Photosensitive resin composition and color filter

Abstract

The present invention provides a photosensitive resin composition capable of forming a resin cured film having excellent developability and good low-temperature curability, and sufficient hardness and solvent resistance. The photosensitive resin composition of the present invention comprises a resin (A), a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D). The resin (A) contains a constituent unit (a-1) having at least one group selected from the group consisting of an active methylene group and an active methine group, a constituent unit (a-2) having a group that reacts by the action of light and / or heat, and a constituent unit (a-3) having an acid group.

Description

Technology Field

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

[0002] The present application claims priority based on Japanese Patent Application No. 2021-207178 filed in Japan on December 21, 2021, and incorporates the contents thereof herein by reference. Background Technology

[0003] Conventionally, there are image display elements such as displays that are equipped with a color filter. The color filter is typically formed by using a method of curing a resin composition on a substrate by baking it at a temperature of over 200°C.

[0004] In recent years, with the increasing flexibility and wearability of displays, there has been a transition from glass to organic materials such as resins in substrate materials. Furthermore, in order to realize image display devices with even higher brightness and high contrast, there has been a transition from pigments to dyes and / or fluorescent compounds and quantum dots in colorants used in color filters.

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

[0006] Patent Document 1 discloses a colored photocurable resin composition comprising a photocurable compound (A), a binder resin (B), a photoinitiator (D), and a solvent (E). The photocurable compound (A) is carboxyl group-containing dipentaerythritol pentaacrylate. The binder resin (B) comprises one or more of a tetrahydropyran structure or a tetrahydrofuran structure in its main chain structure. Prior art literature

[0007] Japanese Patent Publication No. 2015-184675 The problem to be solved

[0008] Organic materials used as substrate materials have lower heat resistance compared to glass. In addition, dyes used as coloring agents for color filters have lower heat resistance compared to pigments. In this regard, it is desired to lower the heating temperature for curing resin compositions used as materials for color filters. Specifically, in accordance with the heat resistance of the substrate material and the coloring agent material, it is sometimes required to set the heating temperature for curing the resin composition that is the material of the color filter to 80 to 150°C.

[0009] However, with conventional resin compositions, a cured product having sufficient hardness and solvent resistance was not obtained when the heating temperature for curing was lowered.

[0010] Color filters containing cured materials with insufficient hardness are prone to scratching. For this reason, there is a risk of display defects caused by scratches on the color filter in an image display device equipped with a color filter. In addition, in color filters equipped in image display devices, there is a tendency to increase the content of coloring agents in the resin composition used as the material for the color filter in order to improve color reproduction. Paints have higher solubility in solvents compared to pigments. For this reason, if the solvent resistance of the color filter is insufficient, the paint contained in the color filter may leach into the solvent, and there is a risk that the color of the color filter may change.

[0011] The present invention has been made in consideration of the above circumstances and aims to provide a photosensitive resin composition and a photosensitive coloring composition capable of forming a resin cured film having excellent developability and good low-temperature curability, as well as sufficient hardness and solvent resistance.

[0012] Furthermore, the present invention aims to provide a resin cured film comprising a cured product of the photosensitive resin composition of the present invention and having sufficient hardness and solvent resistance. Additionally, the present invention aims to provide a color filter having a coloring pattern comprising a cured product of the photosensitive coloring composition of the present invention and having sufficient hardness and solvent resistance. Furthermore, the present invention aims to provide an image display element equipped with this color filter. means of solving the problem

[0013] The present invention includes the following embodiments.

[0014] [1] Suji (A) and,

[0015] Reactive diluent (B) and,

[0016] photopolymerization initiator (C) and,

[0017] Solvent (D)

[0018] A photosensitive resin composition comprising, wherein the resin (A) comprises a constituent unit (a-1) having at least one group selected from the group consisting of an active methylene group and an active methine group, a constituent unit (a-2) having a group that reacts by the action of light and / or heat, and a constituent unit (a-3) having an acid group.

[0019] [2] A photosensitive resin composition described in [1], wherein the above-described constituent unit (a-2) has at least one functional group selected from epoxy group, silyl group, block isocyanato group, isocyanato group, hydroxyl group, mercapto group, oxetanyl group, amino group, furyl group, maleimide group, oxazolidinyl group, oxazolyl group, formyl group, nitro group, and halogen group.

[0020] [3] A photosensitive resin composition described in [2], wherein the above-mentioned 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 block isocyanato group (a-2-3).

[0021] [4] A photosensitive resin composition described in any one of [1] to [3], wherein the acid value of the resin (A) is 10 to 300 KOH mg / g.

[0022] [5] Among the entire constituent units of the above resin (A),

[0023] The above constituent unit (a-1) is 2 to 80 mol%, and

[0024] A photosensitive resin composition described in any one of [1] to [4], wherein the above-mentioned constituent unit (a-2) is 2 to 80 mol%.

[0025] [6] A photosensitive resin composition described in any one of [1] to [5], wherein the above resin (A) further contains other constituent units (a-4).

[0026] [7] A photosensitive resin composition described in any one of [1] to [6], wherein the above-mentioned constituent unit (a-1) is a constituent unit having a structure represented by the following formula (X1) or (X2).

[0027]

[0028]

[0029] (Among equations (X1) and (X2), R 3 R represents a divalent group represented by any one of the following formulas (8) to (10). 4 represents a cyano group (-CN), a nitro group (-NO2), or a group represented by the following formula (11) or the following formula (12). * indicates a binding site. ★ indicates an active methylene carbon or an active methine carbon.)

[0030]

[0031]

[0032] (In formulas (8) to (12), * indicates a bonding site. In formulas (11) and (12), R 5represents a hydrocarbon group having 1 to 24 carbon atoms that may contain hydrogen atoms or heteroatoms.)

[0033] [8] Among the equations (X1) and (X2) that the above constituent unit (a-1) has, R 3 This is a divalent group represented by Equation (8) or Equation (10), and R 4 The photosensitive resin composition described in [7], which is represented by the formula (11).

[0034] [9] The weight average molecular weight of the above resin (A) is 1,000 to 50,000, and

[0035] A photosensitive resin composition described in any one of [1] to [8], wherein the molecular weight distribution (Mw / Mn) of the resin (A) is 1.3 to 3.0.

[0036]

[10] For a total of 100 parts by mass of the components excluding the above solvent (D),

[0037] Containing 10 to 85 parts by mass of the above resin (A),

[0038] Containing 10 to 85 parts by mass of the above-mentioned reactive diluent (B),

[0039] Contains 0.1 to 30 parts by mass of the above photopolymerization initiator (C),

[0040] A photosensitive resin composition described in any one of [1] to [9] containing 30 to 1000 parts by mass of the above solvent (D).

[0041]

[11] A photosensitive resin composition described in any one of [1] to

[10] and

[0042] Colorant (E)

[0043] A photosensitive coloring composition comprising

[0044]

[12] For a total of 100 parts by mass of the components excluding the above solvent (D),

[0045] Containing 10 to 85 parts by mass of the above resin (A),

[0046] Containing 10 to 85 parts by mass of the above-mentioned reactive diluent (B),

[0047] Contains 0.1 to 30 parts by mass of the above photopolymerization initiator (C),

[0048] Containing 30 to 1000 parts by mass of the above solvent (D),

[0049] A photosensitive coloring composition described in

[11] containing (E) 4 to 85 parts by mass of the above coloring agent.

[0050]

[13] A resin cured film comprising a cured product of a photosensitive resin composition as described in any of [1] to

[10] .

[0051]

[14] A color filter having a color pattern comprising a cured product of a photosensitive color composition described in either

[11] or

[12] .

[0052]

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

[14] . Effects of the invention

[0053] According to the present invention, a photosensitive resin composition and a photosensitive coloring composition can be provided, which can form a resin cured film having excellent developability and good low-temperature curability, and sufficient hardness and solvent resistance.

[0054] In addition, according to the present invention, a resin cured film having sufficient hardness and solvent resistance can be provided, comprising a cured product of the photosensitive resin composition of the present invention. In addition, a color filter having sufficient hardness and solvent resistance can be provided, comprising a colored pattern including a cured product of the photosensitive coloring composition of the present invention. Furthermore, an image display element having this color filter can be provided. Brief explanation of the drawing

[0055] FIG. 1 is a schematic cross-sectional view showing an example of a color filter of the present embodiment. Specific details for implementing the invention

[0056] Hereinafter, the photosensitive resin composition, photosensitive coloring composition, resin cured film, color filter, and image display element of the present invention will be described in detail. However, the present invention is not limited only to the embodiments described below.

[0057] In the present 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)acryloyl” means at least one selected from methacryloyl and acryloyl.

[0058] Photosensitive resin composition

[0059] The photosensitive resin composition of the present embodiment comprises a resin (A), a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D).

[0060] [Suzy (A)]

[0061] The resin (A) included in the photosensitive resin composition of the present embodiment has at least one constituent unit (a-1) selected from the group consisting of an active methylene group and an active methine group (hereinafter simply referred to as “constituent unit (a-1)”), a constituent unit (a-2) having a group that reacts by the action of light and / or heat (hereinafter simply referred to as “constituent unit (a-2)”), and a constituent unit (a-3) having an acid group (hereinafter simply referred to as “constituent unit (a-3)”). The resin (A) may have a constituent unit (a-4) included as needed, and the number of repetitions and the order of bonding of each are not particularly limited.

[0062] [Constituent Unit (a-1)]

[0063] The constituent unit (a-1) according to the present embodiment is a constituent unit having at least one group selected from the group consisting of an active methylene group and an active methine group. By having the constituent unit (a-1) in the resin (A), the photosensitive resin composition has good low-temperature curing properties, and even when the photosensitive resin composition is cured at a low temperature, the formed resin cured film has sufficient hardness, solvent resistance, and developability. The active methylene group or active methine group of the constituent unit (a-1) allows hydrogen atoms of the methylene group to be easily detached and promote the cross-linking reaction of the resin. For example, the methylene bond between two carbonyl groups of an acetoacetic acid ester is active and not only easily causes a hydrogen pulling reaction, but as is well known, the acetoacetic acid ester exhibits typical keto-enol tautomerity and can also be conceived to be involved in photocuring. In addition, the active methylene group and the active methine group in this embodiment refer to a methylene group and a methine group that are bonded at both ends to any of the carbon atom of a carbonyl group, the sulfur atom of a sulfonyl group, a cyano group, or a nitro group.

[0064] Structure having an active methylene group

[0065] As a structure having an active methylene group, for example, a structure having the following formula (X1). R 3 and R 4 The methylene group bonded to it is an active methylene group.

[0066]

[0067] (Equation (X1), R 3 R represents a divalent group represented by any one of the following formulas (8) to (10). 4 represents a cyano group (-CN), a nitro group (-NO2), or a group represented by the following formula (11) or the following formula (12). * indicates a binding site. ★ indicates an active methylene carbon.)

