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

Abstract

The present invention provides a photosensitive resin composition and a photosensitive coloring composition capable of forming a resin cured film having excellent developability and good low-temperature curability, and having 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) is an addition reaction product of a hydroxyl group-containing (meth)acrylic resin (a-0), a compound (a-4) containing an isocyanate group and an ethylenically unsaturated group, and a polybasic acid or its anhydride (a-5). The above (a-0) is a copolymer comprising a structural unit derived from a hydroxyl group-containing (meth)acrylate (m-1) and a structural unit derived from a (meth)acrylate (m-2) having one or more groups selected from the group consisting of an active methylene group, an active methine group, an epoxy group, an oxetanyl group, a blocked isocyanato group, and a silyl group.

Description

Technology Field

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

[0002] The present application claims priority based on patent application No. 2022-118208 filed in Japan on July 25, 2022, and incorporates the contents thereof herein. 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 200°C or higher.

[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 as substrate materials for color filters. Furthermore, in order to realize high-brightness and high-contrast image display devices, there has been a transition from pigments to dyes and / or fluorescent compounds and quantum dots as coloring agents used in color filters.

[0005] Conventionally, as a resin composition used as a material for color filters, 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), wherein the photocurable compound (A) is carboxyl group-containing dipentaerythritol pentaacrylate and 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. Furthermore, 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. In addition, dyes have higher solubility in solvents compared to pigments. For this reason, if the solvent resistance of the color filter is insufficient, there is a risk that the dye contained in the color filter will leach out into the solvent, causing the color intensity of the color filter to 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] At least,

[0015] Suzy (A) and,

[0016] Reactive diluent (B) and,

[0017] photopolymerization initiator (C), and,

[0018] It contains a solvent (D),

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

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

[0021] The above hydroxyl group-containing (meth)acrylic resin (a-0) is, at least,

[0022] Structural units derived from hydroxyl group-containing (meth)acrylate (m-1), and

[0023] A structural unit derived from (meth)acrylate (m-2) having one or more groups selected from the group consisting of active methylene groups, active methine groups, epoxy groups, oxetanyl groups, blocked isocyanato groups, and silyl groups

[0024] A photosensitive resin composition characterized by being a copolymer comprising

[0025] [2] The photosensitive resin composition described in [1], wherein the above hydroxyl group-containing (meth)acrylic resin (a-0) is a copolymer of the above hydroxyl group-containing (meth)acrylate (m-1), the above (meth)acrylate (m-2), and other monomers (m-3).

[0026] [3] A photosensitive resin composition described in [2], wherein the other monomer (m-3) above is an alkyl (meth)acrylate having 1 to 12 carbon atoms in the alkyl group.

[0027] [4] When the total of all monomers that serve as the polymerization raw material for the above hydroxyl group-containing (meth)acrylic resin (a-0) is called “monomer M”, among the above monomers (M),

[0028] The content of the above hydroxyl group-containing (meth)acrylate (m-1) is 30 to 95 mol%, and

[0029] A photosensitive resin composition described in any one of [1] to [3], wherein the content of the above (meth)acrylate (m-2) is 5 to 50 mol%.

[0030] [5] A photosensitive resin composition described in any one of [1] to [4], wherein the compound (a-4) containing the isocyanato group and the ethylenically unsaturated group is an isocyanato group-containing (meth)acrylate (a-4a).

[0031] [6] The above isocyanato group-containing (meth)acrylate (a-4a) is an isocyanato group-containing (meth)acrylate having a polyoxyalkylene structure, or an isocyanato group-containing (meth)acrylate having two or more (meth)acryloyloxy groups, in the photosensitive resin composition described in [5].

[0032] [7] A photosensitive resin composition described in any one of [1] to [6], wherein the polybasic acid or its anhydride (a-5) is a tricarboxylic acid or its anhydride.

[0033] [8] A photosensitive resin composition described in any one of [1] to [7], wherein the acid value of the resin (A) is 10 to 300 KOH mg / g.

[0034] [9] A photosensitive resin composition described in any one of [1] to [8], wherein the ethylene unsaturated group equivalent of the resin (A) is 200 to 5000 g / mol.

[0035]

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

[0036]

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

[10] , wherein the amount of compound (a-4) containing the isocyanato group and ethylenically unsaturated group is 1 to 60 moles per 100 moles of the monomer (M).

[0037]

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

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

[0038]

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

[0039] A photosensitive resin composition described in any one of [1] to

[12] , wherein the molecular weight distribution (Mw / Mn) of the resin (A) is 1.3 to 5.0.

[0040]

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

[0041] Containing 10 to 85 parts by mass of the above resin (A),

[0042] Containing 10 to 85 parts by mass of the above-mentioned reactive diluent (B),

[0043] Contains 0.1 to 30 parts by mass of the above photopolymerization initiator (C),

[0044] A photosensitive resin composition described in any one of [1] to

[13] containing 30 to 1000 parts by mass of the above solvent (D).

[0045]

[15] A photosensitive resin composition and a colorant (E) as described in any of [1] to

[14] ,

[0046] For a total of 100 parts by mass of the components excluding the above solvent (D),

[0047] A photosensitive coloring composition containing 4 to 79 parts by mass of the above coloring agent (E).

[0048]

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

[14] .

[0049]

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

[15] .

[0050]

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

[17] . Effects of the invention

[0051] 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.

[0052] 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

[0053] 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

[0054] 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.

[0055] In this specification, “(meth)acrylic acid” means at least one selected from methacrylic acid and acrylic acid. “(meth)acrylate” means at least one selected from methacrylate and acrylate, and “(meth)acryloyl” means at least one selected from methacryloyl and acryloyl.

[0056] Photosensitive resin composition

[0057] The photosensitive resin composition of the present embodiment comprises at least a resin (A), a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D).

[0058] [Suzy (A)]

[0059] The resin (A) included in the photosensitive resin composition of the present embodiment is an ethylene unsaturated group and a carboxyl group modified (meth)acrylic resin. By using an ethylene unsaturated group modified (meth)acrylic resin, the developability of the photosensitive resin composition is improved, and a cured film having a finer pattern can be obtained. By using a carboxyl group modified (meth)acrylic resin, the developability of the photosensitive resin composition is improved, and curing at a lower temperature becomes possible, thereby improving the hardness or solvent resistance of the cured product. Examples of the ethylene unsaturated group include vinyl groups, allyl groups, (meth)acryloyloxy groups, etc. It is preferable that the ethylene unsaturated group is a (meth)acryloyloxy group.

[0060] "Ethylene unsaturated group modified" resin and "carboxyl group modified" resin each refer to a resin in which only an ethylene unsaturated group-containing compound or only a carboxyl group-containing compound is added to a raw resin, thereby introducing an ethylene unsaturated group or a carboxyl group.

[0061] "Ethylene unsaturated group and carboxyl group modified" resin refers to a resin in which an ethylene unsaturated group-containing compound and a carboxyl group-containing compound are added to a raw resin to introduce an ethylene unsaturated group and a carboxyl group. The order of the addition reactions of the ethylene unsaturated group-containing compound and the carboxyl group-containing compound to the raw resin may be either first or simultaneous.

[0062] The above ethylenically unsaturated and carboxyl group modified (meth)acrylic resin is an addition reaction product of a hydroxyl group-containing (meth)acrylic resin (a-0), a compound (a-4) containing an isocyanato group and an ethylenically unsaturated group, and a polybasic acid or its anhydride (a-5). Ethyleneenically unsaturated groups are introduced into the resin (A) by the reaction between the hydroxyl groups of the hydroxyl group-containing (meth)acrylic resin (a-0) and the isocyanato groups of the compound (a-4) containing an ethylenically unsaturated group. Carboxylic groups are introduced into the resin (A) by the reaction between the hydroxyl groups of the hydroxyl group-containing (meth)acrylic resin (a-0) and the polybasic acid or its anhydride (a-5). The amount of each can be freely adjusted for the purpose of improving developability, low-temperature curing properties, and the hardness or solvent resistance of the cured film.

