Photosensitive resin composition and method for producing photosensitive resin composition

Abstract

The photosensitive resin composition of the present application is a photosensitive resin composition characterized by containing a resin (A), a reactive diluent (B), a solvent (C), a photopolymerization initiator (D), and a colorant (E). The above resin (A) contains a structural unit (a) having an aromatic ring skeleton, a structural unit (b) having a carboxyl group, a structural unit (c), and a structural unit (d) having a bridged alicyclic hydrocarbon group having 7 to 20 carbon atoms, the above structural unit (c) being at least one selected from a structural unit (c-1) having a (meth)acryloyloxy group and a structural unit (c-2) having a functional group reactive with a carboxyl group. The content of the above structural unit (a) having an aromatic ring skeleton is 5 to 50 mol% relative to the total amount of the structural units of the above resin (A).

Description

Technical Field

[0001] This invention relates to photosensitive resin compositions, image display elements, and methods for manufacturing photosensitive resin compositions.

[0002] This application claims priority based on Japanese Patent Application No. 2020-205539 filed on December 11, 2020, the contents of which are incorporated herein by reference. Background Technology

[0003] In recent years, from the perspective of saving resources and energy, photosensitive resin compositions that can be cured by active energy rays such as ultraviolet rays and electron beams have been widely used in various coating, printing, paint, and adhesive fields. In the field of electronic materials such as printed wiring boards, photosensitive resin compositions are used as solder resists and photoresists for color filters.

[0004] Color filters generally consist of a transparent substrate such as a glass substrate, red (R), green (G), and blue (B) pixels formed on the transparent substrate, a black matrix formed at the boundaries of the pixels, and a protective film formed on the pixels and the black matrix. Color filters are typically manufactured by sequentially forming the black matrix, each pixel, and the protective film on the transparent substrate.

[0005] Various manufacturing methods have been proposed for forming individual pixels and black matrices. Currently, photolithography has become the mainstream method for forming individual pixels and black matrices. This photolithography method uses a photosensitive resin composition as a resist and involves repeated coating, exposure, development, and baking. Pixels and black matrices formed using this method exhibit excellent lightfastness and heat resistance, with fewer defects such as pinholes.

[0006] Generally, the photosensitive resin composition used in photolithography contains resin, reactive diluent, photopolymerization initiator, colorant, and solvent. The photosensitive resin composition used in photolithography needs to be developable.

[0007] Conventionally, resins used in photosensitive resin compositions have included copolymers of unsaturated carboxylic acids and / or unsaturated carboxylic anhydrides, free radical polymerizable compounds having epoxy groups, and other free radical polymerizable compounds (see, for example, Patent Document 1).

[0008] Furthermore, as a resin used in photosensitive resin compositions, a resin composition comprising: a copolymer synthesized using glycidyl (meth)acrylate, without acid groups, and having a weight-average molecular weight of 1,000 to 50,000 when converted from polystyrene; and a copolymer having acid groups and having a weight-average molecular weight of 1,000 to 50,000 when converted from polystyrene (for example, see Patent Document 2).

[0009] Existing technical documents

[0010] Patent documents

[0011] Patent Document 1: Japanese Patent Application Publication No. 06-043643

[0012] Patent Document 2: Japanese Patent Application Publication No. 2015-222279 Summary of the Invention

[0013] The problem that the invention aims to solve

[0014] Recently, stricter dimensional accuracy is required in liquid crystal display elements and the components forming them. Therefore, superior developability is required for photosensitive resin compositions used as materials for black matrices, color filters, and black columnar spacers. Furthermore, to improve the display characteristics of the liquid crystal display element, the cured film formed by the photosensitive resin composition used in the above applications needs to have good colorant dispersibility. Moreover, to prevent degradation of the liquid crystal display element, the cured film formed by the photosensitive resin composition used in the above applications is required to have a high elastic recovery rate.

[0015] The present invention was made to solve the problems mentioned above, and its object is to provide a photosensitive resin composition with excellent colorant dispersibility, developability and elastic recovery.

[0016] Methods for solving problems

[0017] The present invention includes the following solutions.

[0018] The first aspect of the present invention provides the following photosensitive resin composition. [1] A photosensitive resin composition, characterized in that it contains...

[0019] Resin (A),

[0020] Reactive diluent (B),

[0021] Solvent (C)

[0022] Photopolymerization initiator (D), and

[0023] Colorant (E),

[0024] The above-mentioned resin (A) has

[0025] Structural unit with aromatic ring skeleton (a)

[0026] Structural units with carboxyl groups (b)

[0027] Structural unit (c), and

[0028] Structural units (d) with bridged alicyclic hydrocarbon groups having 7–20 carbon atoms.

[0029] The aforementioned structural unit (c) is selected from at least one structural unit having a (meth)acryloyloxy group (c-1) and a structural unit having a functional group that reacts with a carboxyl group (c-2).

[0030] The content of the structural unit (a) having an aromatic ring skeleton is 5 to 50 mol% relative to the total amount of structural units of the resin (A) described above.

[0031] The photosensitive resin composition of the first aspect of the present invention preferably has the features described below [2] to [9]. It is also preferable that any combination of two or more of the features described below [2] to [9] is also preferred.

[0032] [2] According to the photosensitive resin composition of [1], the structural unit (b) having a carboxyl group is selected from one or more structural units (b-1) derived from unsaturated carboxylic acids, structural units (b-2) derived from polybasic acids, and structural units (b-3) derived from polybasic acid anhydrides.

[0033] [3] According to the photosensitive resin composition of [1] or [2], the above resin (A) contains a structural unit (c-1) having (meth)acryloyloxy group.

[0034] [4] In any one of the photosensitive resin compositions according to [1] to [3], the above-mentioned structural unit (a) having an aromatic ring skeleton is selected from one or more structural units derived from styrene and structural units derived from (meth)acrylate.

[0035] [5] The photosensitive resin composition according to any one of [1] to [4], wherein the resin (A) comprises resin (A-1) and resin (A-2),

[0036] The content of the above-mentioned structural unit (a) having an aromatic ring skeleton in the above-mentioned resin (A-1) is 5 to 30 mol% relative to the total amount of structural units in the resin (A-1).

[0037] The content of the above-mentioned structural unit (a) having an aromatic ring skeleton in the above-mentioned resin (A-2) is 35 mol% to 50 mol% relative to the total amount of structural units of the resin (A-2).

[0038] [6] The photosensitive resin composition according to any one of [1] to [5] contains, relative to the total amount of the above-mentioned resin (A), 10 to 90% by mass of the above-mentioned resin (A-1) and 10 to 90% by mass of the above-mentioned resin (A-2).

[0039] The aforementioned resin (A-1) is obtained by adding a carboxyl-containing (meth)acrylic acid compound to the epoxy group of a resin precursor (A-1) having an epoxy group, and further adding a polybasic acid or polybasic acid anhydride to the hydroxyl group generated by ring opening of the aforementioned epoxy group.

[0040] The above-mentioned resin (A-2) is obtained by adding an epoxy-containing (meth)acrylate or an isocyanate-containing (meth)acrylate to a portion of the carboxyl group of a resin (A-2) precursor having a carboxyl group.

[0041] The aforementioned epoxy-containing resin (A-1) precursor is a polymer of a polymeric monomer containing an aromatic ring, an epoxy-containing (meth)acrylate, and a polymeric monomer having a bridged alicyclic hydrocarbon group having 7 to 20 carbon atoms.

[0042] The aforementioned carboxyl-containing resin (A-2) precursor is a polymer of a polymeric monomer containing an aromatic ring, a polymeric monomer containing a carboxyl group, or a polymeric monomer with a bridged alicyclic hydrocarbon group having 7 to 20 carbon atoms.

[0043] [7] In any one of [1] to [8], the colorant (E) is an organic black pigment.

[0044] [8] The photosensitive resin composition according to any one of [1] to [7] further contains a dispersant (F).

[0045] [9] The photosensitive resin composition according to any one of [1] to [8] contains 2 to 20% by mass of the above resin (A).

[0046] Contains 3-20% by mass of the above-mentioned reactive diluent (B).

[0047] Contains 50-90% by mass of the above solvent (C), and

[0048] Contains 3-30% by mass of the above-mentioned colorant (E).

[0049] A second aspect of the present invention provides the following black columnar spacers.

[0050]

[10] A black columnar spacer, which is composed of a cured product of the photosensitive resin composition described in any one of [1] to [9].

[0051] The third aspect of the present invention provides the following image display element.

[0052]

[11] An image display element, characterized in that it comprises the black columnar spacers described in

[10] .

[0053] The fourth aspect of the present invention provides a method for manufacturing the following photosensitive resin composition.

[0054]

[12] A method for manufacturing a photosensitive resin composition, characterized in that it comprises the following steps in sequence:

[0055] Process I: The process of mixing resin (A1), solvent (C1), colorant (E), and dispersant (F) of any composition; and

[0056] Step II: The step of mixing the resin (A2), reactive diluent (B), solvent (C2), photopolymerization initiator (D), and the mixture obtained in Step I.

[0057] The above-mentioned resin (A1) and the above-mentioned resin (A2) respectively have

[0058] Structural unit with aromatic ring skeleton (a)

[0059] Structural units with carboxyl groups (b)

[0060] Structural unit (c), and

[0061] Structural units (d) with bridged alicyclic hydrocarbon groups having 7–20 carbon atoms.

[0062] The aforementioned structural unit (c) is selected from at least one structural unit having a (meth)acryloyloxy group (c-1) and a structural unit having a functional group that reacts with a carboxyl group (c-2).

[0063] The content of the above-mentioned aromatic ring skeleton structural unit (a) in each of the above-mentioned resins (A1) and (A2) is 5 to 60 mol relative to the total amount of structural units.