[0068]

[0069]

[0070] (In formulas (8) to (12), * indicates a bonding site. In formulas (11) and (12), R 5 represents a hydrocarbon group having 1 to 24 carbon atoms that may contain hydrogen atoms or heteroatoms.)

[0071] R that equation (X1) has 3 Among them, a divalent group represented by either Formula (8) or Formula (10) is preferred from the perspective of having good low-temperature curability as a photosensitive resin composition and excellent physical properties required for a color filter, and a divalent group represented by Formula (10) is more preferred.

[0072] R that equation (X1) has 4 Among them, from the perspective that the low-temperature curing properties as a photosensitive resin composition are good and the physical properties required for a color filter are excellent, Equation (11) and Equation (12) are preferred, and Equation (11) is more preferred.

[0073] R in equation (X1) 4 R in Equation (11) and Equation (12) represents the mechanism indicated by Equation (11) or Equation (12). 5 The hydrocarbon group having 1 to 24 carbon atoms that may contain heteroatoms, specifically, may include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, a methoxy group, an ethoxy group, a propoxy group, a hexoxy group, a cyclohexoxy group, and a group represented by the following formulas (13) to (15).

[0074]

[0075] (In formulas (13) to (15), * indicates a bonding site.)

[0076] Among these, as a hydrocarbon group having 1 to 24 carbon atoms that may contain heteroatoms, an alkyl group having 1 to 10 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an alkyl group having 1 to 3 carbon atoms is even more preferred.

[0077] R 5 As such, from the perspective of having good low-temperature curing properties and excellent physical properties required for color filters, a hydrogen atom and an alkyl group having 1 to 10 carbon atoms are preferred, a hydrogen atom and an alkyl group having 1 to 3 carbon atoms are more preferred, and a hydrogen atom and a methyl group are even more preferred.

[0078] Structure containing an active metin group

[0079] As a structure having an active methine group, for example, a structure having the following formula (X2). R 3 The metine group bonded to the cyclohexane ring is the active metine group.

[0080]

[0081] (In formula (X2), * indicates the binding site. ★ indicates the active methine carbon. R 3 The definition or desirable range of is the same as that of Equation (X1).

[0082] The constituent unit (a-1) according to the present embodiment is preferably 2 to 80 mol% of the total constituent units of the resin (A), more preferably 105 to 70 mol%, and even more preferably 4010 to 65 mol%. If the content of constituent unit (a-1) is 2 mol% or more, the photosensitive resin composition using the resin composition containing the resin (A) as a raw material has good low-temperature curing properties capable of forming a resin cured film having sufficient hardness and solvent resistance. If the content of constituent unit (a-1) is 80 mol% or less, the content of constituent units (a-2) and (a-3) having functional groups among the total constituent units can be sufficiently secured.

[0083] As a method for introducing a constituent unit (a-1) into resin (A), examples include a method of introducing a monomer (ma-1) having at least one group selected from the group consisting of an ethylenically unsaturated group, an active methylene group, and an active methine group (hereinafter also simply referred to as "monomer (ma-1)") by copolymerizing it with other monomers containing ethylenically unsaturated groups, or a method of polymerizing a precursor of resin (A) and then introducing an active methylene group or an active methine group to form resin (A). As for the latter method, for example, a precursor of resin (A) having a hydroxyl group can be polymerized and reacted with a diketene such as 4-methyleneoxetan-2-one to obtain a resin (A) with an introduced active methylene group.

[0084] The method of introducing the constituent unit (a-1) into resin (A) is not limited to the above.

[0085] The monomer (ma-1) is not particularly limited as long as it is a compound having at least one group selected from the group consisting of an ethylenically unsaturated group, an active methylene group, and an active methine group. Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, a (meth)acryloyloxy group, etc. Among these, the (meth)acryloyloxy group is preferred from the perspective of ease of polymerization for obtaining resin (A).

[0086] As a monomer (ma-1), for example, a compound represented by the following formula (1) or (2) can be used.

[0087]

[0088]

[0089] (In equations (1) and (2), R 1 represents a hydrocarbon group having 1 to 24 carbon atoms that may contain hydrogen atoms or heteroatoms. X represents a divalent group represented by any of the following formulas (3) to (7). R 2represents a single bond, or a divalent hydrocarbon group having 1 to 20 carbon atoms. R 3 and R 4 The definition or preferred range is the same as that of Formulas (X1) and (X2). ★ indicates an active methylene carbon or an active methine carbon.)

[0090]

[0091] (In formulas (3) to (7), * indicates a bonding site.)

[0092] Among equations (1) and (2), R 1 The hydrocarbon group having 1 to 24 carbon atoms that may contain heteroatoms, specifically, may include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, a methoxy group, an ethoxy group, a propoxy group, a hexoxy group, a cyclohexoxy group, and a group represented by the following formulas (13) to (15).

[0093]

[0094] (In formulas (13) to (15), * indicates a bonding site.)

[0095] Among these, as a hydrocarbon group having 1 to 24 carbon atoms that may contain heteroatoms, an alkyl group having 1 to 10 carbon atoms is preferred, an alkyl group having 1 to 6 carbon atoms is more preferred, and an alkyl group having 1 to 3 carbon atoms is even more preferred.

[0096] R 1 As such, from the perspective of ease of reaction when polymerizing resin (A), a hydrogen atom and an alkyl group having 1 to 10 carbon atoms are preferred, a hydrogen atom and an alkyl group having 1 to 3 carbon atoms are more preferred, and a hydrogen atom and a methyl group are even more preferred.

[0097] Among formulas (1) and (2), as the divalent group represented by X, the group represented by formulas (4) and (5) is preferred in terms of ease of reaction when polymerizing resin (A), and the group represented by formula (4) is more preferred.

[0098] As a monomer (ma-1), a compound represented by the following formula (m1) is preferred in terms of ease of reaction when polymerizing resin (A), low-temperature curing properties as a resin composition, and properties of the resin cured film.

[0099]

[0100] (In equation (m1), R 6 represents a hydrogen atom or a hydrocarbon group having 1 to 2 carbon atoms, and R 7 ...represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.)

[0101] In equation (m1), R 6 The hydrocarbon group having 1 to 2 carbon atoms shown here is preferably a methyl group or an ethyl group, and more preferably a methyl group, in terms of developability as a photosensitive resin composition.

[0102] In equation (m1), R 7 The hydrocarbon group having 1 to 10 carbon atoms represented here may have a ring structure. From the perspective of low-temperature curability as a photosensitive resin composition, R 7 The hydrocarbon group represented here is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably has 1 to 2 carbon atoms.

[0103] Among the compounds represented by formula (m1), in particular, R 6 This methyl group, R 7 A compound having 1 to 4 carbon atoms, which is an alkyl group, is preferred.

[0104] As a compound represented by the above formula (1), specifically, the following compounds may be used.

[0105]

[0106]

[0107] As a compound represented by the above formula (2), specifically, the following compounds may be used.

[0108]

[0109] Formulas (16) to (22), (31), (32), (33) and (36) are compounds having CH3-CH2=CH-, but compounds in which CH3-CH2=CH- is substituted with H-CH2=CH- in these formulas may also be included.

[0110] [Constituent Unit (a-2)]

[0111] The constituent unit (a-2) of the resin (A) according to the present embodiment has a group that reacts by the action of light and / or heat, without including an active methylene group and an active methine group. The constituent unit (a-2) included in the resin (A) may be only one type or two or more types.

[0112] A photosensitive resin composition using a resin composition containing resin (A) according to the present embodiment as a raw material contains a constituent unit (a-2) having a group that reacts by the action of light and / or heat. By this, the photosensitive resin composition has good low-temperature curability. Low-temperature curability means a characteristic that can form a resin cured film having sufficient hardness and solvent resistance.

[0113] The functional group having a constituent unit (a-2) according to the present embodiment is at least one selected from an epoxy group, a silyl group, a block isocyanato group, a mercapto group, an isocyanato group, a hydroxyl group, an oxetanyl group, an amino group, a furyl group, a maleimide group, an oxazolidinyl group, an oxazolyl group, a formyl group, a nitro group, and a halogen group. Among these, a functional group that reacts by the action of heat is preferred, a group that reacts under temperature conditions of 40°C to 180°C is more preferred, a group that reacts under temperature conditions of 50°C to 170°C is even more preferred, and a group that reacts under temperature conditions of 60°C to 160°C is most preferred. In terms of ease of availability and reactivity when synthesizing resin (A), a constituent unit having an epoxy group (a-2-1), a constituent unit having a silyl group (a-2-2), and a constituent unit having a block isocyanato group (a-2-3) are more preferred.

[0114] The content of the constituent unit (a-2) in relation to the present embodiment is preferably 2 to 80 mol% of the total constituent units of the resin (A), more preferably 5 to 60 mol%, and even more preferably 10 to 40 mol%. If the content of the constituent unit (a-2) is 2 mol% or more, the photosensitive resin composition using the resin composition containing the resin (A) as a raw material has good low-temperature curing properties capable of forming a resin cured film having sufficient hardness and solvent resistance. If the content of the constituent unit (a-2) is 80 mol% or less, the content of constituent units (a-1) and (a-3) having functional groups among the total constituent units can be sufficiently secured.

[0115] As a method for introducing a constituent unit (a-2) into the resin (A) according to the present embodiment, a method of introducing a monomer (ma-2) having an ethylenically unsaturated group and the aforementioned functional group (hereinafter simply referred to as “monomer (ma-2)”) by copolymerizing it with other monomers containing ethylenically unsaturated groups, or a method of polymerizing a precursor of the resin (A) and then introducing the aforementioned functional group to form the resin (A).

[0116] The monomer (ma-2) is not particularly limited as long as it is a compound having an ethylenically unsaturated group and the aforementioned functional group, without containing an active methylene group, an active methine group, or a carboxyl group. Examples of ethylenically unsaturated groups include vinyl groups, allyl groups, (meth)acryloyloxy groups, etc. Among these, (meth)acryloyloxy groups are preferred from the perspective of ease of polymerization for obtaining resin (A).

[0117] From the view that the photosensitive resin composition using monomer (ma-2) has good low-temperature curing properties, or that the hardness or solvent resistance of the resin cured film of the photosensitive resin composition is good, the monomer (ma-2) is preferably an ethylene unsaturated compound containing an epoxy group (ma-2-1), an ethylene unsaturated compound containing a silyl group (ma-2-2), or an ethylene unsaturated compound containing a block isocyanato group (ma-2-3).

[0118] Specific examples of epoxy group-containing ethylenically unsaturated compounds (ma-2-1) include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, (meth)acrylates having a dicyclic epoxy group and their lactone adducts, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, epoxides of dicyclopentenyl (meth)acrylate, and epoxides of dicyclopentenyloxyethyl (meth)acrylate, etc., which contain epoxy groups. Among these, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and (meth)acrylate having a cyclocyclic epoxy group are preferred in terms of ease of availability and reactivity when synthesizing resin (A), and glycidyl (meth)acrylate is more preferred.

