TW202406946A - Photosensitive resin composition, resin cured film and image display element - Google Patents

Abstract

Provided are a photosensitive resin composition and a photosensitive coloring composition which exhibit excellent developability and favorable low-temperature curability, and which can be used to form a cured resin film having sufficient hardness and solvent resistance. This photosensitive resin composition contains a resin (A), a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D). The resin (A) is a product of an addition reaction between: a hydroxyl group-containing (meth)acrylic resin (a-0); a compound (a-4) having an isocyanate group and an ethylenically unsaturated group; and a polybasic acid or anhydride thereof (a-5). Component (a-0) is a copolymer that contains a structural unit derived from a hydroxyl group-containing (meth)acrylate (m-1) 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

Photosensitive resin composition, resin cured film and image display element

The present invention relates to a photosensitive resin composition, a resin cured film and an image display element. This application claims priority based on Japanese Application No. 2022-118208 filed in Japan on July 25, 2022, the content of which is incorporated herein by reference.

Conventionally, as image display elements such as monitors, there are image display elements equipped with color filters. Generally speaking, a color filter is formed by baking a resin composition on a substrate at a temperature exceeding 200°C to harden the resin composition. In recent years, as displays have become more flexible and wearable, substrate materials for color filters have been switching from glass to organic materials such as resin. In addition, in order to realize image display elements with further high brightness and high contrast, the colorants used in color filters are switching from pigments to dyes and/or fluorescent compounds and quantum dots. .

Conventionally, there is a description of a resin composition used as a material of a color filter, for example, Patent Document 1. Patent Document 1 discloses a colored photocurable resin composition, including: a photocurable compound (A), a binder resin (B), a photoinitiator (D), and a solvent (E), wherein the photocurable compound (A) is carboxyl group-containing dipenterythritol pentaacrylate, and the binder resin (B) contains at least one of a tetrahydropyran structure or a tetrahydrofuran structure in the main chain structure. [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2015-184675

[Problem to be solved by the invention]

Organic 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. Due to these factors, it is desired to lower the heating temperature for curing resin compositions used as materials for color filters. Specifically, depending on the heat resistance of the substrate material and the colorant material, the heating temperature for hardening the resin composition used as the color filter material may be required to be set to 80 to 150°C.

However, if the heating temperature for curing conventional resin compositions is lowered, a cured product with sufficient hardness and solvent resistance cannot be obtained. Color filters composed of hardened materials with insufficient hardness are easily damaged. Therefore, in an image display device equipped with a color filter, there is a risk of display failure caused by scratches on the color filter. Furthermore, in color filters included in image display elements, in order to improve 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. Furthermore, dyes have higher solubility in solvents than pigments. Therefore, when the solvent resistance of the color filter is insufficient, the dye contained in the color filter may dissolve in the solvent, and the chromaticity of the color filter may change.

The present invention was made in view of the above-mentioned circumstances, and its object is to provide a photosensitive resin composition and a photosensitive coloring composition that can form a resin having excellent developability and good low-temperature curability, and having sufficient hardness and solvent resistance. Hardened film. Furthermore, an object of the present invention is to provide a resin cured film composed of a cured product of the photosensitive resin composition of the present invention and having sufficient hardness and solvent resistance. Furthermore, an object is to provide a color filter having a color pattern composed of a cured product of the photosensitive coloring composition of the present invention, and having sufficient hardness and solvent resistance. Furthermore, an object is to provide an image display element including the color filter. [Means to solve the problem]

The present invention includes the following aspects. [1]. A photosensitive resin composition characterized by: It contains at least resin (A), reactive diluent (B), photopolymerization initiator (C) and solvent (D), The aforementioned resin (A) is ethylenically unsaturated and carboxyl modified (meth)acrylic resin, The aforementioned ethylenically unsaturated group and carboxyl modified (meth)acrylic resins are (meth)acrylic resins (a-0) containing hydroxyl groups, compounds (a-4) containing isocyanato groups and ethylenically unsaturated groups, and Addition reaction product of polybasic acid or its anhydride (a-5), The aforementioned hydroxyl-containing (meth)acrylic resin (a-0) is a copolymer containing at least the following structural units: a structural unit derived from the hydroxyl-containing (meth)acrylate (m-1), and, derived from (Meth)acrylate having at least one group selected from the group consisting of active methylene, active methine, epoxy group, oxetanyl group, blocked isocyanate group and silane group (m-2) structural unit. [2]. The photosensitive resin composition according to [1], wherein the hydroxyl-containing (meth)acrylic resin (a-0) is the hydroxyl-containing (meth)acrylate (m-1), A copolymer of the aforementioned (meth)acrylate (m-2) and other monomers (m-3). [3]. The photosensitive resin composition according to [2], wherein the other monomer (m-3) is an alkyl (meth)acrylate having an alkyl group having 1 to 12 carbon atoms. [4]. The photosensitive resin composition according to any one of [1] to [3], wherein all the monomers to be polymerized raw materials for the hydroxyl-containing (meth)acrylic resin (a-0) When the overall setting is "monomer M", in the aforementioned monomer (M), the content of the aforementioned hydroxyl-containing (meth)acrylate (m-1) is 30 to 95 mol%, and the aforementioned (meth)acrylic acid The content of ester (m-2) is 5~50 mol%. [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-containing compound. (meth)acrylate (a-4a). [6]. The photosensitive resin composition according to [5], wherein the isocyanate group-containing (meth)acrylate (a-4a) is an isocyanate group-containing one having a polyoxyalkylene structure. (meth)acrylate, or isocyanato group-containing (meth)acrylate having two or more (meth)acryloxy groups. [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. [8]. The photosensitive resin composition according to any one of [1] to [7], wherein the acid value of the resin (A) is 10 to 300KOHmg/g. [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. [10]. The photosensitive resin composition according to any one of [1] to [9], wherein the denaturation rate of the resin (A) is 20 to 90%. [11]. The photosensitive resin composition according to any one of [1] to [10], wherein the added amount of the compound (a-4) containing an isocyanato group and an ethylenically unsaturated group is, It is 1 to 60 moles relative to 100 moles of the aforementioned monomer (M). [12]. The photosensitive resin composition according to any one of [1] to [11], wherein the addition amount of the aforementioned polybasic acid or its anhydride (a-5) is relative to the aforementioned monomer (M) 100 moles are 1~60 moles. [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, and the molecular weight distribution (Mw) of the resin (A) is /Mn) is 1.3~5.0. [14]. The photosensitive resin composition according to any one of [1] to [13], which contains 10 to 85 parts by mass relative to 100 parts by mass of the total components after excluding the solvent (D). parts of the aforementioned resin (A), containing 10 to 85 parts by mass of the aforementioned reactive diluent (B), containing 0.1 to 30 parts by mass of the aforementioned photopolymerization initiator (C), containing 30 parts by mass to 1000 parts by mass of the aforementioned solvent (D). [15]. A photosensitive coloring composition containing the photosensitive resin composition according to any one of [1] to [14] and a coloring agent (E), relative to the total components after excluding the aforementioned solvent (D) 100 parts by mass contains 4 to 79 parts by mass of the aforementioned colorant (E). [16]. A resin cured film composed of a cured product of the photosensitive resin composition described in any one of [1] to [14]. [17]. A color filter having a coloring pattern composed of a hardened product of the photosensitive coloring composition described in [15]. [18]. An image display element equipped with the color filter described in [17]. [Effects of the invention]

The present invention can provide a photosensitive resin composition and a photosensitive colored composition that can form a resin cured film that has excellent developability and good low-temperature curability, and has sufficient hardness and solvent resistance. Furthermore, the present invention can provide a resin cured film composed of a cured product of the photosensitive resin composition of the present invention and having sufficient hardness and solvent resistance. Furthermore, it is possible to provide a color filter having a colored pattern composed of a cured product of the photosensitive colored composition of the present invention, and having sufficient hardness and solvent resistance. Furthermore, an image display element including the color filter can be provided.

[The best way to implement the invention]

Hereinafter, the photosensitive resin composition, photosensitive colored composition, resin cured film, color filter and image display element of the present invention will be described in detail. However, the present invention is not limited to the embodiments shown below. In this specification, "(meth)acrylic acid" means at least one selected from methacrylic acid and acrylic acid. "(Meth)acrylate" means at least one selected from the group consisting of methacrylate and acrylate, and "(meth)acrylyl" means at least one selected from the group consisting of methacrylate and acrylyl. 1 meaning.

＜Photosensitive resin composition＞ The photosensitive resin composition of this embodiment contains at least a resin (A), a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D).

[Resin (A)] The resin (A) contained in the photosensitive resin composition of this embodiment is an ethylenically unsaturated group and a carboxyl group 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 having a finer pattern can be obtained. By using a carboxyl-modified (meth)acrylic resin, the developability of the photosensitive resin composition can be improved, and the photosensitive resin composition can be cured at a lower temperature, thereby improving the hardness or solvent resistance of the cured product. Examples of the ethylenically unsaturated group include vinyl, allyl, (meth)acryloxy, and the like. The aforementioned ethylenically unsaturated group is preferably a (meth)acryloxy group.

The so-called "ethylenically unsaturated group-modified" resin and "carboxyl-modified" resin refer to the addition of only compounds containing ethylenically unsaturated groups or only the addition of compounds containing carboxyl groups to the raw resin to introduce ethylenically unsaturated groups. The meaning of resin derived from saturated or carboxyl groups. The so-called "ethylenically unsaturated group and carboxyl group modified" resin refers to a resin obtained by adding an ethylenically unsaturated group-containing compound and a carboxyl group-containing compound to the raw material resin to introduce ethylenically unsaturated groups and carboxyl groups. . Regarding the order of the addition reaction of the ethylenically unsaturated group-containing compound and the carboxyl group-containing compound of the raw resin, whichever one may be performed first may be used, or they may be performed at the same time.

The aforementioned ethylenically unsaturated group and carboxyl modified (meth)acrylic resins are (meth)acrylic resins (a-0) containing hydroxyl groups, compounds (a-4) containing isocyanato groups and ethylenically unsaturated groups, and Addition reaction product of polybasic acid or its anhydride (a-5). By the reaction between the hydroxyl group of the (meth)acrylic resin (a-0) containing a hydroxyl group and the isocyanate group of the compound (a-4) containing an isocyanate group and an ethylenically unsaturated group, to introduce ethylenically unsaturated groups into resin (A). A carboxyl group is introduced into the resin (A) by reaction between the hydroxyl group of the hydroxyl-containing (meth)acrylic resin (a-0) and the polybasic acid or its anhydride (a-5). The introduction amount can be freely adjusted for the purpose of improving developability, low-temperature curability, hardness of the cured film, or solvent resistance.