[0063] Meanwhile, a carboxyl group-containing (meth)acrylic resin is obtained by using (meth)acrylic acid, etc., as a constituent monomer of the (meth)acrylic resin, in which a carboxyl group is directly introduced into the main chain of the resin. In the case of such a carboxyl group-containing (meth)acrylic resin, if modification is attempted to introduce an ethylenically unsaturated group by using, for example, a compound (a-4) containing an isocyanato group and an ethylenically unsaturated group described later, a dimer of isocyanato is generated as a byproduct. This is undesirable because the byproduct does not have a developing group, and disadvantages such as reduced developability as a photosensitive resin composition for the purpose of the present invention occur. In that regard, the ethylene unsaturated and carboxyl group modified (meth)acrylic resin according to the present embodiment is a modified resin from the hydroxyl group-containing (meth)acrylic resin (a-0) described below, and it is also preferable that the hydroxyl group-containing (meth)acrylic resin (a-0) does not contain a carboxyl group.

[0064] In addition, as a substitute for the hydroxyl group-containing (meth)acrylic resin (a-0) in the present embodiment, it is not desirable to introduce an ethylene unsaturated group by a compound other than the compound (a-4) containing an isocyanato group and an ethylene unsaturated group, such as an epoxy group-containing (meth)acrylic resin in which an epoxy group is directly introduced into the main chain of the resin or a carboxyl group-containing (meth)acrylic resin in which a carboxyl group is directly introduced into the main chain of the resin, as this results in various disadvantages. For example, when (meth)acryloyloxy groups as ethylenically unsaturated groups are introduced into a resin by reacting (meth)acrylic acid with the epoxy groups of an epoxy group-containing (meth)acrylic resin in which epoxy groups are directly introduced into the main chain of the resin, or by reacting glycidyl (meth)acrylate with the carboxyl groups of a carboxyl group-containing (meth)acrylic resin in which carboxyl groups are directly introduced into the main chain of the resin, it is not desirable because disadvantages such as gelation occur due to reactions at high temperatures during synthesis. In addition, when carboxyl groups are introduced by reacting a polybasic acid or its anhydride (a-5) with the hydroxyl groups generated by ring opening of the epoxy groups of the resin in which ethylenically unsaturated groups were introduced by the above method, it is not desirable because disadvantages such as gelation occur due to reactions at high temperatures during synthesis.

[0065] [Hydroxyl group-containing (meth)acrylic resin (a-0)]

[0066] The hydroxyl group-containing (meth)acrylic resin (a-0) is a copolymer comprising at least a structural unit derived from a hydroxyl group-containing (meth)acrylate (m-1) and a structural unit derived from a (meth)acrylate (m-2) (hereinafter also simply referred to as (meth)acrylate (m-2)) having one or more groups selected from the group consisting of an active methylene group, an active methine group, an epoxy group, an oxetanyl group, a blocked isocyanato group, and a silyl group. The hydroxyl group-containing (meth)acrylic resin (a-0) may, if necessary, include a structural unit derived from another monomer (m-3). In this specification, the totality of all monomers that serve as the polymerization raw materials for the hydroxyl group-containing (meth)acrylic resin (a-0), namely the hydroxyl group-containing (meth)acrylate (m-1), the (meth)acrylate (m-2), and the other monomer (m-3) which is an optional component, are all referred to as "monomer (M)." The amount of monomer (M) refers to the total amount of monomers (m-1), (m-2), and (m-3).

[0067] Furthermore, "structural unit derived from hydroxyl group-containing (meth)acrylate (m-1)" refers to a structural unit formed by radical polymerization of hydroxyl group-containing (meth)acrylate (m-1), and specifically refers to a structural unit in which the polymerizable carbon-carbon double bond of hydroxyl group-containing (meth)acrylate (m-1) becomes a carbon-carbon single bond. Additionally, "structural unit derived from (meth)acrylate (m-2)" refers to a structural unit formed by radical polymerization of (meth)acrylate (m-2), and specifically refers to a structural unit in which the polymerizable carbon-carbon double bond of (meth)acrylate (m-2) becomes a carbon-carbon single bond.

[0068] [Hydroxygen-containing (meth)acrylate (m-1)]

[0069] Hydroxyl group-containing (meth)acrylate (m-1) is not particularly limited to compounds having a hydroxyl group and a (meth)acryloyloxy group. Examples include hydroxyl group-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate. Among these, hydroxyalkyl (meth)acrylate having a hydroxyl group at the alkyl terminal is preferred in terms of ease of availability and ease of modification reaction when introducing (meth)acryloyloxy groups and carboxyl groups into resin (A), particularly hydroxyalkyl (meth)acrylate having 2 to 4 carbon atoms is preferred, and 2-hydroxyethyl (meth)acrylate is most preferred.

[0070] The content of the hydroxyl group-containing (meth)acrylate (m-1) is preferably 30 to 95 mol% with respect to the monomer (M), more preferably 40 to 80 mol%, and even more preferably 45 to 70 mol%. If the content is 30 mol% or more, sufficient modification can be secured when introducing (meth)acryloyloxy groups and carboxyl groups, and a photosensitive resin composition with excellent developability is obtained, and a cured film with excellent hardness and solvent resistance is obtained even when cured at low temperature.

[0071] [(Meth)acrylate (m-2) having one or more groups selected from the group consisting of active methylene groups, active methine groups, epoxy groups, oxetanyl groups, blocked isocyanato groups and silyl groups]

[0072] The (meth)acrylate (m-2) according to the present embodiment is a (meth)acrylate that does not have hydroxyl groups and carboxyl groups, and is one or more compounds selected from the group consisting of (meth)acrylate containing an active methylene group or an active methine group (m-2-1), (meth)acrylate containing an epoxy group or an oxetanyl group (m-2-2), (meth)acrylate containing a blocked isocyanato group (m-2-3), and (meth)acrylate containing a silyl group (m-2-4). The functional group of the (meth)acrylate (m-2) contributes to the improvement of hardness or solvent resistance when the photosensitive resin composition is cured at a low temperature, such as by the functional group itself having crosslinkability due to heat or light, or by reacting with a hydroxyl group derived from the (meth)acrylate (m-1) containing a hydroxyl group to crosslink.

[0073] The content of (meth)acrylate (m-2) in relation to the present embodiment is preferably 5 to 50 mol% with respect to the monomer (M), more preferably 10 to 40 mol%, and even more preferably 15 to 30 mol%. If the content is 5 mol% or more, the amount of functional groups of (meth)acrylate (m-2) introduced can be sufficiently secured, and a photosensitive resin composition with excellent developability is obtained, and a cured film with excellent hardness and solvent resistance is obtained even when cured at low temperature. If the content is 50 mol% or less, the content of hydroxyl group-containing (meth)acrylate (m-1) can be sufficiently secured, and the content of a compound (a-4) containing isocyanato groups and ethylenically unsaturated groups and a polybasic acid or its anhydride (a-5) can be sufficiently secured.

[0074] Among these, using a (meth)acrylate containing a block isocyanato group (m-2-3) can improve low-temperature curability as a photosensitive resin composition and obtain a cured film with superior hardness and solvent resistance. Using a (meth)acrylate containing a silyl group (m-2-4) improves the crosslinking efficiency as a photosensitive resin composition, thereby enabling further fineness of the pattern.

[0075] [Containing active methylene or active methine groups (meth)acrylate (m-2-1)]

[0076] The active methylene group or active methine group of (meth)acrylate (m-2-1) allows hydrogen atoms to be easily detached, thereby promoting the crosslinking reaction of the resin. For example, the methylene bond between two carbonyl groups of acetoacetic acid ester is active and easily causes a hydrogen withdrawal reaction. In addition, as is well known, acetoacetic acid ester exhibits typical keto-enol intermutability and is thought to be involved in photocuring. Furthermore, the active methylene group and active methine group in the present embodiment refer to a methylene group or methine group in which both ends are bonded to a carbon atom of a carbonyl group, a sulfur atom of a sulfonyl group, a cyano group, or a nitro group.