[0119] Specific examples of silyl group-containing ethylenically unsaturated compounds (ma-2-2) include [(meth)acryloyloxy]methyltriethoxysilane, [(meth)acryloyloxy]ethyltriethoxysilane, [(meth)acryloyloxy]propyltriethoxysilane, [(meth)acryloyloxy]octyltriethoxysilane, [(meth)acryloyloxy]propylmethyldiethoxysilane, [(meth)acryloyloxy]ethylmethyldiethoxysilane, [(meth)acryloyloxy]nonylmethyldiethoxysilane, etc. Among these, 3-(meth)acryloyloxypropylmethyldimethoxysilane and 3-(meth)acryloyloxypropylmethyldiethoxysilane are preferred in terms of ease of availability and reactivity when synthesizing resin (A), and 3-(meth)acryloyloxypropylmethyldiethoxysilane is more preferred.

[0120] Specific examples of the ethylenically unsaturated compound (ma-2-3) containing a blocked isocyanate group include monomers having an ethylenically unsaturated bond and a blocked isocyanate group. Examples of the above monomers include compounds in which the isocyanate group in an isocyanate compound having a vinyl group, (meth)acryloyloxy group, etc. in the molecule is blocked by a blocking agent. The reaction between the isocyanate compound and the blocking agent can be carried out regardless of the presence or absence of a solvent. If a solvent is used, it is necessary to use a solvent that is inert to the isocyanate group. During the blocking reaction, organometallic salts such as tin, zinc, and lead, or tertiary amines may be used as catalysts. The reaction can generally be carried out at -20 to 150°C, but it is preferable to carry out at 0 to 100°C. Examples of the above-mentioned isocyanate compound include compounds represented by the following formula (XX1).

[0121]

[0122] In the above equation (XX1), R 11 represents a hydrogen atom or a methyl group, and R 12 -CO-, -COOR 13 -(Here, R 13 (is an alkylene group having 1 to 6 carbon atoms) or -COO-R 14 O-CONH-R 15 -(Here, R 14 is an alkylene group having 2 to 6 carbon atoms, and R 15 represents an alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms that may have substituents. R 12 is, preferably -COOR 13 -is, and here, R 13 It is preferably an alkylene group having 1 to 4 carbon atoms.

[0123] Examples of isocyanate compounds represented by the above formula (XX1) include, specifically, 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, methacryloyl isocyanate, etc. Additionally, an equimolar (1 mol:1 mol) reaction product of 2-hydroxyalkyl (meth)acrylate and a diisocyanate compound may also be used. As for the alkyl group of the above-mentioned 2-hydroxyalkyl (meth)acrylate, an ethyl group or an n-propyl group is preferred, and an ethyl group is more preferred. Examples of the above-mentioned diisocyanate compounds include hexamethylene diisocyanate, 2,4-(or 2,6-)tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 3,5,5-trimethyl-3-isocyanatomethylcyclohexyl isocyanate (IPDI), m-(or p-)xylene diisocyanate, 1,3-(or 1,4-)bis(isocyanatomethyl)cyclohexane, lysine diisocyanate, etc.

[0124] Among these isocyanate compounds, 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, and methacryloyl isocyanate are preferred, and 2-isocyanatoethyl (meth)acrylate and 2-isocyanatopropyl (meth)acrylate are more preferred.

[0125] As blocking agents for blocking isocyanato groups in isocyanate compounds, examples include lactam-based compounds such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam; alcohol-based compounds such as methanol, ethanol, propanol, butanol, ethylene glycol, methylcellosolve, butylcellosolve, methylcarbitol, benzyl alcohol, phenylcellosolve, furfuryl alcohol, and cyclohexanol; phenol-based compounds such as phenol, cresol, xylenol, ethylphenol, o-isopropylphenol, p-tert-butylphenol, p-tert-octylphenol, nonylphenol, dinonylphenol, styrenephenol, oxybenzoic acid ester, thymol, p-naphthol, p-nitrophenol, and p-chlorophenol; Active methylene derivatives such as dimethyl malonicate, diethyl malonicate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, etc.; mercaptan derivatives such as butyl mercaptan, thiophenol, tert-dodecyl mercaptan, etc.; amine derivatives such as diphenylamine, phenylnaphthylamine, aniline, carbazole, etc.; acid amide derivatives such as acetoanilide, acetoanisidide, acetamide, benzamide, etc.; acid imide derivatives such as succinate imide, maleate imide, etc.; imidazole derivatives such as imidazole, 2-methylimidazole, 2-ethylimidazole, etc.; urea derivatives such as urea, thiourea, ethyleneurea, etc.; carbamate derivatives such as N-phenylcarbamate phenyl, 2-oxazolidone, etc.; imine derivatives such as ethyleneimine, polyethyleneimine, etc.; Examples include oxime-based agents such as formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, methyl isobutyl keto-oxime, and cyclohexanone-oxime; and bisulfite-based agents such as sodium bisulfite and potassium bisulfite. Among these, in terms of ease of availability and reactivity when synthesizing resin (A), diethyl malonicate, 3,5-dimethylpyrazole, and methyl ethyl ketoxime are preferred as blocking agents.

[0126] As another specific example of the monomer (ma-2), as a compound other than the epoxy group-containing ethylenically unsaturated compound (ma-2-1), the silyl group-containing ethylenically unsaturated compound (ma-2-2), and the block isocyanato group-containing ethylenically unsaturated compound (ma-2-3), the mercapto group-containing ethylenically unsaturated compound such as 2-mercaptoethyl (meth)acrylate;

[0127] Ethylene unsaturated compounds containing isocyanato groups, such as 2-(meth)acryloyloxyethyl isocyanate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, and 4-isocyanatocyclohexyl (meth)acrylate;

[0128] Hydroxyl group-containing ethylenically unsaturated compounds such as 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate;

[0129] Ethylene unsaturated compounds containing an oxetanyl group, such as (3-ethyloxetane-3-yl(Il))methyl(meth)acrylate;

[0130] Ethylene unsaturated compounds containing amino groups, such as 3-(N,N-dimethylamino)propyl(meth)acrylate, 3-(N,N-diethylamino)propyl(meth)acrylate; ethylene unsaturated compounds containing furyl groups, such as tetrahydrofurfuryl(meth)acrylate;

[0131] Ethyleneic unsaturated compounds containing maleimide groups, such as N-(3,4,5,6-tetrahydrophthalimide)ethyl (meth)acrylate, 2-maleimideethyl (meth)acrylate, 2-benzylmaleimideethyl (meth)acrylate, and 2-phenylmaleimideethyl (meth)acrylate;

[0132] Ethylene unsaturated compounds containing oxazolidinyl groups, such as 2-(2-oxo-3-oxazolidinyl)ethyl (meth)acrylate;

[0133] Oxazolyl group-containing ethylenically unsaturated compounds such as 2-oxazolylethyl (meth)acrylate;

[0134] Ethylene unsaturated compounds containing a formyl group, such as formylphenyl (meth)acrylate; ethylene unsaturated compounds containing a nitro group, such as nitropropyl (meth)acrylate;

[0135] Examples include halogen-containing ethylenically 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-tridecafluorooctyl (meth)acrylate.

[0136] [Constituent Unit (a-3)]

[0137] The constituent unit (a-3) of the resin (A) according to the present embodiment is a constituent unit other than constituent unit (a-1) and constituent unit (a-2), and is a constituent unit having a dispersing group. The constituent unit (a-3) included in the resin (A) may be of only one type or two or more types.

[0138] Examples of acid groups having a constituent unit (a-3) according to the present embodiment include a carboxyl group, a phospho group (-OP(=O)(OH)2), a sulfo group (-S(=O)2OH), etc. Among these, a carboxyl group is preferred from the perspective of developability as a photosensitive resin composition.

[0139] The content of the constituent unit (a-3) is preferably 2 to 60 mol% of the total constituent units of the resin (A), more preferably 4 to 40 mol%, and even more preferably 6 to 30 mol%. If the content of the constituent unit (a-3) is 2 mol% or more, the effect of including the carboxyl group is sufficiently obtained. If the content of the constituent unit (a-3) is 60 mol% or less, the content of constituent units (a-1) and (a-2) can be sufficiently secured.

[0140] As a method for introducing a constituent unit (a-3) into resin (A), a monomer (ma-3) having an ethylenically unsaturated group and an acid group (hereinafter also simply referred to as "monomer (ma-3)") can be introduced by copolymerizing it with other monomers containing an ethylenically unsaturated group, or a method of polymerizing a precursor of resin (A) and then introducing an acid group to form resin (A). As for the latter method, for example, a resin (A) with an acid group introduced can be obtained by polymerizing a precursor of resin (A) having a hydroxyl group and adding a polybasic acid anhydride to the hydroxyl group of the precursor.

[0141] Examples of monomers (ma-3) include unsaturated carboxylic acids or their anhydrides, unsaturated sulfonic acids, unsaturated phosphonic acids, etc. Specific examples of preferred monomers include unsaturated carboxylic acids or their anhydrides such as (meth)acrylic acid, α-bromo(meth)acrylic acid, β-furyl(meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, α-cyanosinnamic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, etc.; unsaturated sulfonic acids such as vinylsulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, p-styrenesulfonic acid, etc. Examples include unsaturated phosphonic acids such as 2-(meth)acryloyloxyethyl acid phosphate and vinylphosphonic acid; 2-(meth)acryloyloxyethyl succinic acid, 2-acryloyloxyethylphthalic acid, and 2-(meth)acryloyloxyethylhexahydrophthalic acid. These monomers may be used individually or in combination of two or more types. Among these, (meth)acrylic acid and unsaturated carboxylic acids are preferred from the perspective of ease of availability and reactivity when synthesizing resin (A), and (meth)acrylic acid is more preferred.

[0142] [Other constituent units (a-4)]

[0143] The resin (A) may, if necessary, contain other constituent units (a-4) other than constituent units (a-1), (a-2), and (a-3). The constituent unit (a-4) included in the resin (A) may be of only one type or two or more types.

[0144] When the resin (A) contains a constituent unit (a-4), the content is preferably 1 to 80 mol% of the total constituent units of the resin (A), more preferably 4 to 70 mol%, and even more preferably 10 to 30 mol%. If the content of the constituent unit (a-4) is 1 mol% or more, the effect of including the constituent unit (a-4) is sufficiently obtained. In addition, if the content of the constituent unit (a-4) is 80 mol% or less, the content of constituent units (a-1), (a-2), and (a-3) can be sufficiently secured.

[0145] As a method for introducing the constituent unit (a-4) into the resin (A), a monomer (ma-4) having an ethylenically unsaturated group that does not have an active methylene group, an active methine group, the aforementioned functional group and acid group, and has an ethylenically unsaturated group (hereinafter simply referred to as “monomer (ma-4)”) can be introduced by copolymerizing it with other monomers containing ethylenically unsaturated groups.