On the other hand, by using (meth)acrylic acid or the like as a constituent monomer of a (meth)acrylic resin, a carboxyl group-containing (meth)acrylic resin in which a carboxyl group is directly introduced into the resin main chain can be obtained. In the case of such a carboxyl group-containing (meth)acrylic resin, for example, if a compound (a-4) containing an isocyanato group and an ethylenically unsaturated group described below is used to introduce an ethylenically unsaturated group, During denaturation, isocyanate dimers will be produced as by-products. The by-product does not have a developing group and has the disadvantage of lowering the developability of the photosensitive resin composition that is the object of the present invention, and is therefore undesirable. From this viewpoint, in the present embodiment, the ethylenically unsaturated group and carboxyl group modified (meth)acrylic resin is preferably a modified resin derived from the hydroxyl group-containing (meth)acrylic resin (a-0) described below, and the aforementioned The hydroxyl group-containing (meth)acrylic resin (a-0) does not contain carboxyl groups.

Furthermore, as an alternative to the aforementioned hydroxyl-containing (meth)acrylic resin (a-0) related to this embodiment, “epoxy group-containing (meth)acrylic resin in which epoxy groups are directly introduced into the resin main chain ” or “carboxyl group-containing (meth)acrylic resin in which carboxyl groups are directly introduced into the resin main chain”, by a compound other than “the compound (a-4) containing an isocyanate group and an ethylenically unsaturated group”. Introducing an ethylenically unsaturated group is undesirable since various disadvantages may occur. For example, an epoxy group-containing (meth)acrylic resin in which an epoxy group is directly introduced into the resin main chain is reacted with (meth)acrylic acid, or the "resin main chain" is reacted with (meth)acrylic acid. "Carboxyl group-containing (meth)acrylic resin" in which the carboxyl group is directly introduced into the chain is reacted with glycidyl (meth)acrylate, etc. to make (meth)acrylic acid which is an ethylenically unsaturated group When oxygen groups are introduced into the resin, disadvantages such as gelation may occur due to high-temperature reactions during synthesis, which is undesirable. Furthermore, when the epoxy group of the resin into which an ethylenically unsaturated group is introduced by the above method is ring-opened to generate a hydroxyl group, and the polybasic acid or its anhydride (a-5) is reacted with the hydroxyl group to introduce a carboxyl group. , which is undesirable due to disadvantages such as gelation due to the high-temperature reaction during synthesis.

[Hydroxy-containing (meth)acrylic resin (a-0)] The hydroxyl-containing (meth)acrylic resin (a-0) is a copolymer containing at least the following structural units: a structural unit derived from the hydroxyl-containing (meth)acrylate (m-1), and derived from a structural unit having (Meth)acrylate (meth)acrylate (meth)acrylate having at least one group selected from the group consisting of active methylene, active methine, epoxy group, oxetanyl group, blocked isocyanate group and silane group Structural unit of m-2) (hereinafter, simply referred to as "(meth)acrylate (m-2)"). If necessary, the aforementioned hydroxyl-containing (meth)acrylic resin (a-0) may also contain structural units derived from other monomers (m-3). In this specification, the total number of all monomers that serve as polymerization raw materials for the hydroxyl-containing (meth)acrylic resin (a-0) (that is, the hydroxyl-containing (meth)acrylate (m-1), The above-mentioned (meth)acrylate (m-2) and the above-mentioned other monomer (m-3) as an optional component) are collectively referred to as "monomer (M)". The amount of monomer (M) means the total amount of the aforementioned monomers (m-1), (m-2) and (m-3).

However, the so-called "structural unit derived from (meth)acrylate (m-1) containing a hydroxyl group" refers to a structure formed by radical polymerization of (meth)acrylate (m-1) containing a hydroxyl group. Specifically, the unit refers to a structural unit in which the polymerizable carbon-carbon double bond of the hydroxyl-containing (meth)acrylate (m-1) becomes a carbon-carbon single bond. Furthermore, "structural unit derived from (meth)acrylate (m-2)" refers to a structural unit formed by radical polymerization of (meth)acrylate (m-2), specifically ( The polymerizable carbon-carbon double bond of meth)acrylate (m-2) becomes the structural unit of carbon-carbon single bond.

[Hydroxy-containing (meth)acrylate (m-1)] 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)acryloxy group. Examples include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, (Meth)acrylates containing hydroxyl groups such as 4-hydroxybutyl (meth)acrylate and 2-hydroxy-3-phenoxypropyl (meth)acrylate. Among these, from the viewpoint of ease of acquisition and ease of denaturation reaction when introducing a (meth)acryloxy group and a carboxyl group into the resin (A), those having a hydroxyl group at the end of an alkyl group are preferred. The hydroxyalkyl (meth)acrylate is preferably a hydroxyalkyl (meth)acrylate having 2 to 4 carbon atoms, and the most preferred one is 2-hydroxyethyl (meth)acrylate.

The content of the hydroxyl-containing (meth)acrylate (m-1) relative to the monomer (M) is preferably 30 to 95 mol%, more preferably 40 to 80 mol%, and more preferably 45 ~70 mol%. When the content is 30 mol% or more, the amount of denaturation when introducing the (meth)acryloxy group and the carboxyl group can be sufficiently ensured, and a photosensitive resin composition with excellent developability can be obtained. This is a cured film that has excellent hardness and solvent resistance even when cured at low temperatures.

[(Meth)acrylic acid having at least one group selected from the group consisting of active methylene, active methine, epoxy group, oxetanyl group, blocked isocyanato group and silane group Esters (m-2)] In this embodiment, the (meth)acrylate (m-2) is a (meth)acrylate that does not have a hydroxyl group or a carboxyl group, and is selected from (meth)acrylic acid containing an active methylene group or an active methine group. Esters (m-2-1), (meth)acrylates (m-2-2) containing epoxy or oxetanyl groups, (meth)acrylates containing blocked isocyanato groups ( m-2-3), and silane group-containing (meth)acrylate (m-2-4). The functional group of (meth)acrylate (m-2) is because the functional group itself has cross-linkability by heat or light, or it is derived from (meth)acrylate (m-2) containing a hydroxyl group. The hydroxyl group of m-1) reacts to generate cross-linking, etc., which contributes to the improvement of hardness or solvent resistance when the photosensitive resin composition is cured at a low temperature.

In this embodiment, the content of (meth)acrylate (m-2) relative to the monomer (M) is preferably 5 to 50 mol%, more preferably 10 to 40 mol%, and more preferably 15~30 mol%. When the content is 5 mol% or more, the introduction amount of the functional group of the (meth)acrylate (m-2) can be sufficiently ensured, and a photosensitive resin composition with excellent developability can be obtained. A cured film having excellent hardness and solvent resistance is obtained even when cured at a low temperature. If the content is 50 mol% or less, the content of the hydroxyl-containing (meth)acrylate (m-1) can be sufficiently ensured, and the compound ((meth)acrylate (m-1)) containing an isocyanato group and an ethylenically unsaturated group can be sufficiently ensured. a-4) and the content of polybasic acid or its anhydride (a-5).

Among them, when (meth)acrylate (m-2-3) containing a blocked isocyanate group is used, the low-temperature curability of the photosensitive resin composition can be improved, and a photosensitive resin composition with better hardness or solvent resistance can be obtained. Hardened film. When the silane group-containing (meth)acrylate (m-2-4) is used, the crosslinking efficiency of the photosensitive resin composition can be improved, and the pattern can be further refined.

[(Meth)acrylate (m-2-1) containing active methylene or active methine] The active methylene group or active methine group contained in (meth)acrylate (m-2-1) easily detaches hydrogen atoms, allowing the cross-linking reaction of the resin to proceed. For example, the methylene bond between the two carbonyl groups of acetoacetate is active. In addition to easily generating a hydrogen abstraction reaction, acetoacetate is known to typically exhibit keto-enol tautomerism. Keto-enol tautomerism, so it is believed to be related to photohardening. Furthermore, the active methylene group and active methine group in this embodiment refer to methylene groups bonded to both ends of any one of the carbon atom of the carbonyl group, the sulfur atom of the sulfonyl group, the cyano group, and the nitro group. , methine.

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

(Formula (X1), R ³ represents a divalent group represented by any one of the following formulas (8) to (10), R ⁴ represents cyano group (-CN), nitro group (-NO ₂ ), the following A group represented by the following formula (11) or the following formula (12), * represents a bonding site, and ★ represents an active methylene carbon)

(In formulas (8) to (12), * represents a bonding site, and in formulas (11) and (12), R ⁵ represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms that may contain heteroatoms).

Among R ³ contained in formula (X1), from the viewpoint of good low-temperature curability as a photosensitive resin composition and excellent physical properties required for color filters, formula (8) and formula (8) are preferred. The divalent base represented by any one of (10) is preferably a divalent base represented by formula (10).

Among R ⁴ contained in formula (X1), from the viewpoint of good low-temperature curability as a photosensitive resin composition and excellent physical properties required for color filters, formula (11) and formula (11) are preferred. (12), and preferably formula (11).

As R ⁴ in the formula (X1), when the formula (11) or the formula (12) is included, the number of carbon atoms represented by R ⁵ in the formula (11) and the formula (12) that may contain a heteroatom is 1~ As for the hydrocarbon group of 24, specific examples include methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, methoxy, ethoxy, propoxy, hexyloxy, and cyclohexyloxy. , the base represented by the following formula (13) to formula (15), etc.

(In formula (13) to formula (15), * represents the bonding part).

Among them, as the hydrocarbon group having 1 to 24 carbon atoms that may contain heteroatoms, an alkyl group having 1 to 10 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an alkyl group having 1 to 3 carbon atoms is more preferred. alkyl.

R ⁵ is preferably a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, and more preferably a hydrogen atom and an alkyl group having a carbon number of 1 to 10, from the viewpoint of good low-temperature curability and excellent physical properties required for a color filter. The alkyl group of 1 to 3 is more preferably a hydrogen atom or a methyl group.

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

(In formula (X2), * represents a bonding site, ★ represents active methine carbon, and the definition or preferred range of R ³ is the same as in formula (X1)).

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).

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

As the (meth)acrylate (m-2-1) containing an active methylene group or an active methine group, among others, the ease of reaction when polymerizing the resin (A) or the low temperature of the photosensitive resin composition From the viewpoint of curability, hardness of the cured film, or solvent resistance, a compound represented by the following formula (m1) is preferred.

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

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

Specific examples of the compound represented by the formula (1) include the following compounds.

Specific examples of the compound represented by the formula (2) include the following compounds.

Formulas (16) to (33) are compounds having CH ₂ =C(CH ₃ )-, but there are also compounds in which CH ₂ =C(CH ₃ )- in this equation is replaced by CH2=CH-. compound.

[(Meth)acrylate (m-2-2) containing an epoxy group or an oxetanyl group] (Meth)acrylate (m-2-2) 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)acrylyl group. Oxygen-based compounds. By using the (meth)acrylate (m-2-2), when the photosensitive resin composition is hardened, it is cross-linked with the carboxyl group derived from the polybasic acid or its acid anhydride (a-5). Therefore, a photosensitive resin composition having good developability can be obtained, and curing having excellent hardness and solvent resistance can be obtained even when cured at a low temperature.

