Photosensitive resin composition and color filter

Abstract

Provided is a photosensitive resin composition which has excellent developability and favorable low-temperature curability, and which can be used to form a cured resin film having sufficient hardness and solvent resistance. This photosensitive resin composition contains a resin (A), a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D). The resin (A) contains a structural unit (a-1) having at least one group selected from the group consisting of an active methylene group and an active methine group, a structural unit (a-2) having a group that reacts due to the action of light and / or heat, and a structural unit (a-3) having an acid group.

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin composition, a photosensitive colored composition, a cured resin film, a color filter, and an image display element. This application claims priority based on Japanese Patent Application No. 2021-207178, filed in Japan on December 21, 2021, and the contents of that application are incorporated herein by reference. [Background technology]

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

[0003] Conventionally, resin compositions used as materials for color filters include, for example, those described in Patent Document 1. Patent Document 1 discloses a colored photocurable resin composition comprising a photocurable compound (A), a binder resin (B), a photoinitiator (D), and a solvent (E). The photocurable compound (A) is a carboxyl group-containing dipentaerythritol pentaacrylate. The binder resin (B) contains one or more tetrahydropyran structures or tetrahydrofuran structures in its main chain structure. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2015-184675 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] Organic materials used as substrate materials have lower heat resistance compared to glass. Similarly, dyes used as colorants in color filters have lower heat resistance compared to pigments. For these reasons, it is desirable to lower the heating temperature required for curing resin compositions used as materials for color filters. Specifically, depending on the heat resistance of the substrate material and colorant material, it may be required to heat the resin composition for curing the color filter to 80-150°C.

[0006] However, with conventional resin compositions, when the heating temperature for curing was lowered, a cured product with sufficient hardness and solvent resistance could not be obtained. Color filters made from cured material with insufficient hardness are easily scratched. Therefore, in image display elements equipped with color filters, there is a risk of display defects caused by scratches on the color filter. Furthermore, in color filters used in image display elements, there is a tendency to increase the content of colorants in the resin composition used as the color filter material in order to improve color reproduction. Paints have higher solubility in solvents compared to pigments. Therefore, if the solvent resistance of the color filter is insufficient, the paint contained in the color filter may dissolve into the solvent, potentially changing the color of the color filter.

[0007] The present invention has been made in view of the above circumstances, and aims to provide a photosensitive resin composition and a photosensitive coloring composition that can form a resin cured film having excellent developability and good low-temperature curability, as well as sufficient hardness and solvent resistance. In addition, an object of the present invention is to provide a resin cured film made of a cured product of the photosensitive resin composition of the present invention and having sufficient hardness and solvent resistance. Another object of the present invention is to provide a color filter having a colored pattern made of a cured product of the photosensitive coloring composition of the present invention and having sufficient hardness and solvent resistance. Furthermore, an object of the present invention is to provide an image display element including this color filter.

Means for Solving the Problems

[0008] The present invention includes the following aspects. [1] A resin (A), a reactive diluent (B), a photopolymerization initiator (C), a solvent (D), and comprising, wherein the resin (A) contains a structural unit (a-1) having at least one group selected from the group consisting of an active methylene group and an active methine group, a structural unit (a-2) having a group that reacts by the action of light and / or heat, and a structural unit (a-3) having an acid group, and is characterized by a photosensitive resin composition. [2] The photosensitive resin composition according to [1], wherein the structural unit (a-2) is a structural unit having at least one functional group selected from the group consisting of an epoxy group, a silyl group, a blocked isocyanato group, an isocyanato group, a hydroxyl group, a mercapto group, an oxetanyl group, an amino group, a furyl group, a maleimide group, an oxazolidinyl group, an oxazolyl group, a formyl group, a nitro group, and a halogen group. [3] The photosensitive resin composition according to [2], wherein the structural unit (a-2) is a structural unit (a-2-1) having an epoxy group, a structural unit (a-2-2) having a silyl group, or a structural unit (a-2-3) having a blocked isocyanato group. [4] The photosensitive resin composition according to any one of [1] to [3], wherein the acid value of the resin (A) is 10 to 300 KOHmg / g. [5] Among all the structural units of the resin (A), the structural unit (a-1) is 2 to 80 mol%, A photosensitive resin composition according to any one of [1] to [4], wherein the constituent unit (a-2) is 2 to 80 mol%. [6] The photosensitive resin composition according to any one of [1] to [5], wherein the resin (A) further contains other constituent units (a-4). [7] The photosensitive resin composition according to any one of [1] to [6], wherein the constituent unit (a-1) is a constituent unit having a structure represented by the following formula (X1) or (X2). [ka] [ka] (In formulas (X1) and (X2), R 3 R represents a divalent group expressed by any of the following formulas (8) to (10). 4 represents a cyano group (-CN), a nitro group (-NO2), a group represented by formula (11) below, or a group represented by formula (12) below. * represents a bonding site. ★ represents an active methylene carbon or active methine carbon. [ka] [ka] (In equations (8) to (12), * represents a bonding site. In equations (11) and (12), R 5 (This represents a hydrocarbon group having 1 to 24 carbon atoms, which may contain a hydrogen atom or a heteroatom.) [8] The constituent unit (a-1) has, in formula (X1) and formula (X2), R 3 is a divalent group represented by formula (8) or formula (10), and R 4 The photosensitive resin composition according to [7], wherein is a group represented by formula (11). [9] The weight-average molecular weight of the resin (A) is 1,000 to 50,000. The photosensitive resin composition according to any one of [1] to [8], wherein the molecular weight distribution (Mw / Mn) of the resin (A) is 1.3 to 3.0.

[10] With respect to 100 parts by mass of the total components excluding the solvent (D), The above resin (A) contains 10 to 85 parts by mass, The reactive diluent (B) is contained in an amount of 10 to 85 parts by mass, The above photopolymerization initiator (C) is contained in an amount of 0.1 to 30 parts by mass, A photosensitive resin composition according to any one of [1] to [9], containing 30 to 1000 parts by mass of the solvent (D).

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

[10] and Coloring agent (E), A photosensitive coloring composition containing [a specific substance].

[12] With respect to 100 parts by mass of the total components excluding the solvent (D), The above resin (A) contains 10 to 85 parts by mass, The reactive diluent (B) is contained in an amount of 10 to 85 parts by mass, The above photopolymerization initiator (C) is contained in an amount of 0.1 to 30 parts by mass, The solvent (D) is contained in an amount of 30 to 1000 parts by mass, death, The photosensitive coloring composition according to

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

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

[10] .

[14] A color filter having a color pattern made of a cured product of a photosensitive colored composition according to any one of

[11] or

[12] .

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

[14] . [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a photosensitive resin composition and a photosensitive coloring composition that can form a resin cured film having excellent developability and good low-temperature curing properties, as well as sufficient hardness and solvent resistance. Furthermore, according to the present invention, a cured resin film having sufficient hardness and solvent resistance can be provided, which is made from a cured product of the photosensitive resin composition of the present invention. A color filter having a colored pattern made from a cured product of the photosensitive colored composition of the present invention, and possessing sufficient hardness and solvent resistance, can also be provided. Furthermore, an image display element comprising this color filter can be provided. [Brief explanation of the drawing]

[0010] [Figure 1] This is a schematic cross-sectional view showing an example of a color filter of this embodiment. [Modes for carrying out the invention]

[0011] The photosensitive resin composition, photosensitive colored composition, resin cured film, color filter, and image display element of the present invention will be described in detail below. However, the present invention is not limited to the embodiments shown below. In this specification, "(meth)acrylic acid" means at least one selected from methacrylic acid and acrylic acid, "(meth)acrylate" means at least one selected from methacrylate and acrylate, and "(meth)acryloyl" means at least one selected from methacryloyl and acryloyl.

[0012] <Photosensitive resin composition> The photosensitive resin composition of this embodiment comprises a resin (A), a reactive diluent (B), a photopolymerization initiator (C), and a solvent (D).

[0013] [Resin (A)] The resin (A) contained in the photosensitive resin composition of this embodiment comprises at least one constituent unit (a-1) selected from the group consisting of an active methylene group and an active methine group (hereinafter also simply referred to as "constituent unit (a-1)"), a constituent unit (a-2) having a group that reacts with the action of light and / or heat (hereinafter also simply referred to as "constituent unit (a-2)"), and a constituent unit (a-3) having an acid group (hereinafter also simply referred to as "constituent unit (a-3)"). The resin (A) may optionally contain constituent units (a-4), and the number of repetitions and bonding order of each are not particularly limited.

[0014] [Constituent unit (a-1)] The constituent unit (a-1) in this embodiment is a constituent unit having at least one group selected from the group consisting of an active methylene group and an active methine group. The presence of constituent unit (a-1) in resin (A) results in a photosensitive resin composition with good low-temperature curability, and even when the photosensitive resin composition is cured at low temperatures, the formed cured resin film has sufficient hardness, solvent resistance, and developability. The active methylene group or active methine group of constituent unit (a-1) readily detaches a hydrogen atom from the methylene group, promoting the crosslinking reaction of the resin. For example, the methylene bond between the two carbonyls of acetoacetate ester is active and readily undergoes a hydrogen abstraction reaction. Furthermore, as is well known, acetoacetate ester exhibits typical keto-enol tautomerism, which may also be related to photocuring. In this embodiment, the activated methylene group and activated methine group refer to a methylene group and a 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.

[0015] <Structure containing an active methylene group> Examples of structures having an active methylene group include the structure having the following formula (X1). 3 and R 4 The methylene group bonded to it is the active methylene group.

[0016] [ka]

[0017] (In formula (X1), R 3 represents a divalent group represented by any one of the following formulas (8) to (10). R 4 represents a cyano group (-CN), a nitro group (-NO2), the following formula (11), or a group represented by the following formula (12). * represents a bonding site. ★ indicates an active methylene carbon.)

[0018]

Chemical formula

[0019]

Chemical formula

[0020] (In formulas (8) to (12), * represents a bonding site. In formulas (11) and (12), R 5 represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms which may contain a hetero atom.).

[0021] Among the Rs that formula (X1) has, 3 from the viewpoint of good low-temperature curability as a photosensitive resin composition and excellent physical properties required for a color filter, a divalent group represented by either formula (8) or formula (10) is preferable, and a divalent group represented by formula (10) is more preferable.

