Photosensitive resin composition and color filter

Abstract

This invention provides a photosensitive resin composition exhibiting excellent image development and good low-temperature curing properties, capable of forming a resin-cured film with sufficient hardness and solvent resistance. The photosensitive resin composition of this invention comprises a resin (A), a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D). The aforementioned resin (A) contains: a constitutive unit (a-1) having at least one group selected from the group consisting of active methylene and active methine groups; a constitutive unit (a-2) having a group that reacts under the action of light and / or heat; and a constitutive unit (a-3) having an acid group.

Description

Technical Field

[0001] This invention relates to photosensitive resin compositions, photosensitive coloring compositions, resin curing films, color filters, and image display elements. This case asserts a priority claim based on Japan Patent Application No. 2021-207178 filed on December 21, 2021, the contents of which are hereby cited. Prior Technology

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

[0003] Previously, resin compositions used as materials for color filters included, for example, those described in Patent Document 1. Patent Document 1 discloses a coloring photocurable resin composition comprising a photocurable compound (A), an adhesive resin (B), a photoinitiator (D), and a solvent (E). The photocurable compound (A) is a dipentaerythritol pentaacrylate containing a carboxyl group. The adhesive resin (B) contains one or more tetrahydropyran or tetrahydrofuran structures in its main chain structure. [Previous Technical Documents] [Patent Literature]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2015-184675 Summary of the Invention

[0005] [The problem that the invention aims to solve]

[0006] Organic materials used as substrate materials have lower heat resistance than glass. Furthermore, dyes used as colorants in color filters have lower heat resistance than pigments. Therefore, it is desirable to reduce the heating temperature used for curing the resin composition used in color filter materials. Specifically, considering the heat resistance of the substrate material and the colorant material, there are cases where the heating temperature for curing the resin composition used in the color filter material is set to 80~150°C.

[0007] However, conventional resin compositions, if the heating temperature used to harden them is lowered, cannot produce a cured product with sufficient hardness and solvent resistance. Color filters made from insufficiently hardened materials are easily damaged. Therefore, in image display elements equipped with color filters, there is a risk of display defects caused by damage to the color filters. Furthermore, in order to improve color reproduction, there is a tendency to increase the content of colorants in the resin composition used as the material for the color filter in image display elements. Compared to pigments, coatings have higher solubility in solvents. Therefore, if the solvent resistance of the color filter is insufficient, the coating contained in the color filter may dissolve in the solvent, potentially causing color changes in the color filter.

[0008] The present invention was made in view of the above circumstances, and its purpose is to provide a photosensitive resin composition and a photosensitive coloring composition that have excellent image development and good low-temperature curing properties, and can form a resin curing film with sufficient hardness and solvent resistance. Furthermore, an object of the present invention is to provide a resin-cured film, which is formed from a cured product of the photosensitive resin composition of the present invention, and has sufficient hardness and solvent resistance. Additionally, an object of the present invention is to provide a color filter having a colored pattern formed from a cured product of the photosensitive coloring composition of the present invention, and having sufficient hardness and solvent resistance. Moreover, an object of the present invention is to provide an image display element incorporating the color filter. [Methods for solving the problem]

[0009] The present invention includes the following states. [1] A photosensitive resin composition comprising: Resin (A), Reactive diluent (B), Photopolymerization initiator (C) and Solvent (D); Its characteristics are: The aforementioned resin (A) contains: a constituent unit (a-1) having at least one group selected from the group consisting of active methylene and active methine, a constituent unit (a-2) having a group that reacts under the action of light and / or heat, and a constituent unit (a-3) having an acid group. [2] The photosensitive resin composition as described in [1], wherein the aforementioned constituent unit (a-2) is a constituent unit having at least one functional group selected from epoxy, silyl, capped isocyanate, isocyanate, hydroxy, mercapto, oxetyl, amino, furanyl, maleimino, acezodinyl, acezolyl, formazolidinyl, nitro, and halogen. [3] The photosensitive resin composition as described in [2], wherein the aforementioned constituent unit (a-2) is a constituent unit having an epoxy group (a-2-1), a constituent unit having a silyl group (a-2-2), or a constituent unit having a capped isocyanate group (a-2-3). [4] The photosensitive resin composition described in any of [1] to [3], wherein the acid value of the aforementioned resin (A) is 10 to 300 KOH mg / g. [5] The photosensitive resin composition described in any of [1] to [4], wherein In all the constituent units of the aforementioned resin (A), The aforementioned constituent unit (a-1) is 2~80 mol%. The aforementioned constituent unit (a-2) is 2~80 mol%. [6] The photosensitive resin composition described in any of [1] to [5], wherein the aforementioned resin (A) further contains other constituent units (a-4). [7] The photosensitive resin composition described in any of [1] to [6], wherein the aforementioned constituent unit (a-1) is a constituent unit having the structure shown in the following formula (X1) or (X2); (In formulas (X1) and (X2), R3 represents a divalent group represented by any of the formulas (8) to (10) below; R4 represents a cyano (-CN), nitro (-NO2), a group represented by formula (11) below or formula (12) below; * represents a bonding site; ★ represents an active methylene carbon or an active methine carbon); (In formulas (8) to (12), * indicates the bonding site; in formulas (11) and (12), R 5 represents a hydrogen atom or a hydrocarbon group with 1 to 24 carbon atoms that may contain heteroatoms). [8] In the photosensitive resin composition described in [7], in the aforementioned formula (X1) and formula (X2) of the aforementioned constituent unit (a-1), R3 is a divalent group shown in formula (8) or formula (10), and R4 is a group shown in formula (11). [9] The photosensitive resin composition described in any of [1] to [8], wherein The aforementioned resin (A) has a weight-average molecular weight of 1000~50000. The molecular weight distribution (Mw / Mn) of the aforementioned resin (A) is 1.3~3.0.

[10] The photosensitive resin composition described in any of [1] to [9], wherein Relative to 100 parts by mass of the components from which the aforementioned solvent (D) has been removed, The resin (A) contains 10 to 85 parts by weight of the aforementioned resin. Containing 10 to 85 parts by weight of the aforementioned reactive diluent (B), Containing 0.1 to 30 parts by weight of the aforementioned photopolymerization initiator (C), The solvent (D) contains 30 to 1000 parts by mass of the aforementioned solvent.

[11] A photosensitive coloring composition comprising a photosensitive resin composition as described in any one of [1] to

[10] and a coloring agent (E).

[12] The photosensitive coloring composition as described in

[11] , wherein Relative to 100 parts by mass of the components from which the aforementioned solvent (D) has been removed, The resin (A) contains 10 to 85 parts by weight of the aforementioned resin. Containing 10 to 85 parts by weight of the aforementioned reactive diluent (B), Containing 0.1 to 30 parts by weight of the aforementioned photopolymerization initiator (C), Containing 30 to 1000 parts by mass of the aforementioned solvent (D), Contains 4 to 85 parts by weight of the aforementioned colorant (E).

[13] A resin-cured film, which is a cured material composed of a photosensitive resin as described in any one of [1] to

[10] .

[14] A color filter having a colored pattern formed from a hardened form of a photosensitive coloring composition as described in any of

[11] or

[12] .

[15] An image display element having a color filter as described in

[14] . [The effects of the invention]

[0010] According to the present invention, photosensitive resin compositions and photosensitive coloring compositions can be provided that have excellent image development and good low-temperature curing properties, and can form resin curing films with sufficient hardness and solvent resistance. Furthermore, according to the present invention, a resin-cured film formed from a cured form of the photosensitive resin composition of the present invention, having sufficient hardness and solvent resistance, can be provided. Additionally, a color filter having a colored pattern formed from a cured form of the photosensitive coloring composition of the present invention, having sufficient hardness and solvent resistance, can be provided. Moreover, an image display element incorporating the color filter can be provided. Simple Explanation of the Diagram

[0011] [Figure 1] is a schematic cross-sectional view showing an example of a color filter of this embodiment. Implementation

[0012] [Forms of Invention]

[0013] The photosensitive resin composition, photosensitive coloring composition, resin curing film, color filter, and image display element of the present invention will be described in detail below. However, the present invention is not limited to the embodiments shown below. In this specification, "(meth)acrylic acid" means at least one selected from methacrylic acid and acrylic acid, "(meth)acrylate" means at least one selected from methacrylate and acrylate, and "(meth)acryl" means at least one selected from methacryl and acrylonitrile.

[0014] <Photosensitive Resin Composition> The photosensitive resin composition of this embodiment includes resin (A), reactive diluent (B), photopolymerization initiator (C), and solvent (D).

[0015] [Resin(A)] The photosensitive resin composition of this embodiment contains a resin (A) having at least one type of constituent unit (a-1) selected from the group consisting of active methylene and active methine (hereinafter referred to as "constituent unit (a-1)"), a constituent unit (a-2) having a group that reacts under the action of light and / or heat (hereinafter referred to as "constituent unit (a-2)"), and a constituent unit (a-3) having an acid group (hereinafter referred to as "constituent unit (a-3)"). The resin (A) may contain constituent units (a-4) as needed, and there is no particular limitation on the number of repetitions and the bonding order of each.

[0016] [Constructing Unit (a-1)] The constituent unit (a-1) of this embodiment is a constituent unit having at least one group selected from the group consisting of active methylene and active methine groups. The resin (A) exhibits improved low-temperature curing properties of the photosensitive resin composition by having the constituent unit (a-1), and even when the photosensitive resin composition is cured at low temperatures, the resulting resin-cured film possesses sufficient hardness, solvent resistance, and image development. The hydrogen atoms of the active methylene or active methine group in the constituent unit (a-1) are easily removed, allowing the resin cross-linking reaction to proceed. For example, the methylene bond between the two carbonyl groups of acetylacetonate is active; in addition to readily undergoing hydrogen abstraction reactions, acetylacetonate, as is well known, exhibits typical keto-enol tautomerism and is also considered to be related to photocuring. Furthermore, the active methylene and active methine groups in this embodiment refer to methylene and methine groups bonded at both ends to the carbon atom of the carbonyl group, the sulfur atom of the sulfonyl group, the cyano group, or the nitro group.

[0017] <Structure containing active methylene groups> The structure having an active methylene group can be exemplified by, for example, a structure having the following formula (X1). The methylene group bonded to R3 and R4 is the active methylene group.

[0018]

[0019] (In formula (X1), R3 represents a divalent group as shown in any of the formulas (8) to (10) below; R4 represents a cyano (-CN), nitro (-NO2), a group as shown in formula (11) below or formula (12) below; * represents a bonding site; ★ represents an active methylene carbon).

[0020]

[0021]

[0022] (In formulas (8) to (12), * indicates the bonding site; in formulas (11) and (12), R 5 represents a hydrogen atom or a hydrocarbon group with 1 to 24 carbon atoms that may contain heteroatoms).

