Resin composition, photosensitive resin composition, cured resin film, color filter, and image display element

Abstract

To provide a photosensitive resin composition which has good storage stability and developability, can form a resin cured film having sufficient hardness and solvent resistance, and has good low-temperature curability, and to provide a resin composition having excellent storage stability contained therein.SOLUTION: The resin composition contains a resin and a solvent. The resin is a resin obtained by adding, to a part of a functional group of a functional group-containing resin precursor, a compound having an ethylenically unsaturated group and a group reactive with the functional group. The functional group-containing resin precursor contains a constituent unit represented by formula (1) (R1 is a hydrogen atom or a methyl group; two of R2-R4 are alkoxy groups and the remaining one is a hydrogen atom or an alkyl group, or one of R2-R4 is an alkoxy group and the remaining two are each a hydrogen atom or an alkyl group; n is an integer of 1-10) and a constituent unit having the functional group. The solvent contains at least one selected from primary and secondary alcohols.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] Conventionally, some image display devices such as displays are equipped with color filters, which are typically formed by baking a resin composition on a substrate at a temperature above 200°C to harden it. In recent years, with the trend toward more flexible and wearable displays, substrate materials are being replaced by organic materials such as resins, etc. Furthermore, in order to realize image display elements with even higher brightness and contrast, colorants used in color filters are being replaced by materials such as dyes, fluorescent compounds, and quantum dots, rather than pigments.

[0003] BACKGROUND ART For example, Patent Document 1 discloses a resin composition that has been conventionally used as a material for color filters. Patent Document 1 discloses a colored photocurable resin composition comprising a photocurable compound (A), a binder resin (B), a photoinitiator (D), and a solvent (E), wherein the photocurable compound (A) is a carboxyl group-containing dipentaerythritol pentaacrylate, and the binder resin (B) contains one or more of a tetrahydropyran structure or a tetrahydrofuran structure in the main chain structure. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2015-184675 Summary of the Invention [Problem to be solved by the invention]

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

[0006] However, when conventional resin compositions are heated at a low temperature for curing, they do not provide a cured product having sufficient hardness and solvent resistance. Color filters made of cured products with insufficient hardness are easily scratched. Therefore, in image display elements equipped with color filters, there is a risk of display defects due to scratches on the color filter. Furthermore, in color filters equipped in image display elements, there is a tendency to increase the content of colorant in the resin composition used as the material for the color filter in order to improve color reproducibility. Paints have a higher solubility in solvents than pigments. Therefore, if the solvent resistance of a color filter is insufficient, there is a risk that the paint contained in the color filter will dissolve in the solvent, causing a change in the chromaticity of the color filter.

[0007] Furthermore, resin compositions used as materials for color filters are required to have sufficient storage stability and developability.

[0008] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a photosensitive resin composition having excellent storage stability and developability, and good low-temperature curing properties that can form a cured resin film having sufficient hardness and solvent resistance, and a resin composition contained in the photosensitive resin composition that has excellent storage stability. Another object of the present invention is to provide a cured resin film that is made of a cured product of the photosensitive resin composition of the present invention and has sufficient hardness and solvent resistance; a color filter that has a colored pattern made of the cured product of the photosensitive resin composition of the present invention; and an image display element that is equipped with this color filter. [Means for solving the problem]

[0009] The present invention includes the following aspects. [1] A composition comprising a resin (A) and a solvent (D), the resin (A) is a resin in which a compound (ma-4) having a group reactive with the functional group and an ethylenically unsaturated group is added to a part of the functional group of the functional group-containing resin precursor (a), the functional group-containing resin precursor (a) contains a structural unit (a-1) represented by the following formula (1) and a structural unit (a-2) having the functional group, The resin composition is characterized in that the solvent (D) contains at least one selected from primary alcohols having 3 to 10 carbon atoms and secondary alcohols having 3 to 10 carbon atoms.

[0010] [ka] (In formula (1), R 1 represents a hydrogen atom or a methyl group. 2 ~R 4 two of which are independently an alkoxy group having 1 to 6 carbon atoms, and the remaining one is one selected from a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, or R 2 ~R 4 One of the groups is an alkoxy group having 1 to 6 carbon atoms, and the remaining two groups are each independently one selected from a hydrogen atom and an alkyl group having 1 to 6 carbon atoms. n is an integer of 1 to 10.

[0011] [2] In the formula (1), R 2 ~R 4The resin composition according to [1], wherein two of the groups are independently an alkoxy group having 1 to 6 carbon atoms, and the remaining group is an alkyl group having 1 to 6 carbon atoms. [3] The resin composition according to [1] or [2], wherein the functional group possessed by the structural unit (a-2) is at least one selected from the group consisting of a carboxy group, a hydroxy group, an isocyanato group, an acid anhydride, and an epoxy group.

[0012] [4] The resin composition according to any one of [1] to [3], wherein the compound (ma-4) is one or more selected from the group consisting of (meth)acryloyl group-containing isocyanates, (meth)acryloyl group-containing hydroxy compounds, (meth)acryloyl group-containing acid anhydrides, (meth)acryloyl group-containing carboxy compounds, (meth)acryloyl group-containing epoxy compounds, and (meth)acryloyl group-containing amino compounds. [5] The functional group of the structural unit (a-2) is at least one selected from a carboxy group and a hydroxy group, The resin composition according to any one of [1] to [4], wherein the compound (ma-4) is a (meth)acryloyl group-containing isocyanate.

[0013] [6] The functional group of the structural unit (a-2) is an isocyanato group, The resin composition according to any one of [1] to [4], wherein the compound (ma-4) is at least one selected from a (meth)acryloyl group-containing hydroxy compound and a (meth)acryloyl group-containing amino compound. [7] The resin composition according to any one of [1] to [6], wherein the resin (A) is a resin in which a compound (ma-5) having a group reactive with the functional group and a carboxy group is further added to a portion of the functional group of the functional group-containing resin precursor (a).

[0014] [8] The resin composition according to any one of [1] to [7], wherein the total content of the primary alcohol and the secondary alcohol is 10 to 95 mass % relative to 100 mass % of the solvent (D).

[0015] [9] A resin composition according to any one of [1] to [8], a reactive diluent (B); A photosensitive resin composition comprising: a photopolymerization initiator (C);

[0016]

[10] The photosensitive resin composition according to [9], further comprising a colorant (E).

[11] For a total of 100 parts by mass of components excluding the solvent (D), The resin (A) is contained in an amount of 10 parts by mass to 85 parts by mass, The reactive diluent (B) is contained in an amount of 10 parts by mass to 85 parts by mass, The photopolymerization initiator (C) is contained in an amount of 0.1 to 30 parts by mass, The solvent (D) is contained in an amount of 20 to 1000 parts by mass, The photosensitive resin composition according to

[10] , comprising 4 to 85 parts by mass of the colorant (E).

[0017]

[12] A cured resin film comprising a cured product of the photosensitive resin composition according to any one of [9] to

[11] .

[13] A color filter having a colored pattern made of a cured product of the photosensitive resin composition according to

[10] or

[11] .

[14] An image display device comprising the color filter according to

[13] . [Effects of the Invention]

[0018] According to the present invention, it is possible to provide a photosensitive resin composition having excellent storage stability and developability, and having good low-temperature curing properties that can form a cured resin film having sufficient hardness and solvent resistance. Furthermore, according to the present invention, it is possible to provide a resin composition having excellent storage stability, which is contained in the photosensitive resin composition of the present invention as a material for the photosensitive resin composition. Furthermore, according to the present invention, there can be provided a cured resin film which is made of a cured product of the photosensitive resin composition of the present invention and has sufficient hardness and solvent resistance, a color filter having a colored pattern made of the cured product of the photosensitive resin composition of the present invention, and an image display element which is equipped with this color filter. [Brief explanation of the drawings]

[0019] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of a color filter according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0020] The resin composition, photosensitive resin composition, cured resin 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 following embodiments. 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.

[0021] <Resin composition> The resin composition of the present embodiment contains a resin (A) and a solvent (D). [Resin (A)] The resin (A) contained in the resin composition of this embodiment is a resin in which a compound (ma-4) (hereinafter sometimes abbreviated as "compound (ma-4)") having a group reactive with the functional group and an ethylenically unsaturated group is added to a portion of the functional group possessed by the functional group-containing resin precursor (a).

[0022] The functional group-containing resin precursor (a) contains a structural unit (a-1) represented by the following formula (1) (hereinafter sometimes abbreviated as "structural unit (a-1)") and a structural unit (a-2) having the functional group (hereinafter sometimes abbreviated as "structural unit (a-2)"). The functional group-containing resin precursor (a) may optionally contain a structural unit (a-3) other than the structural units (a-1) and (a-2) (hereinafter sometimes abbreviated as "structural unit (a-3)"). There are no particular restrictions on the number of repeats and the bonding order of the structural unit (a-1), the structural unit (a-2), and the optionally contained structural unit (a-3) contained in the functional group-containing resin precursor (a).

[0023] [ka] (In formula (1), R 1 represents a hydrogen atom or a methyl group. 2 ~R 4 two of which are independently an alkoxy group having 1 to 6 carbon atoms, and the remaining one is one selected from a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, or R 2 ~R 4 One of the groups is an alkoxy group having 1 to 6 carbon atoms, and the remaining two groups are each independently one selected from a hydrogen atom and an alkyl group having 1 to 6 carbon atoms. n is an integer of 1 to 10.

[0024] [Structural unit (a-1)] The structural unit (a-1) of the functional group-containing resin precursor (a) is represented by the above formula (1). The photosensitive resin composition using the resin composition containing the resin (A) as a raw material has good low-temperature curability, which allows the formation of a cured resin film having sufficient hardness and solvent resistance, because the functional group-containing resin precursor (a) contains the structural unit (a-1) having a silyl group.

[0025] In formula (1), R 1 represents a hydrogen atom or a methyl group. 1 is preferably a methyl group because of the ease of availability of raw materials. In formula (1), n ​​is an integer of 1 to 10. In terms of ease of availability of raw materials, n is preferably an integer of 1 to 4, and more preferably 3.

[0026] In formula (1), R 2 ~R 4 In formula (1), one or two of R are alkoxy groups having 1 to 6 carbon atoms. 2 ~R 4 When two of R are independently an alkoxy group having 1 to 6 carbon atoms, the remaining one is one selected from a hydrogen atom and an alkyl group having 1 to 6 carbon atoms. 2 ~R 4 When one of the groups is an alkoxy group having 1 to 6 carbon atoms, the remaining two groups are each independently one selected from a hydrogen atom and an alkyl group having 1 to 6 carbon atoms.

[0027] In formula (1), R 2 ~R 4 One or two of the R in formula (1) are alkoxy groups having 1 to 6 carbon atoms. 2 ~R 4 One or two of these function as crosslinking points in the resin (A). As a result, a photosensitive resin composition using a resin composition containing the resin (A) as a raw material can form a cured film having sufficient hardness and solvent resistance. The structural unit (a-1) is a structural unit that allows a photosensitive resin composition containing the resin (A) to form a cured resin film having superior hardness and solvent resistance, and therefore, R 2 ~R 4 Preferably, two of R in formula (1) are independently an alkoxy group having 1 to 6 carbon atoms. 2 ~R 4 When two of them are alkoxy groups having 1 to 6 carbon atoms, it is preferable that the two alkoxy groups having 1 to 6 carbon atoms are the same, since this facilitates the production of the functional group-containing resin precursor (a).

[0028] R 2 ~R 4Of these, one or two of the alkoxy groups having 1 to 6 carbon atoms are preferably alkoxy groups having 1 to 4 carbon atoms, more preferably methoxy groups or ethoxy groups, and even more preferably ethoxy groups. This is because excellent developability can be obtained when a resin composition containing resin (A) is used as a raw material for a photosensitive resin composition. Furthermore, when the alkoxy groups having 1 to 6 carbon atoms are ethoxy groups, resin (A) is less susceptible to change over time and has excellent storage stability compared to when they are methoxy groups.

[0029] In addition, in formula (1), R 2 ~R 4 one or two of the groups are selected from a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, and R 2 ~R 4 It is preferable that at least one of the R in formula (1) is an alkyl group having 1 to 6 carbon atoms. In this case, a photosensitive resin composition using a resin composition containing resin (A) as a raw material can form a cured resin film having superior hardness and solvent resistance, compared to when a hydrogen atom is used instead of the alkyl group having 1 to 6 carbon atoms. 2 ~R 4 When two of them are alkyl groups having 1 to 6 carbon atoms, it is preferable that the two alkyl groups having 1 to 6 carbon atoms are the same, since this facilitates the production of the functional group-containing resin precursor (a).

[0030] R 2 ~R 4 When one or two of the groups are alkyl groups having 1 to 6 carbon atoms, the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group. This is because excellent developability can be obtained when a resin composition containing resin (A) is used as a raw material for a photosensitive resin composition.