[0022] Among the Rs that formula (X1) has, 4 from the viewpoint of good low-temperature curability as a photosensitive resin composition and excellent physical properties required for a color filter, formulas (11) and (12) are preferable, and formula (11) is more preferable.

[0023] When R in formula (X1) 4 represents a group represented by the above formula (11) or the above formula (12), R in formulas (11) and (12) 5Examples of hydrocarbon groups having 1 to 24 carbon atoms that may contain heteroatoms include methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, methoxy, ethoxy, propoxy, hexoxy, cyclohexoxy, and groups represented by formulas (13) to (15) below.

[0024] [ka]

[0025] (In equations (13) to (15), * represents a bonding site.)

[0026] In particular, as hydrocarbon groups having 1 to 24 carbon atoms that may contain heteroatoms, alkyl groups having 1 to 10 carbon atoms are preferred, alkyl groups having 1 to 6 carbon atoms are more preferred, and alkyl groups having 1 to 3 carbon atoms are even more preferred.

[0027] R 5 From the viewpoint of 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.

[0028] <Structure containing an active methine group> Examples of structures having an active methine group include the structure having the following formula (X2). 3 The methine group bonded to the cyclohexane ring is the active methine group.

[0029] [ka]

[0030] (In formula (X2), * represents a binding site. ★ represents the active methine carbon. R 3 The definition and preferred range are the same as in equation (X1).

[0031] In this embodiment, the constituent unit (a-1) is preferably 2 to 80 mol%, more preferably 105 to 70 mol%, and even more preferably 4010 to 65 mol% of the total constituent units of resin (A). When the content of constituent unit (a-1) is 2 mol% or more, the photosensitive resin composition using the resin composition containing resin (A) as a raw material will have good low-temperature curability and be able to form a resin cured film with sufficient hardness and solvent resistance. When the content of constituent unit (a-1) is 80 mol% or less, the content of constituent units (a-2) and (a-3) having functional groups in the total constituent units can be sufficiently ensured.

[0032] Methods for introducing the constituent unit (a-1) into resin (A) include copolymerizing a monomer (ma-1) (hereinafter also simply referred to as "monomer (ma-1)") having an ethylenically unsaturated group and at least one group selected from the group consisting of an active methylene group and an active methine group with another ethylenically unsaturated group-containing monomer, or polymerizing a precursor of resin (A) and then introducing an active methylene group or an active methine group to obtain resin (A). In the latter method, for example, a precursor of resin (A) having a hydroxyl group can be polymerized, and the hydroxyl group of the precursor can be reacted with a diketene such as 4-methyleneoxetan-2-one to obtain resin (A) into which an active methylene group has been introduced. The method for introducing the constituent unit (a-1) into resin (A) is not limited to the above.

[0033] The monomer (ma-1) is not particularly limited as long as it is a compound having an ethylenically unsaturated group and at least one group selected from the group consisting of an active methylene group and an active methine group. Examples of ethylenically unsaturated groups include vinyl groups, allyl groups, and (meth)acryloyloxy groups. Among these, (meth)acryloyloxy groups are preferred from the viewpoint of ease of polymerization for obtaining resin (A).

[0034] Examples of monomers (MA-1) include compounds represented by the following formulas (1) or (2).

[0035] [ka]

[0036] [ka]

[0037] (In formulas (1) and (2), R 1 R represents a hydrocarbon group having 1 to 24 carbon atoms, which may contain a hydrogen atom or a heteroatom. X represents a divalent group represented by any of the following formulas (3) to (7). 2 R represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms. 3 and R 4 The definition and preferred range are the same as those in formulas (X1) and (X2). ★ indicates an activated methylene carbon or activated methine carbon.

[0038] [ka]

[0039] (In equations (3) to (7), * represents a bonding site.)

[0040] In formulas (1) and (2), R 1 Examples of hydrocarbon groups having 1 to 24 carbon atoms that may contain heteroatoms include methyl, ethyl, propyl, butyl, hexyl, cyclohexyl, methoxy, ethoxy, propoxy, hexoxy, cyclohexoxy, and groups represented by formulas (13) to (15) below.

[0041] [ka]

[0042] (In equations (13) to (15), * represents a bonding site.)

[0043] In particular, as hydrocarbon groups having 1 to 24 carbon atoms that may contain heteroatoms, alkyl groups having 1 to 10 carbon atoms are preferred, alkyl groups having 1 to 6 carbon atoms are more preferred, and alkyl groups having 1 to 3 carbon atoms are even more preferred.

[0044] R 1 From the viewpoint of ease of reaction when polymerizing resin (A), a hydrogen atom and an alkyl group having 1 to 10 carbon atoms are preferred, a hydrogen atom and an alkyl group having 1 to 3 carbon atoms are more preferred, and a hydrogen atom and a methyl group are even more preferred.

[0045] In formulas (1) and (2), the divalent group represented by X is preferred from the viewpoint of ease of reaction when polymerizing resin (A) to the group represented by formulas (4) and (5), and the group represented by formula (4) is more preferred.

[0046] Among the monomers (ma-1), the compound represented by the following formula (m1) is preferred from the viewpoint of ease of reaction when polymerizing resin (A), low-temperature curability as a resin composition, and properties of the cured resin film.

[0047] [ka]

[0048] (In formula (m1), R 6 R represents a hydrogen atom or a hydrocarbon group with 1 to 2 carbon atoms. 7 (This represents a hydrogen atom or a hydrocarbon group with 1 to 10 carbon atoms.)

[0049] In formula (m1), R 6 The hydrocarbon group having 1 to 2 carbon atoms represented by is preferably a methyl group or an ethyl group, and more preferably a methyl group, from the viewpoint of developability as a photosensitive resin composition. In formula (m1), R 7 The hydrocarbon group having 1 to 10 carbon atoms indicated by may have a ring structure. From the viewpoint of low-temperature curability as a photosensitive resin composition, R 7The hydrocarbon group represented is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably has 1 to 2 carbon atoms.

[0050] Among the compounds represented by formula (m1), R is particularly important in terms of developability as a photosensitive resin composition, hardness as a cured resin film, and solvent resistance. 6 is a methyl group, R 7 Compounds in which the alkyl group has 1 to 4 carbon atoms are preferred.

[0051] Examples of compounds represented by formula (1) include the following:

[0052] [ka]

[0053] [ka]

[0054] Examples of compounds represented by formula (2) include the following:

[0055] [ka]

[0056] Formulas (16) to (22), (31), (32), (33), and (36) are compounds containing CH3-CH2=CH-, but compounds in which CH3-CH2=CH- is replaced with H-CH2=CH- can also be listed.

[0057] [Constituent unit (a-2)] The constituent units (a-2) of the resin (A) according to this embodiment do not contain active methylene groups, active methine groups, or acid groups, but have groups that react to the action of light and / or heat. The constituent units (a-2) contained in the resin (A) may be one type or two or more types.

[0058] The photosensitive resin composition using the resin composition containing resin (A) according to this embodiment as a raw material contains a constituent unit (a-2) having a group that reacts to the action of light and / or heat. As a result, the photosensitive resin composition has good low-temperature curability. Low-temperature curability refers to the property of being able to form a resin cured film with sufficient hardness and solvent resistance.

[0059] The functional group of the constituent unit (a-2) in this embodiment is at least one selected from epoxy group, silyl group, blocked isocyanate group, mercapto group, isocyanate group, hydroxyl group, oxetanyl group, amino group, furyl group, maleimide group, oxazolidinyl group, oxazolyl group, formyl group, nitro group, and halogen group. Among these, functional groups that react with heat are preferred, groups that react under temperature conditions of 40°C to 180°C are more preferred, groups that react under temperature conditions of 50°C to 170°C are even more preferred, and groups that react under temperature conditions of 60°C to 160°C are most preferred. From the viewpoint of availability and reactivity when synthesizing resin (A), constituent units having epoxy group (a-2-1), silyl group (a-2-2), and blocked isocyanate group (a-2-3) are more preferred.

[0060] In this embodiment, the content of constituent unit (a-2) is preferably 2 to 80 mol%, more preferably 5 to 60 mol%, and even more preferably 10 to 40 mol% of the total constituent units of resin (A). When the content of constituent unit (a-2) is 2 mol% or more, the photosensitive resin composition using the resin composition containing resin (A) as a raw material will have good low-temperature curability and be able to form a resin cured film with sufficient hardness and solvent resistance. When the content of constituent unit (a-2) is 80 mol% or less, the content of constituent units (a-1) and (a-3) having functional groups in the total constituent units can be sufficiently ensured.

[0061] Methods for introducing the constituent unit (a-2) into the resin (A) according to this embodiment include introducing it by copolymerizing a monomer (ma-2) having an ethylenically unsaturated group and the aforementioned functional group (hereinafter also simply referred to as "monomer (ma-2)") with another ethylenically unsaturated group-containing monomer, or by polymerizing a precursor of resin (A) and then introducing the aforementioned functional group to obtain resin (A).

[0062] The monomer (ma-2) is not particularly limited as long as it is a compound that does not contain an active methylene group, an active methine group, or a carboxyl group, and has an ethylenically unsaturated group and the aforementioned functional group. Examples of ethylenically unsaturated groups include vinyl groups, allyl groups, and (meth)acryloyloxy groups. Among these, (meth)acryloyloxy groups are preferred from the viewpoint of ease of polymerization for obtaining resin (A).

[0063] From the viewpoint of having good low-temperature curability as a photosensitive resin composition using monomer (ma-2), or good hardness and solvent resistance as a cured resin film of the photosensitive resin composition, monomer (ma-2) is preferably an epoxy group-containing ethylenically unsaturated compound (ma-2-1), a silyl group-containing ethylenically unsaturated compound (ma-2-2), or a blocked isocyanate group-containing ethylenically unsaturated compound (ma-2-3).

[0064] Specific examples of epoxy group-containing ethylenically unsaturated compounds (MA-2-1) 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, epoxidized dicyclopentenyl (meth)acrylate, and epoxy group-containing (meth)acrylates such as epoxidized dicyclopentenyloxyethyl (meth)acrylate. Among these, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and (meth)acrylates having alicyclic epoxy groups are preferred, with glycidyl (meth)acrylate being more preferred, from the viewpoint of ease of availability and reactivity when synthesizing resin (A).

