Photosensitive resin composition, resin cured film, and image display element

Abstract

The present invention provides a photosensitive resin composition that yields a resin-cured film having excellent low-temperature curing properties and sufficient solvent resistance or sufficient hardness. It also provides a color filter with excellent solvent resistance or excellent hardness, and an image display element equipped therewith. [Solution] The photosensitive resin composition of the present invention contains a copolymer (A), a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D). The copolymer (A) contains structural unit (a), structural unit (b), and structural unit (c). Structural unit (a) has one or more selected from an active methylene group to which a methoxycarbonyl group is attached and an active methine group to which a methoxycarbonyl group is attached, and structural unit (c) has an acid group.

Description

[Technical Field]

[0001] This disclosure relates to a photosensitive resin composition, a cured resin film, a color filter, and an image display element. This application claims priority based on Japanese Patent Application No. 2024-011275, filed in Japan on January 29, 2024, and Japanese Patent Application No. 2024-099982, filed in Japan on June 20, 2024, and the contents thereof are incorporated herein by reference. [Background technology]

[0002] Conventionally, some image display elements, such as displays, are equipped with color filters. Color filters are usually formed by baking and curing a resin composition on a substrate at a temperature exceeding 200°C. In recent years, with the increasing flexibility and wearability of displays, there has been a shift in substrate materials from glass to organic materials such as resins. Furthermore, in order to achieve even higher brightness and contrast image display elements, there has been a shift in colorants used in color filters from pigments to dyes and / or fluorescent compounds and quantum dots.

[0003] Organic materials used as substrate materials have lower heat resistance compared to glass. Similarly, dyes used as colorants in color filters have lower heat resistance compared to pigments. For these reasons, it is desirable to lower the heating temperature required for curing resin compositions used as materials for color filters. Specifically, depending on the heat resistance of the substrate material and colorant material, the heating temperature required for curing the resin composition of the color filter is sometimes required to be 80-150°C, and in recent years, particularly 80-100°C. Furthermore, with increasing environmental awareness, the trend towards lowering heating temperatures is attracting attention as a way to conserve energy during manufacturing.

[0004] Lowering the heating temperature for curing the resin composition makes it difficult to obtain sufficient solvent resistance. In color filters used in image display elements, there is a tendency to increase the content of colorants in the resin composition used as the material for the color filter in order to improve color reproduction. Furthermore, dyes have higher solubility in solvents compared to pigments. Therefore, if the solvent resistance of the color filter is insufficient, the dye contained in the color filter may dissolve into the solvent, potentially changing the chromaticity of the color filter.

[0005] Examples of resin compositions capable of exhibiting these two conflicting properties include those described in Patent Documents 1 to 3. Patent Documents 1 and 2 describe examples characterized by copolymers having a thermal crosslinking mechanism derived from their inherent structure, as a necessary condition for providing a desired resin composition. Patent Document 3 describes an example characterized by copolymers with a controlled glass transition temperature (Tg) as a means of promoting the thermal crosslinking mechanism, in order to provide a resin composition aimed at further improving performance. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Patent No. 7189875 [Patent Document 2] Patent No. 7306267 [Patent Document 3] WO2022 / 138159 [Overview of the project] [Problems that the invention aims to solve]

[0007] However, the resin compositions using copolymers described in Patent Documents 1 and 2 cannot sufficiently exhibit curability due to the characteristics of the thermal crosslinking mechanism of the copolymer, and are unable to meet the demand for the low heating temperature range of 80 to 100°C, which is particularly in demand these days. Furthermore, although the resin composition using copolymers described in Patent Document 3 showed improvement in curability in the low heating temperature range, the low glass transition temperature (Tg) can cause tack in the resin composition, potentially contaminating equipment and components that come into contact with the resin composition, thus adversely affecting the manufacturing process and subsequent processes for color filters. Moreover, in order to lower the glass transition temperature (Tg), certain monomers are used to an extreme degree, which may adversely affect performance, such as causing haze and surface roughness due to poor compatibility with colorants and the like.

[0008] The present invention has been made in view of the above circumstances, and aims to provide a photosensitive resin composition and a photosensitive coloring composition that can form a resin cured film having excellent low-temperature curability and sufficient solvent resistance. The present invention also aims to provide a photosensitive resin composition and a photosensitive coloring composition that can form a resin cured film having sufficient hardness. Furthermore, the present invention aims to provide a resin cured film having sufficient solvent resistance, which is made from a cured product of the photosensitive resin composition of the present invention. The present invention aims to provide a resin cured film having sufficient hardness, which is made from a cured product of the photosensitive resin composition of the present invention. Furthermore, the present invention aims to provide a color filter having a color pattern made from a cured product of the photosensitive coloring composition of the present invention and having sufficient hardness and / or solvent resistance, and further aims to provide an image display element equipped with this color filter. [Means for solving the problem]

[0009] The present invention includes the following embodiments. [1] Copolymer (A) and Reactive diluent (B), Photopolymerization initiator (C), Solvent (D) and, A photosensitive resin composition containing, The copolymer (A) contains structural unit (a), structural unit (b), and structural unit (c), The structural unit (a) has one or more selected from an active methylene group to which an alkoxycarbonyl group is attached, and an active methine group to which an alkoxycarbonyl group is attached. The aforementioned structural unit (b) has a hydroxyl group, A photosensitive resin composition in which the aforementioned structural unit (c) has an acid group. [2] The structural unit (a) has a group represented by the following formula (1) or the following formula (2), The structural unit (b) has a group represented by -CH2-OH, The aforementioned structural unit (c) is derived from acrylic acid, The photosensitive resin composition according to [1], wherein the glass transition temperature (Tg) of the copolymer (A) is 20°C or higher. [ka] (In formula (1), R 1 and R 2 Each of these independently represents an alkyl group having 1 to 10 carbon atoms. * represents a linking site. [ka] (In formula (2), R 3 (* represents an alkyl group with 1 to 10 carbon atoms. * represents a linking site.) [3] The photosensitive resin composition according to [2], wherein the copolymer (A) further contains structural units (d) derived from an ethylenically unsaturated compound having an epoxy group or an oxetanyl group. [4] The photosensitive resin composition according to either [2] or [3], wherein the structural unit (a) of the copolymer (A) is a structural unit derived from a compound having a group represented by formula (1) or formula (2) and an acryloyloxy group. [5] The photosensitive resin composition according to [1], wherein the structural unit (a) is one or more selected from an active methylene group to which a methoxycarbonyl group is attached and an active methine group to which a methoxycarbonyl group is attached. [6] The photosensitive resin composition according to [5], wherein the structural unit (a) is a structural unit having one or more selected from the group consisting of a group represented by the following formula (i-1) and a group represented by the following formula (ii-1). [ka] (In equation (i-1), n1 and n2 each represent an integer between 0 and 2 independently. * represents a concatenation.) [ka] (In equation (ii-1), n3 and n4 each independently represent integers between 0 and 2. * represents a concatenation.) [7] The photosensitive resin composition according to any one of [1] to [6], wherein the copolymer (A) further contains structural units (e) derived from (meth)acrylate having a linear or branched alkyl group having 1 to 20 carbon atoms. [8] The photosensitive resin composition according to any one of [1] to [7], wherein the copolymer (A) further contains structural units (f) derived from (meth)acrylate having a crosslinked cyclic hydrocarbon group having 10 to 20 carbon atoms. [9] The photosensitive resin composition according to any one of [5] to [8], wherein the structural unit (a) of the copolymer (A) is a structural unit derived from one or more selected from an active methylene group to which the methoxycarbonyl group is attached and an active methine group to which the methoxycarbonyl group is attached, and a compound having an acryloyloxy group.

[10] The structural unit (b) of the copolymer (A) is -(CH2) n - Structural units having a group represented by -OH (where n is an integer from 2 to 6) and -(OC x H 2x ) m A photosensitive resin composition according to any one of [1] to [9], which is at least one selected from the group consisting of structural units having a group represented by -OH (where x is an integer from 2 to 4 and m is an integer from 2 to 6).

[11] The photosensitive resin composition according to any one of [1] to

[10] , wherein the acid value of the copolymer (A) is 10 to 250 KOH mg / g.

[12] The photosensitive resin composition according to any one of [1] to

[11] , wherein the weight-average molecular weight Mw of the copolymer (A) is 3,000 to 50,000.

[13] The photosensitive resin composition according to any one of [1] to

[12] , wherein the reactive diluent (B) is a compound having multiple ethylenically unsaturated groups.

[14] When the total structural units of the copolymer (A) are set to 100 mol%, The above structural unit (a) contains 1 to 40 mol%, The above structural unit (b) contains 1 to 40 mol%, A photosensitive resin composition according to any one of [1] to

[13] , comprising 1 to 40 mol% of the aforementioned structural unit (c).

[15] The photosensitive resin composition according to any one of [1] to

[14] , wherein the solvent (D) is a glycol ether having a hydroxyl group.

[16] With respect to 100% by mass of the total copolymer (A) and the reactive diluent (B), The copolymer (A) is 10% by mass or more and less than 100% by mass, The reactive diluent (B) is greater than 0% by mass and less than or equal to 90% by mass. For a total of 100 parts by mass of the copolymer (A) and the reactive diluent (B), The photopolymerization initiator (C) is 0.1 to 30 parts by mass, For a total of 100 parts by mass of the components excluding the aforementioned solvent (D), The photosensitive resin composition according to any one of [1] to

[15] , wherein the solvent (D) is 30 to 1000 parts by mass.

[17] A photosensitive resin composition according to any one of [1] to

[16] , further comprising a colorant (E).

[18] The photosensitive resin composition according to

[17] , wherein the coloring agent (E) comprises a pigment.

[19] The hardness of the resin-cured film of the photosensitive resin composition is 3H or higher. The hardness is the hardness measured according to JIS K5600-5-4 when a resin cured film with a thickness of 2.5 μm is formed on a glass substrate, the photosensitive resin composition according to any one of [5] to

[18] . A resin-cured film comprising a cured product of a photosensitive resin composition described in any of

[20]

[17] to

[19] . A color filter having a colored pattern made of a cured product of a photosensitive resin composition described in any of

[21]

[17] to

[19] .

[22] An image display element comprising the color filter described in

[21] . [Effects of the Invention]

[0010] According to this disclosure, it is possible to provide a photosensitive resin composition that gives a resin cured film having solvent resistance or hardness. Furthermore, it is possible to provide a resin cured film with excellent solvent resistance or hardness obtained by curing the above resin composition, and an image display element comprising the same. [Modes for carrying out the invention]

[0011] Embodiments of the present invention will be described in detail below. However, the present invention is not limited to the embodiments shown below. In this specification, "(meth)acryloyloxy group" refers to one or more selected from methacryloyloxy groups and acryloyloxy groups. The same applies to "(meth)acrylic acid" and "(meth)acrylate". Furthermore, in this specification, when "~" is used for a numerical range, the numbers at both ends are the upper and lower limits, respectively, and are included in the numerical range. If multiple upper or lower limits are listed, a numerical range can be created from all combinations of upper and lower limits. Similarly, if multiple numerical ranges are listed, separate numerical ranges can be created by individually selecting and combining upper and lower limits from those ranges.

[0012] In this specification, "structural unit having an XYZ group" means a structural unit that has the same structure as the monomer unit corresponding to a monomer in a polymer produced by addition polymerization of a compound having an XYZ group and an ethylenically unsaturated group as a monomer. For example, when the original monomer (a compound having a hydroxyl group and an ethylenically unsaturated group) is 2-hydroxyethyl methacrylate, the "structural unit having a hydroxyl group" has the chemical structure "-C(CH3)(COOC2H4OH)CH2-". It should be noted that a "structural unit having an XYZ group" also applies when an ethylenically unsaturated compound without an XYZ group is first added polymerized as a monomer, and then an XYZ group is introduced into that monomer unit.

[0013] In this specification, "structural unit derived from an ethylenically unsaturated compound having an XYZ group" means a structural unit that has the same structure as the monomer unit corresponding to the monomer in a polymer produced by addition polymerization of the ethylenically unsaturated compound as a monomer. For example, acrylic acid is a type of ethylenically unsaturated compound having a carboxyl group. The structural unit derived from acrylic acid is "-CH(COOH)-CH2-". In addition, a compound having an ethylenically unsaturated group but without an XYZ group is first added polymerized as a monomer, and then an XYZ group is introduced into that monomer unit, which also falls under the category of "structural unit derived from an ethylenically unsaturated compound having an XYZ group".

[0014] <Photosensitive resin composition> [First Embodiment] The photosensitive resin composition of the first embodiment of the present invention contains a copolymer (A), a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D). The photosensitive resin composition of this embodiment optionally contains a colorant (E). The photosensitive resin composition of this embodiment polymerizes and hardens upon irradiation with light, forming a cured resin film.

[0015] [Copolymer (A)] The copolymer (A) contains a structural unit (a), a structural unit (b), and a structural unit (c). The structural unit (a) has one or more selected from an active methylene group connected with an alkoxycarbonyl group and an active methine group connected with an alkoxycarbonyl group, the structural unit (b) has a hydroxy group, and the structural unit (c) has an acid group. The alkoxycarbonyl group of the structural unit (a) contained in the copolymer (A) undergoes transesterification with the hydroxy group contained in the structural unit (b) to form a crosslinked structure, by thermally curing the resin composition containing the copolymer (A). Therefore, even when the resin composition containing the copolymer (A) is cured at a low temperature of 50°C to 150°C, a cured film excellent in solvent resistance and hardness can be obtained. The alkoxy group of the alkoxycarbonyl group is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 6 carbon atoms, and even more preferably an alkoxy group having 1 to 3 carbon atoms.

[0016] The active methylene group refers to a group in which an electron-withdrawing group is bonded to at least one side (preferably both sides) of the methylene group, and examples of the electron-withdrawing group include a carbonyl group, an ester group, a cyano group, a nitro group, a sulfonyl group, a sulfinyl group, a phosphono group and the like. The active methylene group is preferably a structure in which a carbonyl group or an ester group is bonded to both sides of the methylene group, and particularly preferably a group in which ester groups are bonded to both sides of the methylene group, that is, a -COO-CH2-COO- structure. The structural unit (a) preferably has a group represented by the following formula (i) or the following formula (ii).

[0017] [Chemical Formula] (In formula (i), R 1 and R 2 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 bonding site.) [Chemical Formula] (In formula (ii), R 3 n represents an alkyl group with 1 to 10 carbon atoms. n3 and n4 each independently represent integers from 0 to 2. * represents a linking site. Examples of the photosensitive resin composition of the first embodiment include the photosensitive resin composition of the second embodiment or the photosensitive resin composition of the third embodiment described below.

[0018] [Second Embodiment] The photosensitive resin composition of the second embodiment contains a copolymer (A), a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D). The photosensitive resin composition of this embodiment optionally contains a colorant (E). The photosensitive resin composition of this embodiment polymerizes and hardens upon irradiation with light, forming a cured resin film. The copolymer (A) used in the photosensitive resin composition of this embodiment contains structural units (a) having a group represented by the following formula (1) or formula (2) (hereinafter also simply referred to as "structural unit (a)"), structural units (b) having a group represented by -CH2-OH (hereinafter also simply referred to as "structural unit (b)"), and structural units (c) derived from acrylic acid (hereinafter also simply referred to as "structural unit (c)").

[0019] [ka] (In formula (1), R 1 and R 2 Each of these independently represents an alkyl group having 1 to 10 carbon atoms. * represents a linking site.

[0020] [ka] (In formula (2), R 3 (* represents an alkyl group with 1 to 10 carbon atoms. * represents a linking site.)

[0021] The copolymer (A) of this embodiment may further contain structural units (d) derived from ethylenically unsaturated compounds having epoxy groups or oxetanyl groups (hereinafter also simply referred to as "structural unit (d)"). The copolymer (A) of this embodiment may further contain, if necessary, structural units (e) derived from (meth)acrylate having a cross-linked cyclic hydrocarbon group having 10 to 20 carbon atoms (hereinafter also simply referred to as "structural unit (e)"). The copolymer (A) of this embodiment may further contain, if necessary, structural units (f) derived from (meth)acrylate having a linear or branched alkyl group having 1 to 20 carbon atoms (hereinafter also simply referred to as "structural unit (f)").

[0022] "Structural unit (a)" The structural unit (a) having a group represented by formula (1) or formula (2) in the copolymer (A) is a structural unit derived from a monomer (ma) having a group represented by formula (1) or formula (2) (hereinafter also simply referred to as "monomer (ma)"). The group represented by formula (1) or formula (2) in the structural unit (a) contained in copolymer (A) undergoes transesterification with the hydroxyl group of the structural unit (b) by thermal curing of the resin composition containing copolymer (A), thereby generating a crosslinked structure. Therefore, a cured film with excellent solvent resistance can be obtained from the resin composition containing copolymer (A) even when cured at a low temperature of 50°C to 150°C.

[0023] R in equation (1) above 1 and R 2 Each of these is an alkyl group having 1 to 10 carbon atoms. 1 and R 2 Each of them is preferably an alkyl group having 2 to 6 carbon atoms, and more preferably an alkyl group having 2 to 3 carbon atoms, R 1 and R 2 It is most preferable that both are ethyl groups having 2 carbon atoms. R 1 and R 2 When is an ethyl group, when the resin composition containing copolymer (A) is heat-cured, R1 and R 2 The ethanol is produced by transesterification with the hydroxyl group of structural unit (b). The ethanol produced during the thermal curing of the resin composition is preferable because it is easily evaporated and removed by the heating required to thermally cure the resin composition.