[0031] The structural unit (a-1) is R 2 ~R 4Preferably, two of R are independently an alkoxy group having 1 to 6 carbon atoms, and the remaining one is an alkyl group having 1 to 6 carbon atoms. In this case, a photosensitive resin composition using a resin composition containing resin (A) as a raw material can form a cured resin film having superior hardness and solvent resistance. 2 ~R 4 In comparison with the case where all of are alkoxy groups having 1 to 6 carbon atoms, the storage stability of a resin composition containing the resin (A) and a photosensitive resin composition using this as a raw material is improved.

[0032] Specific examples of the structural unit (a-1) represented by formula (1) include a structural unit derived from 3-(meth)acryloyloxypropylmethyldimethoxysilane (in formula (1), R 1 is a hydrogen atom or a methyl group, and R 2 is a methyl group, and R 3 and R 4 is a methoxy group, and n is 3), a structural unit derived from 3-(meth)acryloyloxypropylethyldimethoxysilane (in formula (1), R 1 is a hydrogen atom or a methyl group, and R 2 is an ethyl group, and R 3 and R 4 is a methoxy group, and n is 3), a structural unit derived from 3-(meth)acryloyloxypropylmethyldiethoxysilane (in formula (1), R 1 is a hydrogen atom or a methyl group, and R 2 is a methyl group, and R 3 and R 4 is an ethoxy group, and n is 3), a structural unit derived from 3-(meth)acryloyloxypropylethyldiethoxysilane (in formula (1), R 1 is a hydrogen atom or a methyl group, and R 2 is an ethyl group, and R 3 and R 4 is an ethoxy group and n is 3).

[0033] Among these, from the viewpoints of ease of material availability and reactivity during synthesis of the functional group-containing resin precursor (a), structural units derived from 3-(meth)acryloyloxypropylmethyldimethoxysilane and structural units derived from 3-(meth)acryloyloxypropylmethyldiethoxysilane are preferred as structural unit (a-1). The structural unit (a-1) contained in the functional group-containing resin precursor (a) may be of one type, or may be of two or more types.

[0034] The content of the structural unit (a-1) is preferably 2 to 80 mol %, more preferably 5 to 70 mol %, and even more preferably 5 to 60 mol %, of all structural units of the functional group-containing resin precursor (a). When the content of the structural unit (a-1) is 2 mol % or more, a photosensitive resin composition using a resin composition containing resin (A) as a raw material exhibits good low-temperature curing properties, allowing the formation of a cured resin film with sufficient hardness and solvent resistance. When the content of the structural unit (a-1) is 80 mol % or less, the content of the structural unit (a-2) having a functional group in all structural units of the functional group-containing resin precursor (a) can be sufficiently ensured. Therefore, a resin (A) to which a sufficient amount of compound (ma-4) is added can be obtained. A photosensitive resin composition containing a resin (A) having a sufficient amount of ethylenically unsaturated groups derived from compound (ma-4) can form a cured resin film with better solvent resistance.

[0035] [Structural unit (a-2) having a functional group] The structural unit (a-2) of the functional group-containing resin precursor (a) does not contain silicon and has a functional group in the functional group-containing resin precursor (a). The structural unit (a-2) contained in the functional group-containing resin precursor (a) may be of one type or two or more types.

[0036] In the resin composition containing resin (A), the functional group-containing resin precursor (a) contains the structural unit (a-2), and thus a compound (ma-4) having an ethylenically unsaturated group is added to a portion of the functional group of the functional group-containing resin precursor (a). The photosensitive resin composition using the resin composition of this embodiment as a raw material contains resin (A) to which compound (ma-4) is added, and therefore can form a cured resin film with good hardness and solvent resistance.

[0037] The functional group possessed by the structural unit (a-2) is preferably one or more selected from a carboxy group, a hydroxy group, an isocyanato group, an acid anhydride, and an epoxy group, and particularly preferably includes one or more selected from a carboxy group and a hydroxy group. When the functional group of the structural unit (a-2) contains a carboxy group, the carboxy group of the functional group-containing resin precursor (a) can be reacted with a group of the compound (ma-4) that is reactive with the functional group of the structural unit (a-2), thereby adding the compound (ma-4) to the functional group-containing resin precursor (a), thereby producing a resin (A) having an ethylenically unsaturated group content. Furthermore, of the carboxy groups of the structural unit (a-2) contained in the functional group-containing resin precursor (a), the remaining carboxy groups that are not added with the compound (ma-4) can impart developability to a photosensitive resin composition containing the resin composition of this embodiment.

[0038] The structural unit (a-2) is preferably a structural unit derived from a functional group-containing ethylenically unsaturated compound (ma-2). The functional group-containing ethylenically unsaturated compound (ma-2) is not particularly limited as long as it does not contain silicon and has a functional group and an ethylenically unsaturated group. Examples of functional group-containing ethylenically unsaturated compounds (ma-2) include carboxy group-containing ethylenically unsaturated compounds (ma-21), hydroxy group-containing ethylenically unsaturated compounds (ma-22), isocyanato group-containing ethylenically unsaturated compounds (ma-23), epoxy group-containing ethylenically unsaturated compounds (ma-24), and ethylenically unsaturated group-containing acid anhydrides (ma-25).

[0039] Examples of the carboxy group-containing ethylenically unsaturated compound (ma-21) include (meth)acrylic acid, crotonic acid, cinnamic acid, vinyl sulfonic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, etc. Among these, (meth)acrylic acid is preferred from the viewpoints of availability, reactivity during synthesis of the functional group-containing resin precursor (a), and reactivity during modification of the functional group-containing resin precursor (a) to obtain the resin (A) to which the compound (ma-4) is added.

[0040] Examples of the hydroxy group-containing ethylenically unsaturated compound (ma-22) include hydroxy group-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate. Among these, from the viewpoints of availability, reactivity during synthesis of the functional group-containing resin precursor (a), and reactivity during modification of the functional group-containing resin precursor (a) to obtain the resin (A) to which the compound (ma-4) is added, hydroxyalkyl (meth)acrylates having a hydroxy group at the alkyl group terminal are preferred, and 2-hydroxyethyl (meth)acrylate is particularly preferred.

[0041] Examples of the isocyanato group-containing ethylenically unsaturated compound (ma-23) include isocyanato group-containing (meth)acrylates 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. Among these, isocyanatoalkyl (meth)acrylates having an isocyanato group at the alkyl group terminal are preferred, and 2-(meth)acryloyloxyethyl isocyanate is particularly preferred, from the viewpoints of availability, reactivity during synthesis of the functional group-containing resin precursor (a), and reactivity during modification of the functional group-containing resin precursor (a) to obtain the resin (A) to which the compound (ma-4) is added.

[0042] Examples of epoxy group-containing ethylenically unsaturated compounds (ma-24) include epoxy group-containing (meth)acrylates such as 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 epoxidized dicyclopentenyloxyethyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoints of availability, reactivity during synthesis of functional group-containing resin precursor (a), and reactivity during modification of functional group-containing resin precursor (a) to obtain resin (A) to which compound (ma-4) is added.

[0043] Examples of ethylenically unsaturated group-containing acid anhydrides (ma-25) include maleic anhydride, itaconic anhydride, ethylmaleic anhydride, methylitaconic anhydride, chloromaleic anhydride, citraconic anhydride, 2-norbornene-5,6-dicarboxylic anhydride, and 4-[2-(methacryloyloxy)ethoxycarbonyl]phthalic anhydride.

[0044] The content of the structural unit (a-2) is preferably 10 to 98 mol %, more preferably 30 to 95 mol %, and even more preferably 40 to 95 mol % of all structural units of the functional group-containing resin precursor (a). When the content of the structural unit (a-2) is 10 mol % or more, a sufficient amount of compound (ma-4) can be added to the functional groups of the functional group-containing resin precursor (a), thereby producing a resin (A) having a sufficient amount of ethylenically unsaturated groups. A photosensitive resin composition containing a resin (A) to which a sufficient amount of compound (ma-4) has been added can form a cured resin film with good solvent resistance. When the content of the structural unit (a-2) is 98 mol % or less, a sufficient amount of structural unit (a-1) can be ensured.

[0045] When the structural unit (a-2) contains a structural unit derived from a carboxyl group-containing ethylenically unsaturated compound (ma-21), the content thereof is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and even more preferably 20 to 50 mol%, of all structural units of the functional group-containing resin precursor (a). When the content of the structural unit derived from the carboxyl group-containing ethylenically unsaturated compound (ma-21) is 5 mol% or more, the effect of the functional group containing a carboxyl group in the structural unit (a-2) can be fully obtained. Furthermore, when the content of the structural unit derived from the carboxyl group-containing ethylenically unsaturated compound (ma-21) is 70 mol% or less, it is preferable because it is easier to adjust the development time.

[0046] [Other structural units (a-3)] The functional group-containing resin precursor (a) may contain a structural unit (a-3) other than the structural units (a-1) and (a-2) as necessary. The structural unit (a-3) does not contain a group represented by the above formula (1) or a functional group. The structural unit (a-3) contained in the functional group-containing resin precursor (a) may be of only one type, or may be of two or more types.

[0047] The structural unit (a-3) is preferably a structural unit derived from an ethylenically unsaturated compound (ma-3) other than the compound that becomes the structural unit (a-1) or the structural unit (a-2) by polymerization. Examples of other ethylenically unsaturated compounds (ma-3) include dienes such as butadiene, (meth)acrylic acid esters, (meth)acrylic acid amides, styrenes, unsaturated dicarboxylic acid diesters, and other vinyl compounds.

[0048] Specific examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, benzyl (meth)acrylate, isoamyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, ethylcyclohexyl (meth)acrylate, rosin (meth)acrylate, norbornyl (meth)acrylate, 5-methylnorbornyl (meth)acrylate, and allyl (meth)acrylate. acrylate, tetrahydrofurfuryl (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, triphenylmethyl (meth)acrylate, cumyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, naphthalene (meth)acrylate, anthracene (meth)acrylate, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, hexamethylpiperidyl (meth)acrylate, and the like.

[0049] As the (meth)acrylic acid ester, a compound having a blocked isocyanato group obtained by blocking the isocyanato group of an isocyanato group-containing (meth)acrylate with a blocking agent may be used. Examples of the isocyanato group-containing (meth)acrylate include the compounds exemplified as the isocyanato group-containing ethylenically unsaturated compound (ma-23) described above, which is a compound that becomes the structural unit (a-2).

[0050] Specific examples of blocking agents used for blocking the isocyanato groups include lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam; alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol, and cyclohexanol; phenols such as phenol, cresol, xylenol, ethylphenol, o-isopropylphenol, and butylphenols such as p-tert-butylphenol, p-tert-octylphenol, nonylphenol, dinonylphenol, styrenated phenol, oxybenzoic acid esters, thymol, p-naphthol, p-nitrophenol, and p-chlorophenol; and dimethyl malonate, diethyl malonate, methyl acetoacetate, acetoacetate, and the like. Examples of such amines include active methylene-based amines such as ethyl acetate and acetylacetone; mercaptan-based amines such as diphenylamine, phenylnaphthylamine, aniline, and carbazole; acid amide-based amines such as acetanilide, acetanisidide, acetic acid amide, and benzamide; acid imide-based amines such as succinimide and maleimide; imidazole-based amines such as imidazole, 2-methylimidazole, and 2-ethylimidazole; urea-based amines such as urea, thiourea, and ethyleneurea; carbamate-based amines such as N-phenylphenylcarbamate and 2-oxazolidone; imine-based amines such as ethyleneimine and polyethyleneimine; oxime-based amines such as formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, and cyclohexanone oxime; and bisulfite-based amines such as sodium bisulfite and potassium bisulfite.

[0051] Specific examples of (meth)acrylic acid amides include (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diethylamide, (meth)acrylic acid N,N-dipropylamide, (meth)acrylic acid N,N-di-isopropylamide, (meth)acrylic acid anthracenylamide, N-isopropyl(meth)acrylamide, (meth)acrylic morpholine, and diacetone(meth)acrylamide.

[0052] Specific examples of styrenes include styrene, α-, o-, m-, p-alkyl, nitro, cyano and amide derivatives of styrene. Specific examples of the unsaturated dicarboxylic acid diester include diethyl citraconate, diethyl maleate, diethyl fumarate, and diethyl itaconate.