[0065] Specific examples of silyl group-containing ethylenically unsaturated compounds (MA-2-2) include [(meth)acryloyloxy]methyltriethoxysilane, [(meth)acryloyloxy]ethyltriethoxysilane, [(meth)acryloyloxy]propyltriethoxysilane, [(meth)acryloyloxy]octyltriethoxysilane, [(meth)acryloyloxy]propylmethyldiethoxysilane, [(meth)acryloyloxy]ethylmethyldiethoxysilane, and [(meth)acryloyloxy]nonylmethyldiethoxysilane. Among these, 3-(meth)acryloyloxypropylmethyldimethoxysilane and 3-(meth)acryloyloxypropylmethyldiethoxysilane are preferred, and 3-(meth)acryloyloxypropylmethyldiethoxysilane is more preferred, from the viewpoint of ease of availability and reactivity when synthesizing resin (A).

[0066] Specific examples of blocked isocyanate group-containing ethylenically unsaturated compounds (MA-2-3) include monomers having an ethylenically unsaturated bond and a blocked isocyanate group. Examples of such monomers include compounds in which the isocyanate group in an isocyanate compound having a vinyl group, a (meth)acryloyloxy group, etc. in the molecule is blocked with a blocking agent. The reaction between the isocyanate compound and the blocking agent can be carried out with or without the presence of a solvent. If a solvent is used, it is necessary to use a solvent that is inert to the isocyanate group. Organometallic salts such as tin, zinc, lead, or tertiary amines may be used as catalysts in the blocking reaction. The reaction can generally be carried out at -20 to 150°C, but it is preferable to carry it out at 0 to 100°C. An example of the above-mentioned isocyanate compound is the compound represented by the following formula (XX1).

[0067] [ka]

[0068] In the above formula (XX1), R 11 R represents a hydrogen atom or a methyl group. 12 -CO-, -COOR 13 -(Here, R 13 (where is an alkylene group with 1 to 6 carbon atoms) or -COO-R 14 O-CONH-R 15 -(Here, R 14 R is an alkylene group with 2 to 6 carbon atoms. 15 R represents an alkylene group having 2 to 12 carbon atoms or an arylene group having 6 to 12 carbon atoms, which may have substituents. 12 Preferably -COOR 13 -and here, R 13 This is preferably an alkylene group having 1 to 4 carbon atoms.

[0069] Examples of isocyanate compounds represented by the above formula (XX1) include 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, and methacryloyl isocyanate. Equimolar (1 mole:1 mole) reaction products of 2-hydroxyalkyl (meth)acrylate and diisocyanate compounds can also be used. The alkyl group of the above-mentioned 2-hydroxyalkyl (meth)acrylate is preferably an ethyl group or an n-propyl group, with the ethyl group being more preferred. Examples of the diisocyanate compounds mentioned above include hexamethylene diisocyanate, 2,4-(or 2,6-)tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 3,5,5-trimethyl-3-isocyanatomethylcyclohexyl isocyanate (IPDI), m-(or p-)xylene diisocyanate, 1,3-(or 1,4-)bis(isocyanatomethyl)cyclohexane, and lysine diisocyanate.

[0070] Among these isocyanate compounds, 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, and methacryloyl isocyanate are preferred, with 2-isocyanatoethyl (meth)acrylate and 2-isocyanatopropyl (meth)acrylate being more preferred.

[0071] Blocking agents for isocyanate compounds include, for example, lactam compounds such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam; alcohol compounds such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol, and cyclohexanol; phenol compounds such as phenol, cresol, xylenol, ethylphenol, o-isopropylphenol, p-tert-butylphenol, p-tert-octylphenol, nonylphenol, dinonylphenol, styrene-phenol, oxybenzoic acid esters, thymol, p-naphthol, p-nitrophenol, and p-chlorophenol; and dimethyl malonate, diethyl malonate, methyl acetoacetate. Examples include active methylene compounds such as ethyl acetoacetate and acetylacetone; mercaptan compounds such as butyl mercaptan, thiophenol, and tert-dodecyl mercaptan; amine compounds such as diphenylamine, phenylnaphthylamine, aniline, and carbazole; acid amide compounds such as acetanilide, acetanisidide, acetic acid amide, and benzamide; acid imide compounds such as succinimide and maleimide; imidazole compounds such as imidazole, 2-methylimidazole, and 2-ethylimidazole; urea compounds such as urea, thiourea, and ethyleneurea; carbamidate compounds such as phenyl N-phenylcarbamate and 2-oxazolidone; imine compounds such as ethyleneimine and polyethyleneimine; oxime compounds such as formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, and cyclohexanone oxime; and bisulfite compounds such as sodium bisulfite and potassium bisulfite. Among these, diethyl malonate, 3,5-dimethylpyrazole, and methyl ethyl ketoxime are preferred as blocking agents, from the viewpoint of ease of availability and reactivity when synthesizing resin (A).

[0072] Other specific examples of monomers (MA-2) include ethylenically unsaturated compounds containing epoxy groups (MA-2-1), ethylenically unsaturated compounds containing silyl groups (MA-2-2), and ethylenically unsaturated compounds containing blocked isocyanate groups (MA-2-3), as well as mercapto group-containing ethylenically unsaturated compounds such as 2-mercaptoethyl (meth)acrylate; Isocyanato group-containing ethylenically unsaturated compounds such as 2-(meth)acryloyloxyethyl isocyanate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, and 4-isocyanatocyclohexyl (meth)acrylate; Hydroxyl group-containing ethylenically unsaturated compounds such as 2-hydroxyethyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate; Oxetanyl group-containing ethylenically unsaturated compounds such as (3-ethyloxetan-3-yl)methyl (meth)acrylate; Amino group-containing ethylenically unsaturated compounds such as 3-(N,N-dimethylamino)propyl (meth)acrylate and 3-(N,N-diethylamino)propyl (meth)acrylate; furyl group-containing ethylenically unsaturated compounds such as tetrahydrofurfuryl (meth)acrylate; Maleimide group-containing ethylenically unsaturated compounds such as N-(3,4,5,6-tetrahydrophthalimide)ethyl (meth)acrylate, 2-maleimide ethyl (meth)acrylate, 2-benzylmaleimide ethyl (meth)acrylate, and 2-phenylmaleimide ethyl (meth)acrylate; Oxazolidinyl group-containing ethylenically unsaturated compounds such as 2-(2-oxo-3-oxazolidinyl)ethyl (meth)acrylate; Oxazolyl group-containing ethylenically unsaturated compounds such as 2-oxazolylethyl (meth)acrylate; Formyl group-containing ethylenically unsaturated compounds such as formylphenyl (meth)acrylate; nitro group-containing ethylenically unsaturated compounds such as nitropropyl (meth)acrylate; Examples include halogen-containing ethylenically unsaturated compounds such as 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 1H,1H,5H-octafluoropentyl (meth)acrylate, and 1H,1H,2H,2H-tridecafluorooctyl (meth)acrylate.

[0073] [Constituent Unit (a-3)] The constituent unit (a-3) of the resin (A) according to this embodiment is a constituent unit other than constituent units (a-1) and (a-2), and is a constituent unit having an acid group. The constituent unit (a-3) contained in the resin (A) may be only one type or may be two or more types.

[0074] Examples of acidic groups that the constituent unit (a-3) in this embodiment may have include carboxyl groups, phosphol groups (-OP(=O)(OH)2), and sulfol groups (-S(=O)2OH). Among these, carboxyl groups are preferred from the viewpoint of developability as a photosensitive resin composition.

[0075] The content of constituent unit (a-3) is preferably 2 to 60 mol%, more preferably 4 to 40 mol%, and even more preferably 6 to 30 mol% of the total constituent units of resin (A). When the content of constituent unit (a-3) is 2 mol% or more, the effects of including the carboxyl group are sufficiently obtained. When the content of constituent unit (a-3) is 60 mol% or less, the content of constituent units (a-1) and (a-2) can be sufficiently ensured.

[0076] Methods for introducing constituent units (a-3) into resin (A) include copolymerizing a monomer (ma-3) having an ethylenically unsaturated group and an acidic group (hereinafter also simply referred to as "monomer (ma-3)") with another ethylenically unsaturated group-containing monomer, and introducing an acidic group after polymerization of a precursor of resin (A) to obtain resin (A). In the latter method, for example, a resin (A) with an acidic group can be obtained by polymerizing a precursor of resin (A) having a hydroxyl group and adding a polybasic acid anhydride to the hydroxyl group of the precursor.

[0077] Examples of monomers (MA-3) include unsaturated carboxylic acids or their anhydrides, unsaturated sulfonic acids, and unsaturated phosphonic acids. Specific examples of preferred monomers include unsaturated carboxylic acids or their anhydrides such as (meth)acrylic acid, α-bromo(meth)acrylic acid, β-furyl(meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, α-cyanocinnamic acid, maleic acid, maleic anhydride, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, and citraconic anhydride; unsaturated sulfonic acids such as vinyl sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, and p-styrenesulfonic acid; unsaturated phosphonic acids such as 2-(meth)acryloyloxyethyl acid phosphate and vinylphosphonic acid; and 2-(meth)acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, and 2-(meth)acryloyloxyethyl hexahydrophthalic acid. These monomers may be used individually or in combination of two or more. Among these, (meth)acrylic acid and unsaturated carboxylic acids are preferred, with (meth)acrylic acid being more preferred, from the viewpoint of availability and reactivity when synthesizing resin (A).

[0078] [Other constituent units (a-4)] Resin (A) may contain other constituent units (a-4) in addition to constituent units (a-1), (a-2), and (a-3) as needed. The constituent units (a-4) contained in resin (A) may be one type or two or more types.

[0079] When resin (A) contains constituent unit (a-4), its content is preferably 1 to 80 mol%, more preferably 4 to 70 mol%, and even more preferably 10 to 30 mol% of the total constituent units of resin (A). If the content of constituent unit (a-4) is 1 mol% or more, the effects of including constituent unit (a-4) can be fully obtained. Furthermore, if the content of constituent unit (a-4) is 80 mol% or less, the content of constituent units (a-1), (a-2), and (a-3) can be sufficiently ensured.

