KR102594321B1 - Photosensitive resin composition and image display device - Google Patents

Abstract

A photosensitive resin composition is provided that yields a cured resin film that has good developability and colorant dispersibility and has a high elastic recovery rate. It contains a resin (A), a photopolymerization initiator (B), a solvent (C), a colorant (D), and a reactive diluent (E), and the resin (A) is a condensate of a dihydric phenol compound and an aldehyde compound. A photosensitive resin composition, characterized in that it is a reaction product of an epoxy resin (a1) of epichlorohydrin, a reaction product of a monocarboxylic acid (a2) containing an ethylenically unsaturated group, and a polybasic acid (a3). In the resin (A), the ratio of each structural unit derived from the components (a1) to (a3) is the ethylenically unsaturated group-containing monocarboxylic acid per 1.00 mol of the moiety derived from the epoxy group of the epoxy resin (a1). The structural unit derived from the boxylic acid (a2) is 0.85 to 1.00 mol, and the structural unit derived from the polybasic acid (a3) is 0.10 to 0.70 mol.

Description

Photosensitive resin composition and image display device

The present invention relates to a photosensitive resin composition and an image display device.

This application claims priority based on Patent Application No. 2020-019204 filed in Japan on February 6, 2020, and uses the contents herein.

Conventionally, in liquid crystal display panels, spacer particles are used to keep the distance (cell gap) between two substrates constant. As spacer particles, glass beads, plastic beads, etc. having a predetermined particle size are used. Usually, spacer particles are randomly arranged on a transparent substrate such as a glass substrate. If spacer particles are present in the pixel formation area of the liquid crystal display panel, problems such as reflection of the spacer particles or incident light being scattered may cause a decrease in contrast.

To solve this problem, dot-shaped or striped spacers formed by photolithography using a photosensitive resin composition have been adopted instead of spacer particles. This spacer can be formed by applying a photosensitive resin composition on a substrate, exposing it to ultraviolet rays through a predetermined mask, and then developing it. Therefore, a spacer made of a cured photosensitive resin composition can be formed only in certain places other than the pixel formation area in the liquid crystal display panel. Therefore, the above problem in the case of using spacer particles can be solved by forming the spacer by photolithography using a photosensitive resin composition.

Additionally, in organic EL display panels, resists for partitions that separate each color are used. However, since the partition wall is transparent, it causes color mixing and reflects light from the outside. It is necessary to mount a circular polarizer to prevent reflection.

To solve this problem, a method of preventing light reflection by using a black PDL (Pixel Defining Layer) in which the partition area is colored black is being considered. If reflected light can be prevented without mounting a circular polarizer, it becomes possible to produce a display that can be folded or bent.

Examples of photosensitive resin compositions used as materials for spacers provided in liquid crystal display panels include the radiation-sensitive resin composition described in Patent Document 1.

Additionally, Patent Document 2 describes a photosensitive composition that is preferably used as a resist for forming color filters, black matrices, black column spacers, etc.

Additionally, Patent Document 3 describes a photosensitive resin composition for a black column spacer containing an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, and a light-shielding agent.

Japanese Patent Publication No. 2001-302712 Japanese Patent Publication No. 2011-170075 Japanese Patent Publication No. 2013-134263

Recently, liquid crystal display elements and black matrices, color filters, black column spacers, etc. that form liquid crystal display elements; For each member such as black PDL forming an organic EL display panel, stricter dimensional accuracy is required. For this reason, photosensitive resin compositions that can be used as these materials are required to have better developability. In addition, in order to improve the display characteristics of a liquid crystal display element, the resin cured film obtained by curing the photosensitive resin composition used for the above application must have good colorant dispersibility. In addition, in order to prevent deterioration of the liquid crystal display element due to external impact, the resin cured film obtained by curing the photosensitive resin composition used for the above application is required to have a high elastic recovery rate.

The present invention was made in view of the above circumstances, and its object is to provide a photosensitive resin composition that has excellent developability, good colorant dispersibility, and yields a cured resin film having a high elastic recovery rate.

Another object of the present invention is to provide a cured resin film of the photosensitive resin composition of the present invention and an image display device including the same.

The structure of the present invention to solve the above problems is as follows.

[1] Resin (A),

A photopolymerization initiator (B),

Solvent (C),

A colorant (D),

Reactive Diluent (E)

Contains,

The resin (A) has a structure (a11) derived from an epoxy resin (a1), a structure (a21) derived from a monocarboxylic acid (a2) containing an ethylenically unsaturated group, and a structure (a3) derived from a polybasic acid (a3). a31),

The resin (A) is a reaction product of the polybasic acid (a3) added to the reaction product (R1) of the epoxy resin (a1) and the ethylenically unsaturated group-containing monocarboxylic acid (a2),

The epoxy resin (a1) is a reaction product of phenol resin (a4) and epihalohydrin,

The phenol resin (a4) is a condensate of a dihydric phenol compound and an aldehyde compound,

In the resin (A), the ratio of each structural unit derived from the components (a1) to (a3) is the ethylenically unsaturated group-containing monocarboxylic acid per 1.00 mol of the moiety derived from the epoxy group of the epoxy resin (a1). The structural unit derived from the boxylic acid (a2) is 0.85 to 1.00 mol, and the structural unit derived from the polybasic acid (a3) is 0.10 to 0.70 mol.

A photosensitive resin composition characterized in that.

[2] When the total of the resin (A), photopolymerization initiator (B), colorant (D), and reactive diluent (E) is 100 parts by mass,

1 to 50 parts by mass of the resin (A),

0.01 to 5 parts by mass of the photopolymerization initiator (B),

10 to 2000 parts by mass of the solvent (C),

1 to 50 parts by mass of the colorant (D) and

1 to 60 parts by mass of the reactive diluent (E)

The photosensitive resin composition described in [1] containing.

[3] The photosensitive resin composition according to [1] or [2], wherein the acid value of the resin (A) is 20 to 300 KOH mg/g and the unsaturated group equivalent is 100 to 4000 g/mole.

[4] The photosensitive resin composition according to any one of [1] to [3], wherein the colorant (D) contains an inorganic black pigment and an organic black pigment.

[5] The photosensitive resin composition according to any one of [1] to [4], wherein the phenol resin (a4) is a condensate of bisphenol A and formaldehyde.

[6] Among [1] to [5], wherein the ethylenically unsaturated group-containing monocarboxylic acid (a2) is at least one selected from the group consisting of (meth)acrylic acid and 2-(meth)acryloyloxyethylsuccinic acid. The photosensitive resin composition described in any one.

[7] The photosensitive resin composition according to any one of [1] to [6], wherein the polybasic acid (a3) is at least one selected from tetrahydrophthalic anhydride, succinic anhydride, and 1,2,4-cyclohexanetricarboxylic anhydride. .

[8] A cured resin film of the photosensitive resin composition according to any one of [1] to [7].

[9] An image display device comprising the resin cured film according to [8].