[0064] The fourth aspect of the present invention also preferably has the following features.

[0065]

[13] In the method for manufacturing the photosensitive resin composition according to

[12] , the resin (A1) is either resin (A-1) or resin (A-2).

[0066] The resin (A2) described above is the other resin (A1) among the resins (A-1) and (A-2) described above, which is different from the resin (A1).

[0067] The content of the above-mentioned structural unit (a) having an aromatic ring skeleton in the above-mentioned resin (A-1) is 5 to 30 mol% relative to the total amount of structural units of the above-mentioned resin (A-1).

[0068] The content of the above-mentioned structural unit (a) having an aromatic ring skeleton in the above-mentioned resin (A-2) is 35 mol% to 50 mol% relative to the total amount of structural units of the resin (A-2).

[0069] The effects of the invention

[0070] According to the present invention, a photosensitive resin composition with excellent colorant dispersibility, developability, and elastic recovery can be provided. The resin-cured film obtained by curing the photosensitive resin composition of the present invention exhibits excellent colorant dispersibility and elastic recovery. Detailed Implementation

[0071] The embodiments of the present invention will now be described in detail. However, the present invention is not limited to the embodiments shown below. For example, the present invention is not limited to the following examples, and without departing from the spirit of the present invention, additions, omissions, substitutions, and changes can be made to the numbers, quantities, ratios, compositions, types, positions, materials, and structures.

[0072] In addition, in this specification, "(meth)acryloyloxy" means at least one selected from acryloyloxy and methacryloyloxy, "(meth)acrylic acid" means at least one selected from acrylic acid and methacrylic acid, and "(meth)acrylate" means at least one selected from acrylate and methacrylate.

[0073] The so-called "structural unit" is the monomer unit that makes up resin (A).

[0074] The term "content of structural units" refers to the content (mol%) relative to the total number of moles constituting the monomer.

[0075] The so-called "structural unit derived from monomer" refers to a structural unit derived from a specific monomer among the monomers that constitute resin (A).

[0076] <Photosensitive Resin Composition>

[0077] The photosensitive resin composition of the present invention will now be described in detail.

[0078] The photosensitive resin composition of this embodiment contains a resin (A), a reactive diluent (B), a solvent (C), a photopolymerization initiator (D), and a colorant (E). The photosensitive resin composition of this embodiment may contain a dispersant (F) if desired.

[0079] [Resin(A)]

[0080] The resin (A) of this embodiment contains at least: a structural unit (a) having an aromatic ring skeleton (hereinafter also simply referred to as "structural unit (a)"), a structural unit (b) having a carboxyl group (hereinafter also simply referred to as "structural unit (b)"), a structural unit (c), and a structural unit (d) having a bridged alicyclic hydrocarbon group having 7 to 20 carbon atoms (hereinafter also simply referred to as "structural unit (d)"). The structural unit (c) is selected from at least one of a structural unit (c-1) having a (meth)acryloyloxy group (hereinafter also simply referred to as "structural unit (c-1)") and a structural unit (c-2) having a functional group that reacts with a carboxyl group (hereinafter also simply referred to as "structural unit (c-2)").

[0081] “Structural Unit (a)”

[0082] Structural unit (a) has an aromatic ring backbone. By having structural unit (a) in the resin (A), a photosensitive resin composition with better dispersibility of the colorant (E) is obtained. In particular, when a pigment is used as the colorant (E), the effect of improved dispersibility due to the presence of structural unit (a) in the resin (A) is significantly obtained. Structural unit (a) is introduced by using a polymerizable monomer (m-1) containing an aromatic ring as the polymerizable monomer used in manufacturing the resin (A) by copolymerization (derived from a polymerizable monomer containing an aromatic ring). Examples of aromatic ring-containing polymerizable monomers (m-1) include, for example, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, p-nitrostyrene, p-cyanostrene, p-acetaminostyrene, and other aromatic vinyl compounds; benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxy-polyethylene glycol (meth)acrylate (trade name: Light Acrylate P-200A, manufactured by Kyoei Chemical Co., Ltd.), o-phenoxybenzyl (meth)acrylate, m-phenoxybenzyl (meth)acrylate, p-phenoxybenzyl (meth)acrylate, etc. Among these, styrene and benzyl (meth)acrylate are preferred from the viewpoint of improving ease of acquisition and developability. These aromatic ring-containing polymerizable monomers (m-1) can be used alone or in combination with two or more. That is, preferably, the structural unit (a) having an aromatic ring skeleton is one or more selected from structural units derived from styrene and structural units derived from (meth)acrylate.

[0083] “Structural Unit (b)”

[0084] Structural unit (b) does not have an aromatic ring skeleton but has a carboxyl group. The carboxyl group can be an anhydride. The structural unit (b) having a carboxyl group is preferably selected from one or more structural units (b-1) derived from unsaturated carboxylic acids, structural units (b-2) derived from polybasic acids, and structural units (b-3) derived from polybasic acid anhydrides. Structural unit (b) can generally be introduced into resin (A) by the following two methods.

[0085] The first method involves introducing a carboxyl-containing polymerizable monomer as the polymerizable monomer used in the copolymerization of resin (A) to introduce the monomer (derived from a carboxyl-containing polymerizable monomer). Examples of carboxyl-containing polymerizable monomers (m-2) include, for instance, (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, α-bromo(meth)acrylic acid, β-furanyl(meth)acrylic acid, crotonic acid, propynic acid, cinnamic acid, α-cyanocinonic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, monomethyl fumarate, monoethyl itaconic acid, and other unsaturated carboxylic acids. These carboxyl-containing polymerizable monomers can be used alone or in combination. From the viewpoint of ease of acquisition and reactivity, (meth)acrylic acid is preferred.

[0086] The second method involves using an epoxy-containing (meth)acrylate (m-3) as a polymerizable monomer in the process of manufacturing resin (A) by copolymerization, thereby opening the epoxy ring by reacting the carboxyl group of the carboxyl-containing compound with the epoxy group, and introducing the carboxyl group by adding a polybasic acid (n-1) or polybasic acid anhydride (n-2) with the hydroxyl group generated at this time.

[0087] Examples of (meth)acrylates (m-3) containing epoxy groups include glycidyl methacrylate, 2-glycidyloxyethyl (meth)acrylate, 3,4-epoxycyclohexylmeth (meth)acrylate having an alicyclic epoxy group, its lactone adducts (e.g., Daicel Chemical Industry Co., Ltd. Cyclomer (registered trademark) A200, M100), mono(meth)acrylate of 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, epoxide of dicyclopentenyl (meth)acrylate, epoxide of dicyclopentenyloxyethyl (meth)acrylate, etc.

[0088] These epoxy-containing (meth)acrylates (m-3) can be used alone or in combination. Among them, glycidyl (meth)acrylate is preferred from the viewpoint of ease of acquisition and reactivity. Furthermore, unsaturated carboxylic acids mentioned in the first method described above can be used as compounds containing carboxyl groups. Among these, (meth)acrylic acid is preferred from the viewpoint of reactivity.

[0089] Examples of polybasic acids (n-1) include tetrahydrophthalic acid, hexahydrophthalic acid, 4-methylhexahydrophthalic acid, and succinic acid.

[0090] As polybasic acid anhydrides (n-2), the anhydrides of the aforementioned polybasic acids can be cited. These polybasic acids and polybasic acid anhydrides can be used alone or in combination. Among them, tetrahydrophthalic anhydride is preferred from the viewpoint of improving developability.

[0091] In the second method, when the carboxyl group of a carboxyl-containing compound undergoes an addition reaction with the epoxy group contained in the precursor, the epoxy group of the precursor is left to remain directly without reacting with a portion of it, thus remaining as a structural unit (c-2) having a functional group that reacts with the carboxyl group. Alternatively, a carboxyl-containing compound having a (meth)acryloyloxy group can undergo an addition reaction with the epoxy group of the precursor to introduce a structural unit (c-1) having a (meth)acryloyloxy group.

[0092] “Structural Unit (c)”

[0093] “Structural Unit (c-1)”

[0094] The structural unit (c-1) does not have an aromatic ring skeleton and a carboxyl group, but has a (meth)acryloyloxy group. The structural unit (c-1) can generally be introduced into resin (A) by the following two methods.

[0095] The first method involves introducing a carboxyl-containing (meth)acrylate compound by adding an epoxy group to a (meth)acrylate compound (m-3) as a polymerizable monomer used in the production of resin (A) by copolymerization. The epoxy-containing (meth)acrylate (m-3) can be the substance described above.

[0096] Examples of carboxyl-containing (meth)acrylic acid compounds (m-2) include (meth)acrylic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, α-bromo(meth)acrylic acid, and β-furanyl(meth)acrylic acid. Among these, (meth)acrylic acid is preferred from the viewpoint of reactivity and ease of acquisition during the synthesis of resin (A). These carboxyl-containing (meth)acrylic acid compounds can be used alone or in combination with two or more.

[0097] The second method involves introducing a monomer containing a carboxyl group as a polymerizable monomer used in the production of resin (A) by copolymerization, by adding an epoxy-containing (meth)acrylate (m-3) or an isocyanate-containing (meth)acrylate (m-4) to the carboxyl group. As the monomer containing a carboxyl group, unsaturated carboxylic acids, as mentioned above as polymerizable monomers containing carboxyl groups, can be used. As the epoxy-containing (meth)acrylate (m-3), the aforementioned substance can be used. As the isocyanate-containing (meth)acrylate (m-4), 2-isocyanate-ethyl (meth)acrylate, etc., can be mentioned.

