m-a) and 3-40 mol% (m-pb), more preferably 8-40 mol% (m-a) and 5-35 mol% (m-pb), and even more preferably 10-30 mol% (m-a) and 10-30 mol% (m-pb).
• the monomer (m-c) may be used as the raw material monomer for the resin precursor (PA) in addition to the monomers (m-a) and (m-pb).
• the proportion of monomer (m-c) in the raw material monomers used as the raw material for the resin precursor (PA) is preferably 3 to 40 mol%, more preferably 5 to 30 mol%, and even more preferably 8 to 25 mol%.
• monomer (m-d) When producing a resin precursor (PA) containing structural unit (d), monomer (m-d) may be used as the raw material monomer for resin precursor (PA) in addition to monomers (m-a) and (m-pb).
• the ratio of monomer (m-d) in the raw material monomers used as the raw material for resin precursor (PA) is preferably 5 to 45 mol%, more preferably 10 to 40 mol%, and even more preferably 15 to 35 mol%.
• the monomer (m-e) may be used as the raw material monomer for the resin precursor (PA) in addition to the monomers (m-a) and (m-pb).
• the proportion of the monomer (m-e) in the raw material monomers used as the raw material for the resin precursor (PA) is preferably 1 to 50 mol%, more preferably 3 to 45 mol%, and even more preferably 5 to 40 mol%.
• the copolymerization reaction of the raw material monomers (monomers (m-a) and (m-pb), and monomers (m-c), (m-d), and (m-e) used as necessary) used in producing the resin precursor (PA) can be carried out in the presence or absence of a polymerization solvent according to a radical polymerization method known in the art. Specifically, for example, a method can be used in which the raw material monomers, a polymerization initiator, and a polymerization solvent are mixed to prepare a raw material monomer solution, and the polymerization reaction is carried out in a nitrogen gas atmosphere at a temperature of 50 to 100°C for 1 to 20 hours.
• the solvents that can be used as the solvent (PD) described below can be used alone or in combination of two or more.
• the temperature at which the raw material monomers are copolymerized is preferably lower than the temperature at which the dissociation rate of the blocked isocyanato group of monomer (m-d) having a blocked isocyanato group and an ethylenically unsaturated bond becomes 80% or more in 30 minutes. This is to prevent the blocked isocyanato group of monomer (m-d) from dissociating in the raw material monomer solution during the copolymerization reaction to generate isocyanato groups, which then react with the hydroxyl group of hydroxyl group-containing monomer (m-c) to form gels.
• the temperature at which the raw material monomers are copolymerized is 20 to 50°C lower than the temperature at which the dissociation rate of the blocked isocyanato group of monomer (m-d) becomes 80% or more in 30 minutes.
• the temperature at which the raw material monomers are copolymerized can be 50 to 100°C, preferably 60 to 90°C, and more preferably 65 to 85°C.
• Polymerization initiators used in copolymerizing raw material monomers include, for example, 2,2'-azobis(2,4-dimethylvaleronitrile), azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, and t-butylperoxy-2-ethylhexanoate.
• the polymerization initiators may be used alone or in combination of two or more.
• the amount of polymerization initiator used may be 0.5 to 20 parts by mass, and preferably 1.0 to 16 parts by mass, per 100 parts by mass of raw material monomer (total amount of monomers charged).
• additives such as polymerization inhibitors, chain transfer agents, photosensitizers, fillers, and plasticizers may be used as necessary, provided they do not impair the effects of the present invention.
• the copolymer (A) can be produced by converting the structural unit (pb) contained in the resin precursor (PA) to the structural unit (b) in the presence of a basic catalyst and a solvent (PD).
• a resin precursor composition containing the resin precursor (PA), a basic catalyst, and a solvent (PD) is held at a temperature of, for example, 0 to 150° C. for 0.1 to 10 hours.
• the basic catalyst is not particularly limited as long as it can form a double bond between the carbon atom to which R 2 is bonded and the carbon atom to which R 3 is bonded in the group represented by formula (1) in the structural unit (pb) contained in the resin precursor (PA).
• the basic catalyst may be used alone or in combination of two or more kinds.
• the basic catalyst used preferably has a pKa (acidity constant) of 12.5 or more at 25°C.
• Basic catalysts with a pKa of 12.5 or more at 25°C include those with a pKa of 12.5 or more in aqueous solution, and those that are too acidic to be measured in aqueous solution, but whose pKa in aqueous solution converted from the results of measurement in an organic solvent is 12.5 or more.
• the basic catalyst is preferably a compound represented by the following formula (6).
• R 11 N CR 12 -NR 13 R 14 ... (6)
• R 11 , R 13 and R 14 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
• R 12 is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group represented by -N(R 15 ) 2 (wherein R 15 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and the two R 15s may be the same or different); and any two or more of R 11 , R 12 , R 13 , R 14 and the two R 15s may be bonded to form a cyclic structure.)
• the basic catalyst may be a compound represented by formula (7).
• R16N CR17 - NR18R19 ... (7)
• R 16 , R 17 , R 18 and R 19 are hydrocarbon groups, R 16 and R 19 are bonded to form a cyclic structure, the sum of the numbers of carbon atoms of R 16 and R 19 is 3 to 20, R 17 and R 18 are bonded to form a cyclic structure, and the sum of the numbers of carbon atoms of R 17 and R 18 is 3 to 20.