The photosensitive resin composition of the present invention has excellent developability, high dimensional accuracy, and good colorant dispersibility, so that a cured resin film with a high elastic recovery rate is obtained. Therefore, the photosensitive resin composition of the present invention is suitable as a material for black PDL, black matrix, color filter, and black column spacer.

The resin composition cured film of the present invention is suitable as a black PDL, black matrix, color filter, and black column spacer as a member of an image display device.

Hereinafter, embodiments of the photosensitive resin composition of the present invention, its resin cured film, and an image display device will be described in detail. Additionally, the present invention is not limited to the embodiments described below.

[Photosensitive resin composition]

The photosensitive resin composition of this embodiment contains a resin (A), a photopolymerization initiator (B), a solvent (C), a colorant (D), and a reactive diluent (E).

[Suzy (A)]

Resin (A) has a structure (a11) derived from an epoxy resin (a1), a structure (a21) derived from a monocarboxylic acid (a2) containing an ethylenically unsaturated group, and a structure (a3) derived from a polybasic acid (a3). a31). Resin (A) is a reaction product obtained by adding the polybasic acid (a3) to the reaction product (R1) of the epoxy resin (a1) and the ethylenically unsaturated group-containing monocarboxylic acid (a2). The epoxy resin (a1) is a reaction product of phenol resin (a4) and epihalohydrin, and the phenol resin (a4) is a condensate of a dihydric phenol compound and an aldehyde compound.

The ratio of each structural unit derived from the components (a1) to (a3) in the resin (A) is as follows. The structural unit derived from the ethylenically unsaturated group-containing monocarboxylic acid (a2) is 0.85 to 1.00 mol per 1.00 mol of the epoxy group-derived portion of the epoxy resin (a1). The structural unit derived from the polybasic acid (a3) is 0.10 to 0.70 mol per 1.00 mol of the epoxy group-derived portion of the epoxy resin (a1).

Resin (A) may contain structural units derived from other optional components as long as the effect of the present invention is not impaired.

The dihydric phenol compound is a compound containing two aromatic hydroxyl groups in one molecule. For example, bisphenol A, bisphenol F, 4,4'-dihydroxybenzophenone, bis(4-hydroxyphenyl)ether, bis(4-hydroxy-3-methylphenyl)ether, bis(3,5- Dimethyl-4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxy-3-methylphenyl) sulfide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfide Feed, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxy-3-methylphenyl)sulfone, bis(3,5-dimethyl-4-hydroxyphenyl)sulfone, 1,1'-bis(3- bisphenols such as t-butyl-6-methyl-4-hydroxyphenyl)butane;

Deoxybenzenes such as hydroquinone and resorcinol;

divalent naphthols such as dihydroxynaphthalene, bis(hydroxynaphthyl)methane, and 1,1'-binaphthol;

Bis(4-hydroxyphenyl)dicyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane, 1,1-bis Dihydric phenols containing an alicyclic structure, such as (3,5-dimethyl-4-hydroxyphenyl)cyclohexane;

Other examples include, but are not particularly limited to, 4,4'-dihydroxybiphenyl-3,3',5,5'-tetramethylbiphenyl. These may be used individually, or two or more types may be mixed and used. Among them, from the viewpoint of developability, colorant dispersibility, and elastic recovery rate when used in a photosensitive resin composition, compounds having two 4-hydroxyphenyl groups are preferable, bisphenols are more preferable, and bisphenol A and bisphenol F are preferable. It is more desirable.

The aldehyde compound is not particularly limited as long as it is a compound having one or more formyl groups per molecule, and examples include formaldehyde, acetaldehyde, benzaldehyde, crotonaldehyde, and hydroxybenzaldehyde. These may be used individually, or two or more types may be mixed and used. Among them, formaldehyde is preferable from the viewpoint of developability, colorant dispersibility, and elastic recovery rate when used in a photosensitive resin composition.

As the epihalohydrin, epichlorohydrin, epiiodohydrin, epiblomohydrin, β-methylepichlorohydrin, etc. can be used. From the viewpoint of reactivity with a condensate of a dihydric phenol compound and an aldehyde compound, epichlorohydrin is preferable. In addition, the reaction product of phenol resin (a4) and epihalohydrin is not limited to what is actually obtained by reacting phenol resin (a4) and epihalohydrin. The structure of the reactant may be the same as the above reactant. For example, after converting the hydroxyl group of phenol resin (a4) into allyl ether, the allyl group may be oxidized to obtain glycidyl ether.

The weight average molecular weight of the phenol resin (a4) is preferably 3,000 to 30,000, more preferably 4,000 to 20,000, and even more preferably 5,000 to 15,000.

The weight average molecular weight of the epoxy resin (a1) is preferably 4,000 to 30,000, more preferably 5,000 to 20,000, and even more preferably 6,000 to 15,000.

Additionally, the epoxy equivalent weight is preferably 100 to 5000, more preferably 150 to 1000, and even more preferably 200 to 600.

The ethylenically unsaturated group-containing monocarboxylic acid (a2) is not particularly limited as long as it is a compound having an ethylenically unsaturated group and one carboxyl group in one molecule, but includes (meth)acrylic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, α-bromo(meth)acrylic acid, β-furyl(meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, α-cyanocinnamic acid, monomethyl maleate , monoethyl maleate, monoisopropyl maleate, monomethyl fumarate, monoethyl itaconate, etc. These may be used individually, or two or more types may be used. Among these, (meth)acrylic acid and 2-(meth)acryloyloxyethylsuccinic acid are preferable from the viewpoint of ease of availability and reactivity with epoxy resin (a1).

Examples of the polybasic acid (a3) include maleic anhydride, itaconic anhydride, citraconic anhydride, succinic anhydride, tetrahydrophthalic anhydride, and 1,2,4-cyclohexanetricarboxylic anhydride.

The ratio of each structural unit derived from components (a1) to (a3) in the resin (A) used in this embodiment is as follows.

The structural unit derived from the ethylenically unsaturated group-containing monocarboxylic acid (a2) is 0.85 to 1.00 mol, preferably 0.90 to 1.00 mol, per 1.00 mol of the epoxy group-derived portion of the epoxy resin (a1), and 0.95 to 1.00 mol. It is more preferable that it is a mole. Particularly preferably, the structural unit derived from the ethylenically unsaturated group-containing monocarboxylic acid (a2) is 0.99 to 1.00 mol, that is, it is preferable that the resin (A) contains substantially no epoxy groups remaining unreacted. . If the structural unit derived from the ethylenically unsaturated group-containing monocarboxylic acid (a2) is 0.85 mol or more, the unsaturated group is sufficiently contained in the resin (A). Therefore, as a photosensitive resin composition, a cured resin film having excellent curability and developability, good colorant dispersibility, and high hardness and elastic recovery rate is obtained.

Furthermore, the structural unit derived from the polybasic acid (a3) is preferably 0.10 to 0.70 mol, more preferably 0.15 to 0.50 mol, and even more preferably 0.20 to 0.40 mol, relative to 1.00 mol of the epoxy group-derived portion of the epoxy resin (a1). desirable. If the structural unit derived from the polybasic acid (a3) is 0.10 mol or more, the acid value of the resin (A) is sufficiently high, no residue is generated in the unexposed area during the development process, and good developability is obtained as a photosensitive resin composition. In addition, if the structural unit derived from the polybasic acid (a3) is 0.70 mol or less, good developability is obtained without insufficient exposed portions in the development process.