[0098] Structural unit (c-2) does not have an aromatic ring skeleton, a carboxyl group, or a (meth)acryloyloxy group, but has a functional group that reacts with the carboxyl group. The functional group that reacts with the carboxyl group in structural unit (c-2) is not particularly limited, but examples generally include epoxy groups, oxetyl groups, isocyanate groups, etc., with epoxy groups being particularly preferred. Structural unit (c-2) is introduced by using a polymerizable monomer containing a functional group that reacts with the carboxyl group as the polymerizable monomer used in manufacturing resin (A) by copolymerization (derived from a polymerizable monomer containing a functional group that reacts with the carboxyl group).

[0099] In addition to the aforementioned epoxy-containing (meth)acrylates (m-3), other polymerizable monomers containing functional groups that react with carboxyl groups include oxetane (meth)acrylates, (3-methyloxetane-3-yl)methyl methacrylate, (3-ethyloxetane-3-yl)methyl methacrylate, (3-methyloxetane-3-yl)ethyl methacrylate, (3-ethyloxetane-3-yl)ethyl methacrylate, (3-chloromethyloxetane-3-yl)methyl methacrylate, and (oxetane-2-yl)methacrylate. Methyl methacrylate, (2-methyloxetane-2-yl)methyl methacrylate, (2-ethyloxetane-2-yl)methyl methacrylate, (1-methyl-1-oxetane-2-phenyl)-3-(meth)acrylate, (1-methyl-1-oxetane)-2-trifluoromethyl-3-(meth)acrylate, (1-methyl-1-oxetane)-4-trifluoromethyl-2-(meth)acrylate, and other (meth)acrylates containing oxetane groups; 2-isocyanate-ethyl (meth)acrylate, and other (meth)acrylates containing isocyanate groups, etc. These polymerizable monomers containing functional groups that react with carboxyl groups can be used alone or in combination.

[0100] The method of introducing structural units (b) having a carboxyl group, structural units (c-1) having a (meth)acryloyloxy group, and structural units (c-2) having a functional group that reacts with the carboxyl group into resin (A) can be achieved by appropriately combining the methods of introducing the above-mentioned structural units (b), (c-1), and (c-2). A preferred method is to use an epoxy-containing (meth)acrylate (m-3) as a polymerizable monomer used as a precursor in the copolymerization of resin (A), thereby adding a carboxyl-containing (meth)acrylate compound to a portion of the epoxy group to open the epoxy group, and then adding a polyacid anhydride to a portion of the hydroxyl group generated at this time. That is, as structural units introduced into resin (A), examples include structural units (b) having carboxyl groups (derived from structural units of polybasic acid anhydrides), structural units (c-1) having (meth)acryloyloxy groups (derived from structural units of (meth)acrylic compounds (m-2) containing carboxyl groups), and structural units (c-2) having functional groups that react with carboxyl groups (derived from structural units of (meth)acrylates containing epoxy groups that are unreacted epoxy residues). Alternatively, a polymerizable monomer containing carboxyl groups can be used as the polymerizable monomer used as a precursor for manufacturing resin (A) by copolymerization, and an epoxy-containing (meth)acrylate or an isocyanate-containing (meth)acrylate can be added to a portion of the carboxyl group derived from the polymerizable monomer containing carboxyl groups. That is, as structural units introduced into resin (A), examples include structural units (b) having carboxyl groups and structural units (c-1) having (meth)acryloyloxy groups.

[0101] “Structural Unit (d)”

[0102] Structural unit (d) lacks an aromatic ring skeleton, a carboxyl group, a (meth)acryloyloxy group, and a functional group that reacts with the carboxyl group, and has a bridged alicyclic hydrocarbon group with 7 to 20 carbon atoms. By having structural unit (d) in resin (A), a photosensitive resin composition providing a cured film with superior elastic recovery can be obtained. Structural unit (d) is introduced by using a polymerizable monomer (m-5) having a bridged alicyclic hydrocarbon group with 7 to 20 carbon atoms as the polymerizable monomer used in manufacturing resin (A) by copolymerization (derived from a polymerizable monomer having a bridged alicyclic hydrocarbon group with 7 to 20 carbon atoms).

[0103] Examples of polymerizable monomers (m-5) having bridged alicyclic hydrocarbon groups with 7 to 20 carbon atoms include, for example, dicyclopentenyl (meth)acrylate, tricyclodecanyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, norbornene (bicyclo[2.2.1]hept-2-ene), and 5-methylbicyclo [2.2.1]Hept-2-ene, 5-ethylbicyclo[2.2.1]Hept-2-ene, Tetracyclo[4.4.0.12,5.17,10]Dodec-3-ene, 8-Methyltetracyclo[4.4.0.12,5.17,10]Dodec-3-ene, 8-Ethyltetracyclo[4.4.0.12,5.17,10]Dodec-3-ene, Dicyclopentadiene, Tricyclo[5.2.1.02,6]Dec-8- Alkenes, tricyclic [5.2.1.02,6]dec-3-ene, tricyclic [4.4.0.12,5]undec-3-ene, tricyclic [6.2.1.01,8]undec-9-ene, tricyclic [6.2.1.01,8]undec-4-ene, tetracyclic [4.4.0.12,5.17,10.01,6]dodec-3-ene, 8-methyltetracyclic [4.4.0.12,5.17,10.01, [6] Dodecane-3-ene, 8-ethyltetracyclo[4.4.0.12,5.17,12] dodecane-3-ene, 8-ethyltetracyclo[4.4.0.12,5.17,10.01,6] dodecane-3-ene, pentacyclic[6.5.1.13,6.02,7.09,13] pentadecane-4-ene, pentacyclic[7.4.0.12,5.19,12.08,13] pentadecane-3-ene, etc. Among them, tricyclodecyl (meth)acrylate is preferred from the viewpoint of heat resistance. These polymerizable monomers having bridged alicyclic hydrocarbon groups with 7 to 20 carbon atoms can be used alone or in combination.

[0104] "Other structural units (e)"

[0105] The resin (A) of this embodiment may have structural units (e) derived from free radical polymerizable monomers (m-6) having olefinic carbon-carbon double bonds, in addition to the structural units described above, as needed.

[0106] Examples of free radical polymerizable monomers (m-6) possessing olefinic carbon-carbon double bonds include, for example, butadiene, isoprene, chloroprene, and other diene compounds; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, benzyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, methylcyclohexyl(meth)acrylate, ethylcyclohexyl(meth)acrylate, 1,4-cyclohexanediethanol mono(meth)acrylate, etc. Rosin acrylate, norborneol alkyl acrylate, 5-methylnorborneol alkyl (meth)acrylate, 5-ethylnorborneol alkyl (meth)acrylate, tetrahydrofurfuryl acrylate, 1,1,1-trifluoroethyl acrylate, perfluoroethyl acrylate, perfluoro-n-propyl acrylate, perfluoro-isopropyl acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, triphenylmethyl (meth)acrylate, phenyl acrylate, cumyl acrylate, 4-phenoxyphenyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypoly Ethylene glycol (meth)acrylate, nonylphenoxy polyethylene glycol mono(meth)acrylate, biphenyloxyethyl (meth)acrylate, naphthyl (meth)acrylate, anthracene (meth)acrylate, products of the reaction of (meth)acryloyloxyethyl isocyanate (i.e., 2-isocyanate-based ethyl (meth)acrylate) with ε-caprolactam, products of the reaction of (meth)acryloyloxyethyl isocyanate with propylene glycol monomethyl ether, etc. (meth)acrylate compounds; (meth)acrylamide, (meth)acrylate N,N-dimethylamide, (meth)acrylate N,N-diethylamide, (meth)acrylate N,N-dipropylamide, (meth)acrylate N,N-dipropylamide, (meth)acrylate (Methacrylamides) such as N,N-di-isopropylamide and anthraquinone (methacrylamide); vinyl compounds such as methacrylanilide, methacrylonitrile, acrolein, vinyl chloride, 1,1-dichloroethylene, vinyl fluoride, 1,1-difluoroethylene, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, and vinyltoluene; unsaturated dicarboxylic acid diesters such as diethyl citrate, diethyl maleate, diethyl fumarate, and diethyl itacrylate; and monomaleimide compounds such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, and N-(4-hydroxyphenyl)maleimide.

[0107] (Ratio of structural units in resin (A))

[0108] In this embodiment, the resin (A) used has a content of 5 to 50 mol% of the structural unit (a) having an aromatic ring skeleton relative to the total amount of structural units (total moles of the constituent monomers). If the content of structural unit (a) is 5 mol% or more, the photosensitive resin composition exhibits good colorant dispersibility and good developability. If the content of structural unit (a) is 50 mol% or less, the contents of structural units (b), (c), and (d) can be adequately ensured, thus obtaining a photosensitive resin composition that achieves a balance of necessary properties such as photocurability, developability, and elastic recovery rate of the cured product. Depending on the requirements, the content of the above-mentioned structural unit (a) can be 5 to 10 mol%, 10 to 20 mol%, 20 to 30 mol%, 30 to 40 mol%, or 40 to 50 mol%.

[0109] In this embodiment, the resin (A) is obtained by using two resins (A-1) and resin (A-2) with different contents of the aforementioned aromatic ring skeleton structural unit (a) in combination, thereby achieving a synergistic effect and obtaining a photosensitive resin composition that provides a cured film with improved elastic recovery rate and improved colorant dispersibility and developability. The content of the aforementioned aromatic ring skeleton structural unit (a) of the aforementioned resin (A-1) relative to the total amount of structural units of resin (A-1) is preferably 5 to 30 mol%, more preferably 5 to 25 mol%. The aforementioned content is also preferably 5 to 8 mol%, 5 to 10 mol%, 5 to 15 mol%, or 10 to 20 mol% as needed. The content of the aforementioned aromatic ring skeleton structural unit (a) of the aforementioned resin (A-2) relative to the total amount of structural units of resin (A-2) is preferably 35 mol% to 50 mol%, more preferably 40 to 50 mol%. The aforementioned content is also preferably 38 to 50 mol% or 42 to 45 mol% as needed.