• the sum of the number of carbon atoms of R 16 and R 19 forming the cyclic structure is 3 to 20, and from the viewpoint of availability, it is preferably 3 to 10.
• the sum of the number of carbon atoms of R 17 and R 18 forming the cyclic structure is 3 to 20, and from the viewpoint of availability, it is preferably 3 to 10.
• basic catalysts include one or more selected from 1,8-diazabicyclo[5.4.0]-7-undecene (DBU) (pKa 12.5), 1,5-diazabicyclo[4.3.0]-5-nonene (pKa 12.7), and 1,1,3,3-tetramethylguanidine (pKa 13.6).
• DBU 1,8-diazabicyclo[5.4.0]-7-undecene
• pKa 12.7 1,5-diazabicyclo[4.3.0]-5-nonene
• 1,1,3,3-tetramethylguanidine pKa 13.6
• it is preferable to use 1,8-diazabicyclo[5.4.0]-7-undecene from the standpoints of catalytic activity, compatibility with solvents, and ease of availability.
• the content of the basic catalyst is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the resin precursor (PA).
• the content of the basic catalyst is 0.01 parts by mass or more, the reaction rate for converting the structural unit (pb) contained in the resin precursor (PA) to the structural unit (b) tends to be sufficiently fast, which is preferable.
• the content of the basic catalyst is 10 parts by mass or less, the effect of the basic catalyst can be suppressed when curing a photosensitive resin composition containing the copolymer (A) produced using the resin precursor composition.
• solvent (PD) examples include (poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, and 3-methoxy-1-butanol; hydroxy group-containing carboxylic acid esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, and methyl 2-hydroxy-3-methylbutyrate; and hydroxy group-containing solvents such as diethylene glycol; as well as ethylene glycol monomethyl ether acetate
• (Poly)alkylene glycol monoalkyl ether acetates such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, and other ethers; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and other ketones; methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl ether, Examples of the solvent (PD) include esters such as dipropionate, ethyl acetate, n-butyl acetate, i-propyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-butyl propionate, eth
• ethers from the viewpoints of availability, cost, and stability during resist preparation, and more specifically, it is more preferable to use one or more selected from propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, and 3-methoxy-1-butanol.
• the content of the solvent (PD) is preferably 30 to 1,000 parts by mass, and more preferably 50 to 800 parts by mass, per 100 parts by mass of the total of the components other than the solvent (PD) contained in the resin precursor composition.
• a content of the solvent (PD) of 30 parts by mass or more is preferable because a stable polymerization reaction can be performed.
• a content of the solvent (PD) of 1,000 parts by mass or less is preferable because the viscosity of the resin precursor composition can be appropriately adjusted.
• the conversion reaction for converting the structural unit (pb) to the structural unit (b) is preferably carried out under temperature conditions below the temperature at which the dissociation rate of the blocked isocyanato group of the structural unit (d) having a blocked isocyanato group becomes 80% or more in 30 minutes. This is to prevent the blocked isocyanato group of the structural unit (d) from dissociating to generate an isocyanato group in the resin precursor composition during the conversion reaction, which then reacts with the hydroxy group of the structural unit (c) having a hydroxy group to form a gel.
• the temperature conditions for carrying out the above conversion reaction are more preferably 20 to 50°C lower than the temperature at which the dissociation rate of the blocked isocyanato group of the structural unit (d) becomes 80% or more in 30 minutes.
• the temperature of the conversion reaction for converting the structural unit (pb) to the structural unit (b) can be 0 to 150°C, preferably 50 to 120°C, and more preferably 60 to 100°C.
• the retention time for holding the resin precursor composition under the above temperature conditions to carry out the above conversion reaction can be 0.1 to 10 hours, preferably 0.3 to 5 hours, and more preferably 0.5 to 3 hours.
• the retention time can be appropriately determined depending on the content of the structural unit (pb) contained in the resin precursor (PA) in the resin precursor composition, the content of the basic catalyst, the temperature conditions, etc.
• the atmosphere in the reaction vessel in which the above conversion reaction takes place can be, for example, an atmosphere containing air, dry air, nitrogen gas, helium gas, etc., and is preferably a dry air or nitrogen gas atmosphere.
• the pressure inside the reaction vessel in which the above conversion reaction is carried out is not particularly limited, but it is preferable that it be normal pressure.
• reaction path In the conversion reaction from the resin precursor (PA) to the copolymer (A), it is presumed that the structural unit (pb) contained in the resin precursor (PA) is converted to the structural unit (b) via the reaction pathway shown below.
• a group having a heterocycle represented by formula (1-3) and/or formula (1-4) is formed.
• the group having a heterocycle represented by formula (1-3) is formed by a dealcoholization reaction (-R 4 OH) of the ester moiety containing R 4 in the group represented by formula (1).
• the group having a heterocycle represented by formula (1-4) is formed by a dealcoholization reaction (-R 1 OH) of the ester moiety containing R 1 in the group represented by formula (1).
• R 1 , R 2 and R 3 are the same as R 1 , R 2 and R 3 in formula (1), and * represents a linking site with a residue obtained by removing the group of formula (1-3) from the structural unit (pb).
• R 2 , R 3 and R 4 are the same as R 2 , R 3 and R 4 in formula (1), and * represents a linking site with a residue obtained by removing the group of formula (1-4) from the structural unit (pb).
• R 1 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
• R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
• * represents a linking site with a residue obtained by removing the group of formula (1-1) from structural unit (b).
