JP2023060757A - Resin composition, photosensitive resin composition, resin cured film, color filter, and image display element - Google Patents

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 The present invention relates to a resin composition, a photosensitive resin composition, a cured resin film, a color filter and an image display device.

2. Description of the Related Art Conventionally, some image display elements such as displays are equipped with color filters. A color filter is usually formed using a method of curing a resin composition on a substrate by baking at a temperature of over 200°C.
In recent years, as displays have become more flexible and wearable, substrate materials are being switched from glass to organic materials such as resins. In addition, in order to realize image display devices with higher luminance and higher contrast, colorants used in color filters are being switched from pigments to materials such as dyes, fluorescent compounds, and quantum dots. .

Conventionally, as a resin composition used as a material for color filters, there is one described in Patent Document 1, for example.
Patent Document 1 contains a photocurable compound (A), a binder resin (B), a photoinitiator (D), and a solvent (E), and the photocurable compound (A) is a carboxy group-containing dipenta A colored photocurable resin composition is disclosed in which the binder resin (B) is erythritol pentaacrylate and contains one or more of a tetrahydropyran structure or a tetrahydrofuran structure in the main chain structure.

JP 2015-184675 A

Organic materials used as substrate materials are inferior in heat resistance to glass. Dyes used as colorants for color filters are inferior in heat resistance to pigments. For these reasons, it is desired to lower the heating temperature for curing resin compositions used as materials for color filters. Specifically, depending on the heat resistance of the substrate material and the colorant material, the heating temperature for curing the resin composition, which is the material of the color filter, may be required to be 80 to 150°C. .

However, when the heating temperature for curing the conventional resin composition is lowered, a cured product having sufficient hardness and solvent resistance cannot be obtained.
A color filter made of a cured product with insufficient hardness is easily scratched. For this reason, in an image display device having color filters, there is a possibility that defective display may occur due to scratches on the color filters. In color filters provided in image display devices, there is a tendency to increase the content of colorants in resin compositions used as materials for color filters in order to improve color reproducibility. Paints are highly soluble in solvents compared to pigments. Therefore, if the solvent resistance of the color filter is insufficient, the paint contained in the color filter may be eluted into the solvent, changing the chromaticity of the color filter.

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

The present invention has been made in view of the above circumstances, and has excellent storage stability and developability, and has good low-temperature curing and good photosensitivity capable of forming a cured resin film having sufficient hardness and solvent resistance. An object of the present invention is to provide a resin composition and a resin composition that is contained in the photosensitive resin composition and has excellent storage stability.
In addition, the present invention comprises a cured resin film having sufficient hardness and solvent resistance comprising a cured product of the photosensitive resin composition of the present invention, and a colored pattern comprising a cured product of the photosensitive resin composition of the present invention. It is an object of the present invention to provide a color filter and an image display device equipped with this color filter.

The present invention includes the following aspects.
[1] containing a resin (A) and a solvent (D),
In the resin (A), a compound (ma-4) having a group reactive with the functional group and an ethylenically unsaturated group is added to some of the functional groups of the functional group-containing resin precursor (a). It is a resin that
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, wherein 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.

（式（１）中、Ｒ^１は水素原子又はメチル基を表す。Ｒ^２～Ｒ^４のうち２つが各々独立して炭素原子数１～６のアルコキシ基であって、残る１つが水素原子及び炭素原子数１～６のアルキル基から選択される一種である、またはＲ^２～Ｒ^４のうち１つが炭素原子数１～６のアルコキシ基であって、残る２つが各々独立して水素原子及び炭素原子数１～６のアルキル基から選択される一種である。ｎは１～１０の整数である。）

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

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

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

[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 one or more selected from (meth)acryloyl group-containing hydroxy compounds and (meth)acryloyl group-containing amino compounds. thing.
[7] The resin (A) contains a compound (ma-5) having a group reactive with the functional group and a carboxy group as part of the functional groups of the functional group-containing resin precursor (a). The resin composition according to any one of [1] to [6], which is an additional resin.

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

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

[10] The photosensitive resin composition according to [9], further containing a coloring agent (E).
[11] With respect to a total of 100 parts by mass of the components excluding the solvent (D),
Containing 10 parts by mass to 85 parts by mass of the resin (A),
Containing 10 parts by mass to 85 parts by mass of the reactive diluent (B),
0.1 parts by mass to 30 parts by mass of the photopolymerization initiator (C),
Containing 20 parts by mass to 1000 parts by mass of the solvent (D),
The photosensitive resin composition according to [10], which contains (E) 4 parts by mass to 85 parts by mass of the coloring agent.

[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 comprising a cured product of the photosensitive resin composition of [10] or [11].
[14] An image display device comprising the color filter of [13].

According to the present invention, it is possible to provide a photosensitive resin composition having excellent storage stability and developability, and good low-temperature curability, capable of forming a cured resin film having sufficient hardness and solvent resistance.
Moreover, according to the present invention, it is possible to provide a resin composition having excellent storage stability that is contained in the photosensitive resin composition as a material for the photosensitive resin composition of the present invention.
Further, according to the present invention, there are provided a cured resin film having sufficient hardness and solvent resistance, which is made of a cured product of the photosensitive resin composition of the present invention, and a colored pattern made of a cured product of the photosensitive resin composition of the present invention. and an image display device comprising this color filter.

It is a schematic sectional view showing an example of a color filter of this embodiment.

The resin composition, photosensitive resin composition, cured resin film, color filter and image display device of the present invention are described in detail below. However, the present invention is not limited to only the embodiments shown below.
As used herein, "(meth)acrylic acid" means at least one selected from methacrylic acid and acrylic acid, and "(meth)acrylate" means at least one selected from methacrylate and acrylate. and "(meth)acryloyl" means at least one selected from methacryloyl and acryloyl.

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

The functional group-containing resin precursor (a) comprises a structural unit (a-1) represented by the following formula (1) (hereinafter sometimes abbreviated as "structural unit (a-1)") and the functional It contains a structural unit (a-2) having a group (hereinafter sometimes abbreviated as "structural unit (a-2)"). The functional group-containing resin precursor (a) may optionally contain other structural units (a-3) other than the structural units (a-1) and (a-2) (hereinafter referred to as "structural unit (a-3) " may be abbreviated.) may be contained. The repeating number and 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) are It is not particularly limited.

（式（１）中、Ｒ^１は水素原子又はメチル基を表す。Ｒ^２～Ｒ^４のうち２つが各々独立して炭素原子数１～６のアルコキシ基であって、残る１つが水素原子及び炭素原子数１～６のアルキル基から選択される一種である、またはＲ^２～Ｒ^４のうち１つが炭素原子数１～６のアルコキシ基であって、残る２つが各々独立して水素原子及び炭素原子数１～６のアルキル基から選択される一種である。ｎは１～１０の整数である。）

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

[Constituent 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 contains the structural unit (a-1) having a silyl group in the functional group-containing resin precursor (a), It has good low-temperature curability so that a cured resin film having sufficient hardness and solvent resistance can be formed.

In formula (1), R ¹ represents a hydrogen atom or a methyl group. R ¹ is preferably a methyl group due to the availability of raw materials.
In formula (1), n is an integer of 1-10. n is preferably an integer of 1 to 4, more preferably 3, in view of the availability of raw materials.

In formula (1), one or two of R ² to R ⁴ are alkoxy groups having 1 to 6 carbon atoms. In formula (1), when two of R ² to R ⁴ are each independently an alkoxy group having 1 to 6 carbon atoms, the remaining one is selected from a hydrogen atom and an alkyl group having 1 to 6 carbon atoms. It is a kind of Further, when one of R ² to R ⁴ is an alkoxy group having 1 to 6 carbon atoms, the remaining two are each independently selected from a hydrogen atom and an alkyl group having 1 to 6 carbon atoms. be.

In formula (1), one or two of R ² to R ⁴ are alkoxy groups having 1 to 6 carbon atoms. Therefore, one or two of R ² to R ⁴ in formula (1) function as crosslinking points in resin (A). As a result, the photosensitive resin composition using the 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) enables the photosensitive resin composition containing the resin (A) to form a cured resin film having superior hardness and solvent resistance. It is preferred that two of ² to R ⁴ are each independently an alkoxy group having 1 to 6 carbon atoms. When two of R ² to R ⁴ in formula (1) are alkoxy groups having 1 to 6 carbon atoms, the production of the functional group-containing resin precursor (a) is facilitated. The alkoxy groups of numbers 1 to 6 are preferably the same.

The alkoxy group having 1 to 6 carbon atoms which is one or two of R ² to R ⁴ is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group. It is preferably an ethoxy group, more preferably an ethoxy group. This is because excellent developability can be obtained when the resin composition containing the resin (A) is used as a raw material of the photosensitive resin composition. In addition, when the alkoxy group having 1 to 6 carbon atoms is an ethoxy group, the resin (A) is less likely to change over time and has excellent storage stability, as compared with the case where it is a methoxy group.

In formula (1), one or two of R ² to R ⁴ are one selected from hydrogen atoms and alkyl groups having 1 to 6 carbon atoms, and at least one of R ² to R ⁴ It is preferred that one is an alkyl group having 1 to 6 carbon atoms. In this case, the photosensitive resin composition using the resin composition containing the resin (A) as a raw material has better hardness than the case of having a hydrogen atom instead of the alkyl group having 1 to 6 carbon atoms. This is because a cured resin film having solvent resistance can be formed. When two of R ² to R ⁴ in formula (1) are alkyl groups having 1 to 6 carbon atoms, the production of the functional group-containing resin precursor (a) is easy, so two carbon atoms It is preferred that the alkyl groups of numbers 1 to 6 are the same.

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

In the structural unit (a-1), two of R ² to R ⁴ in formula (1) are each independently an alkoxy group having 1 to 6 carbon atoms, and the remaining one is an alkoxy group having 1 to 6 carbon atoms. 6 alkyl groups are preferred. In this case, a photosensitive resin composition using a resin composition containing the resin (A) as a raw material can form a cured resin film having superior hardness and solvent resistance. In addition, compared with the case where all of R ² to R ⁴ are alkoxy groups having 1 to 6 carbon atoms, the resin composition containing the resin (A) and the photosensitive resin composition using this as a raw material Good storage stability.