[0110] When two different resins (A-1) and resin (A-2) are used together as resin (A), the ratio of resin (A-1) to resin (A) is preferably 10-90% by mass, more preferably 30-70% by mass, and even more preferably 45-65% by mass. The above ratio can be 48-60% by mass, 50-58% by mass, etc. The ratio of resin (A-2) to resin (A) is preferably 10-90% by mass, more preferably 30-70% by mass, and even more preferably 35-55% by mass. The above ratio can be 38-53% by mass, 40-50% by mass, etc.

[0111] A preferred composition of resin (A-1) is obtained by adding a carboxyl-containing (meth)acrylic acid compound (m-2) to the epoxy group of a polymer precursor of resin (A), which is a polymer containing an aromatic ring polymerizable monomer (m-1), an epoxy group-containing (meth)acrylic ester (m-3), and a polymerizable monomer having 7 to 20 carbon atoms (m-5), and further adding a polybasic acid (n-2) or a polybasic acid anhydride (n-3) to the hydroxyl group generated by ring-opening of the above-mentioned epoxy group. By making resin (A-1) with such a composition, it is possible to achieve a balance in the content of other structural units while controlling the content of the above-mentioned structural unit (a) with an aromatic ring skeleton, thereby obtaining a photosensitive resin composition with excellent colorant dispersibility and developability, and a cured film with excellent elastic recovery rate.

[0112] A preferred composition of resin (A-2) is a resin obtained by adding an epoxy-containing (meth)acrylate (m-3) or an isocyanate-containing (meth)acrylate (m-4) to a portion of the carboxyl group of a polymer precursor of resin (A), which consists of an aromatic ring-containing polymerizable monomer (m-1), a carboxyl group-containing polymerizable monomer (m-2), and a bridged alicyclic hydrocarbon group having 7 to 20 carbon atoms (m-5). By configuring resin (A-2) in this way, a balance can be achieved in the content of other structural units while controlling the content of the aforementioned structural unit (a) with an aromatic ring backbone. Therefore, a photosensitive resin composition with excellent colorant dispersibility and developability can be obtained, as well as a cured film with excellent elastic recovery.

[0113] The content of the aforementioned carboxyl-containing structural unit (b) relative to the total amount of structural units (total moles of the monomers) is preferably 5 to 50 mol%, more preferably 8 to 40 mol%, even more preferably 10 to 30 mol%, and particularly preferably 13 to 25 mol%. The above amounts are also preferably 15 to 23 mol% or 18 to 20 mol%. If the content of structural unit (b) is 5 mol% or more, a photosensitive resin composition with good developability is obtained. If the content of structural unit (b) is 50 mol% or less, it can prevent the exposed portion from being washed away during development, thus preventing a decrease in residual film yield.

[0114] The content of the structural unit (c-1) having (meth)acryloyloxy group relative to the total amount of structural units (total moles of the monomer) is preferably 5 to 50 mol%, more preferably 10 to 40 mol%, and even more preferably 12 to 30 mol%. The above amounts are also preferably 15 to 28 mol% or 18 to 25 mol%. If the content of the structural unit (c-1) is 5 mol% or more, a photosensitive resin composition with good photocurability, solvent resistance, and developability is obtained. If the content of the structural unit (c-1) is 50 mol% or less, the photocurability can be suppressed within an appropriate range, and residue from unexposed areas can be prevented during development. In the case of the above-described resin (A-1), the content of the structural unit (c-1) is particularly preferably 20 to 30 mol%, and in the case of the above-described resin (A-2), it is particularly preferably 10 to 20 mol%.

[0115] The content of the structural unit (c-2) having a functional group that reacts with a carboxyl group is preferably 0 to 20 mol% relative to the total amount of structural units (the total number of moles constituting the monomer), more preferably 0 to 15 mol%, even more preferably 0 to 10 mol%, and particularly preferably 0 to 5 mol%. If the content of the structural unit (c-2) is 20 mol% or less, a photosensitive resin composition with good developability is obtained. The content of the structural unit (c-1) is particularly preferably 0.1 to 5 mol% in the case of the above-mentioned resin (A-1), and particularly preferably 0 mol% in the case of the above-mentioned resin (A-2).

[0116] The content of the structural unit (d) having a bridged alicyclic hydrocarbon group with 7 to 20 carbon atoms is preferably 1 to 40 mol% relative to the total amount of structural units (total moles of the monomer), more preferably 3 to 35 mol%, and even more preferably 5 to 30 mol%. The above amount can be 8 to 25 mol%, 10 to 20 mol%, 15 to 18 mol%, etc., as needed. If the content of structural unit (d) is 1 mol% or more, a cured film with excellent elastic recovery is obtained. If the content of structural unit (d) is 40 mol% or less, a photosensitive resin composition with excellent curability is obtained. In the case of the above-described resin (A-1), the content of structural unit (d) is particularly preferably 10 to 30 mol%, and in the case of the above-described resin (A-2), it is particularly preferably 5 to 10 mol%.

[0117] In resin (A), structural units (e) other than structural units (a), (b), (c), and (d) can be introduced as needed.

[0118] When introducing structural unit (e) other than structural unit (a), structural unit (b), structural unit (c), and structural unit (d), the total number of structural units (the total number of moles constituting the monomer) is preferably more than 0 mol% and less than 60 mol%, more preferably more than 0 mol% and less than 50 mol%.

[0119] As an example of introducing structural unit (e) other than structural units (a) to (d), besides using a free radical polymerizable monomer with an olefinic carbon-carbon double bond other than the polymerizable monomers used for introducing structural units (a) to (d) to synthesize resin (A), the following examples can also be cited. For example, in the preferred configuration of the above-described resin (A-1), when a carboxyl-containing (meth)acrylate compound is added to the epoxy group of the resin (A) precursor, which is a polymer containing an epoxy group, structural units derived from the epoxy group-containing (meth)acrylate with unreacted epoxy groups remaining are counted as structural units (c-2) having functional groups that react with carboxyl groups. Furthermore, structural units derived from the epoxy group-containing (meth)acrylate with epoxy groups disappearing after addition to the carboxyl-containing (meth)acrylate compound are counted as structural units (e) other than structural units (a), (b), (c), and (d).

[0120] (Method for manufacturing resin (A))

[0121] The reaction conditions for the copolymerization reaction to obtain the resin (A) used in this embodiment, or the reaction conditions for the copolymerization reaction to obtain the resin (A) precursor before the addition reaction, can be appropriately set according to conventional methods. For example, the copolymerization reaction can be carried out for about 1 to 12 hours at 50–150°C, more preferably 60–140°C, while adding the polymerizable monomer and polymerization initiator dropwise in the solvent. The addition reaction to the resin (A) precursor can be carried out for about 3 to 12 hours at 50–150°C, more preferably 80–130°C, by adding the resin (A) precursor and the monomer for the addition reaction to the solvent, and further adding the addition reaction catalyst. Furthermore, the addition reaction can be carried out even if it includes the solvent used in the copolymerization reaction to obtain the resin (A) precursor. Therefore, after the copolymerization reaction to obtain the resin (A) precursor is completed, the solvent can be left unremoved, and the addition reaction can proceed.

[0122] There are no particular limitations on the solvents that can be used in copolymerization reactions; well-known substances can be used appropriately. Specific examples of solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether. Ethers and other (poly)alkylene glycol monoalkyl ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. (poly)alkylene glycol monoalkyl ether acetates; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ether compounds; methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and other ketone compounds; methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate 2-Hydroxy-2-methylpropionate, 2-Hydroxy-2-methylpropionate, 3-methoxypropionate, 3-methoxypropionate, 3-ethoxypropionate, ethyl ethoxylate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-butyl acetate, n-propyl acetate, isopropyl acetate, ethyl acetate Ester compounds such as n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate, etc.; aromatic hydrocarbon compounds such as toluene and xylene; carboxylic acid amide compounds such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide, etc. These solvents can be used alone or in combination.

[0123] Among them, the preferred solvents are (poly)alkylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and (poly)alkylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, i.e., glycol ether solvents.

[0124] The amount of solvent used in the copolymerization reaction is not particularly limited, but when the total amount of monomers added is set to 100 parts by mass, it is generally 30 to 1000 parts by mass, preferably 50 to 800 parts by mass. If the amount of solvent used is less than 1000 parts by mass, the decrease in molecular weight of resin (A) caused by chain transfer can be effectively suppressed, and the viscosity of resin (A) can be controlled within an appropriate range, which is therefore preferred. On the other hand, if the amount of solvent used is 30 parts by mass or more, abnormal copolymerization can be prevented, and the copolymerization reaction can proceed stably, which is therefore preferred. In addition, coloring and gelation of resin (A) can also be prevented.

[0125] There are no particular limitations on the polymerization initiators that can be used in copolymerization reactions, and known substances can be used appropriately. Specific examples of polymerization initiators include azobisisobutyronitrile, azobisisovalerate, benzoyl peroxide, and tert-butylperoxide-2-ethylhexanoate. These polymerization initiators can be used alone or in combination. There are no particular limitations on the amount of polymerization initiator used, but when the total amount of monomer added is set to 100 parts by weight, it is generally 0.5 to 20 parts by weight, preferably 0.7 to 15 parts by weight, and more preferably 1 to 10 parts by weight.