• R 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
• R 4 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
• * represents a linking site with a residue obtained by removing the group of formula (1-2) from the structural unit (b).
• reaction pathways of formulas (1), (1-4), and (1-2) have a lower activation barrier than the reaction pathways of formulas (1), (1-3), and (1-1) for the conversion reaction that converts the above-mentioned structural unit (pb) to structural unit (b), and are the main conversion route. Therefore, it is presumed that the structural unit having the group represented by formula (1-2) and the structural unit having the group represented by formula (1-1) are mixed in copolymer (A), and that the structural unit having the group represented by formula (1-2) is present in greater numbers than the structural unit having the group represented by formula (1-1).
• the photosensitive resin composition of one embodiment contains a copolymer (A), a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D).
• the photosensitive coloring composition of one embodiment further contains a colorant (E).
• the content of the copolymer (A) in the photosensitive resin composition or the photosensitive coloring composition is preferably 10 parts by mass or more, more preferably 30 parts by mass or more, and even more preferably 60 parts by mass or more, relative to 100 parts by mass of the total of the copolymer (A) and the reactive diluent (B).
• the content of the copolymer (A) in the photosensitive resin composition or the photosensitive coloring composition is preferably 90 parts by mass or less, more preferably 85 parts by mass or less, and even more preferably 80 parts by mass or less, relative to 100 parts by mass of the total of the copolymer (A) and the reactive diluent (B). Any combination of these lower and upper limits may be used.
• the content of the copolymer (A) in the photosensitive resin composition or the photosensitive coloring composition is preferably 10 to 90 parts by mass, more preferably 30 to 85 parts by mass, and even more preferably 60 to 80 parts by mass, relative to 100 parts by mass of the total of the copolymer (A) and the reactive diluent (B).
• the content of copolymer (A) is 10 parts by mass or more, a photosensitive resin composition or a photosensitive coloring composition can be obtained that has better low-temperature curing properties and can form a cured product with good solvent resistance.
• the content of copolymer (A) is 90 parts by mass or less, the content of reactive diluent (B) can be sufficiently secured, so that the strength of the cured product and the adhesion to the substrate are good.
• the reactive diluent (B) is a monomer having at least one ethylenically unsaturated bond as a polymerizable functional group in the molecule.
• the reactive diluent (B) may be a monofunctional monomer or a polyfunctional monomer having a plurality of polymerizable functional groups.
• the viscosity of the photosensitive resin composition or the photosensitive coloring composition can be set to an appropriate range according to the application.
• the photosensitive resin composition or the photosensitive coloring composition contains the reactive diluent (B), it has good photocurability and can form a cured product with good strength and adhesion to the substrate.
• the reactive diluent (B) may be used alone or in combination of two or more.
• Monofunctional monomers used as reactive diluents (B) include (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxymethyl (meth)acrylamide, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 5 ...
• Examples of the monofunctional monomer include (meth)acrylates such as 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, glycerin mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, and half (meth)acrylates of phthalic acid derivatives; aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, ⁇ -chloromethylstyrene, and vinyl toluene; and carboxylic acid esters such as vinyl acetate and vinyl propionate.
• the monofunctional monomers may be used alone or in combination of two or more.
• the polyfunctional monomers used as the reactive diluent (B) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, trimethylol glycol di(meth)acrylate, tetra ...
• acrylpropane tri(meth)acrylate glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloxy ...
• methacrylate examples include (meth)acrylates such as tris(hydroxyethyl)isocyanurate tri(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (for example, a reaction product of tolylene diisocyanate, trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, or the like with 2-hydroxyethyl (meth)acrylate), and tris(hydroxyethyl)isocyanurate tri(meth)acrylate; aromatic vinyl compounds such as divinylbenzene, diallyl phthalate, and diallyl benzene phosphonate; dicarboxylic acid esters
• a polyfunctional (meth)acrylate as the reactive diluent (B) because it is possible to obtain a photosensitive resin composition or a photosensitive coloring composition with good photocurability, and it is more preferable to use a polyfunctional (meth)acrylate having three or more functional groups, and it is even more preferable to use trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, or dipentaerythritol hexa(meth)acrylate.
• the content of the reactive diluent (B) in the photosensitive resin composition or the photosensitive coloring composition is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and even more preferably 30 parts by mass or more, relative to 100 parts by mass of the total of the copolymer (A) and the reactive diluent (B).
• the content of the reactive diluent (B) in the photosensitive resin composition or the photosensitive coloring composition is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, and even more preferably 60 parts by mass or less, relative to 100 parts by mass of the total of the copolymer (A) and the reactive diluent (B). Any combination of these lower and upper limits may be used.
• the content of the reactive diluent (B) in the photosensitive resin composition or the photosensitive coloring composition is preferably 10 to 90 parts by mass, more preferably 15 to 70 parts by mass, and even more preferably 30 to 60 parts by mass, relative to 100 parts by mass of the total of the copolymer (A) and the reactive diluent (B).
• the content of the reactive diluent (B) is 10 parts by mass or more, the effect of containing the reactive diluent (B) becomes significant.
• the content of the reactive diluent (B) is 90 parts by mass or less, the content of the copolymer (A) can be sufficiently secured, so that a photosensitive resin composition or a photosensitive coloring composition having even better low-temperature curing properties can be obtained.