Specific examples of the structural unit (a-1) represented by formula (1) include, for example, a structural unit derived from 3-(meth)acryloyloxypropylmethyldimethoxysilane (in formula (1), R ¹ is a hydrogen atom or a methyl group, R ² is a methyl group, R ³ and R ⁴ are methoxy groups, and n is 3), a structural unit derived from 3-(meth)acryloyloxypropylethyldimethoxysilane (formula ( 1) in which R ¹ is a hydrogen atom or a methyl group, R ² is an ethyl group, R ³ and R ⁴ are a methoxy group, and n is 3), 3-(meth)acryloyloxypropylmethyl Structural unit derived from diethoxysilane (in formula (1), R ¹ is a hydrogen atom or a methyl group, R ² is a methyl group, R ³ and R ⁴ are ethoxy groups, 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, R ² is an ethyl group, R ³ and R ⁴ are ethoxy and n is 3) and the like.

Among these, from the viewpoint of material availability and reactivity when synthesizing the functional group-containing resin precursor (a), the structural unit (a-1) is 3-(meth)acryloyloxypropylmethyl Structural units derived from dimethoxysilane and structural units derived from 3-(meth)acryloyloxypropylmethyldiethoxysilane are preferred.
The structural unit (a-1) contained in the functional group-containing resin precursor (a) may be of only one type, or may be of two or more types.

The content of the structural unit (a-1) is preferably 2 to 80 mol%, more preferably 5 to 70 mol%, of the total structural units of the functional group-containing resin precursor (a). More preferably 5 to 60 mol %. When the content of the structural unit (a-1) is 2 mol% or more, the photosensitive resin composition using the resin composition containing the resin (A) as a raw material has sufficient hardness and solvent resistance. It has good low-temperature curability and can form a cured film. 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 the structural units of the functional group-containing resin precursor (a) is sufficiently increased. can be secured to Therefore, the resin (A) to which the compound (ma-4) is sufficiently added can be obtained. A photosensitive resin composition containing the resin (A) having a sufficient amount of ethylenically unsaturated groups derived from the compound (ma-4) can form a cured resin film having better solvent resistance.

[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 the 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.

In the resin composition containing the resin (A), since the functional group-containing resin precursor (a) contains the structural unit (a-2), one of the functional groups of the functional group-containing resin precursor (a) Part is added with a compound (ma-4) having an ethylenically unsaturated group amount. Since the photosensitive resin composition using the resin composition of the present embodiment as a raw material contains the resin (A) to which the compound (ma-4) is added, a resin cured film having good hardness and solvent resistance is formed. can.

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, particularly selected from a carboxy group and a hydroxy group. It is preferable to include one or more of the
When the functional group possessed by the structural unit (a-2) contains a carboxy group, the carboxy group possessed by the functional group-containing resin precursor (a) and the structural unit (a-2 possessed by the compound (ma-4) ) is reacted with a reactive group to add the compound (ma-4) to the functional group-containing resin precursor (a) to obtain a resin (A) having an amount of ethylenically unsaturated groups. can be Moreover, among the carboxy groups possessed by the structural unit (a-2) contained in the functional group-containing resin precursor (a), the carboxy group remaining without addition of the compound (ma-4) is Developability can be imparted to the photosensitive resin composition containing the resin composition.

The structural unit (a-2) is preferably a structural unit derived from the 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 is a compound containing no silicon and having a functional group and an ethylenically unsaturated group.
The functional group-containing ethylenically unsaturated compound (ma-2) includes, for example, a carboxy group-containing ethylenically unsaturated compound (ma-21), a hydroxy group-containing ethylenically unsaturated compound (ma-22), an isocyanato group-containing ethylene ethylenically unsaturated compound (ma-23), epoxy group-containing ethylenically unsaturated compound (ma-24), and ethylenically unsaturated group-containing acid anhydride (ma-25).

Carboxy group-containing ethylenically unsaturated compounds (ma-21) include, for example, (meth)acrylic acid, crotonic acid, cinnamic acid, vinylsulfonic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth) Acryloyloxyethyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate and the like. Among these, from the viewpoint of availability, reactivity when synthesizing the functional group-containing resin precursor (a), modification of the functional group-containing resin precursor (a) to add the compound (ma-4) (Meth)acrylic acid is preferred from the viewpoint of reactivity when obtaining the resin (A).

Examples of the hydroxy group-containing ethylenically unsaturated compound (ma-22) include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2,3-dihydroxy Hydroxy group-containing (meth)acrylates such as propyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate can be mentioned. Among these, from the viewpoint of availability, reactivity when synthesizing the functional group-containing resin precursor (a), modification of the functional group-containing resin precursor (a) to add the compound (ma-4) Hydroxyalkyl (meth)acrylates having a hydroxy group at the end of the alkyl group are preferred, and 2-hydroxyethyl (meth)acrylate is particularly preferred, from the viewpoint of reactivity when obtaining the resin (A) having a hydroxy group.

Examples of the isocyanato group-containing ethylenically unsaturated compound (ma-23) include, for example, 2-(meth)acryloyloxyethyl isocyanate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2- Examples thereof include isocyanato group-containing (meth)acrylates such as isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, and 4-isocyanatocyclohexyl (meth)acrylate. Among these, from the viewpoint of availability, reactivity when synthesizing the functional group-containing resin precursor (a), modification of the functional group-containing resin precursor (a) to add the compound (ma-4) From the viewpoint of reactivity when obtaining the resin (A) having a high molecular weight, isocyanatoalkyl (meth)acrylates having an isocyanato group at the end of the alkyl group are preferred, and 2-(meth)acryloyloxyethyl isocyanate is particularly preferred.

Examples of the epoxy group-containing ethylenically unsaturated compound (ma-24) include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, alicyclic epoxy group-containing (meth)acrylates, and lactones thereof. Epoxy groups such as adducts, 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate, epoxidized dicyclopentenyl (meth)acrylate, and epoxidized dicyclopentenyloxyethyl (meth)acrylate containing (meth)acrylates. Among these, from the viewpoint of availability, reactivity when synthesizing the functional group-containing resin precursor (a), modification of the functional group-containing resin precursor (a) to add the compound (ma-4) Glycidyl (meth)acrylate is preferred from the viewpoint of reactivity when obtaining the resin (A).

Ethylenically unsaturated group-containing acid anhydrides (ma-25) include, for example, maleic anhydride, itaconic anhydride, ethyl maleic anhydride, methyl itaconic anhydride, chloromaleic anhydride, citraconic anhydride, 2-norbornene- 5,6-dicarboxylic anhydride, 4-[2-(methacryloyloxy)ethoxycarbonyl]phthalic anhydride and the like.

The content of the structural unit (a-2) is preferably 10 to 98 mol%, more preferably 30 to 95 mol%, based on the total structural units of the functional group-containing resin precursor (a). More preferably 40 to 95 mol %. When the content of the structural unit (a-2) is 10 mol% or more, the ethylenic The resin (A) can have a sufficient amount of unsaturated groups. A photosensitive resin composition containing the resin (A) to which the compound (ma-4) is sufficiently added can form a cured resin film having good solvent resistance. When the content of the structural unit (a-2) is 98 mol% or less, the content of the structural unit (a-1) can be sufficiently ensured.

When the structural unit (a-2) contains a structural unit derived from the carboxy group-containing ethylenically unsaturated compound (ma-21), the content thereof is the total structural units of the functional group-containing resin precursor (a). , preferably 5 to 70 mol %, more preferably 10 to 60 mol %, even more preferably 20 to 50 mol %. 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 containing the carboxyl group in the functional group of the structural unit (a-2) is enhanced. get enough. Further, it is preferred that the content of structural units derived from the carboxyl group-containing ethylenically unsaturated compound (ma-21) is 70 mol % or less, because development time can be easily adjusted.

[Other structural units (a-3)]
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). Structural unit (a-3) does not contain a group represented by formula (1) and a functional group. The structural unit (a-3) contained in the functional group-containing resin precursor (a) may be of one type or two or more types.

The structural unit (a-3) is a structure derived from another ethylenically unsaturated compound (ma-3) other than the compound that becomes the structural unit (a-1) or the structural unit (a-2) by polymerization. Units are preferred.
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 Examples include vinyl compounds.

Specific examples of (meth)acrylates 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, allyl (meth)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, tetra methylpiperidyl (meth)acrylate, hexamethylpiperidyl (meth)acrylate and the like.

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

Specific examples of blocking agents used for blocking the above isocyanato groups include lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam and β-propiolactam; methanol, ethanol, propanol, butanol, ethylene. alcohols such as glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol and cyclohexanol; butyl phenols such as phenol, cresol, xylenol, ethylphenol, o-isopropylphenol and p-tert-butylphenol , p-tert-octylphenol, nonylphenol, dinonylphenol, styrenated phenol, oxybenzoic acid ester, thymol, p-naphthol, p-nitrophenol, p-chlorophenol; dimethyl malonate, diethyl malonate, aceto Active methylene compounds such as methyl acetate, ethyl acetoacetate and acetylacetone; Mercaptan compounds such as butyl mercaptan, thiophenol and tert-dodecylmercaptan; Amine compounds such as diphenylamine, phenylnaphthylamine, aniline and carbazole; acid amides such as; acid imides such as succinimide and maleic acid imide; imidazoles such as imidazole, 2-methylimidazole and 2-ethylimidazole; urea systems such as urea, thiourea and ethylene urea; N-phenyl carbamates such as phenyl carbamate and 2-oxazolidone; imines such as ethyleneimine and polyethyleneimine; oximes such as formaldoxime, acetoaldoxime, acetoxime, methylethylketoxime, methylisobutylketoxime and cyclohexanone oxime; Examples include bisulfites such as sodium bisulfite and potassium bisulfite.

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, diacetone (meth) acrylamide and the like.

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

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]dodeca-3-ene, 8-methyltetracyclo[4.4.0.12,5. 17,10]dodeca-3-ene, 8-ethyltetracyclo[4.4.0.12,5.17,10]dodeca-3-ene, dicyclopentadiene, tricyclo[5.2.1.02, 6]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, tetracyclo[4.4.0.12,5.17,10.01,6] dodec-3-ene, 8-methyltetracyclo[4.4.0.12,5.17,10.01,6]dodeca-3-ene, 8-ethylidenetetracyclo[4.4.0.12, 5.17,12]dodeca-3-ene, 8-ethylidenetetracyclo[4.4.0.12,5.17,10.01,6]dodeca-3-ene, pentacyclo[6.5.1. 13,6.02,7.09,13]pentadeca-4-ene, pentacyclo[7.4.0.12,5.19,12.08,13]pentadeca-3-ene, (meth)acrylic anilide , (meth)acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinylpyridine, vinyl acetate, vinyltoluene, and the like.