[0126] There is no particular limitation on the type of addition reaction catalyst used to initiate the addition reaction between the monomer and the resin (A) precursor, and it can be selected according to the needs. Examples of addition reaction catalysts include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, and chromium chelates. These addition reaction catalysts can be used alone or in combination. There is no particular limitation on the amount of addition reaction catalyst used, but when the amount of resin (A) precursor is set to 100 parts by mass, it is generally 0.01 to 5 parts by mass, preferably 0.1 to 2 parts by mass, and more preferably 0.2 to 1 part by mass.

[0127] Preferably, a polymerization inhibitor is added to prevent gelation during the addition reaction of the monomer with the resin (A) precursor. The type of polymerization inhibitor is not particularly limited and is selected as needed. Examples of polymerization inhibitors include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, and butylated hydroxytoluene. These inhibitors can be used alone or in combination. The amount of polymerization inhibitor used is not particularly limited, but when the amount of resin (A) precursor is set to 100 parts by mass, it is generally 0.01 to 5 parts by mass, preferably 0.1 to 2 parts by mass, and more preferably 0.2 to 1 part by mass.

[0128] (Characteristics of Resin (A))

[0129] The resin (A) used in this invention has a weight-average molecular weight (MA) obtained by gel permeation chromatography (GPC) converted to polystyrene, preferably between 1,000 and 50,000, more preferably between 3,000 and 40,000, and even more preferably between 5,000 and 20,000. If the MA is 1,000 or higher, pattern defects do not occur after alkaline development, and this is therefore preferred. On the other hand, if the MA is 50,000 or lower, the development time becomes appropriate, which is practical in use, and therefore preferred.

[0130] Regarding the acid value (JIS K6901 5.3) of the resin (A) used in this invention, there are no limitations as long as the desired effect of this invention is achieved, but it is generally 20 to 300 KOH mg / g, preferably 30 to 200 KOH mg / g. If the acid value is 20 KOH mg / g or higher, the developability becomes good, and therefore it is preferred. On the other hand, if the acid value is 300 KOH mg / g or lower, the exposed portion (photocured portion) is not easily dissolved in the alkaline developer, and therefore it is preferred.

[0131] Regarding the unsaturated group equivalent of the resin (A) used in this invention, there are no limitations as long as the desired effect of this invention is achieved, but it is generally 100 to 4000 g / mol, preferably 200 to 2000 g / mol, and more preferably 300 to 500 g / mol. If the unsaturated group equivalent is 100 g / mol or more, it is effective in improving the physical properties of the coating film and its alkaline developability, and is therefore preferred. On the other hand, if the unsaturated group equivalent is 4000 g / mol or less, it is effective in further improving sensitivity, and is therefore preferred. Furthermore, the so-called unsaturated group equivalent is the mass of resin (A) containing 1 mole of unsaturated bonds (olefinic carbon-carbon double bonds). The unsaturated group equivalent can be obtained by dividing the mass of resin (A) by the number of unsaturated groups in resin (A) (g / mol). In addition, in this specification, the unsaturated group equivalent is a theoretical value calculated from the amount of raw material added to introduce unsaturated groups.

[0132] Regarding the epoxy equivalent of the resin (A) used in this invention, there are no limitations as long as the desired effect of this invention is achieved, but it is generally 100 to 4000 g / mol, preferably 200 to 2000 g / mol, and more preferably 300 to 500 g / mol. If the epoxy equivalent is 100 g / mol or more, it is effective in improving the physical properties and storage stability of the coating film and is preferred. Conversely, if the epoxy equivalent is 4000 g / mol or less, it is effective in further improving solvent resistance. In addition, the epoxy equivalent mentioned above refers to the mass of polymer per mole of epoxy groups. This value can be obtained by dividing the mass of the polymer by the amount of epoxy groups in the polymer (g / mol). In this specification, "epoxy equivalent" is a theoretical value calculated from the amount of raw material added to introduce epoxy groups.

[0133] (Mixing amount of resin (A))

[0134] The amount of resin (A) mixed is not particularly limited, but it is preferably 5 to 40 parts by mass, more preferably 10 to 30 parts by mass, relative to 100 parts by mass of the total amount of the photosensitive resin composition excluding solvent (C). If the amount of resin (A) mixed is 5% by mass or more, it exhibits good curability and is therefore preferred. On the other hand, if the amount of resin (A) mixed is 40 parts by mass or less, it exhibits good coatability and is therefore preferred.

[0135] [Reactive diluent (B)]

[0136] The reactive diluent (B) used in this embodiment is a compound having at least one olefinic unsaturated group in its molecule. Preferably, it is a compound having multiple olefinic unsaturated groups. By using the reactive diluent (B), the strength of the cured film and its adhesion to the substrate can be improved.

[0137] Examples of monofunctional monomers used as reactive diluents (B) include, for example, (meth)acrylamide, hydroxymethyl (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxymethyl (meth)acrylamide, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-phenoxy-2 Methacrylate compounds include hydroxypropyl methacrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, glyceryl mono(meth)acrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, and hemi(meth)acrylates of phthalic acid derivatives; aromatic vinyl compounds such as styrene, α-methylstyrene, α-chloromethylstyrene, and vinyltoluene; and carboxylic acid esters such as vinyl acetate and vinyl propionate. These monofunctional monomers can be used alone or in combination.

[0138] Examples of multifunctional monomers used as reactive diluents (B) include, for example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glyceryl di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, and 2-hydroxy-3-(meth)acryloyloxypropyl(meth)propene. This includes esters, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, diglycidyl phthalate di(meth)acrylate, triglycerides, glyceryl polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (i.e., toluene diisocyanate), trimethylhexamethylene diisocyanate and 1,6-hexamethylene diisocyanate, and other reactants with 2-hydroxyethyl (meth)acrylate, tri(hydroxyethyl) isocyanate, and other (meth)acrylate compounds; aromatic vinyl compounds such as divinylbenzene, diallyl phthalate, and diallylphenylphosphonate; dicarboxylic acid ester compounds such as divinyl adipate; triallyl cyanurate, methylene bis(meth)acrylamide, (meth)acrylamide methylene ether, and condensates of polyols and N-hydroxymethyl (meth)acrylamide. These multifunctional monomers can be used alone or in combination.

[0139] From the perspective of adhesion, dipentaerythritol hexa(meth)acrylate is preferred.

[0140] The amount of reactive diluent (B) is not particularly limited, but it is preferably 10 to 50 parts by mass, more preferably 20 to 40 parts by mass, relative to 100 parts by mass of the total amount of the photosensitive resin composition excluding solvent (C). If the amount of reactive diluent (B) is 10 parts by mass or more, the photosensitive resin composition exhibits good photocurability, and this is therefore preferred. If the amount of reactive diluent (B) is 40 parts by mass or less, residue is less likely to occur in the unexposed areas after exposure and development of the coating of the photosensitive resin composition, and this is also preferred.

[0141] [Solvent (C)]

[0142] The solvent (C) used in this embodiment is not particularly limited as long as it is a non-reactive solvent that can dissolve the resin (A) and does not react with the resin (A), and can be selected arbitrarily. Furthermore, the solvent (C) is preferably compatible with the aforementioned reactive diluent (B). As the solvent (C), the same substance that can be used when manufacturing the resin (A) can be used. Preferably, the solvent (C) is a (poly)alkylene glycol monoalkyl ether such as propylene glycol monomethyl ether and a (poly)alkylene glycol monoalkyl ether acetate such as propylene glycol monomethyl ether acetate.

[0143] Solvent (C) can be appropriately added to the isolated resin (A) solution from the copolymerized resin (A). However, it is not necessary to isolate the target resin (A) from the resin solution. Alternatively, the solvent contained at the end of the copolymerization reaction can be used directly as solvent (C) without separating it from the resin (A) solution. Other solvents can be added to the resin (A) solution as needed. Furthermore, solvents contained in other components used in adjusting the photosensitive resin composition can also be used directly as solvent (C).

[0144] The amount of solvent (C) is not particularly limited, but it is preferably 150 to 300 parts by mass, more preferably 200 to 250 parts by mass, relative to 100 parts by mass of the total amount of the photosensitive resin composition excluding solvent (C). If the amount of solvent (C) is 150 parts by mass or more, the photosensitive resin composition exhibits good coatability, and is therefore preferred. On the other hand, if the amount of solvent (C) is 300 parts by mass or less, the coating film has sufficient thickness, and is therefore preferred.

[0145] [Photopolymerization Initiator (D)]

[0146] The photopolymerization initiator (D) used in this embodiment is not particularly limited, and examples include, for instance, benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, and benzoin butyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4-(1-tert-butyldioxy-1-methylethyl)acetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1-one, etc. Ethyl ketone compounds; anthraquinone compounds such as 2-methylanthraquinone, 2-pentylanthraquinone, 2-tert-butylanthraquinone, and 1-chloroanthraquinone; xanthonone compounds such as xanthonone, thioxanthonone, 2,4-dimethylthioxanthonone, 2,4-diisopropylthioxanthonone, and 2-chlorothioxanthonone; ketal compounds such as acetophenone dimethyl ketal and benzoyl dimethyl ketal; benzophenone compounds such as 4-(1-tert-butyldioxy-1-methylethyl)benzophenone and 3,3',4,4'-tetra(tert-butyldioxycarbonyl)benzophenone; and acylphosphine oxide compounds, etc. These photopolymerization initiators can be used alone or in combination.

[0147] The amount of photopolymerization initiator (D) is not particularly limited, but relative to 100 parts by weight of the total amount of the photosensitive resin composition excluding solvent (C), it is preferably 0.03 to 15 parts by weight, more preferably 0.1 to 10 parts by weight, and even more preferably 0.3 to 6 parts by weight. The above amounts can be 0.5 to 8 parts by weight, 1 to 5 parts by weight, etc., depending on the requirements. If the amount of photopolymerization initiator (D) is 0.03 parts by weight or more, the photosensitive resin composition has sufficient photocurability, which is therefore preferred. On the other hand, if the amount of photopolymerization initiator (D) is 15 parts by weight or less, residue in the unexposed areas after development is less likely to occur, which is also preferred.