Specific examples of the epoxy group-containing (meth)acrylate include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and alicyclic ring-containing (meth)acrylate. Oxy (meth)acrylate and its lactone adduct, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, (meth)acrylic acid bicyclo Epoxides of pentenyl esters, epoxides of dicyclopentenyloxyethyl (meth)acrylate, etc. Among these, from the viewpoint of ease of acquisition and reactivity in synthetic resin (A), glycidyl (meth)acrylate and (meth)acrylic acid having an alicyclic epoxy group are preferred. The ester is preferably 3,4-epoxycyclohexylmethyl (meth)acrylate or glycidyl (meth)acrylate.

Specific examples of the oxetanyl group-containing (meth)acrylate include (meth)acrylic acid (3-ethyloxetan-3-yl)methyl ester, methyl (meth)acrylate ) acrylate, 4-[3-(3-ethyloxetane-3-ylmethoxy)propoxy]styrene, 4-[6-(3-ethyloxetane- 3-ylmethoxy)hexyloxy]styrene, 4-[5-(3-ethyloxetan-3-ylmethoxy)pentyloxy]styrene, 2-vinyl-2 -Methyloxetane. Among these, (3-ethyloxetan-3-yl)methyl (meth)acrylate is preferred from the viewpoint of ease of acquisition and reactivity when synthesizing the resin (A). . Among the (meth)acrylates (m-2-2), those having an epoxy group or an oxetanyl group are preferred from the viewpoint of ease of acquisition and reactivity when synthesizing the resin (A). A (cyclo)alkyl (meth)acrylate with 2 to 12 carbon atoms.

[(Meth)acrylate containing blocked isocyanate groups (m-2-3)] (Meth)acrylate (m-2-3) does not contain a hydroxyl group, an active methylene group, an active methine group, an epoxy group, an oxetanyl group, and a carboxyl group, but has a blocked isocyanate group. Compounds with (meth)acryloxy groups. By using (meth)acrylate (m-2-3), the low-temperature curability of the photosensitive resin composition can be improved, and at the same time, the low-temperature curability of the photosensitive resin composition can be improved. Cross-linking of hydroxyl groups and isocyanate groups generated by deblocking results in a cured film with excellent hardness and solvent resistance. Examples of the (meth)acrylate (m-2-3) include compounds in which the isocyanate group in an isocyanate group-containing (meth)acrylate is blocked with a blocking agent. The reaction between isocyanate-containing (meth)acrylate and blocking agent can be carried out regardless of the presence of solvent. When using a solvent, a solvent that is inert to isocyanate groups must be used. During the blocking reaction, organic metal salts of tin, zinc, lead, etc., tertiary amines, etc. can also be used as catalysts. Generally speaking, the reaction can be carried out at -20~150°C, preferably at 0~100°C. Examples of the isocyanate compound include compounds represented by the following formula (XX1).

In the above formula (XX1), R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² represents -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, and R ¹⁵ is an alkylene group having 2 to 12 carbon atoms or an alkylene group having 6 carbon atoms which may have a substituent. (arylene group of 12), R ¹² is preferably -COOR ¹³ -, and here, R ¹³ is preferably an alkylene group having 1 to 4 carbon atoms.

Specific examples of the isocyanate compound represented by the above formula (XX1) include 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, and (meth)acrylate. ) 3-isocyanatopropyl acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate ester, 4-cyclohexyl isocyanate (meth)acrylate, methacryloyl isocyanate, etc. Furthermore, a molar (1 mol: 1 mol) reaction product such as 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-)xylene diisocyanate, 1,3-(or 1,4-)bis( Isocyanatomethyl)cyclohexane, lysine diisocyanate, etc.

Among these isocyanate compounds, preferred are: (meth)acrylic acid 2-isocyanatoethyl, (meth)acrylic acid 2-isocyanatopropyl, (meth)acrylic acid 3-isocyanate Propyl ester, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, (meth)acrylic acid 4-isocyanatocyclohexyl and methacrylyl isocyanate; more preferably: (meth)acrylic acid 2-isocyanatoethyl and (meth)acrylic acid 2-isocyanatopropyl.

Examples of the blocking agent that blocks the isocyanate group in the isocyanate compound include ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam. Lactam series such as amide; methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, bran Alcohol series such as base alcohol and cyclohexanol; butylphenol, p-tert-octyl such as phenol, cresol, xylenol, ethylphenol, o-isopropylphenol, p-tert-butylphenol, etc. Phenols such as phenol, nonylphenol, dinonylphenol, styrenated phenol, hydroxybenzoate, thymol, p-naphthol, p-nitrophenol, p-chlorophenol; dimethyl malonate Active methylene series such as diethyl malonate, methyl acetoacetate, ethyl acetate, acetylacetone, etc.; butyl mercaptan, thiophenol, tert-dodecyl mercaptan, etc. Thiol series; amine series such as diphenylamine, phenylnaphthylamine, aniline, carbazole, etc.; acid amide such as acetaniline, methoxyacetanilide (acetanisidide), acetamide, benzylamide, etc. systems; acid imine systems such as succinic acid imide and maleic acid imide; imidazole systems such as imidazole, 2-methylimidazole, 2-ethylimidazole, etc.; ureas such as urea, thiourea, ethylene urea, etc. System; N-phenyl carbamate phenyl ester, 2-oxazolidinone and other carbamate series: imine series such as ethyleneimine and polyethyleneimine; formaldehyde oxime, acetaldehyde oxime, acetone oxime, Oxime systems such as methyl ethyl ketoxime, methyl isobutyl ketoxime, and cyclohexanone oxime; bisulfite systems such as sodium bisulfite and potassium bisulfite, etc. Among these, from the viewpoint of ease of acquisition and reactivity in synthetic resin (A), preferred terminal blocking agents are diethyl malonate, 3,5-dimethylpyrazole, and hydroxybenzoin. Among acid esters and methyl ethyl ketoxime, from the viewpoint of low-temperature curability, 3,5-dimethylpyrazole is more preferred.

[Silane group-containing (meth)acrylate (m-2-4)] (Meth)acrylates (m-2-4) containing silane groups do not contain hydroxyl groups, active methylene groups, active methine groups, epoxy groups, oxetanyl groups, blocked isocyanate groups, and Carboxyl group, but a compound with silyl group and (meth)acryloxy group. Specific examples include [(meth)acryloxy]methyltriethoxysilane, [(meth)acryloxy]ethyltriethoxysilane, and [(meth)acryloxy] Oxy]propyltriethoxysilane, [(meth)acryloxy]octyltriethoxysilane, [(meth)acryloxy]propylmethyldiethoxysilane, [ (Meth)acryloxy]ethylmethyldiethoxysilane, [(meth)acryloxy]nonylmethyldiethoxysilane, etc. Among these, from the viewpoint of ease of acquisition and reactivity in synthetic resin (A), preferred are [(meth)acryloxy]alkylmethyldialkoxysilane, [(meth)acryloxy]alkylmethyldialkoxysilane, Meth)acryloxy]alkylethyl dialkoxysilane, preferably 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxysilane Oxypropylmethyldiethoxysilane, more preferably 3-(meth)acryloxypropylmethyldiethoxysilane.

[Other monomers (m-3)] If necessary, the hydroxyl-containing (meth)acrylic resin (a-0) may also have other components other than the hydroxyl-containing (meth)acrylate (m-1) and (meth)acrylate (m-2). The monomer (m-3) is used as the constituent monomer. Examples of other monomers (m-3) include dienes such as butadiene, (meth)acrylates, styrenes, unsaturated dicarboxylic acid diesters, and other vinyl compounds. For the reasons mentioned above, it is preferable that the other monomer (m-3) does not have a carboxyl group.

Specific examples of (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, Tert-butyl (meth)acrylate, amyl (meth)acrylate, neopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isopentyl (meth)acrylate, (meth)acrylate Alkyl (meth)acrylate such as dodecyl acrylate; cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylcyclohexyl (meth)acrylate, (meth)acrylate Alicyclic alkyl (meth)acrylates such as norbornyl acrylate, dicyclopentyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, etc.; (meth)acrylate Aromatic (methyl)acrylate containing benzyl acrylate, triphenylmethyl (meth)acrylate, cumyl (meth)acrylate, naphthalene (meth)acrylate, anthracene (meth)acrylate, etc. base) acrylate; rosin (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, etc.

Specific examples of styrenes include styrene and α-, o-, m-, and p-alkyl derivatives of styrene. Specific examples of unsaturated dicarboxylic acid diesters include diethyl citraconic acid, diethyl maleate, diethyl fumarate, and diethyl itaconate.

Specific examples of other vinyl compounds include norbornene (bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, and 5-ethyl Bicyclo[2.2.1]hept-2-ene, tetracyclo[4.4.0.12,5.17,10]dode-3-ene, 8-methyltetracyclo[4.4.0.12,5.17,10]dode-3 -ene, 8-ethyltetracyclo[4.4.0.12,5.17,10]dode-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]Undec-4-ene, tetracyclo[4.4.0.12,5.17,10.01,6]dode-3-ene, 8-methyltetracyclo[4.4.0.12,5.17,10.01,6]dode-3 -ene, 8-ethylenetetracyclo[4.4.0.12,5.17,12]dode-3-ene, 8-ethylenetetracyclo[4.4.0.12,5.17,10.01,6]dode-3-ene , Pentacyclo[6.5.1.13,6.02,7.09,13]pentadeca-4-ene, Pentacyclo[7.4.0.12,5.19,12.08,13]pentadeca-3-ene, (meth)acrylamide benzene, Vinyl pyridine, vinyl acetate, vinyl toluene, etc.

Among them, (meth)acrylates and other vinyl compounds are preferable from the viewpoint of ease of acquisition and reactivity when synthetic resin (A) is used, and those with a carbon number of 1 are preferable. ~12 alkyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentyl (meth)acrylate, styrene, vinyltoluene and norbornene, and preferably (meth)acrylic acid Methyl ester, 2-ethylhexyl (meth)acrylate and dicyclopentyl (meth)acrylate. In particular, from the viewpoint of improving the developability of the photosensitive resin composition, alkyl (meth)acrylate and alicyclic alkyl (meth)acrylate having 6 to 12 carbon atoms are preferred, and more preferred are Preferred ones are 2-ethylhexyl (meth)acrylate and dicyclopentyl (meth)acrylate.

The content of other monomers (m-3) relative to the monomer (M) is preferably 1 to 50 mol%, more preferably 3 to 40 mol%, and more preferably 5 to 35 mol%. .