• the photopolymerization initiator (C) is not particularly limited, and examples thereof include 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl-]-,-1-(O-acetyloxime); benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, and other benzoin and alkyl ethers thereof; acetophenone compounds such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4'-(1-t-butyldioxy-1-methylethyl)acetophenone;2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one;2-benzyl-2-dimethylamino-1-(4-morpholinyl)-1-propan-1-one;(1-phenyl)
• the content of the photopolymerization initiator (C) in the photosensitive resin composition or the photosensitive coloring composition is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1 part by mass or more, relative to 100 parts by mass of the total of the copolymer (A) and the reactive diluent (B).
• the content of the photopolymerization initiator (C) in the photosensitive resin composition or the photosensitive coloring composition is preferably 30 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, relative to 100 parts by mass of the total of the copolymer (A) and the reactive diluent (B). Any combination of these lower and upper limits may be used.
• the content of the photopolymerization initiator (C) in the photosensitive resin composition or the photosensitive coloring composition is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and even more preferably 1 to 10 parts by mass, relative to 100 parts by mass of the total of the copolymer (A) and the reactive diluent (B).
• the content of the photopolymerization initiator (C) is 0.1 parts by mass or more, a photosensitive resin composition or a photosensitive coloring composition having good photocurability can be obtained.
• the content of the photopolymerization initiator (C) is 30 parts by mass or less, it is possible to prevent the physical properties of the cured product of the photosensitive resin composition or the photosensitive coloring composition from being adversely affected by an excessive amount of the photopolymerization initiator (C).
• solvent (D) As the solvent (D), the same solvent (PD) used in the production of the copolymer (A) can be used.
• the solvent (D) in the photosensitive resin composition or the photosensitive coloring composition and the solvent (PD) used in the production of the copolymer (A) may be the same or different.
• the content of the solvent (D) in the photosensitive resin composition or the photosensitive coloring composition is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, per 100 parts by mass of the copolymer (A) and the reactive diluent (B).
• the content of the solvent (D) in the photosensitive resin composition or the photosensitive coloring composition is preferably 1,000 parts by mass or less, more preferably 800 parts by mass or less, per 100 parts by mass of the copolymer (A) and the reactive diluent (B). Any combination of these lower and upper limits may be used.
• the content of the solvent (D) in the photosensitive resin composition or the photosensitive coloring composition is preferably 30 to 1,000 parts by mass, more preferably 50 to 800 parts by mass, per 100 parts by mass of the copolymer (A) and the reactive diluent (B).
• the content of the solvent (D) is 30 parts by mass or more, the viscosity of the photosensitive resin composition or the photosensitive coloring composition can be set to an appropriate range.
• the solvent (D) can be easily removed when removing the solvent (D) from the coating film formed by applying the photosensitive resin composition or the photosensitive coloring composition to a substrate.
• the photosensitive coloring composition may further contain a colorant (E).
• the photosensitive coloring composition containing the colorant (E) can be used as a material for a color filter.
• the colorant (E) is not particularly limited as long as it is soluble or dispersible in the solvent (D), and examples include dyes and pigments.
• an acid dye having an acid group such as a carboxy group or a sulfo group, a salt of an acid dye with a nitrogen compound, a sulfonamide adduct of an acid dye, etc., from the viewpoints of solubility in the solvent (D) and the alkaline developer, interaction with other components in the photosensitive coloring composition, heat resistance, etc.
• dyes examples include: acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; solvent blue 38, 44, 70; acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 3 1, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 2 60, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow
• pigments examples include yellow pigments such as C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, and 214; orange pigments such as C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, and 73; C.I.
• the colorant (E) can be appropriately determined depending on, for example, the color of the desired colored pattern (black matrix and pixels).
• the colorant (E) may be used alone or in combination of two or more kinds.
• a dye and a pigment may be used in combination.
• a known dispersant may be blended in the photosensitive coloring composition in order to improve the dispersibility of the pigment.
• the dispersant it is preferable to use a polymer dispersant that has excellent dispersion stability over time.
• polymer dispersants include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic modified ester-based dispersants.
• the polymer dispersant those commercially available under the trade names EFKA (manufactured by EFKA CHEMICALS B.V.), Disperbyk (manufactured by BYK-Chemie), Disparlon (manufactured by Kusumoto Chemicals Co., Ltd.), and SOLSPERSE (manufactured by Lubrizol Corporation) may be used.
• the content of the dispersant may be appropriately set depending on the type and amount of the pigment used as the colorant (E).
• the content of the colorant (E) in the photosensitive coloring composition is preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, relative to 100 parts by mass of the total of the copolymer (A) and the reactive diluent (B).
• the content of the colorant (E) in the photosensitive coloring composition is preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and even more preferably 60 parts by mass or less, relative to 100 parts by mass of the total of the copolymer (A) and the reactive diluent (B). Any combination of these lower and upper limits may be used.
• the content of the colorant (E) in the photosensitive coloring composition is preferably 3 to 80 parts by mass, more preferably 5 to 70 parts by mass, and even more preferably 10 to 60 parts by mass, relative to 100 parts by mass of the total of the copolymer (A) and the reactive diluent (B).
• the content of the colorant (E) is 3 parts by mass or more, the effect of containing the colorant (E) becomes significant, and a photosensitive coloring composition suitable as a material for a colored pattern of a color filter is obtained.
• the content of colorant (E) is 80 parts by mass or less, colorant (E) does not interfere with the curing properties of the photosensitive coloring composition, and a photosensitive coloring composition with good low-temperature curing properties can be obtained.