[0053] Specific examples of other vinyl compounds include norbornene (bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, tetracyclo[4.4.0.12,5.17,10]dodec-3-ene, 8-methyltetracyclo[4.4.0.12,5.17,10]dodec-3-ene, 8-ethyl ... Tetrtetracyclo[4.4.0.12,5.17,10]dodec-3-ene, dicyclopentadiene, tricyclo[5.2.1.02,6]dec-8-ene, tricyclo[5.2.1.02,6]dec-3-ene, tricyclo[4.4.0.12,5]undec-3-ene, tricyclo[6.2.1.01,8]undec-9-ene, tricyclo[6.2.1.01,8]undec-4-ene -ene, tetracyclo[4.4.0.12,5.17,10.01,6]dodec-3-ene, 8-methyltetracyclo[4.4.0.12,5.17,10.01,6]dodec-3-ene, 8-ethylidenetetracyclo[4.4.0.12,5.17,12]dodec-3-ene, 8-ethylidenetetracyclo[4.4.0.12,5.17,10.01,6]dodec-3-ene, pentacyclo[4.4.0.12,5.17,10.01,6]dodec-3-ene, Examples of the vinyl ether include cyclo[6.5.1.13,6.02,7.09,13]pentadec-4-ene, pentacyclo[7.4.0.12,5.19,12.08,13]pentadec-3-ene, (meth)acrylic acid anilide, (meth)acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylpyridine, vinyl acetate, and vinyltoluene.

[0054] Among these, as the other ethylenically unsaturated compounds (ma-3), from the viewpoints of ease of availability and reactivity when synthesizing the functional group-containing resin precursor (a), (meth)acrylic acid esters and other vinyl compounds are preferred, with methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, styrene, vinyltoluene and norbornene being preferred, and dicyclopentanyl (meth)acrylate, styrene and vinyltoluene being more preferred.

[0055] When the functional group-containing resin precursor (a) contains the structural unit (a-3), its content is preferably 1 to 50 mol %, more preferably 3 to 40 mol %, and even more preferably 5 to 30 mol %, of all structural units in the functional group-containing resin precursor (a). When the content of the structural unit (a-3) is 1 mol % or more, the effects of including the structural unit (a-3) can be fully obtained. Furthermore, when the content of the structural unit (a-3) is 50 mol % or less, the contents of the structural unit (a-1) and the structural unit (a-2) can be fully ensured.

[0056] [Compound (ma-4)] The compound (ma-4) has a group reactive with the functional group of the functional group-containing resin precursor (a) and an ethylenically unsaturated group. The compound (ma-4) added to a part of the functional group of the functional group-containing resin precursor (a) may be one type or two or more types. Since resin (A) is obtained by adding compound (ma-4) to some of the functional groups of functional group-containing resin precursor (a) to introduce an ethylenically unsaturated group, a photosensitive resin composition using a resin composition containing resin (A) as a raw material can form a cured resin film with excellent hardness and solvent resistance.

[0057] Examples of the ethylenically unsaturated group contained in the compound (ma-4) include a (meth)acryloyl group, a vinyl group, an allyl group, and the like, with a (meth)acryloyl group being preferred. When the ethylenically unsaturated group contained in the compound (ma-4) is a (meth)acryloyl group, the photosensitive resin composition containing the resin (A) can form a cured resin film with better solvent resistance. Furthermore, when the resin composition containing the resin (A) is used as a raw material for the photosensitive resin composition, excellent developability can be obtained.

[0058] Examples of the compound (ma-4) in which the ethylenically unsaturated group is a (meth)acryloyl group include a (meth)acryloyl group-containing carboxy compound, a (meth)acryloyl group-containing hydroxy compound, a (meth)acryloyl group-containing isocyanate, a (meth)acryloyl group-containing epoxy compound, a (meth)acryloyl group-containing acid anhydride, and a (meth)acryloyl group-containing amino compound.

[0059] Examples of the (meth)acryloyl group-containing carboxy compound include the compounds exemplified above as the carboxy group-containing ethylenically unsaturated compound (ma-21), which is the compound that becomes the structural unit (a-2). Examples of the (meth)acryloyl group-containing hydroxy compound include the hydroxy group-containing (meth)acrylates exemplified above as the hydroxy group-containing ethylenically unsaturated compound (ma-22), which is the compound that becomes the structural unit (a-2).

[0060] Examples of the (meth)acryloyl group-containing isocyanate include the isocyanato group-containing (meth)acrylates exemplified as the above-mentioned isocyanato group-containing ethylenically unsaturated compound (ma-23), which is the compound that becomes the structural unit (a-2). Examples of the (meth)acryloyl group-containing epoxy compound include the epoxy group-containing (meth)acrylates exemplified above as the epoxy group-containing ethylenically unsaturated compound (ma-24), which is the compound that becomes the structural unit (a-2).

[0061] An example of the (meth)acryloyl group-containing acid anhydride is 4-[2-(methacryloyloxy)ethoxycarbonyl]phthalic anhydride. Examples of (meth)acryloyl group-containing amino compounds include 3-(N,N-dimethylamino)propyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, and N-tert-butylaminoethyl (meth)acrylate.

[0062] The amount of compound (ma-4) added to the functional group-containing resin precursor (a) is preferably 1 to 40 moles, more preferably 5 to 30 moles, and even more preferably 6 to 25 moles, per 100 moles of the total structural units of the functional group-containing resin precursor (a). When the amount of compound (ma-4) added is 1 mole or more, sufficient compound (ma-4) is added, resulting in a resin (A) having sufficient ethylenically unsaturated groups. Therefore, a photosensitive resin composition using a resin composition containing resin (A) as a raw material can form a cured resin film with excellent hardness and solvent resistance. When the amount of compound (ma-4) added is 40 moles or less, the remaining unreacted compound (ma-4) can be suppressed after the reaction of modifying the functional group-containing resin precursor (a) to obtain resin (A) to which compound (ma-4) is added. Therefore, the storage stability of the resin composition containing resin (A) obtained by modifying the functional group-containing resin precursor (a) is improved.

[0063] The addition ratio of compound (ma-4) relative to the functional groups of the functional group-containing resin precursor (a), in other words, the ratio of compound (ma-4) relative to the content of structural units (a-2) in all structural units of the functional group-containing resin precursor (a), is preferably 1 to 80 mol%, more preferably 5 to 70 mol%, and even more preferably 10 to 60 mol%. When the addition ratio of compound (ma-4) is 1 mol% or more, sufficient addition of compound (ma-4) results in a resin (A) having a sufficient amount of ethylenically unsaturated groups. When the addition ratio of compound (ma-4) is 80 mol% or less, the remaining unreacted compound (ma-4) after the reaction to modify the functional group-containing resin precursor (a) to obtain resin (A) to which compound (ma-4) is added can be suppressed. Therefore, the storage stability of the resin composition containing resin (A) obtained by modifying functional group-containing resin precursor (a) is improved, and outgassing and other issues can be suppressed when obtaining a cured resin film made of a photosensitive resin composition using the resin composition as a raw material.

[0064] [Compound (ma-5)] If necessary, a compound (ma-5) may be added to a portion of the functional groups of the functional group-containing resin precursor (a). The compound (ma-5) does not have an ethylenically unsaturated group, but has a group reactive with the functional group of the functional group-containing resin precursor (a) and a carboxy group. The carboxy group of the compound (ma-5) can impart developability to a photosensitive resin composition containing the resin composition of this embodiment. Therefore, when the functional group-containing resin precursor (a) does not have a carboxy group, that is, when the functional group of the structural unit (a-2) does not contain a carboxy group, it is preferable that the compound (ma-5) be added to the functional group-containing resin precursor (a). The compound (ma-5) added to a portion of the functional group of the functional group-containing resin precursor (a) may be only one type, or two or more types.

[0065] Examples of the group reactive with the functional group of the compound (ma-5) include a hydroxy group and an amino group. Specific examples of the compound (ma-5) include 3-hydroxypropionic acid, alanine, glycine, 4-hydroxybenzoic acid, and 4-aminobenzoic acid.

[0066] When compound (ma-5) is added to functional group-containing resin precursor (a), the amount added is preferably 1 to 50 moles, more preferably 5 to 40 moles, and even more preferably 10 to 30 moles, per 100 moles of all structural units of functional group-containing resin precursor (a). When the amount of compound (ma-5) added is 1 mole or more, sufficient compound (ma-5) is added, resulting in resin (A) having sufficient carboxy groups. Therefore, sufficient developability can be imparted to a photosensitive resin composition containing a resin composition containing resin (A). When the content of compound (ma-5) is 50 moles or less, the remaining unreacted compound (ma-5) can be suppressed in the reaction for modifying functional group-containing resin precursor (a) to obtain resin (A) having compound (ma-5) added thereto. As a result, the influence of unreacted compound (ma-5) on the resin composition containing resin (A) obtained by modifying functional group-containing resin precursor (a) can be suppressed, resulting in good storage stability. Furthermore, when the amount of compound (ma-5) added is 50 moles or less, the proportion of functional group-containing resin precursor (a) to which compound (ma-5) is not added in resin (A) can be sufficiently ensured, and therefore, a photosensitive resin composition containing resin (A) can form a cured resin film having sufficient hardness and solvent resistance.

[0067] When compound (ma-5) is added to functional group-containing resin precursor (a), the total addition ratio of compound (ma-4) and compound (ma-5) to the functional groups of functional group-containing resin precursor (a), in other words, the total ratio of compound (ma-4) and compound (ma-5) to the content of structural unit (a-2) in all structural units of functional group-containing resin precursor (a), is preferably 2 to 90 mol%, more preferably 10 to 85 mol%, and even more preferably 20 to 85 mol%. When the total addition ratio of compound (ma-4) and compound (ma-5) is 2 mol% or more, the resin (A) can fully exhibit the effects of adding compound (ma-4) and compound (ma-5). When the total addition rate of compound (ma-4) and compound (ma-5) is 90 mol% or less, it is possible to prevent unreacted compound (ma-4) and / or compound (ma-5) from remaining after the reaction of modifying functional group-containing resin precursor (a) to obtain resin (A) to which compound (ma-4) and compound (ma-5) are added. As a result, the storage stability of the resin composition containing resin (A) obtained by modifying functional group-containing resin precursor (a) is improved, and outgassing and the like generated when obtaining a cured resin film made of a photosensitive resin composition using the resin composition as a raw material can be prevented.

[0068] The resin (A) is a resin in which the combination of the functional group of the structural unit (a-2) and the compound (ma-4) (or the combination of the functional group of the structural unit (a-2) and the compound (ma-4) and the compound (ma-5)) is as shown below. <1> ~ <5> Particularly preferred is a combination of any of the following: <1> ~ <5> Any of the above combinations is preferable because it is easy to produce in terms of reactivity.

[0069] <1> Resin (A) in which the functional group of the structural unit (a-2) is an isocyanato group, compound (ma-4) is one or more compounds selected from the group consisting of a (meth)acryloyl group-containing hydroxy compound, a (meth)acryloyl group-containing amino compound, and a (meth)acryloyl group-containing carboxy compound, and further, compound (ma-5) is added as necessary. <1> In the combination of (a), the compound (ma-4) is more preferably at least one selected from a (meth)acryloyl group-containing hydroxy compound and a (meth)acryloyl group-containing amino compound.

[0070] <2> Resin (A) in which the functional group possessed by the structural unit (a-2) is a hydroxy group, and the compound (ma-4) is at least one selected from the group consisting of a (meth)acryloyl group-containing isocyanate, a (meth)acryloyl group-containing acid anhydride, and a (meth)acryloyl group-containing carboxy compound. <2> In the combination of (a), the compound (ma-4) is more preferably a (meth)acryloyl group-containing isocyanate. <3> Resin (A) in which the functional group possessed by the structural unit (a-2) is an acid anhydride, and the compound (ma-4) is a (meth)acryloyl group-containing hydroxy compound.

[0071] <4> Resin (A) in which the functional group of the structural unit (a-2) is a carboxy group, and the compound (ma-4) is at least one selected from the group consisting of a (meth)acryloyl group-containing isocyanate compound, a (meth)acryloyl group-containing hydroxy compound, and a (meth)acryloyl group-containing epoxy compound. <4> In the combination of (a), the compound (ma-4) is more preferably a (meth)acryloyl group-containing isocyanate. <5> Resin (A) in which the functional group of the structural unit (a-2) is an epoxy group, and the compound (ma-4) is a (meth)acryloyl group-containing carboxy compound, and further, if necessary, the compound (ma-5) is added.

[0072] "Weight average molecular weight (Mw)" The weight-average molecular weight (Mw) of resin (A), in terms of polystyrene, is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, and most preferably 3,000 to 10,000. When the weight-average molecular weight (Mw) of resin (A) is 1,000 or more, when a resin composition containing resin (A) is used as a raw material for a photosensitive resin composition, the resulting photosensitive resin composition is less susceptible to defects such as chipping in the cured resin film after development. 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.