Among these, as the other ethylenically unsaturated compound (ma-3), from the viewpoint of availability and reactivity in synthesizing the functional group-containing resin precursor (a), (meth)acrylic acid Esters and other vinyl compounds are preferred, and methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, styrene, vinyltoluene and norbornene are preferred. Cyclopentanyl (meth)acrylate, styrene, and vinyltoluene are more preferred.

When the functional group-containing resin precursor (a) contains the structural unit (a-3), the content thereof should be 1 to 50 mol% of the total structural units of the functional group-containing resin precursor (a). is preferred, 3 to 40 mol % is more preferred, and 5 to 30 mol % is even more preferred. When the content of the structural unit (a-3) is 1 mol % or more, the effect of including the structural unit (a-3) can be sufficiently obtained. Also, when the content of the structural unit (a-3) is 50 mol % or less, the content of the structural unit (a-1) and the structural unit (a-2) can be sufficiently ensured.

[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 of one type or two or more types.
Because the resin (A) has an ethylenically unsaturated group introduced by adding the compound (ma-4) to some of the functional groups of the functional group-containing resin precursor (a). A photosensitive resin composition using a resin composition containing the resin (A) as a raw material can form a cured resin film having excellent hardness and solvent resistance.

Examples of the ethylenically unsaturated group possessed by the compound (ma-4) include a (meth)acryloyl group, a vinyl group and an allyl group, with a (meth)acryloyl group being preferred. When the ethylenically unsaturated group possessed by the compound (ma-4) is a (meth)acryloyl group, the photosensitive resin composition containing the resin (A) can form a cured resin film having superior solvent resistance. . Moreover, excellent developability can be obtained when the resin composition containing the resin (A) is used as a raw material for the photosensitive resin composition.

Examples of the compound (ma-4) in which the ethylenically unsaturated group is a (meth)acryloyl group include (meth)acryloyl group-containing carboxy compounds, (meth)acryloyl group-containing hydroxy compounds, (meth)acryloyl group-containing isocyanates, (meth)acryloyl group-containing epoxy compounds, (meth)acryloyl group-containing acid anhydrides, (meth)acryloyl group-containing amino compounds, and the like.

Examples of the (meth)acryloyl group-containing carboxy compound include the compounds exemplified as the above-mentioned carboxy group-containing ethylenically unsaturated compound (ma-21), which is the compound that serves as the structural unit (a-2).
Examples of the (meth)acryloyl group-containing hydroxy compound include hydroxy group-containing (meth)acrylates exemplified as the above-described hydroxy group-containing ethylenically unsaturated compound (ma-22), which is a compound that serves as the structural unit (a-2). be done.

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

(Meth)acryloyl group-containing acid anhydrides include, for example, 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, N-tert-butylaminoethyl (meth)acrylate and the like.

The amount of the compound (ma-4) added to the functional group-containing resin precursor (a) is 1 to 40 mol per 100 mol of all structural units of the functional group-containing resin precursor (a). is preferred, 5 to 30 mol is more preferred, and 6 to 25 mol is even more preferred. When the amount of the compound (ma-4) added is 1 mol or more, the compound (ma-4) is sufficiently added to give the resin (A) having a sufficient number of ethylenically unsaturated groups. Therefore, a photosensitive resin composition using a resin composition containing the resin (A) as a raw material can form a cured resin film having excellent hardness and solvent resistance. When the addition amount of the compound (ma-4) is 40 mol or less, after the reaction of modifying the functional group-containing resin precursor (a) to obtain the resin (A) to which the compound (ma-4) is added, Remaining unreacted compound (ma-4) can be suppressed. Therefore, the storage stability of the resin composition containing the resin (A) obtained by modifying the functional group-containing resin precursor (a) is improved.

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

[Compound (ma-5)]
If necessary, a compound (ma-5) may be added to some of the functional groups of the functional group-containing resin precursor (a). The compound (ma-5) has no ethylenically unsaturated group and has a group reactive with the functional group of the functional group-containing resin precursor (a) and a carboxy group. The carboxy group possessed by the compound (ma-5) can impart developability to the photosensitive resin composition containing the resin composition of the present 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, the functional group-containing resin precursor ( Compound (ma-5) is preferably added to a). The compound (ma-5) added to a part of the functional groups of the functional group-containing resin precursor (a) may be of one type or two or more types.

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 compound (ma-5) include 3-hydroxypropionic acid, alanine, glycine, 4-hydroxybenzoic acid, 4-aminobenzoic acid and the like.

When the compound (ma-5) is added to the functional group-containing resin precursor (a), the amount added is 1 to 50 per 100 mol of all structural units of the functional group-containing resin precursor (a). mol, more preferably 5 to 40 mol, even more preferably 10 to 30 mol. When the amount of the compound (ma-5) added is 1 mol or more, the compound (ma-5) is sufficiently added to give the resin (A) having a sufficient number of carboxy groups. Therefore, sufficient developability can be imparted to the photosensitive resin composition containing the resin (A). When the content of the compound (ma-5) is 50 mol or less, in the reaction for modifying the functional group-containing resin precursor (a) to obtain the resin (A) to which the compound (ma-5) is added, , the remaining unreacted compound (ma-5) can be suppressed. As a result, the resin composition containing the resin (A) obtained by modifying the functional group-containing resin precursor (a) can suppress the influence of containing the unreacted compound (ma-5), Good storage stability. Further, when the added amount of the compound (ma-5) is 50 mol or less, the ratio of the functional group-containing resin precursor (a) to which the compound (ma-5) is not added in the resin (A) is sufficiently increased. can be secured. Therefore, the photosensitive resin composition containing the resin (A) can form a cured resin film having sufficient hardness and solvent resistance.

When the compound (ma-5) is added to the functional group-containing resin precursor (a), the compound (ma-4) and the compound (ma-5) are added to the functional group of the functional group-containing resin precursor (a). Total addition ratio, in other words, ratio of total amount of compound (ma-4) and compound (ma-5) to 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 %, even more preferably 20 to 85 mol %. When the total addition rate of the compound (ma-4) and the compound (ma-5) is 2 mol% or more, the effect due to the addition of the compound (ma-4) and the compound (ma-5) is sufficient. It becomes resin (A) obtained in. When the total addition rate of the compound (ma-4) and the compound (ma-5) is 90 mol% or less, the functional group-containing resin precursor (a) is modified to produce the compound (ma-4) and the compound (ma It is possible to prevent the unreacted compound (ma-4) and/or the compound (ma-5) from remaining after the reaction to obtain the resin (A) to which -5) is added. Therefore, the storage stability of the resin composition containing the resin (A) obtained by modifying the functional group-containing resin precursor (a) is improved, and the photosensitive resin composition using the resin composition as a raw material. It is possible to suppress outgassing and the like generated when obtaining a cured resin film consisting of.

As the resin (A), a combination of the functional group of the structural unit (a-2) and the compound (ma-4) (or the functional group of the structural unit (a-2) and the compound (ma-4) and The combination with compound (ma-5)) is particularly preferably any combination of <1> to <5> shown below. Any combination of <1> to <5> shown below is preferable because production is easy in terms of reactivity.

<1> The functional group possessed by the structural unit (a-2) is an isocyanato group, and the compound (ma-4) is a (meth)acryloyl group-containing hydroxy compound, a (meth)acryloyl group-containing amino compound, and a (meth) ) Resin (A), which is one or more selected from acryloyl group-containing carboxy compounds, and optionally compound (ma-5) is added. In combination <1>, compound (ma-4) is more preferably one or more selected from (meth)acryloyl group-containing hydroxy compounds and (meth)acryloyl group-containing amino compounds.

<2> The functional group possessed by the structural unit (a-2) is a hydroxy group, and the compound (ma-4) is a (meth)acryloyl group-containing isocyanate, a (meth)acryloyl group-containing acid anhydride, and a (meth)acryloyl group-containing acid anhydride. ) Resin (A) which is one or more selected from acryloyl group-containing carboxy compounds. In combination <2>, 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.

<4> The functional group possessed by the structural unit (a-2) is a carboxy group, and the compound (ma-4) is a (meth)acryloyl group-containing isocyanate compound, a (meth)acryloyl group-containing hydroxy compound, and a (meth) ) Resin (A) which is one or more selected from acryloyl group-containing epoxy compounds. In combination <4>, compound (ma-4) is more preferably a (meth)acryloyl group-containing isocyanate.
<5> A resin in which the functional group of the structural unit (a-2) is an epoxy group, the compound (ma-4) is a (meth)acryloyl group-containing carboxy compound, and optionally a compound ( Resin (A) to which ma-5) was added.

"Weight average molecular weight (Mw)"
The weight average molecular weight (Mw) of the resin (A) is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, and most preferably 3,000 to 10,000 in terms of polystyrene. When the weight-average molecular weight (Mw) of the resin (A) is 1000 or more, when the resin composition containing the resin (A) is used as a raw material of the photosensitive resin composition, the cured resin film after development may be chipped. It is possible to obtain a photosensitive resin composition that is less likely to cause the problem of When the weight-average molecular weight of the resin (A) is 50,000 or less, the photosensitive resin composition containing the resin (A) has sufficiently short development time and excellent practicality.

The value of the weight average molecular weight (Mw) of the resin (A) in the present embodiment is measured using gel permeation chromatography (GPC) under the following conditions and calculated in terms of polystyrene. .
Column: Shodex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko Co., Ltd.)
Column temperature: 40°C
Sample: Tetrahydrofuran solution containing 0.2% by mass of resin (A) Developing solvent: Tetrahydrofuran Detector: Differential refractometer (trade name: Shodex (registered trademark) RI-71S, manufactured by Showa Denko KK)
Flow rate: 1 mL/min

The molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the resin (A) is preferably 1.3 to 5.0, more preferably 1.5 to 4.0. , 1.5 to 3.0. When the molecular weight distribution (Mw/Mn) of the resin (A) is 1.3 or more, the weight average molecular weight (Mw), the optimization of the target numerical range such as the acid value, and the reaction during the production of the resin (A) Conditions, etc. can be set within a certain range, and efficient production can be achieved. When the molecular weight distribution (Mw/Mn) of the resin (A) is 3.0 or less, when the resin composition containing the resin (A) is used as a raw material for a photosensitive resin composition, performance such as developability is affected. A photosensitive resin composition free from variations is obtained.
The molecular weight distribution (Mw/Mn) is calculated using the chromatogram of the GPC measurement described above.