• the resin composition of one embodiment may contain known additives such as coupling agents, leveling agents, and thermal polymerization inhibitors as needed.
• the amount of the additives to be added is not particularly limited as long as it is within a range that does not inhibit the effects of the present invention.
• the photosensitive resin composition of one embodiment can be produced by a method of mixing the copolymer (A), the reactive diluent (B), the photopolymerization initiator (C), and the solvent (D) using a known mixing device.
• the photosensitive coloring composition of one embodiment can be produced by a method of mixing the copolymer (A), the reactive diluent (B), the photopolymerization initiator (C), the solvent (D), and the coloring agent (E) using a known mixing device.
• a reaction liquid containing a copolymer (A) obtained by converting the structural unit (pb) to the structural unit (b) in a resin precursor composition and a solvent (PD) may be used as is as a raw material.
• the solvent (PD) contained in the reaction liquid can be used as a part or all of the solvent (D) contained in the photosensitive resin composition or the photosensitive coloring composition.
• the copolymer (A) isolated by a known method from a reaction solution containing the above-mentioned copolymer (A) and a solvent (PD) may be used as a raw material.
• the photosensitive resin composition or photosensitive coloring composition contains a copolymer (A) having a structural unit (b) having a group represented by formula (1-1) or formula (1-2), a reactive diluent (B), and a photopolymerization initiator (C), so that when irradiated with light, the reactive diluent (B) polymerizes together with the ethylenically unsaturated group contained in the structural unit (b) of the copolymer (A), resulting in good photocurability.
• a reactive diluent (B) a reactive diluent
• C photopolymerization initiator
• the photosensitive resin composition or the photosensitive coloring composition contains a copolymer (A) having a structural unit (c) having a hydroxyl group and a structural unit (d) having a blocked isocyanato group, the composition has even better low-temperature curing properties.
• a cured product when a cured product is formed using a photosensitive resin composition or a photosensitive coloring composition, it can be cured at a lower temperature compared to when a conventional resin composition is used. Therefore, when a baking process is performed after a coating film formed on a substrate is exposed to light, the photosensitive resin composition or the photosensitive coloring composition can form a cured product with excellent solvent resistance because the crosslinking reaction proceeds sufficiently even if the baking process temperature is lowered.
• a cured product when a cured product is formed using a photosensitive resin composition or a photosensitive coloring composition, less energy is required for heating to cause curing.
• a photosensitive resin composition or a photosensitive coloring composition by using a photosensitive resin composition or a photosensitive coloring composition, a cured product can be formed on a substrate with low heat resistance, such as a resin substrate, without causing any damage to the substrate.
• the photosensitive coloring composition even when a colorant with low heat resistance is used as the colorant (E), a cured product can be formed in which the inherent properties of the colorant (E) are exerted.
• the photosensitive coloring composition provides a cured product with excellent solvent resistance even when the baking temperature is low, so the colorant (E) is less likely to dissolve. Therefore, it is possible to increase the content of the colorant (E) in the photosensitive coloring composition.
• a photosensitive coloring composition with a high content of the colorant (E) can be used, for example, as a material for the color pattern of a color filter to form a color filter with excellent color reproducibility.
• the copolymer (A) contained in the photosensitive resin composition or photosensitive coloring composition has a structural unit (a) having an acid group
• the photosensitive resin composition or photosensitive coloring composition has good alkaline developability. Since such a photosensitive resin composition or photosensitive coloring composition has excellent alkaline developability, for example, it is possible to form a cured product having excellent solvent resistance and a predetermined pattern shape by applying it to a substrate to form a coating film, exposing it through a photomask corresponding to a predetermined pattern shape, developing the unexposed parts with an alkaline aqueous solution, and then baking at a sufficiently low temperature.
• the photosensitive resin composition and the photosensitive coloring composition can be suitably used as materials for color filters.
• photosensitive resin compositions and photosensitive coloring compositions are extremely useful as materials for forming components of image display elements, such as color filter pixels, black matrices, color filter protective films, photospacers, liquid crystal alignment protrusions, microlenses, and insulating films for touch panels.
• the cured resin film in one embodiment is made of a cured product of a photosensitive resin composition or a photosensitive coloring composition.
• the resin cured film can be produced, for example, by applying a photosensitive resin composition or a photosensitive coloring composition onto a substrate, volatilizing and removing the solvent (D) to form a coating film, exposing the coating film to light for photocuring, and then carrying out a baking process.
• a photosensitive resin composition or a photosensitive coloring composition is applied onto a substrate, and the solvent (D) is removed by volatilization to form a coating film.
• the coating film is exposed to light through a photomask having a predetermined pattern shape to photo-cure the exposed parts.
• the unexposed parts of the coating film are developed with an alkaline aqueous solution. After that, the developed coating film is baked to form a cured resin film having a predetermined pattern shape.
• the conditions of the baking treatment carried out when producing a resin cured film can be appropriately determined according to the composition of the photosensitive resin composition or photosensitive coloring composition, the film thickness of the coating film, the material of the substrate, etc.
• the baking treatment can be carried out at a temperature of, for example, 70°C to 250°C.
• the blocked isocyanato group of the structural unit (d) having a blocked isocyanato group contained in the copolymer (A) in the photosensitive resin composition or photosensitive coloring composition is sufficiently dissociated. This generates an isocyanato group, which reacts with the hydroxy group of the structural unit (c) having a hydroxy group.