[0073] The weight average molecular weight (Mw) of the resin (A) in this embodiment is measured using gel permeation chromatography (GPC) under the following conditions and calculated in terms of polystyrene. Column: Showdex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko K.K.) Column temperature: 40℃ Sample: Tetrahydrofuran solution containing 0.2% by mass of resin (A) Developing solvent: tetrahydrofuran Detector: Differential refractometer (product name: Showdex (registered trademark) RI-71S, manufactured by Showa Denko K.K.) Flow rate: 1mL / min

[0074] 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 more, it is possible to optimize the target numerical ranges of the weight average molecular weight (Mw), acid value, etc., and to set the reaction conditions for producing resin (A) within a certain range, thereby enabling efficient production. When the molecular weight distribution (Mw / Mn) of resin (A) is 3.0 or less, when a resin composition containing resin (A) is used as a raw material for a photosensitive resin composition, a photosensitive resin composition can be obtained that does not exhibit variations in performance such as developability. The molecular weight distribution (Mw / Mn) is calculated using the chromatogram obtained by the GPC measurement.

[0075] "Acid value" The acid value of resin (A) is not particularly limited, but is preferably 10 KOHmg / g to 300 KOHmg / g, more preferably 20 KOHmg / g to 200 KOHmg / g, and most preferably 25 KOHmg / g to 150 KOHmg / g. When the acid value of resin (A) is 10 KOHmg / g or more, a photosensitive resin composition containing resin (A) can be used as a raw material for a photosensitive resin composition, resulting in a photosensitive resin composition with better developability. When the acid value of resin (A) is 300 KOHmg / g or less, a photosensitive resin composition containing resin (A) can be used as a raw material for a photosensitive resin composition, resulting in a photosensitive resin composition with good developability, as the exposed portion (photocured portion) does not dissolve in an alkaline developer.

[0076] The acid value of resin (A) is a value measured using a mixed indicator of bromothymol blue and phenol red in accordance with JIS K6901 5.3. The acid value of resin (A) means the number of milligrams of potassium hydroxide required to neutralize the acidic components contained in 1 g of resin (A).

[0077] "Silyl group equivalent" The silyl group equivalent of resin (A) is not particularly limited, but is preferably 200 g / mol to 5000 g / mol, more preferably 300 g / mol to 4000 g / mol, and most preferably 300 g / mol to 3000 g / mol. When the silyl group equivalent of resin (A) is 200 g / mol or more, a photosensitive resin composition containing resin (A) can form a cured resin film with superior hardness. Furthermore, when the silyl group equivalent of resin (A) is 200 g / mol or more, a photosensitive resin composition containing resin (A) can be used as a raw material for a photosensitive resin composition, resulting in a photosensitive resin composition with superior developability. Furthermore, when the silyl group equivalent of resin (A) is 5000 g / mol or less, a photosensitive resin composition containing resin (A) can form a cured resin film with superior hardness.

[0078] The silyl group equivalent of resin (A) is the molecular weight of resin (A) divided by the average number of silyl groups per molecule. The silyl group equivalent of resin (A) is a calculated value based on the amounts of polymerizable unsaturated compounds (raw material monomers) used as raw materials in synthesizing resin (A), compound (ma-4), and optionally compound (ma-5). If one molecule of resin (A) contains different types of silyl groups, all silyl groups are counted as silyl groups, regardless of their type.

[0079] "Double bond equivalent" The double bond equivalent of resin (A) is not particularly limited, but is preferably 200 g / mol to 5000 g / mol, more preferably 300 g / mol to 4000 g / mol, and most preferably 300 g / mol to 3000 g / mol. When the double bond equivalent of resin (A) is 200 g / mol or more, a photosensitive resin composition containing resin (A) can form a cured resin film with superior hardness. Furthermore, when the double bond equivalent of resin (A) is 200 g / mol or more, a photosensitive resin composition containing resin (A) can be used as a raw material to obtain a photosensitive resin composition with superior developability. Furthermore, when the double bond equivalent of resin (A) is 5000 g / mol or less, a photosensitive resin composition containing resin (A) can form a cured resin film with superior hardness.

[0080] The double bond equivalent of resin (A) is the molecular weight of resin (A) divided by the average number of unsaturated groups per molecule. The double bond equivalent of resin (A) is a calculated value based on the amounts of polymerizable unsaturated compounds (raw material monomers) used as raw materials when synthesizing resin (A), compound (ma-4), and optionally compound (ma-5). When different types of unsaturated groups are contained in one molecule of resin (A), all unsaturated groups are counted as unsaturated groups, regardless of their type.

[0081] <Method for producing resin (A)> To produce the resin (A) contained in the resin composition of this embodiment, first, a functional group-containing resin precursor (a) is produced, and then, the compound (ma-4) is added to some of the functional groups of the functional group-containing resin precursor (a) to obtain the resin (A).

[0082] (Production of functional group-containing resin precursor (a)) The functional group-containing resin precursor (a) can be produced, for example, by the following production method. That is, in the presence of a polymerization solvent, raw material monomers consisting of a compound (ma-1) represented by the following formula (2), a functional group-containing ethylenically unsaturated compound (ma-2), and optionally other ethylenically unsaturated compounds (ma-3) are copolymerized using a polymerization initiator according to a radical polymerization method known in the art. This produces the functional group-containing resin precursor (a).

[0083] [ka] (R in Equation (2) 1 ~R 4 and n is R in formula (1). 1 ~R 4 and n.)

[0084] 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, for example, at 50°C to 130°C for 1 hour to 20 hours while stirring. The compound (ma-1) represented by formula (2), the functional group-containing ethylenically unsaturated compound (ma-2), and the other ethylenically unsaturated compound (ma-3) used as needed can be any of the compounds listed as raw materials (origins) for each of the structural units (a-1) to (a-3) described above.

[0085] (Polymerization solvent) The polymerization solvent used in producing the functional group-containing resin precursor (a) is not particularly limited as long as it is a solvent inert to the copolymerization reaction of the raw material monomers. The polymerization solvent used in producing the functional group-containing resin precursor (a) may be the same as the solvent contained in the solvent (D) contained in the resin composition, or may be partially or completely different from the solvent contained in the solvent (D). When the polymerization solvent used in producing the functional group-containing resin precursor (a) is partially or completely the same as the solvent contained in the solvent (D) contained in the resin composition, it can be used as part of the solvent (D) without separating or removing the polymerization solvent from the reaction solution after the copolymerization reaction is completed, which is preferable.

[0086] Examples of polymerization solvents used in producing the functional group-containing resin precursor (a) include those exemplified as other solvents that may be contained in the solvent (D) described below. Among these, (poly)alkylene glycol monoalkyl ether acetates are preferred because they have good compatibility with the primary alcohol having 3 to 10 carbon atoms and the secondary alcohol having 3 to 10 carbon atoms contained in the solvent (D) and also have good solubility for the resin (A). Propylene glycol monomethyl ether acetate is particularly preferred. It is preferable not to use alcohol as the polymerization solvent because it inhibits the addition reaction between the functional group in the functional group-containing resin precursor (a) and the group in the compound (ma-4) that is reactive with the functional group.

[0087] The amount of polymerization solvent used in producing the functional group-containing resin precursor (a) is not particularly limited, but is preferably 30 to 1,000 parts by mass, and more preferably 50 to 800 parts by mass, per 100 parts by mass of the raw material monomers. When the amount of polymerization solvent used is 30 parts by mass or more, the copolymerization reaction of the raw material monomers can be carried out stably, and coloration and gelation of the functional group-containing resin precursor (a) can be prevented. When the amount of polymerization solvent used is 1,000 parts by mass or less, a decrease in the molecular weight of the functional group-containing resin precursor (a) due to chain transfer can be suppressed, and the viscosity of the reaction solution can be controlled within an appropriate range.

[0088] (Polymerization initiator) The polymerization initiator that can be used in the copolymerization reaction of the raw material monomers is not particularly limited, and examples thereof include 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(isobutyrate) dimethyl, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate, etc. These polymerization initiators may be used alone or in combination of two or more. The amount of the 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, relative to 100 parts by mass of the raw material monomer.

[0089] (Addition reaction of compound (ma-4) (modification reaction of functional group-containing resin precursor (a))) Next, compound (ma-4) is added to some of the functional groups of functional group-containing resin precursor (a), and, if necessary, compound (ma-5) may be added to some of the functional groups of functional group-containing resin precursor (a). The addition reaction between the functional group of the functional group-containing resin precursor (a) and the compound (ma-4), or the addition reaction between the functional group of the functional group-containing resin precursor (a) and the compound (ma-4) and the compound (ma-5), can be carried out according to conventional methods.

[0090] For example, a method can be used in which compound (ma-4) (or compound (ma-4) and compound (ma-5)) is added to a reaction solution in which functional group-containing resin precursor (a) has been synthesized, and an addition reaction is carried out. Furthermore, in this addition reaction (modification reaction), there is no particular problem even if the reaction solution contains the polymerization solvent used in the copolymerization to produce functional group-containing resin precursor (a). Therefore, the addition reaction can be carried out without removing the polymerization solvent from the reaction solution after the copolymerization reaction to produce functional group-containing resin precursor (a) has been completed.

[0091] When compound (ma-5) is added to functional group-containing resin precursor (a), compound (ma-5) may be added to the reaction solution simultaneously with compound (ma-4), or may be added to the reaction solution separately from compound (ma-4). That is, the addition reaction between the functional group of functional group-containing resin precursor (a) and compound (ma-5) may be carried out before, after, or simultaneously with the addition reaction between the functional group of functional group-containing resin precursor (a) and compound (ma-4).

[0092] The reaction temperature in the addition reaction can be appropriately determined depending on the type of functional group possessed by the functional group-containing resin precursor (a) and the type of group reactive with the functional group possessed by compound (ma-4) (or compound (ma-4) and compound (ma-5)). Specifically, the reaction temperature is preferably 30°C to 150°C, and more preferably 50°C to 120°C. By setting the reaction temperature to 30°C or higher, the addition reaction can be allowed to proceed sufficiently. Furthermore, by setting the reaction temperature to 150°C or lower, gelation of the reaction solution can be suppressed and decomposition of the bond formed by the addition reaction can be suppressed.

[0093] (polymerization inhibitor) When the addition reaction is carried out, a polymerization inhibitor may be added to the reaction solution as needed to prevent gelation of the reaction solution due to the addition reaction. The polymerization inhibitor is not particularly limited, but examples thereof include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, and dibutylhydroxytoluene.

[0094] (catalyst) When carrying out the addition reaction, a catalyst may be added to the reaction solution as needed to promote the reaction. The catalyst is not particularly limited, but examples thereof include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, metal chelate compounds such as chromium, and tin compounds such as tin 2-ethylhexanoate and dibutyltin dilaurate (DBTDL).

[0095] [Solvent (D)] The solvent (D) contained in the resin composition of this embodiment is not particularly limited as long as it contains at least one selected from primary alcohols having 3 to 10 carbon atoms and secondary alcohols having 3 to 10 carbon atoms, is inactive to the resin (A), and is capable of dissolving the resin (A). The solvent (D) may or may not contain the polymerization solvent used in producing the functional group-containing resin precursor (a). When the solvent (D) contains the polymerization solvent used in producing the functional group-containing resin precursor (a), the addition reaction for producing the resin (A) can be carried out without removing the polymerization solvent from the reaction solution after the copolymerization reaction for producing the functional group-containing resin precursor (a) is completed, and the polymerization solvent can be used as it is as part or all of the solvent (D) for the resin composition without separating or removing it from the reaction solution after the addition reaction is completed.

[0096] The case where the solvent (D) does not contain the polymerization solvent used in producing the functional group-containing resin precursor (a) refers to the case where the resin (A) used as the raw material for the resin composition is one that has been separated and removed from the reaction solution in which the resin (A) was produced. In this case, regardless of the type and amount of the polymerization solvent used in producing the functional group-containing resin precursor (a), the type and content of the solvent (D) can be appropriately selected depending on the type of resin (A) and the intended use of the resin composition. That is, when the resin (A) is one that has been separated and removed from the reaction solution in which the resin (A) was produced, the solvent (D) may be the same as or different from the polymerization solvent used in producing the functional group-containing resin precursor (a).

[0097] The solvent (D) contains at least one selected from primary alcohols having 3 to 10 carbon atoms and secondary alcohols having 3 to 10 carbon atoms. Primary alcohols having 3 to 10 carbon atoms and secondary alcohols having 3 to 10 carbon atoms have stronger solvation in water than, for example, tertiary alcohols and non-alcohols, and can suppress the hydrolysis reaction of the alkoxysilyl group in the structural unit (a-1) represented by formula (1). Therefore, it is possible to prevent the hydrolysis reaction of the alkoxysilyl group from generating a silanol group, which would then undergo a self-condensation reaction, thereby increasing the molecular weight of the resin (A). Therefore, by including the primary alcohol and / or secondary alcohol in the solvent (D), the resin composition containing the solvent (D) exhibits good storage stability. The solvent (D) may be used singly or in combination of two or more.

