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
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • 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
  • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
  • C08F265/02—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of acids, salts or anhydrides
• • 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
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/20—Carboxylic acid amides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
  • G02F1/133509—Filters, e.g. light shielding masks
  • G02F1/133514—Colour 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
  • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
  • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
  • H10H29/00—Integrated devices, or assemblies of multiple devices, comprising at least one light-emitting semiconductor element covered by group H10H20/00
  • H10H29/80—Constructional details
  • H10H29/85—Packages
  • H10H29/8517—Colour filters

Definitions

• the present disclosure relates to a resin composition, a modified resin composition, a photosensitive resin composition, a photosensitive colored composition, a cured resin film, an image display element, a method for producing a resin composition, and a method for producing a modified resin composition.
• 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 disclosure provides a resin composition that can efficiently introduce ethylenically unsaturated groups into a resin. It also provides a modified resin composition that contains a copolymer into which a sufficient amount of ethylenically unsaturated groups have been introduced. It also provides a modified resin composition that contributes to improved developability and gives a cured resin film having excellent solvent resistance, as well as a photosensitive resin composition and a photosensitive coloring composition that use the same. The present disclosure further provides a cured resin film having excellent solvent resistance, and an image display element that includes the same.
• a copolymer (A), A basic catalyst (B); A solvent (C); A resin composition comprising: The copolymer (A) is A structural unit (a) having an acid group; A structural unit (pb) having a group represented by the following formula (1), A copolymer containing The content of the basic catalyst (B) is 0.5 to 10 parts by mass based on 100 parts by mass of the copolymer (A).
• 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).
• a modified resin composition comprising:
• the modified copolymer (A2) is A structural unit (a) having an acid group;
• Modification rate [%] [structural unit (b) / (structural unit (pb) + (b))] [
• 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).
• 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
• 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).
• 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)
• the method includes a step (I) of preparing a resin composition containing a copolymer (A), a basic catalyst (B), and a solvent (C),
• the copolymer (A) is A structural unit (a) having an acid group;
• a copolymer containing The content of the basic catalyst (B) is 0.5 to 10 parts by mass per 100 parts by mass of the copolymer (A).
• 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 modified copolymer (A2) is A structural unit (a) having an acid group;
• a method for producing a modified resin composition comprising the steps of: (In formula (1), 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, and * represents a linking site with a residue remaining after removing the group of formula (1) 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
• a resin composition that can efficiently introduce ethylenically unsaturated groups into a resin. It is also possible to provide a modified resin composition that contains a copolymer into which a sufficient amount of ethylenically unsaturated groups have been introduced. Furthermore, it is possible to provide a modified resin composition that contributes to improved developability and gives a cured resin film having excellent solvent resistance, as well as a photosensitive resin composition and a photosensitive coloring composition that use the modified resin composition. It is also possible to provide a cured resin film having excellent solvent resistance, a color filter, and an image display element that includes the modified resin composition and the photosensitive coloring composition that are cured.
• (meth)acrylic acid means methacrylic acid or acrylic acid
• (meth)acrylate means acrylate or methacrylate
• (meth)acryloyl means acryloyl or methacryloyl
• (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 resin composition of one embodiment contains a copolymer (A), a basic catalyst (B), and a solvent (C).
• the copolymer (A) does not contain the structural unit (b) described later, but contains a structural unit (a) having an acid group and a structural unit (pb) having a group represented by the following formula (1). Since the copolymer (A) has the structural unit (pb) having a group represented by the following formula (1), the conversion to the structural unit (b) proceeds under the action of the basic catalyst (B) described later, and an ethylenically unsaturated group is introduced into the copolymer (A). By using this in a photosensitive resin composition, the developability is improved and a resin cured film having good solvent resistance can be obtained.
• 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 copolymer (A) may further contain, as necessary, a structural unit (c) having a hydroxyl group, a structural unit (d) having a blocked isocyanato group, or a combination thereof.
• the copolymer (A) may further contain, as necessary, a structural unit (e) other than the structural units (a) to (d) and (pb).
• the structural unit (a) having an acid group (also simply referred to as “structural unit (a)”) is not particularly limited as long as it is a structural unit having an acid group and does not have an ethylenically unsaturated group.
• a modified copolymer (A2) obtained by converting the copolymer (A) is used in a photosensitive resin composition, good alkaline developability can be obtained.
• 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, 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, ⁇ -bromo(
• 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 the 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 the copolymer (A).
• the content of the structural unit (a) is 5 mol % or more, good developability of the photosensitive resin composition using the modified copolymer (A2) obtained by converting the copolymer (A) can be obtained.
• the content of the structural unit (a) is 50 mol % or less, the content of the structural unit (pb) can be sufficiently ensured, and therefore the effect attributable to the structural unit (b) can be sufficiently ensured.
• the structural unit (pb) having a group represented by formula (1) is a structural unit having no acid group and no ethylenically unsaturated group and having a group represented by the following formula (1).
• 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 group represented by formula (1) does not have to be of one type.
• R1 in each structural unit may be different, R2 in each structural unit may be different, R3 in each structural unit may be different, and R4 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) to a structural unit (b) having a group represented by formula (1-1) or formula (1-2) described later 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 (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 monomer (m-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).