[0148] [Coloring agent (E)]

[0149] The colorant (E) is not particularly limited as long as it is dissolved or dispersed in the solvent (C). Examples of colorants (E) include dyes and pigments. As colorants (E), only dyes, only pigments, or a combination of dyes and pigments can be used. When using the resin-cured film of the photosensitive resin composition of this embodiment as any of a black matrix, a color filter, or a black columnar spacer, two or more of the aforementioned colorants (E) can be used alone or in combination, depending on the purpose of the component formed from the resin-cured film. For example, when a black substance is used as the colorant (E), the resin-cured film of the photosensitive resin composition is suitable as both a black matrix and a black columnar spacer.

[0150] Examples of dyes include, for instance, 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; Acid Chrome Violet K; Acid Magenta; Acid Green 1, 3, 5, 25, 27, 50; Acid Orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 7 3, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274; Acid Violet 6B, 7, 9, 17, 19; Acid Yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; Food Yellow 3 and their derivatives, etc.

[0151] Among these dyes, acid dyes based on azo, xanthones, anthraquinones, or phthalocyanines are preferred.

[0152] These dyes can be used alone or in combination of two or more.

[0153] Examples of pigments include CI pigments such as Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, and 214; Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, and 73; and Red 9, 97, 105, 122, and 12... Red pigments such as 3, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, and 265; CI pigments Blue 15, 15:3, 15:4, 15:6, and 60; CI pigments Violet 1, 19, 23, 29, 32, 36, and 38; CI pigments Green 7, 36, and 58; CI pigments Brown 23 and 25; and black pigments such as aniline black, perylene black, titanium black, cyanine black, lignin black, lactam organic black, RGB black, carbon black, and iron oxide.

[0154] These pigments can be used alone or in combination of two or more.

[0155] From the viewpoint of the optical density of the image display element having the resin-cured film of the photosensitive resin composition of this embodiment, an organic black pigment is preferred as the black pigment, and a lactam-based organic black pigment is more preferred.

[0156] The amount of colorant (E) is not particularly limited, but relative to 100 parts by mass of the total amount of the photosensitive resin composition excluding solvent (C), it is preferably 10 to 50 parts by mass, more preferably 15 to 45 parts by mass, and even more preferably 20 to 40 parts by mass. The above amounts can be 25 to 45 parts by mass, 30 to 35 parts by mass, etc., as needed. If the amount of colorant (E) is 10 parts by mass or more, the cured film has sufficient color reproduction and sufficient opacity when using black pigment as colorant (E), which is therefore preferred. On the other hand, if the amount of colorant (E) is 50 parts by mass or less, residue is less likely to form in the unexposed areas after development, which is also preferred.

[0157] [Dispersant (F)]

[0158] The photosensitive resin composition of this embodiment may contain a dispersant (F). The dispersant (F) can be any known dispersant without particular limitation. By using the dispersant (F), the dispersibility of the colorant is improved, especially when a pigment is used as the colorant (E). As the dispersant (F), a polymeric dispersant is preferred from the perspective of excellent dispersion stability over time. The polymeric dispersant can be chosen arbitrarily, and examples include, for instance, urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, sorbitol aliphatic ester-based dispersants, and aliphatic modified ester-based dispersants. As such polymeric dispersants, substances commercially available under trade names such as EFKA (registered trademark, manufactured by BASF Japan), Disperbyk (registered trademark, manufactured by Big Kemmy), Disparon (registered trademark, manufactured by Kusumoto Chemical Co., Ltd.), and SOLSPERSE (registered trademark, manufactured by Zeneka) can be used. The mixing amount of the dispersant can be appropriately set according to the type of pigments, etc., used.

[0159] The amount of dispersant (F) is not particularly limited, but relative to 100 parts by mass of the total amount of the photosensitive resin composition excluding solvent (C), it is preferably 0.03 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.3 to 6 parts by mass. The above amounts can be 1 to 8 parts by mass, 2 to 5 parts by mass, etc., as needed. If the amount of dispersant (F) is 0.03 parts by mass or more, the dispersibility is further improved, which is therefore preferred. On the other hand, if the amount of dispersant (F) is 15 parts by mass or less, residue is less likely to form in the unexposed areas after development, which is also preferred.

[0160] The photosensitive resin composition of this embodiment may contain known additives such as coupling agents, leveling agents, and heat-resistant polymerization inhibitors, without impairing the effects of the present invention. The amount of these additives mixed is not particularly limited as long as it does not impair the effects of the present invention.

[0161] <Method for manufacturing photosensitive resin composition>

[0162] The photosensitive resin composition of this embodiment can be manufactured by mixing the above-mentioned components using a known mixing device.

[0163] As one embodiment of the method for manufacturing the photosensitive resin composition, a manufacturing method comprising the following steps I and II in sequence can be cited.

[0164] Process I: A process of mixing resin (A1), solvent (C1), colorant (E), and dispersant (F) of any composition.

[0165] Step II: A step of mixing the resin (A2), reactive diluent (B), solvent (C2), photopolymerization initiator (D), and the mixture obtained in Step I.

[0166] The solvent (C1) of step I and the solvent (C2) of step II, which are mixed as solvents (C) in the photosensitive resin composition, may be of the same type or different types. Furthermore, the solvent (C1) or solvent (C2) used in each step may be either the solvent (C) mentioned above or two or more types.

[0167] Similarly, the resin (A1) of step I and the resin (A2) of step II, which are mixed as resin (A) in the photosensitive resin composition, can be of the same type or different types. Furthermore, the resin (A1) or resin (A2) used in each step can be resin (A) alone or two or more types.

[0168] From the viewpoint of further improving the overall properties of the photosensitive resin composition, including colorant dispersibility, development time, and elastic recovery rate of the cured product, it is preferable to use different types of resins (A) for the resin (A1) in step I and the resin (A2) in step II. The combination of different types of resins (A) used for resins (A1) and resins (A2) is not particularly limited, but from the viewpoint of improving the colorant dispersibility, development time, and elastic recovery rate of the cured product in a balanced manner, a synergistic effect is achieved by using two resins (A-1) and resin (A-2) with different contents of the aforementioned aromatic ring skeleton structural unit (a). As described above, the content of the aforementioned aromatic ring skeleton structural unit (a) of the resin (A-1) relative to the total amount of structural units of the resin (A-1) is preferably 5 to 30 mol%, more preferably 5 to 25 mol%. The content of the above-mentioned structural unit (a) having an aromatic ring skeleton in the above-mentioned resin (A-2) relative to the total amount of structural units of the resin (A-2) is preferably 35 mol% to 50 mol%, more preferably 40 to 50 mol%.

[0169] <Resin Cured Film>

[0170] The resin-cured film in this embodiment is a resin-cured film in which the photosensitive resin composition of this embodiment has been photocured.

[0171] The resin-cured film of this embodiment is suitable as a black matrix, color filter, black columnar spacer, or BPDL as a component of an image display element because of its good colorant dispersibility, solvent resistance, and elastic recovery rate.

[0172] <Method for manufacturing resin-cured films>

[0173] The resin-cured film of this embodiment can be manufactured, for example, by the method shown below.

[0174] First, a photosensitive resin composition is coated onto the surface to be formed of the resin-cured film to form a resin layer (coating). Next, the resin layer is exposed through a mask with a predetermined pattern, causing the exposed portions to photocur. Then, the unexposed portions of the resin layer are developed with a developer to create a resin-cured film with a predetermined pattern. Finally, the resin-cured film is post-baked (heat-treated) as needed.

[0175] When exposing the resin layer, a halftone mask with a specified pattern can be used. In this case, the unexposed and half-exposed areas are developed with a developer to form a resin-cured film with the specified pattern.

[0176] There are no particular limitations on the material of the substrate. Examples include glass substrate, silicon substrate, polycarbonate substrate, polyester substrate, polyamide substrate, polyamide-imide substrate, polyimide substrate, aluminum substrate, printed wiring substrate, array substrate, etc.

[0177] There are no particular limitations on the method of coating the photosensitive resin composition, and examples include screen printing, roller coating, curtain coating, spraying, and spin coating.

[0178] After coating the photosensitive resin composition, heating is performed as needed using a circulating oven, infrared heater, hot plate, or other heating methods to evaporate the solvent (C) contained in the resin layer. There are no particular limitations on the heating conditions after coating; they can be appropriately set according to the composition of the photosensitive resin composition. For example, the heating temperature after coating can be 50℃ to 120℃, and the heating time can be 30 seconds to 30 minutes.

[0179] The exposure method for the resin layer is not particularly limited; examples include irradiation with active energy rays such as ultraviolet light or excimer laser light. The amount of energy rays used for irradiation can be appropriately set according to the composition of the photosensitive resin composition. For example, 30–2000 mJ / cm² is preferred. 2 However, it is not limited to this range. As for the light source used for exposure, there are no particular restrictions, and any type of light source can be selected, such as low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, xenon lamps, metal halide lamps, etc.

[0180] The alkaline developer used for development is not particularly limited, and 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; and aqueous solutions of tetramethylammonium, 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and their sulfates, hydrochlorides, or p-toluenesulfonates, etc., which are p-phenylenediamine compounds. Furthermore, defoamers, surfactants, etc., can be added to these alkaline developers as needed. Additionally, it is preferable to wash with water and dry the solution after development using the alkaline developer.

[0181] By post-baking the resin-cured film formed through alkali development, the curing of the resin can be further advanced. The post-baking conditions are not particularly limited and can be chosen arbitrarily. Preferred conditions for heat treatment can be selected based on the composition of the photosensitive resin composition. For example, heating at a temperature of 130°C to 250°C for 10 minutes to 4 hours is preferred, and heating for 20 minutes to 2 hours is more preferable.