[0077] 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.

[0078]

[0079] (Equation (X1), R 3 R represents a divalent group represented by any of the following formulas (8) to (10). 4 represents a cyano group (-CN), a nitro group (-NO2), a group represented by the following formula (11), or the following formula (12). * indicates a binding site. ★ indicates an active methylene carbon.)

[0080]

[0081]

[0082] (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.)

[0083] 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.

[0084] 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.

[0085] R in equation (X1) 4 As such, if Equation (11) or Equation (12) is included, R in Equation (11) and 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).

[0086]

[0087] (In formulas (13) to (15), * indicates a bonding site.)

[0088] 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.

[0089] 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.

[0090] 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.

[0091]

[0092] (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).

[0093] As (meth)acrylates (m-2-1) containing active methylene groups or active methine groups, examples include compounds represented by the following formulas (1) or (2).

[0094]

[0095]

[0096] (In equations (1) and (2), R 6 R represents a hydrogen atom, or a methyl group. 2 represents 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.)

[0097] As a (meth)acrylate (m-2-1) containing an active methylene group or an active methine group, a compound represented by the following formula (m1) is preferred in terms of ease of reaction when polymerizing resin (A), low-temperature curing ability as a photosensitive resin composition, and hardness or solvent resistance of the cured film.

[0098]

[0099] (In equation (m1), R 6 represents a hydrogen atom or a methyl group, and R 7 ...represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.)

[0100] 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.

[0101] As a compound represented by the above formula (1), specifically, the following compounds may be used.

[0102]

[0103] As a compound represented by the above formula (2), specifically, the following compounds may be used.

[0104]

[0105] Formulas (16) to (33) are compounds having CH2=C(CH3)-, but compounds in which CH2=C(CH3)- is substituted with CH2=CH- can also be cited.

[0106] [Epoxy or oxetanyl group-containing (meth)acrylate (m-2-2)]

[0107] (Meth)acrylate (m-2-2) is a compound that does not contain hydroxyl groups, active methylene groups, active methine groups, or carboxyl groups, but has epoxy groups or oxetanyl groups and (meth)acryloyloxy groups. By using (meth)acrylate (m-2-2), when curing a photosensitive resin composition, crosslinking with carboxyl groups derived from polybasic acid or its anhydride (a-5) proceeds. Therefore, a photosensitive resin composition with good developability is obtained, and a cured film with excellent hardness and solvent resistance is obtained even when cured at low temperatures.

[0108] Specific examples of epoxy group-containing (meth)acrylates include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, (meth)acrylates having alicyclic epoxy groups and their lactone adducts, 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, epoxides of dicyclopentenyl (meth)acrylate, and epoxides of dicyclopentenyloxyethyl (meth)acrylate. Among these, glycidyl (meth)acrylates and (meth)acrylates having alicyclic epoxy groups are preferred from the viewpoint of ease of availability and reactivity when synthesizing resin (A), and 3,4-epoxycyclohexylmethyl (meth)acrylates and glycidyl (meth)acrylates are more preferred.

[0109] Specific examples of oxetanyl group-containing (meth)acrylates include (3-ethyloxetane-3-yl)methyl(meth)acrylate, methyl(meth)acrylate, 4-[3-(3-ethyloxetane-3-ylmethoxy)propoxy]styrene, 4-[6-(3-ethyloxetane-3-ylmethoxy)hexyloxy]styrene, 4-[5-(3-ethyloxetane-3-ylmethoxy)pentyloxy]styrene, and 2-vinyl-2-methyloxetane. Among these, (3-ethyloxetane-3-yl)methyl(meth)acrylate is preferred from the perspective of ease of availability and reactivity when synthesizing resin (A).

[0110] Among (meth)acrylates (m-2-2), (cyclo)alkyl (meth)acrylates having 2 to 12 carbon atoms having an epoxy group and an oxetanyl group are preferred in terms of ease of availability and reactivity when synthesizing resin (A).

[0111] [Block isocyanate group containing (meth)acrylate (m-2-3)]

[0112] (Meth)acrylate (m-2-3) is a compound having blocked isocyanato groups and (meth)acryloyloxy groups, without containing hydroxyl groups, active methylene groups, active methine groups, epoxy groups, oxetanyl groups, or carboxyl groups. By using (meth)acrylate (m-2-3), the low-temperature curing properties of the photosensitive resin composition are improved, and a cured film with excellent hardness and solvent resistance is obtained by crosslinking the hydroxyl groups derived from the hydroxyl group-containing (meth)acrylate (m-1) with the isocyanato groups generated by deblocking. (Meth)acrylate (m-2-3) may be, for example, a compound in which the isocyanato groups in the isocyanato group-containing (meth)acrylate are blocked by a blocking agent. The reaction between the isocyanato group-containing (meth)acrylate and the blocking agent can be carried out regardless of the presence or absence of a solvent. When using a solvent, it is necessary to use a solvent that is inert to the isocyanato 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 the reaction at 0 to 100°C. Examples of the above-mentioned isocyanato compounds include compounds represented by the following formula (XX1).

[0113]

[0114] In the above equation (XX1), R 11 represents a hydrogen atom or a methyl group, and R 12 -CO-, -COOR 13 -(Here, R13 (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 - and, here, R 13 It is preferably an alkylene group having 1 to 4 carbon atoms.

[0115] Examples of isocyanato 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 isocyanato, etc. Additionally, an equimolar (1 mol:1 mol) reaction product of 2-hydroxyalkyl (meth)acrylate and a diisocyanato 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-isocyanatemethylcyclohexyl isocyanate (IPDI), m-(or p-)xylene diisocyanate, 1,3-(or 1,4-)bis(isocyanatemethyl)cyclohexane, lysine diisocyanate, etc.

[0116] Among these isocyanato 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 isocyanato are preferred, and 2-isocyanatoethyl (meth)acrylate and 2-isocyanatopropyl (meth)acrylate are more preferred.

[0117] As blocking agents for blocking isocyanato groups in isocyanato 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 esters, 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 acetanilide, 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 formaldooxime, acetaldooxime, acetooxime, methyl ethyl ketooxime, methyl isobutyl ketooxime, and cyclohexanoneoxime; 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), the blocking agent is preferably diethyl malonicate, 3,5-dimethylpyrazole, oxybenzoic acid ester, and methyl ethyl ketoxime, and in terms of low-temperature curing properties, 3,5-dimethylpyrazole is more preferred.

[0118] [Silyl group-containing (meth)acrylate (m-2-4)]

[0119] The silyl group-containing (meth)acrylate (m-2-4) is a compound having a silyl group and a (meth)acryloyloxy group, and not containing a hydroxyl group, an active methylene group, an active methine group, an epoxy group, an oxetanyl group, a blocked isocyanato group, or a carboxyl group. Specific examples 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, [(meth)acryloyloxy]alkylmethyldialkoxysilane and [(meth)acryloyloxy]alkylethyldialkoxysilane are preferred in terms of ease of availability and reactivity when synthesizing resin (A), 3-(meth)acryloyloxypropylmethyldimethoxysilane and 3-(meth)acryloyloxypropylmethyldiethoxysilane are more preferred, and 3-(meth)acryloyloxypropylmethyldiethoxysilane is even more preferred.

[0120] [Other monomers (m-3)]

[0121] The hydroxyl group-containing (meth)acrylic resin (a-0) may, if necessary, have other monomers (m-3) other than the hydroxyl group-containing (meth)acrylate (m-1) and (meth)acrylate (m-2) as constituent monomers. Examples of other monomers (m-3) include dienes such as butadiene, (meth)acrylic acid esters, styrenes, unsaturated dicarboxylic acid diesters, and other vinyl compounds. For the reasons stated above, it is preferable that the other monomer (m-3) does not have a carboxyl group.