[0146] Examples of monomers (ma-4) include dienes such as butadiene, (meth)acrylic acid esters, styrenes, unsaturated dicarboxylic acid diesters, and other vinyl compounds.

[0147] Specific examples of (meth)acrylic acid esters include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isoamyl (meth)acrylate, and dodecyl (meth)acrylate;

[0148] Alicyclic alkyl (meth)acrylates such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylcyclohexyl (meth)acrylate, norbornyl (meth)acrylate, dicyclofentanyl (meth)acrylate, isobornyl (meth)acrylate, and adamantyl (meth)acrylate;

[0149] Aromatic (meth)acrylates containing benzyl (meth)acrylate, triphenylmethyl (meth)acrylate, cumyl (meth)acrylate, naphthalene (meth)acrylate, anthracene (meth)acrylate, etc.;

[0150] Examples include rosin (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, etc.

[0151] Specific examples of styrenes include styrene and α-, o-, m-, p- alkyl derivatives of styrene.

[0152] Specific examples of unsaturated dicarboxylic acid diesters include diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconate, etc.

[0153] Specific examples of other vinyl compounds include norbornene (bicyclo[2.2.1]hept-2-en), 5-methylbicyclo[2.2.1]hept-2-en, 5-ethylbicyclo[2.2.1]hept-2-en, tetracyclo[4.4.0.12,5.17,10]dodeca-3-en, 8-methyltetracyclo[4.4.0.12,5.17,10]dodeca-3-en, 8-ethyltetracyclo[4.4.0.12,5.17,10]dodeca-3-en, dicyclopentadiene, tricyclo[5.2.1.02,6]dec-8-en, tricyclo[5.2.1.02,6]dec-3-en, Tricyclo[4.4.0.12,5]undeca-3-en, tricyclo[6.2.1.01,8]undeca-9-en, tricyclo[6.2.1.01,8]undeca-4-en, tetracyclo[4.4.0.12,5.17,10.01,6]dodeca-3-en, 8-methyltetracyclo[4.4.0.12,5.17,10.01,6]dodeca-3-en, 8-ethylidenetetraceclo[4.4.0.12,5.17,12]dodeca-3-en, 8-ethylidenetetraceclo[4.4.0.12,5.17,10.01,6]dodeca-3-en, Examples include pentacyclo[6.5.1.13,6.02,7.09,13]pentadec-4-en, pentacyclo[7.4.0.12, 5.19,12.08,13]pentadec-3-en, (meth)acrylate anilide, vinylpyridine, vinyl acetate, vinyltoluene, etc.

[0154] Among these, (meth)acrylic acid esters and other vinyl compounds are preferred in terms of ease of availability and reactivity when synthesizing resin (A), methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, dicyclofentanyl (meth)acrylate, styrene, vinyltoluene, and norbornene are preferred, and methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and dicyclofentanyl (meth)acrylate are more preferred.

[0155] Weight-average molecular weight (Mw)

[0156] The weight average molecular weight (Mw) of the resin (A) according to the present embodiment is preferably 1,000 to 50,000 in terms of polystyrene, more preferably 2,000 to 30,000, and most preferably 3,000 to 12,000. If the weight average molecular weight (Mw) of the resin (A) is 1,000 or more, when the resin composition containing the resin (A) is used as a raw material for a photosensitive resin composition, a photosensitive resin composition is obtained in which problems such as defects in the resin cured film after development are unlikely to occur. If the weight average molecular weight of the resin (A) is 50,000 or less, the photosensitive resin composition containing the resin (A) has a sufficiently short development time and excellent practicality.

[0157] The weight average molecular weight (Mw) of the resin (A) in this embodiment is calculated by measuring under the following conditions using gel permeation chromatography (GPC) and converting it to polystyrene.

[0158] Column: Showdex (Registered Trademark) LF-804+LF-804 (Manufactured by Showa Denko Co., Ltd.)

[0159] Column temperature: 40℃

[0160] Sample: Tetrahydrofuran solution containing 0.2 mass% of resin (A).

[0161] Developing solvent: Tetrahydrofuran

[0162] Detector: Differential Refractometer (Product Name: SHODEX (Registered Trademark) RI-71S, Manufactured by Showa Denko Co., Ltd.)

[0163] Flow rate: 1 mL / min

[0164] The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the resin (A) is preferably 1.3 to 5.0, more preferably 1.5 to 4.0, and most preferably 1.5 to 3.0. If the molecular weight distribution (Mw / Mn) of the resin (A) is 1.3 or higher, the optimization of target numerical ranges such as weight average molecular weight (Mw) and acid value, and reaction conditions when manufacturing the resin (A) can be set with a certain range, allowing for efficient manufacturing. If the molecular weight distribution (Mw / Mn) of the resin (A) is 3.0 or lower, a photosensitive resin composition is obtained in which no variation in performance, such as developability, occurs when a resin composition containing the resin (A) is used as a raw material for a photosensitive resin composition.

[0165] In addition, the molecular weight distribution (Mw / Mn) is calculated using the chromatogram of the above GPC measurement.

[0166] "Sanga"

[0167] The acid value of the resin (A) is not particularly limited, but 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 the resin (A) is 10 KOH mg / g or higher, a photosensitive resin composition having better developability is obtained when a resin composition containing the resin (A) is used as a raw material for a photosensitive resin composition. If the acid value of the resin (A) is 300 KOH mg / g or lower, a photosensitive resin composition having good developability is obtained when a resin composition containing the resin (A) is used as a raw material for a photosensitive resin composition, in which the exposed portion (photocured portion) is not dissolved by the alkaline developer.

[0168] In addition, the acid value of resin (A) is a value measured using a mixed indicator of bromothymol blue and phenol red in accordance with JIS K6901 5.3. The acid value of resin (A) refers to the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of resin (A).

[0169] Sensory Equivalent

[0170] The functional group equivalent of the resin (A) according to the present embodiment is the equivalent of the aforementioned functional group included in the constituent unit (a-2) included in the resin (A). The functional group equivalent is not particularly limited, but is preferably 200 g / mol to 5000 g / mol, more preferably 300 g / mol to 4000 g / mol, and most preferably 300 g / mol to 3000 g / mol. If the functional group equivalent of the resin (A) is 200 g / mol or more, the photosensitive resin composition containing the resin (A) can form a resin cured film having better hardness. In addition, if the functional group equivalent of the resin (A) is 200 g / mol or more, when the resin composition containing the resin (A) is used as a raw material for a photosensitive resin composition, a photosensitive resin composition having better developability is obtained. In addition, if the functional group equivalent of resin (A) is 5000 g / mol or less, the photosensitive resin composition containing resin (A) can form a resin cured film having better hardness.

[0171] In addition, the functional group equivalent of resin (A) is the value obtained by dividing the molecular weight of resin (A) by the average number of the aforementioned functional groups included in the constituent unit (a-2) per molecule. The functional group equivalent of resin (A) is a calculated value obtained based on the input amount of the polymerizable unsaturated compound (raw material monomer) used as a raw material when synthesizing resin (A). If different types of functional groups are included in one molecule of resin (A), all functional groups are counted as the number of functional groups regardless of the type of functional group.

[0172] "Active methylene group and active methine group equivalents"

[0173] The equivalents of the active methylene group and the active methine group of the resin (A) are not particularly limited, but are 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 equivalents of the active methylene group and the active methine group of the resin (A) are 200 g / mol or more, the photosensitive resin composition containing the resin (A) can form a resin cured film having better hardness. In addition, if the equivalents of the active methylene group and the active methine group of the resin (A) are 200 g / mol or more, when the resin composition containing the resin (A) is used as a raw material for the photosensitive resin composition, a photosensitive resin composition having better developability is obtained. In addition, if the active methylene group equivalent of resin (A) is 5000 g / mol or less, the photosensitive resin composition containing resin (A) can form a resin cured film having better hardness.

[0174] In addition, the equivalents of active methylene groups and active methine groups of resin (A) are the value obtained by dividing the molecular weight of resin (A) by the average number of active methylene groups and active methine groups per molecule. The equivalents of active methylene groups and active methine groups of resin (A) are calculated values ​​based on the input amount of polymerizable unsaturated compound (raw material monomer) used as a raw material when synthesizing resin (A). If different types of active methylene groups and active methine groups are included in one molecule of resin (A), all active methylene groups and active methine groups are counted as the number of active methylene groups and active methine groups, regardless of the type of active methylene groups and active methine groups.

[0175] Hydroxyl equivalent

[0176] When the resin (A) contains hydroxyl groups, the hydroxyl 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 hydroxyl group equivalent of the resin (A) is 200 g / mol or more, the photosensitive resin composition containing the resin (A) can form a resin cured film having better hardness. In addition, if the hydroxyl group equivalent of the resin (A) is 5000 g / mol or less, the photosensitive resin composition containing the resin (A) can form a resin cured film having better hardness.

[0177] In addition, the hydroxyl group equivalent of resin (A) is the value obtained by dividing the molecular weight of resin (A) by the average number of hydroxyl groups per molecule. The hydroxyl group equivalent of resin (A) is a calculated value obtained based on the input amount of polymerizable unsaturated compound (raw material monomer) used as a raw material when synthesizing resin (A). If different types of hydroxyl groups are included in one molecule of resin (A), all hydroxyl groups are counted as the number of hydroxyl groups regardless of the type of hydroxyl group.

[0178] <Method for manufacturing resin (A)>

[0179] In order to produce the resin (A) included in the resin composition of the present embodiment, it may be produced using, for example, the manufacturing method described below. That is, a raw monomer comprising monomers (ma-1) to (ma-3) and, if necessary, other monomers (ma-4) is copolymerized using a polymerization initiator according to a radical polymerization method known in the art. By this, the resin (A) is obtained.

[0180] Specifically, a method may be used in which a raw material monomer is dissolved in a polymerization solvent to prepare a raw material monomer solution, a polymerization initiator is added to the raw material monomer solution, and a copolymerization reaction is carried out while stirring for 1 to 20 hours at, for example, 50°C to 130°C.

[0181] (Polymerization solvent)

[0182] As for the polymerization solvent used when manufacturing resin (A), it is sufficient to be a solvent that is inert to the copolymerization reaction of raw monomers and is not particularly limited. The polymerization solvent used when manufacturing resin (A) may be the same as the solvent included in the solvent (D) contained in the resin composition described later, or it may be different in part or in whole from the solvent included in the solvent (D). If the polymerization solvent used when manufacturing resin (A) is in part or in whole the same as the solvent included in the solvent (D) contained in the resin composition, it is preferable that the polymerization solvent be used as part of the solvent (D) without separating or removing the polymerization solvent from the reaction solution after the copolymerization reaction is completed.

