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

Abstract

The invention provides a photosensitive resin composition and a photosensitive coloring composition, which have excellent developability and good low-temperature curability and can form a resin cured film with sufficient hardness and solvent resistance. The photosensitive resin composition includes a resin (A), a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D). The resin (A) is an addition reaction product of a (meth) acrylic resin (a-0) containing a hydroxyl group, a compound (a-4) containing an isocyanate group and an ethylenically unsaturated group, and a polybasic acid or an acid anhydride (a-5) thereof. (a-0) is a copolymer containing a structural unit derived from a (meth) acrylate (m-1) containing a hydroxyl group and a structural unit derived from a (meth) acrylate (m-2) having one or more groups selected from the group consisting of an active methylene group, an active methine group, an epoxy group, an oxetanyl group, a blocked isocyanate group, and a silyl group.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, a cured resin film and an image display element.

[0002] This application claims priority based on Japanese Patent Application No. 2022-118208 filed in Japan on July 25, 2022, the contents of which are incorporated herein by reference. Background Art

[0003] Conventionally, there are image display devices such as displays that include color filters. Color filters are generally formed by baking a resin composition at a temperature higher than 200° C. on a substrate to cure the resin composition.

[0004] In recent years, as displays have become more flexible and wearable, the substrate material of color filters has been replaced from glass to organic raw materials such as resin. In addition, in order to further realize high-brightness and high-contrast image display elements, the colorants used in color filters have been replaced from pigments to dyes and / or fluorescent compounds and quantum dots.

[0005] Conventionally, there is a resin composition used as a material for a color filter, for example, a resin composition described in Patent Document 1.

[0006] Patent document 1 discloses a colored photocurable resin composition comprising a photocurable compound (A), a binder resin (B), a photoinitiator (D) and a solvent (E), wherein the photocurable compound (A) is dipentaerythritol pentaacrylate containing a carboxyl group, and the binder resin (B) contains one or more of a tetrahydropyran structure or a tetrahydrofuran structure in the main chain structure.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Publication No. 2015-184675 Summary of the invention

[0010] Problems to be solved by the invention

[0011] Organic raw materials used as substrate materials have poor heat resistance compared to glass. In addition, dyes used as colorants for color filters have poor heat resistance compared to pigments. Therefore, in the resin composition used as a material for the color filter, it is desirable to lower the heating temperature for curing it. Specifically, depending on the heat resistance of the substrate material and the colorant material, it is sometimes required to set the heating temperature for curing the resin composition used as a material for the color filter to 80 to 150°C.

[0012] However, with conventional resin compositions, if the heating temperature for curing is lowered, a cured product having sufficient hardness and solvent resistance cannot be obtained.

[0013] The color filter composed of the solidified material with insufficient hardness is easily scratched. Therefore, in the image display element equipped with the color filter, there is a worry that the display is poor due to the damage of the color filter. In addition, in the color filter equipped with the image display element, in order to improve the color reproducibility, there is a tendency to increase the content of the colorant in the resin composition used as the material of the color filter. In addition, compared with the pigment, the solubility of the dye in the solvent is high. Therefore, if the solvent resistance of the color filter is insufficient, the dye contained in the color filter will be dissolved into the solvent, and there is a worry that the chromaticity of the color filter changes.

[0014] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a photosensitive resin composition and a photosensitive coloring composition which have excellent developability and good low-temperature curability and can form a resin cured film having sufficient hardness and solvent resistance.

[0015] In addition, the present invention aims to provide a resin cured film having sufficient hardness and solvent resistance, which is composed of a cured product of the photosensitive resin composition of the present invention. In addition, the present invention aims to provide a color filter having sufficient hardness and solvent resistance, which has a colored pattern composed of a cured product of the photosensitive coloring composition of the present invention. In addition, the present invention aims to provide an image display element comprising the color filter.

[0016] Means for solving problems

[0017] The present invention includes the following aspects.

[0018] [1] A photosensitive resin composition comprising at least a resin (A), a reactive diluent (B), a photopolymerization initiator (C) and a solvent (D),

[0019] The resin (A) is an ethylenically unsaturated group and a carboxyl group-modified (meth) acrylic resin,

[0020] The ethylenically unsaturated group and carboxyl modified (meth) acrylic resin is an addition reaction product of a hydroxyl-containing (meth) acrylic resin (a-0), a compound containing an isocyanate group and an ethylenically unsaturated group (a-4), and a polyacid or its anhydride (a-5).

[0021] The hydroxyl-containing (meth) acrylic resin (a-0) is a copolymer comprising at least a structural unit derived from a hydroxyl-containing (meth) acrylate (m-1) and a structural unit derived from a (meth) acrylate (m-2), wherein the (meth) acrylate (m-2) has one or more groups selected from an active methylene group, an active methine group, an epoxy group, an oxetane group, a blocked isocyanate group and a silyl group.

[0022] [2] The photosensitive resin composition according to [1], wherein the hydroxyl-containing (meth)acrylic resin (a-0) is a copolymer of the hydroxyl-containing (meth)acrylate (m-1), the (meth)acrylate (m-2), and another monomer (m-3).

[0023] [3] The photosensitive resin composition according to [2], wherein the other monomer (m-3) is an alkyl (meth)acrylate having an alkyl group with 1 to 12 carbon atoms.

[0024] [4] The photosensitive resin composition according to any one of [1] to [3], wherein all monomers used as polymerization raw materials of the hydroxyl group-containing (meth)acrylic resin (a-0) are collectively referred to as "monomers M", wherein among the monomers (M),

[0025] The content of the hydroxyl-containing (meth)acrylate (m-1) is 30 to 95 mol%,

[0026] The content of the (meth)acrylate (m-2) is 5 to 50 mol %.

[0027] [5] The photosensitive resin composition according to any one of [1] to [4], wherein the compound (a-4) containing an isocyanate group and an ethylenically unsaturated group is an isocyanate group-containing (meth)acrylate (a-4a).

[0028] [6] The photosensitive resin composition according to [5], wherein the isocyanate group-containing (meth)acrylate (a-4a) is an isocyanate group-containing (meth)acrylate having a polyoxyalkylene structure, or an isocyanate group-containing (meth)acrylate having two or more (meth)acryloyloxy groups.

[0029] [7] The photosensitive resin composition according to any one of [1] to [6], wherein the polybasic acid or its anhydride (a-5) is a tricarboxylic acid or its anhydride.

[0030] [8] The photosensitive resin composition according to any one of [1] to [7], wherein the acid value of the resin (A) is 10 to 300 KOHmg / g.

[0031] [9] The photosensitive resin composition according to any one of [1] to [8], wherein the ethylenically unsaturated group equivalent of the resin (A) is 200 to 5000 g / mol.

[0032]

[10] The photosensitive resin composition according to any one of [1] to [9], wherein the modification rate of the resin (A) is 20 to 90%.

[0033]

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

[10] , wherein the amount of the compound (a-4) containing an isocyanate group and an ethylenically unsaturated group added is 1 to 60 mol relative to 100 mol of the monomer (M).

[0034]

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

[11] , wherein the amount of the polybasic acid or its anhydride (a-5) added is 1 to 60 mol per 100 mol of the monomer (M).

[0035]

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

[12] , wherein the weight average molecular weight of the resin (A) is 1,000 to 50,000,

[0036] The molecular weight distribution (Mw / Mn) of the resin (A) is 1.3 to 5.0.

[0037]

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

[13] , wherein the amount of the photosensitive resin composition is 100 parts by mass of the total amount of the components other than the solvent (D).

[0038] Containing 10 to 85 parts by mass of the resin (A),

[0039] Containing 10 to 85 parts by mass of the reactive diluent (B),

[0040] 0.1 to 30 parts by mass of the photopolymerization initiator (C) is contained,

[0041] The solvent (D) is contained in an amount of 30 to 1,000 parts by mass.

[0042]

[15] A photosensitive coloring composition comprising the photosensitive resin composition according to any one of [1] to

[14] and a colorant (E),

[0043] With respect to 100 parts by mass of the total of the components other than the solvent (D),

[0044] The colorant (E) is contained in an amount of 4 to 79 parts by mass.

[0045]

[16] A cured resin film comprising a cured product of the photosensitive resin composition according to any one of [1] to

[14] .

[0046]

[17] A color filter having a colored pattern composed of a cured product of the photosensitive coloring composition according to

[15] .

[0047]

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

[17] .

[0048] Effects of the Invention

[0049] According to the present invention, there can be provided a photosensitive resin composition and a photosensitive coloring composition which have excellent developability and good low-temperature curability and can form a resin cured film having sufficient hardness and solvent resistance.

[0050] In addition, according to the present invention, a resin cured film having sufficient hardness and solvent resistance can be provided, which is composed of a cured product of the photosensitive resin composition of the present invention. In addition, a color filter having sufficient hardness and solvent resistance can be provided, which has a colored pattern composed of a cured product of the photosensitive coloring composition of the present invention. In addition, an image display element can be provided, which includes the color filter. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] [ Figure 1 ] is a schematic cross-sectional view showing an example of a color filter according to the present embodiment. DETAILED DESCRIPTION

[0052] Hereinafter, the photosensitive resin composition, the photosensitive coloring composition, the resin cured film, the color filter, and the image display element of the present invention will be described in detail. However, the present invention is not limited only to the embodiments described below.

[0053] In the present specification, "(meth)acrylic acid" refers to at least one selected from methacrylic acid and acrylic acid. "(meth)acrylate" refers to at least one selected from methacrylate and acrylate. "(meth)acryloyl" refers to at least one selected from methacryloyl and acryloyl.

[0054] <Photosensitive resin composition>

[0055] The photosensitive resin composition of the present embodiment contains at least a resin (A), a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D).

[0056] 〔Resin (A)〕

[0057] The resin (A) contained in the photosensitive resin composition of the present embodiment is an ethylenically unsaturated group and a carboxyl-modified (meth) acrylic resin. By using a (meth) acrylic resin modified with an ethylenically unsaturated group, the developability of the photosensitive resin composition can be improved, and a cured film with a finer pattern can be obtained. By using a (meth) acrylic resin modified with a carboxyl group, the developability of the photosensitive resin composition can be improved, and it can be cured at a lower temperature, and the hardness and solvent resistance of the cured product can be improved. As the above-mentioned ethylenically unsaturated group, vinyl, allyl, (meth) acryloyloxy, etc. can be cited. The above-mentioned ethylenically unsaturated group is preferably a (meth) acryloyloxy.

[0058] The "ethylenically unsaturated group-modified" resin and the "carboxyl group-modified" resin refer to resins into which ethylenically unsaturated groups or carboxyl groups are introduced by adding only compounds containing ethylenically unsaturated groups or only compounds containing carboxyl groups to a base resin, respectively.

[0059] The so-called "ethylenically unsaturated group and carboxyl group modified" resin refers to a resin into which an ethylenically unsaturated group and a carboxyl group-containing compound are introduced by adding an ethylenically unsaturated group-containing compound and a carboxyl group-containing compound to a base resin. The order of addition reaction of the ethylenically unsaturated group-containing compound and the carboxyl group-containing compound to the base resin may be either one first or simultaneously.

[0060] The above-mentioned ethylenically unsaturated group and carboxyl modified (meth) acrylic resin are addition reaction products of (meth) acrylic resin (a-0) containing hydroxyl group, compound (a-4) containing isocyanate group and ethylenically unsaturated group, and polybasic acid or its anhydride (a-5). By the reaction of the hydroxyl group possessed by the (meth) acrylic resin (a-0) containing hydroxyl group and the isocyanate group possessed by the compound (a-4) containing isocyanate group and ethylenically unsaturated group, ethylenically unsaturated group is introduced into resin (A). By the reaction of the hydroxyl group possessed by the (meth) acrylic resin (a-0) containing hydroxyl group and polybasic acid or its anhydride (a-5), carboxyl group is introduced into resin (A). The amount of introduction can be freely adjusted in order to improve developability, low temperature curing property, hardness of cured film, and solvent resistance.

[0061] On the other hand, by using (meth) acrylic acid and the like as the constituent monomers of the (meth) acrylic resin, a carboxyl-containing (meth) acrylic resin in which a carboxyl group is directly introduced into the main chain of the resin can be obtained. In the case of such a carboxyl-containing (meth) acrylic resin, if a modification is applied to introduce an ethylenically unsaturated group, for example, using a compound (a-4) containing an isocyanate group and an ethylenically unsaturated group described later, a dimer of isocyanate is produced as a by-product. The by-product does not have a developing group, and in addition, it produces disadvantages such as reduced developability of the target photosensitive resin composition of the present invention, so it is not preferred. From this point of view, the above-mentioned ethylenically unsaturated group and carboxyl-modified (meth) acrylic resin involved in this embodiment is preferably a modified resin from a hydroxyl-containing (meth) acrylic resin (a-0) described later, and the above-mentioned hydroxyl-containing (meth) acrylic resin (a-0) does not contain a carboxyl group.