[0080] One method for introducing the constituent unit (a-4) into resin (A) is to copolymerize a monomer (ma-4) (hereinafter also simply referred to as "monomer (ma-4)") which does not have an active methylene group, an active methine group, the aforementioned functional group, or an acid group, but has an ethylenically unsaturated group, with another monomer containing an ethylenically unsaturated group.

[0081] Examples of monomers (MA-4) include dienes such as butadiene, (meth)acrylic acid esters, styrenes, unsaturated dicarboxylic acid diesters, and other vinyl compounds.

[0082] 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; Alicyclic alkyl (meth)acrylates such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylcyclohexyl (meth)acrylate, norbornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, and adamantyl (meth)acrylate; Aromatic (meth)acrylates such as benzyl (meth)acrylate, triphenylmethyl (meth)acrylate, cumyl (meth)acrylate, naphthalene (meth)acrylate, and anthracene (meth)acrylate; Examples include rosin (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and 2-(2-vinyloxyethoxy)ethyl (meth)acrylate.

[0083] Specific examples of styrenes include styrene and α-, o-, m-, and p-alkyl derivatives of styrene. Specific examples of unsaturated dicarboxylic acid diesters include diethyl citraconate, diethyl maleate, diethyl fumarate, and diethyl itaconate.

[0084] Other specific examples of vinyl compounds include norbornene (bicyclo[2.2.1]hepto-2-ene), 5-methylbicyclo[2.2.1]hepto-2-ene, 5-ethylbicyclo[2.2.1]hepto-2-ene, tetracyclo[4.4.0.12,5.17,10]dodeca-3-ene, 8-methyltetracyclo[4.4.0.12,5.17,10]dodeca-3-ene, 8-ethyltetracyclo[4.4.0.12,5.17,10]dodeca-3-ene, dicyclopentadiene, tricyclo[5.2.1.02,6]deca-8-ene, tricyclo[5.2.1.02,6]deca-3-ene, tricyclo[4.4.0.12,5]undeca-3-ene, tricyclo[6.2.1.01,8]undeca-9- Ene, tricyclo[6.2.1.01,8]undeca-4-ene, tetracyclo[4.4.0.12,5.17,10.01,6]dodeca-3-ene, 8-methyltetracyclo[4.4.0.12,5.17,10.01,6]dodeca-3-ene, 8-ethylidenetetracyclo[4.4.0.12,5.17,12]dodeca-3-ene, 8-ethylidene Examples include lacycyclo[4.4.0.12,5.17,10.01,6]dodeca-3-ene, pentacyclo[6.5.1.13,6.02,7.09,13]pentadeca-4-ene, pentacyclo[7.4.0.12,5.19,12.08,13]pentadeca-3-ene, (meth)acrylate anilide, vinylpyridine, vinyl acetate, vinyltoluene, etc.

[0085] Among these, (meth)acrylic acid esters and other vinyl compounds are preferred from the viewpoint of ease of availability and reactivity when synthesizing resin (A), with methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, styrene, vinyltoluene and norbornene being preferred, and methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and dicyclopentanyl (meth)acrylate being more preferred.

[0086] "Weight average molecular weight (Mw)" In this embodiment, the weight-average molecular weight (Mw) of resin (A) is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, and most preferably 3,000 to 12,000, in terms of polystyrene equivalent. When the weight-average molecular weight (Mw) of resin (A) is 1,000 or more, a photosensitive resin composition can be obtained in which defects such as chipping of the cured resin film after development are less likely to occur when a resin composition containing resin (A) is used as a raw material for a photosensitive resin composition. When the weight-average molecular weight of resin (A) is 50,000 or less, the photosensitive resin composition containing resin (A) has a sufficiently short development time and is highly practical.

[0087] The weight-average molecular weight (Mw) of resin (A) in this embodiment is measured using gel permeation chromatography (GPC) under the following conditions and calculated in polystyrene equivalent. Column: SHODEX® LF-804 + LF-804 (manufactured by Showa Denko Corporation) Column temperature: 40℃ Sample: A tetrahydrofuran solution containing 0.2% by mass of resin (A). Developing solvent: tetrahydrofuran Detector: Differential refractometer (Product name: SHODEX® RI-71S, manufactured by Showa Denko Corporation) Flow rate: 1mL / min

[0088] The molecular weight distribution (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) of resin (A) is preferably 1.3 to 5.0, more preferably 1.5 to 4.0, and most preferably 1.5 to 3.0. When the molecular weight distribution (Mw / Mn) of resin (A) is 1.3 or higher, the target numerical ranges for weight-average molecular weight (Mw), acid value, etc., and the reaction conditions when producing resin (A) can be set within a certain range, enabling efficient production. When the molecular weight distribution (Mw / Mn) of resin (A) is 3.0 or lower, a photosensitive resin composition can be obtained in which there is no variation in performance such as developability when a resin composition containing resin (A) is used as a raw material for a photosensitive resin composition. The molecular weight distribution (Mw / Mn) is calculated using the chromatogram obtained from the GPC measurement described above.

[0089] "Acid value" The acid value of resin (A) is not particularly limited, but is preferably 10KOHmg / g to 300KOHmg / g, more preferably 20KOHmg / g to 200KOHmg / g, and most preferably 25KOHmg / g to 150KOHmg / g. When the acid value of resin (A) is 10KOHmg / g or higher, a photosensitive resin composition with better developability can be obtained when a resin composition containing resin (A) is used as a raw material for a photosensitive resin composition. When the acid value of resin (A) is 300KOHmg / 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) does not dissolve in the alkaline developer, and a photosensitive resin composition with good developability can be obtained.

[0090] The acid value of resin (A) was measured using a mixed indicator of bromothymol blue and phenol red in accordance with JIS K6901 5.3. The acid value of resin (A) refers to the number of milligrams of potassium hydroxide required to neutralize the acidic components contained in 1 g of resin (A).

[0091] "Functional group equivalent" In this embodiment, the functional group equivalent of resin (A) refers to the equivalent amount of the aforementioned functional group contained in the constituent unit (a-2) contained in 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. When the functional group equivalent of resin (A) is 200 g / mol or more, the photosensitive resin composition containing resin (A) can form a resin cured film with superior hardness. Furthermore, when the functional group equivalent of resin (A) is 200 g / mol or more, a photosensitive resin composition with better developability can be obtained when the resin composition containing resin (A) is used as a raw material for a photosensitive resin composition. Furthermore, when the functional group equivalent of resin (A) is 5000 g / mol or less, the photosensitive resin composition containing resin (A) can form a resin cured film with superior hardness.

[0092] 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 contained in the constituent units (a-2) per molecule. The functional group equivalent of resin (A) is a calculated value based on the amount of polymerizable unsaturated compound (raw material monomer) used as a raw material when synthesizing resin (A). If a single molecule of resin (A) contains different types of functional groups, all functional groups are counted as part of the functional group count, regardless of the type of functional group.

[0093] "Activated methylene group and activated methine group equivalents" The equivalent amounts of active methylene groups and active methine groups in resin (A) are not particularly limited, but are preferably 200 g / mol to 5000 g / mol, more preferably 300 g / mol to 4000 g / mol, and most preferably 300 g / mol to 3000 g / mol. When the equivalent amounts of active methylene groups and active methine groups in resin (A) are 200 g / mol or more, the photosensitive resin composition containing resin (A) can form a cured resin film with superior hardness. Furthermore, when the equivalent amounts of active methylene groups and active methine groups in resin (A) are 200 g / mol or more, a photosensitive resin composition with better developability can be obtained when the resin composition containing resin (A) is used as a raw material for a photosensitive resin composition. Furthermore, when the equivalent amount of active methylene groups in resin (A) is 5000 g / mol or less, the photosensitive resin composition containing resin (A) can form a cured resin film with superior hardness.

[0094] The equivalent amounts of active methylene groups and active methine groups in resin (A) are calculated by dividing the molecular weight of resin (A) by the average number of active methylene groups and active methine groups per molecule. The equivalent amounts of active methylene groups and active methine groups in resin (A) are calculated values ​​based on the amount of polymerizable unsaturated compounds (raw material monomers) used as raw materials when synthesizing resin (A). If a single molecule of resin (A) contains different types of active methylene groups and active methine groups, all active methylene groups and active methine groups are counted as the number of active methylene groups and active methine groups, regardless of the type of active methylene group and active methine group.

[0095] "Hydroxyl equivalent" When resin (A) contains hydroxyl groups, the hydroxyl group equivalent is not particularly limited, but is preferably 200 g / mol to 5000 g / mol, more preferably 300 g / mol to 4000 g / mol, and most preferably 300 g / mol to 3000 g / mol. When the hydroxyl group equivalent of resin (A) is 200 g / mol or more, the photosensitive resin composition containing resin (A) can form a resin cured film with superior hardness. Furthermore, when the hydroxyl group equivalent of resin (A) is 5000 g / mol or less, the photosensitive resin composition containing resin (A) can form a resin cured film with superior hardness.

[0096] The hydroxyl group equivalent of resin (A) is calculated by dividing the molecular weight of resin (A) by the average number of hydroxyl groups per molecule. The hydroxyl group equivalent of resin (A) is a calculated value based on the amount of polymerizable unsaturated compound (raw material monomer) used as a raw material when synthesizing resin (A). If a single molecule of resin (A) contains different types of hydroxyl groups, all hydroxyl groups are counted as part of the total number of hydroxyl groups, regardless of their type.

[0097] <Method for manufacturing resin (A)> The resin (A) contained in the resin composition of this embodiment can be produced, for example, by the following production method. That is, raw material monomers consisting of monomers (ma-1) to (ma-3) and other monomers (ma-4) as needed are copolymerized using a polymerization initiator according to a radical polymerization method known in the art. This yields resin (A).

[0098] Specifically, a method can be used in which raw material monomers are dissolved in a polymerization solvent to prepare a raw material monomer solution, a polymerization initiator is added to the raw material monomer solution, and the copolymerization reaction is carried out with stirring at, for example, 50°C to 130°C for 1 to 20 hours.

[0099] (Polymerizing solvent) The polymerization solvent used in producing resin (A) is not particularly limited, as long as it is inert to the copolymerization reaction of the raw material monomers. The polymerization solvent used in producing resin (A) may be the same as the solvent contained in solvent (D) of the resin composition described later, or it may be partially or entirely different from the solvent contained in solvent (D). When the polymerization solvent used in producing resin (A) is partially or entirely the same as the solvent contained in solvent (D) of the resin composition, it is preferable that the polymerization solvent be used as part of solvent (D) without separating or removing it from the reaction solution after the copolymerization reaction is complete.