"acid value"
The acid value of the resin (A) is not particularly limited, but is preferably 10 KOHmg/g to 300 KOHmg/g, more preferably 20KOHmg/g to 200KOHmg/g, most preferably 25KOHmg/g to 150KOHmg/g. be. When the acid value of the resin (A) is 10 KOHmg/g or more, the photosensitive resin composition has better developability when the resin composition containing the resin (A) is used as a raw material of the photosensitive resin composition. you get something. When the acid value of the resin (A) is 300 KOHmg/g or less, when the resin composition containing the resin (A) is used as a raw material for the photosensitive resin composition, the exposed portion (photocured Part) does not dissolve, and a photosensitive resin composition having good developability can be obtained.

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

"Silyl group equivalent"
The silyl group equivalent weight 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. is. When the silyl group equivalent of the resin (A) is 200 g/mol or more, the photosensitive resin composition containing the resin (A) can form a cured resin film having superior hardness. Further, when the silyl group equivalent of the resin (A) is 200 g/mol or more, when the resin composition containing the resin (A) is used as a raw material of the photosensitive resin composition, the photosensitive resin composition has better developability. A flexible resin composition is obtained. Moreover, when the silyl group equivalent of the resin (A) is 5000 g/mol or less, the photosensitive resin composition containing the resin (A) can form a cured resin film having superior hardness.

The silyl group equivalent of resin (A) is a value obtained by dividing the molecular weight of resin (A) by the average number of silyl groups per molecule. The silyl group equivalent of the resin (A) is composed of the polymerizable unsaturated compound (raw material monomer) used as a raw material when synthesizing the resin (A), the compound (ma-4), and the compound used as necessary ( It is a calculated value calculated based on the charged amount of ma-5). When one molecule of resin (A) contains different types of silyl groups, all silyl groups are counted as the number of silyl groups regardless of the type of silyl group.

"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, most preferably 300 g/mol to 3000 g/mol. mol. When the double bond equivalent of the resin (A) is 200 g/mol or more, the photosensitive resin composition containing the resin (A) can form a resin cured film having superior hardness. Further, when the double bond equivalent of the resin (A) is 200 g/mol or more, when the resin composition containing the resin (A) is used as a raw material of the photosensitive resin composition, it has better developability. A photosensitive resin composition is obtained. Moreover, when the double bond equivalent of the resin (A) is 5000 g/mol or less, the photosensitive resin composition containing the resin (A) can form a cured resin film having superior hardness.

The double bond equivalent of Resin (A) is a value obtained by dividing the molecular weight of Resin (A) by the average number of unsaturated groups per molecule. The double bond equivalent of the resin (A) is the polymerizable unsaturated compound (raw material monomer) used as a raw material when synthesizing the resin (A), the compound (ma-4), and the compound used as necessary. It is a calculated value calculated based on the charged amount of (ma-5). When one molecule of resin (A) contains different types of unsaturated groups, all unsaturated groups are counted as the number of unsaturated groups, regardless of the types of unsaturated groups.

<Method for producing resin (A)>
To produce the resin (A) contained in the resin composition of the present embodiment, first, a functional group-containing resin precursor (a) is produced. Then, the resin (A) is obtained by adding the compound (ma-4) to some of the functional groups of the functional group-containing resin precursor (a).

(Production of functional group-containing resin precursor (a))
The functional group-containing resin precursor (a) can be produced, for example, using the production method shown below. That is, in the presence of a polymerization solvent, a compound (ma-1) represented by the following formula (2), a functional group-containing ethylenically unsaturated compound (ma-2), and optionally other and an ethylenically unsaturated compound (ma-3) are copolymerized using a polymerization initiator according to a radical polymerization method known in the art. Thereby, a functional group-containing resin precursor (a) is obtained.

（式（２）中のＲ^１～Ｒ^４及びｎは、式（１）中のＲ^１～Ｒ^４及びｎと同じである。）

(R ¹ to R ⁴ and n in formula (2) are the same as R ¹ to R ⁴ and n in formula (1).)

Specifically, after dissolving the raw material monomer in a polymerization solvent to prepare a raw material monomer solution, a polymerization initiator is added to the raw material monomer solution, and stirred at 50° C. to 130° C. for 1 hour to 20 hours, for example. It is possible to use a method of conducting a copolymerization reaction while
The compound (ma-1) represented by formula (2), the functional group-containing ethylenically unsaturated compound (ma-2), and optionally other ethylenically unsaturated compounds (ma-3) include: Any of the compounds exemplified as raw materials (derived from) of the structural units (a-1) to (a-3) can be used.

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

Examples of the solvent for polymerization used in producing the functional group-containing resin precursor (a) include the same solvents as those exemplified as other solvents that may be contained in the solvent (D) described later. Among these, the 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) is good, and the dissolution of the resin (A) It is preferable to use (poly)alkylene glycol monoalkyl ether acetates, and it is particularly preferable to use propylene glycol monomethyl ether acetate because of their good properties. Alcohol is not used as a solvent for polymerization because it inhibits the addition reaction between the functional group of the functional group-containing resin precursor (a) and the group reactive with the functional group of the compound (ma-4). is preferred.

The amount of the polymerization solvent used in producing the functional group-containing resin precursor (a) is not particularly limited, but is preferably 30 parts by mass to 1000 parts by mass with respect to 100 parts by mass of the raw material monomer. It is preferably 50 parts by mass to 800 parts by mass. When the amount of the polymerization solvent used is 30 parts by mass or more, the copolymerization reaction of the raw material monomers can be stably carried out, and coloration and gelation of the functional group-containing resin precursor (a) can be prevented. When the amount of the polymerization solvent used is 1000 parts by mass or less, the decrease in the molecular weight of the functional group-containing resin precursor (a) due to the chain transfer effect can be suppressed, and the viscosity of the reaction solution can be controlled within an appropriate range.

(Polymerization initiator)
The polymerization initiator that can be used in the copolymerization reaction of the raw material monomers is not particularly limited. valeronitrile), 2,2′-azobis(isobutyrate)dimethyl, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate and the like. These polymerization initiators may be used individually by 1 type, and may be used in combination of 2 or more type.
The amount of the polymerization initiator used is not particularly limited, but is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 16 parts by mass with respect to 100 parts by mass of the raw material monomer. .

(Addition reaction of compound (ma-4) (modification reaction of functional group-containing resin precursor (a)))
Next, the compound (ma-4) is added to part of the functional groups of the functional group-containing resin precursor (a). At this time, if necessary, the compound (ma-5) may be added to part of the functional groups of the functional group-containing resin precursor (a).
addition reaction between the functional group of the functional group-containing resin precursor (a) and the compound (ma-4), or the functional group of the functional group-containing resin precursor (a), the compound (ma-4) and the compound The addition reaction with (ma-5) can be carried out according to a conventional method.

For example, a method is used in which the compound (ma-4) (or the compound (ma-4) and the compound (ma-5)) is added to the reaction solution obtained by synthesizing the functional group-containing resin precursor (a) for an addition reaction. be able to. Moreover, in this addition reaction (modification reaction), there is no particular problem even if the reaction solution contains the polymerization solvent used in the copolymerization for producing the functional group-containing resin precursor (a). Therefore, the addition reaction can be carried out without removing the solvent for polymerization from the reaction solution after the completion of the copolymerization reaction for producing the functional group-containing resin precursor (a).

When the compound (ma-5) is added to the functional group-containing resin precursor (a), the compound (ma-5) may be added to the reaction solution at the same time as the compound (ma-4), or the compound (ma- It may be added to the reaction solution separately from 4). That is, the addition reaction between the functional group of the functional group-containing resin precursor (a) and the compound (ma-5) is the reaction between the functional group of the functional group-containing resin precursor (a) and the compound (ma-4). It may be performed before, after, or simultaneously with the addition reaction.

The reaction temperature in the addition reaction is the functional group possessed by the functional group-containing resin precursor (a) and the functional group possessed by the compound (ma-4) (or the compound (ma-4) and the compound (ma-5)). It can be appropriately assayed according to the type of group reactive with . Specifically, the reaction temperature is preferably 30°C to 150°C, more preferably 50°C to 120°C. By setting the reaction temperature to 30° C. or higher, the addition reaction can proceed sufficiently. In addition, 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.

(Polymerization inhibitor)
When carrying out the addition reaction, a polymerization inhibitor may be added to the reaction solution, if necessary, in order 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.

(catalyst)
When carrying out the addition reaction, a catalyst may be added to the reaction solution to promote the reaction, if necessary. Examples of catalysts include, but are not limited to, tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, metal chelate compounds such as chromium, Examples include tin compounds such as tin 2-ethylhexanoate and dibutyltin dilaurate (DBTDL).

[Solvent (D)]
The solvent (D) contained in the resin composition of the present embodiment contains at least one selected from primary alcohols having 3 to 10 carbon atoms and secondary alcohols having 3 to 10 carbon atoms, and the resin There is no particular limitation as long as the solvent is inert to (A) and 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 for producing the functional group-containing resin precursor (a), the copolymerization reaction for producing the functional group-containing resin precursor (a) is Carrying out the addition reaction for producing the resin (A) without removing the polymerization solvent from the reaction solution after the completion of the addition reaction, and separating and removing the polymerization solvent from the reaction solution after the completion of the addition reaction. It can be used as it is as part or all of the solvent (D) of the resin composition.

The case where the solvent (D) does not contain the solvent for polymerization used in producing the functional group-containing resin precursor (a) means that the resin (A) used as a raw material for the resin composition is the resin ( A) is separated and removed from the reaction solution in which A) is produced. In this case, the solvent (D ) can be selected as appropriate. That is, when the resin (A) is separated and removed from the reaction solution in which the resin (A) is generated, the solvent (D) is used for producing the functional group-containing resin precursor (a). The same type of solvent as the polymerization solvent used may be used, or a different one may be used.