[0024] Also, R in equation (2) above 3 R is an alkyl group having 1 to 10 carbon atoms. 3 The group 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 having 2 carbon atoms. R 3 When is an ethyl group, when the resin composition containing copolymer (A) is heat-cured, R 3 The ethanol is produced by transesterification with the hydroxyl group of structural unit (b). The ethanol produced during the thermal curing of the resin composition is preferable because it is easily evaporated and removed by the heating required to thermally cure the resin composition.

[0025] The monomer (ma) that gives structural unit (a) is not particularly limited, as long as it is a compound copolymerizable with the hydroxymethyl group-containing monomer (mb) and acrylic acid described later. As monomer (ma), for example, from the viewpoint of reactivity when synthesizing copolymer (A), monomers having a group represented by formula (1) or formula (2) above and an ethylenically unsaturated bond can be used. Specifically, as groups having an ethylenically unsaturated bond, vinyl groups and (meth)acryloyloxy groups can be mentioned. From the viewpoint of freedom in monomer blending ratio, (meth)acryloyloxy groups are preferred, and from the viewpoint of solvent resistance of the cured product of the photosensitive resin composition and reduction of dye elution when a dye is used as a colorant (E), acryloyloxy groups are preferred.

[0026] Examples of monomers (ma) having a group represented by formula (1) or formula (2) above and an ethylenically unsaturated bond include reaction products of ethylenically unsaturated group-containing isocyanate compounds with malonic acid diesters or acetoacetate esters. These monomers (ma) may be used individually or in combination of two or more.

[0027] The isocyanate compound containing an ethylenically unsaturated group that generates the monomer (ma) is preferably a compound represented by the following formula (3).

[0028] [ka] (In formula (3), R 4 R represents a hydrogen atom or a methyl group. 5 -CO-, -COOR 6 -(Here, R 6 ) or -COO-R 7 O-CONH-R 8 -(Here, R 7 R is an alkylene group with 2 to 6 carbon atoms. 8 This represents an alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms, which may have substituents.

[0029] R in equation (3) 4 R represents a hydrogen atom or a methyl group. From the viewpoint of solvent resistance of the cured product of the photosensitive resin composition and reduction of dye elution when a dye is used as a colorant (E), 4 A hydrogen atom is preferred. R in equation (3) 5 -CO-, -COOR 6 - or -COO-R 7 O-CONH-R 8 - indicates that R 6 R is an alkylene group with 1 to 6 carbon atoms. 7 R is an alkylene group with 2 to 6 carbon atoms. 8 R is an alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms, which may have substituents. Among these, R in formula (3) 5 -COOR 6 - is preferable R 5 ga-COOR 6-If R 6 This is preferably an alkylene group having 1 to 4 carbon atoms.

[0030] Examples of isocyanate compounds containing an ethylenically unsaturated group represented by the above formula (3) 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 (meth)acryloyl isocyanate.

[0031] Furthermore, as the ethylenically unsaturated group-containing isocyanate compound represented by formula (3) above, equimolar (1 mole:1 mole) reaction products of 2-hydroxyalkyl (meth)acrylate and diisocyanate compound can also be used. The alkyl group contained in the 2-hydroxyalkyl (meth)acrylate above is preferably an ethyl group or an n-propyl group, with the ethyl group being more preferred. Examples of the diisocyanate compounds above 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, and the like.

[0032] Among these ethylenically unsaturated group-containing isocyanate compounds, 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 (meth)acryloyl isocyanate are preferred, with 2-isocyanatoethyl (meth)acrylate and 2-isocyanatopropyl (meth)acrylate being more preferred. These ethylenically unsaturated group-containing isocyanate compounds may be used individually or in combination of two or more.

[0033] Examples of malonic acid diesters to be reacted with ethylenically unsaturated group-containing isocyanate compounds include dimethyl malonate, diethyl malonate, di(n-propyl) malonate, and di(i-propyl) malonate. Diethyl malonate or dimethyl malonate are preferred due to their availability, cost, and quality. Examples of acetoacetate esters to be reacted with ethylenically unsaturated group-containing isocyanate compounds include methyl acetoacetate and ethyl acetoacetate.

[0034] The reaction between an ethylenically unsaturated group-containing isocyanate compound and a malonic acid diester or acetoacetate ester can be carried out with or without the presence of a solvent. When the above reaction is carried out using a solvent, a solvent that is inert to the isocyanate group should be used. In the above reaction, organometallic salts such as tin, zinc, and lead, or tertiary amines may be used as catalysts. The above reaction can generally be carried out at temperatures of -20 to 150°C, and preferably at temperatures of 25 to 130°C. A sufficient reaction rate can be obtained if the reaction temperature is above -20°C. Furthermore, if the reaction temperature is below 150°C, polymerization of the starting material having a C=C (double bond) can be prevented, which prevents the monomer (ma) that gives the structural unit (a) generated after the reaction from gelling.

[0035] Specific examples of monomers (ma) include, for example, AOI-DEM, MOI-DEM, AOI-DMM, MOI-DMM, AOI-OBE, MOI-OBE, and others. AOI-DEM: Karenz (trademark) AOI-DEM, reaction product of 2-isocyanatoethyl acrylate and diethyl malonate (malonate-2-[[[[2-[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester, manufactured by Resonaq Corporation. MOI-DEM: Karenz (trademark) MOI-DEM, reaction product of 2-isocyanatoethyl methacrylate and diethyl malonate (malonate-2-[[[2-methyl1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester, manufactured by Resonaq Corporation. AOI-DMM: Karenz (trademark) AOI-DMM, reaction product of 2-isocyanatoethyl acrylate and dimethyl malonate (malonate-2-[[[[2-[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-dimethyl ester, manufactured by Resonaq Corporation. MOI-DMM: Karenz (trademark) MOI-DMM, reaction product of 2-isocyanatoethyl methacrylate and dimethyl malonate (malonate-2-[[[2-methyl1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-dimethyl ester, manufactured by Resonaq Corporation. AOI-OBE: Karens (trademark) AOI-OBE, reaction product of 2-isocyanatoethyl acrylate and ethyl acetoethyl acetate, manufactured by Resonaq Corporation. MOI-OBE: Karens (trademark) MOI-OBE, reaction product of 2-isocyanatoethyl methacrylate and ethyl acetoethyl, manufactured by Resonaq Corporation.

[0036] "Structural unit (b)" The structural unit (b) having a group represented by -CH2-OH, which constitutes the copolymer (A) above, does not have a group represented by formula (1) or formula (2) above, but has a group represented by -CH2-OH. Structural unit (b) is a structural unit derived from monomer (mb) having a group represented by -CH2-OH (hereinafter also simply referred to as "monomer (mb)"). The hydroxyl group of structural unit (b) contained in copolymer (A) undergoes transesterification with the group represented by formula (1) or formula (2) of structural unit (a) by thermal curing of the resin composition containing copolymer (A), thereby creating a crosslinked structure.

[0037] Structural unit (b) is -(CH2) from the viewpoint of low-temperature curing properties. n - Structural units having a group represented by -OH (where n is an integer from 2 to 6) and -(OC x H 2x ) m It is more preferable that the structural unit is selected from the group consisting of structural units having a group represented by -OH (where x is an integer from 2 to 4 and m is an integer from 2 to 10). -(CH2) n -The n of the group represented by -OH is preferably 2 to 4, more preferably 2 and 4. x H 2x ) m -The x of the group represented by -OH is preferably 2 to 3, more preferably 2. x H 2x ) m The value of m in the group represented by -OH is preferably 2 to 6, more preferably 4 to 6.

[0038] The monomer (mb) that gives structural unit (b) is not particularly limited, as long as it does not have a group represented by formula (1) or formula (2) above, and has an ethylenically unsaturated group and a group represented by -CH2-OH. Examples of ethylenically unsaturated groups contained in monomer (mb) include vinyl groups, (meth)acryloyloxy groups, etc. Examples of monomer (mb) include (meth)acrylic acid ester derivatives having a group represented by -CH2-OH. Specific examples of such monomers (mb) include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, etc. These monomers (mb) may be used individually or in combination of two or more.

[0039] As monomers (mb), among the above monomers, hydroxyalkyl (meth)acrylate and polyalkylene glycol mono(meth)acrylate are preferred from the viewpoint of reactivity in synthesizing copolymer (A), low-temperature curability of the resin composition containing copolymer (A), and ease of availability. As hydroxyalkyl (meth)acrylates, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate are preferred, and 2-hydroxyethyl (meth)acrylate is more preferred from the viewpoint of controlling the glass transition temperature of copolymer (A) to a high level and obtaining solvent resistance as a cured product. As polyalkylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate is preferred from the viewpoint of solvent resistance, and -(OC x H 2x ) m Polyethylene glycol mono(meth)acrylate with -OH x = 2 and m = 2-6 is more preferable.

[0040] "Structural unit (c)" Structural unit (c) is a structural unit derived from acrylic acid that constitutes the copolymer (A), and is "-CH(COOH)-CH2-". The presence of structural unit (c) in copolymer (A) increases the proportion of acrylic-derived structures and decreases the proportion of methacrylic-derived structures in the main chain of copolymer (A) compared to the case where methacrylic-derived structural units are present (the proportion of methyl groups bonded to carbon atoms in the main chain decreases). This is thought to reduce steric hindrance near the main chain and increase the degree of freedom of motion such as rotation and bending of the main chain, thereby increasing the efficiency of intermolecular crosslinking. Therefore, compared to the case where methacrylic-derived structural units are present, good solvent resistance can be obtained even when curing is performed under low-temperature conditions, and dye elution from the cured product can be reduced when a dye is used as a colorant (E). The copolymer (A) of this embodiment may use other polymerizable monomers containing acid groups other than acrylic acid (e.g., methacrylic acid) as constituent monomers, as long as the effects of the present invention are not impaired. However, for the reasons mentioned above, it is preferable not to use them.

[0041] "Structural unit (d)" The copolymer (A) of this embodiment may further contain structural units (d) derived from an ethylenically unsaturated compound having an epoxy group or an oxetanyl group, if necessary. The structural units (d) derived from an ethylenically unsaturated compound having an epoxy group or an oxetanyl group do not have the group represented by formula (1) or formula (2) above, a hydroxyl group, and a carboxyl group, and are derived from a monomer (md) (hereinafter also simply referred to as "monomer (md)") having an epoxy group or an oxetanyl group and an ethylenically unsaturated group. The presence of structural units (d) in copolymer (A) improves the low-temperature curability as a photosensitive resin composition and yields a resin cured film with good solvent resistance.

[0042] The monomer (md) that gives the structural unit (d) is a polymerizable monomer containing an epoxy group. Specific examples of such monomers include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate having an alicyclic epoxy group and its lactone adducts (e.g., Cyclomer® A200, M100 manufactured by Daicel Corporation), mono(meth)acrylic acid esters of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, epoxidized dicyclopentenyl (meth)acrylate, and epoxidized dicyclopentenyloxyethyl (meth)acrylate. Among these, epoxy group-containing (meth)acrylates are preferred, and glycidyl (meth)acrylates are more preferred, from the viewpoint of ease of availability and reactivity. Furthermore, specific examples of polymerizable monomers having an oxetanyl group include (3-ethyloxetan-3-yl)methyl (meth)acrylate, 4-[3-(3-ethyloxetan-3-ylmethoxy)propoxy]styrene, 4-[6-(3-ethyloxetan-3-ylmethoxy)hexyloxy]styrene, 4-[5-(3-ethyloxetan-3-ylmethoxy)pentyloxy]styrene, and 2-vinyl-2-methyloxetan. Among these, oxetanyl group-containing (meth)acrylates are preferred from the viewpoint of ease of availability and reactivity, and (3-ethyloxetan-3-yl)methyl (meth)acrylate is more preferred. These polymerizable monomers may be used individually or in combination of two or more.

[0043] "Structural unit (e)" The copolymer (A) of this embodiment may further contain structural units (e) derived from (meth)acrylate having a cross-linked cyclic hydrocarbon group having 10 to 20 carbon atoms, if necessary. The structural units (e) derived from (meth)acrylate having a cross-linked cyclic hydrocarbon group having 10 to 20 carbon atoms do not have the group represented by formula (1) or formula (2) above, a hydroxyl group, a carboxyl group, an epoxy group, and an oxetanyl group, and are structural units derived from monomers (me) (hereinafter also simply referred to as "monomer (me)") having a cross-linked cyclic hydrocarbon group having 10 to 20 carbon atoms and ethylenically unsaturated material. By having structural units (e) in copolymer (A), the glass transition temperature of copolymer (A) can be controlled to a high level, and solvent resistance and surface uniformity as a cured product can be obtained. Furthermore, when a dye is used as a colorant (E) in a photosensitive resin composition, it is possible to create appropriate voids to confine the dye in the resin, and dye elution from the cured product can be reduced.

[0044] The monomer (me) that gives the above structural unit (e) is more preferably adamantyl (meth)acrylate or a (meth)acrylate having the structure shown in the following formula (5).

[0045] [ka]

[0046] In formula (5), R 7 ~R 9 Each of these independently represents either a hydrogen atom or a methyl group. 10 and R 11 represents a hydrogen atom or a methyl group, or may be bonded to form a saturated or unsaturated ring. The ring is preferably a 5-membered or 6-membered ring. * represents a bond connected to a (meth)acryloyloxy group.

[0047] Specific examples of (meth)acrylates having the structure shown in formula (5) above include dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, and the like. Among these, dicyclopentanyl (meth)acrylate is particularly preferred from the viewpoint of being able to control the glass transition temperature of copolymer (A) to a high degree and having excellent heat resistance. These may be used individually or in combination of two or more.

[0048] "Structural unit (f)" The copolymer (A) of this embodiment may further contain structural units (f) derived from (meth)acrylate having a linear or branched alkyl group having 1 to 20 carbon atoms, if necessary. The structural units (f) derived from (meth)acrylate having a linear or branched alkyl group having 1 to 20 carbon atoms do not have the group represented by formula (1) or formula (2) above, a hydroxyl group, a carboxyl group, an epoxy group, an oxetanyl group, or a cyclic hydrocarbon group, and are structural units derived from monomers (mf) (hereinafter also simply referred to as "monomer (mf)") having a linear or branched alkyl group having 1 to 20 carbon atoms and ethylenically unsaturated compounds. By having structural units (f) in copolymer (A), the flexibility of the photosensitive resin composition can be adjusted and appropriate substrate adhesion can be imparted.

[0049] The monomers (mf) that provide the structural unit (f) specifically include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, and dodecyl (meth)acrylate. Among these, alkyl (meth)acrylates having a linear alkyl group with 1 to 6 carbon atoms are preferred from the viewpoint of not inhibiting the thermosetting reaction of copolymer (A) in terms of stereostructure, and methyl (meth)acrylate and ethyl (meth)acrylate are preferred. In addition, from the viewpoint of being able to appropriately adjust substrate adhesion, alkyl (meth)acrylates having a branched alkyl group with 4 to 10 carbon atoms are preferred, and iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate are more preferred. These may be used individually or in combination of two or more types.

[0050] "Other structural units (g)" The copolymer (A) of this embodiment may optionally contain other structural units (g) other than the above structural units (a) to (f). The other structural units (g) are structural units derived from other monomers (mg) (hereinafter also simply referred to as "monomer (mg)") that can copolymerize with monomers (ma) to (mf). Examples of monomers (mg) that provide structural units (g) include aromatic vinyl compounds, cyclic olefins having a norbornene structure, dienes, (meth)acrylamides, vinyl compounds, unsaturated dicarboxylic acid diesters, monomaleimides, (meth)acrylamides, (meth)acrylonitriles, and acrolein. Examples of aromatic vinyl compounds include styrene, α-methylstyrene, o-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, methoxystyrene, p-nitrostyrene, p-cyanostyrene, and p-acetylaminostyrene. Examples of cyclic olefins having a norbornene structure include norbornene (bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, and tetracyclo[4.4.0.1 2,5 .1 7,10 ] Dodeca-3-ene, 8-ethyltetracyclo[4.4.0.1 2,5 .1 7,10 ] Dodeca-3-ene, dicyclopentadiene, tricyclo[5.2.1.0 2,6 Deca-8-en, tricyclo[4.4.0.1 2,5 ]Undeca-3-ene, tricyclo[6.2.1.0 1,8 ]Undeka-9-ene, tetracyclo[4.4.0.1 2,5 .1 7,10 .0 1,6 ] Dodeca-3-ene, 8-ethylidenetetracyclo[4.4.0.1 2,5 .1 7,12 ] Dodeca-3-ene, pentacyclo[6.5.1.1 3,6 .0 2,7 .0 9,13 Examples include pentadeca-4-en. Examples of dienes include butadiene, isoprene, and chloroprene. Examples of (meth)acrylic acid esters include benzyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoro-n-propyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, triphenylmethyl (meth)acrylate, phenyl (meth)acrylate, cumyl (meth)acrylate, 4-phenoxyphenyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolyethylene glycol mono (meth)acrylate, biphenyloxyethyl (meth)acrylate, naphthalene (meth)acrylate, anthracene (meth)acrylate, and ethoxylated phenyl (meth)acrylate. Examples of (meth)acrylamide include (meth)acrylamide, (meth)acrylate N,N-dimethylamide, (meth)acrylate N,N-diisopropylamide, and (meth)acrylate anthracenilamide. Examples of vinyl compounds include vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, and vinyltoluene. Examples of unsaturated dicarboxylic acid diesters include diethyl citraconate, diethyl maleate, diethyl fumarate, and diethyl itaconate. Examples of monomaleimides include N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, and N-(4-hydroxyphenyl)maleimide.