[0100] The solvent used for polymerization is not particularly limited, as long as it dissolves the monomer and the copolymer to be produced and does not inhibit the polymerization reaction. When the copolymer to be produced is a (meth)acrylic acid polymer, glycol ether solvents are preferred from the viewpoint of solubility. Specifically, examples include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monophenyl ether, propylene glycol monomethyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether. These solvents may be used individually or in combination of two or more. Among these, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferred from the viewpoint of availability and reactivity.

[0101] The amount of polymerization solvent used in the production of resin (A) is not particularly limited, but is preferably 30 to 1000 parts by mass, and more preferably 50 to 800 parts by mass, per 100 parts by mass of raw material monomer. When the amount of polymerization solvent used is 30 parts by mass or more, the copolymerization reaction of the raw material monomer can be carried out stably, and discoloration and gelation of resin (A) can be prevented. When the amount of polymerization solvent used is 1000 parts by mass or less, the decrease in molecular weight of resin (A) due to chain transfer can be suppressed, and the viscosity of the reaction solution can be controlled within an appropriate range.

[0102] (Polymerization initiator) Polymerization initiators that can be used in copolymerization reactions of raw material monomers are not particularly limited, but examples include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(isobutyrate)dimethyl, benzoyl peroxide, and t-butylperoxy-2-ethylhexanoate. These polymerization initiators may be used individually or in combination of two or more. The amount of polymerization initiator used is not particularly limited, but is preferably 0.1 to 20 parts by mass, and more preferably 0.5 to 16 parts by mass, per 100 parts by mass of raw material monomer.

[0103] The content of resin (A) in the photosensitive resin composition of this embodiment is preferably 10 to 85 parts by mass, more preferably 15 to 75 parts by mass, and most preferably 25 to 65 parts by mass, when the total amount of components excluding solvent (D) contained in the photosensitive resin composition is 100 parts by mass. When the content of reactive diluent (A) is within the above range, the viscosity and low-temperature curability of the photosensitive resin composition become more appropriate.

[0104] [Reactive Diluent (B)] The reactive diluent (B) included in the photosensitive resin composition of this embodiment may be any low molecular weight compound having an ethylenically unsaturated group such as a vinyl group, an allyl group, or a (meth)acryloyloxy group, and is not particularly limited. Specific examples of the reactive diluent (B) include aromatic vinyl monomers; polycarboxylic acid monomers such as vinyl acetate and vinyl adipate; monofunctional (meth)acrylates; polyfunctional (meth)acrylates; triallyl cyanurate, etc.

[0105] Specific examples of aromatic vinyl monomers include styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, divinylbenzene, diallyl phthalate, and diallylbenzenephosphonate.

[0106] Specific examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, β-hydroxyethyl (meth)acrylate, and hydroxypropyl (meth)acrylate.

[0107] 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.

[0108] Among these, polyfunctional (meth)acrylates are preferred as the reactive diluent (B) in order to improve curability (reactivity), and in particular, dipentaerythritol penta(meth)acrylate and / or dipentaerythritol hexa(meth)acrylate are preferred. These reactive diluents (B) may be used individually or in combination of two or more.

[0109] The content of the reactive diluent (B) in the photosensitive resin composition of this embodiment is preferably 10 to 85 parts by mass, more preferably 15 to 75 parts by mass, and most preferably 25 to 65 parts by mass, when the total amount of components excluding the solvent (D) contained in the photosensitive resin composition is 100 parts by mass. When the content of the reactive diluent (B) is within the above range, the viscosity and photocurability of the photosensitive resin composition become more appropriate.

[0110] [Photopolymerization initiator (C)] The photopolymerization initiator (C) included in the photosensitive resin composition of this embodiment is not particularly limited as long as it is a compound that generates radicals upon light irradiation. Examples of photopolymerization initiators (C) include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, and benzoin ethyl ether; acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, and 4-(1-t-butyldioxy-1-methylethyl)acetophenone; alkylphenones such as 1-hydroxycyclohexylphenyl ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone; and ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal. Examples include benzophenones such as benzophenone, 4-(1-t-butyldioxy-1-methylethyl)benzophenone, and 3,3',4,4'-tetrakis(t-butyldioxycarbonyl)benzophenone; oxime esters such as 1,2-octanedione, 1-[4-(phenylthio)-2-(o-benzoyl oxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl], and 1-(o-acetyl oxime); 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-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.

[0111] The content of the photopolymerization initiator (C) in the photosensitive resin composition of this 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) contained 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 cured resin film.

[0112] [Solvent (D)] The solvent (D) contained in the resin composition of this embodiment is not particularly limited, as long as it is inert to the resin (A) and capable of dissolving the resin (A). The solvent (D) may or may not contain the polymerization solvent used in the production of resin (A). If solvent (D) contains the polymerization solvent used to produce resin (A), the addition reaction to produce resin (A) can be carried out without removing the polymerization solvent from the reaction solution after the copolymerization reaction for resin (A) is completed, and the polymerization solvent can be used as is as part or all of solvent (D) in the resin composition without separating or removing it from the reaction solution after the addition reaction is completed.

[0113] The case where the polymerization solvent used to produce resin (A) is not contained in solvent (D) is when the resin (A) used as a raw material for the resin composition is separated and removed from the reaction solution that produced resin (A). In this case, regardless of the type and amount of polymerization solvent used to produce resin (A), the type and content of solvent (D) can be appropriately selected according to the type of resin (A) and the intended use of the resin composition. That is, if resin (A) is used that has been separated and removed from the reaction solution that produced resin (A), then solvent (D) may be of the same type as the polymerization solvent used to produce resin (A), or a different type may be used.

[0114] The solvent (D) is not particularly limited, but when the resin (A) is a (meth)acrylic acid polymer, glycol ether solvents are preferred from the viewpoint of solubility. Specifically, examples include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, polyethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, ethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monophenyl ether, propylene glycol monomethyl ether acetate, ethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, and dipropylene glycol dimethyl ether. These solvents may be used individually or in combination of two or more. Among these, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferred from the viewpoint of availability and reactivity.

[0115] The solvent (D) may include other solvents capable of dissolving the resin (A).

[0116] Examples include monoalcohols and (poly)alkylene glycol monoalkyl ethers. 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. Other specific examples of solvents include tertiary alcohols such as tert-butyl alcohol and diacetone alcohol; (poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, and 3-methoxypropionate. Examples include esters such as methyl acetate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl-3-methoxybutyl acetate, 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, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate; aromatic hydrocarbons such as toluene and xylene; and carboxylic acid amides such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide.

[0117] The solvent (D) content in the resin composition of this 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 amount of components excluding solvent (D) in the resin composition is 100 parts by mass. When the solvent (D) content is within the above range, the viscosity of the resin composition can be adjusted to an appropriate range.

[0118] [Other additives] The photosensitive resin composition of this embodiment may optionally contain one or more known additives such as leveling agents, thermal polymerization inhibitors, and sensitizers. The amount of these additives is not particularly limited, as long as it does not hinder the effects of the present invention.

[0119] Furthermore, the photosensitive resin composition of this embodiment may contain amines, hydrazides, aldehydes, and metal salts as crosslinking agents to enhance curability. Examples of crosslinking agents include MXDA and 1,3-BAC, manufactured by Mitsubishi Gas Chemical Company, Inc.; ADH and APA-280, manufactured by Otsuka Chemical Co., Ltd.; SEQUAREZ 755, manufactured by OMNOVA Solutions Inc.; and ZIRCOZOL ZC-2 and ZC-7, manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd.

[0120] Furthermore, the photosensitive resin composition of this embodiment may contain an acid generator and a base generator to enhance curability. In particular, from the viewpoint of latent properties, it is preferable to use a photoacid generator, a photobase generator, a thermal acid generator, or a thermal base generator, and from the viewpoint of storage stability, a photoacid generator and a photobase generator are even more preferable. Examples of photoacid generators include sulfonium salt compounds such as CPI-200K, CPI-210S, CPI-310B, and CPI-410S, manufactured by Sunapro 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 Pure Chemical Industries, Ltd.

[0121] [Viscosity of photosensitive resin composition] The viscosity of the photosensitive resin composition of this embodiment can be appropriately adjusted according to the thickness of the resin cured film made from the cured product of the photosensitive resin composition. For example, when the thickness of the resin cured film is adjusted to 1 to 4 μm, the viscosity of the photosensitive resin composition is preferably 1 mP·s to 25 mP·s, more preferably 2 mP·s to 20 mP·s, and most preferably 3 mP·s to 15 mP·s.

[0122] <Photosensitive coloring composition> The photosensitive colored composition of this embodiment comprises the photosensitive resin composition of this embodiment and a colorant (E). [Coloring agent (E)] As the coloring agent (E), known dyes and / or pigments can be used. When a dye is used as the coloring agent (E), a coloring pattern with higher brightness can be obtained compared to when a pigment is used, and a photosensitive coloring composition that exhibits good alkali developability can be obtained.

[0123] As dyes, it is preferable to use acid dyes having acidic groups such as carboxyl groups, salts of acid dyes with nitrogen compounds, or sulfonamide forms of acid dyes, from the viewpoint of solubility in solvent (D) and alkaline developer, interaction with other components in the photosensitive resin composition, and heat resistance. Examples of such dyes include acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; solvent blue 38, 44 (VALIFAST BLUE 2620); acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red1, 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, 11 4,129,133,134,138,143,145,150,151,158,176,183,198,211,215,216,217,249,252,257,260,266,274;acid violet 6B, 7, 9, 17, 19;acid Examples include yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; food yellow 3; solvent yellow 82 and their derivatives. Among these, azo, xanthene, anthraquinone, or phthalocyanine acid dyes are preferred. Depending on the desired pixel color, one of these dyes may be used alone, or two or more may be used in combination.