[0023] From the viewpoint that R 3 in formula (X1) has good low-temperature curing properties as a photosensitive resin composition and excellent physical properties required for color filters, it is preferable to be the divalent group shown in either formula (8) or formula (10), and more preferably the divalent group shown in formula (10).

[0024] Of the R 4 in formula (X1), from the viewpoint that it has good low-temperature curing properties as a photosensitive resin composition and excellent physical properties required for color filters, formula (11) and formula (12) are preferred, and formula (11) is more preferred.

[0025] When R 4 in formula (X1) represents the group shown in formula (11) or formula (12) above, it can be a hydrocarbon group containing 1 to 24 carbon atoms, as shown by R 5 in formula (11) and formula (12). Specifically, examples include methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, methoxy, ethoxy, propoxy, hexoxy, cyclohexyloxy, and the groups shown in formulas (13) to (15) below.

[0026]

[0027] (In equations (13) to (15), * indicates the bonding location).

[0028] Among them, the hydrocarbon group containing heteroatoms with 1 to 24 carbon atoms is preferably an alkyl group with 1 to 10 carbon atoms, more preferably an alkyl group with 1 to 6 carbon atoms, and even more preferably an alkyl group with 1 to 3 carbon atoms.

[0029] From the viewpoint that R5 has good low-temperature curing properties and excellent physical properties required for color filters, it is preferable to have hydrogen atoms and alkyl groups having 1 to 10 carbon atoms, more preferably hydrogen atoms and alkyl groups having 1 to 3 carbon atoms, and even more preferably hydrogen atoms and methyl groups.

[0030] <Structure containing active methine> As a structure with an active methine, an example is a structure having the following formula (X2). The methine bonded to R3 and the cyclohexane ring is an active methine.

[0031]

[0032] (In formula (X2), * indicates the bonding site; ★ indicates the active methylene carbon; the definition or preferred range of R3 is the same as that in formula (X1).

[0033] In this embodiment, the constituent unit (a-1) is preferably 2-80 mol% of all the constituent units of resin (A), more preferably 105-70 mol%, and even more preferably 4010-65 mol%. If the content of constituent unit (a-1) is 2 mol% or more, a photosensitive resin composition using a resin composition containing resin (A) as a raw material can form a resin curing film with sufficient hardness and solvent resistance, and good low-temperature curing properties. If the content of constituent unit (a-1) is 80 mol% or less, the content of constituent units (a-2) and (a-3) with functional groups in all the constituent units can be sufficiently ensured.

[0034] One method for introducing the constituent unit (a-1) into resin (A) is to copolymerize a monomer (ma-1) having an vinyl unsaturated group and at least one group selected from the group consisting of active methylene and active methine groups (hereinafter referred to simply as "monomer (ma-1)") with other monomers containing vinyl unsaturated groups. This method involves introducing an active methylene or active methine group after the precursor of the polymerized resin (A) has been polymerized, thus forming resin (A). As an example of the latter method, a resin (A) can be obtained by polymerizing a precursor of resin (A) containing hydroxyl groups, allowing the hydroxyl groups of the precursor to react with diene ketones such as 4-methylenecyclohexaeno-2-one. The method of introducing the constituent unit (a-1) into the resin (A) is not limited to the above.

[0035] The monomer (ma-1) is not particularly limited as long as it is a compound having an vinyl unsaturated group and at least one group selected from the group consisting of an active methylene group and an active methine group. Examples of vinyl unsaturated groups include vinyl, allyl, and (meth)acryloxy. Among these, (meth)acryloxy is preferred from the viewpoint of ease of polymerization for obtaining resin (A).

[0036] As a monomer (ma-1), for example, compounds represented by the following formula (1) or (2) can be cited.

[0037]

[0038]

[0039] (In formulas (1) and (2), R1 represents a hydrogen atom or a hydrocarbon group with 1 to 24 carbon atoms that may contain heteroatoms; X represents a divalent group as shown in any of formulas (3) to (7) below; R2 represents a single bond or a divalent hydrocarbon group with 1 to 20 carbon atoms; the definitions or preferred ranges of R3 and R4 are the same as those in formulas (X1) and (X2); ★ represents active methylene carbon or active methine carbon).

[0040]

[0041] (In equations (3) to (7), * indicates the bonding location).

[0042] In formulas (1) and (2), the hydrocarbon group represented by R1 may contain 1 to 24 carbon atoms of heteroatoms. Specifically, examples include methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, methoxy, ethoxy, propoxy, hexoxy, cyclohexyloxy, and the groups represented by formulas (13) to (15) below.

[0043]

[0044] (In equations (13) to (15), * indicates the bonding location).

[0045] Among them, the hydrocarbon group containing heteroatoms with 1 to 24 carbon atoms is preferably an alkyl group with 1 to 10 carbon atoms, more preferably an alkyl group with 1 to 6 carbon atoms, and even more preferably an alkyl group with 1 to 3 carbon atoms.

[0046] As R1, from the viewpoint of the ease of reaction when polymerizing resin (A), it is preferable to have hydrogen atoms and alkyl groups having 1 to 10 carbon atoms, more preferably hydrogen atoms and alkyl groups having 1 to 3 carbon atoms, and even more preferably hydrogen atoms and methyl groups.

[0047] In formulas (1) and (2), the divalent group represented by X is preferably represented by formulas (4) and (5) from the viewpoint of the ease of reaction when polymerizing resin (A), and more preferably represented by formula (4).

[0048] As a monomer (ma-1), especially from the viewpoint of the ease of reaction when polymerizing resin (A), or the low-temperature curing properties of the resin composition and the physical properties of the resin-cured film, the compound shown in the following formula (m1) is preferred.

[0049]

[0050] (In formula (m1), R6 represents a hydrogen atom or a hydrocarbon group with 1 to 2 carbon atoms, and R7 represents a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms).

[0051] In formula (m1), the hydrocarbon group with 1 to 2 carbon atoms represented by R 6 is preferably methyl or ethyl from the viewpoint of image development as a component of a photosensitive resin, and more preferably methyl. In formula (m1), the hydrocarbon group represented by R 7, having 1 to 10 carbon atoms, may have a ring structure. From the viewpoint of low-temperature curing properties as a composition of photosensitive resin, 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.

[0052] As for the compound shown in formula (m1), from the viewpoint of image development as a component of a photosensitive resin, hardness as a resin curing film, and solvent resistance, it is preferred to have R6 as a methyl group and R7 as an alkyl group having 1 to 4 carbon atoms.

[0053] Specifically, the following compounds can be cited as examples of compounds represented by the aforementioned formula (1).

[0054]

[0055]

[0056] Specifically, the following compounds can be cited as examples of compounds represented by the aforementioned formula (2).

[0057]

[0058] Formulas (16) to (22), (31), (32), (33) and (36) are compounds having CH 3-CH 2=CH-, but examples can be given of compounds in which CH 3-CH 2=CH- is replaced by H-CH 2=CH-.

[0059] [Constructing Unit (a-2)] The resin (A) of this embodiment contains a-2 units that do not contain active methylene or active methine groups or acid groups, and has groups that react under the action of light and / or heat. The resin (A) may contain only one type of constituent unit (a-2) or two or more types.

[0060] The photosensitive resin composition using a resin composition comprising the resin (A) of this embodiment as a raw material contains a constituent unit (a-2) having a group that reacts under the action of light and / or heat. Therefore, the photosensitive resin composition exhibits excellent low-temperature curing properties. Low-temperature curing properties refer to the characteristic of forming a resin-cured film with sufficient hardness and solvent resistance.

[0061] The functional group of the constituent unit (a-2) in this embodiment is at least one selected from epoxy, silyl, terminal isocyanate, mercapto, isocyanate, hydroxyl, oxetyl, amino, furanyl, maleimino, azolidinyl, azoloyl, formazanyl, nitro, and halogen. Among these, the functional group that reacts under the action of heat is preferred, more preferably the group that reacts at a temperature of 40°C to 180°C, even more preferably the group that reacts at a temperature of 50°C to 170°C, and most preferably the group that reacts at a temperature of 60°C to 160°C. From the viewpoint of ease of acquisition and reactivity in the synthesis of resin (A), the constituent unit having an epoxy group (a-2-1), the constituent unit having a silyl group (a-2-2), and the constituent unit having a terminal isocyanate group (a-2-3) are preferred.

[0062] The content of constituent unit (a-2) in this embodiment is preferably 2-80 mol% of all constituent units of resin (A), more preferably 5-60 mol%, and even more preferably 10-40 mol%. If the content of constituent unit (a-2) is 2 mol% or more, the photosensitive resin composition using the resin composition containing resin (A) as a raw material can form a resin curing film with sufficient hardness and solvent resistance, and good low-temperature curing properties. If the content of constituent unit (a-2) is 80 mol% or less, the content of functional constituent units (a-1) and (a-3) in all constituent units can be sufficiently ensured.

[0063] As a method for introducing the constituent unit (a-2) into the resin (A) of this embodiment, examples include introducing it by copolymerizing a monomer (ma-2) having an ethylene unsaturated group and the aforementioned functional group (hereinafter also referred to as "monomer (ma-2)") with other monomers containing ethylene unsaturated groups, or introducing the aforementioned functional group into the precursor of the resin (A) after polymerization to form the resin (A).

[0064] The monomer (ma-2) is not particularly limited as long as it does not contain reactive methylene, reactive methine, or carboxyl groups, but is a compound having an vinyl unsaturated group and the aforementioned functional groups. Examples of vinyl unsaturated groups include vinyl, allyl, and (meth)acryloxy. Among these, (meth)acryloxy is preferred from the viewpoint of ease of polymerization in obtaining resin (A).

[0065] From the viewpoint that the photosensitive resin composition using monomer (ma-2) has good low-temperature curing properties, or that the resin-cured film of the photosensitive resin composition has good hardness or solvent resistance, the monomer (ma-2) is preferably an epoxy-containing vinyl unsaturated compound (ma-2-1), a silyl-containing vinyl unsaturated compound (ma-2-2), or an isocyanate-terminated vinyl unsaturated compound (ma-2-3).

[0066] Specific examples of epoxy-containing vinyl unsaturated compounds (ma-2-1) include glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, (meth)acrylates having alicyclic epoxy groups and their lactone adducts, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, epoxides of dicyclopentenyl (meth)acrylate, and epoxides of dicyclopentenyloxyethyl (meth)acrylate, etc., all of which are epoxy-containing (meth)acrylates. Among these, from the viewpoint of ease of acquisition and reactivity in synthesizing resin (A), glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, and (meth)acrylates having alicyclic epoxy groups are preferred, and glycidyl methacrylate is even more preferred.