[0183] As for the solvent used for polymerization, it is not particularly limited as long as it dissolves the monomer and the copolymer to be produced and does not inhibit the polymerization reaction. When the copolymer to be produced is a (meth)acrylic acid-based polymer, a glycol ether solvent is preferred in terms 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 mono2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monophenyl ether, propylene glycol monomethyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether. These solvents may be used alone or two or more may be used. Among these, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferred in terms of availability and reactivity.

[0184] The amount of polymerization solvent used when manufacturing resin (A) is not particularly limited, but is preferably 30 to 1000 parts by mass and more preferably 50 to 800 parts by mass per 100 parts by mass of raw monomer. 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 discoloration and gelation of the resin (A) can be prevented. If the amount of polymerization solvent used is 1000 parts by mass or less, the decrease in the molecular weight of the resin (A) due to chain transfer action can be suppressed, and the viscosity of the reaction solution can be controlled within an appropriate range.

[0185] (Polymer initiator)

[0186] Polymerization initiators that can be used in the copolymerization reaction of raw material monomers are not particularly limited, but examples include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(isobutyric acid)dimethyl, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, etc. These polymerization initiators may be used individually or in combination of two or more types.

[0187] The amount of polymerization initiator used is not particularly limited, but is preferably 0.1 to 20 parts by mass and more preferably 0.5 to 16 parts by mass per 100 parts by mass of raw monomer.

[0188] The content of resin (A) in the photosensitive resin composition of the present embodiment is preferably 10 to 85 parts by mass, more preferably 15 to 75 parts by mass, and most preferably 25 to 65 parts by mass, when the total sum of the components excluding the solvent (D) included in the photosensitive resin composition is 100 parts by mass. If the content of the reactive diluent (A) is within the above range, the viscosity and low-temperature curability of the photosensitive resin composition become more suitable.

[0189] [Reactive diluent (B)]

[0190] As for the (B) reactive diluent included in the photosensitive resin composition of the present embodiment, it may be a low molecular weight compound having an ethylenically unsaturated group such as a vinyl group, an allyl group, or a (meth)acryloyloxy group, and is not particularly limited. Specific examples of the reactive diluent (B) include aromatic vinyl monomers; polycarboxylic acid monomers such as vinyl acetate and vinyl adipoyl acetate; monofunctional (meth)acrylates; polyfunctional (meth)acrylates; triallyl cyanurate, etc.

[0191] Specific examples of aromatic vinyl monomers include styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, divinylbenzene, diallyl phthalate, diallylbenzene phosphonate, etc.

[0192] Specific examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, β-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, etc.

[0193] Specific examples of polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tri(meth)acrylate of tris(hydroxyethyl)isocyanurate.

[0194] Among these, as a reactive diluent (B), polyfunctional (meth)acrylates are preferred to improve curability (reactivity), and particularly dipentaerythritol penta(meth)acrylate and / or dipentaerythritol hexa(meth)acrylate are preferred.

[0195] These reactive diluents (B) may be used as a single type or in combination of two or more types.

[0196] The content of the reactive diluent (B) in the photosensitive resin composition of the present embodiment is preferably 10 to 85 parts by mass, more preferably 15 to 75 parts by mass, and most preferably 25 to 65 parts by mass, when the total sum of the components excluding the solvent (D) included in the photosensitive resin composition is 100 parts by mass. If the content of the reactive diluent (B) is within the above range, the viscosity and photocurability of the photosensitive resin composition become more suitable.

[0197] [Photopolymerization initiator (C)]

[0198] As for the photopolymerization initiator (C) included in the photosensitive resin composition of the present embodiment, it is not particularly limited as long as it is a compound that generates radicals upon light irradiation. Examples of photopolymerization initiators (C) include benzoins and their 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-t-butyldioxy-1-methylethyl)acetophenone; alkylphenones such as 1-hydroxycyclohexylphenyl ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one; and anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone. Thioxantones such as 2,4-dimethylthioxantone, 2,4-diisopropylthioxantone, 2-chlorothioxantone; ketals such as acetophenone dimethyl ketal, benzyl dimethyl ketal; benzophenones such as benzophenone, 4-(1-t-butyldioxy-1-methylethyl)benzophenone, 3,3',4,4'-tetrakis(t-butyldioxycarbonyl)benzophenone; oxime esters such as 1,2-octanedione, 1-[4-(phenylthio)-2-(o-benzoyloxime)], ethanolone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl(Il)], 1-(o-acetyloxime); Examples include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1; acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; and xanthones. These photopolymerization initiators (C) may be used individually or in combination of two or more types.

[0199] The content of the photopolymerization initiator (C) in the photosensitive resin composition of the present embodiment is preferably 0.1 to 30 parts by mass, more preferably 0.3 to 20 parts by mass, and most preferably 0.5 to 10 parts by mass, when the total amount of components excluding the solvent (D) included in the photosensitive resin composition is 100 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 have an adverse effect on the storage stability of the photosensitive resin composition and the performance of the resin cured film.

[0200] [Solvent (D)]

[0201] The solvent (D) included in the resin composition of the present embodiment is a solvent that is inert to the resin (A) and capable of dissolving the resin (A), and is not particularly limited.

[0202] The solvent (D) may or may not contain the polymerization solvent used when manufacturing the resin (A).

[0203] If the solvent (D) contains a polymerization solvent used when manufacturing resin (A), an addition reaction to manufacture resin (A) can be carried out without removing the polymerization solvent from the reaction solution after the copolymerization reaction to manufacture resin (A) is completed, and the polymerization solvent can be used as part or all of the solvent (D) of the resin composition without separating or removing it from the reaction solution after the addition reaction is completed.

[0204] The case in which the polymerization solvent used to produce the resin (A) is not included in the solvent (D) is the case in which the resin (A) used as a raw material for the resin composition is separated and removed from the reaction solution that produced the resin (A). In this case, regardless of the type and amount of the polymerization solvent used to produce the resin (A), the type and content of the solvent (D) can be appropriately selected according to the type of resin (A), the use of the resin composition, etc. That is, when the resin (A) is used as the one separated and removed from the reaction solution that produced the resin (A), the solvent (D) may be of the same type as the polymerization solvent used to produce the resin (A), or a different one may be used.

[0205] The solvent (D) is not particularly limited, but when the resin (A) is a (meth)acrylic acid-based polymer, a glycol ether solvent is preferred in terms 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 mono2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monophenyl ether, propylene glycol monomethyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether. These solvents may be used alone or in combination of two or more. Among these, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferred in terms of availability and reactivity.

[0206] The solvent (D) may include other solvents capable of dissolving the resin (A).

[0207] Examples include monoalcohols, (poly)alkylene glycol monoalkyl ethers, etc.

[0208] Specific examples of monoalcohols include primary alcohols such as propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, and dodecyl alcohol; and secondary alcohols such as benzyl alcohol.

[0209] Specific examples of other solvents include tertiary alcohols such as tert-butyl alcohol and diacetone alcohol; (poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; and ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone. 2-Methyl hydroxypropionate, 2-Ethyl hydroxypropionate, 2-Methyl-2-hydroxypropionate, 2-Ethyl-2-hydroxypropionate, 3-Methyl methoxypropionate, 3-Ethyl methoxypropionate, 3-Methyl ethoxypropionate, 3-Ethoxypropionate, Ethyl ethoxypropionate, Ethoxyacetate, Ethyl hydroxyacetate, 2-Methyl-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-amyl acetate, i-amyl acetate, n-butyl propionate, Examples include esters such as ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and 2-ethyl oxobutyrate; aromatic hydrocarbons such as toluene and xylene; and carboxylic acid amides such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0210] The content of the solvent (D) in the resin composition of the present embodiment is preferably 30 to 1000 parts by mass when the total sum of the components excluding the solvent (D) in the resin composition is 100 parts by mass, more preferably 50 to 800 parts by mass, and most preferably 100 to 700 parts by mass. If the content of the solvent (D) is within the above range, the viscosity of the resin composition can be adjusted to an appropriate range.

[0211] [Other Additives]

[0212] The photosensitive resin composition of the present embodiment may, if necessary, contain one or more known additives such as leveling agents, thermal polymerization inhibitors, and sensitizers. The content of these additives may be within a range that does not impede the effects of the present invention and is not particularly limited.

[0213] Additionally, the photosensitive resin composition of the present embodiment may contain amines, hydrazides, aldehydes, and metal salts as crosslinking agents to increase curability. Examples of crosslinking agents include MXDA, 1,3-BAC manufactured by Mitsubishi Gas Chemical Co., Ltd.; ADH, APA-280 manufactured by Otsuka Chemical Co., Ltd.; SEQUAREZ 755 manufactured by OMNOVA Solutions; and ZIRCOZOL ZC-2, 7 manufactured by No. 1 Rare Element Chemical Co., Ltd.

[0214] Additionally, the photosensitive resin composition of the present embodiment may contain an acid generator and a base generator to increase curability. In particular, from the perspective of potential, it is preferable to use a photogenerator, a photobase generator, a thermal acid generator, or a thermal base generator, and from the perspective of storage stability, a photogenerator and a photobase generator are more preferable. Examples of photogenerators include sulfonium salt compounds such as CPI-200K, CPI-210S, CPI-310B, and CPI-410S manufactured by San Apro Co., Ltd., and iodonium salt compounds such as IK-1. Examples of photobase generators include WPBG-266, WPBG-300, and WPBG-345 manufactured by Fujifilm Wako Junyaku Co., Ltd.

[0215] [Viscosity of photosensitive resin composition]

[0216] The viscosity of the photosensitive resin composition of the present embodiment can be appropriately adjusted according to the thickness of the resin cured film containing the cured product of the photosensitive resin composition. For example, when the thickness of the resin cured film is adjusted to 1 to 4 μm, the viscosity of the photosensitive resin composition is preferably 1 mP·s to 25 mP·s, more preferably 2 mP·s to 20 mP·s, and most preferably 3 mP·s to 15 mP·s.

[0217] Photosensitive Coloring Composition

[0218] The photosensitive coloring composition of the present embodiment comprises the photosensitive resin composition of the present embodiment and a coloring agent (E).

[0219] [Colorant (E)]

[0220] As a coloring agent (E), known dyes and / or pigments may be used. When a dye is used as the coloring agent (E), a photosensitive coloring composition is obtained that exhibits good alkali developability and a coloring pattern with high brightness compared to when a pigment is used.

[0221] As for the dye, it is preferable to use an acid dye having an acidic group such as a carboxyl group, a salt of an acid dye with a nitrogen compound, or a sulfonamide of an acid dye, from the perspective of solubility with the solvent (D) and alkaline developer, interaction with other components in the photosensitive resin composition, and heat resistance. Examples of such dyes include acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; solvent blue 38, 44 (VALIFAST BLUE 2620); acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; Examples include 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 derivatives thereof. Among these, azo, xanthen, anthraquinone, or phthalocyanine acid dyes are preferred.These dyes may be used individually or in combination of two or more types, depending on the color of the desired pixel.