[Compound (a-4) containing an isocyanato group and an ethylenically unsaturated group] Compound (a-4) containing an isocyanato group and an ethylenically unsaturated group, 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, or an epoxy group. It is not particularly limited as long as it is a compound containing a group, an oxetanyl group, a blocked isocyanate group and a silyl group. When the aforementioned ethylenically unsaturated group is a (meth)acryloxy group, the compound (a-4) containing an isocyanate group and an ethylenically unsaturated group is an isocyanate group-containing (methyl) group. Acrylate (a-4a). Examples of the isocyanato group-containing (meth)acrylate (a-4a) include 2-(meth)acryloxyethyl isocyanate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-di(meth)acrylate Methyl ethyl ester, 4-isocyanatocyclohexyl (meth)acrylate, 2-(2-isocyanatoethyloxy)ethyl (meth)acrylate, 1,1-(bis(meth)acrylate base)acrylyloxymethyl)ethyl isocyanate, etc. Among them, from the viewpoint of ease of acquisition and ease of synthesis of the resin (A), isocyanatoalkyl (meth)acrylate is more preferred, and 2-(meth)acryloxy is more preferred. Ethyl isocyanate. Furthermore, the number of carbon atoms in the alkyl group of the isocyanatoalkyl (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 more preferred. It is 2-(2-isocyanatoethyloxy)ethyl (meth)acrylate. From the viewpoint of improving the developability by improving the photosensitivity of the photosensitive resin composition, a compound containing two or more ethylenically unsaturated groups and an isocyanate group is preferred. When the ethylenically unsaturated group is a (meth)acryloxy group, from the viewpoint of improving the developability by improving the sensitivity of the photosensitive resin composition, etc., it is preferable to have two or more The isocyanate group-containing (meth)acrylate having a (meth)acryloxy group is preferably 1,1-(bis(meth)acryloxymethyl)ethyl isocyanate.

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

[Polybasic acid or its anhydride (a-5)] The polybasic acid or its acid anhydride (a-5) is a compound having 2 or more carboxyl groups or its acid anhydride. Examples of the polybasic acid include adipic acid, itaconic acid, succinic acid, oxalic acid, malonic acid, phthalic acid, fumaric acid, maleic acid, glutaric acid, tartaric acid, glutamic acid, and sebacic acid. wait. Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, succinic anhydride, cyclohexanetricarboxylic anhydride, and the like. Among them, from the viewpoint of the hardness of the cured film, polybasic acid anhydrides having an alicyclic structure are preferred, and maleic anhydride, itaconic acid anhydride, ethyl maleic anhydride, methyliconic acid anhydride, and chloromaleic anhydride are more preferred. Anhydride, citraconic anhydride, 2-norbornene-5,6-dicarboxylic anhydride, 4-[2-(methacryloxy)ethoxycarbonyl]phthalic anhydride, succinic anhydride, tetrahydrogen Phthalic anhydride and cyclohexanetricarboxylic anhydride are more preferred from the viewpoint of increasing the amount of carboxyl groups introduced to improve low-temperature curability.

The addition amount of the aforementioned polybasic acid or its anhydride (a-5) is preferably 1 to 60 mol based on 100 mol of the monomer (M) constituting the hydroxyl-containing (meth)acrylic resin (a-0). It is preferably 3 to 50 moles, more preferably 5 to 45 moles. As long as the addition amount of the polybasic acid or its acid anhydride (a-5) is 1 mol or more, sufficient developability can be obtained as a photosensitive resin composition. As long as the addition amount is 60 mol or less, the introduction amount of the compound (a-4) containing an isocyanate group and an ethylenically unsaturated group can be ensured sufficiently, and good photocurability can be obtained as a photosensitive resin composition. . In particular, from the viewpoint of improving the hardness and solvent resistance of the cured film during low-temperature curing, the addition amount of the polybasic acid or its anhydride (a-5) is preferably 35 to 60 moles.

The denaturation rate of resin (A) (that is, the introduction amount (total molar number) of the compound (a-4) containing an isocyanato group and an ethylenically unsaturated group and the polybasic acid or its anhydride (a-5) The hydroxyl group-containing (meth)acrylic resin (a-0) has a hydroxyl group (ratio of molar number), preferably 20 to 90%, more preferably 30 to 85%, more preferably 45 to 80% . As long as the denaturation rate is 20% or more, the introduction amount of ethylenically unsaturated groups and carboxyl groups can be ensured sufficiently, and a photosensitive resin composition with excellent developability can be obtained, and the hardness or A cured film that remains excellent in solvent resistance. As long as the denaturation rate is 90% or less, gelation during synthesis of the resin (A) can be suppressed, residual monomers can be reduced, and the generation of residues during development of the photosensitive resin composition can be suppressed.

"Weight average molecular weight (Mw)" In this embodiment, the weight average molecular weight (Mw) of the resin (A) in terms of polystyrene is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, and most preferably 3,500 to 25,000. If the weight average molecular weight (Mw) of the resin (A) is 1,000 or more, when the resin composition containing the resin (A) is used as a raw material of the photosensitive resin composition, the resin cured film after development will be less likely to be chipped. Defects in the photosensitive resin composition. If the weight average molecular weight of the resin (A) is 50,000 or less, the photosensitive resin composition containing the resin (A) can sufficiently shorten the development time and become excellent in practicality.

The value of the weight average molecular weight (Mw) of the resin (A) in this embodiment is measured according to the following conditions using gel permeation chromatography (GPC) and calculated in terms of polystyrene. Pipe string: Shodex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko Co., Ltd.) Tube string temperature: 40℃ Sample: Tetrahydrofuran solution with a resin (A) content of 0.2% by mass Developing agent: tetrahydrofuran Detector: Differential refractometer (trade name: Shodex (registered trademark) RI-71S, manufactured by Showa Denko Co., Ltd.) Flow rate: 1mL/min

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, the target numerical ranges of the weight average molecular weight (Mw), acid value, etc. can be optimized and the resin (A) can be manufactured. The reaction conditions and the like can be set with a certain degree of latitude, allowing efficient production. When 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, performance such as developability can be obtained without deterioration. The deviation of the photosensitive resin composition. Note that the molecular weight distribution (Mw/Mn) was calculated using the chromatogram measured by the above-mentioned GPC.

"Acid price" The acid value of the resin (A) is not particularly limited, but is preferably 10KOHmg/g~300KOHmg/g, more preferably 50KOHmg/g~300KOHmg/g, and most preferably 100KOHmg/g~300KOHmg/g. When 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 with better developability can be obtained. . If the acid value of the resin (A) is 300KOHmg/g or less, when the resin composition containing the resin (A) is used as a raw material of the photosensitive resin composition, the exposed part (photohardened part) will not be affected by the alkali developer. By dissolving, a photosensitive resin composition with good developability can be obtained.

Note that the acid value of resin (A) is a value measured in accordance with JIS K6901 5.3 using a mixed indicator of bromothymol blue and phenol red. The acid value of the resin (A) means the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of the resin (A).

"Ethylenically unsaturated group equivalent" The ethylenically unsaturated group equivalent of the resin (A) is not particularly limited, but is preferably 200g/mol~5000g/mol, more preferably 300g/mol~4000g/mol, and most preferably 300g/mol~3000g/mol. When the ethylenically unsaturated 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 with more excellent hardness. In addition, when the ethylenically unsaturated group equivalent of the resin (A) is 200 g/mol or more, the amount of carboxyl groups introduced into the resin (A) can be sufficiently ensured, and a photosensitive resin composition with better developability can be obtained. In addition, when the ethylenically unsaturated 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. From the viewpoint that the amount of ethylenically unsaturated groups can be sufficiently ensured, the photocurability of the photosensitive resin composition can be achieved, and a more refined pattern can be achieved, the ethylenically unsaturated group equivalent may be 1500 g/mol or less. , can also be below 800g/mol.

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

"Functional group equivalent" The functional group equivalent of the resin (A) in this embodiment refers to the functional group () contained in the structural unit derived from the (meth)acrylate (m-2) contained in the resin (A). Equivalents of active methylene, active methine, epoxy, oxetanyl, blocked isocyanate and silanyl groups). The aforementioned functional group equivalent is not particularly limited, but is preferably 200g/mol~5000g/mol, more preferably 300g/mol~4000g/mol, and most preferably 300g/mol~3000g/mol. When 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 with more excellent hardness. Furthermore, when the functional group equivalent of the resin (A) is 200 g/mol or more, when the resin composition containing the resin (A) is used as a raw material for the photosensitive resin composition, photosensitivity with better developability can be obtained. Resin composition. In addition, 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.

Note that the functional group equivalent of resin (A) is the molecular weight of resin (A) divided by the aforementioned functional groups contained in the structural unit derived from (meth)acrylate (m-2) per molecule. average the number and get the value. The functional group equivalent of the resin (A) is a calculated value based on the input amount of the monomer (M) used as a raw material when synthesizing the resin (A). When one molecule of resin (A) contains different types of functional groups, all functional groups are counted as the number of functional groups regardless of the type of functional groups.

<Production method of hydroxyl-containing (meth)acrylic resin (a-0)> The hydroxyl-containing (meth)acrylic resin (a-0) can be produced by, for example, the following production method. That is, in the presence of a solvent for polymerization, the monomer (M) is copolymerized using a polymerization initiator according to a radical polymerization method well known in this technical field.

Specifically, the following method can be used: the monomer (M) is dissolved in a polymerization solvent to adjust the raw material solution, and then the polymerization initiator is added to the raw material solution at, for example, 50°C to 130°C, 1 Hours to 20 hours, the copolymerization reaction is carried out while stirring.

(solvent for polymerization) The polymerization solvent used when producing the hydroxyl-containing (meth)acrylic resin (a-0) is not particularly limited as long as it is inert to the copolymerization reaction of the monomer (M). The polymerization solvent used when producing the hydroxyl-containing (meth)acrylic resin (a-0) may be the same as the solvent (D) contained in the resin composition described below, or may be the same solvent ( D) The solvents included are partially or entirely different. If the polymerization solvent used in producing the resin (A) is partially or entirely the same as the solvent (D) contained in the resin composition, there is no need to remove the polymerization solvent from the reaction solution after the copolymerization reaction. It is preferably separated and removed from the solvent (D) and can be used as part of the solvent (D).

The solvent used during polymerization is not particularly limited as long as it can dissolve the monomer (M) and the resulting copolymer and does not hinder the polymerization reaction. When the produced copolymer is a (meth)acrylic polymer, from the viewpoint of the solubility, a glycol ether solvent is preferred. Specific examples include 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 mono2-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, diethyl Glycol methyl ethyl ether, diethylene glycol dibutyl ether and dipropylene glycol dimethyl ether, etc. These solvents may be used alone, or two or more types may be used. Among these, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferred from the viewpoint of availability and reactivity.

The usage amount of the polymerization solvent used when producing the hydroxyl-containing (meth)acrylic resin (a-0) is not particularly limited, but is preferably 30 to 1,000 parts by mass relative to 100 parts by mass of the monomer (M). parts, preferably 50 parts by mass to 800 parts by mass. When the usage amount of the polymerization solvent is 30 parts by mass or more, the copolymerization reaction of the monomer (M) can be carried out stably, and the coloring and gelation of the hydroxyl-containing (meth)acrylic resin (a-0) can be prevented. . When the usage amount of the polymerization solvent is 1000 parts by mass or less, the decrease in the molecular weight of the hydroxyl-containing (meth)acrylic resin (a-0) due to chain transfer can be suppressed, and the viscosity of the reaction solution can be controlled. within appropriate limits.

(polymerization initiator) 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, t-butylperoxy-2-ethylhexanoate, etc. These polymerization initiators may be used individually by 1 type, or in combination of 2 or more types. The usage amount of the polymerization initiator is not particularly limited, but is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 16 parts by mass relative to 100 parts by mass of the monomer (M).