[0067] Specific examples of silyl-containing vinyl unsaturated compounds (ma-2-2) include [(meth)propenyloxy]methyltriethoxysilane, [(meth)propenyloxy]ethyltriethoxysilane, [(meth)propenyloxy]propyltriethoxysilane, [(meth)propenyloxy]octyltriethoxysilane, [(meth)propenyloxy]propylmethyldiethoxysilane, [(meth)propenyloxy]ethylmethyldiethoxysilane, and [(meth)propenyloxy]nonylmethyldiethoxysilane. Of these, from the viewpoint of ease of acquisition and reactivity in the synthesis of resin (A), 3-(meth)propenyloxypropylmethyldimethoxysilane and 3-(meth)propenyloxypropylmethyldiethoxysilane are preferred, and 3-(meth)propenyloxypropylmethyldiethoxysilane is even more preferred.

[0068] Specific examples of vinyl unsaturated compounds (ma-2-3) containing terminal isocyanate groups include monomers having vinyl unsaturated bonds and terminal isocyanate groups. Examples of such monomers include compounds obtained by capping the isocyanate groups in isocyanate compounds containing vinyl or (meth)acryloxy groups with a capping agent. The reaction between the isocyanate compound and the capping agent can proceed regardless of the presence or absence of a solvent. When using a solvent, it is essential to use a solvent that is inert to the isocyanate groups. Organometallic salts such as tin, zinc, and lead, or tertiary amines can be used as catalysts in the capping reaction. The reaction can generally be carried out at -20 to 150°C, preferably at 0 to 100°C. Examples of the aforementioned isocyanate compounds include compounds represented by the following formula (XX1).

[0069]

[0070] In the above formula (XX1), R11 represents a hydrogen atom or a methyl group, and R12 is -CO-, -COOR13- (here, R13 is an alkyl group with 1 to 6 carbon atoms) or -COO-R14O-CONH-R15- (here, R14 is an alkyl group with 2 to 6 carbon atoms, R15 is an alkyl group with 2 to 12 carbon atoms that may have substituents, or an aryl group with 6 to 12 carbon atoms). R12 is preferably -COOR13-, and here, R13 is preferably an alkyl group with 1 to 4 carbon atoms.

[0071] Specifically, examples of isocyanate compounds represented by formula (XX1) above include 2-isocyanoethyl (meth)acrylate, 2-isocyanopropyl (meth)acrylate, 3-isocyanopropyl (meth)acrylate, 2-isocyano-1-methylethyl (meth)acrylate, 2-isocyano-1,1-dimethylethyl (meth)acrylate, 4-isocyanocyclohexyl (meth)acrylate, and methacrylic acid isocyanate. Alternatively, a product of the reaction of 2-hydroxyalkyl (meth)acrylate with a diisocyanate compound in equal moles (1 mole:1 mole) can also be used. The alkyl group of the above-mentioned 2-hydroxyalkyl (meth)acrylate is preferably ethyl or n-propyl, and more preferably ethyl. Examples of the aforementioned diisocyanate compounds include hexamethylene diisocyanate, 2,4-(or 2,6-)toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 3,5,5-trimethyl-3-isocyanomethylcyclohexyl isocyanate (IPDI), m-(or p-)xylene diisocyanate, 1,3-(or 1,4-)bis(isocyanomethyl)cyclohexane, and lysine diisocyanate.

[0072] Among these isocyanate compounds, 2-isocyanoethyl (meth)acrylate, 2-isocyanopropyl (meth)acrylate, 3-isocyanopropyl (meth)acrylate, 2-isocyano-1-methylethyl (meth)acrylate, 2-isocyano-1,1-dimethylethyl (meth)acrylate, 4-isocyanocyclohexyl (meth)acrylate and methacrylic isocyanate are preferred, and 2-isocyanoethyl (meth)acrylate and 2-isocyanopropyl (meth)acrylate are even more preferred.

[0073] Examples of end-capping agents for capping isocyanate groups in isocyanate compounds include endoamines such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam; alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl ceroxysulfonyl, butyl ceroxysulfonyl, methyl carbitol, benzyl alcohol, phenyl ceroxysulfonyl, furfuryl alcohol, and cyclohexanol; phenols such as phenol, cresol, xylenol, ethylphenol, o-isopropylphenol, p-tert-butylphenol, p-tert-octylphenol, nonylphenol, dinonylphenol, styrylphenol, hydroxybenzoate, thymol, p-naphthol, p-nitrophenol, and p-chlorophenol; and dimethyl malonate, diethyl malonate, methyl acetate, and acetic acid. The active methylene groups of ethyl acetate, acetoacetone, etc.; the thiol groups of butyl mercaptan, thiophenol, tri-dodecyl mercaptan, etc.; the amine groups of diphenylamine, phenylnaphthylamine, aniline, carbazole, etc.; the acid-acetylamine groups of acetoaniline, methoxyacetoaniline, acetate, benzoylamine, etc.; the acid-acetylamine groups of succinate acetylimine, maleate acetylimine, etc.; imidazole, 2-methylimidazole, 2 Imidazole-based compounds such as ethylimidazole; urea-based compounds such as urea, thiourea, and ethylene urea; carbamate-based compounds such as phenyl N-phenylcarbamate and 2-acezolinone; imine-based compounds such as ethyleneimine and polyethyleneimine; oxime-based compounds such as formaldehyde oxime, acetaldehyde oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, and cyclohexanone oxime; and bisulfite-based compounds such as sodium bisulfite and potassium bisulfite. Among these, from the viewpoint of ease of acquisition and reactivity during the synthesis of resin (A), diethyl malonate, 3,5-dimethylpyrazole, and methyl ethyl ketone oxime are preferred end-capping agents.

[0074] Other specific examples of monomers (ma-2) include thiol-containing vinyl unsaturated compounds other than epoxy-containing vinyl unsaturated compounds (ma-2-1), silyl-containing vinyl unsaturated compounds (ma-2-2), and end-capped isocyanate-containing vinyl unsaturated compounds (ma-2-3), such as 2-mercaptoethyl (meth)acrylate. 2-(meth)acryloxyethyl isocyanate, 2-isocyanopropyl (meth)acrylate, 3-isocyanopropyl (meth)acrylate, 2-isocyano-1-methylethyl (meth)acrylate, 2-isocyano-1,1-dimethylethyl (meth)acrylate, 4-isocyanocyclohexyl (meth)acrylate, and other isocyanate-containing vinyl unsaturated compounds; Hydroxyl-containing vinyl unsaturated compounds such as 2-hydroxyethyl methacrylate, 2-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, and 2-hydroxy-3-phenoxypropyl methacrylate; (3-ethylcycloheterobutane-3-yl)methyl(meth)acrylate and other oxy-heterobutyl vinyl unsaturated compounds; 3-(N,N-dimethylamino)propyl (meth)acrylate, 3-(N,N-diethylamino)propyl (meth)acrylate, and other amine-containing vinyl unsaturated compounds; tetrahydrofurfuryl (meth)acrylate and other furan-containing vinyl unsaturated compounds; N-(3,4,5,6-tetrahydrophthalimide)ethyl (meth)acrylate, 2-maleimide ethyl (meth)acrylate, 2-benzylmaleimide ethyl (meth)acrylate, 2-phenylmaleimide ethyl (meth)acrylate, and other vinyl unsaturated compounds containing maleimide groups; 2-(2-O-3-Azolidinediyl)ethyl (meth)acrylate and other vinyl unsaturated compounds containing an acezolidinyl group; 2-Azolylethyl (meth)acrylate and other vinyl unsaturated compounds containing an acetazole group; Ethylene unsaturated compounds containing methyl groups, such as methylphenyl (meth)acrylate; nitropropyl (meth)acrylate and other nitroethyl ethyl unsaturated compounds containing nitro groups; Halogenated vinyl unsaturated compounds such as 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, and 1H,1H,2H,2H-tridecylfluorooctyl (meth)acrylate.

[0075] [Constructing Unit (a-3)] The resin (A) of this embodiment contains a-3, which is a constituent unit other than the constituent units (a-1) and (a-2), and is a constituent unit with an acid group. The resin (A) may contain only one type of constituent unit (a-3) or two or more types.

[0076] Examples of acid groups in the constituent unit (a-3) of this embodiment include carboxyl groups, phosphonic acid groups (-OP(=O)(OH) 2), and sulfonic acid groups (-S(=O) 2OH). Among these, from the viewpoint of image development as a component of a photosensitive resin, carboxyl groups are preferred.

[0077] Of all the constituent units of resin (A), the content of constituent unit (a-3) is preferably 2 to 60 mol%, more preferably 4 to 40 mol%, and even more preferably 6 to 30 mol%. If the content of constituent unit (a-3) is 2 mol% or more, the effect caused by the presence of carboxyl groups is sufficiently obtained. If the content of constituent unit (a-3) is 60 mol% or less, the content of constituent units (a-1) and (a-2) can be sufficiently ensured.

[0078] As a method for introducing the constituent unit (a-3) into the resin (A), examples include introducing it by copolymerizing a monomer (ma-3) having an ethylene unsaturated group and an acid group (hereinafter referred to as "monomer (ma-3)") with other monomers containing ethylene unsaturated groups, or by polymerizing the precursor of the resin (A) and then introducing the acid group to form the resin (A). As the latter method, for example, a resin (A) with an acid group can be obtained by polymerizing a precursor of the resin (A) having hydroxyl groups and then adding a polyacid anhydride to the hydroxyl groups of the precursor.

[0079] Examples of monomers (ma-3) include unsaturated carboxylic acids or their anhydrides, unsaturated sulfonic acids, and unsaturated phosphonic acids. Specific examples of preferred monomers include unsaturated carboxylic acids or their anhydrides such as (meth)acrylic acid, α-bromo(meth)acrylic acid, β-furanyl(meth)acrylic acid, crotonic acid, propynic acid, cinnamic acid, α-cyanocinonic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, itconic acid, itconic anhydride, citracic acid, and citracic anhydride; unsaturated sulfonic acids such as vinylsulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamide sulfonic acid, and p-styrene sulfonic acid; unsaturated phosphonic acids such as 2-(meth)acryloxyethyl phosphate and vinylphosphonic acid; and 2-(meth)acryloxyethyl succinic acid, 2-acryloxyethyl phthalic acid, and 2-(meth)acryloxyethyl hexahydrophthalic acid. These single systems can be used alone or in combination of two or more. Among these, from the viewpoint of ease of acquisition and reactivity in the synthesis of resin (A), (meth)acrylic acid and unsaturated carboxylic acid are preferred, and (meth)acrylic acid is even more preferred.

[0080] [Other constituent units (a-4)] Resin (A) may contain other constituent units (a-4) besides the constituent units (a-1), (a-2), and (a-3) as needed. The constituent unit (a-4) contained in resin (A) may be only one type or two or more types.

[0081] When resin (A) contains constituent unit (a-4), its content is preferably 1 to 80 mol%, more preferably 4 to 70 mol%, and even more preferably 10 to 30 mol%, out of all constituent units in resin (A). If the content of constituent unit (a-4) is 1 mol% or more, the effect of containing constituent unit (a-4) is sufficiently obtained. Furthermore, if the content of constituent unit (a-4) is 80 mol% or less, the content of constituent units (a-1), (a-2), and (a-3) can be sufficiently ensured.