[0222] As pigments, for example, yellow pigments such as CI pigment yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; orange pigments such as CI pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265; blue pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, 60; violet pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38; green pigments such as CI Pigment Green 7, 36, 58; brown pigments such as CI Pigment Brown 23, 25; Examples of black pigments include CI pigment black 1, 7, carbon black, titanium black, and iron oxide. Depending on the color of the desired pixel, one of these pigments may be used alone, or two or more may be used in combination.

[0223] When a pigment is used as the coloring agent (E), a known dispersant may be incorporated into the photosensitive coloring composition to improve the dispersibility of the coloring agent (E). As the dispersant, it is preferable to use a polymeric dispersant that has excellent dispersion stability over time. Examples of polymeric dispersants include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic modified ester-based dispersants. As such polymeric dispersants, commercially available products under trade names such as EFKA (manufactured by EFKA Chemicals BV), Disperbyk (manufactured by B.C.), Dispalon (manufactured by Kusumoto Kasei Co., Ltd.), and SOLSPERSE (manufactured by Zeneca) may be used. The amount of the dispersant incorporated can be appropriately set according to the type and amount of the pigment, etc. used as the coloring agent (E).

[0224] The content of the coloring agent (E) in the photosensitive coloring composition of the present embodiment 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, when the total amount of components excluding the solvent (D) included in the photosensitive coloring composition is 100 parts by mass. If the content of the coloring agent (E) is 4 parts by mass or more, the effect of containing the coloring agent (E) becomes significant, and the photosensitive coloring composition becomes suitable as a material for the coloring pattern of a color filter. If the content of the coloring agent (E) is 85 parts by mass or less, the coloring agent (E) in the photosensitive coloring composition does not impede the curability of the photosensitive coloring composition, and the low-temperature curability is good.

[0225] [Other Additives]

[0226] The photosensitive coloring composition of the present embodiment may, if necessary, contain one or more known additives such as leveling agents, thermal polymerization inhibitors, and sensitizers. The content of these additives may be within a range that does not impede the effects of the present invention and is not particularly limited.

[0227] In addition, the photosensitive coloring composition of the present embodiment may contain amines, hydrazides, aldehydes, and metal salts as crosslinking agents to increase curability. Examples of crosslinking agents include MXDA, 1,3-BAC manufactured by Mitsubishi Gas Chemical Co., Ltd., ADH, APA-280 manufactured by Otsuka Chemical Co., Ltd., SEQUAREZ 755 manufactured by OMNOVA Solutions, and ZIRCOZOL ZC-2, 7 manufactured by No. 1 Rare Element Chemical Co., Ltd.

[0228] In addition, the photosensitive coloring composition of the present embodiment may contain an acid generator and a base generator to increase curability. In particular, from the perspective of potentiality, it is preferable to use a photogenerator, a photobase generator, a thermal acid generator, or a thermal base generator, and from the perspective of storage stability, a photogenerator and a photobase generator are more preferable. Examples of photogenerators include sulfonium salt compounds such as CPI-200K, CPI-210S, CPI-310B, and CPI-410S manufactured by San Apro Co., Ltd., and iodonium salt compounds such as IK-1. Examples of photobase generators include WPBG-266, WPBG-300, and WPBG-345 manufactured by Fujifilm Wako Junyaku Co., Ltd.

[0229] [Viscosity of photosensitive coloring composition]

[0230] The viscosity of the photosensitive coloring composition of the present embodiment can be appropriately adjusted according to the thickness of the resin cured film containing the cured product of the photosensitive coloring composition. For example, when the thickness of the resin cured film is adjusted to 1 to 4 μm, the viscosity of the photosensitive coloring composition is preferably 1 mP·s to 25 mP·s, more preferably 2 mP·s to 20 mP·s, and most preferably 3 mP·s to 15 mP·s.

[0231] Method for manufacturing a photosensitive resin composition

[0232] The photosensitive resin composition of the present embodiment can be prepared by mixing a resin (A), a reactive diluent (B), a photopolymerization initiator (C), a solvent (D), and an additive used as needed using a known mixing device.

[0233] The photosensitive resin composition of the present embodiment has good low-temperature curing properties and can form a resin cured film having sufficient hardness and solvent resistance. Furthermore, since the photosensitive resin composition of the present embodiment has excellent alkali developability, fine patterns can be formed by developing with an alkaline aqueous solution. Therefore, the photosensitive resin composition of the present embodiment is suitable for use as a resist.

[0234] Method for preparing a photosensitive coloring composition

[0235] The photosensitive coloring composition of the present embodiment can be prepared by mixing a resin (A), a reactive diluent (B), a photopolymerization initiator (C), a solvent (D), a coloring agent (E), and an additive used as needed using a known mixing device.

[0236] The photosensitive resin composition of the present embodiment has good low-temperature curing properties and can form a resin cured film having sufficient hardness and solvent resistance. Furthermore, since the photosensitive resin composition of the present embodiment has excellent alkali developability, fine patterns can be formed by developing with an alkaline aqueous solution. Therefore, the photosensitive resin composition of the present embodiment is suitable for use as a resist.

[0237] In addition, the photosensitive coloring composition of the present embodiment can be suitably used as a material for coloring patterns such as pixels of a color filter or a black matrix.

[0238] <Resin hardening film>

[0239] Next, the resin cured film of the present embodiment will be described in detail.

[0240] The resin cured film of the present embodiment comprises a cured product of the photosensitive resin composition of the present embodiment or the photosensitive coloring composition of the present embodiment.

[0241] The resin cured film of the present embodiment can be formed by a method comprising, for example, a coating process in which a photosensitive resin composition of the present embodiment is applied onto a substrate to form a coating film, a pre-bake process in which the coating film formed by the coating process is dried, an exposure process in which light is irradiated onto the dried coating film to photocur it, and a post-bake process in which the photocured coating film is heat-cured.

[0242] When forming a resin cured film having a predetermined pattern by photolithography using the photosensitive resin composition of the present embodiment, the method described below may be used, for example. That is, the coating process and pre-bake process described above are performed. Then, in the exposure process, light is irradiated onto the dried coating film through a photomask having a predetermined pattern to photocur the exposed portion. After the exposure process, post-exposure heat treatment is performed as necessary. Then, a development process is performed to dissolve and develop the unexposed portion of the coating film using a developer, and a post-bake process is performed to heat-cur the photocured coating film.

[0243] [Coating Process]

[0244] In the coating process, the photosensitive resin composition of the present embodiment or the photosensitive coloring composition of the present embodiment is applied onto a substrate to form a coating film. In the present embodiment, known materials may be used as the substrate on which the photosensitive resin composition or the photosensitive coloring composition is applied, and can be appropriately determined according to the application of the resin cured film.

[0245] The method of applying the photosensitive resin composition or photosensitive coloring composition is not particularly limited, and, for example, screen printing, roll coating, curtain coating, spray coating, spin coating, slit coating, etc. may be used.

[0246] [Pre-baking Process]

[0247] In the pre-baking (pre-heating treatment) process, the coating film formed by the coating process is dried to reduce the amount of solvent remaining in the coating film. In the pre-baking process, the substrate on which the coating film is formed is heated for 10 seconds to 600 seconds, preferably 120 seconds to 180 seconds, at a temperature of, for example, 50°C to 120°C, preferably 70°C to 110°C. As a method for heating the substrate on which the coating film is formed in the pre-baking process, for example, a method using a hot plate can be used.

[0248] [Photolithography Process]

[0249] In the photolithography process, light is irradiated onto the surface of the coating film dried by the prebaking process to photocur the coating film. The light source used for irradiation is not particularly limited, but examples include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, xenon lamps, and metal halide lamps. Furthermore, the amount of exposure in the photolithography process is not particularly limited and can be appropriately set according to the composition of the photosensitive resin composition or photosensitive coloring composition and the thickness of the coating film. When forming a resin cured film having a predetermined pattern, in the photolithography process, light is irradiated onto the surface of the coating film dried by the prebaking process through a photomask having a predetermined pattern to photocur the exposed area.

[0250] [Post-exposure heating process]

[0251] When forming a resin cured film having a predetermined pattern, a post-exposure baking process is performed as needed after the photolithography process. By performing this process, the dissolution contrast between the exposed and unexposed portions of the coating film becomes more pronounced. Unlike the post-baking process described later, the post-exposure baking process does not completely cure the coating film. The post-exposure baking process is performed to more effectively remove the unexposed portions of the coating film while leaving only the exposed portions of the coating film on the substrate by performing a development process. Therefore, it is not an essential process in the method for forming a resin cured film according to the present embodiment.

[0252] When performing a heating process after exposure, it is preferable to heat the substrate after the exposure process at, for example, 40°C to 70°C, and more preferable to heat it at 50°C to 60°C. If the heating temperature is 40°C or higher, sufficient effect of improving the dissolution contrast between the exposed and unexposed portions of the coating film is obtained by performing the heating process after exposure. If the heating temperature is 70°C or lower, acid generated in the exposed portion does not diffuse to the unexposed portion, and good dissolution contrast is obtained. The heating time in the heating process after exposure is preferably 20 seconds to 600 seconds. If the heating time is 20 seconds or higher, the temperature history of the entire coating film can be made uniform. If the heating time is 600 seconds or lower, acid generated in the exposed portion does not diffuse to the unexposed portion, and good dissolution contrast is obtained. As a method for heating the substrate after the exposure process in the heating process after exposure, for example, a hot plate, an oven, or a furnace can be used.

[0253] [Development Process]

[0254] When forming a resin cured film having a predetermined pattern, after the exposure process, if necessary, a post-exposure heating process is performed, and then a developing process is performed to develop the unexposed portions of the coating film. As the developing solution used in the developing process, any alkaline aqueous solution conventionally used for developing photosensitive resin compositions or photosensitive coloring compositions may be used.

[0255] Examples of alkaline aqueous solutions are not particularly limited, but include aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, etc.; aqueous solutions of amine-based compounds such as ethylamine, diethylamine, dimethyl ethanolamine; aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide; aqueous solutions of p-phenylenediamine-based 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-methanesulfonamideethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and their sulfates, hydrochlorides, or p-toluenesulfonates. Among these alkaline aqueous solutions, it is preferable to use an aqueous solution of a p-phenylenediamine-based compound.

[0256] In alkaline aqueous solutions, one or more additives such as defoaming agents and surfactants may be added as needed.

[0257] Development conditions in the development process, such as development temperature and development time, can be appropriately determined according to the composition of the photosensitive resin composition, the composition of the developer, the thickness of the coating film, etc.

[0258] In the development process, it is preferable to use the above alkaline aqueous solution to dissolve the unexposed portions of the coating film, develop the film, and then wash and dry it.

[0259] [Post-bake process]

[0260] In this embodiment, after the development process, a post-bake process is performed to heat-cur the photocured coating film to form a resin-cured film. The heating temperature and heating time in the post-bake process 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.