＜Manufacturing method of resin (A)＞ The compound (a-4) containing an isocyanato group and an ethylenically unsaturated group and a polybasic acid or its anhydride (a-5) are added to a (meth)acrylic resin (a-0) containing a hydroxyl group. It has a part of the hydroxyl group, and resin (A) can be obtained. The addition reaction can be carried out according to conventional methods.

For example, the following method can be used: adding a compound (a-4) containing an isocyanato group and an ethylenically unsaturated group and a polybasic acid or its anhydride (a-5) to synthesize hydroxyl-containing (meth)acrylic acid A method of performing an addition reaction in the reaction solution of resin (a-0). Furthermore, in this addition reaction (denaturation reaction), the reaction solution contains a polymerization solvent used for copolymerization to produce a hydroxyl-containing (meth)acrylic resin (a-0). There is no particular requirement. problem. Therefore, after the copolymerization reaction for producing the hydroxyl-containing (meth)acrylic resin (a-0) is completed, the addition reaction can be carried out without removing the polymerization solvent from the reaction solution.

The order of adding the compound (a-4) containing an isocyanato group and an ethylenically unsaturated group and the polybasic acid or its anhydride (a-5) is not particularly limited, and they may be added simultaneously or separately. From the viewpoint of suppressing the by-product of isocyanate dimer, it is preferable to first add and react the compound (a-4) containing an isocyanate group and an ethylenically unsaturated group, and then add a polybasic acid or Its acid anhydride (a-5) is reacted.

The reaction temperature of the above-mentioned addition reaction can be appropriately set according to the type of each raw material. Specifically, it is preferably 30°C to 150°C, and further preferably 50°C to 120°C. By setting the reaction temperature to 30° C. or higher, the addition reaction can fully proceed. In addition, by setting the reaction temperature to 150° C. or lower, gelation of the reaction solution can be suppressed, and decomposition of the bonds formed due to the addition reaction can be suppressed.

(polymerization inhibitor) When performing the aforementioned addition reaction, in order to prevent gelation of the reaction solution due to the addition reaction, a polymerization inhibitor may be added to the reaction solution as necessary. The polymerization inhibitor is not particularly limited, and examples thereof include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, dibutylhydroxytoluene, and the like.

(catalyst) When performing the aforementioned addition reaction, a catalyst may also be added to the reaction solution in order to promote the reaction if necessary. The catalyst is not particularly limited, and examples thereof include: tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzyl ammonium chloride, phosphorus compounds such as triphenylphosphine, and metals such as chromium Chelating compounds, lithium-like metal chelating compounds, 2-ethylhexanoate tin compounds, dibutyltin dilaurate (DBTDL)-like tin compounds, etc.

The content of the resin (A) in the photosensitive resin composition of this embodiment is preferably 10 parts by mass when the sum of the components excluding the solvent (D) contained in the photosensitive resin composition is 100 parts by mass. parts to 85 parts by mass, preferably 15 to 75 parts by mass, and most preferably 24 to 60 parts by mass. If the content of the resin (A) is within the above range, the viscosity and low-temperature curability of the photosensitive resin composition will become more suitable.

[Reactive diluent (B)] The (B) reactive diluent contained in the photosensitive resin composition of this embodiment is any low molecular weight one having an ethylenically unsaturated group such as a vinyl group, an allyl group, or a (meth)acryloxy group. Any compound may be used and is not particularly limited. In order to improve the hardening property (reactivity), a reactive diluent (polyfunctional reactive diluent) having a plurality of ethylenically unsaturated groups is preferred. Specific examples of the reactive diluent (B) include aromatic vinyl monomers; polycarboxylic acid monomers such as vinyl acetate and vinyl adipate; and monofunctional (meth)acrylates. Class; multifunctional (meth)acrylates; triallyl cyanurate, etc.

Specific examples of aromatic vinyl monomers include styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, divinylbenzene, and diallyl phthalate. ester, diallyl phenylphosphonate, etc.

Specific examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, (meth)acrylate β-hydroxyethyl methacrylate, hydroxypropyl (meth)acrylate, etc.

Specific examples of polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and ethylene glycol di(meth)acrylate. Glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, neopentylerythritol tetra(meth)acrylate, dixin Pentaerythritol penta(meth)acrylate, dineopenterythritol hexa(meth)acrylate, tri(meth)acrylate of ginseng(hydroxyethyl)isocyanurate, etc.

Among them, as the reactive diluent (B), in order to improve the curing property (reactivity), polyfunctional (meth)acrylates are preferred, especially dineopenterythritol penta(meth)acrylate. Ester and/or dipenterythritol hexa(meth)acrylate are preferred. These reactive diluents (B) may be used individually by 1 type, and may be used in combination of 2 or more types.

The content of the reactive diluent (B) in the photosensitive resin composition of this embodiment is preferably 100 parts by mass when the total of the components excluding the solvent (D) contained in the photosensitive resin composition is The amount is 10 parts by mass to 85 parts by mass, 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 will become more suitable.

[Photopolymerization initiator (C)] The photopolymerization initiator (C) contained in the photosensitive resin composition of this embodiment is not particularly limited as long as it is a compound that can generate radicals by light irradiation. Examples of the photopolymerization initiator (C) include benzoin, benzoin methyl ether, benzoin ethyl ether and its alkyl ethers; acetophenone, 2,2- Dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4-(1-t-butyldioxy-1-methylethyl)acetophenone, etc. Ketones; alkyl ketones such as 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, etc.; 2-methylanthraquinone, 2-pentylanthraquinone , 2-t-butylanthraquinone, 1-chloroanthraquinone and other anthraquinones; 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone Thioxanthones, etc.; ketals such as acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.; benzophenone, 4-(1-t-butyldioxy-1-methyl Benzophenones such as ethyl)benzophenone and 3,3',4,4'-(t-butyldioxycarbonyl)benzophenone; 1,2-octanedione, 1-[4-(phenylthio)-2-(o-benzoyl oxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H- Oxime esters such as carbazol-3-yl], 1-(o-acetyl oxime); 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propane -1-one; 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone-1; 2,4,6-trimethylbenzoyldiphenyl Phosphine oxides, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, etc.; xanthones, etc. These photopolymerization initiators (C) may be used individually by 1 type, and may be used in combination of 2 or more types.

The content of the photopolymerization initiator (C) in the photosensitive resin composition of this embodiment is smaller than the total content of the components excluding the solvent (D) contained in the photosensitive resin composition when it is 100 parts by mass. Preferably it is 0.1-30 parts by mass, more preferably 0.3-20 parts by mass, and most preferably 0.5-10 parts by mass. If the content of the photopolymerization initiator (C) is 0.1 parts by mass or more, the photosensitive resin composition will have sufficient photocurability. If the content of the photopolymerization initiator (C) is 30 parts by mass or less, the photopolymerization initiator (C) will not have an adverse effect on the storage stability of the photosensitive resin composition and the performance of the resin cured film.

[Solvent (D)] The solvent (D) contained in the resin composition of this embodiment is any solvent that is inert to the resin (A) and the reactive diluent (B) and can dissolve the resin (A) and the reactive diluent (B). That’s it, there is no particular limit. The solvent (D) may or may not contain the polymerization solvent used when producing the resin (A). When the solvent (D) contains the polymerization solvent used when producing the resin (A), there is no need to remove the polymerization solvent from the reaction solution after the copolymerization reaction for producing the resin (A) is completed. The addition reaction for producing the resin (A) is carried out, and after the addition reaction is completed, the polymerization solvent can be directly used as part of the solvent (D) of the resin composition without separating or removing it from the reaction solution. Use them all.

When the solvent (D) does not include the polymerization solvent used in the production of the resin (A), it means that the resin (A) is used as a raw material of the resin composition. After the resin (A) is produced, separation and removal from the reaction solution. In this case, regardless of the type and usage amount of the polymerization solvent used in producing the resin (A), the solvent (D) can be appropriately selected depending on the type of the resin (A), the use of the resin composition, etc. Type and content. That is, when the resin (A) is separated and removed from the reaction solution to produce the resin (A), the solvent (D) can be the same polymerization solvent used when producing the resin (A). For the same type of solvent, different solvents can also be used.

The solvent (D) is not particularly limited, but when the resin (A) is a (meth)acrylic polymer, from the viewpoint of the solubility, a glycol ether solvent is preferred. Specific examples include 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 mono2-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, diethyl Glycol methyl ethyl ether, diethylene glycol dibutyl ether and dipropylene glycol dimethyl ether, etc. These solvents may be used alone, or two or more types may be used. Among these, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferred from the viewpoint of availability and reactivity.

The solvent (D) may also include other solvents that can dissolve the resin (A) and the reactive diluent (B).

Examples thereof include monoalcohols, (poly)alkylene glycol monoalkyl ethers, and the like. Specific examples of the monoalcohols include primary alcohols such as propanol, butanol, pentanol, hexanol, octanol, nonanol, decanol, and dodecanol; and secondary alcohols such as benzyl alcohol. Specific examples of other solvents include tertiary alcohols such as tert-butanol and diacetone alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and propylene glycol. (poly)alkylene glycol monoalkyl ether acetates such as monomethyl ether acetate and propylene glycol monoethyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, etc. Other ethers such as methyl ether, diethylene glycol diethyl ether, tetrahydrofuran, etc.; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; methyl 2-hydroxypropionate. Ester, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, 3-methoxy Ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate , 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-butyl acetate, n-propyl acetate, acetic acid i-propyl ester, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, butyric acid i-propyl ester, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate, etc. Esters; aromatic hydrocarbons such as toluene and xylene; carboxylic acid amides such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, etc. Class etc.

The content of the solvent (D) in the resin composition of this embodiment is preferably 30 to 1,000 parts by mass when the sum of the components excluding the solvent (D) in the resin composition is 100 parts by mass. It is 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 within an appropriate range.

[Other additives] The photosensitive resin composition of this embodiment may contain one or more well-known additives such as leveling agents, thermal polymerization inhibitors, and sensitizers as necessary. The content of these additives is not particularly limited as long as it is within a range that does not hinder the effects of the present invention.

Furthermore, the photosensitive resin composition of this embodiment may contain an amine, a hydrazine, an aldehyde, or a metal salt as a crosslinking agent in order to improve curability. Examples of cross-linking agents include MXDA and 1,3-BAC, trade names manufactured by Mitsubishi Gas Chemical Co., Ltd., ADH and APA-280, trade names manufactured by Otsuka Chemical Co., Ltd., and SEQUAREZ, trade names manufactured by OMNOVA Solutions. 755, trade name ZIRCOZOL ZC-2, 7, etc. manufactured by Daiichi Element Chemical Industry Co., Ltd.

Furthermore, the photosensitive resin composition of this embodiment may contain an acid generator or a base generator in order to improve curability. In particular, from the viewpoint of potentiality, it is preferable to use a photoacid generator, a photobase generator, a thermal acid generator, or a thermal base generator; from the viewpoint of storage stability, it is more preferable to use a photoacid generator agent, photobase generator. Examples of photoacid generators include sulfonium salt compounds such as CPI-200K, CPI-210S, CPI-310B, CPI-410S, etc., manufactured by San-Apro Chemical Co., Ltd., and iodonium compounds such as IK-1. Salt compounds, etc. Examples of photobase generators include WPBG-266, WPBG-300, and WPBG-345, trade names manufactured by FUJIFILM Wako Chemicals Co., Ltd.