[0082] As a method for introducing the constituent unit (a-4) into the resin (A), one example is the method of introducing the monomer (ma-4) (hereinafter referred to as "monomer (ma-4)"), which does not have active methylene, active methine, the aforementioned functional groups and acid groups, but has vinyl unsaturated groups, by copolymerizing it with other monomers containing vinyl unsaturated groups.

[0083] Examples of monomers (ma-4) include dienes such as butadiene, (meth)acrylates, styrene, unsaturated dicarboxylic acid diesters, and other vinyl compounds.

[0084] Specific examples of (meth)acrylates include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, tributyl methacrylate, amyl methacrylate, neopentyl methacrylate, 2-ethylhexyl methacrylate, isoamyl methacrylate, and alkyl methacrylates such as methacrylate dodecyl ester. Cyclopentyl methacrylate, cyclohexyl methacrylate, ethylcyclohexyl methacrylate, norborneol methacrylate, dicyclopentyl methacrylate, isoborneol methacrylate, adamantane methacrylate, and other cycloalkyl methacrylates; Aromatic (meth)acrylates such as benzyl (meth)acrylate, triphenyl (meth)acrylate, cumyl (meth)acrylate, naphthyl (meth)acrylate, anthracene (meth)acrylate, etc. Rosin (meth) acrylate, 1,1,1-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-(2-ethyleneoxyethoxy)ethyl (meth) acrylate, etc.

[0085] Specific examples of styrene include styrene and its α-, O-, M-, and P-alkyl derivatives. Specific examples of unsaturated dicarboxylic acid diesters include diethyl citrate, diethyl maleate, diethyl fumarate, and diethyl itconate.

[0086] Specific examples of other vinyl compounds include norcamphene (bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, tetracyclo[4.4.0.12,5.17,10]dodec-3-ene, 8-methyltetracyclo[4.4.0.12,5.17,10]dodec-3-ene, 8-ethyltetracyclo[4.4.0.12,5.17,10]dodec-3-ene, dicyclopentadiene, tricyclo[5.2.1.02,6]dec-8-ene, tricyclo[5.2.1.02,6]dec-3-ene, tricyclo[4.4.0.12,5]undec-3-ene, and tricyclo[6.2.1.01,8]undec-9-ene. Tricyclic[6.2.1.01,8]undecyl-4-ene, tetracyclic[4.4.0.12,5.17,10.01,6]dodecyl-3-ene, 8-methyltetracyclic[4.4.0.12,5.17,10.01,6]dodecyl-3-ene, 8-ethylenetetracyclic[4.4.0.12,5.17,12]dodecyl-3-ene, 8-ethylenetetracyclic[4.4.0.12,5.17,10.01,6]dodecyl-3-ene, pentadecyl[6.5.1.13,6.02,7.09,13]pentadecanyl-4-ene, pentadecyl[7.4.0.12,5.19,12.08,13]pentadecanyl-3-ene, (meth)acrylate phenylene, vinylpyridine, vinyl acetate, vinyltoluene, etc.

[0087] Of these, from the viewpoint of ease of acquisition and reactivity in the synthesis of resin (A), (meth)acrylates and other vinyl compounds are preferred, more preferably methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentyl (meth)acrylate, styrene, vinyltoluene and norbornene, and especially preferably methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and dicyclopentyl (meth)acrylate.

[0088] "Weight-average molecular weight (Mw)" The weight-average molecular weight (Mw) of the resin (A) in this embodiment, converted to polystyrene, is preferably 1000-50000, more preferably 2000-30000, and most preferably 3000-12000. If the weight-average molecular weight (Mw) of the resin (A) is 1000 or higher, then when using a resin composition containing resin (A) as a raw material for a photosensitive resin composition, a photosensitive resin composition is obtained in which defects such as gaps are less likely to occur in the resin hardened film after development. If the weight-average molecular weight of the resin (A) is 50000 or lower, then the photosensitive resin composition containing resin (A) has a sufficiently short development time and excellent practicality.

[0089] The weight-average molecular weight (Mw) of the resin (A) in this embodiment was determined by gel permeation chromatography (GPC) under the following conditions and converted to polystyrene. Tube String: Shodex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko Co., Ltd.) Column temperature: 40℃ Sample: A tetrahydrofuran solution containing 0.2% by mass of resin (A) Developing solvent: tetrahydrofuran Detector: Differential refractometer (trade name: Shodex RI-71S, manufactured by Showa Denko Co., Ltd.) Flow rate: 1 mL / min

[0090] The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of resin (A) is preferably 1.3 to 5.0, more preferably 1.5 to 4.0, and most preferably 1.5 to 3.0. If the molecular weight distribution (Mw / Mn) of resin (A) is 1.3 or higher, the target values ​​of the weight average molecular weight (Mw), acid value, etc., and the reaction conditions during the manufacture of resin (A) can be optimized within a certain range, allowing for efficient manufacturing. If the molecular weight distribution (Mw / Mn) of resin (A) is 3.0 or lower, when using a resin composition containing resin (A) as a raw material for a photosensitive resin composition, a photosensitive resin composition in which performance such as imaging properties does not deviate can be obtained. Furthermore, the molecular weight distribution (Mw / Mn) was calculated using the chromatography chromatograms obtained by the aforementioned GPC.

[0091] Acid value The acid value of resin (A) is not particularly limited, but it is preferably 10 KOH mg / g to 300 KOH mg / g, more preferably 20 KOH mg / g to 200 KOH mg / g, and most preferably 25 KOH mg / g to 150 KOH mg / g. If the acid value of resin (A) is 10 KOH mg / g or higher, then when using a resin composition containing resin (A) as a raw material for a photosensitive resin composition, a photosensitive resin composition with better imaging properties is obtained. If the acid value of resin (A) is 300 KOH mg / g or lower, then when using a resin composition containing resin (A) as a raw material for a photosensitive resin composition, the exposed portion (photocured portion) does not dissolve in the alkaline developing solution, resulting in a photosensitive resin composition with good imaging properties.

[0092] Furthermore, the acid value of resin (A) is determined according to JIS K6901 5.3 using a mixed indicator of bromothymol blue and phenol red. The acid value of resin (A) refers to the number of mg of potassium hydroxide required to neutralize the acidic components contained in 1g of resin (A).

[0093] "Functional group equivalent" The functional group equivalent of the resin (A) in this embodiment is the equivalent of the aforementioned functional groups contained in the constituent unit (a-2) contained in the resin (A). The aforementioned functional group equivalent is not particularly limited, but is preferably 200 g / mol to 5000 g / mol, more preferably 300 g / mol to 4000 g / mol, and most preferably 300 g / mol to 3000 g / mol. If the functional group equivalent of the resin (A) is 200 g / mol or more, the photosensitive resin composition containing the resin (A) can form a resin curing film with superior hardness. Furthermore, if the functional group equivalent of the resin (A) is 200 g / mol or more, when using a resin composition containing the resin (A) as a raw material for a photosensitive resin composition, a photosensitive resin composition with better imaging properties can be obtained. In addition, if the functional group equivalent of resin (A) is less than 5000 g / mol, the photosensitive resin composition containing resin (A) can form a resin curing film with superior hardness.

[0094] Furthermore, the functional group equivalent of resin (A) is obtained by dividing the molecular weight of resin (A) by the average number of the aforementioned functional groups contained in each molecule of constituent unit (a-2). The functional group equivalent of resin (A) is a calculated value based on the amount of polymerizable unsaturated compound (raw material monomer) used as a raw material in the synthesis of 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 group.

[0095] "Equivalent amounts of active methylene and active methine groups" The equivalent amount of active methylene and active methine groups in resin (A) is not particularly limited, but is preferably 200 g / mol to 5000 g / mol, more preferably 300 g / mol to 4000 g / mol, and most preferably 300 g / mol to 3000 g / mol. If the equivalent amount of active methylene and active methine groups in resin (A) is 200 g / mol or more, the photosensitive resin composition containing resin (A) can form a resin curing film with superior hardness. Furthermore, if the equivalent amount of active methylene and active methine groups in resin (A) is 200 g / mol or more, when using a resin composition containing resin (A) as a raw material for a photosensitive resin composition, a photosensitive resin composition with better imaging properties can be obtained. Furthermore, if the equivalent amount of active methylene groups in resin (A) is 5000 g / mol or less, the photosensitive resin composition containing resin (A) can form a resin curing film with superior hardness.

[0096] Furthermore, the equivalent of active methylene and active methine groups in resin (A) is obtained by dividing the molecular weight of resin (A) by the average number of active methylene and active methine groups per molecule. The equivalent of active methylene and active methine groups in resin (A) is calculated based on the amount of polymerizable unsaturated compounds (raw material monomers) used as raw materials in the synthesis of resin (A). When one molecule of resin (A) contains different types of active methylene and active methine groups, regardless of the type of active methylene and active methine groups, all active methylene and active methine groups are counted as the number of active methylene and active methine groups.

[0097] Hydroxyl equivalent When resin (A) contains hydroxyl groups, the hydroxyl equivalent is not particularly limited, but it is preferably 200 g / mol to 5000 g / mol, more preferably 300 g / mol to 4000 g / mol, and most preferably 300 g / mol to 3000 g / mol. If the hydroxyl equivalent of resin (A) is 200 g / mol or more, the photosensitive resin composition system containing resin (A) can form a resin-cured film with superior hardness. Furthermore, if the hydroxyl equivalent of resin (A) is 5000 g / mol or less, the photosensitive resin composition system containing resin (A) can form a resin-cured film with superior hardness.

[0098] Furthermore, the hydroxyl equivalent of resin (A) is obtained by dividing the molecular weight of resin (A) by the average number of hydroxyl groups per molecule. The hydroxyl equivalent of resin (A) is a calculated value based on the amount of polymerizable unsaturated compounds (raw material monomers) used as raw materials in the synthesis of resin (A). When one molecule of resin (A) contains different types of hydroxyl groups, all hydroxyl groups are counted as the number of hydroxyl groups, regardless of their type.

[0099] <Manufacturing Method of Resin (A)> To manufacture the resin (A) contained in the resin composition of this embodiment, the manufacturing method shown below can be used, for example. That is, raw material monomers consisting of monomers (ma-1) to (ma-3) and other monomers (ma-4) as needed are copolymerized using a polymerization initiator according to a free radical polymerization method well known in the art. Resin (A) is thus obtained.

[0100] Specifically, the following method can be used: dissolving the raw material monomer in a polymerization solvent to prepare a raw material monomer solution, and then adding a polymerization initiator to the raw material monomer solution, for example, copolymerizing the raw material monomer at 50°C to 130°C for 1 hour to 20 hours while stirring.