[0062] In addition, as a substitute for the above-mentioned hydroxyl-containing (meth) acrylic resin (a-0) involved in the present embodiment, when an ethylenically unsaturated group is introduced into an epoxy-containing (meth) acrylic resin having an epoxy group directly introduced into the main chain of the resin or a carboxyl-containing (meth) acrylic resin having a carboxyl group directly introduced into the main chain of the resin using a compound other than the compound (a-4) containing an isocyanate group and an ethylenically unsaturated group, various disadvantages may occur, and therefore it is not preferred. For example, when the epoxy group of the epoxy-containing (meth) acrylic resin having an epoxy group directly introduced into the main chain of the resin is reacted with (meth) acrylic acid, or the carboxyl group of the carboxyl-containing (meth) acrylic resin having a carboxyl group directly introduced into the main chain of the resin is reacted with glycidyl (meth) acrylate, etc., thereby introducing a (meth) acryloyloxy group as an ethylenically unsaturated group into the resin, disadvantages such as gelation may occur due to the reaction at a high temperature during synthesis, and therefore it is not preferred. When a carboxyl group is introduced by reacting the hydroxyl group generated by ring-opening the epoxy group of the resin into which the ethylenically unsaturated group is introduced with the polybasic acid or its anhydride (a-5), disadvantages such as gelation occur due to the high temperature reaction during synthesis, which is not preferred.

[0063] [Hydroxyl-containing (meth)acrylic resin (a-0)]

[0064] The hydroxyl-containing (meth) acrylic resin (a-0) is a copolymer containing at least a structural unit derived from a hydroxyl-containing (meth) acrylic ester (m-1) and a structural unit derived from a (meth) acrylic ester (m-2) having one or more groups selected from an active methylene group, an active methine group, an epoxy group, an oxetane group, a blocked isocyanate group and a silyl group (hereinafter, also referred to as (meth) acrylic ester (m-2)). The above-mentioned hydroxyl-containing (meth) acrylic resin (a-0) may contain structural units derived from other monomers (m-3) as needed. In this specification, all monomers that will become the polymerization raw materials of the above-mentioned hydroxyl-containing (meth) acrylic resin (a-0), that is, the above-mentioned hydroxyl-containing (meth) acrylic ester (m-1), the above-mentioned (meth) acrylic ester (m-2) and the above-mentioned other monomers (m-3) as optional components are collectively referred to as "monomer (M). The amount of monomer (M) refers to the total amount of the above-mentioned monomers (m-1), (m-2) and (m-3).

[0065] It should be noted that the so-called "structural unit derived from the hydroxyl-containing (meth)acrylate (m-1)" refers to a structural unit formed by free radical polymerization of the hydroxyl-containing (meth)acrylate (m-1), and specifically refers to a structural unit obtained by converting the polymerizable carbon-carbon double bond of the hydroxyl-containing (meth)acrylate (m-1) into a carbon-carbon single bond. In addition, the so-called "structural unit derived from the (meth)acrylate (m-2)" refers to a structural unit formed by free radical polymerization of the (meth)acrylate (m-2), and specifically refers to a structural unit obtained by converting the polymerizable carbon-carbon double bond of the (meth)acrylate (m-2) into a carbon-carbon single bond.

[0066] [Hydroxy-containing (meth)acrylate (m-1)]

[0067] The hydroxyl-containing (meth)acrylate (m-1) is not particularly limited as long as it is a compound having a hydroxyl group and a (meth)acryloyloxy group. Examples thereof include hydroxyl-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate. Among them, from the viewpoint of ease of acquisition and ease of modification reaction when introducing a (meth)acryloyloxy group and a carboxyl group into the resin (A), a hydroxyalkyl (meth)acrylate having a hydroxyl group at the alkyl terminal is preferred, a hydroxyalkyl (meth)acrylate having 2 to 4 carbon atoms is particularly preferred, and 2-hydroxyethyl (meth)acrylate is most preferred.

[0068] The content of the hydroxyl group-containing (meth)acrylate (m-1) is preferably 30 to 95 mol%, more preferably 40 to 80 mol%, and further preferably 45 to 70 mol% relative to the monomer (M). When the content is 30 mol% or more, the modification amount when the (meth)acryloyloxy group and the carboxyl group are introduced can be sufficiently ensured, and a photosensitive resin composition with excellent developability can be obtained, and even in the case of low-temperature curing, a cured film with excellent hardness and solvent resistance can be obtained.

[0069] [(Meth)acrylate (m-2) having one or more groups selected from the group consisting of an active methylene group, an active methine group, an epoxy group, an oxetanyl group, a blocked isocyanate group, and a silyl group]

[0070] The (meth)acrylate (m-2) involved in the present embodiment is a (meth)acrylate having no hydroxyl group and no carboxyl group, and is one or more compounds selected from (meth)acrylate (m-2-1) containing an active methylene group or an active methine group, (meth)acrylate (m-2-2) containing an epoxy group or an oxetane group, (meth)acrylate (m-2-3) containing a blocked isocyanate group, and (meth)acrylate (m-2-4) containing a silyl group. The functional group of the (meth)acrylate (m-2) itself has crosslinking properties by heat or light, or reacts with the hydroxyl group from the (meth)acrylate (m-1) containing a hydroxyl group to crosslink, which contributes to improving the hardness and solvent resistance of the photosensitive resin composition when it is cured at low temperature.

[0071] The content of the (meth)acrylate (m-2) involved in the present embodiment is preferably 5 to 50 mol%, more preferably 10 to 40 mol%, and further preferably 15 to 30 mol% relative to the monomer (M). If the content is 5 mol% or more, the amount of the functional group introduced by the (meth)acrylate (m-2) can be sufficiently ensured, and a photosensitive resin composition with excellent developability can be obtained, and even in the case of low-temperature curing, a cured film with excellent hardness and solvent resistance can be obtained. If the content is 50 mol% or less, the content of the (meth)acrylate (m-1) containing a hydroxyl group can be sufficiently ensured, and the content of the compound (a-4) containing an isocyanate group and an ethylenically unsaturated group and the polyacid or its anhydride (a-5) can be sufficiently ensured.

[0072] Among them, if a (meth)acrylate containing a blocked isocyanate group (m-2-3) is used, the low-temperature curability of the photosensitive resin composition can be improved, and a cured film with better hardness and solvent resistance can be obtained. If a (meth)acrylate containing a silyl group (m-2-4) is used, the crosslinking efficiency of the photosensitive resin composition is improved, and the pattern can be further refined.

[0073] [(Meth)acrylate containing active methylene or active methine (m-2-1)]

[0074] In the active methylene or active methine possessed by (methyl) acrylate (m-2-1), hydrogen atoms are easily separated, thereby carrying out the cross-linking reaction of resin. For example, the methylene bond between the two carbonyl groups of acetoacetate is active and is prone to hydrogen abstraction reaction. In addition, as is well known, acetoacetate shows typical keto-enol tautomerism, and it is also believed that it is related to photocuring. It should be noted that the active methylene and active methine in the present embodiment refer to the methylene and methine bonded to any one of the carbon atom of the carbonyl group, the sulfur atom of the sulfonyl group, the cyano group, and the nitro group at both ends.

[0075] Examples of the structure having an active methylene group include a structure having the following formula (X1). 3 and R 4 The bonded methylene group is an active methylene group.

[0076]

[0077] (In formula (X1), R 3 represents a divalent group represented by any one of the following formulae (8) to (10). 4 represents a cyano group (-CN), a nitro group (-NO2), a group represented by the following formula (11) or the following formula (12). * represents a bonding site. ★ represents an active methylene carbon.)

[0078]

[0079] (In formula (8) to formula (12), * represents a bonding site. In formula (11) and formula (12), R 5 represents a hydrocarbon group having 1 to 24 carbon atoms which may contain a hydrogen atom or a hetero atom).

[0080] R in formula (X1) 3 Among them, from the viewpoint of good low-temperature curability as a photosensitive resin composition and excellent physical properties required for a color filter, a divalent group represented by either formula (8) or formula (10) is preferred, and a divalent group represented by formula (10) is more preferred.

[0081] R in formula (X1) 4 Among them, from the viewpoint of good low-temperature curability as a photosensitive resin composition and excellent physical properties required for a color filter, formula (11) and formula (12) are preferred, and formula (11) is more preferred.

[0082] In the case where the formula (11) or (12) is included as R in the formula (X1)4 In the case of 5 Specific examples of the hydrocarbon group having 1 to 24 carbon atoms which may contain a heteroatom include methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, methoxy, ethoxy, propoxy, hexyloxy, cyclohexyloxy, and groups represented by the following formulae (13) to (15).

[0083]

[0084] (In formula (13) to formula (15), * represents a bonding site.)

[0085] Among them, the hydrocarbon group having 1 to 24 carbon atoms which may contain a hetero atom is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably an alkyl group having 1 to 3 carbon atoms.

[0086] As R 5 From the viewpoint of good low-temperature curing property and excellent physical properties required for color filters, preferably a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom and an alkyl group having 1 to 3 carbon atoms, further preferably a hydrogen atom and a methyl group.

[0087] Examples of the structure having an active methine group include a structure having the following formula (X2). 3 The methine group bonded to the cyclohexane ring is an active methine group.

[0088]

[0089] (In formula (X2), * represents a bonding site. ★ represents an active methine carbon. R 3 The definition and preferred range of are the same as those of formula (X1).

[0090] Examples of the (meth)acrylate (m-2-1) containing an active methylene group or an active methine group include compounds represented by the following formula (1) or (2).

[0091]

[0092] (In formula (1) and (2), R 6 represents a hydrogen atom or a methyl group. 2 represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms. 3 and R 4 The definition and preferred range of are the same as those in formula (X1) and formula (X2). ★ represents active methylene carbon or active methine carbon.

[0093] As the (meth)acrylate (m-2-1) containing an active methylene group or an active methine group, a compound represented by the following formula (m1) is preferred from the viewpoints of the easiness of the reaction when polymerizing to obtain the resin (A), the low-temperature curability as a photosensitive resin composition, the hardness of the cured film, and the solvent resistance.

[0094]

[0095] (In formula (m1), R 6 represents a hydrogen atom or a methyl group, R 7 represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms. )

[0096] In formula (m1), R 7 The hydrocarbon group having 1 to 10 carbon atoms represented by may have a ring structure. From the viewpoint of low temperature curability of the photosensitive resin composition, R 7 The hydrocarbon group represented is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably an alkyl group having 1 to 2 carbon atoms.

[0097] Specific examples of the compound represented by the above formula (1) include the following compounds.

[0098]

[0099] Specific examples of the compound represented by the above formula (2) include the following compounds.

[0100]

[0101] Formulae (16) to (33) are compounds having CH2=C(CH3)-, but compounds in which CH2=C(CH3)- in these formulae is replaced with CH2=CH- can also be mentioned.

[0102] [(Meth)acrylate containing epoxy group or oxetane group (m-2-2)]

[0103] (Meth)acrylate (m-2-2) is a compound that does not contain a hydroxyl group, an active methylene group, an active methine group, and a carboxyl group, but has an epoxy group or an oxetanyl group and a (meth)acryloyloxy group. By using (meth)acrylate (m-2-2), when the photosensitive resin composition is cured, crosslinking with the carboxyl group from the polyacid or its anhydride (a-5) is performed. Therefore, a photosensitive resin composition with good developability can be obtained, and even in the case of low-temperature curing, a cured film with excellent hardness and solvent resistance can be obtained.

[0104] Specific examples of the (meth)acrylate containing an epoxy group include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, (meth)acrylate having an alicyclic epoxy group and its lactone adduct, 3',4'-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexylmethyl ester, epoxides of dicyclopentenyl (meth)acrylate, and epoxides of dicyclopentenyloxyethyl (meth)acrylate, etc. Among them, from the viewpoint of easy availability and reactivity when synthesizing the resin (A), glycidyl (meth)acrylate and (meth)acrylate having an alicyclic epoxy group are preferred, and 3,4-epoxycyclohexylmethyl (meth)acrylate and glycidyl (meth)acrylate are more preferred.