[0182] The resin-cured film manufactured in this manner exhibits excellent colorant dispersibility and elastic recovery.

[0183] <Image display element>

[0184] Specific examples of image display elements include liquid crystal display elements and organic EL display elements. There are no restrictions on the manufacture of image display elements; they can be manufactured using conventional methods.

[0185] Example

[0186] The present invention will be further described in detail below through examples and comparative examples, but the present invention is not limited to the following examples.

[0187] The following shows an example of the synthesis of resin (A).

[0188] [Synthesis example 1]

[0189] In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 140g of propylene glycol monomethyl ether acetate was added as a solvent. While purging the flask with nitrogen, the mixture was stirred until it reached 120°C.

[0190] Next, a mixture of monomers consisting of 68.0 g of tricyclodecyl methacrylate (molar ratio 0.3), 11.0 g of styrene (molar ratio 0.1), and 88.0 g of glycidyl methacrylate (molar ratio 0.6) was prepared, and 18.4 g of tert-butylperoxide-2-ethylhexanoate (polymerization initiator, manufactured by Nippon Oil Co., Ltd., Perbyl O (registered trademark)) was added dropwise to a flask over 2 hours. After the addition was complete, the mixture was stirred at 120°C for another 2 hours to carry out a copolymerization reaction, generating a precursor for resin (A-1). Then, the flask was purged with air, and 43.4 g of acrylic acid (molar ratio 0.58), 1.1 g of triphenylphosphine (catalyst), and 0.1 g of methylhydroquinone (polymerization inhibitor) were added to the above resin (A-1) precursor solution. The reaction was then continued at 110°C for 10 hours. Next, 61.0 g of tetrahydrophthalic anhydride (molar ratio 0.39) was added to the flask, and the reaction was continued at 110 °C for 3 hours to obtain a solution of resin (A-1) (resin sample No. p1). The resin solution contained resin (A-1) with an acid value of 79 KOH mg / g, a weight-average molecular weight of 8300, and an unsaturated group equivalent of 480.

[0191] Propylene glycol monomethyl ether acetate was further added to the resin solution to prepare the resin (A-1) solution of Synthesis Example 1 (solid content concentration 44% by mass). The term "solid content" refers to the residual components after heating the resin solution at 130°C for 2 hours; resin (A-1) and the polymerization initiator were the main components.

[0192] [Synthetic Examples 2-5, Comparative Synthetic Example 1]

[0193] Using the materials in Table 1, except for the procedures performed in the same manner as in Synthesis Example 1, solutions of the resin (A-1) of Synthesis Examples 2-5 and Comparative Synthesis Example 1 (resin samples No. p2-5, No. cp1) were obtained. Propylene glycol monomethyl ether acetate was further added to these resin solutions to prepare solutions of the resin (A-1) of Synthesis Examples 2-5 and Comparative Synthesis Example 1 (solid content concentration 44% by mass).

[0194] The acid value, weight-average molecular weight, and unsaturated group equivalent of resin (A-1) (resin samples No. p2~5, No. cp1) are shown in Table 1.

[0195] [Synthesis example 6]

[0196] In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 140g of propylene glycol monomethyl ether acetate was added as a solvent. While purging the flask with nitrogen, the mixture was stirred until it reached 120°C.

[0197] Next, a mixture of monomers consisting of 24.9 g of tricyclodecyl methacrylate (molar ratio 0.1), 99.6 g of benzyl methacrylate (molar ratio 0.5), and 38.9 g of methacrylic acid (molar ratio 0.4) was prepared, and 4.3 g of tert-butylperoxide-2-ethylhexanoate (polymerization initiator, manufactured by Nippon Oil Co., Ltd., Perbuchel (registered trademark) O) was added dropwise to a flask over 2 hours. After the addition was complete, the mixture was stirred at 120°C for another 2 hours to carry out a copolymerization reaction, synthesizing the precursor of resin (A-2). Then, the flask was purged with air, and 24.1 g of glycidyl methacrylate (molar ratio 0.15), 1.8 g of triphenylphosphine (catalyst), and 1.0 g of methylhydroquinone (polymerization inhibitor) were added to the above resin (A-2) precursor solution. The reaction was then continued at 110°C for 10 hours to obtain a solution of resin (A-2). The resin (A-2) contained in this resin solution had an acid value of 80 KOH mg / g, a weight-average molecular weight of 9000, and an unsaturated group equivalent of 1200.

[0198] Propylene glycol monomethyl ether acetate was further added to the resin solution to prepare a solution of resin (A-2) (resin sample No. p6) of Synthesis Example 6 (solid component concentration 40% by mass).

[0199] [Synthesis Example 7, Comparison with Synthesis Example 2]

[0200] Using the materials in Table 1, except for the procedures described in Synthesis Example 6, a solution of resin (A-2) was obtained. Propylene glycol monomethyl ether acetate was further added to this resin solution to prepare solutions of resin (A-2) (resin samples No. p7, No. cp2) of Synthesis Example 7 and Comparative Synthesis Example 2 (solid content concentration 40% by mass).

[0201] The acid value, weight-average molecular weight, and unsaturated group equivalent of resin (A-2) (resin samples No. p1~p7, mp1, mp2) are shown in Table 1.

[0202]

[0203] <Methods for Determining Physical Properties>

[0204] The acid value, unsaturated group equivalent, and weight-average molecular weight described in the synthetic examples are values ​​obtained by the methods described below.

[0205] (1) Acid value: The acid value of resin (A) was determined according to JIS K6901 5.3.2 using a mixed indicator of bromothymol blue and phenol red. It refers to the number of mg of potassium hydroxide required to neutralize the acidic components contained in 1g of resin (A).

[0206] (2) Unsaturated group equivalent: is the mass of polymer per mole of polymeric unsaturated bonds, calculated based on the amount of monomer used.

[0207] (3) Weight-average molecular weight (Mw): This refers to the weight-average molecular weight converted from standard polystyrene, determined using gel permeation chromatography (GPC) under the following conditions. Column: Shodex (registered trademark) LF-804+LF-804 (manufactured by Showa Denko Co., Ltd.)

[0208] Column temperature: 40℃

[0209] Sample: 0.2% tetrahydrofuran solution of the copolymer

[0210] Developing solvent: Tetrahydrofuran

[0211] Detector: Differential refractometer (Showa Denko Co., Ltd.) (RI-71S)

[0212] Flow rate: 1 mL / min

[0213] The following shows an example of the preparation of a colorant dispersion (paint paste) in which resin (A1), solvent (C1), colorant (E), and dispersant (F) are mixed.

[0214] [Production example 1]

[0215] A paint slurry (sample No. m1) was prepared by mixing the following ingredients in Synthesis Example 1 (resin sample No. p1) as resin (A1) with 10.7 parts by weight of solid content: 200 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) as solvent (C1); 35.7 parts by weight of 3,7-bis(2-oxo-1H-indole 3(2H)-ylidene)benzo[1,2-b:4,5-b']difuran-2,6-(3H,7H)-dione (IBS0100CF, product name: Irgaphor Black S 0100CF, manufactured by BASF) as colorant (E) and 3.7 parts by weight of Ajispear PB822 (PB822, manufactured by Ajinomoto Film Techno Co., Ltd.) as dispersant (F) with a paint shaker for 3 hours. The amount of solvent contained in the resin (A-1) solution of Synthesis Example 1 was included in the solvent (C1) as a mixing component.

[0216] [Make examples 2-4, 6, 7, and compare with examples 1 and 2]

[0217] Using the mixing (parts by mass) described in Table 2 below, except as described in Preparation Example 1, paint pastes (sample No. m2-m4, m6, m7, cm1, cm2) of Preparation Examples 2-4, 6, 7 and Comparative Preparation Examples 1 and 2 were prepared.

[0218]

[0219] The following are examples of photosensitive resin compositions in which resin (A2), reactive diluent (B), solvent (C2), photopolymerization initiator (D), and the paint paste of the above-described preparation example are mixed.

[0220] [Example 1]

[0221] The following were prepared: 9.3 parts by weight of resin (A2) from Synthesis Example 1 (Resin Sample No. p1); 37 parts by weight of dipentaerythritol hexaacrylate (DPHA, product name: A-DPH, manufactured by Shin-Nakamura Kogyo Co., Ltd.) as reactive diluent (B); 33 parts by weight of propylene glycol monomethyl ether acetate as solvent (C2); 3.7 parts by weight of acetone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(o-acetyl oxime) (OXE 02, product name: IRGACURE OXE 02, manufactured by BASF) as photopolymerization initiator (D); and 200 parts by weight of PGMEA and IBS0100CF from Synthesis Example 1 (Paint Slurry Sample No. m1, Resin (A-1) from Synthesis Example 1, Resin Sample No. p1, with a solid content of 10.7 parts by weight); Paint paste (Paint Slurry Sample No. m1, Resin (A-1) from Synthesis Example 1, Resin Sample No. p1 with a solid content of 10.7 parts by weight); Paint paste (Paint Slurry Sample No. m1, Resin (A-1) from Synthesis Example 1, Resin Sample No. p1, with a solid content of 10.7 parts by weight); Paint paste (Paint Slurry Sample No. m1, Resin (A-1) from Synthesis Example 1, Resin Sample No. p1); Paint paste (Paint Slurry Sample No. m1, Resin (A-1) from Synthesis Example 1, Resin Sample No. p1); Paint paste (Paint Slurry Sample No. m1, Resin (A-1) from Synthesis Example 1, Resin Sample No. p1); Paint paste (Paint Slurry Sample No. m1, Res A photosensitive resin composition was prepared by mixing 35.7 parts by weight of a mixture of 3.7 parts by weight of Azispray PB822. In the mixing of Table 3, 10.7 parts by weight of resin (A1) contained in the paint paste (marked with "*1" in Table 3. "*1" refers to the resin contained in the paint paste.) and 9.3 parts by weight of the newly added resin (A2) (resin sample No. p1) are listed as the total of the resin (A) component, converted to solid components. The amount of solvent contained in the resin (A-1) solution of Synthetic Example 1 is included in the solvent (C) component as a mixing component. In addition, 200 parts by weight of solvent (C1) contained in the paint paste and 33 parts by weight of the newly added solvent (C2) are listed as the total of the solvent (C) component.