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 of 3 to 10 carbon atoms and secondary alcohols of 3 to 10 carbon atoms, for example, are strongly solvated in water compared to tertiary alcohols and non-alcohols, and have the formula (1 ) can suppress the hydrolysis reaction of the alkoxysilyl group of the structural unit (a-1) represented by ). Therefore, it is possible to prevent the formation of silanol groups by the hydrolysis reaction of the alkoxysilyl groups and increase the molecular weight of the resin (A) due to the self-condensation reaction of the silanol groups. Therefore, by including the primary alcohol and/or secondary alcohol in the solvent (D), the resin composition containing this will have good storage stability. A solvent (D) may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of primary alcohols having 3 to 10 carbon atoms and secondary alcohol solvents having 3 to 10 carbon atoms contained in the solvent (D) include monoalcohols and (poly)alkylene glycol monoalkyl ethers. and the like.
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; benzyl alcohol, etc. secondary alcohols of

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, tripropylene glycol monoethyl ether and the like.

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 easily available. And from the viewpoint of storage stability as a resin composition, (poly)alkylene glycol monoalkyl ethers are preferred, and 3-methoxy-1-butanol is more preferred.

The solvent (D) is at least one solvent selected from primary alcohols having 3 to 10 carbon atoms and secondary alcohols having 3 to 10 carbon atoms, and is capable of dissolving the resin (A). Other solvents may also be included.

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

Among these, the compatibility with primary alcohols having 3 to 10 carbon atoms and secondary alcohols having 3 to 10 carbon atoms is good, and the solubility of the resin (A) is good. As another solvent, it is preferable to use (poly)alkylene glycol monoalkyl ether acetates, and it is particularly preferable to use propylene glycol monomethyl ether acetate.

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, with respect to 100% by mass of the solvent (D), It is preferably 10% by mass to 95% by mass, more preferably 20% by mass to 90% by mass, even more preferably 20% by mass to 80% by mass. 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.

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

The content of the solvent (D) in the resin composition of the present embodiment is preferably 30 parts by mass to 1000 parts by mass with respect to the total 100 parts by mass of the components excluding the solvent (D) in the resin composition, More preferably 50 to 800 parts by mass, most preferably 100 to 700 parts by mass. 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.

In addition to the above components, the resin composition of the present embodiment may contain known additives such as leveling agents and thermal polymerization inhibitors in order to impart predetermined properties. The content of the additive contained in the resin composition is not particularly limited as long as it does not impair the effects of the present invention.

<Method for producing resin composition>
The resin composition of the present embodiment can be produced by mixing the above resin (A) and solvent (D) using a known method. When the solvent (D) contains the solvent for polymerization used in producing the functional group-containing resin precursor (a), the resin composition of the present embodiment produces the functional group-containing resin precursor (a). It may be a reaction solution containing the resin (A) obtained by carrying out an addition reaction for producing the resin (A) using the reaction solution in which the copolymerization reaction for the above was carried out.

The resin composition of the present embodiment contains the above resin (A) and solvent (D), and the resin (A) is part of the functional groups of the functional group-containing resin precursor (a) (ma- 4) is added. Therefore, the resin composition of this embodiment has excellent storage stability.
In addition, the resin composition of the present embodiment has good low-temperature curability and is suitable as a material for the photosensitive resin composition of the present embodiment capable of forming a cured resin film having sufficient hardness and solvent resistance.

<Photosensitive resin composition>
Next, the photosensitive resin composition of this embodiment will be described in detail.
The photosensitive resin composition of the present embodiment includes the resin composition of the present embodiment containing the above resin (A) and solvent (D), a reactive diluent (B), and a photopolymerization initiator (C). and The photosensitive resin composition of this embodiment may contain a coloring agent (E), if necessary.

The content of the resin (A) in the photosensitive resin composition of the present embodiment is preferably 10 parts by mass to 100 parts by mass in total of the components excluding the solvent (D) contained in the photosensitive resin composition. 85 parts by mass, more preferably 15 to 75 parts by mass, most preferably 25 to 60 parts by mass. When the content of the resin (A) is 10 parts by mass or more, the developability is good, and a cured resin film with good hardness and solvent resistance can be obtained. When the content of the resin (A) is 85 parts by mass or less, the photosensitive resin composition has good photocurability.

The content of the solvent (D) in the photosensitive resin composition of the present embodiment is preferably 20 parts by mass to 100 parts by mass in total of the components excluding the solvent (D) contained in the photosensitive resin composition. 1000 parts by mass, more preferably 30 to 800 parts by mass, most preferably 50 to 700 parts by mass. 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.

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

Specific examples of aromatic vinyl monomers include styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, divinylbenzene, diallyl phthalate, diallylbenzene phosphonate and the like.
Specific examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, β-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, ) acrylates and the like.

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. ) acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tris(hydroxyethyl) isocyanurate tri(meth) acrylates and the like.

Among these, the reactive diluent (B) is preferably polyfunctional (meth)acrylates, particularly dipentaerythritol penta ( Preference is given to meth)acrylates and/or dipentaerythritol hexa(meth)acrylates.
These reactive diluents (B) may be used singly or in combination of two or more.

The content of the reactive diluent (B) in the photosensitive resin composition of the present embodiment is preferably 10 parts by mass with respect to the total 100 parts by mass of the components excluding the solvent (D) contained in the photosensitive resin composition. parts to 85 parts by mass, more preferably 15 to 75 parts by mass, and most preferably 25 to 60 parts by mass. When the content of the reactive diluent (B) is within the above range, the viscosity and photocurability of the photosensitive resin composition become more appropriate.

[Photoinitiator (C)]
The photopolymerization initiator (C) contained in the photosensitive resin composition of the present 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, benzoin methyl ether, benzoin ethyl ether and other benzoin and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, Acetophenones such as 4-(1-t-butyldioxy-1-methylethyl)acetophenone; Alkylphenones such as 1-hydroxycyclohexylphenyl ketone and 2-hydroxy-2-methyl-1-phenylpropan-1-one;2 -anthraquinones such as methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; acetophenone dimethyl Ketals such as ketal and benzyl dimethyl ketal; Benzophenones; 1,2-octanedione, 1-[4-(phenylthio)-2-(o-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole -3-yl], 1-(o-acetyloxime) and other oxime esters; 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; xanthone and the like. One of these photopolymerization initiators (C) may be used alone, or two or more thereof may be used in combination.

The content of the photopolymerization initiator (C) in the photosensitive resin composition of the present embodiment is preferably 0.5 parts per 100 parts by mass in total of the components excluding the solvent (D) contained in the photosensitive resin composition. It is 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. When the content of the photopolymerization initiator (C) is 0.1 parts 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 and the performance of the cured resin film.

[Colorant (E)]
The photosensitive resin composition of the present embodiment may further contain a coloring agent (E), if necessary. 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 high luminance can be obtained and the photosensitive resin composition exhibits good alkali developability as compared with the case of using a pigment.

As the dye, from the viewpoint of solubility in the solvent (D) and alkaline developer, interaction with other components in the photosensitive resin composition, heat resistance, etc., acid dyes having an acidic group such as a carboxy group, acid It is preferable to use salts of dyes with nitrogen compounds, sulfonamides of acid dyes, and the like. Examples of such dyes include VALIFAST BLUE 2620; acid alizarin violet N; acid black 1, 2, 24, 48; 83, 90, 92, 112, 113, 120, 129, 147; acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; 51, 52, 56, 63, 74, 95; , 69, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211 , 215, 216, 217, 249, 252, 257, 260, 266, 274; 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 singly or in combination of two or more, depending on the desired pixel color.

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

When a pigment is used as the colorant (E), a known dispersant may be added to the photosensitive resin composition from the viewpoint of improving the dispersibility of the colorant (E). As the dispersant, it is preferable to use a polymer dispersant that exhibits excellent dispersion stability over time. Examples of polymer dispersants include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene glycol diester dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified esters. system dispersants and the like. Examples of such polymer dispersants include trade names such as EFKA (manufactured by EFKA Chemicals BV (EFKA)), Disperbyk (manufactured by BYK Chemie), Disparlon (manufactured by Kusumoto Kasei Co., Ltd.), and SOLSPERSE (manufactured by Zeneca). You may use what is marketed. The blending amount of the dispersant may be appropriately set according to the type and amount of the pigment used as the colorant (E).

The content of the coloring agent (E) in the photosensitive resin composition of the present embodiment is preferably 4 parts by mass to 100 parts by mass in total of the components excluding the solvent (D) contained in the photosensitive resin composition. 85 parts by mass, more preferably 9 to 70 parts by mass, and most preferably 14 to 49 parts by mass. When the content of the coloring agent (E) is 4 parts by mass or more, the effect of containing the coloring agent (E) becomes remarkable, and the photosensitive resin composition is suitable as a material for a colored pattern of a color filter. When the content of the coloring agent (E) is 85 parts by mass or less, the coloring agent (E) in the photosensitive resin composition does not interfere with the curability of the photosensitive resin composition and can be cured at a low temperature. It will be of good quality.

The photosensitive resin composition of the present embodiment comprises a resin composition containing a resin (A) and a solvent (D), a reactive diluent (B), a photopolymerization initiator (C), and optionally In addition to the colorant (E) contained, if necessary, one or more known additives such as leveling agents, thermal polymerization inhibitors and sensitizers may be contained. The content of these additives is not particularly limited as long as it does not impair the effects of the present invention.

Furthermore, the photosensitive resin composition of the present embodiment may contain an acid generator and a base generator in order to enhance curability. In particular, from the viewpoint of latency, it is preferable to use a photoacid generator, a photobase generator, a thermal acid generator, and a thermal base generator. From the viewpoint of storage stability, a photoacid generator and a photobase generator are preferably used. More preferred. Examples of the photoacid generator 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 the photobase generator include trade names WPBG-266, WPBG-300, WPBG-345 manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., and the like.

The viscosity of the photosensitive resin composition of the present embodiment can be appropriately adjusted according to the thickness of the cured resin film made of 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. More preferably, it is 3 mP·s to 15 mP·s.

<Method for producing a photosensitive resin composition>
The photosensitive resin composition of the present embodiment comprises a resin composition containing a resin (A) and a solvent (D), a reactive diluent (B), a photopolymerization initiator (C), and optionally It can be produced by mixing the contained coloring agent (E) and/or additives using a known mixing device.