[0122] 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; and 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. Examples include aromatic (meth)acrylates such as benzyl (meth)acrylate, triphenylmethyl (meth)acrylate, cumyl (meth)acrylate, naphthalene (meth)acrylate, and anthracene (meth)acrylate; rosin (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and 2-(2-vinyloxyethoxy)ethyl (meth)acrylate.

[0123] Specific examples of styrenes include styrene and α-, o-, m-, p- alkyl derivatives of styrene.

[0124] Specific examples of unsaturated dicarboxylic acid diesters include diethyl citraconic acid, diethyl maleate, diethyl fumarate, diethyl itaconate, etc.

[0125] 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.

[0126] Among these, (meth)acrylic acid esters and other vinyl compounds are preferred in terms of ease of availability and reactivity when synthesizing resin (A), alkyl (meth)acrylates having 1 to 12 carbon atoms, benzyl (meth)acrylates, dicyclofentanyl (meth)acrylates, styrene, vinyltoluene, and norbornene are preferred, and methyl (meth)acrylates, 2-ethylhexyl (meth)acrylates, and dicyclofentanyl (meth)acrylates are more preferred. In particular, in terms of improving the developability of the photosensitive resin composition, alkyl (meth)acrylates having 6 to 12 carbon atoms and alicyclic alkyl (meth)acrylates are preferred, and 2-ethylhexyl (meth)acrylates and dicyclofentanyl (meth)acrylates are more preferred.

[0127] The content of the other monomer (m-3) is preferably 1 to 50 mol% with respect to the monomer (M), more preferably 3 to 40 mol%, and even more preferably 5 to 35 mol%.

[0128] [Compound containing isocyanato groups and ethylenically unsaturated groups (a-4)]

[0129] Compound (a-4) containing an isocyanato group and an ethylenically unsaturated group is not particularly limited as long as it has an isocyanato group and an ethylenically unsaturated group and does not have a hydroxyl group, an active methylene group, an active methine group, an epoxy group, an oxetanyl group, a blocked isocyanato group, or a silyl group. If the ethylenically unsaturated group is a (meth)acryloyloxy group, the compound (a-4) containing an isocyanato group and an ethylenically unsaturated group is an isocyanato group-containing (meth)acrylate (a-4a). Examples of isocyanato group-containing (meth)acrylates (a-4a) include 2-(meth)acryloyloxyethyl isocyanato, 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, 2-(2-isocyanatoethyloxy)ethyl (meth)acrylate, 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanato, etc. Among these, isocyanatoalkyl (meth)acrylate is preferred in terms of ease of availability and ease of synthesis of resin (A), and 2-(meth)acryloyloxyethylisocyanato is more preferred. In addition, the number of carbon atoms in the alkyl group of the isocyanatoalkyl (meth)acrylate is preferred to be 2 to 10. In terms of improving developability as a photosensitive resin composition and forming finer patterns, isocyanato group-containing (meth)acrylate having a polyoxyalkylene structure is preferred, and 2-(2-isocyanatoethyloxy)ethyl (meth)acrylate is more preferred.

[0130] From the perspective of improving developability by enhancing light sensitivity as a photosensitive resin composition, a compound containing two or more ethylenically unsaturated groups and an isocyanato group is preferred. When the ethylenically unsaturated group is a (meth)acryloyloxy group, from the perspective of improving developability by enhancing light sensitivity as a photosensitive resin composition, a (meth)acrylate containing an isocyanato group having two or more (meth)acryloyloxy groups is preferred, and 1,1-(bis(meth)acryloyloxymethyl)ethylisocyanato is more preferred.

[0131] The amount of compound (a-4) containing isocyanato groups and ethylenically unsaturated groups added is preferably 1 to 60 moles per 100 moles of monomer (M) constituting the hydroxyl group-containing (meth)acrylic resin (a-0), more preferably 3 to 50 moles, and even more preferably 5 to 40 moles. If the amount of compound (a-4) containing isocyanato groups and ethylenically unsaturated groups added is 1 mole or more, sufficient photocurability can be imparted as a photosensitive resin composition. If the amount added is 60 moles or less, gelation during the synthesis of the resin (A) can be prevented, and the amount of polybasic acid or its anhydride (a-5) introduced can be sufficiently secured, and good developability as a photosensitive resin composition is obtained. In particular, from the perspective of miniaturization of the development pattern, the amount of compound (a-4) containing isocyanato groups and ethylenically unsaturated groups added is preferably 30 to 50 moles per 100 moles of monomer (M) constituting the hydroxyl group-containing (meth)acrylic resin (a-0).

[0132] [Polybasic acid or its anhydride (a-5)]

[0133] Polybasic acid or its anhydride (a-5) is a compound having two or more carboxyl groups or its anhydride. Examples of polybasic acids include adipic acid, itaconic acid, succinic acid, oxalic acid, malonic acid, phthalic acid, fumaric acid, maleic acid, glutaric acid, tartaric acid, glutamic acid, sebacic acid, etc. Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, succinic anhydride, cyclohexanetricarboxylic acid anhydride, etc. Among them, from the perspective of the hardness of the cured film, polybasic acid anhydrides having a ring structure are preferred, maleic anhydride, itaconic anhydride, ethyl maleic anhydride, methyl itaconic anhydride, chlormaleic anhydride, citraconic anhydride, 2-norbornene-5,6-dicarboxylic acid anhydride, 4-[2-(methacryloyloxy)ethoxycarbonyl]phthalic anhydride, succinic anhydride, tetrahydrophthalic anhydride, and cyclohexanetricarboxylic acid anhydride are more preferred, and from the perspective of improving low-temperature curability by increasing the amount of carboxyl groups introduced, tetrahydrophthalic anhydride and cyclohexanetricarboxylic acid anhydride are even more preferred.

[0134] The amount of the polybasic acid or its anhydride (a-5) added is preferably 1 to 60 moles per 100 moles of monomer (M) constituting the hydroxyl group-containing (meth)acrylic resin (a-0), more preferably 3 to 50 moles, and even more preferably 5 to 45 moles. If the amount of the polybasic acid or its anhydride (a-5) added is 1 mole or more, sufficient developability as a photosensitive resin composition is obtained. If the amount added is 60 moles or less, sufficient amount of compound (a-4) containing isocyanato groups and ethylenically unsaturated groups can be introduced, and good photocurability as a photosensitive resin composition is obtained. Particularly from the perspective of improving the hardness and solvent resistance of the cured film during low-temperature curing, the amount of the polybasic acid or its anhydride (a-5) added is preferably 35 to 60 moles.

[0135] The modification rate of the resin (A), that is, the ratio of the amount of compound (a-4) containing isocyanato groups and ethylenically unsaturated groups and polybasic acid or its anhydride (a-5) introduced (total moles) to the hydroxyl groups (moles) of the hydroxyl group-containing (meth)acrylic resin (a-0), is preferably 20 to 90%, more preferably 30 to 85%, and even more preferably 45 to 80%. If the modification rate is 20% or higher, sufficient amounts of ethylenically unsaturated groups and carboxyl groups introduced can be secured, and a photosensitive resin composition with excellent developability is obtained, and a cured film with excellent hardness and solvent resistance is obtained even when cured at low temperature. If the modification rate is 90% or lower, gelation during the synthesis of the resin (A) is suppressed, and residual monomers are reduced, thereby suppressing the generation of residues during development as a photosensitive resin composition.

[0136] Weight-average molecular weight (Mw)

[0137] 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 3,500 to 25,000. If the weight average molecular weight (Mw) of the resin (A) is 1,000 or more, when the resin composition containing the resin (A) is used as a raw material 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 has excellent practicality.