• 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 may be any solvent that is inactive to the isocyanato group, and any known solvent may 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, for ease of 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 isocyanate compound having a (meth)acryloyl group or a (meth)acryloyloxy group is preferred, and an isocyanato group-containing (meth)acrylate is more preferred, such as 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, etc.
• (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 even more preferred.
• 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 (pb) 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 content of the structural unit (pb) is 3 mol % or more, a sufficient amount of ethylenically unsaturated groups can be introduced into the copolymer (A) by a conversion reaction.
• the modified copolymer (A2) into which the ethylenically unsaturated groups have been introduced in the photosensitive resin composition, good low-temperature curing properties and developability can be obtained.
• the content of the structural unit (pb) is 40 mol % or less, the content of the structural unit (a) can be sufficiently ensured, and by using the modified copolymer (A2) in the photosensitive resin composition, sufficient developability can be obtained.
• the copolymer (A) may contain a structural unit (c) having a hydroxyl group (also simply referred to as “structural unit (c)”) as necessary.
• the 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.
• crosslinking with the structural unit (d) having a blocked isocyanato group described below progresses upon heating.
• the modified copolymer (A2) obtained by converting 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 modified copolymer (A2), 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.
• the low-temperature curing property of the photosensitive resin composition using the modified copolymer (A2) obtained by converting the copolymer (A) is improved.
• the content of the structural unit (c) is 40 mol % or less, the contents of the structural unit (a) and the structural unit (pb) can be sufficiently ensured, so that a sufficient amount of ethylenically unsaturated groups can be introduced into the copolymer (A). Therefore, the cured product of the photosensitive resin composition using the modified copolymer (A2) after conversion has sufficient developability.
• the content of the structural unit (d) can be sufficiently ensured, so that the amount of crosslinking with the structural unit (c) can be sufficiently ensured.
• the copolymer (A) may contain a structural unit (d) having a blocked isocyanato group (also simply referred to as "structural unit (d)”) as necessary.
• the structural unit (d) is not particularly limited as long as it is a structural unit that does not have an acid group and an ethylenically unsaturated group, does not fall under the structural unit (pb), and has a blocked isocyanato group.
• crosslinking with the structural unit (c) having a hydroxy group proceeds upon heating.
• the crosslinking is formed, for example, by a reaction between an isocyanato group generated by dissociation of the blocking agent and a hydroxy 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 a hydroxy group, as described below, even if the blocking agent does not dissociate.
• the modified copolymer (A2) 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- Examples 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 mass loss rate of the blocked isocyanato group-containing compound measured by HPLC analysis after preparing an n-octanol solution containing a 20% by mass concentration of the blocked isocyanato group-containing compound, 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.
• the blocked isocyanato group-containing compound used is a compound in which the isocyanato group of 2-isocyanatoethyl acrylate is blocked with the blocking agent to be measured.
• 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 modified copolymer (A2).
• a photosensitive resin composition using the modified copolymer (A2) obtained by converting 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 modified copolymer (A2) 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 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 is an ethyl group
• ethanol is generated by transesterification of R7 with the hydroxy group of the structural unit (c) during thermal curing of the photosensitive resin composition containing the modified copolymer (A2). This is preferable because the ethanol generated during thermal curing of the photosensitive resin composition is easily evaporated and removed by heating for thermal curing of 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 (Resonac Co., Ltd.) and Karenz (trademark) AOI-DEM (Resonac Co., Ltd.).
• 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.
• the low-temperature curing property of the photosensitive resin composition using the modified copolymer (A2) obtained by converting the copolymer (A) is improved.
• the content of the structural unit (d) is 45 mol% or less, the content of the structural unit (a) and the structural unit (pb) can be sufficiently ensured, and the content of the structural unit (a) and the structural unit (b) of the modified copolymer (A2) can be sufficiently ensured, so that the cured product can have sufficient developability.
• 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 a structural unit (e) (also simply referred to as "structural unit (e)") other than the structural units (a) to (d) and the structural unit (pb) as necessary.
• 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 hydroxyl group, or a blocked isocyanato group.
• copolymer (A) contains the structural unit (e), it can be given additionally required functions.
• the other structural unit (e) is a structural unit derived from a monomer (m-e) (also simply called monomer (m-e)) having another ethylenically unsaturated group that is copolymerizable with the monomers (m-a), (m-pb), (m-c), and (m-d).
• m-e monomer having another ethylenically unsaturated group that is copolymerizable with the monomers (m-a), (m-pb), (m-c), and (m-d).
• 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).
• its content of structural unit (e) 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).
• the basic catalyst (B) 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 copolymer (A).
• the basic catalyst (B) may be used alone or in combination of two or more kinds.
• Basic catalysts having a pKa of 4 or more at 25°C include those having a pKa of 4 or more in aqueous solution, and those that are too acidic to be measured in aqueous solution and have a pKa of 4 or more in aqueous solution converted from the measurement results in an organic solvent.
• the pKa of the basic catalyst (B) at 25°C may be 15 or less, 13 or less, or 11 or less.
• the pKa of the basic catalyst (B) at 25°C may be 4 or more, 5 or more, 6 or more, or 7 or more. Any combination of these lower and upper limits may be used. If the pKa of the basic catalyst (B) at 25°C is 15 or less, it is possible to suppress a decrease in activity due to the formation of a salt with the acid group of the structural unit (a).