[0098] Examples of the primary alcohol solvent having 3 to 10 carbon atoms and the secondary alcohol solvent having 3 to 10 carbon atoms contained in the solvent (D) 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, dodecyl alcohol, and 3-methoxy-1-butanol; and secondary alcohols such as benzyl alcohol.

[0099] Specific examples of (poly)alkylene glycol monoalkyl ethers 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.

[0100] The solvent (D) contained in the resin composition of the present embodiment preferably contains a primary alcohol having 3 to 10 carbon atoms from the viewpoint of storage stability as a resin composition, and is preferably a (poly)alkylene glycol monoalkyl ether, more preferably 3-methoxy-1-butanol, from the viewpoint of easy availability and storage stability as a resin composition.

[0101] The solvent (D) may contain other solvents capable of dissolving the resin (A) in addition to at least one solvent selected from primary alcohols having 3 to 10 carbon atoms and secondary alcohols having 3 to 10 carbon atoms.

[0102] Specific examples of other solvents include tertiary alcohols such as tert-butyl alcohol and diacetone alcohol; (poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; 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. esters such as methyl phosphate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-butyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-butyl propionate, 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.

[0103] Among these, it is preferable to use (poly)alkylene glycol monoalkyl ether acetates as other solvents, and it is particularly preferable to use propylene glycol monomethyl ether acetate, because these have good compatibility with primary alcohols having 3 to 10 carbon atoms and secondary alcohols having 3 to 10 carbon atoms and also have good solubility for resin (A).

[0104] The total content of the primary alcohol having 3 to 10 carbon atoms and the secondary alcohol having 3 to 10 carbon atoms contained in the solvent (D) is preferably 10 to 95 mass%, more preferably 20 to 90 mass%, and even more preferably 20 to 80 mass%, relative to 100 mass% of the solvent (D). When the total content of the primary alcohol having 3 to 10 carbon atoms and the secondary alcohol having 3 to 10 carbon atoms is within the above range, the storage stability of the resin composition is further improved.

[0105] The content of the other solvent contained in solvent (D) is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 80% by mass, and even more preferably 20% by mass to 80% by mass, relative to 100% by mass of solvent (D). When the content of the other solvent contained in solvent (D) is within the above range, the content of one or more selected from primary alcohols having 3 to 10 carbon atoms and secondary alcohols having 3 to 10 carbon atoms contained in solvent (D) can be ensured.

[0106] The content of the solvent (D) 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, relative to 100 parts by mass of the total of the components in the resin composition excluding the solvent (D). When the content of the solvent (D) is within the above range, the viscosity of the resin composition can be adjusted to an appropriate range.

[0107] In addition to the above components, the resin composition of the present embodiment may contain known additives such as a leveling agent, a thermal polymerization inhibitor, etc. The content of the additives contained in the resin composition is not particularly limited as long as it does not impair the effects of the present invention.

[0108] <Method of manufacturing resin composition> The resin composition of this embodiment can be produced by mixing the resin (A) and the solvent (D) by a known method. When the solvent (D) contains the polymerization solvent used in producing the functional group-containing resin precursor (a), the resin composition of this embodiment may be a reaction solution containing the resin (A) obtained by carrying out an addition reaction to produce the resin (A) using a reaction solution in which a copolymerization reaction to produce the functional group-containing resin precursor (a) has been carried out.

[0109] The resin composition of this embodiment contains the resin (A) and the solvent (D), and the resin (A) is a functional group-containing resin precursor (a) to which (ma-4) is added to some of the functional groups. Therefore, the resin composition of this embodiment has excellent storage stability. Furthermore, the resin composition of this embodiment has good low-temperature curing properties and is suitable as a material for the photosensitive resin composition of this embodiment, which can form a cured resin film having sufficient hardness and solvent resistance.

[0110] <Photosensitive resin composition> Next, the photosensitive resin composition of this embodiment will be described in detail. The photosensitive resin composition of the present embodiment contains the resin composition of the present embodiment containing the resin (A) and the solvent (D), a reactive diluent (B), and a photopolymerization initiator (C). The photosensitive resin composition of the present embodiment may contain a colorant (E) as needed.

[0111] 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 60 parts by mass, relative to 100 parts by mass of the total components contained in the photosensitive resin composition excluding solvent (D). When the content of resin (A) is 10 parts by mass or more, good developability is obtained, and a cured resin film with good hardness and solvent resistance is obtained. When the content of resin (A) is 85 parts by mass or less, the photosensitive resin composition has good photocurability.

[0112] The content of the solvent (D) in the photosensitive resin composition of this embodiment is preferably 20 to 1000 parts by mass, more preferably 30 to 800 parts by mass, and most preferably 50 to 700 parts by mass, relative to 100 parts by mass of the total of the components contained in the photosensitive resin composition excluding the solvent (D). When the content of the solvent (D) is within the above range, the viscosity of the photosensitive resin composition can be adjusted to an appropriate range.

[0113] [Reactive diluent (B)] The reactive diluent (B) contained in the photosensitive resin composition of this embodiment is not particularly limited as long as it is a low-molecular-weight compound having an ethylenically unsaturated group such as a vinyl group, an allyl group, or a (meth)acryloyloxy group. 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, and triallyl cyanurate.

[0114] Specific examples of aromatic vinyl monomers include styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, divinylbenzene, diallyl phthalate, and diallyl benzene phosphonate. 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.

[0115] 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 tris(hydroxyethyl)isocyanurate tri(meth)acrylate.

[0116] Among these, polyfunctional (meth)acrylates are preferred as the reactive diluent (B) because they can produce a photosensitive resin composition with good photocurability (reactivity), and dipentaerythritol penta(meth)acrylate and / or dipentaerythritol hexa(meth)acrylate are particularly preferred. These reactive diluents (B) may be used singly or in combination of two or more.

[0117] 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 60 parts by mass, relative to 100 parts by mass of the total of the components contained in the photosensitive resin composition excluding the solvent (D). 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.

[0118] [Photopolymerization initiator (C)] The photopolymerization initiator (C) contained in the photosensitive resin composition of this embodiment is not particularly limited as long as it is a compound that generates radicals upon irradiation with light. Examples of the photopolymerization initiator (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-hydroxycyclohexyl phenyl 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. 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-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], and 1-(o-acetyloxime); 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1; acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; and xanthones. These photopolymerization initiators (C) may be used singly or in combination of two or more.

[0119] 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 15 parts by mass, relative to 100 parts by mass of the total of all components contained in the photosensitive resin composition excluding the solvent (D). When the content of the photopolymerization initiator (C) is 0.1 part by mass or more, the photosensitive resin composition has sufficient photocurability. When the content of the photopolymerization initiator (C) is 30 parts by mass or less, the photopolymerization initiator (C) does not adversely affect the storage stability of the photosensitive resin composition or the performance of the cured resin film.

[0120] [Colorant (E)] The photosensitive resin composition of this embodiment may further contain a colorant (E) as needed. Known dyes and / or pigments can be used as the colorant (E). When a dye is used as the colorant (E), a colored pattern with higher brightness can be obtained compared to when a pigment is used, and the photosensitive resin composition exhibits good alkali developability.

[0121] As the dye, from the viewpoints of solubility in the solvent (D) and the alkaline developer, interaction with other components in the photosensitive resin composition, heat resistance, etc., it is preferable to use an acid dye having an acidic group such as a carboxy group, a salt of an acid dye with a nitrogen compound, a sulfonamide of an acid dye, etc. Examples of such dyes include VALIFAST BLUE 2620; 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 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 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 derivatives thereof. Among these, azo-based, xanthene-based, anthraquinone-based, or phthalocyanine-based acid dyes are preferred. These dyes may be used alone or in combination of two or more, depending on the desired pixel color.

[0122] 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, and 214; orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, and 73; and CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 16 Examples of suitable pigments include red pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, and 60; 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, 7, carbon black, titanium black, and iron oxide. These pigments may be used alone or in combination depending on the desired pixel color.

[0123] When a pigment is used as the colorant (E), a known dispersant may be blended into the photosensitive resin composition to improve the dispersibility of the colorant (E). It is preferable to use a polymeric dispersant that exhibits excellent dispersion stability over time. Examples of polymeric dispersants include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic modified ester-based dispersants. Commercially available polymeric dispersants include those sold under the trade names EFKA (manufactured by EFKA Chemicals BV), Disperbyk (manufactured by BYK), Disparlon (manufactured by Kusumoto Chemicals Co., Ltd.), and SOLSPERSE (manufactured by Zeneca). The amount of dispersant blended may be appropriately determined depending on the type and amount of the pigment used as the colorant (E).

[0124] The content of colorant (E) in the photosensitive resin composition of this embodiment is preferably 4 to 85 parts by mass, more preferably 9 to 70 parts by mass, and most preferably 14 to 49 parts by mass, based on 100 parts by mass of the total components of the photosensitive resin composition excluding solvent (D). When the content of colorant (E) is 4 parts by mass or more, the effect of containing colorant (E) becomes significant, resulting in a photosensitive resin composition suitable as a material for colored patterns in color filters. When the content of colorant (E) is 85 parts by mass or less, the colorant (E) in the photosensitive resin composition does not interfere with the curability of the photosensitive resin composition, and the photosensitive resin composition has good low-temperature curability.

[0125] The photosensitive resin composition of this embodiment may contain, in addition to a resin composition containing a resin (A) and a solvent (D), a reactive diluent (B), a photopolymerization initiator (C), and an optional colorant (E), one or more known additives such as a leveling agent, a thermal polymerization inhibitor, a sensitizer, etc. The content of these additives is not particularly limited as long as it does not impair the effects of the present invention.

[0126] Furthermore, the photosensitive resin composition of this embodiment may contain an acid generator or a base generator to enhance curability. In particular, from the viewpoint of latency, it is preferable to use a photoacid generator, photobase generator, thermal acid generator, or thermal base generator, and from the viewpoint of storage stability, a photoacid generator or photobase generator is more preferable. Examples of photoacid generators include sulfonium salt compounds such as CPI-200K, CPI-210S, CPI-310B, and CPI-410S, manufactured by San-Apro Chemical Co., Ltd., and iodonium salt compounds such as IK-1. Examples of photobase generators include WPBG-266, WPBG-300, and WPBG-345, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0127] The viscosity of the photosensitive resin composition of this embodiment can be adjusted appropriately depending on the thickness of the cured resin film made from the cured product of the photosensitive resin composition. For example, when the thickness of the cured resin 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.

[0128] <Method for producing photosensitive resin composition> The photosensitive resin composition of the present embodiment can be produced by mixing a resin composition containing a resin (A) and a solvent (D), a reactive diluent (B), a photopolymerization initiator (C), and, if necessary, a colorant (E) and / or additives, using a known mixing device.

[0129] The photosensitive resin composition of this embodiment has good storage stability because it contains a resin composition containing a resin (A) and a solvent (D), a reactive diluent (B), and a photopolymerization initiator (C). Therefore, the photosensitive resin composition of this embodiment can easily form a coating film of uniform thickness by coating, and can easily form a cured resin film of uniform thickness by curing the coating film.

[0130] Furthermore, the photosensitive resin composition of this embodiment has excellent low-temperature curing properties and can form a cured resin film with sufficient hardness and solvent resistance. Furthermore, since the photosensitive resin composition of this embodiment has excellent alkaline developability, fine patterns can be formed by developing it with an alkaline aqueous solution. Furthermore, the photosensitive resin composition of this embodiment can easily form a coating film with a uniform thickness, so that residues are less likely to remain in the unexposed areas between patterns during the development process performed to form a patterned cured resin film. Therefore, even if the minimum development dimension is 10 μm or less, a cured resin film with a clear pattern shape without residues between patterns can be formed. Therefore, the photosensitive resin composition of this embodiment is suitable for use as a resist. Furthermore, when the photosensitive resin composition of the present embodiment contains a colorant (E), it can be suitably used as a material for colored patterns such as pixels and black matrices of color filters.

[0131] <Cured resin film> Next, the cured resin film of this embodiment will be described in detail. The cured resin film of this embodiment is made of a cured product of the photosensitive resin composition of this embodiment. The cured resin film of the present embodiment can be formed, for example, by a method including a coating step of coating the photosensitive resin composition of the present embodiment onto a substrate to form a coating film, a pre-baking step of drying the coating film formed by the coating step, an exposure step of irradiating the dried coating film with light to photo-cure it, and a post-baking step of thermally curing the photo-cured coating film.