[0051] "The proportion of each structural unit" The content of structural unit (a) is preferably 1 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, when the total amount of structural units constituting the copolymer (A) is taken as 100 mol%. The content of structural unit (a) is preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 25 mol% or less, when the total amount of structural units constituting the copolymer (A) is taken as 100 mol%. Any combination of these lower and upper limits is acceptable. If the content of structural unit (a) is 1 mol% or more, a sufficient amount of crosslinking by transesterification with the hydroxyl group of structural unit (c) can be ensured, and the solvent resistance of the cured product is good even when the photosensitive resin composition is cured at low temperatures. If the content of structural unit (a) is 40 mol% or less, a sufficient amount of the crosslinking partner structural unit (c) can be ensured. In addition, a sufficient amount of structural unit (b) can be ensured, and the developability of the photosensitive resin composition is good.

[0052] The content of structural unit (b) is preferably 1 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or more, when the total amount of structural units constituting the copolymer (A) is 100 mol%. The content of structural unit (b) is preferably 70 mol% or less, more preferably 60 mol% or less, even more preferably 50 mol% or less, and even more preferably 40 mol% or less, when the total amount of structural units constituting the copolymer (A) is 100 mol%. Any combination of these lower and upper limits is acceptable. When the content of structural unit (b) is 1 mol% or more, the developability of the photosensitive resin composition is good. When the content of structural unit (b) is 70 mol% or less, it is easy to adjust the developability and storage stability of the photosensitive resin composition, and sufficient crosslinking between structural unit (a) and structural unit (c) can be ensured, resulting in good low-temperature curing properties and solvent resistance of the cured product as a photosensitive resin composition.

[0053] The content of structural unit (c) is preferably 1 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, when the total amount of structural units constituting the copolymer (A) is 100 mol%. The content of structural unit (c) is preferably 70 mol% or less, more preferably 60 mol% or less, even more preferably 50 mol% or less, and even more preferably 30 mol% or less, when the total amount of structural units constituting the copolymer (A) is 100 mol%. Any combination of these lower and upper limits is acceptable. When the content of structural unit (c) is 1 mol% or more, a sufficient amount of crosslinking by transesterification with structural unit (a) can be ensured, and the solvent resistance of the cured product is good even when the photosensitive resin composition is cured at low temperatures. Furthermore, the developability of the photosensitive resin composition can be adjusted to a desired range. When the content of structural unit (c) is 70 mol% or less, a sufficient amount of the crosslinking partner structural unit (a) can be ensured. Furthermore, a sufficient amount of structural unit (b) can be ensured, and the developability of the photosensitive resin composition is good.

[0054] If the copolymer (A) contains structural unit (d), the content of structural unit (d) is preferably 1 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more, when the total amount of structural units constituting the copolymer (A) is 100 mol%. The content of structural unit (d) is preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less, when the total amount of structural units constituting the copolymer (A) is 100 mol%. Any combination of these lower and upper limits is acceptable. If the content of structural unit (d) is 1 mol% or more, crosslinking with structural unit (b) is promoted, resulting in good low-temperature curability when used as a photosensitive resin composition. If the content of structural unit (d) is 40 mol% or less, the storage stability of the photosensitive resin composition is good.

[0055] If the copolymer (A) contains structural unit (e), the content of structural unit (e) is preferably 1 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more, when the total amount of structural units constituting the copolymer (A) is 100 mol%. The content of structural unit (e) is preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less, when the total amount of structural units constituting the copolymer (A) is 100 mol%. Any combination of these lower and upper limits is acceptable. When the content of structural unit (e) is 1 mol% or more, the properties derived from structural unit (e) are well expressed. When the content of structural unit (e) is 40 mol% or less, the content of structural units (a) to (c) can be sufficiently ensured, resulting in good low-temperature curing properties of the photosensitive resin composition and good solvent resistance of the cured product.

[0056] If the copolymer (A) contains structural unit (f), the content of structural unit (f) is preferably 1 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more, when the total amount of structural units constituting the copolymer (A) is 100 mol%. The content of structural unit (f) is preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 25 mol% or less, when the total amount of structural units constituting the copolymer (A) is 100 mol%. Any combination of these lower and upper limits is acceptable. When the content of structural unit (f) is 1 mol% or more, the properties derived from structural unit (f) are well expressed. When the content of structural unit (f) is 40 mol% or less, the content of structural units (a) to (c) can be sufficiently ensured, resulting in good low-temperature curing properties of the photosensitive resin composition and good solvent resistance of the cured product.

[0057] When the copolymer (A) contains structural units (g), the content of structural units (g) is preferably 0.5 to 25 mol% or more, more preferably 1 to 20 mol% or more, and even more preferably 5 to 15 mol% or more, when the total amount of structural units constituting the copolymer (A) is taken as 100 mol%. When the content of structural units (g) is within the above range, the function of structural units (g) can be imparted to the photosensitive resin composition without impairing the functions of structural units (a) to (c).

[0058] The acid value of the copolymer (A) is, Preferably, the concentration is 10KOH mg / g or more. More preferably, 15KOH mg / g or more. More preferably, the concentration is 20 kOH mg / g or higher. The acid value of the copolymer (A) is, Preferably, the concentration is 250 kOH mg / g or less. More preferably, the concentration is 200 kOH mg / g or less. More preferably, it is 150 KOH mg / g or less. More preferably, the concentration is 100 kOH mg / g or less. Any combination of these lower and upper limits is acceptable. When the acid value of the copolymer (A) is 10KOH mg / g or higher, the developability is good when used as a photosensitive resin composition. If the acid value of the copolymer (A) is 250 KOH mg / g or less, the photosensitive resin composition has good storage stability.

[0059] The copolymer (A) preferably has a molecular weight of 3000 or more, more preferably 5000 or more, and even more preferably 6000 or more. The weight-average molecular weight of copolymer (A) is preferably 25000 or less, more preferably 20000 or less, and even more preferably 15000 or less. Any combination of these lower and upper limits is acceptable. If the weight-average molecular weight of copolymer (A) is 3000 or more, the copolymerization reaction of copolymer (A) can be carried out stably, and copolymer (A) with highly reproducible physical properties can be provided. If the weight-average molecular weight of copolymer (A) is 25000 or less, the copolymerization reaction of copolymer (A) can be carried out stably, and copolymer (A) with highly reproducible physical properties can be provided, as well as good developability when used as a photosensitive resin composition. Insoluble matter of the photosensitive resin composition described later can be easily removed by filtration.

[0060] In this specification, weight-average molecular weight refers to the weight-average molecular weight and number-average molecular weight on a standard polystyrene basis, measured using gel permeation chromatography (GPC) under the following conditions. Column: SHODEX (trademark) LF-804 + LF-804 (manufactured by Resonac Co., Ltd.) Column temperature: 40℃ Sample: 0.2% by mass solution of the substance to be measured Developing solvent: tetrahydrofuran Detector: Differential refractometer (Showdex® RI-71S) (manufactured by Resonac Corporation) Flow rate: 1mL / min

[0061] The glass transition temperature of the copolymer (A) is The temperature is 20℃ or higher. Preferably, the temperature is 25°C or higher. More preferably, the temperature is 30°C or higher. The glass transition temperature of the copolymer (A) is Preferably, the temperature is 90°C or lower. More preferably, the temperature is 80°C or lower. More preferably, the temperature is 70°C or lower. Any combination of these lower and upper limits is acceptable. If the glass transition temperature of the copolymer (A) is below 20°C, tack may occur when it is made into a photosensitive resin composition, potentially contaminating equipment and components that come into contact with the resin composition, thus adversely affecting the manufacturing process of color filters and subsequent processes. Furthermore, poor compatibility with colorants and other materials may lead to haze formation and surface roughness. If the glass transition temperature of the copolymer (A) is 90°C or lower, optimal substrate adhesion and pattern shape can be achieved when the photosensitive resin composition is cured and developed.

[0062] In this specification, the glass transition temperature is the value measured under the following conditions: It was measured using a DSC (Differential Scanning Calorimeter, measuring instrument: Seiko DSC6200) under a nitrogen gas flow at a heating rate of 10°C / min in accordance with JIS-K7121 (midpoint glass transition temperature: Tmg).

[0063] The content of copolymer (A) in the photosensitive resin composition of this embodiment is, relative to 100% by mass of the total of copolymer (A) and the reactive diluent (B), Preferably, it is 10% by mass or more. More preferably 25% by mass or more, More preferably, it is 40% by mass or more. The content of the reactive diluent (B) is, relative to 100% by mass of the total of the copolymer (A) and the reactive diluent (B), Preferably less than 100% by mass, More preferably, 80% by mass or less. More preferably, it is 60% by mass or less. Any combination of these lower and upper limits is acceptable. When the content of copolymer (A) is within the above range, the viscosity and photocurability of the photosensitive resin composition become more appropriate.

[0064] [Reactive Diluent (B)] The reactive diluent (B) included in the photosensitive resin composition of this embodiment may be any low molecular weight compound having an ethylenically unsaturated group such as a vinyl group, an allyl group, or a (meth)acryloyloxy group, and is not particularly limited. The reactive diluent (B) is preferably a reactive compound having multiple ethylenically unsaturated groups (a polyfunctional reactive diluent) in order to improve the curability (reactivity) of the photosensitive composition. Specific examples of the reactive diluent (B) include aromatic vinyl monomers; polycarboxylic acid monomers such as vinyl acetate and vinyl adipate; monofunctional (meth)acrylates; polyfunctional (meth)acrylates; and triallyl cyanurate.

[0065] Specific examples of aromatic vinyl monomers include styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, divinylbenzene, diallyl phthalate, and diallylbenzenephosphonate.

[0066] Specific examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, β-hydroxyethyl (meth)acrylate, and hydroxypropyl (meth)acrylate.

[0067] Specific examples of polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tri(meth)acrylate of tris(hydroxyethyl) isocyanurate.

[0068] Among these, polyfunctional (meth)acrylates are preferred as the reactive diluent (B) to improve curability (reactivity), and dipentaerythritol penta(meth)acrylate and / or dipentaerythritol hexa(meth)acrylate are particularly preferred. These reactive diluents (B) may be used individually or in combination of two or more.

[0069] The content of the reactive diluent (B) in the photosensitive resin composition of this embodiment is, relative to 100% by mass of the total of the copolymer (A) and the reactive diluent (B), Preferably, it is greater than 0% by mass, More preferably 20% by mass or more. More preferably, it is 40% by mass or more. The content of the reactive diluent (B) is, relative to 100% by mass of the total of the copolymer (A) and the reactive diluent (B), Preferably, it is 90% by mass or less. More preferably, 75% by mass or less. More preferably, it is 60% by mass or less. Any combination of these lower and upper limits is acceptable. When the content of reactive diluent (B) is within the above range, the viscosity and photocurability of the photosensitive resin composition become more appropriate.

[0070] [Photopolymerization initiator (C)] The photopolymerization initiator (C) is not particularly limited, but examples include: 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl-]-,-1-(O-acetyloxime); benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin butyl ether; 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-morpholino Examples include anthraquinone compounds such as nophenyl)butanone-1, 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; xanthones; thioxanthone compounds such as thioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone; ketal compounds such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone compounds such as benzophenone, 4-(1-t-butyldioxy-1-methylethyl)benzophenone, and 3,3',4,4'-tetrakis(t-butyldioxycarbonyl)benzophenone; and acylphosphine oxide-based photopolymerization initiators. The photopolymerization initiator (C) may be used alone or in combination of two or more types.

[0071] The content of the photopolymerization initiator (C) in the photosensitive resin 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 part by mass or more, based on 100 parts by mass of the total of the copolymer (A) and the reactive diluent (B). The content of the photopolymerization initiator (C) in the photosensitive resin composition 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, based on 100 parts by mass of the total of the copolymer (A) and the reactive diluent (B). Any combination of these lower and upper limits is acceptable. When the content of the photopolymerization initiator (C) is 0.1 parts by mass or more, a photosensitive resin composition with good photocurability can be obtained. When the content of the photopolymerization initiator (C) is 30 parts by mass or less, it is possible to prevent adverse effects on the physical properties of the cured product of the photosensitive resin composition due to an excessive amount of the photopolymerization initiator (C).

[0072] [Solvent (D)] The solvent (D) is not particularly limited as long as it can dissolve the copolymer (A), the reactive diluent (B), and the photopolymerization initiator (C). Examples of solvents (D) 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; hydroxyl group-containing carboxylic acid esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyethyl acetate, and methyl 2-hydroxy-3-methylbutyrate; and hydroxyl group-containing solvents such as diethylene glycol; as well as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol (Poly)alkylene glycol monoalkyl ether acetates such as methyl monoethyl ether acetate; ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutyl acetate, and 3-methyl-3-methoxybutyl acetate. Examples of solvents include esters such as lupropionate, ethyl acetate, n-butyl acetate, i-propyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate; aromatic hydrocarbons such as toluene and xylene; and hydroxyl group-free solvents such as carboxylic acid amides such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. Solvent (D) may be used alone or in combination of two or more.

[0073] Among these solvents (D), ethers are preferred from the viewpoint of ease of availability, cost, and stability during resist preparation. Specifically, it is 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. More preferably, glycol ethers having hydroxyl groups are used, and it is even more preferable to use one or more selected from propylene glycol monomethyl ether and ethylene glycol monomethyl ether.

[0074] The solvent (D) content in the photosensitive resin composition is preferably 30 parts by mass or more, and more preferably 50 parts by mass or more, per 100 parts by mass of the total components excluding the solvent (D). The solvent (D) content in the photosensitive resin composition is preferably 1,000 parts by mass or less, and more preferably 800 parts by mass or less, per 100 parts by mass of the total components excluding the solvent (D). Any combination of these lower and upper limits is acceptable. When the solvent (D) content is 30 parts by mass or more, the viscosity of the photosensitive resin composition can be kept within an appropriate range. When the solvent (D) content is 1,000 parts by mass or less, the solvent (D) can be easily removed from the coating film formed by applying the photosensitive resin composition to a substrate.

[0075] [Coloring agent (E)] The photosensitive resin composition may optionally contain a colorant (E). A photosensitive resin composition containing a colorant (E) can be used as a material for a color filter.

[0076] The coloring agent (E) is not particularly limited as long as it is soluble or dispersed in the solvent (D), and examples include dyes and pigments.

[0077] As dyes, it is preferable to use acidic dyes having acidic groups such as carboxyl groups and sulfo groups, salts of acidic dyes with nitrogen compounds, or sulfonamide adducts of acidic dyes, from the viewpoint of solubility in solvent (D) and alkaline developer, interaction with other components in the photosensitive resin composition, and heat resistance.

[0078] Examples of such dyes include acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; solvent blue 38, 44, 70; acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 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, 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow Examples include 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; food yellow 3 and its derivatives. Among these, azo, xanthene, anthraquinone, or phthalocyanine acid dyes are preferred. The dyes can be used individually or in combination of two or more.

[0079] Examples of pigments include yellow pigments such as CI 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, 214; orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; and CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 1 Examples include red pigments such as 68, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, and 265; blue pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, and 60; violet pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, and 38; green pigments such as CI Pigment Green 7, 36, 58, and 59; brown pigments such as CI Pigment Brown 23 and 25; and black pigments such as CI Pigment Black 1 and 7, carbon black, titanium black, and iron oxide. Pigments can be used individually or in combination of two or more types.

[0080] The colorant (E) can be appropriately determined, for example, according to the desired coloring pattern (black matrix and pixels). The colorant (E) may be used alone or in combination of two or more types. When using two or more types of colorant (E), dyes and pigments may be used in combination.

[0081] When a pigment is used as the colorant (E), a known dispersant may be added to the photosensitive resin composition to improve the dispersibility of the pigment. It is preferable to use a polymeric dispersant that exhibits excellent dispersion stability over time. Examples of polymeric 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. As polymeric dispersants, commercially available products under trade names such as EFKA (manufactured by EFKA Chemicals BV), Disperbyk (manufactured by Bic Chemie), Disparon (manufactured by Kusumoto Chemicals Co., Ltd.), and SOLSPERSE (manufactured by Lubrizol) may be used. The dispersant content should be appropriately set according to the type and amount of pigment used as the colorant (E).

[0082] The content of the colorant (E) in the photosensitive resin 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 copolymer (A) and the reactive diluent (B). The content of the colorant (E) in the photosensitive resin 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 copolymer (A) and the reactive diluent (B). Any combination of these lower and upper limits is acceptable. When the content of the colorant (E) is 3 parts by mass or more, the effect of including the colorant (E) becomes significant, and a photosensitive resin composition suitable as a material for the coloring pattern of a color filter is obtained. When the content of the colorant (E) is 80 parts by mass or less, the colorant (E) does not interfere with the curability of the photosensitive resin composition, and a photosensitive resin composition with good low-temperature curability can be obtained.