The photosensitive resin composition of the present embodiment contains a resin composition containing a resin (A) and a solvent (D), a reactive diluent (B), and a photopolymerization initiator (C). Good stability. Therefore, the photosensitive resin composition of the present embodiment can be applied to easily form a coating film having a uniform thickness, and can be cured to easily form a cured resin film having a uniform thickness.

In addition, the photosensitive resin composition of the present embodiment has good low-temperature curability and can form a cured resin film having sufficient hardness and solvent resistance. Moreover, since the photosensitive resin composition of the present embodiment has excellent alkali developability, a fine pattern can be formed by developing with an aqueous alkali solution. In addition, since the photosensitive resin composition of the present embodiment can easily form a coating film having a uniform thickness, in the development step performed when forming a patterned cured resin film, Residue does not easily remain. Therefore, even if the minimum development dimension is 10 μm or less, a cured resin film having a clear pattern shape without residue between patterns can be formed. Therefore, the photosensitive resin composition of this embodiment is suitably used as a resist.
In addition, when the photosensitive resin composition of the present embodiment contains a coloring agent (E), it can be suitably used as a material for colored patterns such as pixels of color filters and black matrix.

<Resin cured film>
Next, the cured resin film of this embodiment will be described in detail.
The cured resin film of the present embodiment is composed of a cured product of the photosensitive resin composition of the present embodiment.
The cured resin film of the present embodiment includes, for example, a coating step of applying the photosensitive resin composition of the present embodiment onto a substrate to form a coating film, and 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.

When a cured resin film having a predetermined pattern is formed by photolithography using the photosensitive resin composition of the present embodiment, for example, the following method can be used. That is, the coating process and the pre-baking process described above are performed. After that, in the exposure step, the dried coating film is irradiated with light through a photomask having a predetermined pattern, and the exposed portion is photocured. After the exposure step, post-exposure heat treatment is performed as necessary. After that, a developing step of dissolving and developing the unexposed portion of the coating film using a developer, and a post-baking step of thermally curing the photo-cured coating film are performed.

[Coating process]
In the coating step, the photosensitive resin composition of the present embodiment is applied onto the substrate to form a coating film. In the present embodiment, a known substrate can be used as the substrate on which the photosensitive resin composition is applied, and the substrate can be appropriately determined according to the intended use of the cured resin film.
The method of applying the photosensitive resin composition is not particularly limited, and for example, a screen printing method, a roll coating method, a curtain coating method, a spray coating method, a spin coating method, a slit coating method, or the like can be used.

[Pre-baking process]
In the pre-baking (pre-heat treatment) step, the coating film formed in the coating step is dried to reduce the amount of residual solvent in the coating film. In the pre-baking step, the substrate on which the coating film is 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, as a method of heating the substrate on which the coating film is formed, for example, a method using a hot plate can be used.

[Exposure process]
In the exposure step, the surface of the coating film dried in the pre-baking step is irradiated with light to photo-cure the coating film. A light source used for light irradiation is not particularly limited, and for example, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be used. Moreover, the exposure amount in the exposure step is not particularly limited, and can be appropriately set according to the composition of the photosensitive resin composition, the thickness of the coating film, and the like.
When forming a cured resin film having a predetermined pattern, in the exposure step, the surface of the coating film dried in the prebaking step is irradiated with light through a photomask having a predetermined pattern, and the exposed portion is exposed to light. Harden.

[Post-exposure heating process]
When forming a cured resin film having a predetermined pattern, a post-exposure baking process is performed after the exposure process, if necessary. By performing this step, the dissolution contrast between the exposed portion and the unexposed portion of the coating film becomes more pronounced. The post-exposure heating process does not completely cure the coating film, unlike the post-baking process described below. The post-exposure heating step is performed in order to leave only the exposed portion of the coating film on the substrate and more reliably remove the unexposed portion of the coating film by performing the developing step. Therefore, it is not an essential step in the method for forming a cured resin film of the present embodiment.

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

[Development process]
In the case of forming a cured resin film having a predetermined pattern, after the exposure step, if necessary, the post-exposure heating step is performed, and then the development step of developing the unexposed portion of the coating film is performed. As a developer used in the development step, any alkaline aqueous solution conventionally used for developing a photosensitive resin composition can be used.

The alkaline aqueous solution is not particularly limited, but for example, aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide; aqueous solutions of amine compounds such as ethylamine, diethylamine, dimethylethanolamine; Aqueous solutions of quaternary ammonium salts such as methylammonium; 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 their sulfates, hydrochlorides or p-toluene Examples thereof include aqueous solutions of p-phenylenediamine compounds such as sulfonates. Among these alkaline aqueous solutions, it is preferable to use an aqueous solution of a p-phenylenediamine compound.

If necessary, one or more additives such as antifoaming agents and surfactants may be added to the alkaline aqueous solution.
Development conditions such as development temperature and development time in the development step can be appropriately determined according to the composition of the photosensitive resin composition, the composition of the developer, the thickness of the coating film, and the like.
In the developing step, it is preferable to dissolve the unexposed portion of the coating film using the aqueous alkali solution described above, develop the film, wash the film with water, and dry the film.

[Post-baking process]
In the present embodiment, after the developing process, a post-baking process 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-baking step are not particularly limited, and can be appropriately set according to the composition of the photosensitive resin composition, the thickness of the coating film, the material of the substrate, and the like.

The heating temperature in the post-baking process can be, for example, 50.degree. C. to 210.degree. When the heating temperature is 210° C. or lower, a material with low heat resistance can be used as the material for the color filter. The heating temperature may be, for example, 150° C. or lower, 120° C. or lower, or 100° C. when forming a colored pattern of a color filter using a resin substrate as a base material for forming a cured resin film. °C or lower. When the heating temperature is 150° C. or less, it is possible to form a colored pattern containing the coloring agent (E) with poor heat resistance, which has been difficult to use as a material for conventional colored patterns, while suppressing deterioration of the coloring agent (E). Further, when the heating temperature is 150° C. or lower, a colored pattern can be formed on a substrate having poor heat resistance, which has been difficult to use as a substrate for conventional color filters. Further, when the heating temperature is set to 150° C. or less, the amount of energy required for curing the coating film is small, which is preferable.

When the heating temperature in the post-baking step is 50° C. or higher, the resin (A) and the reactive diluent (B) are sufficiently crosslinked, so that a cured resin film having sufficient hardness and solvent resistance can be obtained. Moreover, when the heating temperature is 50° C. or higher, the heating time in the post-baking step can be shortened, and a cured resin film can be efficiently formed. The heating temperature in the post-baking step is more preferably 60° C. or higher, still more preferably 70° C. or higher.

The heating time in the post-baking step can be appropriately selected according to the heating temperature, the thickness of the coating film, the composition of the photosensitive resin composition, etc. For example, it can be 10 minutes to 4 hours, preferably 20 minutes to 2 hours.

The cured resin film of the present embodiment is composed of a cured product of the photosensitive resin composition of the present embodiment. Therefore, it has sufficient hardness and solvent resistance. In addition, since the cured resin film of the present embodiment is made of a cured product of a photosensitive resin composition containing the resin (A) and the solvent (D), when the cured resin film has a patterned pattern shape, , even if the minimum development size is 10 μm or less, the pattern becomes clear without residue. This is because the solvent (D) suppresses the hydrolysis reaction of the alkoxysilyl group of the structural unit (a-1) represented by the formula (1) in the photosensitive resin composition, thereby suppressing the hydrolysis reaction of the alkoxysilyl group. This is because the increase in the molecular weight of the resin (A) due to the self-condensation reaction of the silanol groups generated by is suppressed. The high-molecular-weight resin (A) reduces the uniformity of the thickness of the coating film made of the photosensitive resin composition, and causes residues to remain in unexposed areas between patterns after development.
The cured resin film of the present embodiment is preferably used as a material for various insulating films such as a protective film provided on a color filter or the like, an insulating film provided between electrodes of a touch panel, and an interlayer insulating film of a thin film transistor (TFT). can be done.

<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 the color filter of this embodiment. The color filter shown in FIG. and a protective film 4 formed on the black matrix 3 .

The substrate 1 used for the color filter shown in FIG. 1 is not particularly limited, and includes a glass substrate, a silicon substrate, a polycarbonate substrate, a polyester substrate, a polyamide substrate, a polyamideimide substrate, a polyimide substrate, an aluminum substrate, and printed wiring. A substrate, an array substrate, or the like can be appropriately used depending on the application.

The pixels 2 and the black matrix 3 in the color filter shown in FIG. It is a colored pattern made of a cured product of the photosensitive resin composition of the present embodiment containing a coloring agent (E) and optionally additives.
As the protective film 4, one made of a known material can be used. The protective film 4 comprises a resin composition containing a resin (A) and a solvent (D), a reactive diluent (B), a photopolymerization initiator (C), and additives contained as necessary. It may be a resin cured film made of a cured product of the photosensitive resin composition of the present embodiment containing.

In the color filter of the present embodiment shown in FIG. 1, the configuration other than the materials of the pixels 2 and the black matrix 3 can employ known ones. Moreover, 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.

Next, a method for manufacturing the color filter of this embodiment will be described.
First, pixels 2 of RGB and a black matrix 3 are sequentially formed on one surface 1a of the substrate 1 shown in FIG. The pixels 2 and the black matrix 3 can be manufactured using the method for manufacturing a cured resin film (photolithography method) of the present embodiment described above.
Next, a 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 method for manufacturing a cured resin film of the present embodiment described above.
Through the above steps, the color filter of this embodiment shown in FIG. 1 is obtained.

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

<Image display device>
The image display element of this embodiment comprises the color filter of this embodiment having sufficient hardness and solvent resistance. Examples of the image display device of this embodiment include a liquid crystal display device, an organic EL display device, a solid-state imaging device, and the like. Since the image display device of the present embodiment includes the color filter described above, it is difficult for the brightness to decrease due to deterioration of the color filter, and high brightness display is possible.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples and comparative examples. It should be noted that the following examples are intended to facilitate understanding of the content of the present invention. The invention is not limited to only these examples.

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

Next, 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, vinyl A mixture of 11.5 g (0.10 mol) of toluene, 21.4 g of 2,2′-azobis(isobutyrate)dimethyl (polymerization initiator), and 112.0 g of propylene glycol monomethyl ether acetate was added to the flask from the dropping funnel. It was added dropwise over 3 hours.