• R 14 N CR 15 -NR 16 R 17 ...(6)
• R 14 , R 16 and R 17 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms
• R 15 is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group represented by -N(R 18 ) 2 (wherein R 18 is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and the two R 18s may be the same or different); and any two or more of R 14 , R 15 , R 16 , R 17 and the two R 18s may be bonded to form a cyclic structure.
• the basic catalyst (B) also includes, for example, a compound represented by formula (7).
• R 19 N CR 20 -NR 21 R 22 ...(7)
• R 19 , R 20 , R 21 and R 22 are hydrocarbon groups, R 19 and R 22 are bonded to form a cyclic structure, the sum of the numbers of carbon atoms of R 19 and R 22 is 3 to 20, R 20 and R 21 are bonded to form a cyclic structure, and the sum of the numbers of carbon atoms of R 20 and R 21 is 3 to 20.
• the sum of the number of carbon atoms of R 19 and R 22 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 20 and R 21 forming the cyclic structure is 3 to 20, and from the viewpoint of availability, it is preferably 3 to 10.
• compounds represented by formula (6) or formula (7) include 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
• pKa 13.6 1,1,3,3-tetramethylguanidine
• Examples of basic catalysts (B) include alkylamines and cyclic diamines.
• alkylamines examples include diisopropylamine (pKa 11.05), trimethylamine, and triethylamine (pKa 10.7).
• Cyclic diamines include 1,4-diazabicyclo[2.2.2]octane (DABCO) (pKa 8.8).
• the basic catalyst (B) is preferably at least one selected from the group consisting of pyridine and pyridine derivatives, and imidazole compounds.
• pyridine and pyridine derivatives, and imidazole compounds have a relatively low pKa, and therefore maintain activity without forming a salt with the acid group of the structural unit (a), and have high nucleophilicity due to resonance stabilization. Therefore, by using at least one selected from the group consisting of pyridine and pyridine derivatives, and imidazole compounds, the structural unit (pb) contained in the copolymer (A) can be efficiently converted to introduce an ethylenically unsaturated group.
• the copolymer (A) can be efficiently converted to the modified copolymer (A2) described later.
• a photosensitive resin composition using the modified copolymer (A2) can provide a cured film that has excellent low-temperature curing properties and developability, and excellent solvent resistance.
• pyridine and pyridine derivatives include pyridine (pKa 5.2); C1-4 alkylpyridines such as methylpyridine (picoline) (pKa 6.75) and ethylpyridine; di-C1-4 alkylpyridines such as dimethylpyridine (lutidine) (pKa 6.47-6.6); tri-C1-4 alkylpyridines such as trimethylpyridine (collidine) (pKa 7.48); and 4-aminopyridine derivatives having an amino group at the 4th position such as 4-aminopyridine (pKa 9.17), 4-dimethylaminopyridine (pKa 9.7), 4-diethylaminopyridine, 4-pyrrolidinopyridine, 4-piperidinopyridine, and 2-methyl-4-dimethylaminopyridine.
• C1-4 alkylpyridines such as methylpyridine (picoline) (pKa 6.75) and ethylpyridine
• di-C1-4 alkylpyridines such as di
• 4-aminopyridine derivatives are preferred, 4-aminopyridine derivatives having a tertiary amino group at the 4-position are more preferred, 4-dialkylaminopyridine is even more preferred, and 4-dimethylaminopyridine is particularly preferred.
• C1-4 alkyl means that the number of carbon atoms in the alkyl group is 1 to 4.
• Imidazole compounds include 2-methylimidazole (pKa 7.75) and 1,2-dimethylimidazole (pKa 7.8).
• the content of the basic catalyst (B) is 0.5 parts by mass or more, preferably 0.7 parts by mass or more, and more preferably 1.0 parts by mass or more, relative to 100 parts by mass of the copolymer (A).
• the content of the basic catalyst (B) is 10 parts by mass or less, preferably 8.0 parts by mass or less, and more preferably 6.0 parts by mass or less, relative to 100 parts by mass of the copolymer (A). Any combination of these lower and upper limits may be used.
• the conversion rate when converting the structural unit (pb) contained in the copolymer (A) to the structural unit (b) is high, which is preferable.
• the content of the basic catalyst (B) is 10 parts by mass or less, the effect of the basic catalyst (B) can be suppressed when curing a photosensitive resin composition containing the modified copolymer (A2) obtained by converting the copolymer (A).
• solvent (C) 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 monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc.; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl ether, 3-methyl-3-methoxybutyl ether, Examples of the solvent include esters such as ethyl propionate, ethyl acetate, n-butyl acetate, i-propyl acetate, i-butyl acetate, n-
• ethers such as (poly)alkylene glycol monoalkyl ethers, (poly)alkylene glycol monoalkyl ether acetates, and other ethers, 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 solvent (C) 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 solvent (C). If the content of solvent (C) is 30 parts by mass or more, a stable reaction can be carried out when converting the structural unit (pb) contained in copolymer (A), which is preferable. If the content of solvent (C) is 1,000 parts by mass or less, the viscosity of the resin composition can be appropriately adjusted, which is preferable.
• the copolymer (A) can be produced by copolymerizing monomers (m-a) and (m-pb) corresponding to the structural units (a) and (pb) contained in the copolymer (A).
• the proportions of the structural units (a) and (pb) contained in the copolymer (A) are equal to the proportions of the monomers (m-a) and (m-pb) in the total of all the monomers (hereinafter sometimes referred to as "raw material monomers" used as raw materials for the copolymer (A).