[0083] [Other ingredients] In one embodiment of the photosensitive resin composition, in addition to a copolymer (A), a reactive diluent (B), a photopolymerization initiator (C), a solvent (D), and a colorant (E) as needed, known additives such as coupling agents, leveling agents, and thermal polymerization inhibitors may be added as needed. The amount of additives added is not particularly limited, as long as it does not hinder the effects of the present invention.

[0084] <Method for producing copolymer (A)> There are no particular restrictions on the proportion of each monomer used in the copolymerization reaction of copolymer (A). Preferably, monomer (ma) is 1 to 40 mol%, monomer (mb) is 1 to 70 mol%, The monomer (mc) content is 1 to 70 mol%, more preferably 5 to 30 mol%, monomer (mb) content is 10 to 60 mol%, monomer (mc) content is 5 to 60 mol%, and even more preferably 5 to 25 mol%, monomer (mb) content is 20 to 40 mol%, and monomer (mc) content is 10 to 30 mol%. When monomer (md) is further used, preferably monomer (ma) is 1-40 mol%, monomer (mb) is 1-70 mol%, monomer (mc) is 5-70 mol%, and monomer (md) is 1-40 mol%, more preferably monomer (ma) is 5-40 mol%, monomer (ma) is 5-30 mol%, monomer (mb) is 10-60 mol%, monomer (mc) is 5-60 mol%, and monomer (md) is 3-30 mol%, and even more preferably monomer (ma) is 5-40 mol%, monomer (ma) is 5-25 mol%, monomer (mb) is 20-40 mol%, monomer (mc) is 10-30 mol%, and monomer (md) is 5-20 mol%. When monomers (me) and (mf) are further used, preferably monomer (ma) is 1-40 mol%, monomer (mb) is 1-70 mol%, monomer (mc) is 5-70 mol%, monomer (md) is 1-40 mol%, monomer (me) is 1-40 mol%, and monomer (mf) is 1-60 mol%, more preferably monomer (ma) is 5-30 mol%, monomer (mb) is 10-60 mol%, The monomer (mc) is 5-60 mol%, monomer (md) is 3-30 mol%, monomer (me) is 1-40 mol%, and monomer (mf) is 1-40 mol%, and more preferably, monomer (ma) is 5-25 mol%, monomer (mb) is 20-40 mol%, monomer (mc) is 10-30 mol%, monomer (md) is 5-20 mol%, monomer (me) is 1-40 mol%, and monomer (mf) is 1-20 mol%.

[0085] The copolymerization reaction can be carried out in or without the polymerization solvent according to radical polymerization methods known in the art. From the viewpoint of preventing abnormal polymerization and ensuring a stable polymerization reaction, it is preferable to carry out the reaction in the presence of a hydroxyl group-containing organic solvent among the solvents (D) described above. By carrying out the copolymerization reaction in the presence of a hydroxyl group-containing organic solvent, even if the group represented by formula (1) or formula (2) above of the monomer (ma) dissociates to form an isocyanate group, the isocyanate group reacts with the hydroxyl group of the hydroxyl group-containing organic solvent, preventing abnormal polymerization. In the copolymer (A) thus obtained, it is considered that a portion of the blocking agent that was blocking the isocyanate group is replaced by the hydroxyl group-containing organic solvent. For example, these monomers can be dissolved in a hydroxyl group-containing organic solvent, a polymerization initiator can be added to the solution, and the polymerization reaction can be carried out at 50 to 100°C for 1 to 20 hours. In this case, if the polymerization reaction is carried out at the temperature at which the group represented by formula (1) or formula (2) of the monomer (ma) dissociates, the isocyanate group produced by the dissociation of the group represented by formula (1) or formula (2) will react with the carboxyl group of acrylic acid to form a gel. Therefore, it is preferable to carry out the polymerization at a temperature below the dissociation temperature of the group represented by formula (1) or formula (2), preferably at a temperature about 20 to 50°C below the dissociation temperature of the group represented by formula (1) or formula (2).

[0086] Furthermore, the polymerization initiators that can be used in this copolymerization reaction are not particularly limited, but examples include azo-based thermal polymerization initiators such as azobisisobutyronitrile and azobisisovaleronitrile; and peroxide-based thermal polymerization initiators such as benzoyl peroxide and t-butylperoxy-2-ethylhexanoate. These polymerization initiators may be used individually or in combination of two or more. The amount of polymerization initiator used is generally 0.5 to 20 parts by mass, preferably 1.0 to 10 parts by mass, when the total amount of monomer charged is 100 parts by mass.

[0087] As the solvent used in the copolymerization reaction, the same solvent as solvent (D) mentioned above can be used. In addition, propylene glycol monoaryl ether, 1,3-propanediol monoalkyl ether, 1,3-butanediol monoalkyl ether, 1,4-butanediol monoalkyl ether, glycerin monoalkyl ether, glycerin dialkyl ether, methanol, ethanol, propanol, C5-6 cycloalkanediol, C 5-6 Examples include cycloalkanedimethanol, ethyl lactate, and diacetone alcohol. These solvents may be used individually or in combination of two or more.

[0088] <Method for producing a photosensitive resin composition> A photosensitive resin composition according to one embodiment can be produced by mixing a copolymer (A), a reactive diluent (B), a photopolymerization initiator (C), a solvent (D), and a colorant (E) as needed, using a known mixing apparatus.

[0089] When manufacturing a photosensitive resin composition, the reaction solution used to manufacture the copolymer (A) can be used as a raw material. In this case, the solvent (D) contained in the reaction solution can be used as part or all of the solvent (D) contained in the photosensitive resin composition or the photosensitive colored composition.

[0090] The photosensitive resin composition contains a copolymer (A) that includes a structural unit (a) having a group represented by formula (1) or formula (2) above, and a structural unit (b) having a group represented by -CH2-OH, and therefore has good low-temperature curability.

[0091] Therefore, when forming a cured product using a photosensitive resin composition, curing can be performed at a lower temperature compared to when using conventional resin compositions. Consequently, when a coating film formed on a substrate is exposed to light and then subjected to a baking treatment, the crosslinking reaction proceeds sufficiently even at a lower baking treatment temperature, resulting in the formation of a cured product with excellent solvent resistance.

[0092] Therefore, when forming a cured product using a photosensitive resin composition, less energy is required for heating to cure it. In addition, by using a photosensitive resin composition, a cured product can be formed on a substrate with low heat resistance, such as a resin substrate, without damaging the substrate. Furthermore, even when a colorant (E) with low heat resistance is used, a cured product can be formed that exhibits the original properties of the colorant (E).

[0093] The photosensitive resin composition yields a cured product with excellent solvent resistance even at low baking temperatures, so the colorant (E) is less likely to leach out of the cured product. Therefore, it is possible to increase the colorant (E) content in the photosensitive resin composition. A photosensitive resin composition with a high colorant (E) content can be used, for example, as a material for the coloring pattern of a color filter to form a color filter with excellent color reproduction.

[0094] The copolymer (A) contained in the photosensitive resin composition has structural units (c) derived from acrylic acid, and therefore the photosensitive resin composition has good alkali developability. Because such a photosensitive resin composition has excellent alkali developability, for example, 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 areas with an alkaline aqueous solution, and then baking it at a sufficiently low temperature, a cured product with a predetermined pattern shape and excellent solvent resistance can be formed.

[0095] The photosensitive resin composition can be suitably used as a material for color filters.

[0096] Based on these findings, photosensitive resin compositions are extremely useful as materials for forming components of image display elements, such as pixels in color filters, black matrices, color filter protective films, photospacers, liquid crystal alignment protrusions, microlenses, and insulating films for touch panels.

[0097] [Third Embodiment] The photosensitive resin composition of the third embodiment contains a copolymer (A), a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D). The photosensitive resin composition of this embodiment optionally contains a colorant (E). The photosensitive resin composition of this embodiment polymerizes and hardens upon irradiation with light, forming a cured resin film.

[0098] [Copolymer (A)] The copolymer (A) used in the photosensitive resin composition of this embodiment contains a structural unit (a) (hereinafter also simply referred to as "structural unit (a)") having one or more selected from an active methylene group to which a methoxycarbonyl group is attached and an active methine group to which a methoxycarbonyl group is attached, a structural unit (b) (hereinafter also simply referred to as "structural unit (b)") having a hydroxyl group, and a structural unit (c) (hereinafter also simply referred to as "structural unit (c)") having an acid group.

[0099] The copolymer (A) of this embodiment may further contain, if necessary, structural units (e) derived from (meth)acrylate having a linear or branched alkyl group having 1 to 20 carbon atoms (hereinafter also simply referred to as "structural unit (e)"). The copolymer (A) of this embodiment may further contain, if necessary, structural units (f) derived from (meth)acrylate having a cross-linked cyclic hydrocarbon group having 10 to 20 carbon atoms (hereinafter also simply referred to as "structural unit (f)").

[0100] "Structural unit (a)" The copolymer (A) is composed of a structural unit derived from a monomer (ma) (hereinafter also simply referred to as "monomer (ma)") having one or more selected from an active methylene group to which a methoxycarbonyl group is attached, and an active methine group to which a methoxycarbonyl group is attached. The methoxycarbonyl group of structural unit (a) contained in copolymer (A) undergoes transesterification with the hydroxyl group of structural unit (b) when the resin composition containing copolymer (A) is heat-cured, thereby creating a crosslinked structure. As a result, a cured film with excellent solvent resistance and hardness can be obtained from a resin composition containing copolymer (A) even when cured at a low temperature of 50°C to 150°C. Furthermore, methanol is produced when the methoxycarbonyl group of structural unit (a) contained in copolymer (A) undergoes transesterification with the hydroxyl group of structural unit (b). The methanol produced during the heat curing of the resin composition is readily evaporated and removed by the heating required to heat-cur the resin composition, which is preferable. Because the alcohol produced by transesterification is methanol, evaporation, removal from the resin composition, and curing of the resin composition proceed rapidly, resulting in a sufficiently high hardness of the cured resin film.

[0101] An active methylene group refers to a methylene group to which an electron-withdrawing group is bonded to at least one side (preferably both sides). Examples of electron-withdrawing groups include carbonyl groups, ester groups, cyano groups, nitro groups, sulfonyl groups, sulfinyl groups, and phosphono groups. As an active methylene group, a structure in which carbonyl groups or ester groups are bonded to both sides of the methylene group is preferred, and a group in which ester groups are bonded to both sides of the methylene group, i.e., a -COO-CH2-COO- structure, is particularly preferred.

[0102] The structural unit (a) is preferably a structural unit having one or more selected from the group consisting of the group represented by the following formula (i-1) and the group represented by the following formula (ii-1).

[0103] [ka]

[0104] (In equation (i-1), n1 and n2 each represent an integer between 0 and 2 independently. * represents a concatenation.)

[0105] [ka]

[0106] (In equation (ii-1), n3 and n4 each independently represent integers between 0 and 2. * represents a concatenation.)

[0107] In formulas (i-1) and (ii-1) above, n1 to n4 are each independently preferably 0 or 1, and more preferably 0, from the viewpoint of further promoting transesterification and improving low-temperature curability.

[0108] The monomer (ma) that gives structural unit (a) is not particularly limited, as long as it is a compound copolymerizable with monomer (mb) and monomer (mc) described later. As monomer (ma), for example, from the viewpoint of reactivity when synthesizing copolymer (A), monomers having one or more selected from an active methylene group to which a methoxycarbonyl group is attached and an active methine group to which a methoxycarbonyl group is attached, and an ethylenically unsaturated bond can be used. Specifically, as groups having an ethylenically unsaturated bond, vinyl groups and (meth)acryloyloxy groups can be mentioned. From the viewpoint of freedom in monomer blending ratio, (meth)acryloyloxy groups are preferred, and from the viewpoint of solvent resistance and hardness of the cured product of the photosensitive resin composition, and reduction of dye elution when a dye is used as a colorant (E), acryloyloxy groups are preferred.

[0109] Examples of monomers (MA) having one or more selected from the above-mentioned active methylene groups to which a methoxycarbonyl group is attached and active methine groups to which a methoxycarbonyl group is attached, and an ethylenically unsaturated bond include reaction products of ethylenically unsaturated group-containing isocyanate compounds with dimethyl malonate or methyl acetoacetate. These monomers (m-a) may be used alone, or in combination of two or more thereof.

[0110] The ethylenically unsaturated group-containing isocyanate compound that forms the monomer (m-a) is preferably a compound represented by the following formula (3).

[0111] [Chemical Formula] (In formula (3), R 4 represents a hydrogen atom or a methyl group. R 5 represents -CO-, -COOR 6 - (wherein R 6 is an alkylene group having 1 to 6 carbon atoms), or -COO-R 7 O-CONH-R 8 - (wherein R 7 is an alkylene group having 2 to 6 carbon atoms, and R 8 is an optionally substituted alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms).)

[0112] R in formula (3) 4 represents a hydrogen atom or a methyl group. From the viewpoints of solvent resistance and hardness of the cured product of the photosensitive resin composition, and reduction of dye elution when a dye is used as the colorant (E), R 4 is preferably a hydrogen atom. R in formula (3) 5 represents -CO-, -COOR 6 - or -COO-R 7 O-CONH-R 8 -. Here, R 6 is an alkylene group having 1 to 6 carbon atoms. R 7 is an alkylene group having 2 to 6 carbon atoms. Further, R 8 is an optionally substituted alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms. Among these, R in formula (3) 5 is preferably -COOR 6 -. R 5 being -COOR 6-If R 6 This is preferably an alkylene group having 1 to 4 carbon atoms.

[0113] Examples of isocyanate compounds containing an ethylenically unsaturated group represented by the above formula (3) 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 (meth)acryloyl isocyanate.

[0114] Furthermore, as the ethylenically unsaturated group-containing isocyanate compound represented by formula (3) above, equimolar (1 mole:1 mole) reaction products of 2-hydroxyalkyl (meth)acrylate and diisocyanate compound can also be used. The alkyl group contained in the 2-hydroxyalkyl (meth)acrylate above is preferably an ethyl group or an n-propyl group, with the ethyl group being more preferred. Examples of the diisocyanate compounds above 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, and the like.

[0115] Among these ethylenically unsaturated group-containing isocyanate compounds, 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 (meth)acryloyl isocyanate are preferred, with 2-isocyanatoethyl (meth)acrylate and 2-isocyanatopropyl (meth)acrylate being more preferred. These ethylenically unsaturated group-containing isocyanate compounds may be used individually or in combination of two or more.

[0116] The reaction between an ethylenically unsaturated group-containing isocyanate compound and dimethyl malonate or methyl acetoacetate can be carried out with or without the presence of a solvent. When using a solvent, a solvent that is inert to the isocyanate group should be used. For this reaction, organometallic salts such as tin, zinc, or lead, or tertiary amines may be used as catalysts. The above reaction can generally be carried out at temperatures of -20 to 150°C, and preferably at temperatures of 25 to 130°C. A sufficient reaction rate can be obtained if the reaction temperature is above -20°C. Furthermore, if the reaction temperature is below 150°C, polymerization of the starting material having a C=C (double bond) can be prevented, which prevents the monomer (ma) that gives the structural unit (a) generated after the reaction from gelling.

[0117] Specific examples of monomers (ma) include, for example, AOI-DMM, MOI-DMM, AOI-OBM, MOI-OBM, etc. AOI-DMM: Karenz (trademark) AOI-DMM, reaction product of 2-isocyanatoethyl acrylate and dimethyl malonate (malonate-2-[[[[2-[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-dimethyl ester, manufactured by Resonaq Corporation. MOI-DMM: Karenz (trademark) MOI-DMM, reaction product of 2-isocyanatoethyl methacrylate and dimethyl malonate (malonate-2-[[[[2-[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-dimethyl ester, manufactured by Resonaq Corporation. AOI-OBM: Karenz (trademark) AOI-OBM, a reaction product of 2-isocyanatoethyl acrylate and methyl acetoacetate, manufactured by Resonaq Corporation. MOI-OBM: Karens (trademark) MOI-OBM, reaction product of 2-isocyanatoethyl methacrylate and methyl acetoacetate, manufactured by Resonaq Corporation.

[0118] "Structural unit (b)" The structural unit (b) constituting the copolymer (A) is a structural unit derived from a monomer (mb) (hereinafter also simply referred to as "monomer (mb)") that has a hydroxyl group but does not have an active methylene group to which a methoxycarbonyl group is attached, nor an active methine group to which a methoxycarbonyl group is attached. The hydroxyl group of structural unit (b) contained in copolymer (A) undergoes transesterification with the methoxycarbonyl group of structural unit (a) by thermal curing of the resin composition containing copolymer (A), thereby creating a crosslinked structure.

[0119] In particular, structural unit (b) preferably has a group represented by -CH2-OH from the viewpoint of low-temperature curability, and -(CH2) n - Structural units having a group represented by -OH (where n is an integer from 2 to 6) and -(OC x H 2x ) m It is more preferable that the structural unit is selected from the group consisting of structural units having a group represented by -OH (where x is an integer from 2 to 4 and m is an integer from 2 to 10). -(CH2) n -The n of the group represented by -OH is preferably 2 to 4, more preferably 2 and 4. x H 2x ) m -The x of the group represented by -OH is preferably 2 to 3, more preferably 2.x H 2x ) m The value of m in the group represented by -OH is preferably 2 to 6, more preferably 4 to 6.