• the structural unit (d) has a carboxylic acid alkyl ester structure
• crosslinking occurs due to ester exchange between the carboxylic acid alkyl ester structure and the hydroxy group.
• a good degree of curing is obtained, and a cured product having excellent solvent resistance is obtained.
• both a deblocking reaction and an ester exchange reaction can occur, but by adjusting the baking temperature, one of the reactions can be preferentially promoted.
• the baking temperature is preferably 75°C or higher, more preferably 80°C or higher.
• a baking temperature of 250°C or lower is preferable because it is a condition that can be tolerated by materials with low heat resistance, and discoloration of the photosensitive resin composition or the photosensitive coloring composition can be suppressed.
• the photosensitive resin composition and the photosensitive coloring composition have good low-temperature curing properties.
• the baking temperature can be set to 160°C or lower depending on the heat resistance of the substrate on which the resin cured film is formed. For example, when a resin substrate is used as the substrate, the baking temperature may be set to 150°C or lower, 120°C or lower, or 100°C or lower.
• the baking process carried out when producing a resin cured film can be carried out for, for example, 10 minutes to 4 hours, preferably 20 minutes to 2 hours, and can be appropriately determined depending on the composition of the photosensitive resin composition or photosensitive coloring composition, the temperature of the baking process, the thickness of the coating film, etc.
• the cured resin film is made of a photosensitive resin composition or a cured product of a photosensitive coloring composition. Therefore, the cured resin film can be produced by a baking process at a low temperature, and has excellent solvent resistance.
• the color filter of one embodiment has a color pattern made of a cured product of a photosensitive coloring composition.
• the color filter preferably has a color pattern made of a cured product of a photosensitive coloring composition containing 10 to 90 parts by mass of copolymer (A), 10 to 90 parts by mass of reactive diluent (B), 0.1 to 30 parts by mass of photopolymerization initiator (C), 30 to 1,000 parts by mass of solvent (D), and 3 to 80 parts by mass of colorant (E) relative to a total of 100 parts by mass of copolymer (A) and reactive diluent (B).
• the color filter may include, for example, a substrate, RGB pixels formed thereon, a black matrix formed at the boundaries between each pixel, and a protective film formed on the pixels and the black matrix.
• the pixels and black matrix are colored patterns made of the cured product of the above-mentioned photosensitive coloring composition.
• the components other than the materials of the pixels and black matrix can be publicly known.
• the substrate used for the color filter is not particularly limited, and glass substrates, silicon substrates, polycarbonate substrates, polyester substrates, polyamide substrates, polyamideimide substrates, polyimide substrates, aluminum substrates, printed wiring substrates, array substrates, etc. can be used as appropriate depending on the application.
• a colored pattern is formed on a substrate. Specifically, a colored pattern that will become a black matrix formed at the boundaries of each pixel, and a colored pattern that will become each of the RGB pixels are sequentially formed on the substrate by the method described below.
• the colored pattern can be formed by photolithography. Specifically, a photosensitive colored composition is applied onto a substrate to form a coating film. The coating film is then exposed to light through a photomask having a predetermined pattern shape, causing the exposed parts to photocure. The unexposed parts of the coating film are then developed with an alkaline aqueous solution. The developed coating film is then subjected to a baking process, thereby forming a colored pattern having the predetermined pattern shape.
• the method for applying the photosensitive coloring composition is not particularly limited, but any known method such as screen printing, roll coating, curtain coating, spray coating, or spin coating can be used.
• the substrate may be heated using a heating means such as a circulation oven, an infrared heater, or a hot plate, as necessary, to volatilize and remove the solvent (D) contained in the coating film.
• a heating means such as a circulation oven, an infrared heater, or a hot plate, as necessary, to volatilize and remove the solvent (D) contained in the coating film.
• the conditions for heating the substrate to remove the solvent (D) are not particularly limited and may be appropriately set depending on the material of the substrate, the composition of the photosensitive coloring composition, the thickness of the coating film, and the like.
• the substrate may be heated, for example, at a temperature of 50°C to 120°C for 30 seconds to 30 minutes.
• the coating film thus formed is irradiated with active energy rays such as ultraviolet rays and excimer laser light through a negative photomask, partially exposed, and photocured in the exposed portion.
• active energy rays such as ultraviolet rays and excimer laser light
• the amount of active energy radiation irradiated to the coating film may be appropriately selected depending on the composition of the photosensitive coloring composition, and may be, for example, 30 to 2000 mJ/cm 2.
• the light source used for exposure is not particularly limited, but may be a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like.
• the alkaline aqueous solution used for developing the coating film is not particularly limited, but may be an aqueous solution of an inorganic alkaline compound such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, or potassium hydroxide; an aqueous solution of an amine compound such as ethylamine, diethylamine, or dimethylethanolamine; an aqueous solution of a quaternary ammonium salt such as sulfate, hydrochloride, or p-toluenesulfonate of tetramethylammonium; an aqueous solution of an aniline compound or a salt thereof such as 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethylaniline, 3-methyl-4-a
• the conditions for the baking process carried out when manufacturing a color filter can be appropriately determined depending on the composition of the photosensitive coloring composition, the thickness of the coating film, the material of the substrate, etc.
• the baking temperature can be, for example, 70°C to 210°C. When the baking temperature is 70°C or higher, good curing properties are obtained, and a cured product with excellent solvent resistance is obtained.