[0105] Specific examples of the (meth)acrylate containing an oxetane group include (meth)acrylate (3-ethyloxetane-3-yl)methyl ester, (meth)acrylate, 4-[3-(3-ethyloxetane-3-ylmethoxy)propoxy]styrene, 4-[6-(3-ethyloxetane-3-ylmethoxy)hexyloxy]styrene, 4-[5-(3-ethyloxetane-3-ylmethoxy)pentyloxy]styrene, and 2-vinyl-2-methyloxetane. Among them, (meth)acrylate (3-ethyloxetane-3-yl)methyl ester is preferred from the viewpoint of easy availability and reactivity when synthesizing the resin (A).

[0106] Among the (meth)acrylates (m-2-2), from the viewpoint of availability and reactivity in synthesizing the resin (A), (cyclo)alkyl (meth)acrylates having 2 to 12 carbon atoms and having an epoxy group or an oxetanyl group are preferred.

[0107] [(Meth)acrylate containing blocked isocyanate group (m-2-3)]

[0108] (Meth) acrylate (m-2-3) is a compound having a blocked isocyanate group and a (meth) acryloyloxy group without containing a hydroxyl group, an active methylene group, an active methine group, an epoxy group, an oxetane group and a carboxyl group. By using (meth) acrylate (m-2-3), the low temperature curability of the photosensitive resin composition is improved, and the hydroxyl group from the (meth) acrylate (m-1) containing a hydroxyl group is cross-linked with the isocyanate group generated by deblocking, thereby obtaining a cured film with excellent hardness and solvent resistance. (Meth) acrylate (m-2-3) can include, for example, a compound obtained by blocking the isocyanate group in the (meth) acrylate containing an isocyanate group using a blocking agent. The reaction of the (meth) acrylate containing an isocyanate group with the blocking agent can be carried out regardless of the presence or absence of a solvent. When a solvent is used, it is necessary to use a solvent that is inactive for the isocyanate group. In the blocking reaction, organic metal salts such as tin, zinc, and lead, tertiary amines, etc. can be used as catalysts. The reaction can be generally performed at -20 to 150° C., but is preferably performed at 0 to 100° C. Examples of the above-mentioned isocyanate compound include compounds represented by the following formula (XX1).

[0109]

[0110] In the above formula (XX1), R 11 represents a hydrogen atom or a methyl group, R 12 Indicates -CO-, -COOR 13 -(Here, R 13 is an alkylene group having 1 to 6 carbon atoms) or -COO-R 14 O-CONH-R 15 -(Here, R 14 is an alkylene group having 2 to 6 carbon atoms, R 15 is an alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms which may have a substituent). R 12 Preferably -COOR 13 -, here, R 13 An alkylene group having 1 to 4 carbon atoms is preferred.

[0111] As the isocyanate compound represented by the above formula (XX1), specifically, 2-isocyanate ethyl (meth)acrylate, 2-isocyanate propyl (meth)acrylate, 3-isocyanate propyl (meth)acrylate, 2-isocyanate-1-methylethyl (meth)acrylate, 2-isocyanate-1,1-dimethylethyl (meth)acrylate, 4-isocyanate cyclohexyl (meth)acrylate, methacryloyl isocyanate, etc. can be cited. In addition, an equimolar (1 mol: 1 mol) reaction product of 2-hydroxyalkyl (meth)acrylate and a diisocyanate compound can also be used. As the alkyl group of the above-mentioned 2-hydroxyalkyl (meth)acrylate, an ethyl group or an n-propyl group is preferred, and an ethyl group is more preferred. Examples of the diisocyanate compound include hexamethylene diisocyanate, 2,4- (or 2,6-) toluene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), 3,5,5-trimethyl-3-isocyanatomethylcyclohexyl isocyanate (IPDI), m- (or p-) xylylene diisocyanate, 1,3- (or 1,4-) bis (isocyanatomethyl) cyclohexane, and lysine diisocyanate.

[0112] Among these isocyanate compounds, 2-isocyanateethyl(meth)acrylate, 2-isocyanatepropyl(meth)acrylate, 3-isocyanatepropyl(meth)acrylate, 2-isocyanate-1-methylethyl(meth)acrylate, 2-isocyanate-1,1-dimethylethyl(meth)acrylate, 4-isocyanatecyclohexyl(meth)acrylate and methacryloyl isocyanate are preferred, and 2-isocyanateethyl(meth)acrylate and 2-isocyanatepropyl(meth)acrylate are more preferred.

[0113] Examples of the blocking agent for blocking the isocyanate group in the isocyanate compound include lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam; alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol, and cyclohexanol; phenol, cresol, xylenol, ethylphenol, o-isopropylphenol, butylphenol such as p-tert-butylphenol, p-tert-octylphenol, nonylphenol, dinonylphenol, styrenated phenol, hydroxybenzoic acid esters, thymol; Phenol series such as eugenol, p-naphthol, p-nitrophenol, and p-chlorophenol; active methylene series such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone; thiol series such as butyl mercaptan, thiophenol, and tert-dodecyl mercaptan; amine series such as diphenylamine, phenylnaphthylamine, aniline, and carbazole; amide series such as acetanilide, methoxyacetanilide, acetamide, and benzamide; imide series such as succinimide and maleimide; imidazole series such as imidazole, 2-methylimidazole, and 2-ethylimidazole; urea series such as urea, thiourea, and ethylene urea; N-phenylcarbamic acid phenyl ester, 2- The terminal blocking agent includes carbamates such as oxazolidinone, imines such as ethyleneimine and polyethyleneimine, oximes such as formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime and cyclohexanone oxime, and bisulfites such as sodium bisulfite and potassium bisulfite. Among them, the terminal blocking agent is preferably diethyl malonate, 3,5-dimethylpyrazole, hydroxybenzoic acid ester and methyl ethyl ketone oxime from the viewpoint of easy availability and reactivity when synthesizing the resin (A), and more preferably 3,5-dimethylpyrazole from the viewpoint of low temperature curing property.

[0114] [Silyl group-containing (meth)acrylate (m-2-4)]

[0115] The silyl-containing (meth)acrylate (m-2-4) is a compound having a silyl group and a (meth)acryloyloxy group without a hydroxyl group, an active methylene group, an active methine group, an epoxy group, an oxetanyl group, a blocked isocyanate group, and a carboxyl group. Specific examples thereof include [(meth)acryloyloxy]methyltriethoxysilane, [(meth)acryloyloxy]ethyltriethoxysilane, [(meth)acryloyloxy]propyltriethoxysilane, [(meth)acryloyloxy]octyltriethoxysilane, [(meth)acryloyloxy]propylmethyldiethoxysilane, [(meth)acryloyloxy]ethylmethyldiethoxysilane, [(meth)acryloyloxy]nonylmethyldiethoxysilane, and the like. Among them, from the viewpoint of availability and reactivity when synthesizing the resin (A), [(meth)acryloyloxy]alkylmethyldialkoxysilane and [(meth)acryloyloxy]alkylethyldialkoxysilane are preferred, 3-(meth)acryloyloxypropylmethyldimethoxysilane and 3-(meth)acryloyloxypropylmethyldiethoxysilane are more preferred, and 3-(meth)acryloyloxypropylmethyldiethoxysilane is further preferred.

[0116] 〔Other monomers (m-3)〕

[0117] The hydroxyl-containing (meth) acrylic resin (a-0) may have other monomers (m-3) other than the hydroxyl-containing (meth) acrylic ester (m-1) and (meth) acrylic ester (m-2) as constituent monomers as needed. Other monomers (m-3) include, for example, dienes such as butadiene, (meth) acrylic esters, styrenes, unsaturated dicarboxylic acid diesters, and other vinyl compounds. For the above reasons, other monomers (m-3) preferably do not have a carboxyl group.

[0118] Specific examples of (meth)acrylates include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isopentyl (meth)acrylate, and dodecyl (meth)acrylate; cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylcyclohexyl (meth)acrylate, norbornyl (meth)acrylate, dimethicone (meth)acrylate, and the like; Cyclopentyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate and other alicyclic alkyl (meth)acrylates; benzyl (meth)acrylate, triphenylmethyl (meth)acrylate, cumyl (meth)acrylate, naphthalene (meth)acrylate, anthracene (meth)acrylate and other (meth)acrylates containing aromatic groups; rosin (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate and the like.

[0119] Specific examples of styrenes include styrene and α-, o-, m-, and p-alkyl derivatives of styrene.

[0120] Specific examples of the unsaturated dicarboxylic acid diester include diethyl citraconic acid, diethyl maleate, diethyl fumarate, and diethyl itaconate.

[0121] Specific examples of other vinyl compounds include norbornene (bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, tetracyclo[4.4.0.12,5.17,10]dodec-3-ene, 8-methyltetracyclo[4.4.0.12,5.17,10]dodec-3-ene, 8-ethyltetracyclo[4.4.0.12,5.17,10]dodec-3-ene, dicyclopentadiene, tricyclo[5.2.1.02,6]dec-8-ene, tricyclo[5.2.1.02,6]dec-3-ene, tricyclo[4.4.0.12,5]undec-3-ene, tricyclo[6.2.1.01,8]undec-9-ene, Tricyclo[6.2.1.01,8]undecane-4-ene, tetracyclo[4.4.0.12,5.17,10.01,6]dodecane-3-ene, 8-methyltetracyclo[4.4.0.12,5.17,10.01,6]dodecane-3-ene, 8-ethylidenetetracyclo[4.4.0.12,5.17,12]dodecane-3-ene, 8-ethylidenetetracyclo[4.4.0.12,5.17,10.01,6]dodecane-3-ene, pentacyclo[6.5.1.13,6.02,7.09,13]pentadecan-4-ene, pentacyclo[7.4.0.12,5.19,12.08,13]pentadecan-3-ene, (methyl)acrylanilide, vinylpyridine, vinyl acetate, vinyltoluene, etc.

[0122] Among them, from the viewpoint of availability and reactivity when synthesizing the resin (A), (meth)acrylates and other vinyl compounds are preferred, and alkyl (meth)acrylates having 1 to 12 carbon atoms, benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, styrene, vinyltoluene and norbornene are preferred, and methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and dicyclopentanyl (meth)acrylate are more preferred. In particular, from the viewpoint of improving the developability of the photosensitive resin composition, alkyl (meth)acrylates having 6 to 12 carbon atoms and alicyclic alkyl (meth)acrylates are preferred, and 2-ethylhexyl (meth)acrylate and dicyclopentanyl (meth)acrylate are more preferred.

[0123] The content of other monomer (m-3) is preferably 1 to 50 mol %, more preferably 3 to 40 mol %, and further preferably 5 to 35 mol % based on the monomer (M).

[0124] [Compound containing an isocyanate group and an ethylenically unsaturated group (a-4)]

[0125] The compound (a-4) containing an isocyanate group and an ethylenically unsaturated group is not particularly limited as long as it has an isocyanate group and an ethylenically unsaturated group but does not have a hydroxyl group, an active methylene group, an active methine group, an epoxy group, an oxetane group, a blocked isocyanate group, and a silyl group. When the above-mentioned ethylenically unsaturated group is a (meth)acryloyloxy group, the compound (a-4) containing an isocyanate group and an ethylenically unsaturated group is a (meth)acrylate (a-4a) containing an isocyanate group. As the (meth)acrylate (a-4a) containing an isocyanate group, for example, 2-(meth)acryloyloxyethyl isocyanate, 2-isocyanatepropyl (meth)acrylate, 3-isocyanatepropyl (meth)acrylate, 2-isocyanate-1-methylethyl (meth)acrylate, 2-isocyanate-1,1-dimethylethyl (meth)acrylate, 4-isocyanatecyclohexyl (meth)acrylate, 2-(2-isocyanateethyloxy)ethyl (meth)acrylate, 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate, etc. can be mentioned. Among them, from the viewpoint of easy availability and easy synthesis of the resin (A), isocyanatealkyl (meth)acrylate is preferred, and 2-(meth)acryloyloxyethyl isocyanate is more preferred. It should be noted that the carbon number of the alkyl group of the isocyanatealkyl (meth)acrylate is preferably 2 to 10. From the viewpoint of improving the developability of the photosensitive resin composition and forming a finer pattern, an isocyanate group-containing (meth)acrylate having a polyoxyalkylene structure is preferred, and 2-(2-isocyanateethyloxy)ethyl (meth)acrylate is more preferred.

[0126] From the viewpoint of improving the photosensitivity as a photosensitive resin composition and thus improving the developability, a compound containing two or more ethylenically unsaturated groups and an isocyanate group is preferred. When the ethylenically unsaturated group is a (meth)acryloyloxy group, from the viewpoint of improving the photosensitivity as a photosensitive resin composition and thus improving the developability, an isocyanate group-containing (meth)acrylate having two or more (meth)acryloyloxy groups is preferred, and 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate is more preferred.