[0120] The monomer (mb) that gives structural unit (b) is not particularly limited, as long as it does not have an active methylene group to which the methoxycarbonyl group is attached, and an active methine group to which the methoxycarbonyl group is attached, and has an ethylenically unsaturated group and a hydroxyl group. Examples of ethylenically unsaturated groups contained in monomer (mb) include vinyl groups, (meth)acryloyloxy groups, etc. Examples of monomer (mb) include (meth)acrylic acid ester derivatives having a hydroxyl group. Specific examples of such monomers (mb) include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, etc. These monomers (mb) may be used individually or in combination of two or more.

[0121] As monomers (mb), among the above monomers, hydroxyalkyl (meth)acrylate and polyalkylene glycol mono(meth)acrylate are preferred from the viewpoint of reactivity when synthesizing copolymer (A), low-temperature curability of the resin composition containing copolymer (A), and ease of availability. As hydroxyalkyl (meth)acrylates, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate are preferred, and 4-hydroxybutyl (meth)acrylate is more preferred from the viewpoint of obtaining solvent resistance as a cured product. As polyalkylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate is preferred from the viewpoint of solvent resistance, and -(OC x H 2x ) mPolyethylene glycol mono(meth)acrylate with -OH x = 2 and m = 2-6 is more preferable.

[0122] "Structural unit (c)" Structural unit (c) is a structural unit that does not have an active methylene group with a methoxycarbonyl group attached, an active methine group with a methoxycarbonyl group attached, or a hydroxyl group, but has an acid group. Examples of acid groups include carboxyl groups, sulfol groups, and phosphol groups. Among these acid groups, the carboxyl group is preferred due to its availability. Examples of monomers (mc) that provide the structural unit (c) include unsaturated carboxylic acids or their anhydrides, unsaturated sulfonic acids, unsaturated phosphonic acids, and the like. Specifically, examples include unsaturated carboxylic acids or their anhydrides such as (meth)acrylic acid, α-bromo(meth)acrylic acid, β-furyl(meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, α-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. These monomers (mc) may be used individually or in combination of two or more. In particular, (meth)acrylic acid is preferred from the viewpoint of developability as a photosensitive resin composition, and acrylic acid is more preferred from the viewpoint of solvent resistance.

[0123] "Structural unit (e)" The copolymer (A) of this embodiment may further contain, if necessary, structural units (e) derived from (meth)acrylate having a crosslinked cyclic hydrocarbon group having 10 to 20 carbon atoms. The structural unit (e) is the same as the structural unit (e) described in the second embodiment.

[0124] "Structural unit (f)" The copolymer (A) of this embodiment may further contain, if necessary, structural units (f) derived from (meth)acrylate having a linear or branched alkyl group having 1 to 20 carbon atoms. The structural unit (f) is the same as the structural unit (f) described in the second embodiment.

[0125] "Other structural units (g)" The copolymer (A) of this embodiment may optionally contain other structural units (g) other than the above structural units (a) to (e). The structural units (g) are the same as the structural units (g) described in the second embodiment.

[0126] "The proportion of each structural unit" The content of structural unit (a) is preferably 1 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, when the total amount of structural units constituting the copolymer (A) is taken as 100 mol%. The content of structural unit (a) is preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 25 mol% or less, when the total amount of structural units constituting the copolymer (A) is taken as 100 mol%. Any combination of these lower and upper limits is acceptable. If the content of structural unit (a) is 1 mol% or more, a sufficient amount of crosslinking by transesterification with the hydroxyl group of structural unit (b) can be ensured, and the hardness and solvent resistance of the cured product are good even when the photosensitive resin composition is cured at low temperatures. If the content of structural unit (a) is 40 mol% or less, a sufficient amount of the crosslinking partner structural unit (b) can be ensured. In addition, a sufficient amount of structural unit (c) can be ensured, and the developability of the photosensitive resin composition is good.

[0127] The content of structural unit (b) is preferably 1 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, when the total amount of structural units constituting the copolymer (A) is 100 mol%. The content of structural unit (b) is preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 25 mol% or less, when the total amount of structural units constituting the copolymer (A) is 100 mol%. Any combination of these lower and upper limits is acceptable.

[0128] When the content of structural unit (b) is 1 mol% or more, a sufficient amount of crosslinking by transesterification with structural unit (a) can be ensured, and the hardness and solvent resistance of the cured product are good even when the photosensitive resin composition is cured at low temperatures. Furthermore, the developability of the photosensitive resin composition can be adjusted to a desired range. When the content of structural unit (b) is 40 mol% or less, a sufficient amount of the crosslinking partner structural unit (a) can be ensured. Furthermore, a sufficient amount of structural unit (c) can be ensured, and the developability of the photosensitive resin composition is good.

[0129] The content of structural unit (c) is preferably 1 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more, when the total amount of structural units constituting the copolymer (A) is 100 mol%. The content of structural unit (c) is preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 25 mol% or less, when the total amount of structural units constituting the copolymer (A) is 100 mol%. Any combination of these lower and upper limits is acceptable. If the content of structural unit (c) is 1 mol% or more, the developability of the photosensitive resin composition can be adjusted to a desired range. If the content of structural unit (c) is 40 mol% or less, the content of structural unit (a) and structural unit (b) can be sufficiently secured, and the amount of crosslinking by transesterification can be sufficiently secured.

[0130] If the copolymer (A) contains structural unit (e), the content of structural unit (e) is preferably 1 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more, when the total amount of structural units constituting the copolymer (A) is 100 mol%. The content of structural unit (e) is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less, when the total amount of structural units constituting the copolymer (A) is 100 mol%. Any combination of these lower and upper limits is acceptable. When the content of structural unit (e) is 1 mol% or more, the properties derived from structural unit (e) are well expressed. When the content of structural unit (e) is 30 mol% or less, the content of structural units (a) to (c) can be sufficiently ensured, resulting in good low-temperature curing properties of the photosensitive resin composition and good solvent resistance and hardness of the cured product.

[0131] If the copolymer (A) contains structural unit (f), the content of structural unit (f) is preferably 10 mol% or more, more preferably 30 mol% or more, and even more preferably 50 mol% or more, when the total amount of structural units constituting the copolymer (A) is 100 mol%. The content of structural unit (f) is preferably 95 mol% or less, more preferably 80 mol% or less, and even more preferably 70 mol% or less, when the total amount of structural units constituting the copolymer (A) is 100 mol%. Any combination of these lower and upper limits is acceptable. When the content of structural unit (f) is 10 mol% or more, the photosensitive resin composition can be given desired properties such as flexibility and substrate adhesion. When the content of structural unit (f) is 95 mol% or less, the content of structural units (a) to (c) can be sufficiently ensured, the low-temperature curing and developing properties of the photosensitive resin composition can be ensured, and the solvent resistance and hardness of the cured product are good.

[0132] When the copolymer (A) contains structural units (g), the content of structural units (g) is preferably 0.5 to 25 mol% or more, more preferably 1 to 20 mol% or more, and even more preferably 5 to 15 mol% or more, when the total amount of structural units constituting the copolymer (A) is taken as 100 mol%. When the content of structural units (g) is within the above range, the function of structural units (g) can be imparted to the photosensitive resin composition without impairing the functions of structural units (a) to (c).

[0133] "Acid value" The acid value of the copolymer (A) is preferably 10KOH mg / g or more, more preferably 15KOH mg / g or more, and even more preferably 20KOH mg / g or more. The acid value of the copolymer (A) is preferably 250KOH mg / g or less, more preferably 200KOH mg / g or less, even more preferably 150KOH mg / g or less, and even more preferably 100KOH mg / g or less. When the acid value of the copolymer (A) is 10KOH mg / g or higher, the developability is good when used as a photosensitive resin composition. If the acid value of the copolymer (A) is 250 KOH mg / g or less, the photosensitive resin composition has good storage stability. The acid value of the copolymer (A) is the acid value of the curable polymer measured according to JIS K6901 5.3. That is, the acid value represents the number of mg of potassium hydroxide required to neutralize the acidic components contained in 1 g of copolymer.

[0134] "Hydroxyl equivalent" The hydroxyl group equivalent of copolymer (A) is preferably 200 g / mol or more, more preferably 600 g / mol or more, and even more preferably 1000 g / mol or more. The hydroxyl group equivalent of copolymer (A) is preferably 3000 g / mol or less, more preferably 2000 g / mol or less, and even more preferably 1600 g / mol or less. When the hydroxyl group equivalent of copolymer (A) is 200 g / mol or more, the amount of structural unit (a) and structural unit (c) can be sufficiently secured, and a photosensitive resin composition with good developability and low-temperature curing properties can be obtained. When the hydroxyl group equivalent of copolymer (A) is 3000 g / mol or less, sufficient crosslinking with structural unit (a) can be ensured, resulting in a resin-cured film with good solvent resistance and hardness. The hydroxyl group equivalent is the mass of copolymer (A) per mole of hydroxyl groups in copolymer (A). The hydroxyl group equivalent can be determined by dividing the mass of copolymer (A) by the number of hydroxyl groups in the resin (g / mol). In this specification, the hydroxyl group equivalent of copolymer (A) is a theoretical value calculated from the amount of raw material used to introduce hydroxyl groups into the resin.

[0135] "Equivalent amount of alkoxycarbonyl group" The alkoxycarbonyl group equivalent of copolymer (A) is preferably 100 g / mol or more, more preferably 200 g / mol or more, and even more preferably 500 g / mol or more. The alkoxycarbonyl group equivalent of copolymer (A) is preferably 5000 g / mol or less, more preferably 4000 g / mol or less, and even more preferably 3000 g / mol or less. When the alkoxycarbonyl group equivalent of copolymer (A) is 100 g / mol or more, the photosensitive resin composition exhibits good storage stability. When the alkoxycarbonyl group equivalent of copolymer (A) is 5000 g / mol or less, sufficient crosslinking with structural unit (b) can be ensured, resulting in a resin cured film with good solvent resistance and hardness. The alkoxycarbonyl group equivalent is the mass of copolymer (A) per mole of alkoxycarbonyl groups in copolymer (A). The alkoxycarbonyl group equivalent can be determined by dividing the mass of copolymer (A) by the number of alkoxycarbonyl groups in the resin (g / mol). In this specification, the alkoxycarbonyl group equivalent of copolymer (A) is a theoretical value calculated from the amount of raw material used to introduce alkoxycarbonyl groups into the resin.

[0136] "Measurement of weight-average molecular weight, number-average molecular weight, and molecular weight distribution"

[0137] The weight-average molecular weight of the copolymer (A) is preferably 3000 or more, more preferably 5000 or more, and even more preferably 6000 or more. The weight-average molecular weight of the copolymer (A) is preferably 50000 or less, more preferably 40000 or less, and even more preferably 30000 or less. If the weight-average molecular weight of copolymer (A) is 3000 or more, the copolymerization reaction of copolymer (A) can be carried out stably, and copolymer (A) with highly reproducible physical properties can be provided. If the weight-average molecular weight of copolymer (A) is 50000 or less, the copolymerization reaction of copolymer (A) can be carried out stably, and copolymer (A) with highly reproducible physical properties can be provided, as well as good developability when used as a photosensitive resin composition. Insoluble matter of the photosensitive resin composition described later can be easily removed by filtration.

[0138] The number-average molecular weight of the copolymer (A) is preferably 1000 or more, more preferably 2000 or more, and even more preferably 3000 or more. The number-average molecular weight of the copolymer (A) is preferably 25000 or less, more preferably 15000 or less, and even more preferably 10000 or less. If the number average molecular weight of the copolymer (A) is 1000 or more, the copolymerization reaction of copolymer (A) can be carried out stably, and a copolymer (A) with highly reproducible physical properties can be provided. If the number average molecular weight of the copolymer (A) is 25000 or less, the copolymerization reaction of copolymer (A) can be carried out stably, a copolymer (A) with highly reproducible physical properties can be provided, and the developability when used as a photosensitive resin composition is good. Insoluble matter of the photosensitive resin composition described later can be easily removed by filtration.

[0139] The molecular weight distribution of the copolymer (A) is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.1 or higher. The molecular weight distribution of the copolymer (A) is preferably 6.0 or lower, more preferably 5.0 or lower, and even more preferably 4.0 or lower. If the molecular weight distribution of the copolymer (A) is 1.5 or higher, the copolymerization reaction of the copolymer (A) can be carried out stably, and the manufacturing process can be easily controlled. If the molecular weight distribution of the copolymer (A) is 6.0 or lower, a copolymer (A) with highly reproducible physical properties can be provided, and the developability when used as a photosensitive resin composition is good.

[0140] The content of copolymer (A) in the photosensitive resin composition of this embodiment is, relative to 100% by mass of the total of copolymer (A) and the reactive diluent (B), Preferably, it is 10% by mass or more. More preferably 25% by mass or more, More preferably, it is 40% by mass or more. The content of the reactive diluent (B) is, relative to 100% by mass of the total of the copolymer (A) and the reactive diluent (B), Preferably less than 100% by mass, More preferably, 80% by mass or less. More preferably, it is 60% by mass or less. Any combination of these lower and upper limits is acceptable. When the content of copolymer (A) is within the above range, the viscosity and photocurability of the photosensitive resin composition become more appropriate.

[0141] [Reactive Diluent (B)] The reactive diluent (B) contained in the photosensitive resin composition of this embodiment is the same as the reactive diluent (B) contained in the photosensitive resin composition of the second embodiment.

[0142] The content of the reactive diluent (B) in the photosensitive resin composition of this embodiment is the same as the content of the reactive diluent (B) in the photosensitive resin composition of the second embodiment.

[0143] [Photopolymerization initiator (C)] The photopolymerization initiator (C) according to this embodiment is the same as the photopolymerization initiator (C) according to the second embodiment.

[0144] The content of the photopolymerization initiator (C) in the photosensitive resin composition of this embodiment is the same as the content of the photopolymerization initiator (C) in the photosensitive resin composition of the second embodiment.

[0145] [Solvent (D)] The solvent (D) in the photosensitive resin composition of this embodiment is the same as the solvent (D) in the photosensitive resin composition of the second embodiment.

[0146] The content of solvent (D) in the photosensitive resin composition of this embodiment is the same as the content of solvent (D) in the photosensitive resin composition of the second embodiment.

[0147] [Coloring agent (E)] The photosensitive resin composition may optionally contain a colorant (E). A photosensitive resin composition containing a colorant (E) can be used as a material for a color filter. The colorant (E) in the photosensitive resin composition of this embodiment is the same as the colorant (E) in the photosensitive resin composition of the second embodiment.

[0148] When a pigment is used as the coloring agent (E), a known dispersant may be added to the photosensitive resin composition from the viewpoint of improving the dispersibility of the pigment. The dispersant is the same as the dispersant according to the second embodiment.

[0149] The content of the colorant (E) in the photosensitive resin composition of this embodiment is the same as the content of the colorant (E) in the photosensitive resin composition of the second embodiment.

[0150] [Other ingredients] In one embodiment of the photosensitive resin composition, in addition to a copolymer (A), a reactive diluent (B), a photopolymerization initiator (C), a solvent (D), and a colorant (E) as needed, known additives such as dispersants, coupling agents, leveling agents, and thermal polymerization inhibitors may be added as needed. The amount of additives added is not particularly limited, as long as it does not hinder the effects of the present invention.

[0151] <Method for producing copolymer (A)> There are no particular restrictions on the proportions of each monomer used in the copolymerization reaction of copolymer (A). Preferably, monomer (ma) is 1 to 40 mol%, monomer (mb) is 1 to 40 mol%, and monomer (mc) is 1 to 40 mol%, more preferably monomer (ma) is 5 to 30 mol%, monomer (mb) is 5 to 30 mol%, and monomer (mc) is 3 to 30 mol%, and even more preferably monomer (ma) is 10 to 25 mol%, monomer (mb) is 10 to 25 mol%, and monomer (mc) is 5 to 25 mol%. When monomer (mf) is used further, preferably monomer (ma) is 1 to 40 mol%, monomer (mb) is 1 to 40 mol%, monomer (mc) is 1 to 40 mol%, and monomer (mf) is 10 to 95 mol%, more preferably monomer (ma) is 5 to 30 mol%, monomer (mb) is 5 to 30 mol%, monomer (mc) is 3 to 30 mol%, and monomer (mf) is 30 to 90 mol%, and even more preferably monomer (ma) is 10 to 25 mol%, monomer (mb) is 10 to 25 mol%, monomer (mc) is 5 to 25 mol%, and monomer (mf) is 50 to 80 mol%. When monomer (me) is further used, preferably monomer (ma) is 1-40 mol%, monomer (mb) is 1-40 mol%, monomer (mc) is 1-40 mol%, monomer (mf) is 10-95 mol%, monomer (me) is 1-30 mol%, more preferably monomer (ma) is 5-30 mol%, monomer (mb) is 5-30 mol%, monomer (mc) is 3-30 mol%, monomer (mf) is 30-80 mol%, monomer (me) is 3-20 mol%, and even more preferably monomer (ma) is 10-25 mol%, monomer (mb) is 10-25 mol%, monomer (mc) is 5-25 mol%, monomer (mf) is 50-70 mol%, and monomer (me) is 5-10 mol%.