• the baking temperature is preferably 75°C or higher, and more preferably 80°C or higher. When the baking temperature is 210°C or lower, it is preferable because a material with low heat resistance, such as a substrate with low heat resistance, can be used as the material for the color filter.
• the baking temperature can be set to 160°C or less depending on the heat resistance of the substrate on which the resin cured film is formed. For example, when a colored pattern is formed using a resin substrate as the substrate, the baking temperature may be set to 150°C or less, 120°C or less, or 100°C or less.
• the baking process carried out when manufacturing a color filter can be carried out for, for example, 10 minutes to 4 hours, preferably 20 minutes to 2 hours, and can be appropriately determined depending on the composition of the photosensitive coloring composition, the temperature of the baking process, the thickness of the coating film, etc.
• the photosensitive coloring composition has good photocurability and low-temperature curability. Therefore, when a colored pattern is formed using the photosensitive coloring composition of one embodiment, if the baking temperature is the same as when a colored pattern is formed using a conventional photosensitive coloring composition, the baking time can be shortened, and a color filter can be formed efficiently.
• the colored pattern that will become each of the RGB pixels and the colored pattern that will become the black matrix formed at the boundaries of each pixel are formed, and then a protective film is formed on the colored pattern (each of the RGB pixels and the black matrix).
• the method for manufacturing the protective film is not particularly limited, and it may be formed using the photosensitive resin composition of one embodiment, or may be formed using known materials and known methods.
• the color filter has a color pattern made of the cured product of the above-mentioned photosensitive coloring composition. Therefore, the color pattern in the color filter can be formed by a method in which a baking process is performed at a low temperature. This allows the energy required for the baking process to be reduced.
• a colorant (E) with low heat resistance as the colorant contained in the photosensitive coloring composition used as a material for the color filter.
• This allows for a wide range of options for the colorant (E) that can be used. Therefore, for example, it is possible to form a color filter that contains a colorant (E) with low heat resistance and has a coloring pattern that exhibits the inherent properties of the colorant (E) with low heat resistance.
• the colored pattern in the color filter can be formed on a substrate with low heat resistance, such as a resin substrate, without interfering with the substrate. This allows for a wide range of substrate options. Specifically, for example, because a color filter can be formed on a substrate with low heat resistance, such as a resin substrate, displays can be made more flexible. In addition, the colored pattern in the color filter has excellent solvent resistance, so there is little color change.
• a photosensitive coloring composition containing a photopolymerization initiator (C) is used to produce a colored pattern by photocuring the photosensitive coloring composition.
• a photosensitive coloring composition containing a curing accelerator and a known epoxy resin may be used, and a colored pattern made of a cured product of the photosensitive coloring composition containing copolymer (A) may be formed by applying the composition to a substrate by an inkjet method and then heating the composition.
• the image display element according to an embodiment includes a color filter.
• a known configuration other than the color filter can be adopted.
• Specific examples of the image display element include a liquid crystal display element, an organic EL display element, and a solid-state imaging element such as a CCD element or a CMOS element.
• the components of the image display element other than the color filter can be manufactured by known methods. For example, when manufacturing a liquid crystal display element as the image display element, it can be manufactured using the method shown below. First, a color filter is formed on a substrate using the method described above. Then, electrodes, spacers, etc. are formed in sequence on the substrate having the color filter. Next, electrodes, etc. are formed on another substrate, which is then placed opposite the substrate having the color filter and bonded together. Then, a predetermined amount of liquid crystal is injected between the opposing substrates and sealed.
• the image display element is equipped with a color filter that has excellent solvent resistance, so there is little color change.
• copolymer (A) An example of the synthesis of copolymer (A) is shown below.
• Example 1 (Synthesis Example 1) (Synthesis of Resin Precursor (PA))
• a stirrer Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 268.47 g of propylene glycol monomethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed as a solvent (PD), and the mixture was stirred while replacing with nitrogen gas and heated to 78°C.
• PD solvent
• the entire amount of the raw monomer solution was dropped into the solvent (PD) in a flask at normal pressure and in a nitrogen gas atmosphere using a dropping funnel over the course of one hour. After the dropping was completed, the solution in the flask was stirred while undergoing a polymerization reaction at 78°C for three hours to obtain a solution containing the resin precursor (PA) and the solvent (PD).
• Examples 2 to 9 (Synthesis Examples 2 to 9)] Solutions of copolymers (A) of Examples 2 to 9 were obtained in the same manner as in Example 1, except that the monomers and blending amounts shown in Table 1 were used. The weight average molecular weights, ethylenically unsaturated group equivalents, and acid values of copolymers (A) of Examples 2 to 9 were measured by the methods described above and are shown in Table 1. The blocked isocyanato group equivalents and hydroxyl group equivalents of copolymers (A) of Examples 2 to 9 were calculated and are shown in Table 1.
• the entire amount of the raw monomer solution was dropped into the solvent (PD) in a flask at normal pressure and in a nitrogen gas atmosphere using a dropping funnel over the course of one hour. After the dropping was completed, the solution in the flask was stirred while undergoing a polymerization reaction at 78°C for three hours to obtain a solution containing the resin precursor (PA) and the solvent (PD).