[0101] (Polymerization solvent) As a polymerization solvent used in the manufacture of resin (A), any solvent that is inert to the copolymerization reaction of the raw material monomers is acceptable, and there are no particular limitations. The polymerization solvent used in the manufacture of resin (A) may be the same as the solvent contained in solvent (D) contained in the resin composition described later, or it may be partially or entirely different from the solvent contained in solvent (D). When one or more of the polymerization solvent used in the manufacture of resin (A) is the same as the solvent contained in solvent (D) contained in the resin composition, it is preferable not to separate and remove the polymerization solvent from the reaction solution after the copolymerization reaction is completed, but to use it as part of solvent (D).

[0102] As a solvent for polymerization, there are no particular limitations as long as it can dissolve the monomer and the resulting copolymer and does not hinder the polymerization reaction. When the resulting copolymer is a (meth)acrylic acid polymer, glycol ether solvents are preferred from the viewpoint of solubility. Specifically, 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 mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monophenyl ether, propylene glycol monomethyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether. These solvents can be used alone or in combination of two or more. Of these, from the viewpoint of ease of acquisition and reactivity, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferred.

[0103] There is no particular limitation on the amount of polymerization solvent used in the manufacture of resin (A), but it is preferably 30 to 1000 parts by mass relative to 100 parts by mass of the raw monomer, and more preferably 50 to 800 parts by mass. If the amount of polymerization solvent used is 30 parts by mass or more, the copolymerization reaction of the raw monomer can be carried out stably, and the coloring and gelation of resin (A) can be prevented. If the amount of polymerization solvent used is less than 1000 parts by mass, the decrease in molecular weight of resin (A) caused by chain transfer can be suppressed, and the viscosity of the reaction solution can be controlled within an appropriate range.

[0104] (Polymerization initiator) There are no particular limitations on the polymerization initiators that can be used in the copolymerization reaction of raw monomers, but examples include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylpentanonitrile), dimethyl 2,2'-azobis(isobutyric acid) ester, benzoyl peroxide, and tert-butylperoxy-2-ethylhexanoate. These polymerization initiators can be used alone or in combination of two or more. There is no particular limitation on the amount of polymerization initiator used, but it is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of raw monomer, and more preferably 0.5 to 16 parts by mass.

[0105] The content of resin (A) in the photosensitive resin composition of this embodiment, when the total amount of components after removing the solvent (D) contained in the photosensitive resin composition is taken as 100 parts by mass, is preferably 10 parts by mass to 85 parts by mass, more preferably 15 parts by mass to 75 parts by mass, and most preferably 25 parts by mass to 65 parts by mass. If the content of reactive diluent (A) is within the above range, the viscosity and low-temperature curing properties of the photosensitive resin composition are appropriately modified.

[0106] [Reactive diluent (B)] The reactive diluent (B) contained in the photosensitive resin composition of this embodiment can be any low molecular weight compound having vinyl, allyl, or (meth)acryloxy vinyl groups or other vinyl unsaturated groups, and there are no particular limitations. Specific examples of reactive diluent (B) include aromatic vinyl monomers; polycarboxylic acid monomers such as vinyl acetate and vinyl adipate; monofunctional (meth)acrylates; polyfunctional (meth)acrylates; and triallyl cyanurate.

[0107] Specific examples of aromatic vinyl monomers include styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, divinylbenzene, diallyl phthalate, and diallyl phenylphosphonate.

[0108] Specific examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, β-hydroxyethyl (meth)acrylate, and hydroxypropyl (meth)acrylate.

[0109] Specific examples of polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tri(meth)acrylate of tri(hydroxyethyl)isocyanurate.

[0110] Among these, as a reactive diluent (B), in order to improve curability (reactivity), polyfunctional (meth)acrylates are preferred, especially dipentaerythritol pentamethacrylate and / or dipentaerythritol hexamethacrylate. These reactive diluents (B) can be used alone or in combination of two or more.

[0111] The content of reactive diluent (B) in the photosensitive resin composition of this embodiment, when the total amount of components after removing the solvent (D) contained in the photosensitive resin composition is taken as 100 parts by mass, is preferably 10 parts by mass to 85 parts by mass, more preferably 15 parts by mass to 75 parts by mass, and most preferably 25 parts by mass to 65 parts by mass. If the content of reactive diluent (B) is within the above range, the viscosity and photocurability of the photosensitive resin composition are appropriately modified.

[0112] [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 generates free radicals by light irradiation. Examples of photopolymerization initiators (C) include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4-(1-tert-butyldioxy-1-methylethyl)acetophenone; alkyl acetophenones such as 1-hydroxycyclohexylphenyl ketone and 2-hydroxy-2-methyl-1-phenylpropane-1-one; anthraquinones such as 2-methylanthraquinone, 2-pentylanthraquinone, 2-tert-butylanthraquinone, and 1-chloroanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; and benzophenone, 4-(1-tert-butyldioxy-1-methylethyl)acetophenone, etc. Benzophenones such as 3,3',4,4'-tetra(tert-butyldioxycarbonyl)benzophenone; 1,2-octanedione, 1-[4-(phenylthio)-2-(o-benzoxyl)], acetone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl], 1-(o-acetyl)oxime Oxime esters, etc.; 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propane-1-one; 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone-1; acetylated phosphine oxides such as 2,4,6-trimethylbenzyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzyl)phenylphosphine oxide; xanthones, etc. These photopolymerization initiators (C) can be used alone or in combination of two or more.

[0113] The content of the photopolymerization initiator (C) in the photosensitive resin composition of this embodiment, taking the total amount of components after removing the solvent (D) contained in the photosensitive resin composition as 100 parts by mass, is preferably 0.1 parts by mass to 30 parts by mass, more preferably 0.3 parts by mass to 20 parts by mass, and most preferably 0.5 parts by mass to 10 parts by mass. If the content of the photopolymerization initiator (C) is 0.1 parts by mass or more, the photosensitive resin composition has sufficient photocurability. If the content of the photopolymerization initiator (C) is 30 parts by mass or less, the photopolymerization initiator (C) does not adversely affect the storage stability of the photosensitive resin composition or the performance of the resin cured film.

[0114] [Solvent (D)] The solvent (D) contained in the resin composition of this embodiment can be any solvent that is inert to the resin (A) and can dissolve the resin (A), and there is no particular limitation. The solvent (D) may or may not contain the polymerization solvent used in the manufacture of the resin (A). When the solvent (D) contains a polymerization solvent used in the manufacture of resin (A), the polymerization solvent may be used directly as part or all of the solvent (D) of the resin composition without removing it from the reaction solution after the copolymerization reaction for the manufacture of resin (A).

[0115] The case where solvent (D) does not contain the polymerization solvent used in the manufacture of resin (A) refers to the situation where the resin (A), used as a raw material for the resin composition, is separated and removed from the reaction solution in which resin (A) is generated. In this case, regardless of the type and amount of the polymerization solvent used in the manufacture of resin (A), the type and content of solvent (D) can be appropriately selected according to the type of resin (A) and the intended use of the resin composition. That is, when the resin (A) is a solvent separated and removed from the reaction solution in which resin (A) is generated, the solvent (D) can be the same type as the polymerization solvent used in the manufacture of resin (A) or a different type.

[0116] The solvent (D) is not particularly limited, but when the resin (A) is a (meth)acrylic acid polymer, from the viewpoint of solubility, a glycol ether solvent is preferred. Specifically, 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 mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monophenyl ether, propylene glycol monomethyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether. These solvents can be used alone or in combination. Of these, from the viewpoint of ease of acquisition and reactivity, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferred.

[0117] Solvent (D) may contain other solvents that can dissolve resin (A).

[0118] Examples include monools and (poly)alkyl diol monoalkyl ethers. Specific examples of monools 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 butanol and diacetone alcohol; (poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and ethyl 3-ethoxypropionate. Esters such as ethyl acetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-butyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl acetate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate, etc.; aromatic hydrocarbons such as toluene and xylene; carboxylic acids such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide, etc.

[0119] The solvent (D) content in the resin composition of this embodiment, when the total amount of components after removing the solvent (D) from the resin composition is taken as 100 parts by mass, is preferably 30 parts by mass to 1000 parts by mass, more preferably 50 parts by mass to 800 parts by mass, and most preferably 100 parts by mass to 700 parts by mass. If the solvent (D) content is within the above range, the viscosity of the resin composition can be adjusted to an appropriate range.

[0120] [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 needed. The content of these additives is not particularly limited as long as it does not impair the effects of the present invention.

[0121] Furthermore, in order to improve curability, the photosensitive resin composition of this embodiment may contain amines, acetylhydrazine, aldehydes, or metal salts as crosslinking agents. Examples of crosslinking agents include MXDA and 1,3-BAC manufactured by Mitsubishi Gas Chemical Co., Ltd.; ADH and APA-280 manufactured by Otsuka Chemical Co., Ltd.; SEQUAREZ 755 manufactured by OMNOVA Solutions Co., Ltd.; and ZIRCOZOL ZC-2,7 manufactured by Daiichi Rare Element Chemical Industry Co., Ltd.

[0122] Furthermore, the photosensitive resin composition of this embodiment may also contain acid-generating agents and alkali-generating agents to improve curability. In particular, from a potential point of view, it is preferable to use photoacid-generating agents, photoalkali-generating agents, thermal acid-generating agents, and thermal alkali-generating agents; from a storage stability point of view, photoacid-generating agents and photoalkali-generating agents are even more preferred. Examples of photoacid-generating agents include strontium salt compounds such as CPI-200K, CPI-210S, CPI-310B, and CPI-410S manufactured by SAN-APRO Chemical Co., Ltd., and iodonium salt compounds such as IK-1. Examples of photoalkali-generating agents include WPBG-266, WPBG-300, and WPBG-345 manufactured by Fujifilm and Hikari Pure Chemical Co., Ltd.

[0123] [Viscosity of photosensitive resin composition] The viscosity of the photosensitive resin composition in this embodiment can be appropriately adjusted according to the thickness of the resin curing film formed by the cured photosensitive resin composition. For example, when the thickness of the resin curing film is adjusted to 1~4μm, the viscosity of the photosensitive resin composition is preferably 1mP·s~25mP·s, more preferably 2mP·s~20mP·s, and most preferably 3mP·s~15mP·s.

[0124] <Photosensitive coloring composition> The photosensitive coloring composition of this embodiment includes the photosensitive resin composition of this embodiment and the colorant (E). [Coloring agent (E)] As a colorant (E), well-known dyes and / or pigments can be used. When using dyes as colorants (E), compared with the use of pigments, a high-brightness colored pattern can be obtained, and it becomes a photosensitive coloring composition that exhibits good alkaline imaging properties.