[0152] The copolymerization reaction can be carried out in or without the polymerization solvent according to radical polymerization methods known in the art. From the viewpoint of preventing abnormal polymerization and ensuring a stable polymerization reaction, it is preferable to carry out the reaction in the presence of a hydroxyl group-containing organic solvent among the solvents (D) described above. By carrying out the copolymerization reaction in the presence of a hydroxyl group-containing organic solvent, even if the methoxycarbonyl group of monomer (ma) dissociates to form an isocyanate group, the isocyanate group reacts with the hydroxyl group of the hydroxyl group-containing organic solvent, preventing abnormal polymerization. In the copolymer (A) thus obtained, it is considered that a portion of the blocking agent that was blocking the isocyanate group is replaced by the hydroxyl group-containing organic solvent. For example, after dissolving these monomers in a hydroxyl group-containing organic solvent, a polymerization initiator can be added to the solution, and the polymerization reaction can be carried out at 40 to 100°C for 1 to 20 hours. In this case, the higher the polymerization temperature, the more likely unintended side reactions such as crosslinking by transesterification between the methoxycarbonyl group of monomer (ma) and monomer (mb) are to occur, and the more likely a gel is to form. From the viewpoint of reducing gel formation, the temperature in the copolymerization reaction is preferably 80°C or lower, and more preferably 70°C or lower.

[0153] Furthermore, examples of polymerization initiators that can be used in this copolymerization reaction include azo-based thermal polymerization initiators such as azobisisobutyronitrile and azobisisovaleronitrile; and peroxide-based thermal polymerization initiators such as benzoyl peroxide and t-butylperoxy-2-ethylhexanoate. These polymerization initiators may be used individually or in combination of two or more.

[0154] In particular, from the viewpoint of suppressing gel formation during copolymerization, it is preferable to use a polymerization initiator with a 10-hour half-life temperature of 50°C or lower, and it is more preferable to use a peroxide-based thermal polymerization initiator. Examples of such polymerization initiators include 1-methyl-1-phenylethyl 7,7-dimethylperoxyoctanoate and benzoyl peroxide, di(2-phenoxyethyl)peroxydicarbonate, cumyl peroxyneodecanoate (10-hour half-life temperature: 36.5°C), and di(4-t-butylcyclohexyl)peroxydicarbonate (Nippon Oil & Fats Co., Ltd. TCP (90% purity), 1-minute half-life temperature: 92.1°C, 1-hour half-life temperature: 57.5°C, 10-hour half-life temperature: 40.8°C). Diisopropyl peroxydicarbonate (Perloyl IPP manufactured by NOF Corporation (50% purity), 1-minute half-life temperature: 88.3°C, 1-hour half-life temperature: 56.2°C, 10-hour half-life temperature: 40.5°C), Di(2-ethylhexyl)peroxydicarbonate (perloyl OPP manufactured by NOF Corporation (70% purity), 1-minute half-life temperature: 90.6°C, 1-hour half-life temperature: 59.1°C, 10-hour half-life temperature: 43.6°C), Di-sec-butyl peroxydicarbonate (Perloyl SBP manufactured by NOF Corporation (50% purity), 1-minute half-life temperature: 92.4°C, 1-hour half-life temperature: 57.4°C, 10-hour half-life temperature: 40.5°C), 3-Hydroxy-1,1-dimethylbutyl peroxyneodecanoate (10-hour half-life, temperature T) 10 :37℃), Diisobutyryl peroxide (manufactured by NOF Corporation, product name: Perloyl IB, half-life at 10 hours, temperature 32.7°C), Examples include di-n-propyl peroxydicarbonate (manufactured by NOF Corporation, trade name: Perloyl NPP, 10-hour half-life temperature 40.3°C).

[0155] The amount of polymerization initiator used is generally 0.5 to 30 parts by mass, preferably 1 to 25 parts by mass, and more preferably 5 to 20 parts by mass, when the total amount of monomer charged is 100 parts by mass.

[0156] During the copolymerization reaction, a peroxide-based thermal polymerization initiator may be used in combination with a polymerization accelerator. Examples of polymerization accelerators include aliphatic amines, aromatic amines, sulfinic acid derivatives, sulfur-containing reducing inorganic compounds, nitrogen-containing reducing inorganic compounds, borate compounds, barbituric acid derivatives, triazine compounds, halogen compounds, etc., as described in Japanese Patent Application Publication No. 2021-054814. Among these, aromatic amines are preferred from the viewpoint of the ease with which the redox reaction with the peroxide-based polymerization initiator proceeds. Examples of aromatic amine compounds include 2,2-[3-(methylphenyl)imino]bisethanol acetate, 1,1-[(4-methylphenyl)imino]bis(2-propanol), p-tolyldiethanolamine, N,N-bis(2,2,2-trifluoroethyl)-p-toluidine, N,N-di(1-hydroxyethyl)-p-toluidine, N,N-di(2-hydroxypropyl)-p-toluidine, N-(1-cyanoethyl)-N-(1-acetoxyethyl)-m-toluidine, N,N-di(1-chloroethyl)-p-toluidine, N,N-dimethyl-p-toluidine, N-ethyl-N-methylaniline, N,N-dimethylaniline, N,N-dipropyl-o-toluidine, N,N-dipropyl-m-toluidine, N,N-dipropyl-p-toluidine, and ethyl 4-dimethylaminobenzoate. In particular, from the viewpoint of reducing the copolymerization reaction temperature, 1,1-[(4-methylphenyl)imino]bis(2-propanol), N,N-dimethylaniline, and N,N-dimethyl-p-toluidine are preferred. The usage amount of the polymerization accelerator is generally 0.001 to 10 parts by mass, preferably 0.01 to 5 parts by mass, when the total charged amount of monomers is taken as 100 parts by mass.

[0157] As the solvent used for the copolymerization reaction, the same solvents as the aforementioned solvent (D) can be used. In addition, examples thereof also include propylene glycol monoaryl ether, 1,3-propanediol monoalkyl ether, 1,3-butanediol monoalkyl ether, 1,4-butanediol monoalkyl ether, glycerin monoalkyl ether, glycerin dialkyl ether, methanol, ethanol, propanol, C5-6 cycloalkanediol, C 5-6 cycloalkane dimethanol, ethyl lactate, diacetone alcohol and the like. These solvents may be used alone or in combination of two or more thereof.

[0158] <Hardness of the cured resin film of the photosensitive resin composition> In one embodiment, the photosensitive resin composition preferably has a cured resin film hardness of 3H or higher, more preferably 4H or higher. The aforementioned hardness is the hardness measured in accordance with JIS K5600-5-4 when a cured resin film with a film thickness of 2.5 μm is formed on a glass substrate. The following evaluation method may also be further used for the aforementioned hardness. (I) Preparation of cured resin film for evaluation The photosensitive resin composition is applied onto a glass substrate, and heated at 70°C for 3 minutes to volatilize the solvent, thereby forming a coated film. Next, the coated film is irradiated with light having a wavelength of 365 nm at an exposure dose of 200 mJ / cm 2 to be photocured. Then, the glass substrate having the photocured coated film is left to stand in a dryer at 85°C for 30 minutes to thermally cure the coated film, thereby obtaining a cured resin film with a film thickness of 2.5 μm. (II) Hardness measurement The hardness of the produced cured resin film is measured in accordance with JIS K5600-5-4 using a pencil hardness tester (for example, No.553-M, manufactured by Yasuda Seiki Seisakusho).

[0159] <Method for producing a photosensitive resin composition> A photosensitive resin composition according to one embodiment can be produced by mixing a copolymer (A), a reactive diluent (B), a photopolymerization initiator (C), a solvent (D), and a colorant (E) as needed, using a known mixing apparatus.

[0160] When manufacturing a photosensitive resin composition, the reaction solution used to manufacture the copolymer (A) can be used as a raw material. In this case, the solvent (D) contained in the reaction solution can be used as part or all of the solvent (D) contained in the photosensitive resin composition or the photosensitive colored composition.

[0161] The photosensitive resin composition contains a copolymer (A) that includes a structural unit (a) having a methoxycarbonyl group and a structural unit (b) having a hydroxyl group, and therefore has good low-temperature curability.

[0162] Therefore, when forming a cured product using a photosensitive resin composition, curing can be performed at a lower temperature compared to when using conventional resin compositions. Consequently, when a coating film formed on a substrate is exposed to light and then subjected to a baking treatment, the crosslinking reaction proceeds sufficiently even at a lower baking temperature, resulting in the formation of a cured product with excellent solvent resistance and hardness.

[0163] Therefore, when forming a cured product using a photosensitive resin composition, less energy is required for heating to cure it. In addition, by using a photosensitive resin composition, a cured product can be formed on a substrate with low heat resistance, such as a resin substrate, without damaging the substrate. Furthermore, even when a colorant (E) with low heat resistance is used, a cured product can be formed that exhibits the original properties of the colorant (E).

[0164] The photosensitive resin composition yields a cured product with excellent solvent resistance and hardness even at low baking temperatures, so the colorant (E) is less likely to leach out of the cured product. Therefore, it is possible to increase the colorant (E) content in the photosensitive resin composition. A photosensitive resin composition with a high colorant (E) content can be used, for example, as a material for the coloring pattern of a color filter to form a color filter with excellent color reproduction.

[0165] The copolymer (A) contained in the photosensitive resin composition has a structural unit (c) having an acid group, and therefore the photosensitive resin composition has good alkali developability. Because such a photosensitive resin composition has excellent alkali developability, for example, 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 areas with an alkaline aqueous solution, and then baking it at a sufficiently low temperature, a cured product with a predetermined pattern shape and excellent solvent resistance can be formed.

[0166] The photosensitive resin composition can be suitably used as a material for color filters.

[0167] Based on these findings, photosensitive resin compositions are extremely useful as materials for forming components of image display elements, such as pixels in color filters, black matrices, color filter protective films, photospacers, liquid crystal alignment protrusions, microlenses, and insulating films for touch panels.

[0168] <Cured resin film> The resin cured film of one embodiment of the present invention (sometimes referred to as "the resin cured film of this embodiment") consists of a cured product of a photosensitive resin composition.

[0169] A cured resin film can be manufactured, for example, by applying a photosensitive resin composition to a substrate, volatilizing and removing the solvent (D) to form a coating film, exposing the coating film to light-curing, and then performing a baking treatment.

[0170] When forming a resin-cured film having a predetermined pattern shape, for example, the following method can be used. That is, a photosensitive resin composition is applied to a substrate, and the solvent (D) is evaporated and removed to form a coating film. Next, the coating film is exposed to light through a photomask having a predetermined pattern shape to photocur the exposed portion. Then, the unexposed portion of the coating film is developed with an alkaline aqueous solution. After that, the developed coating film is subjected to a baking treatment to form a resin-cured film having a predetermined pattern shape.

[0171] When manufacturing a cured resin film, known methods can be used for the method of applying the photosensitive resin composition, the method of exposing the applied film to light, and the method of developing the film.

[0172] The baking conditions performed when manufacturing a cured resin film can be appropriately determined according to the composition of the photosensitive resin composition, the film thickness of the coating, the material of the substrate, etc. The baking treatment can be performed at a temperature of, for example, 70°C to 250°C. When the baking temperature is 70°C or higher, cross-linking occurs through transesterification between the methoxycarbonyl group of structural unit (a) and the hydroxyl group of structural unit (b) contained in copolymer (A) in the photosensitive resin composition. As a result, a good degree of curing is obtained, and a cured product with excellent solvent resistance and hardness is obtained. Structural unit (a) can undergo both a deblocking reaction to dissociate and produce an isocyanate group, and a transesterification reaction, but by adjusting the baking temperature, one of the reactions can be preferentially promoted. The baking temperature is preferably 75°C or higher, and more preferably 80°C or higher. A baking temperature of 250°C or lower is preferable because it is a condition that materials with low heat resistance can withstand, and discoloration of the photosensitive resin composition can be suppressed. The photosensitive resin composition has good low-temperature curing properties. Therefore, 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 base material, the temperature may be 150°C or lower, 120°C or lower, or 100°C or lower.

[0173] The baking process performed when manufacturing the resin-cured film can be carried out for, for example, 10 minutes to 4 hours, preferably 20 minutes to 2 hours, and can be appropriately determined depending on the composition of the photosensitive resin composition, the temperature of the baking process, the thickness of the coated film, etc.

[0174] The resin-cured film consists of a cured product of a photosensitive resin composition. Therefore, the resin-cured film can be manufactured using a baking method at a low temperature and has excellent solvent resistance.

[0175] <Color Filter> A color filter according to one embodiment of the present invention (sometimes referred to as "the color filter of this embodiment") comprises a colored pattern made of a cured product of a photosensitive resin composition. Preferably, the color filter has a colored pattern made of a cured product of a photosensitive resin composition containing 10 to 100% by mass of copolymer (A), more than 0% to 90% by mass of reactive diluent (B) based on a total of 100% by mass of copolymer (A) and reactive diluent (B), 0.1 to 30 parts by mass of photopolymerization initiator (C), 3 to 80 parts by mass of colorant (E), and 30 to 1,000 parts by mass of solvent (D) based on a total of 100 parts by mass of components excluding solvent (D).

[0176] A color filter may include, for example, a substrate, RGB pixels formed thereon, a black matrix formed at the boundary of each pixel, and a protective film formed on the pixels and the black matrix.

[0177] In a color filter, the pixels and black matrix are colored patterns made from cured products of the above-mentioned photosensitive resin composition. Other components of the color filter, besides the materials of the pixels and black matrix, can be those of known origin.

[0178] The substrate used for the color filter is not particularly limited, and a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyamide-imide substrate, a polyimide substrate, an aluminum substrate, a printed wiring board, an array substrate and the like can be appropriately used according to the application.

[0179] <Method for producing color filter> Next, an exemplary method for producing a color filter will be described. First, a colored pattern is formed on a substrate. Specifically, a colored pattern to be a black matrix formed at the boundary of each pixel, and colored patterns to be respective RGB pixels are sequentially formed on the substrate by the method described below.

[0180] The colored pattern can be formed by a photolithography method. Specifically, the photosensitive resin composition is applied onto a substrate to form a coating film. Thereafter, the coating film is exposed through a photomask having a predetermined pattern shape to photocure the exposed portion. Next, the unexposed portion of the coating film is developed with an alkaline aqueous solution. Thereafter, the developed coating film is subjected to a baking treatment, whereby a colored pattern having a predetermined pattern shape can be formed.

[0181] The method for applying the photosensitive resin composition is not particularly limited, and known methods such as a screen printing method, a roll coating method, a curtain coating method, a spray coating method, and a spin coating method can be used.

[0182] After applying the photosensitive resin composition onto the substrate, the solvent (D) contained in the coating film may be volatilized and removed by heating the substrate using a heating means such as a circulation oven, an infrared heater, or a hot plate as necessary. The conditions for heating the substrate to remove the solvent (D) are not particularly limited, and may be appropriately set according to the material of the substrate, the composition of the photosensitive resin composition, the film thickness of the coating film, and the like. The heating of the substrate can be performed, for example, at a temperature of 50°C to 120°C for 30 seconds to 30 minutes.

[0183] Next, the coated film formed in this manner is irradiated with an active energy ray, such as ultraviolet light or excimer laser light, through a negative-type photomask to partially expose it and photo-cure the exposed portion. The amount of active energy irradiated onto the coated film can be appropriately selected according to the composition of the photosensitive resin composition, for example, 30 to 2000 mJ / cm². 2 This can be done. The light source used for exposure is not particularly limited, but low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, xenon lamps, metal halide lamps, etc., can be used.

[0184] The alkaline aqueous solution used for developing the coating film is not particularly limited, but can be used: aqueous solutions of inorganic alkali compounds such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, and potassium hydroxide; aqueous solutions of amine compounds such as ethylamine, diethylamine, and dimethylethanolamine; aqueous solutions of quaternary ammonium salts such as tetramethylammonium sulfate, hydrochloride, or p-toluenesulfonate; aqueous solutions of aniline compounds and their salts such as 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamideethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and their sulfates, hydrochloride, or p-toluenesulfonate; and aqueous solutions of p-phenylenediamine compounds and their salts. Additives such as defoamers and surfactants may be added to the alkaline aqueous solution as needed.

[0185] After developing the coating film using the above-mentioned alkaline aqueous solution, it is preferable to wash the coating film with water and dry it.

[0186] The baking conditions performed when manufacturing color filters can be appropriately determined according to the composition of the photosensitive resin composition, the film thickness of the coating, the substrate material, 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 and hardness 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 it is possible to use materials with low heat resistance, such as substrates with low heat resistance, as the material for the color filter.

[0187] When forming a colored pattern on a color filter using a conventional photosensitive resin composition, the hardness of the colored pattern is insufficient if the baking temperature is 200°C or lower. In contrast, the photosensitive resin composition of one embodiment has good low-temperature curing properties, so the baking temperature can be lowered compared to when using a conventional photosensitive resin composition while ensuring the hardness of the colored pattern. Specifically, the baking temperature can be 160°C or lower, depending on the heat resistance of the substrate on which the resin cured film is formed. For example, when forming a colored pattern using a resin substrate, the temperature may be 150°C or lower, 120°C or lower, or 100°C or lower.

[0188] The baking process performed when manufacturing color filters 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, the baking temperature, the film thickness of the coating, etc.

[0189] The photosensitive resin composition has good photocurability and low-temperature curability. Therefore, when forming a colored pattern using the photosensitive resin composition of one embodiment, if the baking temperature is the same as when forming a colored pattern using a conventional photosensitive resin composition, the baking time can be shortened, and a color filter can be formed efficiently.