In addition, “1.00 mol of epoxy group-derived moiety” means the number of moles of unreacted epoxy groups before addition of the ethylenically unsaturated group-containing carboxylic acid (a2) or polybasic acid (a3).

The weight average molecular weight of the resin (A) is preferably 1,000 to 20,000, more preferably 3,000 to 10,000, and even more preferably 5,000 to 7,500. A weight average molecular weight of 1000 or more is preferable because notches are unlikely to occur in the developing pattern in the development process after applying and exposing the photosensitive resin composition. If the weight average molecular weight is 20000 or less, it is preferable because the development time can be adjusted to an appropriate range in the development step after applying and exposing the photosensitive resin composition.

The weight average molecular weight is a value measured under the following conditions using gel permeation chromatography (GPC) and converted to standard polystyrene.

Column: Showex (registered trademark) LF-804+LF-804 (manufactured by Showa Denko Co., Ltd.)

Column temperature: 40℃

Sample: 0.2% by mass tetrahydrofuran solution of resin (A)

Development Solvent: Tetrahydrofuran

Detector: Differential refractometer (Shodex (registered trademark) RI-71S) (manufactured by Showa Denko Co., Ltd.)

Flow rate: 1mL/min

The acid value (JIS K6901 5.3) of the resin (A) is not limited as long as the present invention exhibits the desired effect, but is preferably 20 to 300 KOH mg/g, more preferably 30 to 200 KOH mg/g, and 40 to 125 KOH mg/g. This is more preferable. When the acid value is 20 KOHmg/g or more, the developability of the photosensitive resin composition is good. On the other hand, if the acid value is 300 KOHmg/g or less, the portion photocured by applying the photosensitive resin composition and exposing it to light becomes difficult to dissolve in the developing solution, so it is preferable.

The unsaturated group equivalent of the resin (A) of this embodiment is not limited as long as the present invention exhibits the desired effect, but is preferably 100 to 4000 g/mol, more preferably 200 to 2000 g/mol, and even more preferably 250 to 500 g/mol. desirable. When the unsaturated group equivalent is 100 g/mol or more, the developability of the photosensitive resin composition becomes good. On the other hand, if the unsaturated group equivalent is 4000 g/mol or less, the sensitivity of the photosensitive resin composition becomes higher and a more detailed pattern can be formed. In addition, it contributes to improving the hardness of the cured product of the photosensitive resin composition, and a cured resin film with a high elastic recovery rate is obtained.

In addition, the unsaturated group equivalent is the mass of resin (A) per mole of unsaturated bond (ethylenic carbon-carbon double bond) in resin (A). The unsaturated group equivalent can be determined by dividing the mass of the resin (A) by the number of moles of the unsaturated group in the resin (A) (g/mol). In this specification, the unsaturated group equivalent of resin (A) is a theoretical value calculated from the amount of monocarboxylic acid (a2) containing an ethylenically unsaturated group used to introduce an unsaturated group into resin (A).

[Method for producing resin (A)]

Next, the manufacturing method of resin (A) of this embodiment is explained.

As a method for producing the resin (A) of this embodiment, it is preferable to use the method shown below. First, epoxy resin (a1), which is a reaction product of a condensate of a dihydric phenol compound and an aldehyde compound and epihalohydrin, is obtained in a solvent using a catalyst as necessary. The obtained epoxy resin (a1) and the monocarboxylic acid (a2) containing an ethylenically unsaturated group are reacted to synthesize a resin (A) precursor (first step). In this process, the carboxyl group of the monocarboxylic acid (a2) containing an ethylenically unsaturated group undergoes an addition reaction with the epoxy group of the epoxy resin (a1), and the monocarboxylic acid (a2) containing an ethylenically unsaturated group is added to the resulting resin (A) precursor. An unsaturated group derived from boxylic acid (a2) is introduced. And, the epoxy group derived from epoxy resin (a1) generates a hydroxy group by ring-opening addition. Next, resin (A) is synthesized by reacting polybasic acid (a3) with the hydroxy group of the resin (A) precursor (second step).

Reaction conditions in the first step can be appropriately set according to conventional methods. For example, the reaction temperature in the first step is preferably 50 to 150°C, and more preferably 60 to 140°C. The reaction time in the first step is preferably, for example, 1 to 10 hours.

The mixing ratio of the epoxy resin (a1) and the monocarboxylic acid (a2) containing an ethylenically unsaturated group is determined by the equivalent weight of the unsaturated group in the target resin (A) or the monocarboxylic acid containing an ethylenically unsaturated group relative to the epoxy group in the epoxy resin (a1). It can be set appropriately depending on the amount of carboxylic acid (a2) added (ratio of unsaturated group to epoxy group introduced). For example, the mixing ratio of the ethylenically unsaturated group-containing monocarboxylic acid (a2) to 1.00 mol of the epoxy group in the epoxy resin (a1) is preferably 0.85 to 1.10 mol, more preferably 0.90 to 1.00 mol, and 0.95 to 1.00. Moles are more preferred. In particular, in order to produce a resin (A) precursor in which substantially no unreacted epoxy group remains, the mixing ratio of the monocarboxylic acid (a2) containing an ethylenically unsaturated group is set to 1.00 mol or more. If the mixing ratio of the ethylenically unsaturated group-containing monocarboxylic acid (a2) is 0.85 mol or more, the increase in molecular weight due to the reaction between the epoxy groups of the epoxy resin (a1) can be suppressed. If the mixing ratio of the ethylenically unsaturated group-containing monocarboxylic acid (a2) is 1.10 mol or less, good colorant dispersibility and developability and elastic recovery rate of the cured product can be secured as a photosensitive resin composition.

The solvent used in the first step is not particularly limited, and a known solvent can be used as appropriate. Specific examples of solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether. , triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether. , (poly)alkylene glycol monoalkyl ethers such as dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether;

(poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate;

Other ether compounds such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran;

Ketone compounds such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone;

Methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl- 3-methoxybutylpropionate, ethyl acetate, n-butyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-propionate. ester compounds such as butyl, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate;

Aromatic hydrocarbon compounds such as toluene and xylene;

and carboxylic acid amide compounds such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide. These solvents may be used individually, or two or more types may be mixed and used.

Among the above solvents, glycol ether-based solvents are preferable from the viewpoint of gelation inhibition and storage stability as the resin (A). That is, as a solvent, it is preferable to use (poly)alkylene glycol monoalkyl ether such as propylene glycol monomethyl ether, and (poly)alkylene glycol monoalkyl ether acetate such as propylene glycol monomethyl ether acetate.