[Viscosity of photosensitive resin composition] The viscosity of the photosensitive resin composition of this embodiment can be appropriately adjusted in accordance with the thickness of the resin cured film composed of the cured material of the photosensitive resin composition. For example, if the thickness of the resin cured film is adjusted to 1 to 4 μm, the viscosity of the photosensitive resin composition is preferably 1 mP·s to 25 mP·s, and more preferably 2 mP·s at the temperature during coating. ~20mP·s, the best is 3mP·s~15mP·s.

＜Photosensitive coloring composition＞ The photosensitive coloring composition of this embodiment contains the photosensitive resin composition of this embodiment and a coloring agent (E). [Color(E)] As the colorant (E), well-known dyes and/or pigments can be used. When used in an optical 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), compared with the case of using a pigment, a high-brightness colored pattern can be obtained and a photosensitive colored composition showing good alkali developability can be obtained.

As the dye, from the viewpoints of "solubility in the solvent (D) and alkali developer", "interaction with other components in the photosensitive resin composition", "heat resistance", etc., it is preferable to use : Acid dyes having acidic groups such as carboxyl groups, salts of acid dyes with nitrogen compounds, sulfonamides of acid dyes, 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 BLUE2620); 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 1,4,8,14,17,18,26,27,29,31,34,35,37 ,42,44,50,51,52,57,69,73,80,87,88,91,92,94,97,103,111,114,129,133,134,138,143,145,150 ,151,158,176,183,198,211,215,216,217,249,252,257,260,266,274; acid violet 6B,7,9,17,19; acid yellow 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 the like Derivatives etc. Among these, azo-based, xanthene-based, anthraquinone-based or phthalocyanin-based acid dyes are preferred. Depending on the color of the intended pixel, one type of these dyes may be used alone, or two or more types may be used in combination.

Examples of pigments include: C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, Yellow pigments 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214, etc.; C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55 , 59, 61, 64, 65, 71, 73, etc. orange pigments; C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, Red pigments such as 216, 224, 242, 254, 255, 264, 265, etc.; C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 60, etc. blue pigments; C.I. Pigment Violet 1, 19, 23 , 29, 32, 36, 38, etc. purple pigments; C.I. Pigment Green 7, 36, 58, etc. green pigments; C.I. Pigment Brown 23, 25, etc. brown pigments; C.I. Pigment Black 1, 7, carbon black, titanium black, Black pigments such as iron oxide, etc. Depending on the color of the intended pixel, one type of these pigments may be used alone, or two or more types may be used in combination.

When a pigment is used as the colorant (E), from the viewpoint of improving the dispersibility of the colorant (E), a known dispersant may be blended into the photosensitive coloring composition. As a dispersant, it is preferable to use a polymer dispersant having excellent dispersion stability over time. Examples of the polymer dispersant include urethane dispersants, polyethylenimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, and sorbitol. Aliphatic ester dispersants, aliphatic modified ester dispersants, etc. As such polymer dispersants, EFKA (manufactured by EFKA Chemicals B.V. (EFKA) Co., Ltd.), Disperbyk (manufactured by BYK-Chemie Co., Ltd.), Disparlon (manufactured by Kusumoto Chemical Co., Ltd.), SOLSPERSE (manufactured by Zeneca Co., Ltd.), etc. can be used. It is marketed under the trade name. The compounding amount of the dispersant may be appropriately set according to the type and amount of the pigment used as the colorant (E).

The content of the colorant (E) in the photosensitive coloring composition of this embodiment is preferably 4 when the total amount of the components excluding the solvent (D) contained in the photosensitive coloring composition is 100 parts by mass. Parts by mass to 79 parts by mass, 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 obtained by containing the colorant (E) will become significant, and it will become a suitable photosensitive material for coloring patterns of color filters. Sexual coloring composition. If the content of the colorant (E) is 85 parts by mass or less, the colorant (E) in the photosensitive coloring composition will not hinder the curability of the photosensitive coloring composition, and the photosensitivity will be good in low-temperature curability. Coloring composition.

[Other additives] The photosensitive coloring composition of this embodiment may contain the same additives as the other additives described in the photosensitive resin composition as necessary.

[Viscosity of photosensitive coloring composition] The viscosity of the photosensitive coloring composition of this embodiment can be appropriately adjusted in accordance with the thickness of the resin cured film composed of the cured material of the photosensitive coloring composition. For example, if the thickness of the resin cured film is adjusted to 1~4μm, the viscosity of the photosensitive coloring composition is preferably 1mP・s~25mP・s, more preferably 2mP・s~20mP・s, and most preferably 3mP・s~15mP・s.

＜Production method of photosensitive resin composition＞ The photosensitive resin composition of this embodiment can be used by combining a resin (A), a reactive diluent (B), a photopolymerization initiator (C), a solvent (D), and additives used as required. A well-known mixing device is used for mixing and manufacturing.

The photosensitive resin composition of this embodiment has excellent low-temperature curability and can form a resin cured film having sufficient hardness and solvent resistance. Furthermore, since the photosensitive resin composition of this embodiment has excellent alkali developability, it is possible to form a fine pattern by developing using an alkali aqueous solution. Therefore, the photosensitive resin composition of this embodiment is suitable for use as a resist.

＜Production method of photosensitive coloring composition＞ The photosensitive coloring composition of this embodiment can be prepared by combining the resin (A), the reactive diluent (B), the photopolymerization initiator (C), the solvent (D), the colorant (E) and the The additives used are mixed using a well-known mixing device and produced.

The photosensitive resin composition of this embodiment has excellent low-temperature curability and can form a resin cured film having sufficient hardness and solvent resistance. Furthermore, since the photosensitive resin composition of this embodiment has excellent alkali developability, it is possible to form a fine pattern by developing using an alkali aqueous solution. Therefore, the photosensitive resin composition of this embodiment is suitable for use as a resist. Furthermore, the photosensitive colored composition of this embodiment can be suitably used as a material for colored patterns such as pixels of color filters and black matrices.

＜Resin cured film＞ Next, the resin cured film of this embodiment will be described in detail. The resin cured film of this embodiment is composed of the cured product of the photosensitive resin composition of this embodiment or the photosensitive coloring composition of this embodiment. The resin cured film of this embodiment can be formed by performing, for example, a coating step of applying the photosensitive resin composition of this embodiment on a base material to form a coating film; a pre-baking step for drying the coating film, an exposure step for irradiating the dried coating film with light and photohardening it, and a baking step after thermally hardening the photo-cured coating film.

When the photosensitive resin composition of this embodiment is used to form a resin cured film having a specified pattern by photolithography, for example, the following method can be used. That is, the above-mentioned coating step and prebaking step are performed. Thereafter, in the exposure step, the dried coating film is irradiated with light through a mask having a designated pattern, thereby photohardening the exposed portion. After the exposure step, post-exposure heat treatment is performed as necessary. Thereafter, the following steps are performed: a development step of dissolving and developing the unexposed portion of the coating film using a developer, and a baking step of thermally hardening the photocured coating film.

[Coating step] In the coating step, the photosensitive resin composition of this embodiment or the photosensitive coloring composition of this embodiment is applied to a base material to form a coating film. In this embodiment, as the base material for coating the photosensitive resin composition or the photosensitive coloring composition, a well-known base material can be used, and it can be appropriately determined according to the use of the resin cured film. The coating method of the photosensitive resin composition or the photosensitive coloring composition is not particularly limited, and examples thereof include screen printing, roll coating, curtain coating, spray coating, spin coating, slit coating, and the like.

[Pre-baking step] In the prebaking (preheating treatment) step, the coating film formed by the coating step is dried to reduce the residual amount of solvent in the coating film. In the pre-baking step, the substrate on which the coating film is 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°C). seconds) heating. In the prebaking step, an example of a method for heating the base material on which the coating film is formed includes a method using a hot plate.

[Exposure steps] In the exposure step, the surface of the coating film dried in the prebaking step is irradiated with light to photoharden the coating film. The light source used for light irradiation is not particularly limited, 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 step is 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, and the like. When forming a resin cured film having a designated pattern, in the exposure step, the surface of the coating film dried in the prebaking step is irradiated with light through a mask having the designated pattern, so that the exposed portion Light hardening.

[Post-exposure heating step] When forming a resin cured film with a specified pattern, a post-exposure baking step is performed after the exposure step if necessary. By performing this step, the dissolution contrast between the exposed portion and the unexposed portion of the coating film can become more significant. The post-exposure heating step is different from the post-baking step described below in that the post-exposure heating step does not completely harden the coating film. The post-exposure heating step is performed for the purpose of leaving only the exposed portion of the coating film on the substrate after the development step and to more reliably remove the unexposed portion of the coating film. Therefore, this step is not an essential step in the resin cured film forming method of this embodiment.

If a post-exposure heating step is performed, it is preferable to heat the substrate after the exposure step at, for example, 40°C to 70°C, and more preferably at 50°C to 60°C. If the heating temperature is 40°C or above, by performing a post-exposure heating step, the effect of improving the dissolution contrast between the exposed and unexposed parts of the coating film can be fully obtained. If the heating temperature is below 70°C, the acid generated in the exposed parts will not diffuse to the unexposed parts, and good dissolution contrast can be obtained. The heating time in the post-exposure heating step is preferably 20 seconds to 600 seconds. If the heating time is 20 seconds or more, the temperature history of the entire coating film can be made uniform. If the heating time is 600 seconds or less, the acid generated in the exposed parts will not diffuse to the unexposed parts, and good dissolution contrast can be obtained. As a method of heating the base material after the exposure step in the post-exposure heating step, for example, a hot plate, a heating box, a heating furnace, etc. can be used.

[Development step] When forming a resin cured film having a specified pattern, after the exposure step, a post-exposure heating step is performed as necessary, and then a development step is performed to develop the unexposed portion of the coating film. As the developer used in the development step, any alkali aqueous solution conventionally used for development of photosensitive resin compositions or photosensitive colored compositions can be used.

The alkali aqueous solution is not particularly limited, and examples thereof include aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, and potassium hydroxide; and amine compounds such as ethylamine, diethylamine, and dimethylethanolamine. aqueous solution; aqueous solution of quaternary ammonium salts such as tetramethylammonium hydroxide; 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl Base-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamideethylaniline, 3-methyl-4-amino-N- Ethyl-N-β-methoxyethylaniline and aqueous solutions of p-phenylenediamine-based compounds such as sulfate, hydrochloride or p-toluenesulfonate, etc. Among these alkali aqueous solutions, an aqueous solution of a p-phenylenediamine-based compound is preferably used.

According to needs, one or more additives such as defoaming agents and surfactants can be added to the alkali aqueous solution. Development conditions such as development temperature and development time in the development step can be appropriately determined depending on the composition of the photosensitive resin composition, the composition of the developer, the thickness of the coating film, and the like. In the development step, after using the above-mentioned alkali aqueous solution to dissolve the unexposed portion of the coating film and developing it, it is preferable to wash it with water and dry it.