[0132] When a cured resin film having a predetermined pattern is formed by photolithography using the photosensitive resin composition of this embodiment, for example, the following method can be used. That is, the above-mentioned coating step and pre-baking step are performed. Then, in the exposure step, the dried coating film is irradiated with light through a photomask having a predetermined pattern, and the exposed portions are photo-cured. After the exposure step, a post-exposure bake treatment is performed as necessary. Then, a development step is performed in which the unexposed portions of the coating film are dissolved and developed using a developer, and a post-baking step is performed in which the photo-cured coating film is thermally cured.

[0133] [Coating process] In the coating step, the photosensitive resin composition of the present embodiment is coated on a substrate to form a coating film. In the present embodiment, a known substrate can be used as the substrate to which the photosensitive resin composition is coated, and the substrate can be appropriately selected depending on the application of the cured resin film. The method for applying the photosensitive resin composition is not particularly limited, and for example, screen printing, roll coating, curtain coating, spray coating, spin coating, slit coating, etc. can be used.

[0134] [Pre-bake process] In the pre-baking (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-baking step, the substrate on which the coating film has been formed is heated, for example, at a temperature of 50°C to 120°C, preferably 70°C to 110°C, for 10 seconds to 600 seconds, preferably 120 seconds to 180 seconds. In the pre-baking step, the substrate on which the coating film has been formed can be heated, for example, by using a hot plate.

[0135] [Exposure process] In the exposure step, the surface of the coating film dried in the pre-bake step is irradiated with light to photocure the coating film. The light source used for light irradiation is not particularly limited, but for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, etc. can be used. In addition, the exposure dose in the exposure step is not particularly limited, and can be appropriately set depending on the composition of the photosensitive resin composition, the thickness of the coating film, etc. When forming a cured resin film having a predetermined pattern, in the exposure step, the surface of the coating film dried in the pre-bake step is irradiated with light through a photomask having a predetermined pattern, and the exposed portion is photo-cured.

[0136] [Post-exposure baking process] When forming a cured resin film having a predetermined pattern, a post-exposure baking step is performed as needed after the exposure step. By performing this step, the dissolution contrast between the exposed and unexposed portions of the coating film becomes more pronounced. Unlike the post-bake step described below, the post-exposure baking step does not completely cure the coating film. The post-exposure baking step is performed to leave only the exposed portions of the coating film on the substrate and more reliably remove the unexposed portions of the coating film by performing the development step. Therefore, this is not an essential step in the method for forming a cured resin film of this embodiment.

[0137] When a post-exposure baking step is performed, the substrate after the exposure step is preferably heated at, for example, 40°C to 70°C, more preferably 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. When the heating temperature is 70°C or lower, the acid generated in the exposed parts does not diffuse to the unexposed parts, and good dissolution contrast can be obtained. The heating time in the post-exposure baking step is preferably 20 seconds to 600 seconds. When the heating time is 20 seconds or longer, the temperature history of the entire coating film can be made uniform. When the heating time is 600 seconds or shorter, the acid generated in the exposed parts does not diffuse to the unexposed parts, and good dissolution contrast can be obtained. As a method for heating the substrate after the exposure step in the post-exposure baking step, for example, a hot plate, oven, furnace, or the like can be used.

[0138] [Development process] When forming a cured resin film having a predetermined pattern, after the exposure step, a post-exposure baking step is performed as needed, and then a development step is performed to develop the unexposed portions of the coating film. As the developer used in the development step, any aqueous alkaline solution that has conventionally been used for developing photosensitive resin compositions can be used.

[0139] The alkaline aqueous solution is not particularly limited, but examples thereof include aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, etc.; aqueous solutions of amine compounds such as ethylamine, diethylamine, dimethylethanolamine, etc.; aqueous solutions of quaternary ammonium salts such as tetramethylammonium hydroxide; and aqueous solutions of p-phenylenediamine compounds such as 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and sulfates, hydrochlorides, or p-toluenesulfonates thereof. Among these alkaline aqueous solutions, it is preferable to use aqueous solutions of p-phenylenediamine compounds.

[0140] If necessary, one or more additives such as an antifoaming agent and a surfactant may be added to the alkaline aqueous solution. The development conditions in the development step, such as the development temperature and development time, can be appropriately determined depending on the composition of the photosensitive resin composition, the composition of the developer, the thickness of the coating film, and the like. In the development step, it is preferable to dissolve and develop the unexposed portions of the coating film using the above-mentioned aqueous alkaline solution, followed by rinsing with water and drying.

[0141] [Post-bake process] In this embodiment, after the development step, a post-bake step is performed in which the photocured coating film is thermally cured to form a cured resin film. The heating temperature and heating time in the post-bake step are not particularly limited and can be set appropriately depending on the composition of the photosensitive resin composition, the thickness of the coating film, the material of the substrate, etc.

[0142] The heating temperature in the post-baking step can be, for example, 50°C to 210°C. A heating temperature of 210°C or lower allows the use of a material with low heat resistance as the color filter material. For example, when a colored pattern of a color filter is formed using a resin substrate as the base material for forming a cured resin film, the heating temperature may be 150°C or lower, 120°C or lower, or 100°C or lower. A heating temperature of 150°C or lower allows the formation of a colored pattern containing a colorant (E) with poor heat resistance, which has traditionally been difficult to use as a material for colored patterns, while suppressing deterioration of the colorant (E). Furthermore, a heating temperature of 150°C or lower allows the formation of a colored pattern on a substrate with poor heat resistance, which has traditionally been difficult to use as a substrate for color filters. Furthermore, a heating temperature of 150°C or lower is preferable because it reduces the amount of energy required to cure the coating film.

[0143] If the heating temperature in the post-baking step is 50°C or higher, the resin (A) and the reactive diluent (B) are sufficiently crosslinked, resulting in a cured resin film with sufficient hardness and solvent resistance. Furthermore, if the heating temperature is 50°C or higher, the heating time in the post-baking step can be shortened, allowing for efficient formation of a cured resin film. The heating temperature in the post-baking step is more preferably 60°C or higher, and even more preferably 70°C or higher.

[0144] The heating time in the post-baking step can be appropriately selected depending on the heating temperature, the thickness of the coating film, the composition of the photosensitive resin composition, etc., and can be, for example, 10 minutes to 4 hours, and preferably 20 minutes to 2 hours.

[0145] The cured resin film of this embodiment is made of a cured product of the photosensitive resin composition of this embodiment. Therefore, it has sufficient hardness and solvent resistance. Furthermore, because the cured resin film of this embodiment is made of a cured product of a photosensitive resin composition containing resin (A) and solvent (D), when the cured resin film has a patterned shape, it is clear and free of residue between patterns, even when the minimum development dimension is 10 μm or less. This is because the solvent (D) suppresses the hydrolysis reaction of the alkoxysilyl group in the structural unit (a-1) represented by formula (1) in the photosensitive resin composition, thereby suppressing the polymerization of resin (A) due to the self-condensation reaction of the silanol group generated by the hydrolysis reaction of the alkoxysilyl group. High-molecular-weight resin (A) reduces the uniformity of the thickness of the coating film made of the photosensitive resin composition, causing residue to remain in the unexposed areas between the patterns after development. The cured resin film of this embodiment can be suitably used as a material for various insulating films such as a protective film provided on top of a color filter, an insulating film provided between electrodes of a touch panel, and an interlayer insulating film of a thin film transistor (TFT).

[0146] <Color filter> Next, the color filter of this embodiment will be described in detail. Fig. 1 is a schematic cross-sectional view showing an example of a color filter according to the present embodiment. The color filter shown in Fig. 1 includes 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 protective films 4 formed on the pixels 2 and the black matrices 3.

[0147] The substrate 1 used in the color filter shown in FIG. 1 is not particularly limited, and may be a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyamideimide substrate, a polyimide substrate, an aluminum substrate, a printed wiring board, an array substrate, or the like, which may be used as appropriate depending on the application.

[0148] The pixels 2 and black matrix 3 in the color filter shown in FIG. 1 are colored patterns made of a cured product of the photosensitive resin composition of the present embodiment, which contains a resin composition including a resin (A) and a solvent (D), a reactive diluent (B), a photopolymerization initiator (C), a colorant (E), and additives that are contained as needed. A film made of a known material can be used as the protective film 4. The protective film 4 may be a cured resin film made of a cured product of the photosensitive resin composition of the present embodiment, which contains a resin composition containing a resin (A) and a solvent (D), a reactive diluent (B), a photopolymerization initiator (C), and additives that are contained as needed.

[0149] 1, known materials can be used for the configuration of the color filter of this embodiment, except for the materials of the pixels 2 and the black matrix 3. The color filter shown in FIG. 1 is an example of the color filter of the present invention, and the present invention is not limited to the example shown in FIG.

[0150] Next, a method for manufacturing the color filter of this embodiment will be described. First, the RGB pixels 2 and the black matrix 3 are sequentially formed on one surface 1a of the substrate 1 shown in Fig. 1. The pixels 2 and the black matrix 3 can be manufactured using the above-described method for manufacturing a cured resin film (photolithography method) of this embodiment. Next, the protective film 4 is formed on the pixels 2 and the black matrix 3. The protective film 4 can be formed using a known forming method. For example, the protective film 4 can be manufactured using the above-described method for manufacturing a cured resin film according to this embodiment. Through the above steps, the color filter of this embodiment shown in FIG. 1 is obtained.

[0151] The color filter of this embodiment has a colored pattern (pixels 2 and black matrix 3) made of the cured product of the above-mentioned photosensitive resin composition. Therefore, the colored pattern in the color filter of this embodiment has sufficient hardness and solvent resistance.

[0152] <Image display element> The image display element of this embodiment includes the color filter of this embodiment, which has sufficient hardness and solvent resistance. Examples of the image display element of this embodiment include a liquid crystal display element, an organic EL display element, and a solid-state imaging element. Because the image display element of this embodiment includes the color filter, a decrease in brightness due to deterioration of the color filter is unlikely to occur, and a high-brightness display is possible. [Example]

[0153] The present invention will be specifically described below with reference to examples and comparative examples. The examples shown below are intended to facilitate understanding of the present invention. The present invention is not limited to these examples.

[0154] [Synthesis Example 1] Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube, 288.0 g of propylene glycol monomethyl ether acetate as a polymerization solvent was placed, and the mixture was stirred while replacing the atmosphere with nitrogen and heated to 98°C.

[0155] Next, a mixture of 24.3 g (0.29 mol) of methacrylic acid, 103.8 g (0.41 mol) of 3-methacryloyloxypropylmethyldiethoxysilane, 25.3 g (0.20 mol) of 2-hydroxyethyl methacrylate, 11.5 g (0.10 mol) of vinyltoluene, 21.4 g of dimethyl 2,2'-azobis(isobutyrate) (polymerization initiator), and 112.0 g of propylene glycol monomethyl ether acetate was added dropwise from the dropping funnel to the flask over a period of 3 hours.

[0156] After the dropwise addition was completed, the mixture was stirred at 98°C for 3 hours to carry out a copolymerization reaction, producing a copolymer, functional group-containing resin precursor (a). The atmosphere in the flask was then replaced with air, and 13.7g (0.10 mol) of 2-acryloyloxyethyl isocyanate, 0.11g of dibutyltin dilaurate (DBTDL) (addition reaction catalyst), and 0.36g of methylhydroquinone (polymerization inhibitor) were added to the reaction solution in which functional group-containing resin precursor (a) had been synthesized, and an addition reaction was carried out at 60°C for 2 hours.

[0157] This caused the hydroxyl group derived from 2-hydroxyethyl methacrylate to react with the isocyanato group of 2-acryloyloxyethyl isocyanate, cleaving the hydroxyl group derived from 2-hydroxyethyl methacrylate and simultaneously introducing a polymerizable unsaturated bond into the side chain of the functional group-containing resin precursor (a), thereby obtaining resin (A). Note that in the presence of an addition reaction catalyst, the isocyanato group of 2-acryloyloxyethyl isocyanate reacts preferentially with the hydroxyl group derived from 2-hydroxyethyl methacrylate rather than with the carboxyl group derived from methacrylic acid. Next, 400.0 g of 3-methoxy-1-butanol was added as a solvent (enriched solvent for the composition) to the reaction solution containing the resin (A), and the resin composition of Example 1 was obtained.

[0158] [Synthesis Example 2] Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube, 279.0 g of propylene glycol monomethyl ether acetate was placed as a polymerization solvent, and the mixture was stirred while purging with nitrogen and heated to 98°C.

[0159] Next, a mixture of 23.9 g (0.29 mol) of methacrylic acid, 102.0 g (0.41 mol) of 3-methacryloyloxypropylmethyldiethoxysilane, 33.9 g (0.30 mol) of vinyltoluene, 20.8 g of dimethyl 2,2'-azobis(isobutyrate) (polymerization initiator), and 108.5 g of propylene glycol monomethyl ether acetate was added dropwise from the dropping funnel to the flask over a period of 3 hours.