The amount of solvent used in the first step is not particularly limited, but is 30 to 1000 parts by mass, assuming that the total of the epoxy resin (a1) and the monocarboxylic acid (a2) containing an ethylenically unsaturated group as raw materials is 100 parts by mass. Parts by mass are preferable, and 50 to 800 parts by mass are more preferable. It is preferable that the amount of the solvent used is 1000 parts by mass or less because the viscosity of the resin (A) precursor can be controlled to an appropriate range. On the other hand, it is preferable that the amount of the solvent used is 30 parts by mass or more because baking can be prevented from occurring during the reaction and the synthesis reaction can be performed stably. In addition, if the amount of the solvent used is 30 parts by mass or more, coloring and gelation of the resin (A) precursor can be prevented.

In this embodiment, it is preferable to use a catalyst to promote the reaction between the epoxy resin (a1) and the monocarboxylic acid (a2) containing an ethylenically unsaturated group. The catalyst used in this embodiment is not particularly limited and is appropriately selected depending on the type of raw material, etc.

Catalysts used in this embodiment include, for example, tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, chelate compounds of chromium, etc. can be mentioned. These catalysts may be used individually, or two or more types may be mixed and used.

The amount of the catalyst used in this embodiment is not particularly limited, but is generally 0.01 to 0.01 parts by mass when the total of the epoxy resin (a1) and the monocarboxylic acid (a2) containing an ethylenically unsaturated group is 100 parts by mass. It is 5 parts by mass, preferably 0.1 to 2 parts by mass, and more preferably 0.2 to 1 part by mass.

In the first step, it is preferable to use a polymerization inhibitor to prevent gelation of the resin. The polymerization inhibitor used in the first step is not particularly limited and is appropriately selected depending on the raw materials of the resin, etc.

Examples of the polymerization inhibitor used in the first step include hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, butylhydroxytoluene, etc. These polymerization inhibitors may be used individually, or two or more types may be used.

The amount of the polymerization inhibitor used is not particularly limited, but is generally 0.01 to 5 parts by mass when the total of the epoxy resin (a1) and the monocarboxylic acid (a2) containing an ethylenically unsaturated group is 100 parts by mass, Preferably it is 0.1 to 2 parts by mass, more preferably 0.2 to 1 part by mass.

Reaction conditions in the second process can be appropriately set according to conventional methods. For example, the reaction temperature in the second step is preferably 50 to 130°C, and more preferably 60 to 120°C. The reaction time in the first step is preferably, for example, 1 to 10 hours.

The mixing ratio of the resin (A) precursor and the polybasic acid (a3) is the polybasic acid ( The mixing ratio of a3) is preferably 0.10 to 0.70 mol, more preferably 0.15 to 0.50 mol, and still more preferably 0.20 to 0.40 mol. When the mixing ratio of polybasic acid (a3) is 0.10 mol or more, good developability is obtained as a photosensitive resin composition. If the mixing ratio of the polybasic acid (a3) is 0.70 mol or less, side reactions during synthesis can be suppressed, developability as a photosensitive resin composition is improved, and finer patterns can be formed.

The mixing ratio of polybasic acid (a3) to 1.00 mol of the epoxy group-derived portion of epoxy resin (a1) in the resin (A) precursor is preferably 0.10 to 0.70 mol, more preferably 0.15 to 0.50 mol, and 0.20 to 0.40. It is more preferable that it is a mole.

As the solvent used in the second step, the same solvent as the solvent used in the first step can be used, and the solvent used in the first step may be included. That is, the second process may be performed continuously after the first process is completed without removing the solvent used in the first process.

The amount of solvent used in the second step is not particularly limited, but when the total of the epoxy resin (a1), the monocarboxylic acid containing an ethylenically unsaturated group (a2), and the polybasic acid (a3) is 100 parts by mass, 30 parts by mass. - 1000 parts by mass is preferable, and 50 - 800 parts by mass is more preferable. It is preferable that the amount of the solvent used is 1000 parts by mass or less because the viscosity of the resin (A) can be controlled to an appropriate range. On the other hand, it is preferable that the amount of the solvent used is 30 parts by mass or more because baking can be prevented from occurring during the reaction and the synthesis reaction can be performed stably. Additionally, if the amount of the solvent used is 30 parts by mass or more, coloring and gelation of the resin (A) can be prevented.

In the second step, the same catalyst and polymerization inhibitor as those used in the first step can be used. When performing the second process continuously after the first process, the catalyst and polymerization inhibitor used in the first process can be used continuously without removing them, and may be newly added in the second process.

[Photopolymerization initiator (B)]

The photopolymerization initiator (B) is not particularly limited as long as it is a polymerization initiator that generates radicals by light irradiation, and examples include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin butyl ether;

Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4-(1-t-butyldioxy-1-methylethyl)acetophenone, 2-methyl-1-[ Acetophenone compounds such as 4-(methylthio)phenyl]-2-morpholino-propan-1-one and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1;

Anthraquinone compounds such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone;

xanthone compounds such as xanthone, thioxanthone, 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone;

Ketal compounds such as acetophenone dimethyl ketal and benzyl dimethyl ketal;

Benzophenone compounds, such as benzophenone, 4-(1-t-butyldioxy-1-methylethyl)benzophenone, and 3,3',4,4'-tetrakis(t-butyldioxycarbonyl)benzophenone. ;

Acylphosphine oxide compounds, 1.2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], etc. are mentioned. These photopolymerization initiators (C) may be used individually, or two or more types may be used.

[Solvent (C)]

The solvent (C) is not particularly limited as long as it is an inert solvent that can dissolve the resin (A) and does not react with the resin (A), and can be arbitrarily selected depending on the type of resin (A), etc. The solvent (C) preferably has compatibility with the reactive diluent (E) described later.

As the solvent (C), the same solvent that can be used when producing resin (A) can be used, and it is preferable to use a glycol ether-based solvent. That is, as the solvent (C), it is preferable to use (poly)alkylene glycol monoalkyl ether such as propylene glycol monomethyl ether, and (poly)alkylene glycol monoalkyl ether acetate such as propylene glycol monomethyl ether acetate.

When using a solution containing any component other than the solvent (C) as a material for the photosensitive resin composition other than the solvent (C), the solvent contained in the solution may be used as the solvent (C).

[Colorant (D)]

The colorant (D) may be dissolved or dispersed in the solvent (C) and is not particularly limited. Examples of the colorant (D) include dyes and pigments. As the colorant (D), only a dye may be used, only a pigment may be used, or a dye and a pigment may be used in combination. When the resin cured film of the photosensitive resin composition of the present embodiment is used as any of black PDL, black matrix, color filter, and black column spacer, the colorant (D) above is used depending on the purpose of the member formed from the resin cured film, etc. It can be used alone or in combination of two or more types. For example, when a black colorant (D) is used, the cured resin film of the photosensitive resin composition is suitable as a black PDL, black matrix, and black column spacer.

Examples of dyes include, for example, acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 25, 29, 40, 45, 62, 70, 74, 80, 83, 90, 92, 112, 113, 120, 129, 147; acid chrome violet K; acid Fuchsin; acid green 1, 3, 5, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 69, 73, 80, 87, 88, 91 , 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 25 7 , 260, 266, 274; acid violet 6B, 7, 9, 17, 19; acid yellow 1, 3, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116; food yellow 3 and their derivatives.