[0138] 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.

[0139] Column: Showdex (Registered Trademark) LF-804+LF-804 (Manufactured by Showa Denko Co., Ltd.)

[0140] Column temperature: 40℃

[0141] Sample: Tetrahydrofuran solution containing 0.2 mass% of resin (A).

[0142] Developing solvent: Tetrahydrofuran

[0143] Detector: Differential Refractometer (Product Name: SHODEX (Registered Trademark) RI-71S, Manufactured by Showa Denko Co., Ltd.)

[0144] Flow rate: 1 mL / min

[0145] The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the resin (A) is preferably 1.3 to 5.0, more preferably 1.5 to 4.0, and most preferably 1.7 to 3.0. If the molecular weight distribution (Mw / Mn) of the resin (A) is 1.3 or higher, the target numerical range of the weight average molecular weight (Mw), acid value, etc., and the 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 5.0 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.

[0146] In addition, the molecular weight distribution (Mw / Mn) is calculated using the chromatogram of the above GPC measurement.

[0147] "Sanga"

[0148] The acid value of resin (A) is not particularly limited, but is preferably 10 KOH mg / g to 300 KOH mg / g, more preferably 50 KOH mg / g to 300 KOH mg / g, and most preferably 100 KOH mg / g to 300 KOH mg / g. If the acid value of resin (A) is 10 KOH mg / g or higher, a photosensitive resin composition having better developability is obtained when a resin composition containing resin (A) is used as a raw material for a photosensitive resin composition. If the acid value of resin (A) is 300 KOH mg / g or lower, when a resin composition containing resin (A) is used as a raw material for a photosensitive resin composition, the exposed portion (photocured portion) is not dissolved by the alkaline developer, and a photosensitive resin composition having good developability is obtained.

[0149] In addition, the acid value of resin (A) is a value measured using a mixed indicator of bromothymol blue and phenol red according to JIS K6901 5.3. The acid value of resin (A) refers to the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of resin (A).

[0150] Ethylene unsaturated group equivalent

[0151] The ethylenically unsaturated group equivalent of resin (A) is not particularly limited, but is preferably 200 g / mol to 5000 g / mol, more preferably 300 g / mol to 4000 g / mol, and most preferably 300 g / mol to 3000 g / mol. If the ethylenically unsaturated group equivalent of resin (A) is 200 g / mol or more, the photosensitive resin composition containing resin (A) can form a resin cured film having better hardness. In addition, if the ethylenically unsaturated group equivalent of resin (A) is 200 g / mol or more, the amount of carboxyl groups introduced into resin (A) can be sufficiently secured, thereby obtaining a photosensitive resin composition having better developability. In addition, if the ethylenically unsaturated group equivalent of resin (A) is 5000 g / mol or less, the photosensitive resin composition containing resin (A) can form a resin cured film having better hardness. From the perspective of ensuring a sufficient amount of ethylene unsaturated groups to improve the photocurability of the photosensitive resin composition and to further refine the pattern, the equivalent amount of ethylene unsaturated groups may be 1500 g / mol or less, or 800 g / mol or less.

[0152] In addition, the ethylene unsaturated group equivalent of resin (A) is the value obtained by dividing the molecular weight of resin (A) by the average number of unsaturated groups per molecule. The ethylene unsaturated group equivalent of resin (A) is a calculated value 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 unsaturated groups are included in one molecule of resin (A), all unsaturated groups are counted as the number of unsaturated groups regardless of the type of unsaturated group.

[0153] Sensory Equivalent

[0154] The functional group equivalent of the resin (A) according to the present embodiment is the equivalent of the aforementioned functional groups (active methylene group, active methine group, epoxy group, oxetanyl group, blocked isocyanato group and silyl group) included in the constituent unit derived from (meth)acrylate (m-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 superior hardness. In addition, if the functional group equivalent of resin (A) is 200 g / mol or more, a photosensitive resin composition having better developability is obtained when a resin composition containing resin (A) is used as a raw material for a photosensitive resin composition. In addition, if the functional group equivalent of resin (A) is 5000 g / mol or less, a photosensitive resin composition containing resin (A) can form a resin cured film having better hardness.

[0155] 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 derived from (meth)acrylate (m-2) per molecule. The functional group equivalent of resin (A) is a calculated value obtained based on the input amount of monomer (M) 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.

[0156] <Method for manufacturing hydroxyl group-containing (meth)acrylic resin (a-0)>

[0157] A hydroxyl group-containing (meth)acrylic resin (a-0) can be manufactured, for example, using the manufacturing method described below. That is, in the presence of a polymerization solvent, a monomer (M) is copolymerized using a polymerization initiator according to a radical polymerization method known in the art.

[0158] Specifically, a method may be used in which a monomer (M) is dissolved in a polymerization solvent to prepare a raw material solution, a polymerization initiator is added to the raw material solution, and a copolymerization reaction is carried out while stirring at, for example, 50°C to 130°C for 1 to 20 hours.

[0159] (Polymerization solvent)

[0160] As a polymerization solvent used when manufacturing a hydroxyl group-containing (meth)acrylic resin (a-0), it may be a solvent that is inert to the copolymerization reaction of the monomer (M) and is not particularly limited. The polymerization solvent used when manufacturing a hydroxyl group-containing (meth)acrylic resin (a-0) may be the same as the solvent included in the solvent (D) containing the resin composition described below, 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) containing 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.

[0161] As for the solvent used for polymerization, it is not particularly limited as long as it dissolves the monomer (M) 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.

[0162] The amount of polymerization solvent used when preparing the hydroxyl group-containing (meth)acrylic resin (a-0) 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 monomer (M). If the amount of polymerization solvent used is 30 parts by mass or more, the copolymerization reaction of the monomer (M) can be carried out stably, and discoloration and gelation of the hydroxyl group-containing (meth)acrylic resin (a-0) can be prevented. If the amount of polymerization solvent used is 1000 parts by mass or less, the decrease in molecular weight of the hydroxyl group-containing (meth)acrylic resin (a-0) due to chain transfer action can be suppressed, and the viscosity of the reaction solution can be controlled within an appropriate range.

[0163] (Polymer initiator)

[0164] Polymerization initiators that can be used in the copolymerization reaction of monomer (M) 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.

[0165] 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 monomer (M).

[0166] <Method for manufacturing resin (A)>

[0167] Resin (A) is obtained by adding a compound (a-4) containing an isocyanate group and an ethylenically unsaturated group and a polybasic acid or its anhydride (a-5) to a portion of the hydroxyl groups of a hydroxyl group-containing (meth)acrylic resin (a-0).

[0168] Additional reactions can be carried out in accordance with the ordinary method.

[0169] For example, a method can be used in which a compound (a-4) containing an isocyanate group and an ethylenically unsaturated group and a polybasic acid or its anhydride (a-5) are added to the reaction solution in which the hydroxyl group-containing (meth)acrylic resin (a-0) was synthesized to carry out an addition reaction. Furthermore, in this addition reaction (modification reaction), there is no particular problem even if the polymerization solvent used during the copolymerization to produce the hydroxyl group-containing (meth)acrylic resin (a-0) is included in the reaction solution. For this reason, the addition reaction can be carried out without removing the polymerization solvent from the reaction solution after the copolymerization reaction to produce the hydroxyl group-containing (meth)acrylic resin (a-0) has ended.

[0170] The order in which the compound (a-4) containing isocyanato groups and ethylenically unsaturated groups and the polybasic acid or its anhydride (a-5) are added is not particularly limited and may be added simultaneously or separately. From the perspective of suppressing the byproduct of the dimer of isocyanato, it is preferable to first add and react the compound (a-4) containing isocyanato groups and ethylenically unsaturated groups, and then add and react the polybasic acid or its anhydride (a-5).