[0127] The addition amount of the compound (a-4) containing an isocyanate group and an ethylenically unsaturated group is preferably 1 to 60 moles, more preferably 3 to 50 moles, and further preferably 5 to 40 moles relative to 100 moles of the monomer (M) constituting the (meth) acrylic resin (a-0) containing a hydroxyl group. If the addition amount of the compound (a-4) containing an isocyanate group and an ethylenically unsaturated group is 1 mole or more, sufficient photocurability as a photosensitive resin composition can be imparted. If the addition amount is 60 moles or less, gelation during synthesis of the resin (A) can be prevented, and the introduction amount of the polyacid or its anhydride (a-5) can be sufficiently ensured, and good developability as a photosensitive resin composition can be obtained. In particular, from the viewpoint of miniaturization of the development pattern, the addition amount of the compound (a-4) containing an isocyanate group and an ethylenically unsaturated group is preferably 30 to 50 moles relative to 100 moles of the monomer (M) constituting the (meth) acrylic resin (a-0) containing a hydroxyl group.

[0128] [Polyacid or its anhydride (a-5)]

[0129] The polyacid or its anhydride (a-5) is a compound or its anhydride having two or more carboxyl groups. As the polyacid, adipic acid, itaconic acid, succinic acid, oxalic acid, malonic acid, phthalic acid, fumaric acid, maleic acid, glutaric acid, tartaric acid, glutamic acid, sebacic acid, etc. can be mentioned. As the polyacid anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, succinic anhydride, cyclohexanetricarboxylic anhydride, etc. can be mentioned. Among them, from the viewpoint of hardness of the cured film, polyacid anhydrides having an alicyclic structure are preferred, and maleic anhydride, itaconic anhydride, ethylmaleic anhydride, methylitaconic anhydride, chloromaleic anhydride, citraconic anhydride, 2-norbornene-5,6-dicarboxylic anhydride, 4-[2-(methacryloyloxy)ethoxycarbonyl]phthalic anhydride, succinic anhydride, tetrahydrophthalic anhydride, and cyclohexanetricarboxylic anhydride are more preferred. From the viewpoint of increasing the amount of carboxyl groups introduced and thus improving the low-temperature curability, tetrahydrophthalic anhydride and cyclohexanetricarboxylic anhydride are further preferred.

[0130] The amount of the polyacid or its anhydride (a-5) added is preferably 1 to 60 moles, more preferably 3 to 50 moles, and further preferably 5 to 45 moles relative to 100 moles of the monomer (M) constituting the (meth) acrylic resin (a-0) containing a hydroxyl group. If the amount of the polyacid or its anhydride (a-5) added is 1 mole or more, sufficient developability as a photosensitive resin composition can be obtained. If the amount of addition is 60 moles or less, the amount of the compound (a-4) containing an isocyanate group and an ethylenically unsaturated group can be sufficiently ensured, and good photocurability as a photosensitive resin composition can be obtained. In particular, from the viewpoint of improving the hardness and solvent resistance of the cured film during low-temperature curing, the amount of the polyacid or its anhydride (a-5) added is preferably 35 to 60 moles.

[0131] The modification rate of resin (A), i.e., the ratio of the amount (total moles) of the hydroxyl group (moles) of the compound (a-4) containing an isocyanate group and an ethylenically unsaturated group and the polyacid or its anhydride (a-5) relative to the (meth) acrylic resin (a-0) containing a hydroxyl group, is preferably 20 to 90%, more preferably 30 to 85%, and further preferably 45 to 80%. If the modification rate is 20% or more, the amount of ethylenically unsaturated groups and carboxyl groups introduced can be sufficiently ensured, and a photosensitive resin composition with excellent developability can be obtained, and even in the case of low-temperature curing, a cured film with excellent hardness and solvent resistance can be obtained. If the modification rate is 90% or less, gelation during synthesis of resin (A) can be suppressed, and residual monomers can be reduced, thereby suppressing the generation of residues during development of the photosensitive resin composition.

[0132] “Weight average molecular weight (Mw)”

[0133] The weight average molecular weight (Mw) of the resin (A) involved in the present embodiment is preferably 1000 to 50000, more preferably 2000 to 30000, and most preferably 3500 to 25000, in terms of polystyrene. If the weight average molecular weight (Mw) of the resin (A) is 1000 or more, when a resin composition containing the resin (A) is used as a raw material for a photosensitive resin composition, a photosensitive resin composition that is not prone to defects such as defects in the resin cured film after development can be obtained. If the weight average molecular weight of the resin (A) is 50000 or less, the development time of the photosensitive resin composition containing the resin (A) is sufficiently short, and the practicality is excellent.

[0134] The value of the weight average molecular weight (Mw) of the resin (A) in the present embodiment is measured by gel permeation chromatography (GPC) under the following conditions and calculated in terms of polystyrene.

[0135] Column: SHOWDEX (registered trademark) LF-804+LF-804 (manufactured by Showa Denko K.K.)

[0136] Column temperature: 40°C

[0137] Sample: Tetrahydrofuran solution containing 0.2% by mass of resin (A)

[0138] Developing solvent: tetrahydrofuran

[0139] Detector: Differential refractometer (trade name: ショウデオデオムエック (registered trademark) RI-71S, manufactured by Showa Denko K.K.)

[0140] Flow rate: 1mL / min

[0141] The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the resin (A) is preferably 1.3 to 5.0, more preferably 1.5 to 4.0, and most preferably 1.7 to 3.0. If the molecular weight distribution (Mw / Mn) of the resin (A) is 1.3 or more, it is possible to optimize the target numerical range of the weight average molecular weight (Mw), acid value, etc., and to set the reaction conditions for manufacturing the resin (A) with a certain width, and it is possible to manufacture efficiently. If the molecular weight distribution (Mw / Mn) of the resin (A) is 5.0 or less, when a resin composition containing the resin (A) is used as a raw material for a photosensitive resin composition, a photosensitive resin composition that does not have deviations in performance such as developability can be obtained.

[0142] In addition, the molecular weight distribution (Mw / Mn) was calculated using the chromatogram measured by the above-mentioned GPC.

[0143] "Acid Value"

[0144] The acid value of the resin (A) is not particularly limited, but is preferably 10KOHmg / g to 300KOHmg / g, more preferably 50KOHmg / g to 300KOHmg / g, and most preferably 100KOHmg / g to 300KOHmg / g. If the acid value of the resin (A) is 10KOHmg / g or more, when a resin composition containing the resin (A) is used as a raw material for a photosensitive resin composition, a photosensitive resin composition having better developability can be obtained. If the acid value of the resin (A) is 300KOHmg / g or less, when a resin composition containing the resin (A) is used as a raw material for a photosensitive resin composition, a photosensitive resin composition having good developability and in which the exposed portion (photocured portion) does not dissolve in an alkaline developer can be obtained.

[0145] The acid value of the resin (A) is a value measured using a mixed indicator of bromothymol blue and phenol red according to JIS K6901 5.3. The acid value of the resin (A) refers to the number of mg of potassium hydroxide required to neutralize the acidic components contained in 1 g of the resin (A).

[0146] "Ethylenically unsaturated group equivalent weight"

[0147] The ethylenically unsaturated group equivalent of resin (A) is not particularly limited, but is preferably 200 g / mol to 5000 g / mol, more preferably 300 g / mol to 4000 g / mol, and most preferably 300 g / mol to 3000 g / mol. If the ethylenically unsaturated group equivalent of resin (A) is 200 g / mol or more, the photosensitive resin composition containing resin (A) can form a resin cured film with better hardness. In addition, if the ethylenically unsaturated group equivalent of resin (A) is 200 g / mol or more, the amount of carboxyl groups introduced into resin (A) can be fully ensured, and a photosensitive resin composition with better developability can be obtained. In addition, if the ethylenically unsaturated group equivalent of resin (A) is 5000 g / mol or less, the photosensitive resin composition containing resin (A) can form a resin cured film with better hardness. From the viewpoint of sufficiently ensuring the amount of ethylenically unsaturated groups and improving the photocurability of the photosensitive resin composition to achieve further miniaturization of the pattern, the ethylenically unsaturated group equivalent may be 1500 g / mol or less, or 800 g / mol or less.

[0148] It should be noted that the ethylenically unsaturated group equivalent of the resin (A) is a value obtained by dividing the molecular weight of the resin (A) by the average number of unsaturated groups per molecule. The ethylenically unsaturated group equivalent of the resin (A) is a calculated value calculated based on the input amount of the polymerizable unsaturated compound (raw material monomer) used as a raw material when synthesizing the resin (A). When different types of unsaturated groups are contained in one molecule of the resin (A), all unsaturated groups are counted as the number of unsaturated groups regardless of the type of the unsaturated groups.

[0149] “Functional Group Equivalents”

[0150] The functional group equivalent of the resin (A) involved in the present embodiment refers to the equivalent of the functional groups (active methylene, active methine, epoxy, oxetane, blocked isocyanate and silyl) contained in the structural unit from the (meth) acrylate (m-2) contained in the resin (A). The functional group equivalent is not particularly limited, but is preferably 200 g / mol to 5000 g / mol, more preferably 300 g / mol to 4000 g / mol, and most preferably 300 g / mol to 3000 g / mol. If the functional group equivalent of the resin (A) is 200 g / mol or more, the photosensitive resin composition containing the resin (A) can form a resin cured film having a better hardness. In addition, if the functional group equivalent of the resin (A) is 200 g / mol or more, when a resin composition containing the resin (A) is used as a raw material for the photosensitive resin composition, a photosensitive resin composition having better developability can be obtained. Moreover, when the functional group equivalent of the resin (A) is 5000 g / mol or less, the photosensitive resin composition containing the resin (A) can form a resin cured film having more excellent hardness.

[0151] It should be noted that the functional group equivalent of resin (A) is a value obtained by dividing the molecular weight of resin (A) by the average number of the functional groups contained in the structural unit derived from (meth)acrylate (m-2) per molecule. The functional group equivalent of resin (A) is a calculated value calculated based on the input amount of monomer (M) used as a raw material when synthesizing resin (A). When different types of functional groups are contained in one molecule of resin (A), all functional groups are counted as the number of functional groups regardless of the type of functional groups.

[0152] <Method for producing hydroxyl-containing (meth)acrylic resin (a-0)>

[0153] The hydroxyl-containing (meth)acrylic resin (a-0) can be produced, for example, by the following production method: Specifically, the monomer (M) is copolymerized in the presence of a polymerization solvent using a polymerization initiator according to a free radical polymerization method known in the art.

[0154] Specifically, a method can be adopted in which a monomer (M) is dissolved in a polymerization solvent to prepare a raw material solution, a polymerization initiator is added to the raw material solution, and a copolymerization reaction is carried out while stirring at 50° C. to 130° C. for 1 to 20 hours.

[0155] (Polymerization solvent)

[0156] The polymerization solvent used in the manufacture of the (meth) acrylic resin (a-0) containing a hydroxyl group is not particularly limited as long as it is an inactive solvent in the copolymerization reaction of the monomer (M). The polymerization solvent used in the manufacture of the (meth) acrylic resin (a-0) containing a hydroxyl group may be the same as the solvent contained in the solvent (D) contained in the resin composition described later, or may be partially different or completely different from the solvent contained in the solvent (D). In the case where the polymerization solvent used in the manufacture of the resin (A) is partially the same as or completely the same as the solvent contained in the solvent (D) contained in the resin composition, it is preferred to use it as a part of the solvent (D) without separating and removing the polymerization solvent from the reaction solution after the copolymerization reaction is completed.

[0157] As the solvent used in the polymerization, as long as it is a solvent that dissolves the monomer (M) and the generated copolymer and does not hinder the polymerization reaction, it is not particularly limited. In the case where the generated copolymer is a (methyl) acrylic acid polymer, from the viewpoint of its solubility, a glycol ether solvent is preferably used. Specifically, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monophenyl ether, propylene glycol monomethyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether and dipropylene glycol dimethyl ether etc. can be enumerated. These solvents can be used alone, or two or more can be used. Among them, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferred from the viewpoint of availability and reactivity.