Among these dyes, it is preferable to use azo-based, xanthene-based, anthraquinone-based or phthalocyanine-based acid dyes.

These dyes may be used individually, or two or more types may be mixed and used.

Examples of pigments include, for example, C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, Yellow pigments such as 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214;

Orange pigments such as C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. pigment;

Blue pigments such as C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60;

Violet pigments such as C.I. Pigment Violet 1, 19, 23, 29, 32, 36, and 38;

Green pigments such as C.I. Pigment Green 7, 36, and 58;

Brown pigments such as C.I. Pigment Brown 23 and 25;

Black pigments such as aniline black, perylene black, titanium black, cyanine black, lignin black, lactam-based organic black, RGB black, carbon black, and iron oxide can be mentioned.

These pigments may be used individually, or two or more types may be mixed and used.

As a black pigment, from the viewpoint of the optical density of an image display device equipped with a resin cured film of the photosensitive resin composition of the present embodiment, it is preferable to use an inorganic black pigment and an organic black pigment in combination, and carbon black and a lactam-based organic black are used in combination. It is more preferable.

When a pigment is included as the colorant (D), the photosensitive resin composition may contain a known dispersant from the viewpoint of improving the dispersibility of the pigment in the photosensitive resin composition. The content of the dispersant can be appropriately set depending on the type of pigment etc. to be used.

As a dispersant, it is preferable to use a polymer dispersant because it has excellent dispersion stability over time. The polymer dispersant can be selected arbitrarily, and examples include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene glycol diester-based dispersants, sorbitan aliphatic ester-based dispersants, and aliphatic modified ester-based dispersants. etc. can be mentioned. As a polymer dispersant, brand names such as EFKA (registered trademark, manufactured by BASF Japan), Disperbyk (registered trademark, manufactured by Big Chemistry), Dispalon (registered trademark, manufactured by Kusumoto Kasei Co., Ltd.), SOLSPERSE (registered trademark, manufactured by Zeneca Corporation) You may use a commercially available product.

<Reactive diluent (E)>

The photosensitive resin composition of this embodiment contains a reactive diluent (E) in addition to the resin (A), the photopolymerization initiator (B), the solvent (C), and the colorant (D).

The reactive diluent (E) is a compound having at least one ethylenically unsaturated group in the molecule, and is preferably a compound having a plurality of ethylenically unsaturated groups.

When the photosensitive resin composition contains a reactive diluent (E), adjustment of the viscosity and sensitivity of the photosensitive resin composition becomes easy. Additionally, when the resin cured film of the photosensitive resin composition containing the reactive diluent (E) is used as a black PDL, black matrix, color filter, or black column spacer, the strength of the resin cured film becomes good. In addition, the photosensitive resin composition containing the reactive diluent (E) is applied to the surface to be formed of a resin cured film, exposed to light, and then developed to form a resin cured film, which has good adhesion to the surface to be formed.

Monofunctional monomers (monomers having only one ethylenically unsaturated bond) used as the reactive diluent (E) include, for example, (meth)acrylamide, methylol (meth)acrylamide, and methoxymethyl (meth)acrylamide. , Ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxy methoxymethyl (meth)acrylamide, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate , 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-phenoxy-2 -Hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, glycerin mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl (meth) ) Acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, half (meth)acrylate of phthalic acid derivative, etc. Meth)acrylate compound;

Aromatic vinyl compounds such as styrene, α-methylstyrene, α-chloromethylstyrene, and vinyl toluene;

and carboxylic acid esters such as vinyl acetate and vinyl propionate. These monofunctional monomers may be used individually, or two or more types may be used.

Examples of polyfunctional monomers (monomers having multiple ethylenically unsaturated bonds) used as the reactive diluent (E) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate. (meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane Glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol Penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxy Polyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl(meth)acrylate, ethylene glycol diglycyryl ether di(meth)acrylate, diethylene glycol diglycidyl ether di. (meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, glycerin triacrylate, glycerin polyglyceryl etherpol (meth)acrylate, urethane (meth)acrylate (i.e., tolylene diisocyanate), (meth)acrylate compounds such as tri(meth)acrylate of tris(hydroxyethyl)isocyanurate, reaction products of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, etc., and 2-beadoxyethyl(meth)acrylate;

Aromatic vinyl compounds such as divinylbenzene, diallyl phthalate, and diallylbenzene phosphonate;

Dicarboxylic acid ester compounds such as divinyl adipic acid;

triallyl cyanurate;

(meth)acrylamide compounds, such as methylenebis(meth)acrylamide, (meth)acrylamide methylene ether, and a condensate of a polyhydric alcohol and N-methylol (meth)acrylamide, etc. are mentioned. These polyfunctional monomers may be used individually, or two or more types may be used.

<Other ingredients>

In addition, the photosensitive resin composition of this embodiment may contain known additives, such as a coupling agent, a leveling agent, and a thermal polymerization inhibitor, within the range which does not impair the effect of this invention. Examples of the coupling agent include KBM-403 (3-glycidoxypropyltriethoxysilane, manufactured by Shin-Etsu Silicone). The content of these additives is not particularly limited as long as it is within a range that does not impair the effect of the present invention.

The content of resin (A) is preferably 1 to 50 parts by mass, assuming that the total of the resin (A), photopolymerization initiator (B), colorant (D), and reactive diluent (E) of the photosensitive resin composition is 100 parts by mass, and is preferably 10 parts by mass. 40 to 40 parts by mass are more preferable, and 20 to 35 parts by mass are still more preferable. When the content of the resin (A) is 1 part by mass or more, a photosensitive resin composition having good photocurability is obtained. If the content of the resin (A) is 50 parts by mass or less, a photosensitive resin composition with good applicability will be obtained.

The content of the photopolymerization initiator (B) is preferably 0.01 to 10 parts by mass, assuming that the total of the resin (A), the photopolymerization initiator (B), the colorant (D), and the reactive diluent (E) of the photosensitive resin composition is 100 parts by mass, Parts by mass are preferable from 0.1 to 8, and parts by mass are more preferable from 1 to 5 parts by mass. When the content of the photopolymerization initiator (B) is 0.01 parts by mass or more, the photocurability of the photosensitive resin composition is good. If the content of the photopolymerization initiator (B) is 10 parts by mass or less, no residue is generated in the development step after applying and exposing the photosensitive resin composition.

The content of the solvent (C) is preferably 100 to 2000 parts by mass, assuming that the total of the resin (A), photopolymerization initiator (B), colorant (D), and reactive diluent (E) of the photosensitive resin composition is 100 parts by mass, It is more preferable that it is 150 to 1000 parts by mass, and it is still more preferable that it is 200 to 500 parts by mass. When the content of the solvent (C) is 100 parts by mass or more, a photosensitive resin composition with good applicability is obtained. If the content of the solvent (C) is 2000 parts by mass or less, a coating film having a sufficient film thickness can be obtained in the application step of the photosensitive resin composition.