[0171] The reaction temperature in the above addition reaction can be appropriately set according to the type of each raw material, etc. Specifically, it is preferable to set it to 30°C to 150°C, and more preferable to set it to 50°C to 120°C. By setting the reaction temperature to 30°C or higher, the addition reaction can be carried out sufficiently. In addition, by setting the reaction temperature to 150°C or lower, gelation of the reaction solution can be suppressed, and at the same time, the decomposition of the bonds generated by the addition reaction can be suppressed.

[0172] (Polymerization inhibitor)

[0173] When carrying out the above addition reaction, a polymerization inhibitor may be added to the reaction solution as needed to prevent gelation of the reaction solution caused by carrying out the addition reaction. The polymerization inhibitor is not particularly limited, but examples include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, dibutylhydroxytoluene, etc.

[0174] (catalyst)

[0175] When carrying out the above addition reaction, a catalyst may be added to the reaction solution to promote the reaction, if necessary. The catalyst is not particularly limited, but examples include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, metal chelate compounds such as chromium, metal chelate compounds such as lithium, tin compounds such as 2-ethylhexanoate and dibutyltin dilaurate (DBTDL).

[0176] 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 24 to 60 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 resin (A) is within the above range, the viscosity and low-temperature curability of the photosensitive resin composition become more suitable.

[0177] [Reactive diluent (B)]

[0178] 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. To improve curability (reactivity), a reactive diluent having multiple ethylenically unsaturated groups (a polyfunctional reactive diluent) is preferred. 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; trialyl cyanurate, etc.

[0179] Specific examples of aromatic vinyl monomers include styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, divinylbenzene, diallyl phthalate, diallylbenzene phosphonate, etc.

[0180] 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.

[0181] 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.

[0182] 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.

[0183] One of these reactive diluents (B) may be used alone, or two or more may be used in combination.

[0184] 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 24 to 60 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.

[0185] [Photopolymerization initiator (C)]

[0186] The photopolymerization initiator (C) included in the photosensitive resin composition of the present embodiment is not particularly limited as long as it is a compound that generates radicals upon light irradiation. Examples of the photopolymerization initiator (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], 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.

[0187] 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 adversely affect the storage stability of the photosensitive resin composition and the performance of the resin cured film.

[0188] [Solvent (D)]

[0189] The solvent (D) included in the resin composition of the present embodiment is inert to the resin (A) and the reactive diluent (B) and is capable of dissolving the resin (A) and the reactive diluent (B), and is not particularly limited.

[0190] The solvent (D) may or may not contain the polymerization solvent used to manufacture the resin (A).

[0191] If the solvent (D) contains a polymerization solvent used to manufacture the resin (A), the addition reaction to manufacture the resin (A) can be carried out without removing the polymerization solvent from the reaction solution after the copolymerization reaction to manufacture the 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.

[0192] The case in which the polymerization solvent used to produce the resin (A) is not included in the solvent (D) is a 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.

[0193] 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.

[0194] The solvent (D) may include other solvents capable of dissolving the resin (A) and the reactive diluent (B).

[0195] Examples include monoalcohols, (poly)alkylene glycol monoalkyl ethers, etc.

[0196] 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.

[0197] 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.

[0198] The content of the solvent (D) in the resin composition of the present embodiment is preferably 30 to 1000 parts by mass, more preferably 50 to 800 parts by mass, and most preferably 100 to 700 parts by mass, when the total sum of the components excluding the solvent (D) in the resin composition is 100 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.

[0199] [Other Additives]

[0200] The photosensitive resin composition of the present embodiment may, if necessary, contain one or more known additives such as a leveling agent, a thermal polymerization inhibitor, and a sensitizer. 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.

[0201] In addition, the photosensitive resin composition of the present embodiment may contain amine, hydrazide, aldehyde, or metal salt as a crosslinking agent 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, ZIRCOZOL ZC-2, 7 manufactured by No. 1 Rare Element Chemical Co., Ltd.

[0202] 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 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 Afro Chemical 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.

[0203] [Viscosity of photosensitive resin composition]

[0204] 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 at the temperature during coating, more preferably 2 mP·s to 20 mP·s, and most preferably 3 mP·s to 15 mP·s.

[0205] Photosensitive Coloring Composition

[0206] The photosensitive coloring composition of the present embodiment comprises the photosensitive resin composition of the present embodiment and a coloring agent (E).

[0207] [Colorant (E)]

[0208] As the coloring agent (E), known dyes and / or pigments may be used. When used in a filter, it is preferable to use a dye as the coloring agent (E) from the perspective of color reproducibility. When a dye is used as the coloring agent (E), a photosensitive coloring composition is obtained that exhibits good alkali development properties and a coloring pattern with high brightness can be obtained compared to when a pigment is used.

[0209] 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, with respect to solubility in the solvent (D) and alkaline developer, interaction with other components in the photosensitive resin composition, heat resistance, etc. Examples of such dyes include acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; solvent blue 38, 44 (VALIFAST BLUE2620); acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 0, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; 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.

[0210] 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, iron oxide, etc. Depending on the color of the desired pixel, one type of these pigment may be used alone, or two or more types may be used in combination.

[0211] 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).

[0212] The content of the coloring agent (E) in the photosensitive coloring composition of the present embodiment is preferably 4 to 79 parts by mass, more preferably 9 to 69 parts by mass, and most preferably 15 to 50 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.

[0213] [Other Additives]

[0214] The photosensitive coloring composition of the present embodiment may, if necessary, include other additives similar to those described in the photosensitive resin composition.

[0215] [Viscosity of photosensitive coloring composition]

[0216] 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.

[0217] Method for manufacturing a photosensitive resin composition

[0218] 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 additives used as needed using a known mixing device.

[0219] The photosensitive resin composition of the present embodiment has good low-temperature curing properties and can form a resin cured film having sufficient hardness and solvent resistance. In addition, 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.

[0220] Method for preparing a photosensitive coloring composition

[0221] 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.

[0222] The photosensitive resin composition of the present embodiment has good low-temperature curing properties and can form a resin cured film having sufficient hardness and solvent resistance. In addition, 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.

[0223] 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.

[0224] <Resin hardening film>

[0225] Next, the resin cured film of the present embodiment will be described in detail.

[0226] 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.

[0227] 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.

[0228] 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.

[0229] [Coating Process]

[0230] 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.

[0231] 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.

[0232] [Pre-baking Process]

[0233] In the pre-bake (pre-heat 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-bake 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-bake process, for example, a method using a hot plate can be cited.

[0234] [Photolithography Process]

[0235] 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.

[0236] [Post-exposure heating process]

[0237] 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 the development process. Therefore, it is not an essential process in the method for forming a resin cured film according to the present embodiment.

[0238] 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.

[0239] [Development Process]

[0240] When forming a resin cured film having a predetermined pattern, after the exposure process, a post-exposure heating process is performed if necessary, 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.

[0241] 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.

[0242] In alkaline aqueous solutions, one or more additives such as defoaming agents and surfactants may be added as needed.

[0243] Development conditions such as development temperature and development time in the development process 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.

[0244] In the development process, it is preferable to dissolve the unexposed portions of the coating film using the aforementioned alkaline aqueous solution, develop the film, and then wash and dry it.

[0245] [Post-bake process]

[0246] 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.

[0247] The heating temperature in the post-bake process can be, for example, set to 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.

[0248] 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, so 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.

[0249] The heating time in the post-baking 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.

[0250] 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.

[0251] 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).

[0252] Color Filter

[0253] Next, the color filter of the present embodiment will be described in detail.

[0254] 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).

[0255] 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, a PET substrate, etc., depending on the application. When using an organic material substrate such as a resin substrate, a low-temperature heat treatment process is essential, and the photosensitive resin composition of the present embodiment and the photosensitive coloring composition of the present embodiment can exhibit even greater effects. In addition, for example, when using a dye as a coloring agent (E), the photosensitive coloring composition of the present embodiment is used, and as the substrate (1) used in the color filter shown in FIG. 1, a color filter using a resin substrate such as a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyamideimide substrate, a polyimide substrate, a PET substrate, etc. is suitable.