• the proportions of the monomers (m-a) and (m-pb) in the raw material monomers used as the raw materials for copolymer (A) are preferably 5 to 50 mol% (m-a) and 3 to 40 mol% (m-pb), more preferably 8 to 40 mol% (m-a) and 5 to 35 mol% (m-pb), and even more preferably 10 to 30 mol% (m-a) and 10 to 30 mol% (m-pb).
• monomer (m-c) may be used as the raw monomer for copolymer (A) in addition to monomers (m-a) and (m-pb).
• the ratio of monomer (m-c) in the raw monomer used as the raw material for copolymer (A) 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 copolymer (A) containing structural unit (d), monomer (m-d) may be used as the raw monomer for copolymer (A) in addition to monomers (m-a) and (m-pb).
• the ratio of monomer (m-d) in the raw monomer used as the raw material for copolymer (A) is preferably 5 to 45 mol%, more preferably 10 to 40 mol%, and even more preferably 15 to 35 mol%.
• monomer (m-e) may be used as the raw monomer for copolymer (A) in addition to monomers (m-a) and (m-pb).
• the ratio of monomer (m-e) in the raw monomers used as the raw material for copolymer (A) 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 copolymer (A) 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 polymerization solvent used in producing the copolymer (A) may be any of those usable as the solvent (C) either 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 that the effects of the present invention are not impaired.
• the resin composition is obtained by mixing the copolymer (A), the basic catalyst (B), and the solvent (C).
• the resin composition can also be produced by adding the basic catalyst (B) to the reaction solution.
• the solvent used in the synthesis of the copolymer (A) may be used as the solvent (C) as it is, or a new solvent may be added.
• the modified resin composition of one embodiment contains a modified copolymer (A2), a basic catalyst (B), and a solvent (C).
• the modified resin composition may contain a copolymer (A).
• the basic catalyst (B) and the solvent (C) can be the same as those used in the resin composition, and the preferred forms and amounts are also the same.
• the amount of basic catalyst (B) is based on 100 parts by mass of the total of the copolymer (A) and the modified copolymer (A2).
• the modified copolymer (A2) of one embodiment contains a structural unit (a) having an acid group, a structural unit (pb) having a group represented by the following formula (1), and a structural unit (b) having a group represented by the following formula (1-1) or the following formula (1-2).
• the modified copolymer (A2) can be obtained by converting a part of the structural unit (pb) of the copolymer (A) to the structural unit (b) by a dealcoholization reaction and a decarboxylation reaction of the structural unit (pb) by the action of a basic catalyst (B).
• the modified copolymer (A2) has a structural unit (b) having an ethylenically unsaturated group, good photocurability is obtained when the modified copolymer (A2) is used in a photosensitive resin composition, and low-temperature curability is improved.
• the modified copolymer (A2) is used together with a reactive diluent (D) described later, the ethylenically unsaturated group of the structural unit (b) reacts with the reactive diluent (D), and good adhesion of the cured film to the substrate is obtained.
• 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).
• 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)
• the modified copolymer (A2) may further contain a structural unit (c) having a hydroxyl group and a structural unit (d) having a blocked isocyanato group, if necessary.
• the modified copolymer (A2) may further contain a structural unit (e) other than the structural units (a) to (d) and the structural unit (pb), if necessary.
• the structural units (a), (pb), (c), (d), and (e) can be the same as those in copolymer (A). Except for the content of the structural unit (pb), the preferred embodiments are also the same.
• the content of the structural unit (pb) is preferably 1 to 35 mol %, more preferably 2 to 30 mol %, and even more preferably 3 to 25 mol %, of all structural units in the modified copolymer (A2) and the copolymer (A).
• the structural unit (b) having a group represented by formula (1-1) or formula (1-2) (also simply referred to as “structural unit (b)") is a structural unit having no acid group and 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)
• 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 , R 2 , R 3 and R 4 are the same as those defined above for the formula (1).
• the content of the structural unit (b) is preferably 2 to 39 mol %, more preferably 3 to 33 mol %, and even more preferably 7 to 27 mol %, of all structural units in the modified copolymer (A2) and the copolymer (A).
• reaction Pathway In the conversion reaction from copolymer (A) to modified copolymer (A2), it is presumed that the structural unit (pb) contained in copolymer (A) 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).
• the 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 modified copolymer (A2) contains a mixture of structural units having a group represented by formula (1-2) and structural units having a group represented by formula (1-1), and that the structural units having a group represented by formula (1-2) are more abundant than the structural units having a group represented by formula (1-1).
• the ethylenically unsaturated group equivalent of the modified copolymer (A2) is 300 g/mol or more, preferably 500 g/mol or more, and more preferably 1000 g/mol or more. In one embodiment, the ethylenically unsaturated group equivalent of the modified copolymer (A2) is 10000 g/mol or less, preferably 7000 g/mol or less, and more preferably 4000 g/mol or less. The combination of these lower limit values and upper limit values may be any combination. When it is 300 g/mol or more, the storage stability as a photosensitive resin composition is good. When it is 10000 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 the modified copolymer (A2) is determined by dividing the mass of the modified copolymer (A2) by the number of moles of ethylenically unsaturated groups contained in the modified copolymer (A2).