[0124] Examples of pigments include yellow pigments such as CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; and CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 16 Examples include red pigments such as 6, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, and 265; blue pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, and 60; violet pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, and 38; green pigments such as CI Pigment Green 7, 36, and 58; brown pigments such as CI Pigment Brown 23 and 25; and black pigments such as CI Pigment Black 1 and 7, carbon black, titanium black, and iron oxide. These pigments may be used individually or in combination of two or more, depending on the desired pixel color.

[0125] When a pigment is used as the colorant (E), a known dispersant may be added to the photosensitive coloring composition to improve the dispersibility of the colorant (E). It is preferable to use a polymer dispersant that exhibits excellent dispersion stability over time. Examples of polymer 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. Such polymer dispersants may be commercially available under trade names such as EFKA (manufactured by EFKA Chemicals BV), Disperbyk (manufactured by Bic Chemie), Disparon (manufactured by Kusumoto Chemicals Co., Ltd.), and SOLSPERSE (manufactured by Zeneca). The amount of dispersant added should be appropriately determined according to the type and amount of pigment used as the colorant (E).

[0126] The content of the colorant (E) in the photosensitive colored composition of this embodiment is preferably 4 to 85 parts by mass, more preferably 9 to 70 parts by mass, and most preferably 15 to 49 parts by mass, when the total amount of components excluding the solvent (D) contained in the photosensitive colored composition is 100 parts by mass. When the content of the colorant (E) is 4 parts by mass or more, the effect of containing the colorant (E) becomes significant, resulting in a photosensitive colored composition suitable as a material for the coloring pattern of a color filter. When the content of the colorant (E) is 85 parts by mass or less, the colorant (E) in the photosensitive colored composition does not interfere with the curability of the photosensitive colored composition, and good low-temperature curability is achieved.

[0127] [Other additives] The photosensitive coloring composition of this embodiment may optionally contain one or more known additives such as leveling agents, thermal polymerization inhibitors, and sensitizers. The amount of these additives is not particularly limited, as long as it does not hinder the effects of the present invention.

[0128] Furthermore, the photosensitive coloring composition of this embodiment may contain amines, hydrazides, aldehydes, or metal salts as crosslinking agents to enhance curability. Examples of crosslinking agents include MXDA and 1,3-BAC from Mitsubishi Gas Chemical Company, Inc., ADH and APA-280 from Otsuka Chemical Co., Ltd., SEQUAREZ 755 from OMNOVA Solutions, and ZIRCOZOL ZC-2 and 7 from Daiichi Kigenso Kagaku Kogyo Co., Ltd.

[0129] Furthermore, the photosensitive coloring composition of this embodiment may contain an acid generator and a base generator to enhance curability. In particular, from the viewpoint of latent properties, it is preferable to use a photoacid generator, a photobase generator, a thermal acid generator, or a thermal base generator, and from the viewpoint of storage stability, a photoacid generator and a photobase generator are even more preferable. Examples of photoacid generators include sulfonium salt compounds such as CPI-200K, CPI-210S, CPI-310B, and CPI-410S, manufactured by Sunapro 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 Pure Chemical Industries, Ltd.

[0130] [Viscosity of photosensitive colored compositions] The viscosity of the photosensitive coloring composition of this embodiment can be appropriately adjusted according to the thickness of the resin cured film made from 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.

[0131] <Method for producing a photosensitive resin composition> The photosensitive resin composition of this embodiment can be produced 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 apparatus.

[0132] The photosensitive resin composition of this embodiment exhibits good low-temperature curing properties and can form a resin-cured film with sufficient hardness and solvent resistance. Furthermore, since the photosensitive resin composition of this embodiment has excellent alkali developability, fine patterns can be formed by developing it with an alkaline aqueous solution. Therefore, the photosensitive resin composition of this embodiment is suitably used as a resist.

[0133] <Method for producing a photosensitive colored composition> The photosensitive colored composition of this embodiment can be produced by mixing a resin (A), a reactive diluent (B), a photopolymerization initiator (C), a solvent (D), a colorant (E), and additives used as needed, using a known mixing apparatus.

[0134] The photosensitive resin composition of this embodiment exhibits good low-temperature curing properties and can form a resin-cured film with sufficient hardness and solvent resistance. Furthermore, since the photosensitive resin composition of this embodiment has excellent alkali developability, fine patterns can be formed by developing it with an alkaline aqueous solution. Therefore, the photosensitive resin composition of this embodiment is suitably used as a resist. Furthermore, the photosensitive colored composition of this embodiment can be suitably used as a material for colored patterns such as pixels and black matrices of color filters.

[0135] <Cured resin film> Next, the resin cured film of this embodiment will be described in detail. The resin-cured film of this embodiment consists of a cured product of the photosensitive resin composition or the photosensitive colored composition of this embodiment. The resin cured film of this embodiment can be formed, for example, by a method comprising: a coating step of applying the photosensitive resin composition of this embodiment onto a substrate to form a coating film; a pre-bake step of drying the coating film formed in the coating step; an exposure step of irradiating the dried coating film with light to photo-cure it; and a post-bake step of thermally curing the photo-cured coating film.

[0136] When forming a resin-cured film having a predetermined pattern by photolithography using the photosensitive resin composition of this embodiment, for example, the following method can be used. That is, the above-described coating step and pre-baking step are performed. Then, in the exposure step, light is irradiated onto the dried coating film through a photomask having a predetermined pattern, and the exposed portion is photocured. After the exposure step, post-exposure heat treatment is performed as necessary. Then, a developing step is performed in which the unexposed portion of the coating film is dissolved and developed using a developer, and a post-baking step is performed in which the photocured coating film is heat-cured.

[0137] [Coating process] In the coating process, the photosensitive resin composition or the photosensitive colored composition of this embodiment is applied to the substrate to form a coating film. In this embodiment, known substrates can be used as the substrate to which the photosensitive resin composition or photosensitive colored composition is applied, and can be appropriately determined according to the application of the cured resin film. The method for applying the photosensitive resin composition or photosensitive colored composition is not particularly limited, and for example, screen printing, roll coating, curtain coating, spray coating, spin coating, slit coating, etc., can be used.

[0138] [Pre-baking process] In the pre-bake (pre-heat treatment) step, the coating film formed in the coating step is dried to reduce the amount of solvent remaining in the coating film. In the pre-bake step, the substrate on which the coating film has been 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. In the pre-bake step, one example of a method for heating the substrate on which the coating film has been formed is to use a hot plate.

[0139] [Synthesis process] In the exposure process, light is irradiated onto the surface of the coating film dried in the pre-baking process to photo-cure the coating film. The light source used for light irradiation is not particularly limited, but for example, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, xenon lamps, metal halide lamps, etc., can be used. The amount of exposure in the exposure 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 exposure process, light is irradiated onto the surface of the coating film dried in the pre-baking process through a photomask having a predetermined pattern to photo-cure the exposed portion.

[0140] [Post-synthesis heating process] When forming a resin-cured film with a predetermined pattern, a post-exposure baking step is performed as needed after the exposure step. This step makes the dissolution contrast between the exposed and unexposed portions of the coated film more pronounced. Unlike the post-bake step described later, the post-exposure baking step does not completely cure the coated film. The post-exposure baking step is performed to leave only the exposed portions of the coated film on the substrate and to more reliably remove the unexposed portions of the coated film by performing the development step. Therefore, it is not an essential step in the resin-cured film formation method of this embodiment.

[0141] When performing a post-exposure heating step, it is preferable to heat the substrate after the exposure step to, for example, 40°C to 70°C, and more preferably to 50°C to 60°C. When the heating temperature is 40°C or higher, the effect of improving the dissolution contrast between the exposed and unexposed parts of the coating film can be sufficiently obtained by performing the post-exposure heating step. When the heating temperature is 70°C or lower, the acid generated in the exposed parts does not diffuse to the unexposed parts, and a good dissolution contrast can be obtained. The heating time in the post-exposure heating step is preferably 20 seconds to 600 seconds. When the heating time is 20 seconds or more, the temperature history of the entire coating film can be made uniform. When the heating time is 600 seconds or less, the acid generated in the exposed parts does not diffuse to the unexposed parts, and a good dissolution contrast can be obtained. As a method of heating the substrate after the exposure step in the post-exposure heating step, for example, a hot plate, oven, or furnace can be used.

[0142] [Development process] When forming a resin-cured film having a predetermined pattern, after the exposure step, a post-exposure heating step is performed as necessary, followed by a developing step to develop the unexposed portion of the coated film. As the developer used in the developing step, any alkaline aqueous solution conventionally used for developing photosensitive resin compositions or photosensitive colored compositions can be used.

[0143] The alkaline aqueous solution is not particularly limited, but examples include aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, etc.; aqueous solutions of amine compounds such as ethylamine, diethylamine, and dimethylethanolamine; aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide; and aqueous solutions of p-phenylenediamine compounds such as 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-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 compound.

[0144] The alkaline aqueous solution may contain one or more additives, such as defoamers and surfactants, as needed. 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, and the thickness of the coating film. In the development process, it is preferable to dissolve the unexposed portions of the coating film using the above-mentioned alkaline aqueous solution, develop the film, and then wash and dry it.

[0145] [Post-bake process] In this embodiment, after the development process, a post-bake process is performed in which the photocured coating film is heat-cured 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.

[0146] The heating temperature in the post-bake process can be, for example, 50°C to 210°C. If the heating temperature is 210°C or lower, materials with low heat resistance can be used as the material for the color filter. For example, when a resin substrate is used as the base material for forming the resin cured film to form the color pattern of the 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, color patterns containing colorants (E) with poor heat resistance, which were conventionally difficult to use as material for color patterns, can be formed while suppressing the deterioration of the colorants (E). Also, if the heating temperature is 150°C or lower, color patterns can be formed on substrates with poor heat resistance, which were conventionally difficult to use as substrates for color filters. Furthermore, if the heating temperature is 150°C or lower, the amount of energy required to cure the coating film is reduced, which is preferable.

[0147] When the heating temperature in the post-bake process is 50°C or higher, the resin (A) and the reactive diluent (B) are sufficiently crosslinked, resulting in a resin-cured film with sufficient hardness and solvent resistance. Furthermore, when the heating temperature is 50°C or higher, the heating time in the post-bake process is shortened, allowing for efficient formation of the resin-cured film. The heating temperature in the post-bake process is more preferably 60°C or higher, and even more preferably 70°C or higher.