[0256] At least one of the pixel (2) and black matrix (3) in the color filter shown in FIG. 1 is a color pattern comprising a cured product of a photosensitive color composition of the present embodiment comprising a resin composition comprising a resin (A) and a solvent (D), a reactive diluent (B), a photopolymerization initiator (C), a colorant (E), and an additive included as needed.

[0257] 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 cured product of a photosensitive coloring composition of the present embodiment.

[0258] 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 the present invention is not limited to the example shown in FIG. 1.

[0259] Next, a method for manufacturing a color filter of the present embodiment will be described.

[0260] 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.

[0261] 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.

[0262] By the above process, a color filter of the present embodiment shown in FIG. 1 is obtained.

[0263] 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.

[0264] Image display element

[0265] 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.

[0266] Examples

[0267] 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.

[0268] Examples of the synthesis of resin (A) are shown below.

[0269] [Synthesized Example 1]

[0270] 184.6 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.

[0271] Next, a mixture of 114.3 g (0.50 mol) of 2-hydroxyethyl methacrylate, 75.2 g (0.20 mol) of ethylene glycol monoacetoacetate monomethacrylate, 52.7 g (0.30 mol) of methyl methacrylate, 29.6 g of 2,2'-azobis(isobutyric acid)dimethyl (polymerization initiator), and 87.2 g of propylene glycol monomethyl ether acetate was added dropwise from a dropping funnel into the flask over a period of 3 hours.

[0272] After the dropwise addition was finished, a copolymerization reaction was carried out by stirring at 98°C for 3 hours to produce a copolymer containing hydroxyl groups (meth)acrylic resin (a-0). Then, the inside of the flask was replaced with air, and 24.8 g (0.10 mol) of 2-acryloyloxyethyl isocyanato, 0.27 g of dibutyltin dilaurate (DBTDL) (addition reaction catalyst), 0.53 g of methylhydroquinone (polymerization inhibitor), and 5.3 g of propylene glycol monomethyl ether acetate were added to the reaction solution in which the hydroxyl group-containing (meth)acrylic resin (a-0) was synthesized, and an addition reaction was carried out at 60°C for 2 hours.

[0273] By this, a (meth)acryloyloxy group was introduced to part of the hydroxyl group derived from 2-hydroxyethyl methacrylate.

[0274] Next, 53.4 g (0.20 mol) of 1,2,3,6-tetrahydrophthalic anhydride, 1.3 g of lithium naphthenate (addition reaction catalyst), and 66.0 g of propylene glycol monomethyl ether acetate were added, and an addition reaction was carried out at 78°C for 3 hours.

[0275] By this, a carboxyl group was introduced to a portion of the hydroxyl group derived from 2-hydroxyethyl methacrylate.

[0276] Next, 306.8 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.

[0277] [Synthesized Examples 2 to 18]

[0278] Resin compositions of copolymers P2 to P18 of Synthesis Examples 2 to 18 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.

[0279] For copolymers P1 to P18 included in the resin compositions of Synthesis Examples 1 to 18 obtained in this manner, the weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn), acid value, functional group equivalents (active methylene group, epoxy group, oxetanyl group, blocked isocyanato group, silyl group), and ethylenically unsaturated group equivalents were determined, respectively. The results are shown in Table 1.

[0280] [Comparative Synthesis Example 1]

[0281] 201.9 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.

[0282] Next, a mixture of 90.7 g (0.34 mol) of 2-hydroxyethyl methacrylate, 75.1 g (0.17 mol) of ethylene glycol monoacetoacetate monomethacrylate, 99.2 g (0.49 mol) of methyl methacrylate, 32.3 g of 2,2'-azobis(isobutyric acid)dimethyl (polymerization initiator), and 95.4 g of propylene glycol monomethyl ether acetate was added dropwise from a dropping funnel into the flask over a period of 3 hours.

[0283] After the dropwise addition was finished, a copolymerization reaction was carried out by stirring at 98°C for 3 hours to produce a comparative copolymer, a functional group-containing resin (ca). Then, the inside of the flask was replaced with air, and 52.7 g (0.17 mol) of 1,2,3,6-tetrahydrophthalic anhydride, 1.3 g of lithium naphthenate (addition reaction catalyst), 0.53 g of methylhydroquinone (polymerization inhibitor), and 44.8 g of propylene glycol monomethyl ether acetate were added to the reaction solution in which the functional group-containing resin (ca) was synthesized, and an addition reaction was carried out at 78°C for 3 hours.

[0284] Next, 307.9 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 Synthesis Example 1.

[0285] [Comparative Synthesis Examples 2 to 4]

[0286] A resin composition of copolymers cP1 to cP4 of Comparative Synthesis Examples 1 to 4 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.

[0287] For copolymers cP1 to cP4 included in the resin compositions of Comparative Examples 1 to 4 obtained in this manner, the weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn), acid value, functional group equivalents (active methylene group, epoxy group, oxetanyl group, blocked isocyanato group, silyl group), and ethylenically unsaturated group equivalents were determined, respectively. The results are shown in Table 2.

[0288] [Comparative Synthesis Example 5]

[0289] 177.0 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 118°C.

[0290] Next, a mixture of 153.9 g (0.7 mol) of glycidyl methacrylate, 104.9 g (0.27 mol) of MOI-BP, 10.2 g (0.03 mol) of dicyclofentanyl methacrylate, 32.8 g of tert-butylperoxy-2-ethylhexanoate (polymerization initiator), and 70.0 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.

[0291] Afterwards, the inside of the flask was replaced with air, and 78.0 g (0.7 mol) of acrylic acid, 1.4 g of triphenylphosphine (addition reaction catalyst), and 0.7 g of methylhydroquinone (polymerization inhibitor) were added to the above 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 acrylic acid with the epoxy groups derived from glycidyl methacrylate and simultaneously introducing ethylenically unsaturated bonds into the side chains of the copolymer, but gelation occurred during the reaction. Additionally, the reaction was terminated before adding 20.1 g (0.13 mol) of succinic anhydride to the above copolymer solution.

[0292] The functional group (block isocyanato group) equivalent and ethylenically unsaturated group equivalent of the resin of Comparative Synthesis Example 5 were determined. The results are shown in Table 2.

[0293]

[0294]

[0295] Preparation of a photosensitive coloring composition

[0296] (Examples 1 to 18, Comparative Examples 1 to 5)

[0297] (A) As a copolymer, copolymers P1 to P18 and cP1 to cP4 of Synthesis Examples 1 to 18 and Comparative Synthesis Examples 1 to 4 were mixed with components (B), (C), and (E) shown in Table 3 in the proportions shown in Table 3 to prepare photosensitive coloring compositions R1 to R18 and cR1 to cR4 of Examples 1 to 18 and Comparative Examples 1 to 4, respectively. In addition, in Comparative Example 5, a copolymer P2 of Synthesis Example 2 with 3 mass% of a dimer of 2-acryloyloxyethylisocyanato added was used as the (A) copolymer. The obtained (A) copolymer and components (B), (C), and (E) shown in Table 3 were mixed in the proportions shown in Table 3 to prepare the photosensitive coloring composition cR5 of Comparative Example 5.

[0298] 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 additional solvent added when manufacturing the resin composition.

[0299]

[0300] <Evaluation of Photosensitive Coloring Compositions>

[0301] The photosensitive coloring compositions R1 to R18 and cR1 to cR5 prepared in Examples 1 to 18 and Comparative Examples 1 to 5 were evaluated by the method shown below.

[0302] (1) Phenomenality

[0303] Photosensitive coloring compositions R1 to R18 and cR1 to cR5 prepared in Examples 1 to 18 and Comparative Examples 1 to 5 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).

[0304] 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 Semi-Clean 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.