• the ethylenically unsaturated group equivalent is a value calculated from the conversion rate of structural unit (pb) to structural unit (b) calculated from the area ratio of the NMR spectrum obtained under the following conditions using an NMR device (e.g., Bruker ULTRA SHIELD PLUS 400 (400 MHz), Bruker Corporation) and the charged amounts of monomers (m-a), (m-pb), and (m-c) to (m-e) used in producing the copolymer (A).
• the measurement sample may contain the copolymer (A).
• the value obtained for the mixture of the modified copolymer (A2) and the copolymer (A) is determined as the ethylenically unsaturated group equivalent of the modified copolymer (A2).
• the conversion rate from the structural unit (pb) to the structural unit (b) is also a value for a mixture of the modified copolymer (A2) and copolymer (A).
• sample Preparation Method 20 mg of the dried modified copolymer (A2) or a mixture of the modified copolymer (A2) and the copolymer (A) is precisely weighed, dissolved in 1 mL of CDCl 3 in a 20 mL sample bottle, 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 conversion rate of the structural unit (pb) to the structural unit (b) is a value calculated from the area ratio of the NMR spectrum obtained by the same method as above.
• the conversion rate of the structural unit (pb) to the structural unit (b) can be calculated similarly based on the area ratio of the NMR spectrum.
• the modification rate of the modified copolymer (A2) refers to the conversion rate of the structural unit (pb) to the structural unit (b) calculated by the above-mentioned measurement method.
• the modification rate of the modified copolymer (A2) means the modification rate calculated by the following formula (X).
• Modification rate [%] [structural unit (b) / (structural unit (pb) + (b))] [molar ratio] ⁇ 100 ...
• the number of moles of the structural unit (b) in formula (X) means the total number of moles of the structural unit having the formula (1-1) and the structural unit having the formula (1-2).
• the modification rate of the modified copolymer (A2) is 20% or more, preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more.
• the modification rate of the modified copolymer (A2) may be 60% or more.
• the modification rate of the modified copolymer (A2) may be 100%, but from the viewpoint of reducing the influence on developability, solvent resistance, etc. due to the basic catalyst (B) used in the conversion reaction remaining in the photosensitive resin composition, it may be 99% or less, or 95% or less.
• the modified copolymer (A2) contains a structural unit (b) having a group represented by formula (1-1) or formula (1-2) in which at least one or both of R2 and R3 are a hydrocarbon group having 1 to 20 carbon atoms
• the ethylenically unsaturated group equivalent is a value calculated from the amount of halogen bonded to the modified copolymer (A2).
• the amount of halogen bonded to the modified copolymer (A2) is evaluated as follows in accordance with JIS K 0070:1992.
• the dried modified copolymer (A2) 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. A potassium iodide solution and water are added to the solution, and the resulting solution is titrated with a 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 modified copolymer (A2) react with halogen molecules in a 1:1 ratio.
• the ethylenically unsaturated group equivalent of the modified copolymer (A2) is obtained by dividing the mass (g) of the modified copolymer (A2) used in the measurement by the substance amount (mol) of the halogen molecules bonded to the modified copolymer (A2) obtained by this measurement.
• the measurement sample may contain the copolymer (A).
• the value obtained for the mixture of the modified copolymer (A2) and the copolymer (A) is determined as the ethylenically unsaturated group equivalent of the modified copolymer (A2).
• the acid value of the copolymer (A) and the modified copolymer (A2) or the mixture of the copolymer (A) and the modified copolymer (A2) 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) and the modified copolymer (A2) or the mixture of the copolymer (A) and the modified copolymer (A2) 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. 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) and the weight average molecular weight of the modified copolymer (A2) or the mixture of the copolymer (A) and the modified copolymer (A2) 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) and the weight average molecular weight of the modified copolymer (A2) or the mixture of the copolymer (A) and the modified copolymer (A2) is preferably 50000 or less, more preferably 40000 or less, and even more preferably 30000 or less.
• the combination of these lower limit values and upper limit values may be any combination.
• the weight average molecular weight is 1000 or more, when the modified copolymer (A2) is used as a raw material for the photosensitive resin composition, defects such as chipping are unlikely to occur in the resin cured film after development.
• the weight average molecular weight is 50000 or less, the photosensitive resin composition containing the modified copolymer (A2) 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) and the blocked isocyanato group equivalent of the modified copolymer (A2) or the mixture of the copolymer (A) and the modified copolymer (A2) are 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 modified copolymer (A2) has better developability. When it is 2000 g/mol or less, the photosensitive resin composition containing the modified copolymer (A2) can form a resin cured film having superior hardness.
• the "blocked isocyanato group equivalent” is the mass of a polymer per 1 mol of blocked isocyanato groups.
• 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 blocked isocyanato groups contained in the copolymer.
• the “blocked 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) and the hydroxyl group equivalent of the modified copolymer (A2) or the mixture of the copolymer (A) and the modified copolymer (A2) are 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 modified copolymer (A2) has better developability.
• the photosensitive resin composition containing the modified copolymer (A2) 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 modified resin composition can be obtained by converting the structural unit (pb) of the copolymer (A) in the resin composition to the structural unit (b) and modifying the copolymer (A) to the modified copolymer (A2).
• a resin composition containing the copolymer (A), the basic catalyst (B) and the solvent (C) is held at a temperature of, for example, 0 to 150°C for 0.1 to 10 hours.
• the copolymer (A) may remain in the modified resin composition.