[0148] The heating time in the post-bake process can be appropriately selected depending on the heating temperature, the thickness of the coated film, the composition of the photosensitive resin composition, etc. For example, it can be 10 minutes to 4 hours, preferably 20 minutes to 2 hours.

[0149] The resin-cured film of this embodiment consists of a cured product of the photosensitive resin composition or the photosensitive colored composition of this embodiment. Therefore, it has sufficient hardness and solvent resistance. The resin cured film of this embodiment can be suitably used as a material for various insulating films, such as protective films provided on the upper part of color filters, insulating films provided between electrodes of touch panels, and interlayer insulating films of thin-film transistors (TFTs).

[0150] <Color Filter> Next, the color filter of this embodiment will be described in detail. Figure 1 is a schematic cross-sectional view showing an example of a color filter according to this embodiment. The color filter shown in Figure 1 comprises a substrate 1, RGB pixels 2 formed on one surface 1a of the substrate 1, black matrices 3 formed at the boundaries of each pixel 2, and a protective film 4 formed on the pixels 2 and the black matrices 3.

[0151] The substrate 1 used in the color filter shown in Figure 1 is not particularly limited, and can be appropriately used depending on the application, and may consist of glass substrates, silicon substrates, polycarbonate substrates, polyester substrates, polyamide substrates, polyamide-imide substrates, polyimide substrates, aluminum substrates, printed circuit boards, array substrates, etc.

[0152] In the color filter shown in Figure 1, the pixels 2 and black matrix 3 are color patterns made of a cured product of the photosensitive colored composition of this embodiment, which comprises a resin composition containing resin (A) and solvent (D), a reactive diluent (B), a photopolymerization initiator (C), a colorant (E), and additives as needed. The protective film 4 can be made of a known material. The protective film 4 may be a cured resin film made of a cured product of the photosensitive coloring composition of this embodiment, which contains a resin composition containing a resin (A) and a solvent (D), a reactive diluent (B), a photopolymerization initiator (C), and additives as needed.

[0153] In the color filter of this embodiment shown in Figure 1, the components other than the materials of the pixels 2 and the black matrix 3 can be those of known origin. Furthermore, the color filter shown in Figure 1 is just one example of the color filter of the present invention, and the present invention is not limited to the example shown in Figure 1.

[0154] Next, the manufacturing method for the color filter of this embodiment will be described. First, each RGB pixel 2 and the black matrix 3 are sequentially formed on one surface 1a of the substrate 1 shown in Figure 1. The pixels 2 and the black matrix 3 can be manufactured using the resin curing film manufacturing method (photolithography method) of this embodiment described above. 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 formation method. For example, the protective film 4 can be manufactured using the resin curing film manufacturing method of this embodiment described above. Through the above steps, the color filter of this embodiment shown in Figure 1 is obtained.

[0155] The color filter of this embodiment has a colored pattern (pixels 2 and black matrix 3) made of a cured product of the photosensitive colored composition described above. Therefore, the colored pattern in the color filter of this embodiment has sufficient hardness and solvent resistance.

[0156] <Image display element> The image display element of this embodiment is equipped with a color filter of this embodiment having sufficient hardness and solvent resistance. Examples of the image display element of this embodiment include liquid crystal display elements, organic EL display elements, solid-state image sensors, etc. By being equipped with the above-mentioned color filter, the image display element of this embodiment is capable of high-brightness display. [Examples]

[0157] The present invention will be described in detail below with reference to examples and comparative examples. The following examples are provided to facilitate understanding of the present invention. The present invention is not limited to these examples.

[0158] [Synthesis Example 1] 350.0 g of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube as the polymerization solvent, and the mixture was stirred while purging it with nitrogen gas, and the temperature was raised to 98°C.

[0159] Next, a mixture of 215.9 g (0.545 mol) of ethylene glycol monoacetate monomethacrylate, 25.9 g (0.14 mol) of methyl methacrylate, 51.3 g (0.195 mol) of glycidyl methacrylate, 19.1 g (0.120 mol) of methacrylic acid, 37.8 g of 2,2'-azobis(isobutyrate)dimethyl (polymerization initiator), and 143.6 g of propylene glycol monomethyl ether acetate was added dropwise from a dropping funnel to the flask over 3 hours. Next, 156.4 g of propylene glycol monomethyl ether acetate was added to the reaction solution as a solvent (composition additive solvent) to obtain a resin composition of copolymer P1 of Synthesis Example 1 as resin (A) according to this embodiment.

[0160] [Synthesis Examples 2-16] Resin compositions of copolymers P2 to P16 of Synthesis Examples 2 to 16 were obtained in the same manner as in Synthesis Example 1, except that the raw materials listed in Table 1 were used in the proportions listed in Table 1. These are shown in Table 1.

[0161] For copolymers P1 to P16 contained in the resin compositions of Synthesis Examples 1 to 16 obtained in this manner, the weight-average molecular weight (Mw), number-average molecular weight (Mn), molecular weight distribution (Mw / Mn), acid value, functional group (epoxy group, blocked isocyanate group, silyl group, hydroxyl group) equivalents, hydroxyl group equivalents, and active methylene group equivalents were determined, respectively. The results are shown in Table 1.

[0162] [Comparative Synthesis Example 1] 350.0 g of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube as the polymerization solvent, and the mixture was stirred while purging with nitrogen, and the temperature was raised to 98°C.

[0163] Next, a mixture of 212.9 g (0.57 mol) of 2-ethylhexyl acrylate, 28.8 g (0.142 mol) of methyl methacrylate, 51.3 g (0.178 mol) of glycidyl methacrylate, 19.2 g (0.110 mol) of methacrylic acid, 37.8 g of 2,2'-azobis(isobutyrate)dimethyl (polymerization initiator), and 143.6 g of propylene glycol monomethyl ether acetate was added dropwise from a dropping funnel to the flask over 3 hours. Next, 156.4 g of propylene glycol monomethyl ether acetate was added to the reaction solution as a solvent (composition additive solvent) to obtain the polymer cP1 resin composition of Comparative Example 1.

[0164] [Comparative Synthesis Examples 2-9] Resin compositions of copolymers cP1 to cP9 of Comparative Synthesis Examples 1 to 9 were obtained in the same manner as in Comparative Synthesis Example 1, except that the raw materials listed in Table 2 were used in the proportions listed in Table 2.

[0165] For copolymers cP1 to cP9 contained in the resin compositions of Comparative Examples 1 to 9 obtained in this manner, the weight-average molecular weight (Mw), number-average molecular weight (Mn), molecular weight distribution (Mw / Mn), acid value, functional group (epoxy group, blocked isocyanate group, silyl group) equivalents, and active methylene group equivalents were determined, respectively. The results are shown in Table 2.

[0166] [Comparative Synthesis Example 10] In a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, 174.4 g of propylene glycol monomethyl ether acetate was added as the polymerization solvent, and the mixture was stirred while purging with nitrogen gas, and the temperature was raised to 118°C.

[0167] Next, a mixture of 10.7 g (0.03 mol) of dicyclopentanyl methacrylate, 93.5 g (0.27 mol) of ethylene glycol monoacetate monomethacrylate, 160.9 g (0.7 mol) of glycidyl methacrylate, 32.3 g of tert-butyl peroxy-2-ethylhexanoate (polymerization initiator), and 68.9 g of propylene glycol monomethyl ether acetate was added dropwise to the flask from a dropping funnel over a period of 3 hours. After the addition was complete, the temperature was raised to 120°C and the mixture was stirred for 30 minutes to carry out the copolymerization reaction and produce a copolymer. Subsequently, the flask was purged with air, and 81.6 g (0.7 mol) of acrylic acid, 1.4 g of triphenylphosphine (addition reaction catalyst), and 0.7 g of methyl hydroquinone (polymerization inhibitor) were added to the copolymer solution. The reaction was continued at 110°C for 10 hours, aiming to cleave the epoxy groups derived from glycidyl methacrylate through the reaction of acrylic acid and simultaneously introduce ethylenically unsaturated bonds into the side chains of the copolymer. However, gelation occurred during the reaction. The reaction was terminated before adding 21.0 g (0.13 mol) of succinic anhydride to the copolymer solution (Comparative Example 10). The equivalent amounts of functional groups (epoxy, blocked isocyanate, silyl) and active methylene groups in the resin of Comparative Example 10 were determined. The results are shown in Table 2.

[0168] [Table 1]

[0169] [Table 2]

[0170] <Preparation of photosensitive colored composition> (Examples 1-16, Comparative Examples 1-9) (A) As copolymers, copolymers P1 to P16 from Synthesis Examples 1 to 16, cP1 to cP9 from Comparative Synthesis Examples 1 to 9, and components (B), (C), and (E) shown in Table 3 were mixed in the proportions shown in Table 3 to prepare the photosensitive colored compositions R1 to R16 and cR1 to cR9 of Examples 1 to 16 and Comparative Examples 1 to 9, respectively.

[0171] Note that the amount of copolymer in the resin composition shown in Table 3 does not include the polymerization solvent used to synthesize the copolymer. Also, the amount of solvent (D) in Table 3 is the total amount of the polymerization solvent used to synthesize the copolymer in the resin composition and any additional solvent added during the preparation of the resin composition.

[0172] [Table 3]

[0173] <Evaluation of photosensitive colored compositions> The photosensitive colored compositions R1-R16 and cR1-cR9 prepared in Examples 1-16 and Comparative Examples 1-9 were evaluated by the following methods.

[0174] (1) Developability Photosensitive colored compositions R1-R16 and cR1-cR9, prepared in Examples 1-16 and Comparative Examples 1-9, were applied to 5cm square glass substrates (alkali-free glass substrates) by spin coating to a thickness of 2.5 μm after exposure (coating step). The glass substrates coated with the photosensitive colored compositions were heated at 100°C for 3 minutes to evaporate the solvent and dry the coated film (pre-bake step).

[0175] Next, using an ultra-high pressure mercury lamp, 200 mJ / cm² was measured. 2Light was shone onto the surface of the dried coating film via a photomask (exposure step). The exposure step was performed with the photomask positioned 100 μm away from the coating film. The photomask used had a line and space pattern with a width of 3 to 100 μm. Next, semi-clean DL-A10 developer (manufactured by Yokohama Oil & Fat Industry Co., Ltd.) (5-fold dilution) was sprayed onto the surface of the coating film for 60 seconds at a temperature of 23°C and a pressure of 0.1 MPa to remove the unexposed areas (development step). The glass substrate with the developed coating film was left to stand in a 100°C dryer for 30 minutes to heat-cur the coating film (post-bake step) and obtain a colored pattern.