The content of the colorant (D) is preferably 1 to 50 parts by mass, assuming that the total of the resin (A), photopolymerization initiator (B), colorant (D), and reactive diluent (E) of the photosensitive resin composition is 100 parts by mass, and is preferably 10 parts by mass. - 40 parts by mass is more preferable, and 20 - 30 parts by mass is still more preferable. When the content of the colorant (D) is 1 part by mass or more, the cured resin film of the photosensitive resin composition has sufficient color reproducibility. Additionally, when a black colorant (D) is used, the resin cured film has sufficient light-shielding properties. If the content of the colorant (D) is 50 parts by mass or less, residue is unlikely to be generated in the development step after applying and exposing the photosensitive resin composition.

The content of the reactive diluent (E) is preferably 1 to 60 parts by mass, assuming that the total of the resin (A), photopolymerization initiator (B), colorant (D), and reactive diluent (E) of the photosensitive resin composition is 100 parts by mass, 15 to 50 parts by mass is more preferable, and 30 to 45 parts by mass is still more preferable. If the content of the reactive diluent (E) is 1 part by mass or more, a photosensitive resin composition having good curability can be obtained even if it contains a large amount of the colorant (D). If the content of the reactive diluent (E) is 60 parts by mass or less, residues are unlikely to be generated in the development step after applying and exposing the photosensitive resin composition.

[Method for producing photosensitive resin composition]

Next, a method for manufacturing the photosensitive resin composition of this embodiment is explained.

The photosensitive resin composition of this embodiment includes any of the resins (A) of this embodiment, a photopolymerization initiator (B), a solvent (C), a colorant (D), a reactive diluent (E), a dispersant, and an additive. It can be manufactured by mixing one or more of the components using a known mixing device.

The photosensitive resin composition of this embodiment prepares in advance a composition containing a resin (A) and a solvent (C), and then adds a photopolymerization initiator (B), a colorant (D), and a reactive diluent to the composition. It may be manufactured by further adding (E) and one or more of the dispersant and additives and mixing them.

A composition containing a resin (A) and a solvent (C) is, for example, mixed by adding a solvent (C) to the resin (A) isolated from the resin solution that has completed the reaction for synthesizing the resin (A). It can be manufactured by the following method.

In this embodiment, it is not necessarily necessary to isolate the target resin (A) from the resin solution in which the reaction for synthesizing the resin (A) has been completed. Therefore, as a composition containing a resin (A) and a solvent (C), the solvent contained in the resin solution at the time the reaction for synthesizing the resin (A) is completed is not separated from the resin solution, and the solvent contained in the resin solution is not separated from the resin solution after the reaction is completed. The resin solution may be used as is. Additionally, as a composition containing the resin (A) and the solvent (C), a composition obtained by adding and mixing another solvent to the resin solution after completion of the reaction may be used.

Since the photosensitive resin composition of the present embodiment contains the resin (A) of the present embodiment, a cured resin film having excellent developability, good dispersibility of the colorant, and high elastic recovery rate is obtained. Therefore, the photosensitive resin composition of this embodiment is suitable as a material for black PDL, black matrix, color filter, and black column spacer.

In addition, the photosensitive resin composition of the present embodiment has good colorant dispersibility, can sufficiently satisfy general characteristics such as developability even when the colorant (D) is black, and forms a resin cured film with good adhesion to the surface to be formed. can be formed. For this reason, according to the photosensitive resin composition of this embodiment, adhesion to the surface to be formed is good and a black pattern with sufficient light-shielding properties can be formed.

[Resin cured film]

The resin cured film of this embodiment is a resin cured film obtained by photocuring the photosensitive resin composition of this embodiment.

The resin cured film of this embodiment has good colorant dispersibility, solvent resistance, and elastic recovery rate, and is therefore suitable as a black PDL, black matrix, color filter, and black column spacer as a member of an image display device.

[Method for manufacturing resin cured film]

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

First, a photosensitive resin composition is applied on the surface of the resin cured film to form a resin layer (coat film). Next, the resin layer is exposed through a mask with a predetermined pattern, and the exposed portion is photocured. Next, the unexposed portion of the resin layer is developed with a developer to form a cured resin film with a predetermined pattern. Thereafter, post-baking (heat treatment) of the resin cured film is performed as needed.

When exposing the resin layer, a halftone mask with a predetermined pattern may be used. In this case, the unexposed portion and the semi-exposed portion are developed with a developer to form a cured resin film with a predetermined pattern.

The method for applying the photosensitive resin composition is not particularly limited, and examples include screen printing, roll coating, curtain coating, spray coating, and spin coating.

After applying the photosensitive resin composition, if necessary, the solvent (C) contained in the resin layer may be volatilized by heating using a heating means such as a circulation oven, an infrared heater, or a hot plate. The heating conditions after application are not particularly limited and may be set appropriately according to the composition of the photosensitive resin composition. For example, the heating temperature after application can be 50°C to 120°C, and the heating time can be 30 seconds to 30 minutes.

The method of exposing the resin layer is not particularly limited, but examples include a method of irradiating active energy rays such as ultraviolet rays or excimer laser light.

The energy dose irradiated to the resin layer may be appropriately set depending on the composition of the photosensitive resin composition. For example, the energy dose irradiated to the resin layer can be 30 to 2000 mJ/cm2, but is not limited to this range.

The light source used for exposure is not particularly limited, and a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, etc. can be selected and used arbitrarily.

As a developing solution used for development, it is preferable to use an alkaline developing solution because excellent developing properties are obtained. Examples of alkaline developing solutions include aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, and potassium hydroxide; Aqueous solutions of amine compounds such as ethylamine, diethylamine, and dimethylethanolamine; Tetramethylammonium, 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N Aqueous solutions of -ethyl-N-β-methanesulfonamideethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline, and their sulfate, hydrochloride, or p-toluenesulfonate salts; and aqueous solutions of p-phenylenediamine-based compounds.

The developing solution may contain an antifoaming agent, a surfactant, etc. as needed.

After developing with a developer, it is preferable to wash the cured resin film with a predetermined pattern with water and dry it.

In addition, after developing with a developer, it is preferable to post-bake (heat treat) the resin cured film having a predetermined pattern. By performing post-baking, curing of the resin cured film can be further advanced. The post-baking conditions are not particularly limited and can be selected arbitrarily, and may be set appropriately according to the composition of the photosensitive resin composition. For example, the post-bake heating temperature can be 130°C to 250°C. Additionally, the post-bake heating time is preferably 10 minutes to 4 hours, and more preferably 20 minutes to 2 hours.

[Image display device]

The image display device of this embodiment is provided with the resin cured film of this embodiment. Specific examples of the image display device include a liquid crystal display device and an organic EL display device.

As an image display device, it is preferable that one or more members selected from, for example, black PDL, black matrix, color filter, and black column spacer are formed from the resin cured film of the present embodiment.