[0158] The amount of the polymerization solvent used when manufacturing the (meth) acrylic resin (a-0) containing hydroxyl groups is not particularly limited, and is preferably 30 to 1000 parts by mass, more preferably 50 to 800 parts by mass, relative to 100 parts by mass of the monomer (M). If the amount of the polymerization solvent used is 30 parts by mass or more, the copolymerization reaction of the monomer (M) can be stably carried out, and the coloring and gelation of the (meth) acrylic resin (a-0) containing hydroxyl groups can be prevented. If the amount of the polymerization solvent used is 1000 parts by mass or less, the reduction of the molecular weight of the (meth) acrylic resin (a-0) containing hydroxyl groups caused by chain transfer can be suppressed, and the viscosity of the reaction solution can be controlled within an appropriate range.

[0159] (Polymerization initiator)

[0160] The polymerization initiator that can be used in the copolymerization reaction of the monomer (M) is not particularly limited, and examples thereof include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(isobutyric acid)dimethyl ester, benzoyl peroxide, tert-butyl peroxy-2-ethylhexanoate, etc. These polymerization initiators may be used alone or in combination of two or more.

[0161] The amount of the polymerization initiator used is not particularly limited, but is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 16 parts by mass, based on 100 parts by mass of the monomer (M).

[0162] <Method for producing resin (A)>

[0163] The resin (A) can be obtained by adding a compound (a-4) containing an isocyanate group and an ethylenically unsaturated group and a polybasic acid or its anhydride (a-5) to a part of the hydroxyl groups of a hydroxyl-containing (meth)acrylic resin (a-0).

[0164] The addition reaction can be carried out according to a conventional method.

[0165] For example, the following method can be used: in the reaction solution of synthesizing the (meth) acrylic resin (a-0) containing a hydroxyl group, a compound (a-4) containing an isocyanate group and an ethylenically unsaturated group and a polyacid or its anhydride (a-5) are added and subjected to an addition reaction. In addition, in this addition reaction (modification reaction), even if the reaction solution contains a polymerization solvent used in the copolymerization for producing the (meth) acrylic resin (a-0) containing a hydroxyl group, there is no particular problem. Therefore, the addition reaction can be carried out without removing the polymerization solvent from the reaction solution after the copolymerization reaction for producing the (meth) acrylic resin (a-0) containing a hydroxyl group is completed.

[0166] The order of adding the compound (a-4) containing an isocyanate group and an ethylenically unsaturated group and the polyacid or its anhydride (a-5) is not particularly limited, and they may be added simultaneously or separately. From the viewpoint of suppressing the formation of isocyanate dimers by side reactions, it is preferred that the compound (a-4) containing an isocyanate group and an ethylenically unsaturated group is first added and reacted, and then the polyacid or its anhydride (a-5) is added and reacted.

[0167] The reaction temperature in the above addition reaction can be appropriately set according to the types of each raw material, etc. Specifically, it is preferably set to 30°C to 150°C, and more preferably set to 50°C to 120°C. By setting the reaction temperature to 30°C or more, the addition reaction can be fully carried out. In addition, by setting the reaction temperature to 150°C or less, the gelation of the reaction solution can be suppressed, and the decomposition of the bond generated by the addition reaction can be suppressed.

[0168] (Polymerization inhibitor)

[0169] When the addition reaction is performed, a polymerization inhibitor may be added to the reaction solution as needed to prevent gelation of the reaction solution caused by the addition reaction. The polymerization inhibitor is not particularly limited, and examples thereof include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, and dibutylhydroxytoluene.

[0170] (catalyst)

[0171] When carrying out the above-mentioned addition reaction, a catalyst can be added to the reaction solution as required to promote the reaction. As the catalyst, there is no particular limitation, and for example, a tertiary amine such as triethylamine, a quaternary ammonium salt such as triethylbenzylammonium chloride, a phosphorus compound such as triphenylphosphine, a metal chelate such as chromium, a metal chelate such as lithium, 2-ethylhexanoic acid tin, a tin compound such as dibutyltin dilaurate (DBTDL), etc. can be enumerated.

[0172] When the total amount of the components other than the solvent (D) contained in the photosensitive resin composition is 100 parts by mass, the content of the resin (A) in the photosensitive resin composition of the present embodiment is preferably 10 parts by mass to 85 parts by mass, more preferably 15 parts by mass to 75 parts by mass, and most preferably 24 parts by mass to 60 parts by mass. If the content of the resin (A) is within the above range, the viscosity and low temperature curing property of the photosensitive resin composition become more appropriate.

[0173] [Reactive diluent (B)]

[0174] As the reactive diluent (B) contained in the photosensitive resin composition of the present embodiment, it is not particularly limited as long as it is a low molecular weight compound having ethylenically unsaturated groups such as vinyl, allyl, (meth) acryloyloxy, etc. In order to improve the curability (reactivity), a reactive diluent (multifunctional reactive diluent) having multiple ethylenically unsaturated groups is preferred. As specific examples of reactive diluent (B), aromatic vinyl monomers; polycarboxylic acid monomers such as vinyl acetate and vinyl adipate; monofunctional (meth) acrylates; multifunctional (meth) acrylates; triallyl cyanurate, etc. can be cited.

[0175] Specific examples of the aromatic vinyl monomers include styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, divinylbenzene, diallyl phthalate, and diallylphenylphosphonate.

[0176] Specific examples of the monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, β-hydroxyethyl (meth)acrylate, and hydroxypropyl (meth)acrylate.

[0177] Specific examples of the 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(hydroxyethyl)isocyanurate tri(meth)acrylate.

[0178] Among them, as the reactive diluent (B), in order to improve the curability (reactivity), polyfunctional (meth)acrylates are preferred, and dipentaerythritol penta(meth)acrylate and / or dipentaerythritol hexa(meth)acrylate are particularly preferred.

[0179] These reactive diluents (B) may be used alone or in combination of two or more.

[0180] When the total amount of the components other than the solvent (D) contained in the photosensitive resin composition is 100 parts by mass, the content of the reactive diluent (B) in the photosensitive resin composition of the present embodiment is preferably 10 parts by mass to 85 parts by mass, more preferably 15 parts by mass to 75 parts by mass, and most preferably 24 parts by mass to 60 parts by mass. If the content of the reactive diluent (B) is within the above range, the viscosity and photocurability of the photosensitive resin composition become more appropriate.

[0181] [Photopolymerization initiator (C)]

[0182] The photopolymerization initiator (C) contained in the photosensitive resin composition of the present embodiment is not particularly limited as long as it is a compound that generates radicals by light irradiation. Examples of the photopolymerization initiator (C) include benzoins and alkyl ethers thereof such as benzoin, benzoin methyl ether, and benzoin ethyl ether; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4-(1-tert-butyldioxy-1-methylethyl)acetophenone; alkyl phenones such as 1-hydroxycyclohexyl phenyl ketone and 2-hydroxy-2-methyl-1-phenylpropane-1-one; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-tert-butylanthraquinone, and 1-chloroanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzil dimethyl ketal; benzophenone, 4-(1-tert-butyldioxy-1-methylethyl)acetophenone, and the like. Benzophenones such as 1,2-octanedione, 1-[4-(phenylthio)-2-(o-benzoyl oxime)], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone 1-(o-acetyl oxime) and the like; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propane-1-one; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone; acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; xanthones, etc. These photopolymerization initiators (C) may be used alone or in combination of two or more.

[0183] When the total amount of the components other than the solvent (D) contained in the photosensitive resin composition is set to 100 parts by mass, the content of the photopolymerization initiator (C) in the photosensitive resin composition of the present embodiment is preferably 0.1 to 30 parts by mass, more preferably 0.3 to 20 parts by mass, and most preferably 0.5 to 10 parts by mass. If the content of the photopolymerization initiator (C) is 0.1 parts by mass or more, the photosensitive resin composition has sufficient photocurability. If the content of the photopolymerization initiator (C) is 30 parts by mass or less, the photopolymerization initiator (C) will not adversely affect the storage stability of the photosensitive resin composition and the performance of the resin cured film.

[0184] [Solvent (D)]

[0185] The solvent (D) contained in the resin composition of the present embodiment is not particularly limited as long as it is inactive with respect to the resin (A) and the reactive diluent (B) and can dissolve the resin (A) and the reactive diluent (B).

[0186] The solvent (D) may or may not contain the polymerization solvent used in producing the resin (A).

[0187] When the solvent (D) contains the polymerization solvent used in producing the resin (A), the addition reaction for producing the resin (A) may be carried out without removing the polymerization solvent from the reaction solution after the copolymerization reaction for producing the resin (A), and the polymerization solvent may be used as a part or all of the solvent (D) of the resin composition without separating and removing the polymerization solvent from the reaction solution after the addition reaction.

[0188] The so-called situation that the polymerization solvent used when manufacturing resin (A) is not included in the solvent (D) refers to the situation that the resin (A) used as the raw material of the resin composition is separated from the reaction solution that generates the resin (A) and the resin obtained by removing it. In this case, regardless of the type and amount of the polymerization solvent used when manufacturing the resin (A), the type and content of the solvent (D) can be appropriately selected according to the type of the resin (A), the purpose of the resin composition, etc. That is, when using the resin obtained by separating and removing it from the reaction solution that generates the resin (A) as the resin (A), as the solvent (D), a solvent of the same type as the polymerization solvent used when manufacturing the resin (A) can be used, or a different solvent can be used.

[0189] Solvent (D) is not particularly limited. When resin (A) is a (meth) acrylic acid polymer, it is preferably a glycol ether solvent from the viewpoint of its solubility. Specifically, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monophenyl ether, propylene glycol monomethyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether and dipropylene glycol dimethyl ether etc. can be enumerated. These solvents can be used alone, or two or more kinds can be used. Among them, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferred from the viewpoint of availability and reactivity.

[0190] The solvent (D) may contain other solvents capable of dissolving the resin (A) and the reactive diluent (B).

[0191] For example, monoalcohols and (poly)alkylene glycol monoalkyl ethers may be mentioned.

[0192] Specific examples of monoalcohols include primary alcohols such as propanol, butanol, pentanol, hexanol, octanol, nonanol, decanol, and dodecyl alcohol; and secondary alcohols such as benzyl alcohol.

[0193] Specific examples of other solvents include tertiary alcohols such as tert-butyl alcohol and diacetone alcohol; (poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; other 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 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and ethyl 3-ethoxypropionate. Esters such as esters, ethyl ethoxylate, ethyl hydroxylate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-butyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate; aromatic hydrocarbons such as toluene and xylene; carboxylic acid amides such as N-methylpyrrolidone, N,N-dimethylformamide and N,N-dimethylacetamide, etc.

[0194] When the sum of the components other than the solvent (D) in the resin composition is set to 100 parts by mass, the content of the solvent (D) in the resin composition of the present embodiment is preferably 30 parts by mass to 1000 parts by mass, more preferably 50 parts by mass to 800 parts by mass, and most preferably 100 parts by mass to 700 parts by mass. If the content of the solvent (D) is within the above range, the viscosity of the resin composition can be adjusted to an appropriate range.

[0195] 〔Other additives〕

[0196] The photosensitive resin composition of the present embodiment may contain one or more known additives such as a leveling agent, a thermal polymerization inhibitor, and a sensitizer as needed. The content of these additives is not particularly limited as long as it is within a range that does not inhibit the effects of the present invention.

[0197] In addition, the photosensitive resin composition of the present embodiment may contain amine, hydrazide, aldehyde, or metal salt as a crosslinking agent in order to improve curability. Examples of the crosslinking agent include MXDA and 1,3-BAC manufactured by Mitsubishi Gas Chemical Co., Ltd., ADH and APA-280 manufactured by Otsuka Chemical Co., Ltd., SEQUEAREZ 755 manufactured by OMNOVA Solutions, and ZIRCOZOL ZC-2 and 7 manufactured by Daiichi Noble Chemical Co., Ltd.

[0198] In addition, the photosensitive resin composition of the present embodiment may contain an acid generator and an alkali generator to improve curability. In particular, from the perspective of potential, it is preferred to use a photoacid generator, a photobase generator, a thermal acid generator, and a thermal base generator. From the perspective of storage stability, a photoacid generator and a photobase generator are further preferred. Examples of photoacid generators include sulfonium salt compounds such as CPI-200K, CPI-210S, CPI-310B, and CPI-410S manufactured by Sanapro Chemical Co., Ltd., and iodine salts such as IK-1. Salt compounds, etc. Examples of the photobase generator include trade names WPBG-266, WPBG-300, and WPBG-345 manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0199] [Viscosity of photosensitive resin composition]

[0200] The viscosity of the photosensitive resin composition of the present embodiment can be appropriately adjusted according to the thickness of the cured resin film formed by the cured product of the photosensitive resin composition. For example, when the thickness of the cured resin film is adjusted to 1 to 4 μm, the viscosity of the photosensitive resin composition is preferably 1 mP·s to 25 mP·s at the temperature during coating, more preferably 2 mP·s to 20 mP·s, and most preferably 3 mP·s to 15 mP·s.