[0190] Using the coloring pattern manufacturing method described above, a coloring pattern is formed to represent each RGB pixel, and a coloring pattern is formed to represent the black matrix at the boundary of each pixel. After that, a protective film is formed on the coloring pattern (each RGB pixel and the black matrix).

[0191] 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 it may be formed using known materials and known methods.

[0192] A color filter can be obtained through the above process.

[0193] The color filter has a colored pattern made from a cured product of the photosensitive resin composition described above. Therefore, the colored pattern in the color filter can be formed by a baking process at a low temperature. Consequently, the energy required for the baking process can be reduced.

[0194] In addition, it is possible to use a colorant (E) with low heat resistance as the colorant (E) contained in the photosensitive resin composition used as a material for the color filter. This increases the number of usable colorants (E). Therefore, for example, it is possible to form a color filter that contains a colorant (E) with low heat resistance and has a coloring pattern that exhibits the inherent properties of the colorant (E) with low heat resistance.

[0195] Furthermore, the colored patterns in color filters can be formed on substrates with low heat resistance, such as resin substrates, without damaging the substrate itself. This increases the range of usable substrates. Specifically, for example, since color filters can be formed on substrates with low heat resistance, such as resin substrates, flexible displays become possible. In addition, the colored patterns in color filters have excellent solvent resistance and hardness, resulting in minimal color change.

[0196] Here, we have described an example in which a colored pattern is produced using a photosensitive resin composition containing a photopolymerization initiator (C) and a method of photocuring the photosensitive resin composition. However, for example, instead of the photopolymerization initiator (C) contained in the photosensitive resin composition, a photosensitive resin composition containing a curing accelerator and a known epoxy resin may be used, and a colored pattern consisting of a cured product of the photosensitive resin composition containing copolymer (A) may be formed by applying it to a substrate by an inkjet method and then heating it.

[0197] <Image display element> One embodiment of the image display element includes a color filter. Other components of the image display element can be those known to exist. Specific examples of image display elements include solid-state image sensors such as liquid crystal display elements, organic EL display elements, CCD elements, and CMOS elements.

[0198] The components of an image display element other than the color filter can be manufactured by known methods. For example, when manufacturing a liquid crystal display element as an 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 sequentially formed on the substrate having the color filter. Next, electrodes, etc., are formed on another substrate and bonded together with the substrate having the color filter, facing each other. Then, a predetermined amount of liquid crystal is injected between the opposing substrates and sealed.

[0199] The image display element is equipped with a color filter that has excellent solvent resistance and hardness, resulting in minimal color distortion. [Examples]

[0200] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In these examples, parts and percentages all refer to mass unless otherwise specified.

[0201] <Method for measuring weight-average molecular weight> The weight-average molecular weight described below refers to the weight-average molecular weight on a standard polystyrene basis, measured using gel permeation chromatography (GPC) under the following conditions. Column: SHODEX (registered trademark) LF-804 + LF-804 (manufactured by Resonac Co., Ltd.) Column temperature: 40℃ Sample: 0.2% by mass solution of copolymer (A) in tetrahydrofuran Developing solvent: tetrahydrofuran Detector: Differential refractometer (Showdex RI-71S) (manufactured by Showa Denko Corporation) Flow rate: 1mL / min

[0202] <Method for measuring acid value> In accordance with JIS K6901 5.3.2, the amount of potassium hydroxide required to neutralize the acidic component contained in 1 g of the solid content of copolymer (A) was measured. Measuring instrument: 776 Dosimat (Metrohm Corporation) Mixed indicator: A mixed indicator of bromothymol blue and phenol red.

[0203] <Method for measuring glass transition temperature (Tg)> Copolymer (A) obtained in synthesis examples A1-A13 and copolymer (A') obtained in comparative synthesis examples A1-A6 were coated onto a glass substrate, dried under reduced pressure at 50°C for 24 hours, then redissolved in acetone and dried again under reduced pressure at 50°C for 24 hours to remove volatile components. Copolymer (A) or copolymer (A') was measured using DSC (differential scanning calorimeter, measuring instrument: Seiko DSC6200) under a nitrogen gas stream at a heating rate of 10°C / min in accordance with JIS-K7121 (intermediate glass transition temperature: Tgm). The obtained results were defined as the glass transition temperature (Tg) of copolymer (A) or copolymer (A').

[0204] <Method for measuring the exothermic peak temperature of copolymer (A)> Copolymer (A) obtained in synthesis examples A1-A13 and copolymer (A') obtained in comparative synthesis examples A1-A6 were mixed as solid content in 75 parts by mass with dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.). A few drops of this solution were added to an aluminum cup, and then dried under reduced pressure at 40°C for 30 minutes to remove volatile components such as the polymerization reaction solvent. This sample was measured using a DSC (differential scanning calorimetry, measuring instrument: TA Instruments DSC250) under a nitrogen stream at a heating rate of 2°C / min in the range of 50-120°C. The measurement results were plotted with temperature on the x-axis and heat flow on the y-axis. The maximum value of the heat flow was considered as the exothermic peak originating from the reaction between copolymer (A) or copolymer (A') and dipentaerythritol hexaacrylate, and the temperature of that peak was read.

[0205] <Alkoxycarbonyl group equivalent> The theoretical values ​​calculated from the monomers (ma) to (me) and polymerization initiator used in the production of the copolymer are used.

[0206] <Hydroxygen equivalent> Theoretical values ​​calculated from the monomers (ma) to (me) and polymerization initiator used in the production of the copolymer are used.

[0207] Examples of the synthesis of copolymer (A) or copolymer (A') for the photosensitive resin composition of the second embodiment are shown below.

[0208] [Synthesis Example A1] In a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, 278.4 g of propylene glycol monomethyl ether was added as solvent (D). The mixture was then stirred while purging with nitrogen gas and heated to 78°C. Next, 50.0 g (15 mol%) of the reaction product of 2-isocyanatoethyl acrylate and diethyl malonate (malonate-2-[[[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester) (ma), 21.6 g (15 mol%) of 2-hydroxyethyl methacrylate (mb), 21.5 g (27 mol%) of acrylic acid (mc), and 31.5 g (20 mol%) of glycidyl methacrylate (md) were added. A monomer mixture consisting of 36.5 g (15 mol%) dicyclopentanyl methacrylate (me) and 8.9 g (8 mol%) methyl methacrylate (mf) was mixed with 28.9 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.: V-65B) (17.0 parts by mass per 100 parts by mass of the total monomer mixture) as a polymerization initiator, and this mixture was added dropwise from a dropping funnel to the flask over 1 hour. After the addition was complete, the mixture was stirred at 78°C for 3 hours to carry out the copolymerization reaction. Finally, propylene glycol monomethyl ether acetate was added as solvent (D) so that the non-solvent components accounted for 35% by mass, obtaining a mixture containing copolymer (A) (sample number P1) and solvent (D). The composition of solvent (D) was such that propylene glycol monomethyl ether accounted for 49% by mass of the 65% by mass of solvent components, and propylene glycol monomethyl ether acetate accounted for 16% by mass of the 65% by mass of solvent components. Table 1 shows the proportion of each monomer when the total monomer mixture is calculated as 100 mol%, along with the glass transition temperature (Tg), acid value, weight-average molecular weight, and exothermic peak temperature (°C) of copolymer (A).

[0209] <Synthesis examples A2~A6, A9~A11, comparative synthesis examples A1~A5> A mixture containing each copolymer (A) of the Example (sample numbers P1-P6 and P9-P11 respectively) and the copolymer (A') of the Comparative Example (sample numbers cP1-cP5 respectively) and solvent (D) was obtained in the same manner as in Synthesis Example 1, except that the monomer blending ratios were as shown in Table 1. The amount of polymerization initiator added was adjusted according to the desired weight-average molecular weight. The blending ratios of each monomer and the glass transition temperature (Tg), acid value, weight-average molecular weight, and exothermic peak temperature (°C) of each copolymer (A) or copolymer (A') are shown in Table 1.

[0210] <Synthesis examples A7~A8> A mixture containing each copolymer (A) (sample numbers P7-P8) and solvent (D) was obtained in the same manner as in Synthesis Example 1, except that the monomer blending ratios were as shown in Table 1 and propylene glycol monomethyl ether was replaced with 3-methoxy-1-butanol as solvent (D). The amount of polymerization initiator added was adjusted according to the desired weight-average molecular weight. The blending ratios of each monomer and the glass transition temperature (Tg), acid value, weight-average molecular weight, and exothermic peak temperature (°C) of each copolymer (A) are shown in Table 1.

[0211] <Synthesis Examples A12~A13> A mixture containing copolymer (A) (sample numbers P12, P13) and solvent (D) was obtained in the same manner as in Synthesis Example 1, except that the monomer blending ratios were as shown in Table 1, and the amount of polymerization initiator added was 25.0 parts by mass in Synthesis Example 12 and 5.0 parts by mass in Synthesis Example 13, per 100 parts by mass of the total monomer mixture. The blending ratios of each monomer, as well as the glass transition temperature (Tg), acid value, weight-average molecular weight, and exothermic peak temperature (°C) of copolymer (A) are shown in Table 1.

[0212] [Table 1] The compounds used in Table 1 were as follows: AOI-DEM: Karenz (trademark) AOI-DEM, reaction product of 2-isocyanatoethyl acrylate and diethyl malonate (malonate-2-[[[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester, manufactured by Resonaq Corporation) 2HEMA:2-Hydroxyethyl methacrylate (manufactured by Nippon Shokubai Co., Ltd.) 2HEA:2-Hydroxyethyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd.) 4HBA: 4-Hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) PE-200: Polyethylene glycol monomethacrylate (manufactured by NOF Corporation) GLM: Glycerin monomethacrylate (manufactured by NOF Corporation) 2HPA:2-Hydroxypropyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.) AA: Methacrylic acid (manufactured by Nippon Shokubai Co., Ltd.) MAA: Methacrylic acid (manufactured by Kuraray Co., Ltd.) GMA: Glycidyl methacrylate (manufactured by NOF Corporation) TCDMA: Tricyclodecanyl methacrylate (manufactured by Resonaq Corporation) MMA: Methyl methacrylate (manufactured by Mitsubishi Chemical Corporation) 2EHA: 2-Ethylhexyl acrylate (manufactured by Toagosei Co., Ltd.)

[0213] An example of the production of the photosensitive resin composition of the second embodiment is shown below.

[0214] <Examples A1-A13, Comparative Examples A1-A5> A mixture containing 60 parts by mass of the copolymer (A) obtained in synthesis examples A1 to A13, copolymer (A') obtained in comparative synthesis examples A1 to A5 (sample numbers: P1 to P13, cP1 to cP5 respectively) and a solvent (D), a reactive diluent (B) consisting of 20 parts by mass of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.: KAYARAD DPHA), a photopolymerization initiator (C) consisting of 2 parts by mass of 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl-]-,-1-(O-acetyloxime) (manufactured by BASF: Irgacure OXE02), and a colorant (E) consisting of a blue dye (manufactured by Orient Chemical Industries, Ltd.: VALIFAST BLUE) 20 parts by mass of 2620 were mixed, and propylene glycol monomethyl ether was added as solvent (D) to bring the total solid content to 30%. The mixture was then filtered through a 1 μm mesh membrane filter to prepare photosensitive colored compositions No. 1 to 19. However, photosensitive colored composition No. 19 could not be filtered through the filter and was prepared without filtration. The amounts of each component relative to 100% by mass of the total solid content of copolymer (A) or copolymer (A') and reactive diluent (B) were 75% by mass of the solid content of copolymer (A) or copolymer (A'), 25% by mass of the reactive diluent (B), 2.5% by mass of the photopolymerization initiator (C), and 25% by mass of the colorant (E). The mixing ratios are shown in Table 2. The obtained photosensitive resin compositions (each sample number: R1 to R13, cR1 to 5) are shown in Table 3.

[0215] [Table 2]

[0216] <Preparation of color resist 1> The aforementioned photosensitive colored compositions (sample numbers: R1-R13, cR1-5) were spin-coated onto a 5cm square glass substrate (alkali-free glass substrate) so that the average thickness after the development process described later was 2.2 μm. The appearance of the glass substrate after spin-coating was observed visually and by touch, and the quality of the appearance was evaluated on a four-point scale (○, ×), with ○ being considered a pass. The evaluation results are shown in Table 3.

[0217] A: Good exterior condition B: Cosmetic defects (surface roughness, haze, and tack are observed)

[0218] <Preparation of color resist 2> After the spin coating process, substrates with good appearance were selected and heated at 70°C for 1 minute to evaporate the solvent and form a coated film (pre-baking process). Next, a photomask (having a line and space pattern with a width of 30 μm) was placed on the coated film at a distance of 100 μm from the film, and a high-pressure mercury lamp was used to apply pressure of 200 mJ / cm² from above. 2 The surface was irradiated with light. Next, a 100-fold diluted semi-clean DL-A10 developer (manufactured by Yokohama Oil & Fat Industry Co., Ltd.) (0.05% KOH aqueous solution) was sprayed onto the surface of the coating film for 60 seconds at a temperature of 23°C and a discharge pressure of 0.1 MPa to remove the unexposed areas (development process). Finally, the glass substrate with the coating film after the development process was left to stand in a dryer at 85°C or 95°C for 30 minutes to heat-cur the coating film (post-bake process) and a color resist with a colored pattern was obtained.

[0219] <Measurement of residual film percentage of coated film> The aforementioned color resist was immersed in propylene glycol monomethyl ether at 23°C for 5 minutes. The coated film was then removed and dried in air at room temperature, and the film thickness after drying was measured. The residual film percentage was calculated as the relative value when the film thickness after the development process was set to 100%. Table 3 shows the calculated residual film percentages when the post-bake process was performed under 85°C and 95°C conditions.

[0220] <Evaluation of dye elution from coating films> The aforementioned color resists were left to stand in propylene glycol monomethyl ether at 23°C for 5 minutes. The degree of disintegration of the colored pattern upon immersion was visually observed, and the dye elution from the colored pattern was evaluated as follows. The evaluation was based on four levels: ◎○△×, with ◎ and ○ being considered passing grades. The evaluation results are shown in Table 3. A: The pattern remains clear and doesn't fade. B: The pattern fades but remains without disappearing. C: Part of the pattern disappears. D: The entire pattern disappears.

[0221] [Table 3]

[0222] (Consideration) Copolymers (A) obtained in synthesis examples A1 to A13 and the copolymer obtained in comparative synthesis example A2 were detected at lower exothermic peak temperatures relative to 100°C, while copolymers (A') obtained in comparative synthesis examples A1 and A3 to A5 all showed high exothermic peak temperatures of 100°C or higher. Compared with comparative synthesis examples A1, A3, and A4, it was suggested that introducing structural unit (c) derived from acrylic acid provides flexibility that allows the crosslinking reaction of the copolymer to occur satisfactorily at low temperatures, even if the glass transition temperature is 20°C or higher. Furthermore, compared with comparative synthesis example A5, it was suggested that introducing structural unit (b) represented by -CH2-OH, i.e., a primary hydroxyl group, results in a cured product that, unlike secondary or tertiary hydroxyl groups, is highly reactive in crosslinking and exhibits satisfactory curability and solvent resistance at low temperatures.

[0223] This phenomenon also proved to affect the performance of films coated with the photosensitive coloring composition. Comparing the residual film ratio and dye elution from the coated film, the resists of Examples A1 to A13, using copolymer (A) obtained in Synthesis Examples A1 to A13, exhibited a higher residual film ratio and higher dye elution resistance compared to the resists of Comparative Examples A3 to A5, using copolymer (A') obtained in Comparative Synthesis Examples A3 to A5. In both cases, the crosslinking reaction of the copolymers occurred satisfactorily under conditions of 85°C and 95°C, imparting sufficient curability to the photosensitive coloring composition. Furthermore, the dye was robustly encapsulated within this cured photosensitive coloring composition, making it less susceptible to erosion by organic solvents from the outside. In addition, the inclusion of structural units (e) having crosslinked cyclic hydrocarbon groups with 10 to 20 carbon atoms was suggested to create an appropriate space for encapsulating the dye, further improving dye elution resistance. On the other hand, comparative synthesis examples A1 and A2 used copolymer (A') with a low glass transition temperature of 20°C or less, resulting in extremely soft films coated with the photosensitive coloring composition, leading to surface roughness, haze, and tack. Furthermore, the occurrence of tack posed a risk of contaminating evaluation equipment such as tactile meters used to measure film thickness, preventing the process from proceeding to the color resist fabrication stage. This revealed significant industrial constraints on actual production lines.

[0224] The following are examples of the synthesis of copolymer (A) or copolymer (A') for the photosensitive resin composition of the third embodiment.

[0225] [Synthesis Example B1] (Synthesis of copolymer (A)) In a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, 243.0 g of propylene glycol monomethyl ether as solvent (D) was added, and the mixture was stirred while purging with nitrogen, and the temperature was raised to 65°C.

[0226] Next, a raw material monomer solution was prepared by mixing 88.5 g (18 mol%) of AOI-DMM as monomer (ma), 32.8 g (14 mol%) of 2-hydroxyethyl methacrylate as monomer (mb), 17.0 g (11 mol%) of methacrylic acid as monomer (mc), 155.7 g (47 mol%) of 2-ethylhexyl acrylate and 18.0 g (10 mol%) of methyl methacrylate as monomers (me), 38.1 g of perkmyl ND (polymerization initiator) as a polymerization initiator (12.2 parts by mass per 100 parts by mass of the total monomer components), and 140.4 g of propylene glycol monomethyl ether acetate and 118.5 g of propylene glycol monomethyl ether as solvents (D).