After completion of the dropwise addition, the mixture was stirred at 98° C. for 3 hours to carry out a copolymerization reaction to produce a functional group-containing resin precursor (a), which is a copolymer. After that, the inside of the flask was replaced with air, and 13.7 g (0.10 mol) of 2-acryloyloxyethyl isocyanate and dibutyltin dilaurate (DBTDL) were added to the reaction solution in which the functional group-containing resin precursor (a) was synthesized. ) (addition reaction catalyst) 0.11 g and methylhydroquinone (polymerization inhibitor) 0.36 g were added and subjected to an addition reaction at 60° C. for 2 hours.

As a result, the hydroxyl group derived from 2-hydroxyethyl methacrylate and the isocyanato group of 2-acryloyloxyethyl isocyanate are reacted to cleave the hydroxyl group derived from 2-hydroxyethyl methacrylate, and at the same time, the functional group-containing resin precursor (a) A polymerizable unsaturated bond was introduced into the side chain of to obtain a resin (A). In the presence of an addition reaction catalyst, the isocyanato groups of 2-acryloyloxyethyl isocyanate preferentially react with hydroxyl groups derived from 2-hydroxyethyl methacrylate rather than carboxy groups derived from methacrylic acid.
Next, 400.0 g of 3-methoxy-1-butanol was added as a solvent (composition additive solvent) to the reaction solution containing the resin (A) to obtain a resin composition of Example 1.

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

Next, 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, 2,2' A mixture of 20.8 g of dimethyl azobis(isobutyrate) (polymerization initiator) and 108.5 g of propylene glycol monomethyl ether acetate was dropped from the dropping funnel into the flask over 3 hours.

After completion of the dropwise addition, the mixture was stirred at 98° C. for 3 hours to carry out a copolymerization reaction to produce a functional group-containing resin precursor (a), which is a copolymer. After that, the inside of the flask was replaced with air, and 19.6 g (0.145 mol) of 2-acryloyloxyethyl isocyanate and methylhydroquinone (polymerization inhibitor) were added to the reaction solution that synthesized the functional group-containing resin precursor (a). ) was added, and addition reaction was carried out at 60° C. for 2 hours.

As a result, the carboxyl group derived from methacrylic acid is reacted with the isocyanato group of 2-acryloyloxyethyl isocyanate to cleave the carboxyl group derived from methacrylic acid, and at the same time, to the side chain of the functional group-containing resin precursor (a). A polymerizable unsaturated bond was introduced to obtain a resin (A).
Next, 400.0 g of 3-methoxy-1-butanol and 12.5 g of propylene glycol monomethyl ether acetate were added to the reaction solution containing the resin (A) as a solvent (composition additive solvent), and the resin composition of Example 2 was obtained. got stuff

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

Next, 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, A mixture of 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 into the flask over 3 hours.

After the completion of dropping, the mixture was stirred at 98° C. for 3 hours to carry out a copolymerization reaction, thereby producing a copolymer functional group-containing resin precursor (a), which is a copolymer. Thereafter, the inside of the flask was replaced with air, and 12.7 g (0.135 mol) of 2-hydroxyethyl methacrylate and dibutyltin dilaurate (DBTDL) were added to the reaction solution for synthesizing the functional group-containing resin precursor (a). 0.10 g of (addition reaction catalyst) and 0.32 g of methyl hydroquinone (polymerization inhibitor) were added and subjected to an addition reaction at 60° C. for 2 hours.

As a result, the isocyanato group derived from 2-acryloyloxyethyl isocyanate is reacted with the hydroxyl group of 2-hydroxyethyl methacrylate to cleave the isocyanate group derived from 2-acryloyloxyethyl isocyanate, and at the same time, the functional group-containing resin precursor ( A polymerizable unsaturated bond was introduced into the side chain of a).

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 addition reaction solution in the flask, and addition reaction was carried out at 40° C. for 2 hours.
As a result, the isocyanato group derived from 2-acryloyloxyethyl isocyanate is reacted with the amino group of 4-aminobenzoic acid to introduce an acid group into the side chain of the functional group-containing resin precursor (a), resulting in a resin ( A) was obtained.
Next, 400.0 g of 3-methoxy-1-butanol was added as a solvent (composition additive solvent) to the reaction solution containing the resin (A) to obtain a resin composition of Example 3.

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

Next, 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, vinyl A mixture of 12.3 g (0.10 mol) of toluene, 23.0 g of dimethyl 2,2′-azobis(isobutyrate) (polymerization initiator), and 118.0 g of propylene glycol monomethyl ether acetate was added to the flask from the dropping funnel. It was added dropwise over 3 hours.

After completion of the dropwise addition, the mixture was stirred at 98° C. for 3 hours to carry out a copolymerization reaction to produce 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) was synthesized to obtain a resin composition of Comparative Example 1.

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

Next, 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, 2,2' A mixture of 23.0 g of dimethyl azobis(isobutyrate) (polymerization initiator) and 106.2 g of propylene glycol monomethyl ether acetate was dropped from the dropping funnel into the flask over 3 hours.

After completion of the dropwise addition, the mixture was stirred at 98° C. for 3 hours to carry out a copolymerization reaction to produce 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) was synthesized to obtain a resin composition of Comparative Example 2.

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

Next, 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, A mixture of 20.6 g of dimethyl 2,2′-azobis(isobutyrate) (polymerization initiator) and 107.6 g of propylene glycol monomethyl ether acetate was dropped from the dropping funnel into the flask over 3 hours.

After the completion of dropping, the mixture was stirred at 98° C. for 3 hours to carry out a copolymerization reaction, thereby producing a copolymer functional group-containing resin precursor (a), which is a copolymer. Then, the inside of the flask was replaced with air, and 21.1 g (0.20 mol) of 4-aminobenzoic acid and 15.0 g (0.20 mol) of propylene glycol monomethyl ether acetate were added to the reaction solution for synthesizing the functional group-containing resin precursor (a). 9 g was added and reacted at 40° C. for 2 hours.
As a result, the isocyanato groups derived from 2-acryloyloxyethyl isocyanate and the amino groups of 4-aminobenzoic acid were reacted to introduce acid groups into the side chains 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 an acid group was introduced into the side chain of the functional group-containing resin precursor (a) to obtain a resin composition of Comparative Example 3.

[Synthesis Examples 4 to 13, Comparative Synthesis Examples 4 to 8]
Resins of Examples 4 to 13 and Comparative Examples 4 to 8 in the same manner as in Synthesis Example 1 except that the raw materials listed in Tables 1 to 4 were used in the proportions listed in Tables 1 to 4. A composition was obtained.

The resin (A) contained in the resin compositions of Examples 1 to 13 thus obtained, the functional group-containing resin precursor (a) contained in the resin compositions of Comparative Examples 1 and 2, and the resin precursor of Comparative Example 3 Resins in which acid groups are introduced into the side chains of the functional group-containing resin precursor (a) contained in the resin composition, copolymers contained in the resin compositions of Comparative Examples 4, 5 and 8, and those of Comparative Examples 6 and 7 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 of each resin contained in the resin composition were determined. The results are shown in Tables 1-4.

<Evaluation of Resin Composition>
Storage stability of the resin compositions of Examples 1 to 13 and Comparative Examples 1 to 8 was evaluated 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 into a 20 ml glass container and used as a sample, 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′×R24). Subsequently, each sample was stored in a thermostat kept at 12° C. for 3 months. After that, the viscosity was measured again in the same manner as described above.
Then, using the measured viscosity values before and after storage, the viscosity increase rate (rate of increase in viscosity) was obtained from the following formula and evaluated according to the criteria shown below. Tables 1 to 4 show the results.

Thickening rate (%) = (([Viscosity after storage] - [Viscosity before storage]) / [Viscosity before storage]) x 100
The criteria for evaluating the thickening rate are as follows.
◎: Less than 10% thickening rate ○: 10 to 20% thickening rate
△: more than 20% thickening rate

As shown in Table 1 or Table 2, the resin compositions of Synthesis Examples 1 to 13 were evaluated for storage stability as ⊚ or ◯, and all of them were confirmed to have excellent storage stability. .
On the other hand, as shown in Table 3 or Table 4, the resin compositions of Comparative Examples 4 to 7 were all evaluated for storage stability as Δ, indicating insufficient storage stability.

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

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

In addition, the copolymer in the resin composition in Table 5 (the resin (A) contained in the resin compositions of Examples 1 to 13, the functional group-containing resin precursors contained in the resin compositions of Comparative Examples 1 and 2 ( a), a resin obtained by introducing an acid group into the side chain of the functional group-containing resin precursor (a) contained in the resin composition of Comparative Example 3, and a copolymer contained in the resin compositions of Comparative Examples 4, 5, and 8 , the resin contained in the resin compositions of Comparative Examples 6 and 7) does not include the solvent for polymerization used in synthesizing the copolymer. Further, the blending amount of the solvent (D) in Table 5 is the sum of the solvent for polymerization used when synthesizing the copolymer in the resin composition and the solvent additionally added when preparing the resin composition. quantity.

<Evaluation of photosensitive resin composition>
(1) Storage stability of 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 put into a 20 ml glass container to prepare a sample, 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′×R24). Subsequently, each sample was stored in a thermostat kept at 12° C. for 3 months. After that, the viscosity was measured again in the same manner as described above.
Then, using the viscosity measurements before and after storage, the viscosity increase rate (increase rate of viscosity) was obtained from the following formula and evaluated according to the criteria shown below. The results are shown in Table 6 or Table 7.

Thickening rate (%) = (([Viscosity after storage] - [Viscosity before storage]) / [Viscosity before storage]) x 100
"Evaluation Criteria for Thickening Rate"
◎: Less than 10% thickening rate ○: 10 to 20% thickening rate
△: more than 20% thickening rate

(2) Developability The photosensitive resin compositions of Examples 1 to 13 and Comparative Examples 1 to 9 were each applied to a 5 cm square glass substrate (no alkali glass substrate) (coating step). The glass substrate coated with the photosensitive resin composition was heated at 100° C. for 3 minutes to volatilize the solvent and dry the coating film (pre-baking step).