[0201] <Photosensitive Coloring Composition>

[0202] The photosensitive coloring composition of the present embodiment contains the photosensitive resin composition of the present embodiment and a colorant (E).

[0203] [Colorant (E)]

[0204] As the colorant (E), known dyes and / or pigments can be used. When used for a filter, from the viewpoint of color reproducibility, a dye is preferably used as the colorant (E). When a dye is used as the colorant (E), a photosensitive coloring composition having a high brightness coloring pattern and showing good alkali developability can be obtained compared to the case where a pigment is used.

[0205] As the dye, from the viewpoints of solubility in the solvent (D) and the alkaline developer, interaction with other components in the photosensitive resin composition, heat resistance, etc., it is preferred to use an acid dye having an acid group such as a carboxyl group, a salt of an acid dye with a nitrogen compound, a sulfonamide of an acid dye, etc. 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 (VALIFAST BLUE 2620); acid chrome violet K; acid fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 0, 12, 50, 51, 52, 56, 63, 74, 95; acid red 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 (acid violet)6B,7,9,17,19; acid yellow (acid Yellow) 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; Solvent Yellow 82 and their derivatives. Among them, acid dyes of azo, xanthene, anthraquinone or phthalocyanine are preferred. These dyes can be used alone or in combination of two or more depending on the color of the target pixel.

[0206] Examples of the pigment 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, etc.; orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73, etc.; CI Pigment Red 9, 97, 10 5, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and other red pigments; CI pigment blue 15, 15:3, 15:4, 15:6, 60 and other blue pigments; CI pigment violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments; CI pigment green 7, 36, 58 and other green pigments; CI pigment brown 23, 25 and other brown pigments; CI pigment black 1, 7, carbon black, titanium black, iron oxide and other black pigments, etc. These pigments can be used alone or in combination of two or more depending on the color of the target pixel.

[0207] When a pigment is used as a colorant (E), a known dispersant can be mixed in the photosensitive coloring composition from the viewpoint of improving the dispersibility of the colorant (E). As a dispersant, a polymer dispersant with excellent dispersion stability over time is preferably used. As a polymer dispersant, for example, a carbamate dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene glycol diester dispersant, a sorbitan aliphatic ester dispersant, aliphatic modified ester dispersant, etc. can be cited. As such a polymer dispersant, a polymer dispersant sold on the market under the trade names of EFKA (manufactured by EFKA), Disperbyk (manufactured by Bicchem), Desperon (manufactured by Kusumoto Chemicals Co., Ltd.), SOLSPERSE (manufactured by Zeneka Co., Ltd.), etc. can be used. The amount of the dispersant to be blended may be appropriately set depending on the type and amount of the pigment or the like used as the colorant (E).

[0208] When the total of the components other than the solvent (D) contained in the photosensitive coloring composition is 100 parts by mass, the content of the colorant (E) in the photosensitive coloring composition of the present embodiment is preferably 4 parts by mass to 79 parts by mass, more preferably 9 parts by mass to 69 parts by mass, and most preferably 15 parts by mass to 50 parts by mass. If the content of the colorant (E) is 4 parts by mass or more, the effect achieved by containing the colorant (E) becomes significant, and the photosensitive coloring composition is suitable as a material for the coloring pattern of the color filter. If the content of the colorant (E) is 85 parts by mass or less, the colorant (E) in the photosensitive coloring composition does not hinder the curability of the photosensitive coloring composition, and the photosensitive coloring composition has good low-temperature curability.

[0209] 〔Other additives〕

[0210] The photosensitive coloring composition of the present embodiment may contain other additives similar to the additives described in the above-mentioned photosensitive resin composition as needed.

[0211] [Viscosity of photosensitive coloring composition]

[0212] The viscosity of the photosensitive coloring composition of the present embodiment can be appropriately adjusted according to the thickness of the resin cured film composed of the cured product of the photosensitive coloring composition. For example, when the thickness of the resin cured film is adjusted to 1 to 4 μm, the viscosity of the photosensitive coloring composition is preferably 1 mP·s to 25 mP·s, more preferably 2 mP·s to 20 mP·s, and most preferably 3 mP·s to 15 mP·s.

[0213] <Method for producing photosensitive resin composition>

[0214] The photosensitive resin composition of the present embodiment can be produced by mixing the resin (A), the reactive diluent (B), the photopolymerization initiator (C), the solvent (D), and additives used as necessary using a known mixing device.

[0215] The photosensitive resin composition of the present embodiment has good low-temperature curing properties and can form a resin cured film having sufficient hardness and solvent resistance. In addition, the photosensitive resin composition of the present embodiment has excellent alkali developability, and therefore, a fine pattern can be formed by developing with an alkaline aqueous solution. Therefore, the photosensitive resin composition of the present embodiment is suitable for use as a resist.

[0216] <Method for producing photosensitive coloring composition>

[0217] The photosensitive coloring composition of the present embodiment can be produced by mixing the resin (A), the reactive diluent (B), the photopolymerization initiator (C), the solvent (D), the colorant (E), and additives used as needed using a known mixing device.

[0218] The photosensitive resin composition of the present embodiment has good low-temperature curing properties and can form a resin cured film having sufficient hardness and solvent resistance. In addition, the photosensitive resin composition of the present embodiment has excellent alkali developability, and therefore, a fine pattern can be formed by developing with an alkaline aqueous solution. Therefore, the photosensitive resin composition of the present embodiment is suitable for use as a resist.

[0219] Moreover, the photosensitive coloring composition of this embodiment can be suitably used as a material of a coloring pattern, such as a pixel of a color filter and a black matrix.

[0220] <Resin Cured Film>

[0221] Next, the cured resin film according to the present embodiment will be described in detail.

[0222] The cured resin film of the present embodiment is composed of a cured product of the photosensitive resin composition of the present embodiment or the photosensitive coloring composition of the present embodiment.

[0223] The resin cured film of the present embodiment can be formed by, for example, a method of performing the following steps: a coating step of coating the photosensitive resin composition of the present embodiment on a substrate to form a coating film; a pre-baking step of drying the coating film formed by the coating step; an exposure step of irradiating the dried coating film with light to photo-cure it; and a post-baking step of thermally curing the photo-cured coating film.

[0224] When a resin cured film having a predetermined pattern is formed by photolithography using the photosensitive resin composition of the present embodiment, for example, the following method can be used. That is, the above-mentioned coating step and pre-baking step are performed. Then, in the exposure step, light is irradiated to the dried coating film through a photomask having a predetermined pattern to photo-cure the exposed portion. After the exposure step, post-exposure heating treatment is performed as needed. Then, the following steps are performed: a development step, in which the unexposed portion of the coating film is dissolved using a developer to perform development; and a post-baking step, in which the photo-cured coating film is thermally cured.

[0225] [Coating process]

[0226] In the coating step, the photosensitive resin composition of the present embodiment or the photosensitive coloring composition of the present embodiment is coated on the substrate to form a coating film. In the present embodiment, as the substrate on which the photosensitive resin composition or the photosensitive coloring composition is coated, a known substrate can be used, and it can be appropriately determined according to the use of the resin cured film.

[0227] The method for applying the photosensitive resin composition or the photosensitive coloring composition is not particularly limited, and for example, screen printing, roll coating, curtain coating, spray coating, spin coating, slit coating, etc. can be used.

[0228] [Pre-baking process]

[0229] In the pre-baking (pre-heating) step, the coating film formed by the coating step is dried to reduce the amount of residual solvent in the coating film. In the pre-baking step, the substrate with the coating film formed is heated at a temperature of, for example, 50°C to 120°C, preferably 70°C to 110°C, for 10 seconds to 600 seconds, preferably 120 seconds to 180 seconds. In the pre-baking step, as a method for heating the substrate with the coating film formed, for example, a method using a hot plate can be cited.

[0230] [Exposure process]

[0231] In the exposure process, light is irradiated to the surface of the coating film dried in the pre-baking process, so that the coating film is photocured. There is no particular limitation on the light source used for light irradiation, and for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, etc. can be used. In addition, the exposure amount in the exposure process is not particularly limited and can be appropriately set according to the composition of the photosensitive resin composition or the photosensitive coloring composition and the thickness of the coating film. In the case of forming a resin cured film having a predetermined pattern, in the exposure process, light is irradiated to the surface of the coating film dried in the pre-baking process through a photomask having a predetermined pattern, so that the exposed part is photocured.

[0232] [Post-exposure heating process]

[0233] In the case of forming a resin cured film having a prescribed pattern, after the exposure process, post-exposure heating (Post Exposure Baking) is performed as needed. By performing this process, the dissolution contrast between the exposed portion and the unexposed portion of the coating film becomes more significant. The post-exposure heating process is different from the post-baking process described later, and does not completely cure the coating film. The post-exposure heating process is performed in order to make only the exposed portion of the coating film remain on the substrate by performing the development process and to more reliably remove the unexposed portion of the coating film. Therefore, it is not a necessary process in the method for forming a resin cured film of the present embodiment.

[0234] In the case of performing a post-exposure heating process, the substrate after the exposure process is preferably heated at 40°C to 70°C, and more preferably at 50°C to 60°C. If the heating temperature is above 40°C, the effect of improving the dissolution contrast between the exposed part and the unexposed part of the coating film can be fully obtained by performing the post-exposure heating process. If the heating temperature is below 70°C, the acid generated in the exposed part will not diffuse to the unexposed part, and a good dissolution contrast can be obtained. The heating time in the post-exposure heating process is preferably 20 seconds to 600 seconds. If the heating time is more than 20 seconds, the temperature history of the entire coating film can be made uniform. If the heating time is less than 600 seconds, the acid generated in the exposed part will not diffuse to the unexposed part, and a good dissolution contrast can be obtained. As a method for heating the substrate after the exposure process in the post-exposure heating process, for example, a heating plate, an oven or a furnace can be used.

[0235] [Development process]

[0236] When forming a cured resin film having a predetermined pattern, after the exposure step, a post-exposure heating step is performed as needed, and then a developing step of developing the unexposed portion of the coating film is performed. As the developer used in the developing step, any alkaline aqueous solution conventionally used in the development of a photosensitive resin composition or a photosensitive coloring composition can be used.

[0237] The alkaline aqueous solution is not particularly limited, and examples thereof include aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, etc.; aqueous solutions of amine compounds such as ethylamine, diethylamine, dimethylethanolamine, etc.; aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide, etc.; aqueous solutions of p-phenylenediamine compounds 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-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and sulfates, hydrochlorides, or p-toluenesulfonates thereof, etc. Among these alkaline aqueous solutions, aqueous solutions of p-phenylenediamine compounds are preferably used.

[0238] If necessary, one or two or more additives such as a defoaming agent and a surfactant may be added to the alkaline aqueous solution.

[0239] The development conditions such as the development temperature and the development time in the development step can be appropriately determined according to the composition of the photosensitive resin composition, the composition of the developer, the thickness of the coating film, and the like.

[0240] In the development step, it is preferred that the unexposed portion of the coating film is developed by dissolving it with the alkaline aqueous solution, followed by washing with water and drying.

[0241] [Post-baking process]

[0242] In this embodiment, a post-baking process is performed after the development process, that is, the photocured coating film is thermally cured to form a resin cured film. The heating temperature and heating time in the post-baking process are not particularly limited and can be appropriately set according to the composition of the photosensitive resin composition or the photosensitive coloring composition, the thickness of the coating film, the material of the substrate, etc.

[0243] The heating temperature in the post-baking process can be set to, for example, 50°C to 210°C. If the heating temperature is below 210°C, a material with low heat resistance can be used as the material of the color filter. For example, in the case of forming a coloring pattern of a color filter using a resin substrate as a substrate for forming a resin cured film, the heating temperature can be set to below 150°C, below 120°C, or below 100°C. If the heating temperature is below 150°C, a coloring pattern of a colorant (E) with poor heat resistance containing a material that was previously difficult to use as a coloring pattern can be formed, and the degradation of the colorant (E) can be suppressed. In addition, when the heating temperature is below 150°C, a coloring pattern can be formed on a substrate with poor heat resistance that was previously difficult to use as a substrate for a color filter. In addition, when the heating temperature is below 150°C, it is preferred because the energy required for curing the coating film is reduced.

[0244] If the heating temperature in the post-baking process is 50°C or higher, the resin (A) and the reactive diluent (B) are fully cross-linked, so that a resin cured film having sufficient hardness and solvent resistance can be obtained. In addition, if the heating temperature is 50°C or higher, a short heating time in the post-baking process is sufficient, and a resin cured film can be formed efficiently. The heating temperature in the post-baking process is more preferably 60°C or higher, and further preferably 70°C or higher.