[0125] From the viewpoints of solubility in solvents (D) and alkaline developing solutions, interaction with other components in the photosensitive resin composition, and heat resistance, it is preferable to use acid dyes with acidic groups such as carboxyl groups, salts of acid dyes and nitrogen compounds, and sulfonamide forms of acid dyes. 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; and Solvent Blue 38, 44 (VALIFAST). BLUE2620); Acid Chrome Violet K; Acid Magenta; Acid Green 1, 3, 5, 25, 27, 50; Acid Orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134 The following dyes are permitted: 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 its derivatives. Among these, azo, xanthones, anthraquinones, or phthalocyanine acid dyes are preferred. These dyes can be used alone or in combination of two or more, depending on the desired pixel color.

[0126] Examples of CI pigments include yellow pigments such as CI pigments Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, and 214; orange pigments such as CI pigments Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, and 73; and CI pigments Red 9, 97, 105, and 1... CI pigments include: red pigments such as 22, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, and 265; blue pigments such as CI blue 15, 15:3, 15:4, 15:6, and 60; purple pigments such as CI violet 1, 19, 23, 29, 32, 36, and 38; green pigments such as CI green 7, 36, and 58; brown pigments such as CI brown 23 and 25; and black pigments such as CI black 1, 7, carbon black, titanium black, and iron oxide. These pigments are chosen according to the desired pixel color and can be used individually or in combination of two or more.

[0127] When using pigments as colorants (E), from the viewpoint of improving the dispersibility of the colorant (E), well-known dispersants can be incorporated into the photosensitive coloring composition. As a dispersant, a polymeric dispersant with excellent dispersion stability over time is preferred. Examples of polymeric dispersants include carbamate-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic modified ester-based dispersants. Such polymeric dispersants can be commercially available under trade names such as EFKA (manufactured by EFKA Chemicals BV (EFKA) Co., Ltd.), Disperbyk (manufactured by BYK Chemical Co., Ltd.), Disparlon (manufactured by Kusunoki Chemical Co., Ltd.), and SOLSPERSE (manufactured by ZENECA Co., Ltd.). The amount of dispersant incorporated should be appropriately set according to the type and amount of pigment used as the colorant (E).

[0128] The content of colorant (E) in the photosensitive coloring composition of this embodiment, taking the total amount of components after removing the solvent (D) contained in the photosensitive coloring composition as 100 parts by mass, is preferably 4 to 85 parts by mass, more preferably 9 to 70 parts by mass, and most preferably 15 to 49 parts by mass. If the content of colorant (E) is 4 parts by mass or more, the effect caused by the presence of colorant (E) becomes significant, making it a photosensitive coloring composition suitable as a material for color patterning of color filters. If the content of colorant (E) is 85 parts by mass or less, the colorant (E) in the photosensitive coloring composition does not hinder the curing properties of the photosensitive coloring composition, making it a good candidate for low-temperature curing.

[0129] [Other Additives] The photosensitive coloring composition of this embodiment may contain one or more well-known additives such as leveling agents, thermal polymerization inhibitors, and sensitizers, as needed. The content of these additives is not particularly limited as long as it does not impair the effects of the present invention.

[0130] Furthermore, in order to improve curability, the photosensitive coloring composition of this embodiment may contain amines, acetylhydrazine, aldehydes, or metal salts as crosslinking agents. Examples of crosslinking agents include MXDA and 1,3-BAC manufactured by Mitsubishi Gas Chemical Co., Ltd., ADH and APA-280 manufactured by Otsuka Chemical Co., Ltd., SEQUAREZ 755 manufactured by OMNOVA Solutions Co., Ltd., and ZIRCOZOL ZC-2,7 manufactured by Daiichi Rare Element Chemical Industry Co., Ltd.

[0131] Furthermore, the photosensitive coloring composition of this embodiment may also contain acid-generating agents and alkali-generating agents to improve curability. In particular, from a potential point of view, it is preferable to use photoacid-generating agents, photoalkali-generating agents, thermal acid-generating agents, and thermal alkali-generating agents; from the point of view of storage stability, photoacid-generating agents and photoalkali-generating agents are even more preferred. Examples of photoacid-generating agents include strontium salt compounds such as CPI-200K, CPI-210S, CPI-310B, and CPI-410S manufactured by SAN-APRO Chemical Co., Ltd., and iodonium salt compounds such as IK-1. Examples of photoalkali-generating agents include WPBG-266, WPBG-300, and WPBG-345 manufactured by Fujifilm and Hikari Pure Chemical Co., Ltd.

[0132] [Viscosity of photosensitive coloring composition] The viscosity of the photosensitive coloring composition in this embodiment can be appropriately adjusted according to the thickness of the resin curing film formed by the cured photosensitive coloring composition. For example, when the thickness of the resin curing film is adjusted to 1~4 μm, the viscosity of the photosensitive coloring composition is preferably 1 mP·s~25 mP·s, more preferably 2 mP·s~20 mP·s, and most preferably 3 mP·s~15 mP·s.

[0133] <Manufacturing Method of Photosensitive Resin Composition> The photosensitive resin composition of this embodiment can be manufactured by mixing resin (A), reactive diluent (B), photopolymerization initiator (C), solvent (D), and additives as needed using a well-known mixing device.

[0134] The photosensitive resin composition of this embodiment exhibits good low-temperature curing properties, enabling the formation of a resin-cured film with sufficient hardness and solvent resistance. Furthermore, due to its excellent alkaline development properties, the photosensitive resin composition of this embodiment can form fine patterns by using an alkaline aqueous solution for development. Therefore, the photosensitive resin composition of this embodiment is suitable as a resist.

[0135] <Manufacturing Method of Photosensitive Coloring Composition> The photosensitive coloring composition of this embodiment can be manufactured by mixing resin (A), reactive diluent (B), photopolymerization initiator (C), solvent (D), colorant (E) and additives as needed using a well-known mixing device.

[0136] The photosensitive resin composition of this embodiment exhibits good low-temperature curing properties, enabling the formation of a resin-cured film with sufficient hardness and solvent resistance. Furthermore, due to its excellent alkaline development properties, the photosensitive resin composition of this embodiment can form fine patterns by using an alkaline aqueous solution for development. Therefore, the photosensitive resin composition of this embodiment is suitable as a resist. Furthermore, the photosensitive coloring composition system of this embodiment can be used as a material for coloring patterns such as pixels of a color filter and black matrix.

[0137] <Resin-cured film> Next, the resin-cured film of this embodiment will be described in detail. The resin-cured film of this embodiment is formed from a cured product of the photosensitive resin composition of this embodiment or the photosensitive coloring composition of this embodiment. The resin curing film of this embodiment can be formed, for example, by performing the following steps: a coating step of coating the photosensitive resin composition of this embodiment onto a substrate to form a coating film; a baking step of drying the coating film formed by the coating step; an exposure step of irradiating the dried coating film with light to photocur it; and a post-bake step of heat curing the photocured coating film.

[0138] When forming a resin-cured film with a specified pattern using the photosensitive resin composition of this embodiment via photolithography, the following method can be used, for example. That is, the coating and baking steps described above are performed. Then, in the exposure step, the dried coating film is irradiated with light through a photomask with the specified pattern, causing the exposed portions to photocure. After the exposure step, a post-exposure heat treatment is performed as needed. Subsequently, a developing step is performed to dissolve the unexposed portions of the coating film using a developing solution, followed by a baking step to heat-cur the photocured coating film.

[0139] [Coating Steps] In the coating step, the photosensitive resin composition or the photosensitive coloring composition of this embodiment is coated onto a substrate to form a coating film. In this embodiment, the substrate used for coating the photosensitive resin composition or the photosensitive coloring composition can be any well-known material, and the choice can be made according to the intended use of the resin-cured film. There are no particular limitations on the coating method for photosensitive resin compositions or photosensitive coloring compositions. For example, screen printing, roller coating, curtain coating, spray coating, spin coating, slot coating, etc. can be used.

[0140] [Baking Steps] In the baking (preheating) step, the coating film formed in the coating step is dried to reduce the amount of solvent residue in the coating film. In the baking step, the substrate with the coating film is heated at a temperature of, for example, 50°C to 120°C, preferably 70°C to 110°C, for 10 seconds to 600 seconds, preferably 120 seconds to 180 seconds. Methods for heating the substrate with the coating film in the baking step include, for example, using a heating plate.

[0141] [Exposure Steps] In the exposure step, the surface of the coated film dried in the baking step is irradiated with light to photocur the film. There are no particular limitations on the light source used for irradiation; for example, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, xenon lamps, and metal halide lamps can be used. Furthermore, the exposure amount in the exposure step is not particularly limited and can be appropriately set according to the composition of the photosensitive resin or photosensitive coloring composition and the thickness of the coated film. When forming a resin-cured film with a specified pattern, in the exposure step, the surface of the coated film dried in the baking step is irradiated with light through a photomask with a specified pattern to photocur the exposed portion.

[0142] [Post-exposure heating step] When forming a resin-cured film with a specified pattern, a post-exposure baking step may be performed as needed after the exposure step. This step significantly increases the contrast between the dissolved and unexposed portions of the coating film. The post-exposure baking step differs from the post-baking step described later; it is not intended to completely cure the coating film. The purpose of the post-exposure baking step is to ensure that only the exposed portions of the coating film remain on the substrate during the development step, thereby more effectively removing the unexposed portions. Therefore, it is not a necessary step in the resin-cured film formation method of this embodiment.

[0143] When performing the post-exposure heating step, it is preferable to heat the substrate after the exposure step at a temperature of 40°C to 70°C, more preferably at 50°C to 60°C. If the heating temperature is above 40°C, the post-exposure heating step effectively enhances the dissolution contrast between the exposed and unexposed areas of the coating film. If the heating temperature is below 70°C, the acid generated in the exposed areas will not diffuse to the unexposed areas, resulting in a good dissolution contrast. The heating time in the post-exposure heating step is preferably 20 seconds to 600 seconds. If the heating time is above 20 seconds, the temperature process of the entire coating film will be uniform. If the heating time is below 600 seconds, the acid generated in the exposed areas will not diffuse to the unexposed areas, resulting in a good dissolution contrast. Methods for heating the substrate after the exposure step in the post-exposure heating step include, for example, using a heating plate, oven, or furnace.

[0144] [Development Steps] When forming a resin-cured film with a specified pattern, after the exposure step, a post-exposure heating step is performed as needed, followed by a development step to develop the unexposed portions of the coated film. The developing solution used in the development step can be any alkaline aqueous solution previously used for developing photosensitive resin compositions or photosensitive coloring compositions.

[0145] There are no particular limitations on the alkaline aqueous solution. Examples include aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, etc.; aqueous solutions of amine compounds such as ethylamine, diethylamine, dimethylethanolamine, etc.; aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide; and aqueous solutions of p-phenylenediamine compounds such as 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonyl ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and their sulfates, hydrochlorides, or p-toluenesulfonates. Among these alkaline aqueous solutions, aqueous solutions of p-phenylenediamine compounds are preferred.