• the content of the copolymer (A) in the modified resin composition may be 0 to 20 parts by mass, 0 to 10 parts by mass, or 0 to 5 parts by mass, relative to 100 parts by mass of the modified copolymer (A2).
• the modified resin composition does not contain the copolymer (A).
• the temperature condition may be 40° C.
• the temperature condition may be 130° C. or lower, 110° C. or lower, 100° C. or lower, or 90° C. or lower. Any combination of these lower limit values and upper limit values may be used.
• the conversion reaction time may be 30 minutes or more, or 60 minutes or more. The conversion reaction time may be 300 minutes or less, or 180 minutes or less. Any combination of these lower limit values and upper limit values may be used.
• the photosensitive resin composition of one embodiment contains a modified copolymer (A2), a basic catalyst (B), a solvent (C), a reactive diluent (D), and a photopolymerization initiator (E).
• the photosensitive resin composition may contain a copolymer (A).
• the photosensitive coloring composition of one embodiment further contains a colorant (F).
• the total content of the modified copolymer (A2) and the optional 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 modified copolymer (A2), the copolymer (A), and the reactive diluent (D).
• the total content of the modified copolymer (A2) and the optional 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 modified copolymer (A2), the copolymer (A), and the reactive diluent (D). Any combination of these lower limit values and upper limit values may be used.
• the total content of the modified copolymer (A2) and the copolymer (A) is 10 parts by mass or more, a photosensitive resin composition or a photosensitive coloring composition having better low-temperature curing properties and capable of forming a cured product with good solvent resistance can be obtained.
• the total content of the modified copolymer (A2) and the copolymer (A) is 90 parts by mass or less, the content of the reactive diluent (D) can be sufficiently ensured, so that the strength of the cured product and its adhesion to the substrate are good.
• the content of copolymer (A) in the photosensitive resin composition or photosensitive coloring composition may be 0 to 20 parts by mass, 0 to 10 parts by mass, or 0 to 5 parts by mass, per 100 parts by mass of modified copolymer (A2). From the viewpoint of improving the solvent resistance of the cured resin film, copolymer (A) may not be contained.
• the content of the basic catalyst (B) in the photosensitive resin composition or the photosensitive coloring composition may be 0.001 parts by mass or more, 0.01 parts by mass or more, or 0.1 parts by mass or more, per 100 parts by mass of the total of the modified copolymer (A2), the copolymer (A), and the reactive diluent (D).
• the content of the basic catalyst (B) in the photosensitive resin composition or the photosensitive coloring composition is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and even more preferably 3 parts by mass or less, per 100 parts by mass of the total of the modified copolymer (A2), the copolymer (A), and the reactive diluent (D).
• the content of the basic catalyst (B) is 5 parts by mass or less, the effect of the basic catalyst (B) when the photosensitive resin composition is cured can be suppressed.
• solvent (C) As the solvent (C), the same solvent (C) used in the resin composition can be used.
• the solvent (C) in the photosensitive resin composition or the photosensitive coloring composition and the solvent (C) used in the production of the modified copolymer (A2) may be the same or different.
• the content of the solvent (C) 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, relative to 100 parts by mass of the total of the modified copolymer (A2), the copolymer (A), and the reactive diluent (D).
• the content of the solvent (C) 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, relative to 100 parts by mass of the total of the modified copolymer (A2), the copolymer (A), and the reactive diluent (D). Any combination of these lower limit values and upper limit values may be used.
• the viscosity of the photosensitive resin composition or the photosensitive coloring composition can be set to an appropriate range.
• the content of the solvent (C) is 1,000 parts by mass or less, the solvent (C) can be easily removed when removing the solvent (C) from the coating film formed by applying the photosensitive resin composition or the photosensitive coloring composition to a substrate.
• the reactive diluent (D) is a monomer having at least one ethylenically unsaturated bond as a polymerizable functional group in the molecule.
• the reactive diluent (D) 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 (D), it has good photocurability and can form a cured product with good strength and adhesion to the substrate.
• the reactive diluent (D) may be used alone or in combination of two or more.
• Monofunctional monomers used as reactive diluents (D) include (meth)acrylamide compounds such as (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, and 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-phenylpropanediol ...
• (meth)acrylamide compounds such as (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, and butoxyme
• Examples of the monofunctional monomer include (meth)acrylates such as 2-hydroxypropyl (meth)acrylate, 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 (D) 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 (D) 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 (D) 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 modified copolymer (A2), the copolymer (A), and the reactive diluent (D).
• the content of the reactive diluent (D) 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 modified copolymer (A2), the copolymer (A), and the reactive diluent (D).
• any combination of these lower limit values and upper limit values may be used.
• the content of the reactive diluent (D) is 10 parts by mass or more, the effect of containing the reactive diluent (D) becomes significant.
• the content of the reactive diluent (D) is 90 parts by mass or less, the content of the modified copolymer (A2) can be sufficiently ensured, so that a photosensitive resin composition or a photosensitive coloring composition with even better low-temperature curing properties can be obtained.
• the photopolymerization initiator (E) 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 (E) 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 1.0 parts by mass or more, relative to 100 parts by mass of the total of the modified copolymer (A2), the copolymer (A), and the reactive diluent (D).
• the content of the photopolymerization initiator (E) 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 modified copolymer (A2), the copolymer (A), and the reactive diluent (D). Any combination of these lower limit values and upper limit values may be used.