[0245] The heating time in the post-baking step can be appropriately selected depending on the heating temperature, the thickness of the coating film, the composition of the photosensitive resin composition, etc., and can be set to, for example, 10 minutes to 4 hours, preferably 20 minutes to 2 hours.

[0246] The cured resin film of the present embodiment is composed of a cured product of the photosensitive resin composition of the present embodiment or the photosensitive coloring composition of the present embodiment, and therefore has sufficient hardness and solvent resistance.

[0247] The cured resin film of this embodiment can be suitably used as a material for various insulating films such as a protective film provided on a color filter, an insulating film provided between electrodes of a touch panel, and an interlayer insulating film of a thin film transistor (TFT).

[0248] <Color Filters>

[0249] Next, the color filter according to this embodiment will be described in detail.

[0250] Figure 1 This is a schematic cross-sectional view showing an example of the color filter according to this embodiment. Figure 1 The color filter shown includes: a substrate 1 ; RGB pixels 2 formed on one surface 1 a of the substrate 1 ; black matrices 3 formed at boundaries between the pixels 2 ; and a protective film 4 formed on the pixels 2 and the black matrix 3 .

[0251] As Figure 1 The substrate 1 used for the color filter shown is not particularly limited, and a substrate composed of a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyamideimide substrate, a polyimide substrate, an aluminum substrate, a printed wiring substrate, an array substrate, a PET substrate, etc. can be appropriately used according to the application. When an organic raw material substrate such as a resin substrate is used, a low-temperature heat treatment process is required, and the photosensitive resin composition of the present embodiment and the photosensitive coloring composition of the present embodiment can further exert the effect. In addition, for example, when a dye is used as a colorant (E), the photosensitive coloring composition of the present embodiment is used and a resin substrate such as a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyamideimide substrate, a polyimide substrate, a PET substrate, etc. is used as Figure 1 The color filter obtained by using the substrate 1 used in the color filter shown is suitable.

[0252] Figure 1 At least one of the pixels 2 and the black matrix 3 in the color filter shown is a colored pattern composed of a cured product of the photosensitive coloring composition of the present embodiment, wherein the photosensitive coloring composition comprises a resin composition containing a resin (A) and a solvent (D), a reactive diluent (B), a photopolymerization initiator (C), a colorant (E), and additives contained as needed.

[0253] As the protective film 4, a protective film made of a known material can be used. The protective film 4 may be a resin cured film made of a cured product of the photosensitive coloring composition of the present embodiment, the photosensitive coloring composition comprising a resin composition containing a resin (A) and a solvent (D), a reactive diluent (B), a photopolymerization initiator (C), and additives contained as needed.

[0254] exist Figure 1 In the color filter of the present embodiment shown, the configuration other than the materials of the pixels 2 and the black matrix 3 can adopt a known configuration. Figure 1 The color filter shown is an example of the color filter of the present invention, and the present invention is not limited to Figure 1 Example shown.

[0255] Next, a method for manufacturing the color filter according to this embodiment will be described.

[0256] First, in Figure 1 Pixels 2 of RGB and a black matrix 3 are sequentially formed on one surface 1a of the substrate 1. The pixels 2 and the black matrix 3 can be manufactured by the above-mentioned method for manufacturing a cured resin film of this embodiment (photolithography).

[0257] Next, a protective film 4 is formed on the pixel 2 and the black matrix 3. The protective film 4 can be formed by a known formation method. For example, the protective film 4 can be formed by the above-mentioned method for producing a cured resin film of this embodiment.

[0258] Through the above process, we can get Figure 1 The color filter of this embodiment is shown.

[0259] The color filter of the present embodiment has a colored pattern (pixel 2 and black matrix 3) composed of a cured product of the above-mentioned photosensitive coloring composition. Therefore, the colored pattern in the color filter of the present embodiment has sufficient hardness and solvent resistance.

[0260] <Image Display Component>

[0261] The image display element of this embodiment has a color filter of this embodiment with sufficient hardness and solvent resistance. Examples of the image display element of this embodiment include, for example, a liquid crystal display element, an organic EL display element, a solid-state imaging device, etc. Since the image display element of this embodiment has the above-mentioned color filter, it can achieve high brightness display.

[0262] Example

[0263] The present invention will be specifically described below using examples and comparative examples. It should be noted that the examples shown below are intended to make the contents of the present invention easier to understand. The present invention is not limited to these examples.

[0264] A synthesis example of the resin (A) is shown below.

[0265] [Synthesis example 1]

[0266] In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer and a gas inlet tube, 184.6 g of propylene glycol monomethyl ether acetate as a polymerization solvent was placed, and the temperature was raised to 98° C. while stirring and replacing the atmosphere with nitrogen.

[0267] Next, a mixture of 114.3 g (0.50 mol) of 2-hydroxyethyl methacrylate, 75.2 g (0.20 mol) of ethylene glycol monoacetoacetate monomethacrylate, 52.7 g (0.30 mol) of methyl methacrylate, 29.6 g of dimethyl 2,2′-azobis(isobutyrate) (polymerization initiator), and 87.2 g of propylene glycol monomethyl ether acetate was added dropwise from a dropping funnel to the flask over 3 hours.

[0268] After the dropwise addition was completed, the mixture was stirred at 98°C for 3 hours to perform a copolymerization reaction, thereby generating a hydroxyl-containing (meth) acrylic resin (a-0) as a copolymer. Then, the interior of the flask was replaced with air, and 24.8 g (0.10 mol) of 2-acryloyloxyethyl isocyanate, 0.27 g of dibutyltin dilaurate (DBTDL) (addition reaction catalyst), 0.53 g of methylhydroquinone (polymerization inhibitor), and 5.3 g of propylene glycol monomethyl ether acetate were added to the reaction solution in which the hydroxyl-containing (meth) acrylic resin (a-0) was synthesized, and an addition reaction was performed at 60°C for 2 hours.

[0269] Thus, a (meth)acryloyloxy group was introduced into a part of the hydroxyl groups derived from 2-hydroxyethyl methacrylate.

[0270] Next, 53.4 g (0.20 mol) of 1,2,3,6-tetrahydrophthalic anhydride, 1.3 g of lithium naphthenate (addition reaction catalyst), and 66.0 g of propylene glycol monomethyl ether acetate were added, and an addition reaction was performed at 78° C. for 3 hours.

[0271] Thus, carboxyl groups were introduced into part of the hydroxyl groups derived from 2-hydroxyethyl methacrylate.

[0272] Next, 306.8 g of propylene glycol monomethyl ether acetate was added to the reaction solution as a solvent (additional solvent for the composition), thereby obtaining a resin composition of the copolymer P1 of Synthesis Example 1 as the resin (A) according to the present embodiment.

[0273] [Synthesis Examples 2 to 18]

[0274] Resin compositions of copolymers P2 to P18 of Synthesis Examples 2 to 18 were obtained in the same manner as in Synthesis Example 1 except that the raw materials described in Table 1 were used in the ratios described in Table 1.

[0275] The weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn), acid value, functional group (active methylene group, epoxy group, oxetane group, blocked isocyanate group, silyl group) equivalent, and ethylenically unsaturated group equivalent of the copolymers P1 to P18 contained in the resin compositions of Synthesis Examples 1 to 18 thus obtained were determined. The results are shown in Table 1.

[0276] [Comparative Synthesis Example 1]

[0277] In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer and a gas introduction tube, 201.9 g of propylene glycol monomethyl ether acetate as a polymerization solvent was placed, and the temperature was raised to 98° C. while stirring and nitrogen substitution was carried out.

[0278] Next, 90.7 g (0.34 mol) of 2-hydroxyethyl methacrylate, 75.1 g (0.17 mol) of ethylene glycol monoacetoacetate monomethacrylate, 99.2 g (0.49 mol) of methyl methacrylate, 32.3 g of dimethyl 2,2′-azobis(isobutyrate) (polymerization initiator), and 95.4 g of propylene glycol monomethyl ether acetate were added dropwise from a dropping funnel to the flask over 3 hours.

[0279] After the dropwise addition was completed, the mixture was stirred at 98°C for 3 hours to perform a copolymerization reaction, thereby generating a functional group-containing resin (ca) as a comparative copolymer. Then, the interior of the flask was replaced with air, and 52.7 g (0.17 mol) of 1,2,3,6-tetrahydrophthalic anhydride, 1.3 g of lithium cyclohexaneate (addition reaction catalyst), 0.53 g of methylhydroquinone (polymerization inhibitor), and 44.8 g of propylene glycol monomethyl ether acetate were added to the reaction solution in which the functional group-containing resin (ca) was synthesized, and an addition reaction was performed at 78°C for 3 hours.

[0280] Next, 307.9 g of propylene glycol monomethyl ether acetate was added as a solvent (additional solvent for the composition) to the reaction solution, thereby obtaining a resin composition of the copolymer cP1 of Comparative Synthesis Example 1.

[0281] [Comparative Synthesis Examples 2 to 4]

[0282] Resin compositions of copolymers cP1 to cP4 of Comparative Synthesis Examples 1 to 4 were obtained in the same manner as in Comparative Synthesis Example 1, except that the raw materials described in Table 2 were used in the proportions described in Table 2.

[0283] The weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn), acid value, functional group (active methylene group, epoxy group, oxetane group, blocked isocyanate group, silyl group) equivalent, and ethylenically unsaturated group equivalent of the copolymers cP1 to cP4 contained in the resin compositions of Comparative Examples 1 to 4 obtained in this way were determined. The results are shown in Table 2.

[0284] [Comparative Synthesis Example 5]

[0285] In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 177.0 g of propylene glycol monomethyl ether acetate as a polymerization solvent was placed, and the temperature was raised to 118° C. while stirring and nitrogen substitution was performed.

[0286] Next, a mixture of 153.9 g (0.7 mol) of glycidyl methacrylate, 104.9 g (0.27 mol) of MOI-BP, 10.2 g (0.03 mol) of dicyclopentyl methacrylate, 32.8 g of tert-butyl peroxy-2-ethylhexanoate (polymerization initiator), and 70.0 g of propylene glycol monomethyl ether acetate was added dropwise from a dropping funnel to the flask over 3 hours. After the addition was completed, the mixture was heated to 120° C. and stirred for 30 minutes to perform a copolymerization reaction, thereby generating a copolymer.

[0287] Then, the flask was replaced with air, and 78.0 g (0.7 mol) of acrylic acid, 1.4 g of triphenylphosphine (addition reaction catalyst) and 0.7 g of methyl hydroquinone (polymerization inhibitor) were added to the above copolymer solution, and the reaction was continued at 110° C. for 10 hours. The purpose was to cleave the epoxy group from glycidyl methacrylate through the reaction of the epoxy group from glycidyl methacrylate with acrylic acid and introduce ethylenic unsaturated bonds into the side chain of the copolymer, but gelation occurred in the middle of the reaction. It should be noted that the reaction was terminated before 20.1 g (0.13 mol) of succinic anhydride was added to the above copolymer solution.

[0288] The functional group (blocked isocyanate group) equivalent and the ethylenically unsaturated group equivalent of the resin of Comparative Synthesis Example 5 were determined. The results are shown in Table 2.

[0289]

[0290] Table 2

[0291]

[0292] *1: Unit: The number of moles relative to 100 moles of all monomers (M) constituting the hydroxyl group-containing (meth)acrylic resin (a-0).

[0293] <Preparation of Photosensitive Coloring Composition>

[0294] (Examples 1 to 18, Comparative Examples 1 to 5)

[0295] The copolymers P1 to P18 and cP1 to cP4 of Synthesis Examples 1 to 18 and Comparative Synthesis Examples 1 to 4 as the copolymer (A) were mixed with the components (B), (C), and (E) shown in Table 3 in the ratios shown in Table 3 to prepare the photosensitive coloring compositions R1 to R18 and cR1 to cR4 of Examples 1 to 18 and Comparative Examples 1 to 4, respectively. In Comparative Example 5, a product obtained by adding 3% by mass of a dimer of 2-acryloyloxyethyl isocyanate to the copolymer P2 of Synthesis Example 2 was used as the copolymer (A). The obtained copolymer (A) was mixed with the components (B), (C), and (E) shown in Table 3 in the ratios shown in Table 3 to prepare the photosensitive coloring composition cR5 of Comparative Example 5.