[0305] 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.

[0306] Evaluation criteria for residue

[0307] ○: No residue in the unexposed areas between developed patterns

[0308] ×: Residue in unexposed areas between developed patterns

[0309] (2) Pencil hardness

[0310] The photosensitive coloring compositions R1 to R18 and cR1 to cR5 prepared in Examples 1 to 18 and Comparative Examples 1 to 5 were applied onto a square glass substrate (alkali-free glass substrate) measuring 5 cm by 5 cm by a spin coating 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.

[0311] 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 Seki Yasuda Seki Seisakusho) and evaluated according to the following criteria. The results are shown in Table 4 or Table 5.

[0312] Evaluation Criteria for Pencil Hardness

[0313] ○: Pencil hardness 3H or higher

[0314] ×: Pencil hardness less than 3H

[0315] (3) Content

[0316] A glass substrate having a resin cured film was prepared in the same manner as when evaluating pencil hardness (2) above, 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.

[0317] Color change of the resin cured film before and after immersion in propylene glycol monomethyl ether acetate (ΔE * ab) 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.

[0318] Evaluation Criteria for Content Quality

[0319] ○: ΔE * ab is less than 3.0

[0320] ×: ΔE * ab is 3.0 or higher

[0321] (4) Comprehensive judgment

[0322] Resin cured films comprising the cured products of each of the photosensitive coloring compositions R1 to R18 and cR1 to cR5 prepared in Examples 1 to 18 and Comparative Examples 1 to 5 were evaluated according to the criteria shown below. The results are shown in Table 4 or Table 5.

[0323] "metewand"

[0324] ○: Satisfies all of the following items.

[0325] (1) Minimum developed dimensions are 15㎛ or less, and there is no residue of unexposed areas between developed patterns.

[0326] (2) The pencil hardness of the resin cured film is 3H or higher

[0327] (3) Color change ΔE in the evaluation of the solvent resistance of the resin cured film * ab is less than 3.0

[0328] ×: Does not satisfy one or more of the items in ○ above.

[0329]

[0330]

[0331] As shown in Table 4, it was confirmed that the photosensitive coloring compositions R1 to R18 of Examples 1 to 18 all had a minimum developed dimension of 15 μm or less, and also had no residue of unexposed areas between developed patterns and had excellent alkali developability.

[0332] 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 R18 of Examples 1 to 18 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.

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

[0334] More specifically, the copolymers cP1 to cP3 obtained in Comparative Synthesis Examples 1 to 3, which are included in the photosensitive coloring compositions cR1 to cR3 of Comparative Examples 1 to 3, have an ethylenically unsaturated 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 cP4 obtained in Comparative Synthesis Example 4, which is included in the photosensitive resin composition cR4 of Comparative Example 4, generates a dimer of 2-acryloyloxyethylisocyanate as a byproduct during synthesis. As a result, the alkali developability, hardness, and solvent resistance of the resin cured film were reduced. In addition, the photosensitive resin composition cR5 of Comparative Example 5 used the copolymer P2 obtained in Synthesis Example 2 with the dimer of 2-acryloyloxyethylisocyanate added. For this reason, Comparative Example 5, like Comparative Example 4, resulted in a decrease in the alkali development ability, hardness, and solvent resistance of the resin cured film.

[0335] In addition, changes over time were confirmed for the resin composition obtained this time, and a favorable trend was observed in the order of constituent units having active methylene groups, constituent units having blocked isocyanato groups, constituent units having silyl groups, and constituent units having epoxy groups. Industrial applicability

[0336] 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, comprising a cured product of the photosensitive resin composition. 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 can be provided. Additionally, an image display element having this 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

[0337] 1: Substrate 2: Pixel 3: Black Matrix 4: Shield

Claims

Claim 1 At least, comprising a resin (A), a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D), wherein the resin (A) is an ethylenically unsaturated and carboxyl group modified (meth)acrylic resin, and the ethylenically unsaturated and carboxyl group modified (meth)acrylic resin is an addition reaction product of a hydroxyl group-containing (meth)acrylic resin (a-0), a compound (a-4) containing an isocyanato group and an ethylenically unsaturated group, and a polybasic acid or its anhydride (a-5), and wherein the hydroxyl group-containing (meth)acrylic resin (a-0) is a (meth)acrylate having at least one group selected from the group consisting of a structural unit derived from a hydroxyl group-containing (meth)acrylate (m-1) and an active methylene group, an active methine group, an oxetanyl group, a blocked isocyanato group, and a silyl group. A photosensitive resin composition characterized by being a copolymer containing structural units derived from (m-2). Claim 2 A photosensitive resin composition according to claim 1, wherein the hydroxyl group-containing (meth)acrylic resin (a-0) is a copolymer of the hydroxyl group-containing (meth)acrylate (m-1), the (meth)acrylate (m-2), and other monomers (m-3). Claim 3 A photosensitive resin composition according to claim 2, wherein the other monomer (m-3) is an alkyl (meth)acrylate having 1 to 12 carbon atoms in the alkyl group. Claim 4 A photosensitive resin composition according to claim 1, wherein the total of all monomers that serve as the polymerization raw material for the hydroxyl group-containing (meth)acrylic resin (a-0) is referred to as "monomer M," and among the monomers (M), the content of the hydroxyl group-containing (meth)acrylate (m-1) is 30 to 95 mol% and the content of the (meth)acrylate (m-2) is 5 to 50 mol%. Claim 5 A photosensitive resin composition according to any one of claims 1 to 3, wherein the compound (a-4) containing the isocyanate group and the ethylenically unsaturated group is an isocyanate group-containing (meth)acrylate (a-4a). Claim 6 A photosensitive resin composition according to claim 5, wherein the isocyanato group-containing (meth)acrylate (a-4a) is an isocyanato group-containing (meth)acrylate having a polyoxyalkylene structure, or an isocyanato group-containing (meth)acrylate having two or more (meth)acryloyloxy groups. Claim 7 A photosensitive resin composition according to any one of claims 1 to 3, wherein the polybasic acid or its anhydride (a-5) is a tricarboxylic acid or its anhydride. Claim 8 A photosensitive resin composition according to any one of claims 1 to 3, wherein the acid value of the resin (A) is 10 to 300 KOH mg / g. Claim 9 A photosensitive resin composition according to any one of claims 1 to 3, wherein the ethylenically unsaturated group equivalent of the resin (A) is 200 to 5000 g / mol. Claim 10 A photosensitive resin composition according to any one of claims 1 to 3, wherein the modification rate of the resin (A) is 20 to 90%. Claim 11 A photosensitive resin composition according to any one of claims 1 to 3, wherein the amount of compound (a-4) containing isocyanato groups and ethylenically unsaturated groups added is 1 to 60 moles per 100 moles of monomer (M). Claim 12 A photosensitive resin composition according to any one of claims 1 to 3, wherein the amount of added polybasic acid or its anhydride (a-5) is 1 to 60 moles per 100 moles of monomer (M). Claim 13 A photosensitive resin composition according to any one of claims 1 to 3, wherein the weight average molecular weight of the resin (A) is 1,000 to 50,000 and the molecular weight distribution (Mw / Mn) of the resin (A) is 1.3 to 5.

0. Claim 14 A photosensitive resin composition according to any one of claims 1 to 3, wherein, for every 100 parts by mass of the total of the 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 15 A photosensitive coloring composition comprising a photosensitive resin composition and a coloring agent (E) as described in any one of claims 1 to 3, wherein the coloring agent (E) is contained in an amount of 4 to 79 parts by mass per 100 parts by mass of the total of the components excluding the solvent (D). Claim 16 A resin cured film comprising a cured product of a photosensitive resin composition described in any one of claims 1 to 3. Claim 17 A color filter having a coloring pattern comprising a cured product of the photosensitive coloring composition described in paragraph 15. Claim 18 An image display element having a color filter as described in paragraph 17.

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