[0160] After the dropwise addition was completed, the mixture was stirred at 98°C for 3 hours to carry out a copolymerization reaction, producing a copolymer, functional group-containing resin precursor (a). The atmosphere in the flask was then replaced with air, and 19.6g (0.145 mol) of 2-acryloyloxyethyl isocyanate and 0.36g of methylhydroquinone (polymerization inhibitor) were added to the reaction solution in which functional group-containing resin precursor (a) had been synthesized, followed by an addition reaction at 60°C for 2 hours.

[0161] As a result, the carboxyl group derived from methacrylic acid was reacted with the isocyanato group of 2-acryloyloxyethyl isocyanate, cleaving the carboxyl group derived from methacrylic acid and simultaneously introducing a polymerizable unsaturated bond into the side chain of the functional group-containing resin precursor (a), thereby obtaining resin (A). Next, 400.0 g of 3-methoxy-1-butanol and 12.5 g of propylene glycol monomethyl ether acetate were added as a solvent (additive solvent for the composition) to the reaction solution containing the resin (A), and a resin composition of Example 2 was obtained.

[0162] [Synthesis Example 3] Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube, 259.0 g of propylene glycol monomethyl ether acetate was placed as a polymerization solvent, and the mixture was stirred while purging with nitrogen and heated to 98°C.

[0163] Next, a mixture of 103.3 g (0.55 mol) of 3-methacryloyloxypropylmethyldiethoxysilane, 40.7 g (0.40 mol) of 2-acryloyloxyethyl isocyanate, 4.3 g (0.05 mol) of vinyltoluene, 19.3 g of 2,2'-azobis(isobutyrate) dimethyl (polymerization initiator), and 100.8 g of propylene glycol monomethyl ether acetate was added dropwise from the dropping funnel to the flask over a period of 3 hours.

[0164] After the dropwise addition was completed, the mixture was stirred at 98°C for 3 hours to carry out a copolymerization reaction, producing a copolymer functional group-containing resin precursor (a).The atmosphere in the flask was then replaced with air, and 12.7g (0.135 mol) of 2-hydroxyethyl methacrylate, 0.10g of dibutyltin dilaurate (DBTDL) (addition reaction catalyst), and 0.32g of methylhydroquinone (polymerization inhibitor) were added to the reaction solution in which the functional group-containing resin precursor (a) had been synthesized, and an addition reaction was carried out at 60°C for 2 hours.

[0165] As a result, the isocyanato group derived from 2-acryloyloxyethyl isocyanate was reacted with the hydroxyl group of 2-hydroxyethyl methacrylate, cleaving the isocyanato group derived from 2-acryloyloxyethyl isocyanate and simultaneously introducing a polymerizable unsaturated bond into the side chain of the functional group-containing resin precursor (a).

[0166] Next, 19.8 g (0.20 mol) of 4-aminobenzoic acid and 40.2 g of propylene glycol monomethyl ether acetate were added to the reaction solution in the flask, and the addition reaction was carried out at 40° C. for 2 hours. This caused the isocyanato group derived from 2-acryloyloxyethyl isocyanate to react with the amino group of 4-aminobenzoic acid, introducing an acid group into the side chain of the functional group-containing resin precursor (a), thereby obtaining resin (A). Next, 400.0 g of 3-methoxy-1-butanol was added as a solvent (enriched solvent for the composition) to the reaction solution containing the resin (A), and a resin composition of Example 3 was obtained.

[0167] [Comparative Synthesis Example 1] Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube, 282.0 g of propylene glycol monomethyl ether acetate as a polymerization solvent was placed, and the mixture was stirred while replacing the atmosphere with nitrogen and heated to 98°C.

[0168] Next, a mixture of 26.1 g (0.29 mol) of methacrylic acid, 111.4 g (0.41 mol) of 3-methacryloyloxypropylmethyldiethoxysilane, 27.2 g (0.20 mol) of 2-hydroxyethyl methacrylate, 12.3 g (0.10 mol) of vinyltoluene, 23.0 g of dimethyl 2,2'-azobis(isobutyrate) (polymerization initiator), and 118.0 g of propylene glycol monomethyl ether acetate was added dropwise from the dropping funnel to the flask over a period of 3 hours.

[0169] After the dropwise addition was completed, the mixture was stirred at 98°C for 3 hours to carry out a copolymerization reaction, thereby producing a functional group-containing resin precursor (a) which is a copolymer. Next, 400.0 g of 3-methoxy-1-butanol was added to the reaction solution in which the functional group-containing resin precursor (a) had been synthesized, and a resin composition of Comparative Example 1 was obtained.

[0170] [Comparative Synthesis Example 2] Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube, 293.8 g of propylene glycol monomethyl ether acetate was placed as a polymerization solvent, and the mixture was stirred while purging with nitrogen and heated to 98°C.

[0171] Next, a mixture of 26.4 g (0.29 mol) of methacrylic acid, 113.0 g (0.41 mol) of 3-methacryloyloxypropylmethyldiethoxysilane, 37.5 g (0.30 mol) of vinyltoluene, 23.0 g of dimethyl 2,2'-azobis(isobutyrate) (polymerization initiator), and 106.2 g of propylene glycol monomethyl ether acetate was added dropwise from the dropping funnel to the flask over a period of 3 hours.

[0172] After the dropwise addition was completed, the mixture was stirred at 98°C for 3 hours to carry out a copolymerization reaction, thereby producing a functional group-containing resin precursor (a) which is a copolymer. Next, 400.0 g of 3-methoxy-1-butanol was added to the reaction solution in which the functional group-containing resin precursor (a) had been synthesized, and a resin composition of Comparative Example 2 was obtained.

[0173] [Comparative Synthesis Example 3] Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube, 276.5 g of propylene glycol monomethyl ether acetate as a polymerization solvent was placed, and the mixture was stirred while replacing with nitrogen and heated to 98°C.

[0174] Next, a mixture of 110.3 g (0.55 mol) of 3-methacryloyloxypropylmethyldiethoxysilane, 43.5 g (0.40 mol) of 2-acryloyloxyethyl isocyanate, 4.6 g (0.05 mol) of vinyltoluene, 20.6 g of dimethyl 2,2'-azobis(isobutyrate) (polymerization initiator), and 107.6 g of propylene glycol monomethyl ether acetate was added dropwise from the dropping funnel to the flask over a period of 3 hours.

[0175] After the dropwise addition, the mixture was stirred at 98°C for 3 hours to carry out a copolymerization reaction, producing a copolymer functional group-containing resin precursor (a). The atmosphere in the flask was then replaced with air, and 21.1 g (0.20 mol) of 4-aminobenzoic acid and 15.9 g of propylene glycol monomethyl ether acetate were added to the reaction solution in which the functional group-containing resin precursor (a) had been synthesized, and the mixture was reacted at 40°C for 2 hours. This caused the isocyanato group derived from 2-acryloyloxyethyl isocyanate to react with the amino group of 4-aminobenzoic acid, thereby introducing an acid group into the side chain of the functional group-containing resin precursor (a). Next, 400.0 g of 3-methoxy-1-butanol was added to the reaction solution in which acid groups had been introduced into the side chains of the functional group-containing resin precursor (a), and a resin composition of Comparative Example 3 was obtained.

[0176] [Synthesis Examples 4 to 13, Comparative Synthesis Examples 4 to 8] Resin compositions of Examples 4 to 13 and Comparative Examples 4 to 8 were obtained in the same manner as in Synthesis Example 1, except that the raw materials shown in Tables 1 to 4 were used in the proportions shown in Tables 1 to 4.

[0177] The weight-average molecular weight (Mw), number-average molecular weight (Mn), molecular weight distribution (Mw / Mn), acid value, silyl group equivalent, and double bond equivalent were determined for the resin (A) contained in the resin compositions of Examples 1 to 13, the functional group-containing resin precursor (a) contained in the resin compositions of Comparative Examples 1 and 2, the resin with acid groups introduced into the side chains of the functional group-containing resin precursor (a) contained in the resin composition of Comparative Example 3, the copolymer contained in the resin compositions of Comparative Examples 4, 5, and 8, and the resin contained in the resin compositions of Comparative Examples 6 and 7. The results are shown in Tables 1 to 4.

[0178] [Table 1]

[0179] [Table 2]

[0180] [Table 3]

[0181] [Table 4]

[0182] <Evaluation of Resin Composition> The resin compositions of Examples 1 to 13 and Comparative Examples 1 to 8 were evaluated for storage stability according to the following method. 10 g of each of the resin compositions of Examples 1 to 13 and Comparative Examples 1 to 8 was weighed out and placed in a 20 ml glass container to prepare samples, and the viscosity was measured. The viscosity was measured at 25°C and 20 rpm using an E-type viscometer (RE-80 manufactured by Toki Sangyo, rotor 1°34' x R24). Each sample was then stored at 25°C in an incubator maintained at 12°C for three months. Thereafter, the viscosity was measured again using the same method as above. The viscosity increase rate (rate of increase in viscosity) was calculated using the viscosity measurements before and after storage according to the following formula, and evaluated according to the following criteria. The results are shown in Tables 1 to 4.

[0183] Viscosity increase rate (%) = (([Viscosity after storage] - [Viscosity before storage]) / [Viscosity before storage]) x 100 The criteria for evaluating the viscosity increase rate are as follows: ◎: Viscosity increase rate less than 10% 〇: Viscosity increase rate 10-20% △: Viscosity increase rate over 20%

[0184] As shown in Table 1 or Table 2, the resin compositions of Synthesis Examples 1 to 13 were evaluated as having excellent storage stability, with each being rated as excellent or excellent. In contrast, as shown in Table 3 or 4, the resin compositions of Comparative Examples 4 to 7 were all rated fair for storage stability, indicating insufficient storage stability.

[0185] Next, photosensitive resin compositions were prepared using the resin compositions of Examples 1 to 13 and Comparative Examples 1 to 8 according to the methods described below, and were evaluated by the methods described below.

[0186] <Preparation of Photosensitive Resin Composition> The photosensitive resin compositions of Examples 1 to 13 and Comparative Examples 1 to 8 were prepared by mixing the resin compositions of Examples 1 to 13 and Comparative Examples 1 to 8 with the components (B), (C), and (E) shown in Table 5 in the proportions shown in Table 5. The photosensitive resin composition of Comparative Example 9 was prepared in the same manner as the photosensitive resin composition of Example 1, except that a resin composition obtained by mixing the resin composition of Comparative Example 1 and the resin composition of Comparative Example 8 in a mass ratio of 1:1 was used as the resin composition.

[0187] The blending amounts of the copolymers in the resin compositions in Table 5 (resin (A) in the resin compositions of Examples 1 to 13, functional group-containing resin precursor (a) in the resin compositions of Comparative Examples 1 and 2, the resin with an acid group introduced into the side chain of functional group-containing resin precursor (a) in the resin composition of Comparative Example 3, the copolymer in the resin compositions of Comparative Examples 4, 5, and 8, and the resin in the resin composition of Comparative Examples 6 and 7) do not include the polymerization solvent used when synthesizing the copolymers. The blending amount of (D) solvent in Table 5 is the total amount of the polymerization solvent used when synthesizing the copolymer in the resin composition and the solvent added when preparing the resin composition.

[0188] [Table 5]

[0189] <Evaluation of Photosensitive Resin Composition> (1) Storage stability of the photosensitive resin composition The storage stability of the photosensitive resin compositions of Examples 1 to 13 and Comparative Examples 1 to 9 was evaluated according to the following method. 10 g of each of the photosensitive resin compositions of Examples 1 to 13 and Comparative Examples 1 to 9 was weighed out and placed in a 20 ml glass container to prepare samples, and the viscosity was measured. The viscosity was measured at 25°C and 20 rpm using an E-type viscometer (RE-80 manufactured by Toki Sangyo, rotor 1°34' x R24). Each sample was then stored at 25°C in an incubator maintained at 12°C for three months. Thereafter, the viscosity was measured again using the same method as above. The viscosity increase rate (rate of increase in viscosity) was calculated using the viscosity measurements before and after storage according to the following formula, and evaluated according to the following criteria. The results are shown in Table 6 or Table 7.

[0190] Viscosity increase rate (%) = (([Viscosity after storage] - [Viscosity before storage]) / [Viscosity before storage]) x 100 "Evaluation criteria for viscosity increase rate" ◎: Viscosity increase rate less than 10% 〇: Viscosity increase rate 10-20% △: Viscosity increase rate over 20%

[0191] (2) Developability The photosensitive resin compositions of Examples 1 to 13 and Comparative Examples 1 to 9 were each applied onto a 5 cm square glass substrate (alkali-free glass substrate) by spin coating so that the thickness after exposure was 2.5 μm (application step). The glass substrate onto which the photosensitive resin composition was applied was heated at 100°C for 3 minutes to volatilize the solvent and dry the coating film (pre-bake step).