• the content of the photopolymerization initiator (E) 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 (E) 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 due to an excessive amount of the photopolymerization initiator (E).
• the photosensitive coloring composition may further contain a colorant (F).
• the photosensitive coloring composition containing the colorant (F) can be used as a material for a color filter.
• the colorant (F) is not particularly limited as long as it is soluble or dispersible in the solvent (C), 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 (C) 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 o range 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;
• 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 (F) can be appropriately determined depending on, for example, the color of the desired colored pattern (black matrix and pixels).
• the colorant (F) 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 (EFKA CHEMICALS B.V.), Disperbyk (BYK), Disparlon (Kusumoto Chemicals Co., Ltd.), and SOLSPERSE (Lubrizol) 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 (F).
• the content of the colorant (F) 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, based on 100 parts by mass of the total of the modified copolymer (A2), the copolymer (A), and the reactive diluent (D).
• the content of the colorant (F) 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, based on 100 parts by mass of the total of the modified copolymer (A2), the copolymer (A), and the reactive diluent (D). Any combination of these lower and upper limits may be used.
• the content of the colorant (F) is 3 parts by mass or more, the effect of containing the colorant (F) becomes significant, and a photosensitive coloring composition suitable as a material for a color pattern of a color filter can be obtained.
• the content of the colorant (F) is 80 parts by mass or less, the colorant (F) does not interfere with the curing property of the photosensitive coloring composition, and a photosensitive coloring composition with good low-temperature curing property can be obtained.
• the photosensitive resin composition or the photosensitive coloring 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 may be within a range that does not inhibit the effects of the present invention, and is not particularly limited.
• the photosensitive resin composition of one embodiment can be produced by a method of mixing the modified copolymer (A2), the basic catalyst (B), the solvent (C), the reactive diluent (D), the photopolymerization initiator (E), and the copolymer (A) used optionally using a known mixing device.
• the photosensitive coloring composition of one embodiment can be produced by a method of mixing the modified copolymer (A2), the basic catalyst (B), the solvent (C), the reactive diluent (D), the photopolymerization initiator (E), the colorant (F), and the copolymer (A) used optionally using a known mixing device.
• a reaction liquid i.e., a modified resin composition
• a modified copolymer (A2) obtained by converting the structural unit (pb) of the copolymer (A) to the structural unit (b) in the resin composition, a basic catalyst (B), a solvent (C), and an optional component copolymer (A)
• the solvent (C) contained in the reaction liquid can be used as a part or all of the solvent (C) contained in the photosensitive resin composition or the photosensitive coloring composition.
• the photosensitive resin composition or photosensitive coloring composition contains a modified copolymer (A2) having a structural unit (b) having a group represented by formula (1-1) or formula (1-2), a reactive diluent (D), and a photopolymerization initiator (E), so that when irradiated with light, the reactive diluent (D) polymerizes together with the ethylenically unsaturated group contained in the structural unit (b) of the modified copolymer (A2), resulting in good photocurability.
• A2 modified copolymer having a structural unit (b) having a group represented by formula (1-1) or formula (1-2), a reactive diluent (D), and a photopolymerization initiator (E), so that when irradiated with light, the reactive diluent (D) polymerizes together with the ethylenically unsaturated group contained in the structural unit (b) of the modified copolymer (A2), resulting in good photocur
• the photosensitive resin composition or the photosensitive coloring composition contains a modified copolymer (A2) containing 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 (F), a cured product can be formed in which the inherent properties of the colorant (F) are exerted.
• the photosensitive coloring composition provides a cured product with excellent solvent resistance even when the baking temperature is low, so the colorant (F) is less likely to dissolve. Therefore, it is possible to increase the content of the colorant (F) in the photosensitive coloring composition.
• a photosensitive coloring composition with a high content of the colorant (F) can be used, for example, as a material for the coloring pattern of a color filter to form a color filter with excellent color reproducibility.
• the modified copolymer (A2) contained in the photosensitive resin composition or photosensitive coloring composition has a structural unit (a) having an acid group, so that 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 a predetermined pattern shape and excellent solvent resistance 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 (C) 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 (C) 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 resin cured 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 modified copolymer (A2) 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 the deblocking reaction and the 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 cured resin 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 the modified copolymer (A2) and the copolymer (A), 0.05 to 9 parts by mass of the basic catalyst (B), 10 to 90 parts by mass of the reactive diluent (D), 0.1 to 30 parts by mass of the photopolymerization initiator (E), 30 to 1,000 parts by mass of the solvent (C), and 3 to 80 parts by mass of the colorant (F), relative to a total of 100 parts by mass of the modified copolymer (A2), the optional copolymer (A), and the reactive diluent (D).
• 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 successively 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 (C) 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 (C) contained in the coating film.
• the conditions for heating the substrate to remove the solvent (C) 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 tetramethylammonium sulfate, hydrochloride, or p-toluenesulfonate; 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-amin
• 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.
• a protective film is formed on the colored patterns (RGB pixels and 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 (F) 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 (F) that can be used. Therefore, for example, it is possible to form a color filter that contains a colorant (F) with low heat resistance and has a coloring pattern that exhibits the inherent properties of the colorant (F) 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 causing any damage to the substrate.
• a substrate with low heat resistance such as a resin substrate
• 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 (E) 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 the modified copolymer (A2) 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.