[0176] The resulting colored patterns were observed using a Hitachi High-Technologies Corporation S-3400 electron microscope, and the minimum line width (minimum development dimension) that could be developed and the presence or absence of residue in unexposed areas between developed patterns were evaluated. The presence or absence of residue was evaluated according to the following criteria. The results are shown in Table 4 or Table 5. "Evaluation Criteria for Residues" ○: No residue in the unexposed areas between developed patterns. ×: Residue present in unexposed areas between developed patterns.

[0177] (2) Pencil hardness The photosensitive colored compositions R1-R16 and cR1-cR9 prepared in Examples 1-16 and Comparative Examples 1-9 were applied to a 5cm x 5cm square glass substrate (alkali-free glass substrate) by spin coating, and the solvent was evaporated by heating at 100°C for 3 minutes to form a coated film. Next, the coated film was exposed to light with a wavelength of 365nm at an exposure dose of 200mJ / cm². 2 The coating was photocured by irradiation. Next, the glass substrate having the photocured coating film was left to stand in a 100°C dryer for 30 minutes to heat-cur the coating film (post-bake step), obtaining a resin-cured film with a thickness of 2.5 μm.

[0178] The pencil hardness of the resin-cured films prepared in this manner was measured using a pencil hardness tester (No. 553-M, manufactured by Yasuda Seiki Seisakusho) in accordance with JIS K5600-5-4, and evaluated according to the following criteria. The results are shown in Table 4 or Table 5. "Evaluation Criteria for Pencil Hardness" ○:Pencil hardness 3H or higher ×: Pencil hardness less than 3H

[0179] (3) Solvent resistance A glass substrate with a resin-cured film was prepared in the same manner as in (2) above when evaluating pencil hardness, and the absorption spectrum of the resin-cured film was measured using a spectrophotometer (UV-1650PC, Shimadzu Corporation). In addition, 200 mL of propylene glycol monomethyl ether acetate was placed in a 500 mL glass bottle with a lid and left to stand at a temperature of 23°C. The glass substrate with the resin-cured film was placed in this glass bottle and immersed in the propylene glycol monomethyl ether acetate, and left to stand at 23°C for 15 minutes. After that, the glass substrate with the resin-cured film was removed, and the absorption spectrum of the resin-cured film was measured using a spectrophotometer (UV-1650PC, Shimadzu Corporation) in the same manner as before immersion in propylene glycol monomethyl ether acetate.

[0180] Color change (ΔE) of the resin cured film before and after immersion in propylene glycol monomethyl ether acetate. * 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. "Evaluation Criteria for Solvent Resistance" ○:ΔE * ab is less than 3.0 ×:ΔE * ab is 3.0 or higher

[0181] (4) Overall Judgment The cured resin films made from the cured products of the photosensitive colored compositions R1-R16 and cR1-cR9 prepared in Examples 1-16 and Comparative Examples 1-9 were evaluated according to the following criteria. The results are shown in Table 4 or Table 5. "Evaluation Criteria" ○: All of the following conditions must be met. (1) Minimum development size is 15 μm or less, and there is no residue in the unexposed areas between the developed patterns. (2) The pencil hardness of the resin-cured film is 3H or higher. (3) Color change ΔE in the evaluation of solvent resistance of resin cured films * ab is less than 3.0 ×: Does not meet one or more of the above ○ criteria.

[0182] [Table 4]

[0183] [Table 5]

[0184] As shown in Table 4, the photosensitive coloring compositions R1 to R16 of Examples 1 to 16 all had a minimum development dimension of 15 μm or less, and there was no residue in the unexposed areas between the developed patterns, confirming that they had excellent alkaline developability.

[0185] Furthermore, as shown in Table 4, the resin-cured films formed by photocuring the coating films using the photosensitive coloring compositions R1 to R16 of Examples 1 to 16, followed by heat curing at a low temperature of 100°C, had a pencil hardness of 3H or higher, indicating excellent hardness. Moreover, the above-mentioned resin-cured films received a "○" rating for solvent resistance, confirming that they possess excellent solvent resistance.

[0186] In contrast, as shown in Table 5, the photosensitive colored compositions cR1 to cR9 of Comparative Examples 1 to 9 had insufficient alkali developability, pencil hardness, or solvent resistance.

[0187] More specifically, the copolymers cP1 to cP8 obtained in Comparative Synthesis Examples 1 to 8, contained in the photosensitive colored compositions cR1 to cR8 of Comparative Examples 1 to 8, have an active methylene group equivalent of 0. As a result, the cured resin film exhibited inferior alkali developability, hardness, or solvent resistance. Similarly, the copolymer cP9 obtained in Comparative Synthesis Example 9, contained in the photosensitive resin composition cR9 of Comparative Example 9, has a functional group equivalent of 0. As a result, the cured resin film exhibited inferior hardness and solvent resistance. Furthermore, when the resin compositions obtained in this study were examined over time, a favorable trend was observed in the order of constituent units having blocked isocyanate groups, silyl groups, and epoxy groups. Blocked isocyanate groups do not react unless heat is applied, and the reaction of silyl groups can be controlled by using alcohol-based polymerization solvents, while epoxy groups require adjustment of the optimal amount introduced and the amounts of other monomers. [Industrial applicability]

[0188] According to the present invention, it is possible to provide a photosensitive resin composition and a photosensitive coloring composition that can form a resin cured film having excellent developability and good low-temperature curability, as well as sufficient hardness and solvent resistance. Furthermore, according to the present invention, it is possible to provide a resin cured film made of a cured product of the photosensitive resin composition having sufficient hardness and solvent resistance, a color filter having a colored pattern made of a cured product of the photosensitive coloring composition of the present invention having sufficient hardness and solvent resistance, and an image display element equipped with this color filter. The photosensitive resin composition and the photosensitive coloring composition of the present invention can preferably be used, for example, as a transparent film, protective film, insulating film, overcoat, photospacer, black matrix, black column spacer, and resist for color filters. [Explanation of Symbols]

[0189] 1...Substrate, 2...Pixel, 3...Black matrix, 4...Protective film.

Claims

1. Resin (A) and Reactive diluent (B), Photopolymerization initiator (C), Solvent (D) and, Includes, The resin (A) contains a constituent unit (a-1) having at least one group selected from the group consisting of an active methylene group and an active methine group, a constituent unit (a-2) having a group that reacts by the action of light and / or heat, and a constituent unit (a-3) having an acid group. A photosensitive resin composition characterized in that the aforementioned structural unit (a-2) is a structural unit having at least one functional group selected from epoxy group, silyl group, blocked isocyanate group, isocyanate group, mercapto group, oxetanyl group, amino group, furyl group, maleimide group, oxazolidinyl group, oxazolyl group, formyl group, nitro group, and halogen group.

2. The photosensitive resin composition according to claim 1, wherein the constituent unit (a-2) is a constituent unit having at least one functional group selected from epoxy groups, silyl groups, blocked isocyanate groups, and isocyanate groups.

3. The photosensitive resin composition according to claim 1, wherein the constituent unit (a-2) is a constituent unit having an epoxy group (a-2-1), a constituent unit having a silyl group (a-2-2), or a constituent unit having a blocked isocyanate group (a-2-3).

4. The photosensitive resin composition according to any one of claims 1 to 3, wherein the acid value of the resin (A) is 10 to 300 KOH mg / g.

5. Of the entire constituent units of the aforementioned resin (A), The aforementioned constituent unit (a-1) is 2 to 80 mol%, The photosensitive resin composition according to any one of claims 1 to 3, wherein the constituent unit (a-2) is 2 to 80 mol%.

6. The photosensitive resin composition according to any one of claims 1 to 3, wherein the resin (A) further contains other constituent units (a-4).

7. The photosensitive resin composition according to any one of claims 1 to 3, wherein the constituent unit (a-1) is a constituent unit having a structure represented by the following formula (X1) or (X2). 【Chemistry 1】 【Chemistry 2】 (In formulas (X1) and (X2), R ３ R represents a divalent group represented by any of the following formulas (8) to (10). ４ These are cyano groups (-CN) and nitro groups (-NO). ２ ), represents a group represented by the following formula (11) or formula (12). * represents a bonding site. ★ represents an activated methylene carbon or activated methine carbon. 【Transformation 3】 【Chemistry 4】 (In equations (8) to (12), * represents a bonding site. In equations (11) and (12), R ５ This represents a hydrocarbon group having 1 to 24 carbon atoms, which may contain a hydrogen atom or a heteroatom.

8. The constituent unit (a-1) has, in formula (X1) and formula (X2), R ３ is a divalent group represented by formula (8) or formula (10), and R ４ The photosensitive resin composition according to claim 7, wherein is a group represented by formula (11).

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

0.

10. Amount to 100 parts by mass of the total components excluding the solvent (D): The above resin (A) contains 10 to 85 parts by mass, The reactive diluent (B) is contained in an amount of 10 to 85 parts by mass, The above photopolymerization initiator (C) is contained in an amount of 0.1 to 30 parts by mass, A photosensitive resin composition according to any one of claims 1 to 3, comprising 30 to 1,000 parts by mass of the solvent (D).

11. A photosensitive resin composition according to any one of claims 1 to 3 and Coloring agent (E), A photosensitive coloring composition containing [a specific substance].

12. Amount to 100 parts by mass of the total components excluding the solvent (D): The above resin (A) contains 10 to 85 parts by mass, The reactive diluent (B) is contained in an amount of 10 to 85 parts by mass, The above photopolymerization initiator (C) is contained in an amount of 0.1 to 30 parts by mass, The solvent (D) is contained in an amount of 30 to 1000 parts by mass, death, The photosensitive coloring composition according to claim 11, comprising (E) 4 to 85 parts by mass of the coloring agent.

13. A resin-cured film comprising a cured product of the photosensitive resin composition described in any one of claims 1 to 3.

14. A color filter having a colored pattern made of a cured product of the photosensitive colored composition described in claim 11.

15. An image display element comprising the color filter described in claim 14.

Images