[0192] Next, an ultra-high pressure mercury lamp was used to irradiate 200 mJ / cm 2 The surface of the dried coating film was irradiated with light through a photomask (exposure step). The exposure step was performed by placing a photomask 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, a developer containing potassium hydroxide as its main component (product name: Semiclean DL-A10, manufactured by Yokohama Yushi Kogyo Co., Ltd.) was diluted 5 times with water and 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 coating film after the development step was left standing in a dryer at 100°C for 30 minutes to thermally cure the coating film (post-bake step), thereby obtaining a colored pattern.

[0193] The colored patterns thus obtained were observed using an S-3400 electron microscope manufactured by Hitachi High-Technologies Corporation, and the minimum line width (minimum development dimension) that could be developed and the presence or absence of residue in unexposed areas between the developed patterns were evaluated. The presence or absence of residue was evaluated according to the following criteria. The results are shown in Table 6 or Table 7. "Residue evaluation criteria" ○: No residue in the unexposed areas between the developed patterns ×: Residues found in unexposed areas between developed patterns

[0194] (3) Pencil hardness The photosensitive resin compositions of Examples 1 to 13 and Comparative Examples 1 to 9 were applied by spin coating onto square glass substrates (alkali-free glass substrates) measuring 5 cm in length and 5 cm in width, and then heated at 100°C for 3 minutes to volatilize the solvent, forming a coating film. Next, the coating film was irradiated with light having a wavelength of 365 nm at an exposure dose of 200 mJ / cm. 2 The glass substrate with the photocured coating film was then placed in a dryer at 100°C for 30 minutes to thermally cure the coating film (post-baking step), thereby obtaining a cured resin film with a thickness of 2.5 µm.

[0195] The pencil hardness of the cured resin film thus produced 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 6 or Table 7. "Evaluation standard for pencil hardness" ○:Pencil hardness 3H or higher ×: Pencil hardness less than 3H

[0196] (4) Solvent resistance A glass substrate having a cured resin film was prepared in the same manner as in the evaluation of pencil hardness (3) above, and the absorption spectrum of the cured resin film was measured using a spectrophotometer (UV-1650PC, manufactured by Shimadzu Corporation). 200 mL of propylene glycol monomethyl ether acetate was placed in a 500 mL glass bottle with a lid and allowed to stand at a temperature of 23°C. The glass substrate having the cured resin film was placed in the glass bottle, immersed in propylene glycol monomethyl ether acetate, and allowed to stand at 23°C for 15 minutes. The glass substrate having the cured resin film was then removed, and the absorption spectrum of the cured resin film was measured using a spectrophotometer (UV-1650PC, manufactured by Shimadzu Corporation) in the same manner as before immersion in propylene glycol monomethyl ether acetate.

[0197] Color change (ΔE) of the cured resin film before and after immersion in propylene glycol monomethyl ether acetate * The solvent resistance of the cured resin film was evaluated according to the following criteria. The results are shown in Table 6 or Table 7. "Solvent resistance evaluation criteria" ○:ΔE * ab is less than 3.0 ×:ΔE * ab is 3.0 or more

[0198] (5) Overall Judgment The photosensitive resin compositions of Examples 1 to 13 and Comparative Examples 1 to 9 and the cured resin films formed from the cured products thereof were evaluated according to the following criteria. The results are shown in Tables 6 and 7. "Evaluation Criteria" ○: Meets all of the following criteria. (1) The viscosity increase rate of the photosensitive resin composition is 20% or less (2) The minimum development dimension is 15 μm or less, and there is no residue in the unexposed areas between the developed patterns. (3) The pencil hardness of the resin cured film is 3H or more. (4) Color change ΔE in evaluation of solvent resistance of cured resin film * ab is less than 3.0 ×: One or more of the items marked ○ above are not met.

[0199] [Table 6]

[0200] [Table 7]

[0201] As shown in Table 6, the storage stability of the photosensitive resin compositions of Examples 1 to 13 was evaluated as ⊚ or ◯, confirming that all of them had excellent storage stability. Furthermore, the photosensitive resin compositions of Examples 1 to 13 all had a minimum development dimension of 15 μm or less, and no residue was left in the unexposed areas between the developed patterns, confirming that they had excellent alkaline developability.

[0202] Furthermore, as shown in Table 6, the coating films formed using the photosensitive resin compositions of Examples 1 to 13 were photocured and then thermally cured at a low temperature of 100°C to form cured resin films, which had excellent hardness with a pencil hardness of 3H or more. Moreover, the solvent resistance of the cured resin films was evaluated as ○, confirming that they had excellent solvent resistance.

[0203] In contrast, as shown in Table 7, the photosensitive resin compositions of Comparative Examples 1 to 9 all had excellent alkaline developability. However, the photosensitive resin compositions of Comparative Examples 4 to 7 were evaluated as fair in terms of storage stability, indicating insufficient storage stability. Furthermore, the photosensitive resin compositions of Comparative Examples 1 to 3, 8, and 9 all had excellent storage stability, but were insufficient in pencil hardness and solvent resistance.

[0204] More specifically, the resin compositions of Comparative Examples 1 to 3 contained in the photosensitive resin compositions of Comparative Examples 1 to 3 do not contain, as raw materials, the compound (ma-4) having an ethylenically unsaturated group and a group reactive with the functional group of the functional group-containing resin precursor (a), and since the compound (ma-4) is not added to the functional group-containing resin precursor (a), the double bond equivalent is 0. As a result, the hardness and solvent resistance of the cured resin film were poor.

[0205] Furthermore, the resin composition of Comparative Example 8 contained in the photosensitive resin composition of Comparative Example 8 does not contain the compound (ma-1) represented by formula (2) as a raw material monomer, and therefore has a silyl equivalent of 0. As a result, the hardness and solvent resistance of the cured resin film were poor. Furthermore, the resin compositions of Comparative Examples 4 and 5 contained in the photosensitive resin compositions of Comparative Examples 4 and 5 use a raw material monomer containing a tri(methoxy)ethoxy-type alkoxysilyl group instead of the compound (ma-1) represented by formula (2). The tri(methoxy)ethoxy-type alkoxysilyl group undergoes crosslinking more quickly than the di(methoxy)ethoxy-type alkoxysilyl group. For this reason, it is presumed that the resin compositions and photosensitive resin compositions of Comparative Examples 4 and 5 had insufficient storage stability.

[0206] The photosensitive resin compositions of Comparative Examples 6 and 7 contained at least one solvent selected from a primary alcohol having 3 to 10 carbon atoms and a secondary alcohol having 3 to 10 carbon atoms. Therefore, in the resin compositions of Comparative Examples 6 and 7 and photosensitive resin compositions containing them, the hydrolysis reaction of the alkoxysilyl group in the structural unit (a-1) represented by formula (1) in the resin (A) was likely to proceed, resulting in insufficient storage stability. More specifically, in the photosensitive resin compositions of Comparative Examples 6 and 7, the hydrolysis reaction of the alkoxysilyl group in the structural unit (a-1) represented by formula (1) was likely to generate silanol groups, and the self-condensation reaction of the silanol groups likely resulted in the polymerization of the resin (A). Furthermore, in the photosensitive resin compositions of Comparative Examples 6 and 7, the polymerization of the resin (A) was likely to result in a decrease in the uniformity of the coating film thickness, resulting in the resin (A) becoming a development residue, resulting in a lower minimum development dimension compared to the photosensitive resin composition of Example 1. Furthermore, as a result of observing the colored patterns (cured products) for which the developability of Comparative Examples 6 and 7 was evaluated, it was found that residue remained in the unexposed areas between the developed patterns, and the residue evaluation for both was ×. Therefore, the colored patterns made of the cured products of the photosensitive resin compositions of Comparative Examples 6 and 7 had unclear shapes.

[0207] The photosensitive resin composition of Comparative Example 9, which contained a resin composition obtained by mixing the resin composition of Comparative Example 1 and the resin composition of Comparative Example 8 in a 1:1 mass ratio, did not contain resin (A) in which compound (ma-4) was added to functional group-containing resin precursor (a), and therefore the hardness and solvent resistance of the cured resin film were inferior. This suggests that excellent low-temperature curing properties can be obtained by including resin (A) having a polymerizable unsaturated group and a silyl group in the same copolymer. [Industrial Applicability]

[0208] According to the present invention, a photosensitive resin composition having excellent storage stability and developability and good low-temperature curing properties capable of forming a cured resin film having sufficient hardness and solvent resistance can be provided. Furthermore, according to the present invention, a resin composition having excellent storage stability contained in the photosensitive resin composition, a cured resin film having sufficient hardness and solvent resistance composed of a cured product of the photosensitive resin composition, a color filter having sufficient hardness and solvent resistance, and an image display element equipped with this color filter can be provided. The photosensitive resin composition of the present invention can be preferably used, for example, as a transparent film, a protective film, an insulating film, an overcoat, a photospacer, a black matrix, a black column spacer, or a resist for a color filter. [Explanation of symbols]

[0209] 1···Substrate, 2···Pixel, 3···Black matrix, 4···Protective film.

Claims

1. Contains a resin (A) and a solvent (D), the resin (A) is a resin in which a compound (ma-4) having a group reactive with the functional group and an ethylenically unsaturated group is added to a part of the functional group of the functional group-containing resin precursor (a), the functional group-containing resin precursor (a) contains a structural unit (a-1) represented by the following formula (1) and a structural unit (a-2) having the functional group, The solvent (D) comprises a resin composition containing at least one selected from a primary alcohol having 3 to 10 carbon atoms and a secondary alcohol having 3 to 10 carbon atoms; a reactive diluent (B); a photopolymerization initiator (C); A color filter having a colored pattern formed from a cured product of a photosensitive resin composition containing a colorant (E). 【Chemistry 1】 (In formula (1), R １ represents a hydrogen atom or a methyl group. ２ ~R ４ two of which are independently an alkoxy group having 1 to 6 carbon atoms, and the remaining one is one selected from a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, or R ２ ~R ４ one of which is an alkoxy group having 1 to 6 carbon atoms, and the remaining two are each independently one selected from a hydrogen atom and an alkyl group having 1 to 6 carbon atoms; and n is an integer from 1 to 10.

2. The resin composition is a compound represented by the formula (1), wherein R ２ ~R ４ 2. The color filter according to claim 1, wherein two of the groups are independently an alkoxy group having 1 to 6 carbon atoms, and the remaining group is an alkyl group having 1 to 6 carbon atoms.

3. The resin composition is a color filter described in claim 1 or claim 2, wherein the functional group possessed by the structural unit (a-2) is one or more selected from a carboxy group, a hydroxy group, an isocyanato group, an acid anhydride, and an epoxy group.

4. The resin composition is a color filter described in any one of claims 1 to 3, wherein the compound (ma-4) is one or more selected from a (meth)acryloyl group-containing isocyanate, a (meth)acryloyl group-containing hydroxy compound, a (meth)acryloyl group-containing acid anhydride, a (meth)acryloyl group-containing carboxy compound, a (meth)acryloyl group-containing epoxy compound, and a (meth)acryloyl group-containing amino compound.

5. The resin composition, wherein the functional group of the structural unit (a-2) is one or more types selected from a carboxy group and a hydroxy group, 5. The color filter according to claim 1, wherein the compound (ma-4) is a (meth)acryloyl group-containing isocyanate.

6. The resin composition, wherein the functional group of the structural unit (a-2) is an isocyanato group, The color filter according to any one of claims 1 to 4, wherein the compound (ma-4) is at least one selected from the group consisting of a (meth)acryloyl group-containing hydroxy compound and a (meth)acryloyl group-containing amino compound.

7. The resin composition is a color filter described in any one of claims 1 to 6, wherein the resin (A) is a resin in which a compound (ma-5) having a group reactive with the functional group and a carboxy group is further added to a portion of the functional group possessed by the functional group-containing resin precursor (a).

8. A color filter described in any one of claims 1 to 7, wherein the resin composition has a total content of the primary alcohol and the secondary alcohol of 10 to 95 mass% relative to 100 mass% of the solvent (D).

9. The photosensitive resin composition contains, per 100 parts by mass of the total of components excluding the solvent (D), The resin (A) is contained in an amount of 10 parts by mass to 85 parts by mass, The reactive diluent (B) is contained in an amount of 10 parts by mass to 85 parts by mass, The photopolymerization initiator (C) is contained in an amount of 0.1 to 30 parts by mass, The solvent (D) is contained in an amount of 20 parts by mass to 1000 parts by mass, 2. The color filter according to claim 1, comprising the colorant (E) in an amount of 4 to 85 parts by mass.

10. An image display element comprising the color filter described in claim 1.

Images