[0261] The heating temperature in the post-bake process can be, for example, 50°C to 210°C. If the heating temperature is 210°C or lower, a material with low heat resistance can be used as the material for the color filter. For example, when a resin substrate is used as a substrate for forming a resin cured film to form a coloring pattern of a color filter, the heating temperature may be 150°C or lower, 120°C or lower, or 100°C or lower. If the heating temperature is 150°C or lower, a coloring pattern containing a coloring agent (E) with low heat resistance, which was difficult to use as a material for conventional coloring patterns, can be formed while suppressing the degradation of the coloring agent (E). Furthermore, if the heating temperature is 150°C or lower, a coloring pattern can be formed on a substrate with low heat resistance, which was difficult to use as a substrate for conventional color filters. Additionally, if the heating temperature is 150°C or lower, the amount of energy required to cure the coating film is reduced, which is desirable.

[0262] If the heating temperature in the post-bake process is 50°C or higher, the resin (A) and the reactive diluent (B) are sufficiently crosslinked, so a resin cured film having sufficient hardness and solvent resistance is obtained. In addition, if the heating temperature is 50°C or higher, the heating time in the post-bake process is completed in a short time, and the resin cured film can be formed efficiently. The heating temperature in the post-bake process is more preferably 60°C or higher, and even more preferably 70°C or higher.

[0263] The heating time in the post-bake process can be appropriately selected according to the heating temperature, the thickness of the coating film, the composition of the photosensitive resin composition, etc., and, for example, can be 10 minutes to 4 hours, and preferably 20 minutes to 2 hours.

[0264] The resin cured film of the present embodiment comprises a cured product of the photosensitive resin composition of the present embodiment or the photosensitive coloring composition of the present embodiment. For this reason, it has sufficient hardness and solvent resistance.

[0265] The resin cured film of the present embodiment can be suitably used as a material for various insulating films, such as a protective film provided on the upper part of a color filter, an insulating film provided between electrodes of a touch panel, and an interlayer insulating film of a thin-film transistor (TFT).

[0266] Color Filter

[0267] Next, the color filter of the present embodiment will be described in detail.

[0268] FIG. 1 is a schematic cross-sectional view showing an example of a color filter according to the present embodiment. The color filter shown in FIG. 1 comprises a substrate (1), RGB pixels (2) formed on one side (1a) of the substrate (1), a black matrix (3) formed at the boundary of each pixel (2), and a protective film (4) formed on the pixels (2) and on the black matrix (3).

[0269] The substrate (1) used in the color filter shown in FIG. 1 is not particularly limited and may include a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyamideimide substrate, a polyimide substrate, an aluminum substrate, a printed circuit board, an array substrate, etc., depending on the application.

[0270] The pixel (2) and black matrix (3) in the color filter shown in FIG. 1 are a color pattern comprising a cured product of a photosensitive color composition of the present embodiment, comprising a resin composition including a resin (A) and a solvent (D), a reactive diluent (B), a photopolymerization initiator (C), a colorant (E), and an additive included as needed.

[0271] As for the protective film (4), a known material may be used. The protective film (4) may be a resin cured film comprising a resin composition comprising a resin (A) and a solvent (D), a reactive diluent (B), a photopolymerization initiator (C), and an additive included as needed, a photosensitive coloring composition of the present embodiment.

[0272] In the color filter of the present embodiment shown in FIG. 1, the composition other than the materials of the pixel (2) and the black matrix (3) may be known. In addition, the color filter shown in FIG. 1 is an example of the color filter of the present invention and is not limited to the example shown in FIG. 1.

[0273] Next, a method for manufacturing a color filter of the present embodiment will be described.

[0274] First, each RGB pixel (2) and a black matrix (3) are sequentially formed on one side (1a) of the substrate (1) shown in FIG. 1. The pixel (2) and the black matrix (3) can be manufactured using the method for manufacturing a resin cured film of the present embodiment (photolithography method) described above.

[0275] Next, a protective film (4) is formed on the pixel (2) and the black matrix (3). The protective film (4) can be formed using a known forming method. For example, the protective film (4) can be manufactured using the method for manufacturing a resin cured film of the present embodiment described above.

[0276] By the above process, a color filter of the present embodiment shown in FIG. 1 is obtained.

[0277] The color filter of the present embodiment has a color pattern (pixel (2) and black matrix (3)) comprising a cured product of the photosensitive coloring composition described above. Accordingly, the color pattern in the color filter of the present embodiment has sufficient hardness and solvent resistance.

[0278] Image display element

[0279] The image display element of the present embodiment is provided with a color filter of the present embodiment having sufficient hardness and solvent resistance. Examples of the image display element of the present embodiment include, for instance, a liquid crystal display element, an organic EL display element, and a solid-state imaging element. By providing the color filter described above, the image display element of the present embodiment is capable of high-brightness display.

[0280] Examples

[0281] The present invention will be explained in detail below through examples and comparative examples. Furthermore, the examples described below are intended to facilitate a better understanding of the content of the present invention. The present invention is not limited to these examples.

[0282] [Synthesized Example 1]

[0283] 350.0 g of propylene glycol monomethyl ether acetate was added as a polymerization solvent to a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, stirred while purging with nitrogen gas, and heated to 98°C.

[0284] Next, a mixture of 215.9 g (0.545 mol) of ethylene glycol monoacetoacetate monomethacrylate, 25.9 g (0.14 mol) of methyl methacrylate, 51.3 g (0.195 mol) of glycidyl methacrylate, 19.1 g (0.120 mol) 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 into the flask over a period of 3 hours.

[0285] Next, 156.4 g of propylene glycol monomethyl ether acetate was added to the reaction solution as a solvent (additive solvent for the composition) to obtain a resin composition of copolymer P1 of Synthesis Example 1 as the resin (A) according to the present embodiment.

[0286] [Synthesized Examples 2 to 16]

[0287] Resin compositions of copolymers P2 to P16 of Synthesis Examples 2 to 16 were obtained in the same manner as Synthesis Example 1, except that the raw materials listed in Table 1 were used in the proportions listed in Table 1. They are shown in Table 1.

[0288] For copolymers P1 to P16 included in the resin compositions of Synthesis Examples 1 to 16 obtained in this manner, the weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn), acid value, functional group (epoxy group, block isocyanato group, silyl group, hydroxyl group) equivalent, hydroxyl group equivalent, and active methylene group equivalent were determined, respectively. The results are shown in Table 1.

[0289] [Comparative Synthesis Example 1]

[0290] 350.0 g of propylene glycol monomethyl ether acetate was added as a polymerization solvent to a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, stirred while purging with nitrogen, and heated to 98°C.

[0291] Next, a mixture of 212.9 g (0.57 mol) of 2-ethylhexyl acrylate, 28.8 g (0.142 mol) of methyl methacrylate, 51.3 g (0.178 mol) of glycidyl methacrylate, 19.2 g (0.110 mol) 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 into the flask over a period of 3 hours.

[0292] Next, 156.4 g of propylene glycol monomethyl ether acetate was added to the reaction solution as a solvent (additive solvent for the composition) to obtain the resin composition of the copolymer cP1 of Comparative Example 1.

[0293] [Comparative Synthesis Examples 2 to 9]

[0294] A resin composition of copolymers cP1 to cP9 of Comparative Synthesis Examples 1 to 9 was obtained in the same manner as Comparative Synthesis Example 1, except that the raw materials listed in Table 2 were used in the proportions listed in Table 2.

[0295] For copolymers cP1 to cP9 included in the resin compositions of Comparative Examples 1 to 9 obtained in this manner, the weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn), acid value, functional group (epoxy group, block isocyanato group, silyl group) equivalent, and active methylene group equivalent were determined, respectively. The results are shown in Table 2.

[0296] [Comparative Synthesis Example 10]

[0297] 174.4 g of propylene glycol monomethyl ether acetate was added as a polymerization solvent to a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, and the mixture was stirred while purging with nitrogen gas and heated to 118°C.

[0298] Next, a mixture of 10.7 g (0.03 mol) of dicyclofentanyl methacrylate, 93.5 g (0.27 mol) of ethylene glycol monoacetoacetate monomethacrylate, 160.9 g (0.7 mol) of glycidyl methacrylate, 32.3 g of tert-butylperoxy-2-ethylhexanoate (polymerization initiator), and 68.9 g of propylene glycol monomethyl ether acetate was added dropwise into the flask from a dropping funnel over a period of 3 hours. After the addition was finished, the temperature was raised to 120°C and stirred for 30 minutes to carry out a copolymerization reaction, thereby producing a copolymer.

[0299] Thereafter, the inside of the flask was replaced with air, and 81.6 g (0.7 mol) of acrylic acid, 1.4 g of triphenylphosphine (addition reaction catalyst), and 0.7 g of methylhydroquinone (polymerization inhibitor) were added to the copolymer solution. The reaction was continued at 110°C for 10 hours with the aim of cleaving the epoxy groups derived from glycidyl methacrylate through the reaction of the epoxy groups derived from glycidyl methacrylate with acrylic acid, while simultaneously introducing ethylenically unsaturated bonds into the side chains of the copolymer; however, gelation occurred during the reaction. Additionally, the reaction was terminated before adding 21.0 g (0.13 mol) of succinic anhydride to the copolymer solution (Comparative Example 10).

[0300] The equivalents of the resin functional groups (epoxy, blocked isocyanate, silyl) and the active methylene group equivalents of Comparative Example 10 were determined. The results are shown in Table 2.

[0301]

[0302]

[0303] Preparation of a photosensitive coloring composition

[0304] (Examples 1 to 16, Comparative Examples 1 to 9)

[0305] (A) As a copolymer, the copolymers P1 to P16 of Synthesis Examples 1 to 16 and cP1 to cP9 of Comparative Synthesis Examples 1 to 9 were mixed with the components (B), (C), and (E) shown in Table 3 in the proportions shown in Table 3 to prepare the photosensitive coloring compositions R1 to R16 and cR1 to cR9 of Examples 1 to 16 and Comparative Examples 1 to 9, respectively.

[0306] In addition, the amount of copolymer in the resin composition in Table 3 does not include the polymerization solvent used when synthesizing the copolymer. Also, the amount of solvent (D) in Table 3 is the total amount of the polymerization solvent used when synthesizing the copolymer in the resin composition and the solvent additionally added when manufacturing the resin composition.

[0307]

[0308] <Evaluation of Photosensitive Coloring Compositions>

[0309] The photosensitive coloring compositions R1 to R16 and cR1 to cR9 prepared in Examples 1 to 16 and Comparative Examples 1 to 9 were evaluated by the method shown below.

[0310] (1) Phenomenality

[0311] Photosensitive coloring compositions R1 to R16 and cR1 to cR9 prepared in Examples 1 to 16 and Comparative Examples 1 to 9 were each coated onto a square glass substrate (alkali-free glass substrate) with sides of 5 cm by a spin coating method so that the thickness after exposure was 2.5 μm (coating process). The glass substrate coated with the photosensitive coloring composition was heated at 100°C for 3 minutes to volatilize the solvent and dry the coating film (pre-bake process).