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

The heating temperature in the post-baking step can be set to, for example, 50°C to 210°C. If the heating temperature is below 210°C, low heat resistance materials can be used as the color filter material. For example, when a resin substrate is used as a base material for forming a resin cured film to form a colored pattern of a color filter, the heating temperature may be 150°C or lower, 120°C or lower, or 100°C or lower. . If the heating temperature is set to 150°C or lower, the coloring pattern can be formed while suppressing the deterioration of the coloring agent (E) of the coloring pattern including the coloring agent (E) having poor heat resistance. In the past, it was difficult to use it as a material for coloring patterns. Furthermore, if the heating temperature is set to 150° C. or lower, a colored pattern can be formed on a substrate with poor heat resistance that has been difficult to use as a color filter substrate in the past. In addition, it is preferable to set the heating temperature to 150° C. or less because the energy required for hardening the coating film will be reduced.

If the heating temperature in the post-baking step is 50° C. or above, the resin (A) and the reactive diluent (B) will be fully cross-linked, and a resin cured film with sufficient hardness and solvent resistance can be obtained. In addition, if the heating temperature is 50° C. or higher, the heating time in the post-baking step can be shortened, and the resin cured film can be formed efficiently. The heating temperature in the post-baking step is preferably 60°C or higher, more preferably 70°C or higher.

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., for example, it can be set to 10 minutes to 4 hours, preferably 20 minutes to 20 minutes. 2 hours.

The resin cured film of this embodiment is composed of the cured product of the photosensitive resin composition of this embodiment or the photosensitive coloring composition of this embodiment. Therefore, it has sufficient hardness and solvent resistance. The resin cured film of this embodiment can be suitably used as a protective film provided above a color filter, an insulating film provided between electrodes of a touch panel, and an interlayer of a thin film transistor (TFT). Various insulating films such as insulating films.

＜Color Filter＞ Next, the color filter of this embodiment will be described in detail. FIG. 1 is a schematic cross-sectional view showing an example of the color filter of this embodiment. The color filter shown in FIG. 1 includes: a base material 1; RGB pixels 2 formed on one side 1a of the base material 1; black matrices 3 formed on the boundaries of each pixel 2; and and a protective film 4 on the black matrix 3.

The substrate 1 used in the color filter shown in FIG. 1 is not particularly limited. Depending on the application, a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyamide substrate, or a polycarbonate substrate can be appropriately used. Substrates composed of amide-imide substrates, polyimide substrates, aluminum substrates, printed wiring substrates, array substrates, PET substrates, etc. If an organic material substrate such as a resin substrate is used, a low-temperature heat treatment process is required, and the photosensitive resin composition of this embodiment and the photosensitive coloring composition of this embodiment can exert further effects. For example, when the colorant (E) is used as a dye, a color filter is suitable. The photosensitive coloring composition of this embodiment is used as a base for the color filter shown in FIG. 1 For material 1, a resin substrate such as a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyamide imide substrate, a polyimide substrate, or a PET substrate is used.

At least one of the pixels 2 and the black matrix 3 in the color filter shown in FIG. 1 is a colored pattern composed of a hardened product of the photosensitive colored composition of this embodiment. The photosensitive colored composition of this embodiment is The reactive coloring composition includes a resin composition (which includes a resin (A) and a solvent (D)), a reactive diluent (B), a photopolymerization initiator (C), a coloring agent (E) and as needed. Contains additives. As the protective film 4, what is composed of a well-known material can be used. The protective film 4 may also be a resin cured film composed of a cured product of the photosensitive coloring composition of this embodiment, wherein the photosensitive coloring composition of this embodiment includes a resin composition (which contains resin (A) and Solvent (D)), reactive diluent (B), photopolymerization initiator (C), and additives as necessary.

In the color filter of this embodiment shown in FIG. 1 , the components other than the materials of the pixels 2 and the black matrix 3 may be made of known materials. In addition, the color filter shown in FIG. 1 is an example of the color filter of the present invention, and the present invention is not limited to the example shown in FIG. 1 .

Next, the manufacturing method of the color filter of this embodiment is demonstrated. First, each RGB pixel 2 and the black matrix 3 are sequentially formed on one side 1a of the base material 1 shown in FIG. 1 . The pixel 2 and the black matrix 3 can be manufactured using the resin cured film manufacturing method (photolithography method) of this embodiment described above. Next, a protective film 4 is formed on the pixels 2 and the black matrix 3 . The protective film 4 can be formed using a well-known formation method. For example, the protective film 4 can be manufactured using the method for manufacturing the resin cured film of this embodiment described above. Through the above steps, the color filter of this embodiment shown in FIG. 1 can be obtained.

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

＜Image display component＞ The image display element of this embodiment includes the color filter of this embodiment which has sufficient hardness and solvent resistance. Examples of the image display element of this embodiment include a liquid crystal display element, an organic EL display element, a solid-state imaging element, and the like. The image display element of this embodiment is capable of high-brightness display by including the above-mentioned color filter. [Example]

Hereinafter, the present invention will be explained more specifically through Examples and Comparative Examples. Incidentally, the embodiments shown below are examples for making it easier to understand the contents of the present invention. The present invention is not limited only to these embodiments.

The synthesis example of resin (A) is shown below.

[Synthesis example 1] In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 184.6 g of propylene glycol monomethyl ether acetate as a solvent for polymerization was placed, and the temperature was raised to 98°C while stirring while replacing it with nitrogen. .

Next, 114.3 g (0.50 mol) of 2-hydroxyethyl methacrylate, 75.2 g (0.20 mol) of ethylene glycol monoacetoacetate monomethacrylate, and 52.7 g of methyl methacrylate were added. g (0.30 mol), 29.6 g of 2,2'-azobis(isobutyric acid) dimethyl ester (polymerization initiator), and 87.2 g of propylene glycol monomethyl ether acetate, and then mixed for 3 hours. Drain the dripping liquid into the aforementioned flask.

After completion of dropping, the mixture was stirred at 98° C. for 3 hours to perform a copolymerization reaction to produce a hydroxyl-containing (meth)acrylic resin (a-0) as a copolymer. Thereafter, the inside of the flask was replaced with air, and into the reaction solution in which the hydroxyl-containing (meth)acrylic resin (a-0) was synthesized, 24.8 g (0.10 mol) of 2-acryloxyethyl isocyanate, and Add 0.27g of dibutyltin dilaurate (DBTDL) (addition reaction catalyst), 0.53g of methylhydroquinone (polymerization inhibitor), and 5.3g of propylene glycol monomethyl ether acetate at 60°C for 2 hours. reaction. Thereby, a (meth)acrylyloxy group is introduced into a part of the hydroxyl group derived from 2-hydroxyethyl methacrylate.

Next, add 53.4g (0.20 mol) of 1,2,3,6-tetrahydrophthalic anhydride, 1.3g of lithium naphthenate (addition reaction catalyst), and propylene glycol monomethyl ether acetate. 66.0g, and the addition reaction was carried out at 78°C for 3 hours. Thereby, a carboxyl group is introduced into a part of the hydroxyl group derived from 2-hydroxyethyl methacrylate.

Next, 306.8 g of propylene glycol monomethyl ether acetate was added as a solvent (additional solvent for composition) to the reaction solution to obtain the resin of copolymer P1 of Synthesis Example 1 as the resin (A) in this embodiment. composition.

[Synthesis Examples 2~18] The 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 and the ratios described in Table 1 were used. As shown in Table 1.

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

[Comparative synthesis example 1] 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 solvent for polymerization was placed, and the temperature was raised to 98°C while stirring while replacing it with nitrogen. .

Next, 90.7 g (0.34 mol) of 2-hydroxyethyl methacrylate, 75.1 g (0.17 mol) of ethylene glycol methacrylate, and 99.2 g (0.49 mol) of methyl methacrylate were added. , 32.3g of 2,2'-azobis(isobutyric acid)dimethyl ester (polymerization initiator), and 95.4g of propylene glycol monomethyl ether acetate were mixed, and the mixture was dripped over 3 hours. into the aforementioned flask.

After the dripping was completed, the copolymerization reaction was performed by stirring at 98° C. for 3 hours to produce a functional group-containing resin (ca) as a comparative copolymer. Thereafter, the inside of the flask was replaced with air, and 52.7 g (0.17 mol) of 1,2,3,6-tetrahydrophthalic anhydride and 1,2,3,6-tetrahydrophthalic anhydride were added to the reaction solution in which the functional group-containing resin (ca) was synthesized. 1.3g of lithium naphthenate (addition reaction catalyst), 0.53g of methylhydroquinone (polymerization inhibitor), and 44.8g of propylene glycol monomethyl ether acetate were used to perform an addition reaction at 78°C for 3 hours.

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

[Comparative synthesis examples 2~4] The resin compositions of the copolymers cP1 to cP4 of Comparative Synthesis Examples 1 to 4 were obtained in the same manner as Comparative Synthesis Example 1, except that the raw materials described in Table 2 were used and the ratios described in Table 2 were used.

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

[Comparative synthesis example 5] In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction 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 while replacing it with nitrogen. .

Next, 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 dicyclopentanyl methacrylate, tert- After mixing 32.8 g of butylperoxy-2-ethylhexanoate (polymerization initiator) and 70.0 g of propylene glycol monomethyl ether acetate, the mixture was dripped into the aforementioned flask over 3 hours. After the dripping was completed, the temperature was raised to 120° C. and stirred for 30 minutes to perform a copolymerization reaction to generate a copolymer. After that, the inside of 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 methylhydroquinone (polymerization inhibitor) were added to the above-mentioned copolymer. solution and continue the reaction at 110°C for 10 hours. The goal is to cleave the epoxy groups derived from glycidyl methacrylate by reacting the epoxy groups derived from glycidyl methacrylate with acrylic acid. , introducing ethylenically unsaturated bonds into the side chains of the copolymer, but gelation occurs during the reaction. The reaction was completed before adding 20.1 g (0.13 mol) of succinic anhydride into the above-mentioned copolymer solution. 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.

＜Preparation of photosensitive coloring composition＞ (Examples 1 to 18, Comparative Examples 1 to 5) The copolymers P1 to P18 and cP1 to cP4 of Synthesis Examples 1 to 18 and Comparative Synthesis Examples 1 to 4 of (A) copolymers were combined with the components (B), (C) and (E) shown in Table 3, They were mixed at the ratio shown in Table 3 to prepare photosensitive coloring compositions R1 to R18 and cR1 to cR4 of Examples 1 to 18 and Comparative Examples 1 to 4, respectively. Moreover, in Comparative Example 5, the copolymer P2 of Synthesis Example 2, in which 3 mass % of the dimer of 2-acryloxyethyl isocyanate was added, was used as the copolymer (A). The obtained (A) copolymer was mixed with the (B), (C), and (E) components shown in Table 3 in the ratios shown in Table 3 to prepare the photosensitive coloring composition of Comparative Example 5. Material cR5.

Note 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 compounding 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 additionally added when preparing the resin composition.

＜Evaluation of photosensitive coloring composition＞ 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 according to the method shown below.