Next, the surface of the dried coating film was irradiated with light of 200 mJ/cm ² using an ultra-high pressure mercury lamp through a photomask (exposure step). The exposure process was carried out by setting the photomask at a position separated from the coating film by 100 μm. A photomask having a line-and-space pattern with a width of 3 to 100 μm was used. Next, a developer containing potassium hydroxide as a main component (trade name: Semi-clean DL-A10, manufactured by Yokohama Yushi Kogyo Co., Ltd.) was diluted 5 times with water, and the temperature was 23 ° C. and the pressure was 0.1 MPa. , the unexposed portion was removed by spraying for 60 seconds on the surface of the coating film (development step). After the development step, the glass substrate having the coating film was placed in a drier at 100° C. for 30 minutes to thermally cure the coating film (post-baking step) to obtain a colored pattern.

The colored pattern thus obtained was observed using an electron microscope S-3400 manufactured by Hitachi High-Technologies Co., Ltd., and the minimum line width (minimum development dimension) that could be developed and the unexposed area between the developed patterns. The presence or absence of residue was 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 unexposed area between developed patterns ×: Residue in unexposed area between developed patterns

(3) Pencil hardness The photosensitive resin compositions of Examples 1 to 13 and Comparative Examples 1 to 9 were applied on a square glass substrate (non-alkali glass substrate) of 5 cm long and 5 cm wide by a spin coating method. C. for 3 minutes to volatilize the solvent to form a coating film. Next, the coating film was irradiated with light having a wavelength of 365 nm at an exposure amount of 200 mJ/cm ² to be photocured. Next, the glass substrate having the photo-cured coating film is placed in a dryer at 100° C. for 30 minutes to thermally cure the coating film (post-baking step) to cure the resin to a film thickness of 2.5 μm. A membrane was obtained.

The pencil hardness of the cured resin film thus prepared was measured according to JIS K5600-5-4 using a pencil hardness tester (No. 553-M, manufactured by Yasuda Seiki Seisakusho) and evaluated according to the following criteria. . The results are shown in Table 6 or Table 7.
"Evaluation Criteria for Pencil Hardness"
○: Pencil hardness 3H or more ×: Pencil hardness less than 3H

(4) Solvent resistance A glass substrate having a cured resin film was prepared in the same manner as in (3) Evaluation of pencil hardness, and a cured resin film was measured using a spectrophotometer (UV-1650PC, manufactured by Shimadzu Corporation). was measured. In addition, 200 mL of propylene glycol monomethyl ether acetate was placed in a 500 mL capacity glass bottle with a lid and allowed to stand at a temperature of 23°C. A glass substrate having a 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. Thereafter, the glass substrate having the cured resin film is taken out, and the absorption spectrum of the cured resin film is measured using a spectrophotometer (UV-1650PC, manufactured by Shimadzu Corporation) in the same manner as before immersion in propylene glycol monomethyl ether acetate. bottom.

The color change (ΔE ^* ab) of the cured resin film before and after immersion in propylene glycol monomethyl ether acetate was calculated, and 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.
"Evaluation Criteria for Solvent Resistance"
○: ΔE ^* ab is less than 3.0 ×: ΔE ^* ab is 3.0 or more

(5) Comprehensive Judgment The photosensitive resin compositions of Examples 1 to 13 and Comparative Examples 1 to 9 and cured resin films made of cured products thereof were evaluated according to the following criteria. The results are shown in Table 6 or Table 7.
"Evaluation criteria"
○: Satisfies all of the following items.
(1) The viscosity increase rate of the photosensitive resin composition is 20% or less (2) The minimum development size is 15 μm or less, and there is no residue in the unexposed area between developed patterns (3) The pencil hardness of the cured resin film is 3H or more (4) Color change ΔE ^* ab in evaluation of solvent resistance of cured resin film is less than 3.0 ×: Any one or more of the above items ○ are not satisfied.

As shown in Table 6, the photosensitive resin compositions of Examples 1 to 13 were evaluated for storage stability as ⊚ or ◯, confirming that all of them had excellent storage stability. In addition, the photosensitive resin compositions of Examples 1 to 13 all had a minimum development size of 15 μm or less, no residue in unexposed areas between developed patterns, and excellent alkali developability. I was able to confirm that there is.

Further, as shown in Table 6, the coating films formed using the photosensitive resin compositions of Examples 1 to 13 were photocured, and then cured resin films made of cured products thermally cured at a low temperature of 100 ° C. had a pencil hardness of 3H or more and had excellent hardness. Moreover, the above-mentioned cured resin film was evaluated as ○ in terms of solvent resistance, and it was confirmed that it had excellent solvent resistance.

In contrast, as shown in Table 7, the photosensitive resin compositions of Comparative Examples 1 to 9 all had excellent alkali developability. However, the photosensitive resin compositions of Comparative Examples 4 to 7 were evaluated as Δ in storage stability, and the storage stability was insufficient. Moreover, 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.

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

In addition, since 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 the formula (2) as the raw material monomer, the silyl equivalent is is 0. As a result, the hardness and solvent resistance of the cured resin film were inferior.
Further, in the resin compositions of Comparative Examples 4 and 5 contained in the photosensitive resin compositions of Comparative Examples 4 and 5, tri(methoxy ) A raw material monomer containing an ethoxy-type alkoxysilyl group is used. A tri(methoxy)ethoxy-type alkoxysilyl group undergoes cross-linking more rapidly than a di(methoxy)ethoxy-type alkoxysilyl group. Therefore, it is presumed that the resin compositions and photosensitive resin compositions of Comparative Examples 4 and 5 had insufficient storage stability.

The resin compositions of Comparative Examples 6 and 7 contained in the photosensitive resin compositions of Comparative Examples 6 and 7 contained primary alcohols having 3 to 10 carbon atoms and secondary alcohols having 3 to 10 carbon atoms as solvents. It does not contain at least one selected from class alcohols. Therefore, in the resin compositions of Comparative Examples 6 and 7 and the photosensitive resin compositions containing the same, the structural unit (a-1) represented by the formula (1) contained in the resin (A) has an alkoxysilyl group It is presumed that the hydrolysis reaction of was likely to proceed, and sufficient storage stability was not obtained. More specifically, in the photosensitive resin compositions of Comparative Examples 6 and 7, a silanol group is generated by a hydrolysis reaction of the alkoxysilyl group of the structural unit (a-1) represented by formula (1). It is presumed that the resin (A) has a high molecular weight due to the self-condensation reaction of the groups. Further, in the photosensitive resin compositions of Comparative Examples 6 and 7, since the resin (A) had a high molecular weight, the uniformity of the thickness of the coating film was deteriorated and the resin (A) became a development residue. It is presumed that the minimum developed dimension was inferior to that of the curable resin composition. Furthermore, as a result of observing the colored patterns (cured products) evaluated for developability in Comparative Examples 6 and 7, residues remained in the unexposed areas between the developed patterns, and the evaluation of the residues was x in both cases. Therefore, the colored patterns made of the cured photosensitive resin compositions of Comparative Examples 6 and 7 had unclear shapes.

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

According to the present invention, it is possible to provide a photosensitive resin composition having excellent storage stability and developability, and good low-temperature curability, capable of forming a cured resin film having sufficient hardness and solvent resistance. Furthermore, according to the present invention, a resin composition having excellent storage stability contained in a photosensitive resin composition, a cured resin composition comprising a cured product of the photosensitive resin composition and having sufficient hardness and solvent resistance. It is possible to provide a film, a color filter having sufficient hardness and solvent resistance, and an image display element equipped with this color filter. The photosensitive resin composition of the present invention can be preferably used as, for example, transparent films, protective films, insulating films, overcoats, photospacers, black matrices, black column spacers, and color filter resists.

1: substrate, 2: pixel, 3: black matrix, 4: protective film.

Claims (14)

including a resin (A) and a solvent (D),
In the resin (A), a compound (ma-4) having a group reactive with the functional group and an ethylenically unsaturated group is added to some of the functional groups of the functional group-containing resin precursor (a). It is a resin that
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, wherein 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.

(In formula (1), R ¹ represents a hydrogen atom or a methyl group. Two of R ² to R ⁴ are each independently an alkoxy group having 1 to 6 carbon atoms, and the remaining one is a hydrogen atom and is one selected from alkyl groups having 1 to 6 carbon atoms, or one of R ² to R ⁴ is an alkoxy group having 1 to 6 carbon atoms, and the remaining two are each independently a hydrogen atom and It is one selected from alkyl groups having 1 to 6 carbon atoms, and n is an integer of 1 to 10.) 1. In formula (1), two of R ² to R ⁴ are each independently an alkoxy group having 1 to 6 carbon atoms, and the remaining one is an alkyl group having 1 to 6 carbon atoms. The resin composition according to . 3. The resin composition according to claim 1, 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. . The compound (ma-4) is 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, and a (meth)acryloyl group. 4. The resin composition according to any one of claims 1 to 3, which is one or more selected from epoxy compounds containing and (meth)acryloyl group-containing amino compounds. the functional group of the structural unit (a-2) is one or more selected from a carboxy group and a hydroxy group,
The resin composition according to any one of claims 1 to 4, wherein the compound (ma-4) is a (meth)acryloyl group-containing isocyanate. the functional group of the structural unit (a-2) is an isocyanato group,
The compound (ma-4) is one or more selected from (meth)acryloyl group-containing hydroxy compounds and (meth)acryloyl group-containing amino compounds, according to any one of claims 1 to 4. Resin composition. The resin (A) further comprises a compound (ma-5) having a group reactive with the functional group and a carboxy group added to a part of the functional groups of the functional group-containing resin precursor (a). The resin composition according to any one of claims 1 to 6, which is a resin. The total content of the primary alcohol and the secondary alcohol is 10 to 95% by mass with respect to 100% by mass of the solvent (D). The described resin composition. The resin composition according to any one of claims 1 to 8,
a reactive diluent (B);
A photosensitive resin composition comprising a photopolymerization initiator (C). The photosensitive resin composition according to claim 9, further comprising a coloring agent (E). For a total of 100 parts by mass of the components excluding the solvent (D),
Containing 10 parts by mass to 85 parts by mass of the resin (A),
Containing 10 parts by mass to 85 parts by mass of the reactive diluent (B),
0.1 parts by mass to 30 parts by mass of the photopolymerization initiator (C),
Containing 20 parts by mass to 1000 parts by mass of the solvent (D),
11. The photosensitive resin composition according to claim 10, containing 4 parts by mass to 85 parts by mass of the coloring agent (E). A cured resin film comprising a cured product of the photosensitive resin composition according to any one of claims 9 to 11. A color filter having a colored pattern comprising a cured product of the photosensitive resin composition according to claim 10 or 11. An image display device comprising the color filter according to claim 13 .

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