• modified copolymer (A2) is shown below.
• Example 1 (Synthesis Example 1) (Synthesis of Copolymer (A))
• a stirrer Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 282.6 g of propylene glycol monomethyl ether (Tokyo Chemical Industry Co., Ltd.) was placed as solvent (C), and the mixture was stirred while replacing with nitrogen gas and heated to 78°C.
• solvent (C) 282.6 g of propylene glycol monomethyl ether
• the entire amount of the raw monomer solution was dropped into the solvent (C) 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 liquid containing the copolymer (A) and the solvent (C).
• the weight average molecular weight, ethylenically unsaturated group equivalent, modification rate, and acid value of the mixture of the copolymer (A) and the modified copolymer (A2) were measured by the above-mentioned methods and are listed in Table 1.
• the blocked isocyanato group equivalent and hydroxyl group equivalent of the mixture of the copolymer (A) and the modified copolymer (A2) were calculated and are listed in Table 1.
• Propylene glycol monomethyl ether acetate (Tokyo Chemical Industry Co., Ltd.) was added as solvent (C) to the reaction liquid containing the copolymer (A), modified copolymer (A2), and solvent (C) obtained in this manner so that the components other than the solvent were 35 mass %, thereby obtaining a liquid (modified resin composition) containing the modified copolymer (A2) of Example 1.
• Examples 2 to 8 Synthesis Examples 2 to 8
• Comparative Examples 1 and 2 Comparative Synthesis Examples 1 and 2
• the liquid (modified resin composition) containing the modified copolymer (A2) of Examples 2 to 8 and the liquid (modified resin composition) containing the modified copolymer (cA2) of Comparative Examples 1 to 2 were obtained in the same manner as in Example 1, except that the monomers and blending amounts shown in Table 1 were used and the time of the conversion reaction from the structural unit (pb) to the structural unit (b) was set as shown in Table 1.
• the weight average molecular weight, ethylenically unsaturated group equivalent, modification rate, and acid value of the mixtures of the copolymer (A) and the modified copolymer (A2) of Examples 2 to 8 and the mixtures of the copolymer (cA) and the modified copolymer (cA2) of Comparative Examples 1 to 2 were measured by the above-mentioned methods and are shown in Table 1.
• the blocked isocyanato group equivalent and the hydroxyl group equivalent of the mixtures of the copolymer (A) and the modified copolymer (A2) of Examples 2 to 8 and the mixtures of the copolymer (cA) and the modified copolymer (cA2) of Comparative Examples 1 to 2 were calculated and are shown in Table 1.
• Propylene glycol monomethyl ether acetate (Tokyo Chemical Industry Co., Ltd.) was added as solvent (C) to the reaction liquid containing the copolymer (cA), modified copolymer (cA2), and solvent (C) obtained in this manner so that the components other than the solvent were 35 mass %, thereby obtaining a liquid (modified resin composition) containing modified copolymer (cA2) of Comparative Example 3.
• the entire amount of the raw monomer solution prepared was dropped into the solvent (C) in a flask at normal pressure and in a nitrogen gas atmosphere using a dropping funnel over a period of 1 hour. After the dropping was completed, the solution in the flask was stirred while undergoing a polymerization reaction at 78°C for 3 hours to obtain a reaction liquid containing the copolymer (cA) and the solvent (C).
• the weight average molecular weight, ethylenically unsaturated group equivalent, and acid value of the 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 the copolymer (cA) were calculated and are listed in Table 1.
• Propylene glycol monomethyl ether acetate (Tokyo Chemical Industry Co., Ltd.) was added as solvent (C) to the reaction liquid containing the copolymer (cA) and solvent (C) obtained in this manner so that the components other than the solvent were 35 mass %, and a liquid (resin composition) containing copolymer (cA) of Comparative Example 4 was obtained.
• AOI-MDE Methacrylic acid (Kuraray Co., Ltd.)
• AOI-MDE Karenz (trademark) AOI-MDE, 2-[(diethyl malate)carbonylamino]ethyl acrylate (Resonac Corporation)
• AOI-DEM KarenzTM AOI-DEM, reaction product of 2-isocyanatoethyl acrylate and diethyl malonate (malonic acid-2-[[[[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3 diethyl ester, Resonaq Co., Ltd.)
• MOI-BP Karenz (trademark) MOI-BP, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (Resonac Corporation)
• HEMA 2-hydroxyethyl methacrylate (Nippon Shokubai Co., Ltd.)
• the amount of the solvent is not included in the mixture of copolymer (A) and modified copolymer (A2), or the mixture of copolymer (cA) and modified copolymer (cA2), or the amount of copolymer (cA) shown in Table 2.
• the amount of the solvent (C) shown in Table 2 is the sum of the amount of the solvent contained in the modified resin compositions or resin compositions obtained in Synthesis Examples 1 to 8 and Comparative Synthesis Examples 1 to 4, and the amount of the solvent added when preparing the photosensitive coloring composition.
• the photosensitive coloring compositions of Examples 9 to 16 and Comparative Examples 5 to 8 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 (C) 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 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 9 to 16 had a residual film rate (%) of 80% 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 9 to 16 and Comparative Examples 5 to 8 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 (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.
• a photosensitive resin composition that contributes to improved developability and gives a cured resin film with excellent solvent resistance.
• an image display element is provided 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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