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

Next, an ultrahigh-pressure mercury lamp was used to irradiate the surface of the dried coating film with light of 200 mJ/cm ² through a photomask (exposure step). The exposure step was performed with a photomask placed at a distance of 100 μm from the coating film. As the photomask, a photomask having a line and space pattern with a width of 3 to 100 μm is used. Next, SemiClean DL-A10 developer (manufactured by Yokohama Oils & Fats Industry Co., Ltd.) (diluted 5 times) was sprayed on the surface of the coated film for 60 seconds at a temperature of 23°C and a pressure of 0.1 MPa to remove it. Unexposed part (development step). The glass substrate with the coating film after the development step is placed in a dryer at 100° C. for 30 minutes, thereby thermally hardening the coating film (post-baking step) to obtain a colored pattern.

The colored pattern thus obtained was observed using an electron microscope S-3400 manufactured by Hitachi High-Technologies Corporation, and the minimum developable line width (minimum development size) and the difference between the developable patterns were evaluated. The presence or absence of residue in unexposed parts. The presence or absence of residues is evaluated based on the following criteria. The results are shown in Table 4 or Table 5. "Evaluation Criteria for Residues" ○: There is no residue in the unexposed areas between the developable patterns. ×: Residues are present in unexposed areas between developable patterns.

(2) Pencil hardness The photosensitive coloring compositions R1 to R18 and cR1 to cR5 prepared in Examples 1 to 18 and Comparative Examples 1 to 5 were coated on a square glass substrate of 5 cm in length and 5 cm in width by spin coating ( (alkali-free glass substrate), the solvent was evaporated by heating at 100° C. for 3 minutes to form a coating film. Next, the coating film was irradiated with light having a wavelength of 365 nm at an exposure amount of 200 mJ/cm ² to photoharden it. Next, the glass substrate with the photocured coating film was placed in a dryer at 100° C. for 30 minutes to thermally harden the coating film (post-baking step), thereby obtaining a cured resin with a film thickness of 2.5 μm. membrane.

The pencil hardness of the resin cured film thus obtained was measured using a pencil hardness meter (No. 553-M, manufactured by Yasuda Seiki Co., Ltd.) in accordance with JIS K5600-5-4, and evaluated based on the following standards. The results are shown in Table 4 or Table 5. "Evaluation Criteria for Pencil Hardness" ○: Pencil hardness 3H or above ×: Pencil hardness is less than 3H

(3) Solvent resistance In the same manner as the evaluation of pencil hardness in (2) above, a glass substrate with a resin cured film was produced, and the absorption spectrum of the resin cured film was measured using a spectrophotometer (UV-1650PC, manufactured by Shimadzu Corporation). Moreover, 200 mL of propylene glycol monomethyl ether acetate was placed in a capped glass bottle with a capacity of 500 mL, and the mixture was left to stand at a temperature of 23°C. The glass substrate having the resin cured film was placed in the glass bottle, immersed in propylene glycol monomethyl ether acetate, and left to stand at 23° C. for 15 minutes. Thereafter, the glass substrate with the 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 immersion in propylene glycol monomethyl ether acetate.

The color change (ΔE ^* ab) of the resin cured film before and after being immersed in propylene glycol monomethyl ether acetate was calculated, and the solvent resistance of the resin cured film was evaluated based on the following criteria. The results are shown in Table 4 or Table 5. "Evaluation criteria for solvent resistance" ○: ΔE ^＊ ab is less than 3.0 ×: ΔE ^＊ ab is 3.0 or more

(4) Comprehensive judgment Regarding the resin cured film 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, respectively, based on the following benchmarks for evaluation. The results are shown in Table 4 or Table 5. "Evaluation Criteria" ○: All the following items are met. (1) The minimum development size is 15 μm or less, and there is no residue in the unexposed areas between the developable patterns (2) The pencil hardness of the resin cured film is 3H or more (3) The color change ΔE of the solvent resistance evaluation of the resin cured film ^＊ ab is less than 3.0 ×: Unable to satisfy any one or more of the above ○ items.

As shown in Table 4, the photosensitive coloring compositions R1 to R18 of Examples 1 to 18 were all confirmed to have excellent properties when the minimum development size was 15 μm or less and there was no residue in the unexposed areas between the developable patterns. Alkali developability.

Moreover, as shown in Table 4, the coating film formed using the photosensitive coloring compositions R1 to R18 of Examples 1 to 18 was photocured and thermally cured at 100° C. to obtain a cured product. The resin cured film composed of the resin has a pencil hardness of 3H or more and has excellent hardness. Furthermore, the evaluation of the solvent resistance of the above-mentioned resin cured film was ○, and it was confirmed that it has excellent solvent resistance.

In comparison, 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, and solvent resistance.

More specifically, the copolymers cP1 to cP3 obtained by Comparative Synthesis Examples 1 to 3 included in the photosensitive coloring compositions cR1 to cR3 of Comparative Examples 1 to 3 have an ethylenically unsaturated group equivalent of 0. Therefore, the resin cured film has poor alkali developability, hardness, and solvent resistance. Furthermore, the copolymer cP4 obtained in Comparative Synthesis Example 4 included in the photosensitive resin composition cR4 of Comparative Example 4 produced a dimer of 2-acryloxyethyl isocyanate as a by-product during synthesis. Therefore, the resin cured film has poor alkali developability, hardness, and solvent resistance. In addition, the photosensitive resin composition cR5 of Comparative Example 5 was obtained by adding a dimer of 2-acryloxyethyl isocyanate to the copolymer P2 of Synthesis Example 2. Therefore, Comparative Example 5 is a result similar to Comparative Example 4, and the resin cured film is poor in any one of alkali developability, hardness, and solvent resistance. Furthermore, changes over time were confirmed for the resin composition obtained this time. As a result, it was found that the structural units having active methylene groups, the structural units having blocked isocyanate groups, the structural units having silane groups, The order of the structural units having an epoxy group tends to be favorable. [Industrial Applicability]

According to the present invention, it is possible to provide a photosensitive resin composition and a photosensitive colored composition that can form a resin cured film that has excellent developability and good low-temperature curability, and has sufficient hardness and solvent resistance. Furthermore, according to the present invention, it is possible to provide a resin cured film composed of a cured product of a photosensitive resin composition and having sufficient hardness and solvent resistance. It will be possible to provide a color filter having a colored pattern composed of a cured product of the photosensitive colored composition of the present invention and having sufficient hardness and solvent resistance. Furthermore, an image display element including the color filter can be provided. The photosensitive resin composition and photosensitive colored composition of the present invention can be preferably used as, for example, a transparent film, a protective film, an insulating film, a covering film, a photosensitive spacer, a black matrix, a black column spacer, and a color filter. Resistors are used.

1:Substrate 2:pixel 3: black matrix 4: Protective film

[Fig. 1] A schematic cross-sectional view showing an example of the color filter according to this embodiment.

Claims (18)

A photosensitive resin composition characterized by: It contains at least resin (A), reactive diluent (B), photopolymerization initiator (C) and solvent (D), The aforementioned resin (A) is ethylenically unsaturated and carboxyl modified (meth)acrylic resin, The aforementioned ethylenically unsaturated group and carboxyl modified (meth)acrylic resins are (meth)acrylic resins (a-0) containing hydroxyl groups, compounds (a-4) containing isocyanato groups and ethylenically unsaturated groups, and Addition reaction product of polybasic acid or its anhydride (a-5), The aforementioned hydroxyl-containing (meth)acrylic resin (a-0) is a copolymer containing at least the following structural units: a structural unit derived from the hydroxyl-containing (meth)acrylate (m-1), and, derived from (Meth)acrylate having at least one group selected from the group consisting of active methylene, active methine, epoxy group, oxetanyl group, blocked isocyanate group and silane group (m-2) structural unit. The photosensitive resin composition of claim 1, wherein the hydroxyl-containing (meth)acrylic resin (a-0) is the hydroxyl-containing (meth)acrylate (m-1), the (methyl) Copolymer of acrylate (m-2) and other monomers (m-3). The photosensitive resin composition of claim 2, wherein the other monomer (m-3) is an alkyl (meth)acrylate having an alkyl group having 1 to 12 carbon atoms. The photosensitive resin composition according to any one of claims 1 to 3, wherein the total number of all monomers used as polymerization raw materials for the hydroxyl-containing (meth)acrylic resin (a-0) is defined as "monomers" When M", in the aforementioned monomer (M), the content of the aforementioned hydroxyl-containing (meth)acrylate (m-1) is 30 to 95 mol%, and the content of the aforementioned (meth)acrylate (m-2) The content is 5~50 mol%. The photosensitive resin composition according to any one of claims 1 to 3, wherein the compound (a-4) containing an isocyanato group and an ethylenically unsaturated group is (meth)acrylic acid containing an isocyanato group. Ester (a-4a). The photosensitive resin composition of claim 5, wherein the isocyanate group-containing (meth)acrylate (a-4a) is an isocyanate group-containing (methyl)acrylate having a polyoxyalkylene structure. Acrylate, or isocyanato group-containing (meth)acrylate having two or more (meth)acryloxy groups. The photosensitive resin composition according to any one of claims 1 to 3, wherein the polybasic acid or its anhydride (a-5) is a tricarboxylic acid or its anhydride. The photosensitive resin composition according to any one of claims 1 to 3, wherein the acid value of the resin (A) is 10 to 300 KOHmg/g. The photosensitive resin composition according to any one of claims 1 to 3, wherein the ethylenically unsaturated group equivalent of the resin (A) is 200 to 5000 g/mol. The photosensitive resin composition according to any one of claims 1 to 3, wherein the denaturation rate of the resin (A) is 20 to 90%. The photosensitive resin composition according to any one of claims 1 to 3, wherein the addition amount of the compound (a-4) containing an isocyanato group and an ethylenically unsaturated group is relative to the monomer (M )100 moles is 1~60 moles. The photosensitive resin composition according to any one of claims 1 to 3, wherein the addition amount of the aforementioned polybasic acid or its anhydride (a-5) is 1 to 60 based on 100 moles of the aforementioned monomer (M). More. 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, and the molecular weight distribution (Mw/Mn) of the resin (A) is 1.3 to 5.0 . The photosensitive resin composition according to any one of claims 1 to 3, which contains 10 to 85 parts by mass of the resin (A) based on 100 parts by mass of the total components excluding the solvent (D). , containing 10 to 85 parts by mass of the aforementioned reactive diluent (B), 0.1 to 30 parts by mass of the aforementioned photopolymerization initiator (C), and 30 to 1000 parts by mass of the aforementioned solvent ( D). A photosensitive coloring composition containing the photosensitive resin composition of any one of claims 1 to 3 and a colorant (E), containing 4 parts by mass relative to 100 parts by mass of the total components after excluding the aforementioned solvent (D) parts to 79 parts by mass of the aforementioned colorant (E). A resin cured film composed of a cured product of the photosensitive resin composition according to any one of claims 1 to 3. A color filter having a coloring pattern composed of a hardened product of the photosensitive coloring composition of claim 15. An image display element equipped with the color filter of claim 17.

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