[0312] Next, using an ultra-high pressure mercury lamp, 200 mJ / cm² 2Light was irradiated onto the surface of the dried coating film through a photomask (exposure process). The exposure process was performed by installing the photomask at a position 100 μm away from the coating film. As the photomask, one having a line and space pattern with a width of 3 to 100 μm was used. Subsequently, unexposed areas were removed by spraying Semiclean DL-A10 developer (manufactured by Yokohama Yushi Kogyo Co., Ltd.) (5x dilution) onto the surface of the coating film for 60 seconds under conditions of a temperature of 23°C and a pressure of 0.1 MPa (development process). The glass substrate having the coating film after the development process was placed in a dryer at 100°C for 30 minutes to heat-cur the coating film (post-bake process), thereby obtaining a colored pattern.

[0313] The colored pattern obtained in this manner was observed using an electron microscope S-3400 manufactured by Hitachi High Technologies Inc., and the presence or absence of residue in unexposed areas between the developed minimum line width (minimum developed dimension) and the developed pattern was evaluated. The presence or absence of residue was evaluated according to the following criteria. The results are shown in Table 4 or Table 5.

[0314] Evaluation criteria for residue

[0315] ○: No residue in the unexposed areas between developed patterns

[0316] ×: Residue in unexposed areas between developed patterns

[0317] (2) Pencil hardness

[0318] The photosensitive coloring compositions R1 to R16 and cR1 to cR9 prepared in Examples 1 to 16 and Comparative Examples 1 to 9 were applied onto a square glass substrate (alkali-free glass substrate) measuring 5 cm by 5 cm by a spin coat method, and a coating film was formed by heating at 100°C for 3 minutes to volatilize the solvent. Subsequently, light with a wavelength of 365 nm was exposed to the coating film at an exposure dose of 200 mJ / cm² 2The glass substrate having the photocured coating film was irradiated and photocured. Subsequently, the coating film was heat-cured (post-bake process) by leaving the glass substrate having the photocured coating film in a dryer at 100°C for 30 minutes, thereby obtaining a resin-cured film with a thickness of 2.5 μm.

[0319] The pencil hardness of the resin cured film produced in this manner was measured according to JIS K5600-5-4 using a pencil hardness tester (No. 553-M, manufactured by Seiki Yasuda Seisakusho) and evaluated according to the following criteria. The results are shown in Table 4 or Table 5.

[0320] Evaluation Criteria for Pencil Hardness

[0321] ○: Pencil hardness 3H or higher

[0322] ×: Pencil hardness less than 3H

[0323] (3) Content

[0324] In the same manner as when evaluating pencil hardness (2) above, a glass substrate having a resin cured film was prepared, and the absorption spectrum of the resin cured film was measured using a spectrophotometer (UV-1650PC, manufactured by Shimadzu Seisakusho). Additionally, 200 mL of propylene glycol monomethyl ether acetate was placed in a glass bottle with a lid and a capacity of 500 mL, and the mixture was left to stand under a temperature condition of 23°C. A glass substrate having a resin cured film was placed in this glass bottle and immersed in propylene glycol monomethyl ether acetate and left to stand at 23°C for 15 minutes. After that, the glass substrate having a resin cured film was removed, and the absorption spectrum of the resin cured film was measured using a spectrophotometer (UV-1650PC, manufactured by Shimadzu Seisakusho) in the same manner as before immersion in propylene glycol monomethyl ether acetate.

[0325] The color change (ΔE*ab) of the resin cured film before and after immersion in propylene glycol monomethyl ether acetate was calculated, and the solvent resistance of the resin cured film was evaluated according to the following criteria. The results are shown in Table 4 or Table 5.

[0326] Evaluation Criteria for Content Quality

[0327] ○: ΔE*ab is less than 3.0

[0328] ×: ΔE*ab is 3.0 or greater

[0329] (4) Comprehensive judgment

[0330] A resin cured film containing a cured product of each of the photosensitive coloring compositions R1 to R16 and cR1 to cR9 prepared in Examples 1 to 16 and Comparative Examples 1 to 9 was evaluated according to the criteria shown below. The results are shown in Table 4 or Table 5.

[0331] "metewand"

[0332] ○: Satisfies all of the following items.

[0333] (1) Minimum developed dimensions are 15㎛ or less, and there is no residue of unexposed areas between developed patterns.

[0334] (2) The pencil hardness of the resin cured film is 3H or higher

[0335] (3) Color change ΔE*ab less than 3.0 in the evaluation of the solvent resistance of the resin cured film

[0336] ×: Does not satisfy one or more of the items in ○ above.

[0337]

[0338]

[0339] As shown in Table 4, it was confirmed that the photosensitive coloring compositions R1 to R16 of Examples 1 to 16 all have a minimum developed dimension of 15 μm or less, and also have no residue of unexposed areas between developed patterns and have excellent alkali developability.

[0340] In addition, as shown in Table 4, the resin cured film comprising a cured product formed by photocuring a 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 had a pencil hardness of 3H or higher and possessed excellent hardness. Furthermore, it was confirmed that the resin cured film had an evaluation of solvent resistance of ○ and possessed excellent solvent resistance.

[0341] In contrast, as shown in Table 5, the photosensitive coloring compositions cR1 to cR9 of Comparative Examples 1 to 9 had insufficient alkali developability, pencil hardness, or solvent resistance.

[0342] More specifically, the copolymers cP1 to cP8 obtained in Comparative Synthesis Examples 1 to 8, which are included in the photosensitive coloring compositions cR1 to cR8 of Comparative Examples 1 to 8, have an active methylene group equivalent of 0. As a result, the alkali developability, hardness, and solvent resistance of the resin cured film were reduced. In addition, the copolymer cP9 obtained in Comparative Synthesis Example 9, which is included in the photosensitive resin composition cR9 of Comparative Example 9, has a functional group equivalent of 0. As a result, the hardness and solvent resistance of the resin cured film were reduced.

[0343] In addition, the changes over time of the resin composition obtained in this study were confirmed, and a favorable trend was observed in the order of constituent units having blocked isocyanate groups, constituent units having silyl groups, and constituent units having epoxy groups. While the reaction of blocked isocyanate groups does not proceed without the application of heat and the reaction of silyl groups can be controlled by using alcohol-based polymerization solvents, it is necessary to adjust the optimal introduction amount of epoxy groups or the amounts of other monomers. Industrial applicability

[0344] According to the present invention, a photosensitive resin composition and a photosensitive coloring composition can be provided, which can form a resin cured film having excellent developability and good low-temperature curability, and sufficient hardness and solvent resistance. Furthermore, according to the present invention, a resin cured film having sufficient hardness and solvent resistance can be provided, which includes a cured product of the photosensitive resin composition, and a color filter having a coloring pattern having sufficient hardness and solvent resistance can be provided, and an image display element having said color filter can be provided. The photosensitive resin composition and the photosensitive coloring composition of the present invention can preferably be used, for example, as a resist for a transparent film, a protective film, an insulating film, an overcoat, a photospacer, a black matrix, a black column spacer, and a color filter. Explanation of the symbols

[0345] 1: Substrate 2: Pixel 3: Black Matrix 4: Shield

Claims

Claim 1 A photosensitive resin composition comprising a resin (A), a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D), wherein the resin (A) contains a constituent unit (a-1) having at least one group selected from the group consisting of an active methylene group and an active methine group, a constituent unit (a-2) having a group that reacts by the action of light and / or heat, and a constituent unit (a-3) having a carboxyl group, wherein the constituent unit (a-1) is a constituent unit having a structure represented by the following formula (X1) or (X2), and the constituent unit (a-2) is a constituent unit having at least one functional group selected from an epoxy group, a silyl group, a block isocyanato group, and an isocyanato group. (Among equations (X1) and (X2), R 3 R represents a divalent group represented by any one of the following formulas (8) to (10). 4 represents a cyano group (-CN), a nitro group (-NO2), or a group represented by the following formula (11) or the following formula (12). * indicates a binding site. ★ indicates an active methylene carbon or an active methine carbon.) (In formulas (8) to (12), * indicates a bonding site. In formulas (11) and (12), R 5 represents a hydrocarbon group having 1 to 24 carbon atoms that may contain hydrogen atoms or heteroatoms.) Claim 2 A photosensitive resin composition according to claim 1, wherein the constituent unit (a-2) is a constituent unit (a-2-1) having an epoxy group, a constituent unit (a-2-2) having a silyl group, or a constituent unit (a-2-3) having a block isocyanato group. Claim 3 A photosensitive resin composition according to claim 1 or 2, wherein the acid value of the resin (A) is 10 to 300 KOH mg / g. Claim 4 A photosensitive resin composition according to claim 1 or 2, wherein, among the total constituent units of the resin (A), the constituent unit (a-1) is 2 to 80 mol% and the constituent unit (a-2) is 2 to 80 mol%. Claim 5 A photosensitive resin composition according to claim 1 or 2, wherein the resin (A) further contains other constituent units (a-4). Claim 6 In claim 1 or 2, among the formulas (X1) and (X2) having the constituent unit (a-1), R 3 This is a divalent group represented by Equation (8) or Equation (10), and R 4 A photosensitive resin composition, represented by the formula (11). Claim 7 A photosensitive resin composition according to claim 1 or 2, wherein the weight average molecular weight of the resin (A) is 1,000 to 50,000 and the molecular weight distribution (Mw / Mn) of the resin (A) is 1.3 to 3.

0. Claim 8 A photosensitive resin composition according to claim 1 or 2, wherein, for a total of 100 parts by mass of components excluding the solvent (D), the resin (A) is contained in an amount of 10 to 85 parts by mass, the reactive diluent (B) is contained in an amount of 10 to 85 parts by mass, the photopolymerization initiator (C) is contained in an amount of 0.1 to 30 parts by mass, and the solvent (D) is contained in an amount of 30 to 1000 parts by mass. Claim 9 A photosensitive coloring composition comprising a photosensitive resin composition and a coloring agent (E) as described in claim 1 or 2. Claim 10 A photosensitive coloring composition according to claim 9, wherein, for a total of 100 parts by mass of components excluding the solvent (D), the resin (A) is contained in an amount of 10 to 85 parts by mass, the reactive diluent (B) is contained in an amount of 10 to 85 parts by mass, the photopolymerization initiator (C) is contained in an amount of 0.1 to 30 parts by mass, the solvent (D) is contained in an amount of 30 to 1000 parts by mass, and the coloring agent (E) is contained in an amount of 4 to 70 parts by mass. Claim 11 A resin cured film comprising a cured product of the photosensitive resin composition described in claim 1 or 2. Claim 12 A color filter having a coloring pattern comprising a cured product of the photosensitive coloring composition described in claim 9. Claim 13 An image display element having a color filter as described in paragraph 12. Claim 14 delete Claim 15 delete

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