[0222] [Examples 2-17, Comparative Examples 1-8]

[0223] Using the mixtures in Tables 3 to 5, except for the procedures in Example 1, the photosensitive resin compositions of Examples 2 to 17 and Comparative Examples 1 to 8 were prepared.

[0224]

[0225]

[0226]

[0227] <Evaluation of colorant dispersibility>

[0228] The colorant dispersibility of the photosensitive resin composition was evaluated using the method shown below.

[0229] First, the photosensitive resin compositions of Examples 1-17 and Comparative Examples 1-8 were spin-coated onto a 10cm × 10cm IZO substrate with a film thickness of 1.5μm. Then, the substrate was heated at 90°C for 3 minutes to evaporate the solvent. Next, the entire surface of the coating was exposed using a Microlight ML-251D / B manufactured by Usio Electric Co., Ltd., and an irradiation optical unit PM25C-100 (exposure dose 50mJ / cm²). 2 The solution was then photocured. Next, it was developed with a 0.2% (w / w) potassium hydroxide aqueous solution for 120 seconds, and then baked at 230°C for 30 minutes to obtain the desired cured coating. The optical density (OD) of the cured coating with a thickness of 1 μm was measured using a transmission densitometer (361T, X-lite). The results are shown in Tables 6-8. Higher optical density indicates better colorant dispersion.

[0230] <Evaluation of Elastic Recovery Rate>

[0231] A 2.5 μm coating was formed on a substrate using the same method as optical density. Compression displacement and elastic recovery rate were measured by using an elasticity measuring device (DUH-W201S, Shimadzu Corporation) at 25°C under the following measurement conditions.

[0232] The pressing body used as the pressing pattern was a flat pressing body with a diameter of 50 μm, employed in a load-load-removal method. The elastic recovery rate was measured in a test where a load of 300 mN was applied to obtain identifiable results between the compared groups. A loading rate of 3 gf / s and a holding time of 3 seconds were maintained constant. Regarding the elastic recovery rate, a constant load was applied to the flat pressing body for 3 seconds, and then the actual elastic recovery rate of the pattern before and after the load was measured using a three-dimensional thickness measuring device. The elastic recovery rate is the ratio of the distance recovered after a 10-minute recovery time to the distance compressed (compression displacement) when a certain force was applied, expressed by the following formula.

[0233] Elastic recovery rate (%) = [(recovery distance / compression displacement) × 100]

[0234] The results are shown in 6-8.

[0235] <Evaluation of radioactivity>

[0236] The photosensitive resin compositions of Examples 1 to 17 and Comparative Examples 1 to 8 were spin-coated onto a 10cm × 10cm IZO substrate (a substrate with a wiring pattern of IZO formed on its surface) to a coating thickness of 1.5μm. The solvent was then evaporated by heating the IZO substrate at 90°C for 3 minutes. Next, a pattern mask was placed on the coating, and exposure was performed on the mask using a Microlight ML-251D / B manufactured by Usio Electric Co., Ltd., and an illumination optical unit PM25C-100 (exposure dose 120mJ / cm). 2 The light was then used to cure the light. Then, it was developed with a 0.2% (w / w) potassium hydroxide aqueous solution to confirm the development time (the time from when the unexposed area begins to be washed away until the pattern changes disappear) and the development pattern.

[0237] The developing process includes a peeling process where the unexposed areas are peeled off and washed away simultaneously, and a dissolution process where the unexposed areas are dissolved and washed away simultaneously. However, if peeling occurs, there is a possibility of poor display, so dissolution is preferred. Powder dissolution refers to a process in which the unexposed areas dissolve while remaining slightly as powder.

[0238] The results are shown in Tables 6-8.

[0239] ◎(Excellent): Development time is 10-40 seconds and the developed state is completely dissolved.

[0240] ○ (Pass): Development time is 10-40 seconds and the developed form is powder dissolution.

[0241] × (Unacceptable): Development time exceeding 41 seconds and development pattern of complete peeling or powder peeling.

[0242]

[0243]

[0244]

[0245] Based on the above results, the photosensitive resin compositions of Examples 1-17 exhibit excellent colorant dispersibility, developability, and elasticity recovery. On the other hand, the photosensitive resin compositions of Comparative Examples 1-8 show poor evaluation of colorant dispersibility, developability, and elasticity recovery.

[0246] Industry availability

[0247] This invention provides a photosensitive resin composition with excellent colorant dispersibility, developability, and elasticity recovery.

[0248] The photosensitive resin composition of the present invention exhibits excellent colorant dispersibility, developability, and elastic recovery rate. Therefore, the resin-cured film formed by curing the photosensitive resin composition of the present invention also exhibits excellent colorant dispersibility and elastic recovery rate. Such a resin-cured film is suitable as a black matrix, color filter, black columnar spacer, or BPDL (black matrix polymer light) component for image display elements.

Claims

1. A photosensitive resin composition, characterized by comprising: contains resin A, reactive diluent B, solvent C, photopolymerization initiator D, and coloring agent E, the resin A has structural unit a having an aromatic ring skeleton, structural unit b having a carboxyl group, structural unit c-1 having a (meth)acryloyloxy group, and structural unit d having a bridged alicyclic hydrocarbon group having 7 to 20 carbon atoms, the resin A contains resin A-1 and resin A-2, the content of the structural unit a having an aromatic ring skeleton of the resin A-1 is 5 to 30 mol% relative to the total amount of the structural units of the resin A-1, the content of the structural unit a having an aromatic ring skeleton of the resin A-2 is 35 mol% to 50 mol% relative to the total amount of the structural units of the resin A-2.

2. The photosensitive resin composition according to claim 1, the structural unit b having a carboxyl group is one or more selected from the group consisting of a structural unit b-1 derived from an unsaturated carboxylic acid, a structural unit b-2 derived from a polybasic acid, and a structural unit b-3 derived from a polybasic anhydride.

3. The photosensitive resin composition according to claim 1 or 2, the resin A-1 further contains a structural unit c-2 having a functional group that reacts with a carboxyl group.

4. The photosensitive resin composition according to claim 1 or 2, the structural unit a having an aromatic ring skeleton is one or more selected from the group consisting of a structural unit derived from styrene and a structural unit derived from benzyl (meth)acrylate.

5. The photosensitive resin composition according to claim 1 or 2, contains 10 to 90 mass% of the resin A-1 and contains 10 to 90 mass% of the resin A-2 relative to the total amount of the resin A, the resin A-1 is a resin obtained by adding a (meth)acrylic compound containing a carboxyl group to an epoxy group of a resin A-1 precursor having an epoxy group, and then adding a polybasic acid or a polybasic anhydride to a hydroxyl group generated by ring opening of the epoxy group, the resin A-2 is a resin obtained by adding a (meth)acrylate containing an epoxy group or a (meth)acrylate containing an isocyanate group to a part of a carboxyl group of a resin A-2 precursor having a carboxyl group, the resin A-1 precursor having an epoxy group is a polymer of a polymerizable monomer containing an aromatic ring, a (meth)acrylate containing an epoxy group, and a polymerizable monomer having a bridged alicyclic hydrocarbon group having 7 to 20 carbon atoms, the resin A-2 precursor having a carboxyl group is a polymer of a polymerizable monomer containing an aromatic ring, a polymerizable monomer containing a carboxyl group, and a polymerizable monomer having a bridged alicyclic hydrocarbon group having 7 to 20 carbon atoms.

6. The photosensitive resin composition according to claim 1 or 2, the coloring agent E is an organic black pigment.

7. The photosensitive resin composition according to claim 1 or 2, further contains a dispersant F.

8. The photosensitive resin composition according to claim 1 or 2, contains 2 to 20 mass% of the resin A, contains 3 to 20 mass% of the reactive diluent B, contains 50 to 90 mass% of the solvent C, and contains 3 to 30 mass% of the coloring agent E.

9. A black columnar spacer composed of a cured product of the photosensitive resin composition according to any one of claims 1 to 8.

10. An image display element characterized by comprising: The black columnar spacer according to claim 9 is provided.

11. A method for producing a photosensitive resin composition, characterized by comprising: The following steps are sequentially performed: Step I: a step of mixing resin Al, solvent Cl, colorant E, and, as an optional component, dispersant F; and Step II: a step of mixing resin A2, reactive diluent B, solvent C2, photopolymerization initiator D, and the mixture obtained in Step I, the resin Al and the resin A2 each have a structural unit a having an aromatic ring skeleton, a structural unit b having a carboxyl group, a structural unit c-1 having a (meth)acryloyloxy group, and a structural unit d having a bridged alicyclic hydrocarbon group having 7 to 20 carbon atoms, the resin Al is any one of resin A-l and resin A-2, the resin A2 is the other one of the resin Al and the resin A-2, the content of the structural unit a having an aromatic ring skeleton of the resin Al is 5 to 30 mol% relative to the total amount of the structural units of the resin Al, the content of the structural unit a having an aromatic ring skeleton of the resin A-2 is 35 mol% to 50 mol% relative to the total amount of the structural units of the resin A-2.

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