The material of the base forming the surface of the resin cured film is not particularly limited, but examples include glass, silicone, polycarbonate, polyester, polyamide, polyamideimide, polyimide, aluminum, and printed wiring. Examples include a substrate with a wiring pattern formed on the surface of the substrate, an array substrate, etc.

The manufacturing method of the image display device of the present embodiment may include a step of forming the resin cured film of the present embodiment by the above-described manufacturing method, and members other than those formed of the resin cured film may be manufactured according to a conventional method. You can.

The cured resin film obtained by curing the photosensitive resin composition of the present embodiment has excellent developability, good colorant dispersibility and solvent resistance, and a high elastic recovery rate. For this reason, it is suitable as a material for black PDL, black matrix, color filter, and black column spacer provided in an image display device.

Example

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

<Synthesis Example 1>

(1st process)

In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, propylene glycol monomethyl ether acetate (86 g) as a solvent and bisphenol A novolac type epoxy resin (manufactured by Nanya Plastics, product name NPPN-438, epoxy 198g of equivalent 198) was added and stirred to dissolve. Next, acrylic acid (72 g), which is an ethylenically unsaturated group-containing monocarboxylic acid (a2), 0.3 g of methylhydroquinone as an inhibitor, and 0.7 g of triphenylphosphine as a catalyst were added, the inside of the flask was stirred while blowing air, and 120 The temperature was raised to °C and reacted for 2 hours.

(2nd process)

Next, 32 g of succinic anhydride, which is an anhydride of polybasic acid (a3), was added and stirred at 120°C for another 30 minutes to synthesize Resin (A) of Synthesis Example 1.

Propylene glycol monomethyl ether acetate was added as a solvent (C) to the resin (A) solution after completion of the reaction and mixed to obtain a prepared solution (solid content concentration: 40% by mass) containing the resin (A) and the solvent (C). . In addition, the solid content means the heating residue when the composition is heated at 130°C for 2 hours, and the solid content of the prepared solution consists of resin (A) as the main component.

<Synthesis Examples 2 to 7>

Except for using the composition shown in Table 1, resin (A) was synthesized in the same manner as in Synthesis Example 1, propylene glycol monomethyl ether acetate was added, and a prepared solution containing resin (A) and solvent (C) was prepared (solid content). The concentration was 40 mass%).

As the compounds in Table 1, the following were used.

NPPN-438: Bisphenol A novolak type epoxy resin (manufactured by Nanya Plastics, product name NPPN-438, epoxy equivalent weight 198)

AA: Acrylic acid

MAA: methacrylic acid

HOMS: Acryloyloxyethylsuccinic acid

SA: Succinic anhydride

THPA: tetrahydrophthalic anhydride

CHTC: 1,2,4-cyclohexanetricarboxylic acid

<Method of measuring acid value>

According to JIS K6901 5.3.2, measurement was performed using a mixed indicator of bromothymol blue and phenol red. Acid value refers to the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1g of resin (A).

<Unsaturated group equivalent>

It is the mass of the resin (A) per mole of polymerizable unsaturated bonds, and is a calculated value calculated based on the usage amount of the raw materials (a1) to (a3) components.

<Method for measuring weight average molecular weight (Mw)>

It was measured under the following conditions using gel permeation chromatography (GPC) and converted to standard polystyrene.

Column: Showex (registered trademark) LF-804+LF-804 (manufactured by Showa Denko Co., Ltd.)

Column temperature: 40℃

Sample: 0.2% tetrahydrofuran solution of resin (A)

Development Solvent: Tetrahydrofuran

Detector: Differential refractometer (Shodex (registered trademark) RI-71S) (manufactured by Showa Denko Co., Ltd.)

Flow rate: 1mL/min

<Comparative Synthesis Example 1>

In a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, 71 g of propylene glycol monomethyl ether acetate as a solvent, 210 g of cresol novolak-based epoxy (YDCN-704L, epoxy equivalent: 210), and 72 g of acrylic acid. 0.2 g of triphenylphosphine as a catalyst, and 0.7 g of butylhydroxytoluene as a polymerization inhibitor were added, the inside of the flask was stirred while blowing air, the temperature was raised to 120°C, and reaction was performed for 2 hours.

Next, 28.6 g of tetrahydrophthalic anhydride was added to the same flask and stirred at 120°C for another 30 minutes to synthesize a resin.

To the resin solution after completion of the reaction, propylene glycol monomethyl ether acetate was added as a solvent (C) and mixed to obtain a prepared solution (solid content concentration: 40% by mass) containing the resin and the solvent (C).

For the resin synthesized in Comparative Synthesis Example 1, the acid value of the solid content, weight average molecular weight, and unsaturated group equivalent were measured in the same manner as in Synthesis Example 1. As a result, the solid acid value of the resin synthesized in Comparative Synthesis Example 1 was 36KOHmg/g, the weight average molecular weight (Mw) was 7000, and the unsaturated group equivalent was 310.

<Comparative Synthesis Example 2>

164 g of propylene glycol monomethyl ether acetate was added to a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, stirred while purging with nitrogen, and heated to 120°C. Next, 12 g of t-butylperoxy-2- was added to a monomer mixture consisting of 85 g (0.6 mol) of glycidyl methacrylate, 66 g (0.3 mol) of tricyclodecanyl methacrylate, and 10.4 g (0.1 mol) of styrene. Ethylhexanoate (polymerization initiator, manufactured by Nichiyu Corporation, Perbutyl (registered trademark) O) was added dropwise from the dropping funnel into the flask over 2 hours. After the dropwise addition was completed, the mixture was stirred at 120°C for another 2 hours to perform a copolymerization reaction. Next, 42 g of acrylic acid, 0.4 g of methoquinone as a polymerization inhibitor, and 0.5 g of triphenylphosphine as a catalyst were added to the reaction solution, and low-oxygen air containing nitrogen gas was injected so that the oxygen concentration was 4% to 7%, and 110% was added. Heated at ℃ for 10 hours.

After that, it was confirmed that the acid value was 1.0 KOHmg/g or less, 55 g of tetrahydrophthalic anhydride was added, and reaction was performed at 110°C for 2 hours to produce a resin solution with a solid content concentration of 50% by mass (solid content acid value of 80.6KOHmg/g, weight average molecular weight of 9500). ) was obtained.

<Comparative Synthesis Examples 3 to 6>

Except for using the composition shown in Table 1, a resin was synthesized in the same manner as in Synthesis Example 1, propylene glycol monomethyl ether acetate was added to prepare a prepared solution containing the resin (A) and the solvent (C) (solid concentration 40 mass). %).

<Examples 1 to 7, Comparative Examples 1 to 5>

Using the prepared solution containing the resin (A) and solvent (C) of Synthesis Examples 1 to 7 and the resin solution described in Comparative Synthesis Examples 1, 2, 4 to 6, the composition (mass parts) shown in Table 2 was used. The photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 5 were mixed in a 500 ml vial and shaken by hand.

The following compounds were used as listed in Table 2.