[0296] It should be noted that the amount of the copolymer in the resin composition in Table 3 does not include the polymerization solvent used when synthesizing the copolymer. In addition, the amount of the solvent (D) in Table 3 is the total amount of the polymerization solvent used when synthesizing the copolymer in the resin composition and the solvent added when preparing the resin composition.

[0297]

[0298] <Evaluation of Photosensitive Coloring Composition>

[0299] The photosensitive coloring compositions R1 to R18 and cR1 to cR5 prepared in Examples 1 to 18 and Comparative Examples 1 to 5 were evaluated by the methods shown below.

[0300] (1) Developability

[0301] The photosensitive coloring compositions R1 to R18 and cR1 to cR5 prepared in Examples 1 to 18 and Comparative Examples 1 to 5 were applied to a 5 cm square glass substrate (alkali-free glass substrate) by spin coating so that the thickness after exposure was 2.5 μm (coating step). The glass substrate coated with the photosensitive coloring composition was heated at 100° C. for 3 minutes to volatilize the solvent and dry the coated film (pre-baking step).

[0302] Next, an ultra-high pressure mercury lamp was used to emit 200 mJ / cm 2The light is irradiated onto the surface of the dried coating film through a photomask (exposure process). The exposure process is carried out by setting the photomask at a position 100 μm apart from the coating film. As a photomask, a photomask having a line and space pattern with a width of 3 to 100 μm is used. Next, the Semiclean DL-A10 developer (manufactured by Yokohama Oil & Fats Industries) (5 times diluted) is 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 portion (development process). The glass substrate with the coating film after the development process is placed in a dryer at 100°C for 30 minutes to thermally cure the coating film (post-baking process) to obtain a colored pattern.

[0303] The colored pattern thus obtained was observed using an electron microscope S-3400 manufactured by Hitachi HiTech Nologis, and the minimum line width (minimum development dimension) that can be developed and the presence or absence of residues in the unexposed portion between the patterns that can be developed were evaluated. The presence or absence of residues was evaluated based on the following criteria. The results are shown in Table 4 or Table 5.

[0304] "Evaluation criteria for residues"

[0305] ○: No residue in the unexposed area between the developable patterns

[0306] ×: There is residue in the unexposed area between the patterns that can be developed

[0307] (2) Pencil hardness

[0308] The photosensitive coloring compositions R1 to R18 and cR1 to cR5 prepared in Examples 1 to 18 and Comparative Examples 1 to 5 were applied on a 5 cm long by 5 cm wide square glass substrate (alkali-free glass substrate) by spin coating, and heated at 100° C. for 3 minutes to volatilize the solvent to form a coating film. 2 The coating film was irradiated with light having a wavelength of 365 nm at an exposure amount of 100 to photocuring. Next, the glass substrate having the coating film after photocuring was placed in a drying machine at 100° C. for 30 minutes to thermally cure the coating film (post-baking process) to obtain a resin cured film with a film thickness of 2.5 μm.

[0309] The pencil hardness of the resin cured film thus produced was measured using a pencil hardness tester (No. 553-M, manufactured by Yasuda Seiki Co., Ltd.) in accordance with JIS K5600-5-4 and evaluated based on the following criteria.

[0310] "Evaluation criteria for pencil hardness"

[0311] ○: Pencil hardness is 3H or above

[0312] ×: Pencil hardness less than 3H

[0313] (3) Solvent resistance

[0314] In the same manner as in the case of the evaluation of the pencil hardness (2) above, a glass substrate having a resin cured film was prepared, and the absorption spectrum of the resin cured film was measured using a spectrophotometer (UV-1650PC, manufactured by Shimadzu Corporation). In addition, 200 mL of propylene glycol monomethyl ether acetate was placed in a 500 mL glass bottle with a lid, and the mixture was allowed to stand at a temperature of 23°C. A glass substrate having a resin cured film was placed in the glass bottle, immersed in propylene glycol monomethyl ether acetate, and allowed to stand at 23°C for 15 minutes. Then, the glass substrate having a resin cured film was taken out, and the absorption spectrum of the resin cured film was measured using a spectrophotometer (UV-1650PC, manufactured by Shimadzu Corporation) in the same manner as before being immersed in propylene glycol monomethyl ether acetate.

[0315] The color change (ΔE * ab), the solvent resistance of the cured resin film was evaluated according to the following criteria. The results are shown in Table 4 or Table 5.

[0316] "Evaluation criteria for solvent resistance"

[0317] ○: ΔE * ab less than 3.0

[0318] ×: ΔE * ab is 3.0 or more

[0319] (4) Comprehensive judgment

[0320] The cured resin films composed of the cured products of the photosensitive coloring compositions R1 to R18 and cR1 to cR5 prepared in Examples 1 to 18 and Comparative Examples 1 to 5 were evaluated based on the criteria shown below. The results are shown in Table 4 or Table 5.

[0321] “Evaluation Benchmarks”

[0322] ○: All of the following items are satisfied.

[0323] (1) The minimum development size is less than 15 μm, and there is no residue in the unexposed area between the patterns that can be developed

[0324] (2) The pencil hardness of the resin cured film is 3H or above

[0325] (3) Color change ΔE in evaluation of solvent resistance of cured resin film * ab less than 3.0

[0326] ×: Any one or more items among the above items of ○ are not satisfied.

[0327] Table 4

[0328]

[0329] Table 5

[0330]

[0331] As shown in Table 4, the photosensitive coloring compositions R1 to R18 of Examples 1 to 18 all had a minimum development size of 15 μm or less, and all unexposed portions between developable patterns had no residue, and thus were confirmed to have excellent alkali developability.

[0332] In addition, as shown in Table 4, the pencil hardness of the resin cured film composed of the cured product obtained by photocuring the coating film formed using the photosensitive coloring compositions R1 to R18 of Examples 1 to 18 and then thermally curing at a low temperature of 100°C was 3H or more, which was excellent in hardness. In addition, the evaluation of solvent resistance of the above-mentioned resin cured film was ○, and it was confirmed that it had excellent solvent resistance.

[0333] On the other hand, as shown in Table 5, the photosensitive coloring compositions cR1 to cR5 of Comparative Examples 1 to 5 were insufficient in alkali developability, pencil hardness, or solvent resistance.

[0334] In more detail, the ethylenically unsaturated group equivalent of the copolymers cP1 to cP3 obtained from Comparative Synthesis Examples 1 to 3 contained in the photosensitive coloring compositions cR1 to cR3 of Comparative Examples 1 to 3 is 0. Therefore, the result is that the alkali developability, hardness, and solvent resistance of the cured resin film are poor. In addition, the copolymer cP4 obtained from Comparative Synthesis Example 4 contained in the photosensitive resin composition cR4 of Comparative Example 4 produces a dimer of 2-acryloyloxyethyl isocyanate as a by-product during synthesis. Therefore, the result is that the alkali developability, hardness, and solvent resistance of the cured resin film are poor. In addition, the photosensitive resin composition cR5 of Comparative Example 5 uses a composition obtained by adding a dimer of 2-acryloyloxyethyl isocyanate to the copolymer P2 obtained in Synthesis Example 2. Therefore, Comparative Example 5 is also the same as Comparative Example 4, and the result is that the alkali developability, hardness, and solvent resistance of the cured resin film are poor.

[0335] The changes over time of the resin composition obtained this time were checked, and as a result, a tendency was observed that the structural unit having an active methylene group, the structural unit having a blocked isocyanate group, the structural unit having a silyl group, and the structural unit having an epoxy group became better in this order.

[0336] Industrial Applicability

[0337] According to the present invention, a photosensitive resin composition and a photosensitive coloring composition can be provided, which have excellent developability and good low-temperature curing properties, and can form a resin cured film with sufficient hardness and solvent resistance. In addition, according to the present invention, a resin cured film with sufficient hardness and solvent resistance can be provided, which is composed of a cured product of a photosensitive resin composition. A color filter with sufficient hardness and solvent resistance can be provided, which has a colored pattern composed of a cured product of the photosensitive coloring composition of the present invention. In addition, an image display element can be provided, which has the color filter. The photosensitive resin composition and the photosensitive coloring composition of the present invention can be preferably used as, for example, a transparent film, a protective film, an insulating film, a protective layer, a photosensitive spacer, a black matrix, a black columnar spacer, and an etching resist for a color filter.

[0338] Description of Reference Numerals

[0339] 1···substrate, 2···pixel, 3···black matrix, 4···protective film.

Claims

1. A photosensitive resin composition, characterized in that Contains at least a resin (A), a reactive diluent (B), a photopolymerization initiator (C) and a solvent (D), The resin (A) is an ethylenically unsaturated group and a carboxyl group-modified (meth) acrylic resin, The ethylenically unsaturated group and carboxyl modified (meth) acrylic resin is an addition reaction product of a hydroxyl-containing (meth) acrylic resin (a-0), a compound containing an isocyanate group and an ethylenically unsaturated group (a-4), and a polyacid or its anhydride (a-5). The hydroxyl-containing (meth) acrylic resin (a-0) is a copolymer comprising at least a structural unit derived from a hydroxyl-containing (meth) acrylate (m-1) and a structural unit derived from a (meth) acrylate (m-2), wherein the (meth) acrylate (m-2) has one or more groups selected from an active methylene group, an active methine group, an epoxy group, an oxetane group, a blocked isocyanate group and a silyl group. 2 . The photosensitive resin composition according to claim 1 , wherein the hydroxyl-containing (meth)acrylic resin (a-0) is a copolymer of the hydroxyl-containing (meth)acrylate (m-1), the (meth)acrylate (m-2), and another monomer (m-3). 3 . The photosensitive resin composition according to claim 2 , wherein the other monomer (m-3) is an alkyl (meth)acrylate having an alkyl group with 1 to 12 carbon atoms.

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein when all monomers as a polymerization raw material of the hydroxyl-containing (meth) acrylic resin (a-0) are collectively referred to as "monomer M", among the monomers (M), The content of the hydroxyl-containing (meth)acrylate (m-1) is 30 to 95 mol%, The content of the (meth)acrylate (m-2) is 5 to 50 mol %. 5 . The photosensitive resin composition according to claim 1 , wherein the compound (a-4) containing an isocyanate group and an ethylenically unsaturated group is an isocyanate group-containing (meth)acrylate (a-4a).

6. The photosensitive resin composition according to claim 5, wherein the isocyanate group-containing (meth)acrylate (a-4a) is an isocyanate group-containing (meth)acrylate having a polyoxyalkylene structure or an isocyanate group-containing (meth)acrylate having two or more (meth)acryloyloxy groups. 7 . The photosensitive resin composition according to claim 1 , wherein the polybasic acid or its anhydride (a-5) is a tricarboxylic acid or its anhydride. 8 . The photosensitive resin composition according to claim 1 , wherein the acid value of the resin (A) is 10 to 300 KOHmg / g. 9 . The photosensitive resin composition according to claim 1 , wherein the ethylenically unsaturated group equivalent of the resin (A) is 200 to 5000 g / mol. 10 . The photosensitive resin composition according to claim 1 , wherein the modification rate of the resin (A) is 20 to 90%. 11 . The photosensitive resin composition according to claim 1 , wherein an addition amount of the compound (a-4) containing an isocyanate group and an ethylenically unsaturated group is 1 to 60 mol relative to 100 mol of the monomer (M). 12 . The photosensitive resin composition according to claim 1 , wherein the amount of the polybasic acid or its anhydride (a-5) added is 1 to 60 mol relative to 100 mol of the monomer (M).

13. The photosensitive resin composition according to any one of claims 1 to 3, wherein the weight average molecular weight of the resin (A) is 1,000 to 50,000, The molecular weight distribution (Mw / Mn) of the resin (A) is 1.3 to 5.

0.

14. The photosensitive resin composition according to any one of claims 1 to 3, wherein the amount of the photosensitive resin composition is 100 parts by mass of the total amount of the components other than the solvent (D). Containing 10 to 85 parts by mass of the resin (A), Containing 10 to 85 parts by mass of the reactive diluent (B), 0.1 to 30 parts by mass of the photopolymerization initiator (C) is contained, The solvent (D) is contained in an amount of 30 to 1,000 parts by mass.

15. A photosensitive coloring composition comprising the photosensitive resin composition according to any one of claims 1 to 3 and a colorant (E), With respect to 100 parts by mass of the total of the components other than the solvent (D), The colorant (E) is contained in an amount of 4 to 79 parts by mass. 16 . A cured resin film, comprising a cured product of the photosensitive resin composition according to claim 1 . 17 . A color filter having a colored pattern composed of a cured product of the photosensitive coloring composition according to claim 15 . 18 . An image display device comprising the color filter according to claim 17 .

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