[0146] In alkaline aqueous solutions, one or more additives such as defoamers and surfactants may be added as needed. The developing conditions, such as developing temperature and developing time, in the developing process can be appropriately determined according to the composition of the photosensitive resin, the composition of the developing solution, and the thickness of the coating film. In the developing step, after dissolving the unexposed portion of the coated film with the above-mentioned alkaline aqueous solution and developing it, it is preferable to wash it with water and then dry it.

[0147] [Post-baking step] In this embodiment, after the developing step, a baking step is performed to heat-cure the photocured coating film to form a resin-cured film. The heating temperature and heating time in the post-baking step are not particularly limited and can be appropriately set according to the composition of the photosensitive resin composition or photosensitive coloring composition, the thickness of the coating film, the material of the substrate, etc.

[0148] 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, a material with low heat resistance can be used as the material for the color filter. For example, when using a resin substrate as the substrate for forming the resin curing film to form the color pattern of the color filter, the heating temperature can be set to below 150°C, below 120°C, or below 100°C. If the heating temperature is set to below 150°C, the degradation of the colorant (E) can be suppressed while forming a color pattern containing a colorant (E) with poor heat resistance that is difficult to use as a material for the color pattern in the past. Furthermore, when the heating temperature is set to below 150°C, a color pattern can be formed on a substrate with poor heat resistance that is difficult to use as a substrate for the color filter in the past. Additionally, when the heating temperature is set to below 150°C, less energy is required to cure the coating film, making it more suitable.

[0149] If the heating temperature in the post-baking step is 50°C or higher, the resin (A) and reactive diluent (B) will be fully cross-linked, thus obtaining a resin-cured film with sufficient hardness and solvent resistance. Furthermore, if the heating temperature is 50°C or higher, the heating time in the post-baking step is only a short time, allowing for efficient formation of the resin-cured film. The heating temperature in the post-baking step is preferably 60°C or higher, and even more preferably 70°C or higher.

[0150] The heating time in the post-baking step can be appropriately selected according to the heating temperature, the thickness of the coating film, and the composition of the photosensitive resin, for example, it can be set to 10 minutes to 4 hours, preferably 20 minutes to 2 hours.

[0151] The resin-cured film of this embodiment is composed of a cured form 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 curing film of this embodiment can be used as a material for various insulating films, such as protective films installed on the upper part of color filters, insulating films installed between electrodes of touch panels, and interlayer insulating films of thin-film transistors (TFTs).

[0152] <Color Filter> Next, the color filter of this embodiment will be described in detail. Figure 1 is a schematic cross-sectional view showing an example of a color filter according to this embodiment. The color filter shown in Figure 1 includes: a substrate 1, RGB pixels 2 formed on one side 1a of the substrate 1, black matrices 3 formed at the boundaries of each pixel 2, and a protective film 4 formed on the pixel 2 and the black matrices 3.

[0153] The substrate 1 used for the color filter shown in Figure 1 is not particularly limited, and can be made of glass substrate, silicon substrate, polycarbonate substrate, polyester substrate, polyamide substrate, polyamide-imide substrate, polyamide substrate, aluminum substrate, printed wiring substrate, array substrate, etc., depending on the application.

[0154] The pixels 2 and black matrix 3 in the color filter shown in Figure 1 are colored patterns formed by the hardened form of the photosensitive coloring composition of this embodiment. The photosensitive coloring composition includes a resin composition containing resin (A) and solvent (D), a reactive diluent (B), a photopolymerization initiator (C), a colorant (E), and additives as needed. As the protective film 4, it can be made of well-known materials. The protective film 4 can be a resin-cured film made of a cured form of the photosensitive coloring composition of this embodiment, which includes a resin composition containing resin (A) and solvent (D), a reactive diluent (B), a photopolymerization initiator (C), and additives as needed.

[0155] In the color filter of this embodiment shown in FIG1, the components other than the materials of pixel 2 and black matrix 3 can be of well-known types. Furthermore, the color filter shown in FIG1 is an example of the color filter of the present invention, and the present invention is not limited to the example shown in FIG1.

[0156] Next, the manufacturing method of the color filter of this embodiment will be described. First, on one side 1a of the substrate 1 shown in Figure 1, RGB pixels 2 and a black matrix 3 are sequentially formed. The pixels 2 and the black matrix 3 can be manufactured using the resin curing film manufacturing method (photolithography) of this embodiment described above. Next, a protective film 4 is formed on pixel 2 and the black matrix 3. The protective film 4 can be formed using well-known forming methods. For example, the protective film 4 can be manufactured using the resin curing film manufacturing method of this embodiment described above. Through the above steps, the color filter of this embodiment shown in Figure 1 is obtained.

[0157] The color filter of this embodiment has a color pattern (pixels 2 and black matrix 3) formed by a hardened form of the aforementioned photosensitive coloring composition. Therefore, the color pattern in the color filter of this embodiment has sufficient hardness and solvent resistance.

[0158] <Image display element> The image display element of this embodiment includes a color filter that possesses sufficient hardness and solvent resistance. Examples of image display elements of this embodiment include liquid crystal display elements, organic EL display elements, and solid-state imaging elements. The image display element of this embodiment can achieve high brightness display by including the aforementioned color filter. [Example]

[0159] The present invention will now be described in more detail through examples and comparative examples. Furthermore, the examples shown below are provided to facilitate a better understanding of the invention. The invention is not limited to these examples.

[0160] [Synthesis example 1] 350.0 g of propylene glycol monomethyl ether acetate, used as a polymerization solvent, was placed in a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube. The mixture was stirred while being purged with nitrogen, and the temperature was raised to 98°C.

[0161] Next, a mixture of 215.9 g (0.545 moles) of ethylene glycol monoacetate monomethacrylate, 25.9 g (0.14 moles) of methyl methacrylate, 51.3 g (0.195 moles) of glycidyl methacrylate, 19.1 g (0.120 moles) of methacrylic acid, 37.8 g of 2,2'-azobis(isobutyric acid)dimethyl (polymerization initiator), and 143.6 g of propylene glycol monomethyl ether acetate was added dropwise from a dropping funnel to the aforementioned flask over a period of 3 hours. Next, 156.4 g of propylene glycol monomethyl ether acetate as a solvent (the composition uses an added solvent) was added to the reaction solution to obtain the resin composition of copolymer P1, which is the resin (A) of this embodiment in Synthesis Example 1.

[0162] [Synthesis Examples 2~16] Except that the raw materials listed in Table 1 were used in the proportions listed in Table 1, the resin compositions of copolymers P2 to P16 of Synthetic Examples 2 to 16 were obtained in the same manner as in Synthetic Example 1. They are shown in Table 1.

[0163] For the copolymers P1 to P16 contained in the resin compositions of the synthesized Examples 1 to 16 obtained in this way, the weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn), acid value, functional group (epoxy group, terminal isocyanate group, silyl group, hydroxyl group) equivalent, hydroxyl equivalent, and active methylene equivalent were determined. The results are shown in Table 1.

[0164] [Comparative Synthesis Example 1] 350.0 g of propylene glycol monomethyl ether acetate, used as a polymerization solvent, was placed in a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube. The mixture was stirred while being purged with nitrogen, and the temperature was raised to 98°C.

[0165] Next, a mixture of 212.9 g (0.57 moles) of 2-ethylhexyl acrylate, 28.8 g (0.142 moles) of methyl methacrylate, 51.3 g (0.178 moles) of glycidyl methacrylate, 19.2 g (0.110 moles) of methacrylic acid, 37.8 g of dimethyl 2,2'-azobis(isobutyrate) (polymerization initiator), and 143.6 g of propylene glycol monomethyl ether acetate was added dropwise from a dropping funnel to the aforementioned flask over a period of 3 hours. Next, 156.4 g of propylene glycol monomethyl ether acetate was added as a solvent (the solvent added to the composition) to the reaction solution to obtain the resin composition of copolymer cP1 of Comparative Example 1.

[0166] [Compare Synthetic Examples 2-9] Except for using the raw materials listed in Table 2 in the proportions listed in Table 2, resin compositions of copolymers cP1 to cP9 of Comparative Synthesis Examples 1 to 9 were obtained in the same manner as in Comparative Synthesis Example 1.

[0167] For the copolymers cP1 to cP9 contained in the resin compositions of Comparative Examples 1 to 9 obtained in this way, the weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn), acid value, functional group (epoxy group, terminal isocyanate group, silyl group) equivalent, and active methylene equivalent were determined. The results are shown in Table 2.

[0168] [Comparative Synthesis Example 10] 174.4 g of propylene glycol monomethyl ether acetate, used as a polymerization solvent, was added to a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube. The mixture was stirred while being purged with nitrogen, and the temperature was raised to 118°C.

[0169] Next, a mixture of 10.7 g (0.03 moles) of dicyclopentyl methacrylate, 93.5 g (0.27 moles) of ethylene glycol monoacetate monomethacrylate, 160.9 g (0.7 moles) of glycidyl methacrylate, 32.3 g of butylperoxy-2-ethylhexanoate (polymerization initiator), and 68.9 g of propylene glycol monomethyl ether acetate was added dropwise from a dropping funnel to the aforementioned flask over a period of 3 hours. After the addition was complete, the mixture was heated to 120°C and stirred for 30 minutes to initiate a copolymerization reaction, producing a copolymer. Subsequently, the flask was purged with air, and 81.6 g (0.7 moles) of acrylic acid, 1.4 g of triphenylphosphine (addition reaction catalyst), and 0.7 g of methylhydroquinone (polymerization inhibitor) were added to the copolymer solution. The reaction was continued at 110°C for 10 hours. The epoxy groups derived from glycidyl methacrylate were cleaved by the reaction of the epoxy groups with acrylic acid, aiming to introduce vinyl unsaturated bonds into the side chains of the copolymer. However, gelation occurred during the reaction. Furthermore, the reaction was stopped before adding 21.0 g (0.13 moles) of succinic anhydride to the copolymer solution (Comparative Example 10). The equivalents of functional groups (epoxy groups, terminal isocyanates, silyl groups) and the equivalents of active methylene groups in the resin of Comparative Example 10 were determined. The results are shown in Table 2.

[0170]

[0171]

[0172] <Modulation of Photosensitive Coloring Compositions> (Examples 1-16, Comparative Examples 1-9) As copolymer (A), copolymers P1 to P16 of synthetic examples 1 to 16, cP1 to cP9 of comparative synthetic examples 1 to 9, and components (B), (C), and (E) shown in Table 3 were mixed in the proportions shown in Table 3 to prepare photosensitive coloring compositions R1 to R16 and cR1 to cR9 of examples 1 to 16 and comparative examples 1 to 9, respectively.

[0173] Furthermore, the amount of copolymers in the resin compositions listed in Table 3 does not include the polymerization solvents used in synthesizing the copolymers. Also, the amount of solvent (D) in Table 3 is the sum of the polymerization solvents used in synthesizing the copolymers in the resin compositions and the solvents added during the preparation of the resin compositions.