OXE-01: Irgacure OXE01 (light polymerization initiator, manufactured by BASF Japan)

PGMEA: propylene glycol monomethyl ether acetate

DPHA: Dipentaerythritol hexaacrylate (manufactured by Shinnakamura Kogyo Co., Ltd., product name A-DPH)

KBM-403: 3-Glycidoxypropyltriethoxysilane (coupling agent, made by Shin-Etsu Silicone, product name KBM-403)

Black mill base: prepared by the method of “Adjustment of the mill base” below.

<Adjustment of mill base>

0.6 g of carbon black, 3.6 g of lactam black (manufactured by BASF, Irgaphor Black S0100CF), 7.5 g of Azispur PB822 as a dispersant, 2.5 g of the acrylic resin synthesized in Comparative Synthesis Example 2, and 15 g of PGMEA were placed in a metal can along with zirconia beads. A mill base was produced by adding the mixture and shaking it with a paint shaker for 5 hours.

The photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 5 were evaluated for optical density (OD value, colorant dispersibility), elastic recovery rate, development pattern, and fine wire adhesion using the following methods, respectively. The results are shown in Table 3.

<Evaluation of optical density (OD value, colorant dispersibility)>

The photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 5 were coated on a 10 cm x 10 cm IZO (In ₂ O ₃ -ZnO) substrate (a substrate on which a wiring pattern made of IZO was formed). It was spin coated so that the thickness was 1.5㎛. After that, the IZO substrate was heated at 90°C for 3 minutes to volatilize the solvent in the coating film. Next, the entire surface of the coating film was exposed (exposure amount 50 mJ/cm2) using Multi Light ML-251D/B manufactured by Ushio Denki Co., Ltd. and irradiation optical unit PM25C-100, and photocured. Afterwards, it was developed with a 0.2% by mass aqueous potassium hydroxide solution for 120 seconds and further post-baked at 230°C for 30 minutes to obtain a cured resin film with a target thickness of 1.0 μm.

By using a transmission densitometer (361T, X-lite), the optical density (OD) was measured for a resin cured film with a thickness of 1.0 μm.

It can be said that the higher the optical density, the better the colorant dispersibility.

<Evaluation of elastic recovery rate>

For the resin cured film used for evaluation of optical density, the elastic recovery rate at 25°C was measured using an elasticity measuring device (DUH-W201S, Shimazu Seisakusho, Inc.) according to the following measurement conditions.

As a pressing body for pressing the resin cured film, a flat pressing body with a diameter of 50 μm was used. The elastic recovery rate was measured by a test applying a load of 300 mN to obtain identifiable results between the compared groups. The loading rate of 3 gf/sec and the holding time of 3 seconds were kept constant. Regarding the elastic recovery rate, a load of 300 mN was applied to a flat press body for 3 seconds and then unloaded, and the elastic recovery rate of the resin cured film before and after the load was measured using a three-dimensional thickness measuring device. The elastic recovery rate means the ratio of the distance recovered after a 10-minute recovery time (recovery distance) to the distance compressed (compression displacement) when a load of 300 mN is applied, and is expressed by the following equation.

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

<Development form, evaluation of fine wire adhesion>

The photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 5 were spin-coated on a 10 cm x 10 cm glass substrate so that the film thickness was 2.5 μm. Thereafter, the solvent was volatilized by heating the glass substrate at 90°C for 3 minutes. Next, a pattern mask of dots with diameters of 35, 30, 25, 20 to 3 μm at 1 μm intervals is placed on the coating film, and from above the mask, a Multi Light ML-251D/B manufactured by Ushio Denki Co., Ltd. and an irradiation optical unit are applied. It was exposed using PM25C-100 (exposure amount 20mJ/cm2, 80mJ/cm2) and photocured. After that, the thin wire adhesion was evaluated by developing for 120 seconds with a 0.2% by mass aqueous potassium hydroxide solution and confirming the size of the developed minimum pattern.

During development, the developed form was also confirmed. The developability is better when the development mode is dissolution rather than peeling of the coating film.

As shown in Table 3, the photosensitive resin compositions of Examples 1 to 7 had high optical density (colorant dispersibility) and elastic recovery rate of the resin cured film, and were good in evaluation of development form and fine wire adhesion.

On the other hand, the cured resin films of the photosensitive resin compositions of Comparative Examples 1 to 5 were inferior to those of Examples 1 to 7, especially in fine wire adhesion and development form.

Claims (9)

Suzy (A),
A photopolymerization initiator (B),
Solvent (C) and
A colorant (D),
Reactive Diluent (E)
Contains,
The resin (A) has a structure (a11) derived from an epoxy resin (a1), a structure (a21) derived from a monocarboxylic acid (a2) containing an ethylenically unsaturated group, and a structure (a3) derived from a polybasic acid (a3). a31),
The resin (A) is a reaction product in which the polybasic acid (a3) is added to the reaction product (R1) of the epoxy resin (a1) and the monocarboxylic acid (a2) containing an ethylenically unsaturated group,
The epoxy resin (a1) is a reaction product of phenol resin (a4) and epihalohydrin,
The phenol resin (a4) is a condensate of a dihydric phenol compound and an aldehyde compound,
In the resin (A), the ratio of each structural unit derived from the components (a1) to (a3) is the ethylenically unsaturated group-containing monocarboxylic acid per 1.00 mol of the moiety derived from the epoxy group of the epoxy resin (a1). The structural unit derived from the boxylic acid (a2) is 0.85 to 1.00 mol, and the structural unit derived from the polybasic acid (a3) is 0.10 to 0.70 mol.
A photosensitive resin composition characterized in that. According to paragraph 1,
When the total of the resin (A), the photopolymerization initiator (B), the colorant (D), and the reactive diluent (E) is 100 parts by mass,
1 to 50 parts by mass of the resin (A),
0.01 to 5 parts by mass of the photopolymerization initiator (B),
10 to 2000 parts by mass of the solvent (C),
1 to 50 parts by mass of the colorant (D) and
1 to 60 parts by mass of the reactive diluent (E)
A photosensitive resin composition containing. According to claim 1 or 2,
A photosensitive resin composition wherein the resin (A) has an acid value of 20 to 300 KOH mg/g and an unsaturated group equivalent weight of 100 to 4000 g/mole. According to claim 1 or 2,
A photosensitive resin composition wherein the colorant (D) includes an inorganic black pigment and an organic black pigment. According to claim 1 or 2,
A photosensitive resin composition wherein the phenol resin (a4) is a condensate of bisphenol A and formaldehyde. According to claim 1 or 2,
A photosensitive resin composition wherein the ethylenically unsaturated group-containing monocarboxylic acid (a2) is at least one selected from the group consisting of (meth)acrylic acid and 2-(meth)acryloyloxyethylsuccinic acid. According to claim 1 or 2,
A photosensitive resin composition wherein the polybasic acid (a3) is at least one selected from tetrahydrophthalic anhydride, succinic anhydride, and 1,2,4-cyclohexanetricarboxylic anhydride. A cured resin film of the photosensitive resin composition according to claim 1 or 2. An image display device comprising the resin cured film according to claim 8.