[0227] The entire amount of the prepared raw material monomer solution was added dropwise over 1 hour using a dropping funnel to solvent (D) in a flask under atmospheric pressure and nitrogen gas atmosphere. After the addition was complete, the solution in the flask was stirred and polymerized at 65°C for 2 hours to obtain a liquid containing copolymer (A) and solvent (D). To the reaction solution containing copolymer (A) and solvent (D) obtained in this way, propylene glycol monomethyl ether acetate was added as solvent (D) so that the non-solvent components accounted for 35% by mass, to obtain a liquid (resin composition) containing copolymer (A) of synthesis example B1.

[0228] [Synthesis examples B2 to B13] A mixture containing each copolymer (A) (sample numbers P1 to P13, respectively) and solvent (D) was obtained in the same manner as in Synthesis Example B1, except that the monomer blending ratios were as shown in Table 4. The amount of polymerization initiator added was adjusted according to the desired weight-average molecular weight. In addition, a chain transfer agent was added to Synthesis Example B4, and a reducing agent was added to Synthesis Examples B12 and B13, in the amounts shown in Table 4 (parts by mass per 100 parts by mass of the total monomer components), along with the polymerization initiator. The blending ratios of each monomer and the weight-average molecular weight, number-average molecular weight, molecular weight distribution, acid value, alkoxycarbonyl group equivalent, and hydroxyl group equivalent of each copolymer (A) are shown in Table 4.

[0229] [Comparative Synthesis Example B1] In a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, 237.6 g of propylene glycol monomethyl ether was added as solvent (D), and the mixture was stirred while purging with nitrogen, and the temperature was raised to 78°C.

[0230] Next, a raw material monomer solution was prepared by mixing 90.6 g (18 mol%) of AOI-DEM as monomer (m-a'), 30.4 g (14 mol%) of 2-hydroxyethyl methacrylate as monomer (mb), 15.8 g (11 mol%) of methacrylic acid as monomer (mc), 175.4 g (57 mol%) of 2-ethylhexyl acrylate as monomer (me), 37.8 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) as a polymerization initiator (12.1 parts by mass per 100 parts by mass of the total monomer components), and 143.6 g of propylene glycol monomethyl ether acetate and 112.4 g of propylene glycol monomethyl ether as solvent (D).

[0231] The entire amount of the prepared raw material monomer solution was added dropwise over 1 hour using a dropping funnel to solvent (D) in a flask under atmospheric pressure and nitrogen gas atmosphere. After the addition was complete, the solution in the flask was stirred and polymerized at 78°C for 3 hours to obtain a liquid containing copolymer (A) and solvent (D). To the reaction solution containing copolymer (A) and solvent (D) obtained in this way, propylene glycol monomethyl ether acetate was added as solvent (D) so that the non-solvent components accounted for 35% by mass, to obtain a liquid (resin composition) containing copolymer (A) of comparative synthesis example B1.

[0232] [Comparative synthesis example B2] Copolymer cP2 of Comparative Synthesis Example B2 was obtained in the same manner as Comparative Synthesis Example B1, except that the raw materials listed in Table 5 were used in the proportions listed in Table 5. This is shown in Table 5.

[0233] [Comparative synthesis example B3] In a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, 242.9 g of propylene glycol monomethyl ether was added as solvent (D), and the mixture was stirred while purging with nitrogen, and the temperature was raised to 78°C.

[0234] Next, a raw material monomer solution was prepared by mixing 88.5 g (18 mol%) of AOI-DMM as monomer (ma), 32.8 g (14 mol%) of 2-hydroxyethyl methacrylate as monomer (mb), 17.1 g (11 mol%) of methacrylic acid as monomer (mc), 155.8 g (47 mol%) of 2-ethylhexyl acrylate as monomer (me), 37.8 g of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) as a polymerization initiator (12.1 parts by mass per 100 parts by mass of the total monomer components), and 140.5 g of propylene glycol monomethyl ether acetate and 118.6 g of propylene glycol monomethyl ether as solvents (D).

[0235] The entire volume of the prepared raw material monomer solution was added dropwise over 1 hour using a dropping funnel to solvent (D) in a flask under atmospheric pressure and nitrogen gas atmosphere, and gelation occurred.

[0236] For the copolymers cP1 to cP3 of comparative synthesis examples B1 to B3 obtained in this manner, the weight-average molecular weight (Mw), number-average molecular weight (Mn), molecular weight distribution (Mw / Mn), acid value, methoxycarbonyl group equivalent, and hydroxyl group equivalent were determined, respectively. The results are shown in Table 5.

[0237] [Table 4]

[0238] [Table 5]

[0239] The compounds used in Tables 4 and 5 were as follows: AOI-DMM: Karenz (trademark) AOI-DMM, reaction product of isocyanatoethyl acrylate and dimethyl malonate, (2-[[[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-dimethyl malonate, manufactured by Resonaq Corporation) MOI-DMM: Karenz (trademark) MOI-DMM, reaction product of isocyanatoethyl methacrylate and dimethyl malonate, (2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-dimethyl malonate, manufactured by Resonaq Corporation) AOI-DEM: Karenz (trademark) AOI-DEM, reaction product of isocyanatoethyl acrylate and diethyl malonate (malonate-2-[[[1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester, manufactured by Resonaq Corporation) 2-Hydroxyethyl methacrylate: Manufactured by Tokyo Chemical Industry Co., Ltd. 4-Hydroxybutyl acrylate: Manufactured by Tokyo Chemical Industry Co., Ltd. Methacrylic acid: Manufactured by Tokyo Chemical Industry Co., Ltd. Acrylic acid: Manufactured by Tokyo Chemical Industry Co., Ltd. 2-Ethylhexyl acrylate: Manufactured by Tokyo Chemical Industry Co., Ltd. Methyl methacrylate: Manufactured by Tokyo Chemical Industry Co., Ltd. Dicyclopentanyl methacrylate: Manufactured by Tokyo Chemical Industry Co., Ltd. Propylene glycol monomethyl ether acetate: Manufactured by Tokyo Chemical Industry Co., Ltd. Propylene glycol monomethyl ether: Manufactured by Tokyo Chemical Industry Co., Ltd. 3-Methoxy-1-butanol: Manufactured by Tokyo Chemical Industry Co., Ltd. Thioglycolic acid: Manufactured by Tokyo Chemical Industry Co., Ltd. Cobalt octylate: Manufactured by Nippon Chemical Industrial Co., Ltd. Accelerator A: 1,1-[(4-methylphenyl)imino]bis(2-propanol) (manufactured by Wako Pure Chemical Industries, Ltd.) Perkmill ND: Cumil peroxyneodecanoate (manufactured by NOF Corporation) V65: 2,2'-Azobis(2,4-dimethylvaleronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0240] Examples of the photosensitive resin composition of the third embodiment are shown below. <Preparation of photosensitive colored composition> [Examples B1-B13, Comparative Examples B1-B2] As copolymer (A), copolymers P1-P13 and cP1-cP2 from Examples B1-B13 and Comparative Examples B1-B2 were mixed with components (B), (C), and (E) shown in Table 6 in the proportions shown in Table 6 to prepare photosensitive colored compositions R1-R13 and cR1-cR2 from Examples B1-B13 and Comparative Examples B1-B2, respectively.

[0241] Note that the amount of copolymer (A) in the resin composition in Table 6 does not include the polymerization solvent used to synthesize copolymer (A). Also, the amount of solvent (D) in Table 6 is the total amount of the polymerization solvent used to synthesize copolymer (A) in the photosensitive colored resin composition and the solvent added in addition when preparing the photosensitive colored resin composition.

[0242] [Table 6]

[0243] <Evaluation of photosensitive colored compositions> The photosensitive colored compositions R1-R13 and cR1-cR2 of Examples B1-B13 and Comparative Examples B1-B2 were evaluated by the following method.

[0244] (1) Developability Photosensitive colored compositions R1-R13 and cR1-cR2, prepared in Examples B1-B13 and Comparative Examples B1-B2, were applied to 5cm square glass substrates (alkali-free glass substrates) by spin coating to a thickness of 2.5 μm after exposure (coating step). The glass substrates coated with the photosensitive colored compositions were heated at 70°C for 3 minutes to evaporate the solvent and dry the coated film (pre-bake step).

[0245] Next, using an ultra-high pressure mercury lamp, 200 mJ / cm² was measured. 2Light was shone onto the surface of the dried coating film via a photomask (exposure step). The exposure step was performed with the photomask positioned 100 μm away from the coating film. The photomask used had a line and space pattern with a width of 3 to 100 μm. Next, semi-clean DL-A10 developer (manufactured by Yokohama Oil & Fat Industry Co., Ltd.) (5-fold dilution) was sprayed onto the surface of the coating film for 60 seconds at a temperature of 23°C and a pressure of 0.1 MPa to remove the unexposed areas (development step). The glass substrate with the developed coating film was left to stand in an 85°C dryer for 30 minutes to heat-cur the coating film (post-bake step) and obtain a colored pattern.

[0246] The resulting colored patterns were observed using a Hitachi High-Technologies Corporation S-3400 electron microscope, and the minimum line width (minimum development dimension) that could be developed and the presence or absence of residue in unexposed areas between developed patterns were evaluated. The presence or absence of residue was evaluated according to the following criteria. The results are shown in Table 7 or Table 8. "Evaluation Criteria for Residues" ○: No residue in the unexposed areas between developed patterns. ×: Residue present in unexposed areas between developed patterns.

[0247] (2) Pencil hardness The photosensitive colored compositions R1-R13 and cR1-cR2 prepared in Examples B1-B13 and Comparative Examples B1-B2 were applied to a 5cm x 5cm square glass substrate (alkali-free glass substrate) by spin coating, and the solvent was evaporated by heating at 70°C for 3 minutes to form a coated film. Next, the coated film was exposed to light with a wavelength of 365nm at an exposure dose of 200mJ / cm². 2 The coating was photocured by irradiation. Next, the glass substrate having the photocured coating film was left to stand in an 85°C dryer for 30 minutes to heat-cur the coating film (post-bake step), obtaining a resin-cured film with a thickness of 2.5 μm.

[0248] The pencil hardness of the resin-cured films prepared in this manner was measured using a pencil hardness tester (No. 553-M, manufactured by Yasuda Seiki Seisakusho) in accordance with JIS K5600-5-4 and evaluated according to the following criteria. The results are shown in Table 7 or Table 8. "Evaluation Criteria for Pencil Hardness" ○:Pencil hardness 3H or higher ×: Pencil hardness less than 3H

[0249] (4) Overall Judgment The cured resin films made from the cured products of the photosensitive colored compositions R1-R13 and cR1-cR2 prepared in Examples B1-13 and Comparative Examples B1-2 were evaluated according to the following criteria. The results are shown in Table 7 or Table 8.

[0250] "Evaluation Criteria" ○: All of the following conditions must be met. (1) Minimum development size is 15 μm or less, and there is no residue in the unexposed areas between the developed patterns. (2) The pencil hardness of the resin-cured film is 3H or higher. ×: Does not meet one or more of the above ○ criteria.

[0251] [Table 7]

[0252] [Table 8]

[0253] (Consideration) As shown in Table 7, the resin-cured films formed by photocuring coating films using the photosensitive coloring compositions R1 to R13 of Examples B1 to B13, followed by thermocuring at a low temperature of 85°C, had a pencil hardness of 3H or higher, indicating excellent hardness. Furthermore, the above-mentioned resin-cured films received a "○" rating for solvent resistance, confirming their excellent solvent resistance.

[0254] In contrast, as shown in Table 8, the photosensitive coloring compositions cR1 to cR2 of comparative examples B1 to 2 had insufficient pencil hardness or solvent resistance.

[0255] More specifically, the copolymers cP1-cP2 of comparative synthesis examples B1-B2, contained in the photosensitive colored compositions cR1-cR2 of comparative examples B1-B2, undergo transesterification with hydroxyl groups to produce ethanol. However, the reaction proceeds slowly at a curing temperature of 85°C. As a result, the hardness and solvent resistance were inferior. [Industrial applicability]

[0256] According to one embodiment of the present invention, a photosensitive resin composition and a photosensitive coloring composition are provided that can form a resin cured film having excellent low-temperature curability and sufficient hardness and solvent resistance. Furthermore, a resin cured film having sufficient hardness and solvent resistance, made from a cured product of the photosensitive resin composition of the present invention, is provided, and an image display element comprising the same is also provided. The photosensitive resin composition can preferably be used as a resist for transparent films, protective films, insulating films, overcoats, photospacers, black matrices, black column spacers, and color filters.

[0257] According to other embodiments of the present invention, a photosensitive resin composition is provided that yields a resin-cured film having excellent solvent resistance and hardness, and exhibits good developability. Furthermore, a resin-cured film with excellent solvent resistance and an image display element comprising the same are provided. The photosensitive resin composition can preferably be used as a resist for transparent films, protective films, insulating films, overcoats, photospacers, black matrices, black column spacers, and color filters.

Claims

1. Copolymer (A), Reactive diluent (B), Photopolymerization initiator (C), Solvent (D), A photosensitive resin composition containing, The copolymer (A) contains structural unit (a), structural unit (b), and structural unit (c), The structural unit (a) has one or more selected from an active methylene group to which a methoxycarbonyl group is attached, and an active methine group to which a methoxycarbonyl group is attached. The aforementioned structural unit (b) has a hydroxyl group, A photosensitive resin composition in which the structural unit (c) has an acid group.

2. The photosensitive resin composition according to claim 1, wherein the structural unit (a) is a structural unit having one or more selected from the group consisting of a group represented by the following formula (i-1) and a group represented by the following formula (ii-1). 【Chemistry 1】 (In equation (i-1), n1 and n2 each independently represent integers between 0 and 2. * represents a connected part.) 【Chemistry 2】 (In equation (ii-1), n3 and n4 each independently represent integers between 0 and 2. * represents a concatenation.)

3. The photosensitive resin composition according to claim 1 or 2, wherein the copolymer (A) further contains structural units (e) derived from (meth)acrylate having a linear or branched alkyl group having 1 to 20 carbon atoms.

4. The photosensitive resin composition according to claim 1 or 2, wherein the copolymer (A) further contains structural units (f) derived from (meth)acrylate having a crosslinked cyclic hydrocarbon group having 10 to 20 carbon atoms.

5. The photosensitive resin composition according to claim 1 or 2, wherein the structural unit (a) of the copolymer (A) is a structural unit derived from a compound having one or more selected from an active methylene group to which a methoxycarbonyl group is attached and an active methine group to which a methoxycarbonyl group is attached, and an acryloyloxy group.

6. The structural unit (b) of the copolymer (A) is -(CH ２ ) ｎ Structural units having a group represented by -OH (where n is an integer from 2 to 6) and -(O-C ｘ H ２ｘ ) ｍ The photosensitive resin composition according to claim 1 or 2, which is at least one selected from the group consisting of structural units having a group represented by -OH (where x is an integer from 2 to 4 and m is an integer from 2 to 6).

7. The photosensitive resin composition according to claim 1 or 2, wherein the acid value of the copolymer (A) is 10 to 250 KOH mg / g.

8. The photosensitive resin composition according to claim 1 or 2, wherein the weight-average molecular weight Mw of the copolymer (A) is 3,000 to 50,000.

9. The photosensitive resin composition according to claim 1 or 2, wherein the reactive diluent (B) is a compound having a plurality of ethylenically unsaturated groups.

10. When the total structural units of the copolymer (A) are set to 100 mol%, The above structural unit (a) contains 1 to 40 mol%, The above structural unit (b) contains 1 to 40 mol%, The photosensitive resin composition according to claim 1 or 2, comprising 1 to 40 mol% of the structural unit (c).

11. The photosensitive resin composition according to claim 1 or 2, wherein the solvent (D) is a glycol ether having a hydroxyl group.

12. With respect to 100% by mass of the total of the copolymer (A) and the reactive diluent (B), The copolymer (A) is 10% by mass or more and less than 100% by mass, The reactive diluent (B) is greater than 0% by mass and less than or equal to 90% by mass. With respect to a total of 100 parts by mass of the copolymer (A) and the reactive diluent (B), The photopolymerization initiator (C) is 0.1 to 30 parts by mass, Amount to 100 parts by mass of the total components excluding the solvent (D): The photosensitive resin composition according to claim 1 or 2, wherein the solvent (D) is 30 to 1,000 parts by mass.

13. The photosensitive resin composition according to claim 1 or 2, further comprising a coloring agent (E).

14. The photosensitive resin composition according to claim 13, wherein the coloring agent (E) comprises a pigment.

15. The hardness of the cured resin film of the aforementioned photosensitive resin composition is 3H or higher. The photosensitive resin composition according to claim 13, wherein the hardness is the hardness measured according to JIS K5600-5-4 when a resin cured film with a thickness of 2.5 μm is formed on a glass substrate.

16. A resin-cured film comprising a cured product of the photosensitive resin composition described in claim 13.

17. A color filter having a colored pattern made of a cured product of the photosensitive resin composition described in claim 13.

18. An image display element comprising the color filter described in claim 17.

Images