[0174]

[0175] Evaluation of Photosensitive Coloring Compositions The photosensitive coloring compositions R1-R16 and cR1-cR9 prepared in Examples 1-16 and Comparative Examples 1-9 were evaluated by the method shown below.

[0176] (1) Imaging With an exposure thickness of 2.5 μm, the photosensitive coloring compositions R1-R16 and cR1-cR9 prepared in Examples 1-16 and Comparative Examples 1-9 were coated onto a 5 cm square glass substrate (alkali-free glass substrate) using a spin coating method (coating step). The coated glass substrate was then heated at 100°C for 3 minutes to evaporate the solvent and dry the coating film (baking step).

[0177] Next, using an ultra-high pressure mercury lamp, light of 200 mJ / cm² is irradiated onto the surface of the dried coated film through a photomask (exposure step). The exposure step is performed by placing the photomask 100 μm away from the coated film. A photomask with a line and gap pattern of 3–100 μm width is used. Then, unexposed areas are removed by spraying Semicanean DL-A10 developer (manufactured by Yokohama Yushi Kogyo Co., Ltd.) (diluted 5 times) onto the surface of the coated film for 60 seconds at 23°C and 0.1 MPa (development step). The glass substrate with the coated film after the development step is then left to stand in a dryer at 100°C for 30 minutes to thermally harden the coating film (post-baking step), resulting in a colored pattern.

[0178] The resulting chromogenic patterns were observed using a Hitachi High Technology S-3400 electron microscope. The minimum linewidth (minimum developed size) of the developed image and the presence of residue in the unexposed areas between the developed images were evaluated. The presence or absence of residue was evaluated using the following criteria. The results are shown in Table 4 or Table 5. "Evaluation Criteria for Residue" ○: No residue in the unexposed areas between the developed images. ×: Residue exists in the unexposed areas between the developed images.

[0179] (2) Pencil hardness By spin coating, the photosensitive coloring compositions R1-R16 and cR1-cR9 prepared in Examples 1-16 and Comparative Examples 1-9 were coated onto a square glass substrate (alkali-free glass substrate) with dimensions of 5 cm in length and 5 cm in width. The substrate was heated at 100°C for 3 minutes to evaporate the solvent, forming a coated film. Next, the coated film was photocured by irradiating it with light of wavelength 365 nm at an exposure dose of 200 mJ / cm². Then, the glass substrate with the photocured coated film was placed in a dryer at 100°C for 30 minutes to thermally cure the coated film (post-baking step), resulting in a resin-cured film with a thickness of 2.5 μm.

[0180] The pencil hardness of the resin-cured film thus prepared was measured using a pencil hardness tester (No. 553-M, manufactured by Yasuda Seiki Co., Ltd.) according to JIS K5600-5-4, and evaluated using the following criteria. The results are shown in Table 4 or Table 5. "Evaluation Criteria for Pencil Hardness" ○: Pencil hardness 3H or higher ×: Pencil hardness not up to 3H

[0181] (3) Solvent resistance Similar to the evaluation of pencil hardness described in (2) above, a glass substrate with a resin-cured film was prepared, and the absorption spectrum of the resin-cured film was measured using a spectrophotometer (UV-1650PC, manufactured by Shimadzu Corporation). Furthermore, 200 mL of propylene glycol monomethyl ether acetate was placed in a 500 mL capped glass bottle and allowed to stand at 23°C. The glass substrate with the resin-cured film was then placed in the same glass bottle and immersed in propylene glycol monomethyl ether acetate, and allowed to stand at 23°C for 15 minutes. Afterward, the glass substrate with the resin-cured film was removed, 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.

[0182] The color change (ΔE *ab) of the resin-cured film before and after impregnation in propylene glycol monomethyl ether acetate was calculated, and the solvent resistance of the resin-cured film was evaluated using the following criteria. The results are shown in Table 4 or Table 5. Evaluation Criteria for Solvent Resistance ○:ΔE *ab did not reach 3.0 ×:ΔE *ab is 3.0 or higher

[0183] (4) Comprehensive judgment The resin-cured films formed from the cured forms of the photosensitive coloring compositions R1-R16 and cR1-cR9 prepared in Examples 1-16 and Comparative Examples 1-9 were evaluated according to the criteria shown below. The results are shown in Table 4 or Table 5. Evaluation Criteria ○: Meets all of the following criteria. (1) The minimum developing size is less than 15μm, and there is no residue in the unexposed areas between the developed images. (2) The pencil hardness of the resin-cured film is 3H or higher. (3) The color change ΔE *ab in the solvent resistance evaluation of the resin-cured film did not reach 3.0. ×: Does not meet any one or more of the items listed in ○ above.

[0184]

[0185]

[0186] As shown in Table 4, the photosensitive coloring compositions R1 to R16 of Examples 1 to 16 all have a minimum image size of less than 15 μm, and there is no residue in the unexposed areas between the developed images, which confirms that they have excellent alkaline imaging properties.

[0187] Furthermore, as shown in Table 4, the resin-cured film formed by photocuring the coating film using the photosensitive coloring compositions R1 to R16 of Examples 1 to 16, and then heat-curing it at a low temperature of 100°C, has a pencil hardness of 3H or higher, exhibiting excellent hardness. Moreover, the solvent resistance of the aforementioned resin-cured film is rated as 0, confirming its excellent solvent resistance.

[0188] In contrast, as shown in Table 5, the photosensitive coloring compositions cR1 to cR9 of Comparative Examples 1 to 9 have insufficient alkaline imaging properties, pencil hardness, or solvent resistance.

[0189] More specifically, the copolymers cP1 to cP8 obtained from comparative synthesis examples 1 to 8 contained in the photosensitive coloring compositions cR1 to cR8 of comparative examples 1 to 8 have an active methylene equivalent of 0. Therefore, the resulting resin-cured film exhibits poor alkali development, hardness, and solvent resistance. Furthermore, the copolymer cP9 obtained from comparative synthesis example 9 contained in the photosensitive resin composition cR9 of comparative example 9 has a functional group equivalent of 0. Therefore, the resulting resin-cured film exhibits poor hardness and solvent resistance. Furthermore, regarding the resin composition obtained this time, the changes over time were confirmed, and a favorable trend was observed in the order of constituent units with terminal isocyanate groups, silyl groups, and epoxy groups. The reaction does not proceed if the terminal isocyanate groups are not heated. The reaction of silyl groups can be controlled by using alcohol-based polymerization solvents, while the reaction of epoxy groups requires adjustment of the optimal amount of introduced monomers or other monomers. [Potential for Industrial Applications]

[0190] According to the present invention, a photosensitive resin composition and a photosensitive coloring composition are provided, which possess excellent image development and good low-temperature curing properties, and are capable of forming a resin-cured film with sufficient hardness and solvent resistance. Furthermore, according to the present invention, a resin-cured film formed from a cured product of the photosensitive resin composition is provided, possessing sufficient hardness and solvent resistance; a color filter is provided, having a colored pattern formed from a cured product of the photosensitive coloring composition of the present invention, possessing sufficient hardness and solvent resistance; and an image display element incorporating the color filter is provided. The photosensitive resin composition and photosensitive coloring composition of the present invention are, for example, suitable as resists for use as transparent films, protective films, insulating films, overcoats, light spacers, black matrices, black pillar spacers, and color filters.

[0191] 1:Substrate 2: Pixel 3: Black Matrix 4: Protective film

Claims

1. A photosensitive resin composition comprising: a resin (A), a reactive diluent (B) having an vinyl unsaturated group, a photopolymerization initiator (C), and a solvent (D); characterized in that: the aforementioned resin (A) contains: a constitutive unit (a-1) having at least one group selected from the group consisting of active methylene and active methine, a constitutive unit (a-2) having a group that reacts under the action of light and / or heat, and a constitutive unit (a-3) having an acid group, wherein the aforementioned active methylene and the aforementioned active methine are methylene and methine groups bonded at both ends to any one of the following: a carbonyl group, a sulfur atom of a sulfonyl group, a cyano group, or a nitro group; and the aforementioned constitutive unit (a-2) is a constitutive unit having an epoxy group (a-2-1), a constitutive unit having a silyl group (a-2-2), or a constitutive unit having a terminal isocyanate group (a-2-3).

2. The photosensitive resin composition as claimed in claim 1, wherein the acid value of the aforementioned resin (A) is 10~300 KOH mg / g.

3. The photosensitive resin composition of claim 1 or 2, wherein in all the constituent units of the aforementioned resin (A), the aforementioned constituent unit (a-1) is 2 to 80 mol%, and the aforementioned constituent unit (a-2) is 2 to 80 mol.

4. The photosensitive resin composition of claim 1 or 2, wherein the aforementioned resin (A) further contains other constituent units (a-4).

5. The photosensitive resin composition of claim 1 or 2, wherein the aforementioned constituent unit (a-1) is a constituent unit having the structure shown in formula (X1) or (X2) below; (in formula (X1) and formula (X2) below, R3 represents a divalent group shown in any of formulas (8) to (10) below; R4 represents a cyano (-CN), nitro (-NO2), a group shown in formula (11) or formula (12) below; * represents a bonding site; ★ represents an active methylene carbon or an active methine carbon); (in formula (8) to formula (12) above, * represents a bonding site; in formula (11) and formula (12) above, R5 represents a hydrogen atom or a hydrocarbon group with 1 to 24 carbon atoms that may contain heteroatoms).

6. The photosensitive resin composition of claim 5, wherein in the aforementioned constituent unit (a-1) having the aforementioned formula (X1) and the aforementioned formula (X2), R3 is a divalent group as shown in the aforementioned formula (8) or the aforementioned formula (10), and R4 is a group as shown in the aforementioned formula (11).

7. The photosensitive resin composition as claimed in claim 1 or 2, wherein the weight average molecular weight of the aforementioned resin (A) is 1,000 to 50,000, and the molecular weight distribution (Mw / Mn) of the aforementioned resin (A) is 1.3 to 3.

0.

8. The photosensitive resin composition as claimed in claim 1 or 2, wherein, relative to a total of 100 parts by mass of the components after removing the aforementioned solvent (D), it contains 10 to 85 parts by mass of the aforementioned resin (A), 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).

9. A photosensitive coloring composition comprising a photosensitive resin composition as described in any one of claims 1 to 8 and a colorant (E).

10. The photosensitive coloring composition of claim 9, wherein, relative to a total of 100 parts by mass of the components after removing the aforementioned solvent (D), it contains 10 to 85 parts by mass of the aforementioned resin (A), 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), 30 to 1000 parts by mass of the aforementioned solvent (D), and 4 to 85 parts by mass of the aforementioned colorant (E).

11. A resin-cured film, which is formed from a cured product of a photosensitive resin composition as claimed in any one of claims 1 to 8.

12. A color filter having a colored pattern formed from a hardened form of a photosensitive coloring composition as claimed in claim 9 or 10.

13. An image display element having a color filter as claimed in claim 12.

Images