• Propylene glycol monomethyl ether acetate (Tokyo Chemical Industry Co., Ltd.) was added as solvent (D) to the reaction liquid containing the copolymer (cA) and solvent (PD) obtained in this manner so that the components other than the solvent were 35 mass %, and a solution of copolymer (cA) of Comparative Example 1 was obtained.
• the entire amount of the raw monomer solution prepared was dropped into the solvent (PD) in a flask at normal pressure and in a nitrogen gas atmosphere using a dropping funnel over the course of one hour. After the dropping was completed, the solution in the flask was stirred while undergoing a polymerization reaction at 78°C for three hours to obtain a reaction liquid containing copolymer (cA) and solvent (PD).
• the weight average molecular weight, ethylenically unsaturated group equivalent, and acid value of copolymer (cA) were measured by the methods described above and are listed in Table 1.
• the blocked isocyanato group equivalent and hydroxyl group equivalent of copolymer (cA) were calculated and are listed in Table 1.
• AOI-MDE Karenz (trademark) AOI-MDE, 2-[(diethyl malate)carbonylamino]ethyl acrylate (manufactured by Showa Denko K.K.)
• AOI-DEM KarenzTM AOI-DEM, a reaction product of 2-isocyanatoethyl acrylate and diethyl malonate (manufactured by Showa Denko K.K.)
• MOI-BP Karenz (trademark) MOI-BP, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (manufactured by Showa Denko K.K.)
• MOI-BM Karenz (trademark) MOI-BM, 2-[(methylethylketoxime)carbonylamino]ethyl methacrylate (
• the amount of the copolymer (A) or (cA) in Table 2 does not include the amount of the solvent.
• the amount of the solvent (D) in Table 2 is the sum of the amount of the solvent contained in the solution of the copolymer (A) or (cA) obtained in Synthesis Examples 1 to 9 and Comparative Synthesis Examples 1 and 2, and the amount of the solvent added when preparing the photosensitive coloring composition.
• the photosensitive coloring compositions of Examples 10 to 18 and Comparative Examples 3 to 4 were each applied by spin coating onto a square glass substrate (alkali-free glass substrate) measuring 5 cm in length and 5 cm in width in plan view, so that the thickness after exposure was 2.5 ⁇ m, to form a coating film.
• the coating film was then heated at 100° C. for 3 minutes to volatilize and remove the solvent (D) in the coating film.
• the coating film was exposed to ultraviolet light having a wavelength of 365 nm at an energy dose of 100 mJ/ cm2 , and the exposed portion was photocured. After that, the coating film was cured by baking at 100°C for 20 minutes to form a cured film. The thickness of the cured film thus produced was measured with a step gauge. The thickness at this time was designated as X.
• the prepared cured film was immersed in 20 g of propylene glycol monomethyl ether acetate (PGMEA) at 23°C for 15 minutes. After immersion, the coating film was vacuum dried at 40°C for 30 minutes, and the thickness of the coating film was measured with a step gauge. The thickness at this time was designated as Y.
• PGMEA propylene glycol monomethyl ether acetate
• the ratio of the thickness Y of the cured film after immersion in PGMEA to the thickness X of the cured film before immersion in PGMEA was calculated as the film remaining ratio by the following formula, and the solvent resistance of the cured film was evaluated. That is, the closer the film remaining ratio is to 100%, the better the solvent resistance of the cured film is.
• a film remaining ratio of 80% or more was set as the pass line for evaluation.
• the cured films of the resin compositions of Examples 10 to 18 had a residual film rate (%) of 85% or more after immersion in PGMEA, and exhibited good solvent resistance even at a baking temperature as low as 100°C.
• the photosensitive coloring compositions prepared in Examples 10 to 18 and Comparative Examples 3 to 4 were applied onto a 5 cm square glass substrate (alkali-free glass substrate) by spin coating so that the thickness after exposure was 1.5 ⁇ m (coating step).
• the glass substrate onto which the photosensitive coloring composition was applied was heated at 100° C. for 3 minutes to volatilize the solvent and dry the coating film (pre-baking step).
• the surface of the dried coating film was irradiated with 100 mJ/ cm2 light using an ultra-high pressure mercury lamp through a photomask (exposure step).
• the exposure step was performed by placing a photomask at a position 100 ⁇ m away from the coating film.
• the photomask used had a line and space pattern with a width of 3 to 100 ⁇ m.
• the unexposed portion was removed by spraying Semiclean DL-A10 developer (manufactured by Yokohama Yushi Kogyo Co., Ltd.) (diluted 300 times) on the surface of the coating film for 60 seconds under conditions of a temperature of 23 ° C. and a pressure of 0.1 MPa (development step).
• the dissolved form of the coating film when the developer was sprayed was observed, and the solubility was evaluated according to the following criteria.
• the results are shown in Table 2. 1: No residue remains in the unexposed areas, no powder is found in the developer, and the pattern shape is good. 2: No residue remains in the unexposed areas, but powder is found in the developer, and the pattern shape is relatively good. 3: Residue remains in the unexposed areas, and there are some missing parts in the pattern shape. 4: The film peels off in the exposed areas, and no pattern remains.
• the present invention provides a photosensitive resin composition that gives a cured resin film with excellent solvent resistance.
• the present invention also provides an image display element that includes a color filter having a colored pattern made of a cured resin film with excellent solvent resistance.
• the photosensitive resin composition and the photosensitive coloring composition can be preferably used as materials for transparent films, protective films, insulating films, overcoats, photospacers, black matrices, black column spacers, resists for color filters, and the like.

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