KR20220084093A - Photosensitive resin composition and image display device - Google Patents

Abstract

Provided is a photosensitive resin composition from which a cured resin film having good developability and dispersibility of a colorant and having a high elastic recovery factor is obtained. It contains a resin (A), a photoinitiator (B), a solvent (C), a colorant (D), and a reactive diluent (E), wherein the resin (A) is a condensate of a dihydric phenol compound and an aldehyde compound A photosensitive resin composition comprising a reaction product of an epoxy resin of epichlorohydrin (a1) and an ethylenically unsaturated group-containing monocarboxylic acid (a2), and a polybasic acid (a3). The ratio of each structural unit derived from the component (a1) to (a3) in the resin (A) is the ethylenically unsaturated group-containing monocarr with respect to 1.00 mol of the site derived from the epoxy group of the epoxy resin (a1). The structural unit derived from the 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 on February 6, 2020 based on the patent application 2020-019204 for which it applied to Japan, and uses the content here.

Conventionally, in liquid crystal display panels, spacer particles are used in order to keep the distance (cell gap) between two substrates constant. As the spacer particles, glass beads, plastic beads, and the like having a predetermined particle size are used. Usually, the spacer particle|grains are arrange|positioned at random on transparent substrates, such as a glass substrate. When spacer particles are present in the pixel formation region of the liquid crystal display panel, problems such as reflection of the spacer particles or scattering of incident light to lower contrast occur.

In order to solve this problem, dot-shaped or stripe-shaped spacers formed by photolithography using a photosensitive resin composition have been employed instead of spacer particles. This spacer can be formed by the method of apply|coating the photosensitive resin composition on a board|substrate, exposing ultraviolet-ray through a predetermined mask, and then developing. Therefore, the spacer in which the photosensitive resin composition consists of hardened|cured material can be formed only in predetermined places other than the pixel formation area in a liquid crystal display panel. Therefore, by forming the spacer by photolithography using the photosensitive resin composition, the above problem in the case of using the spacer particle can be solved.

In addition, in the organic EL display panel, a resist for a barrier rib that separates each color is used. However, since the barrier ribs are transparent, they reflect color mixtures and light from the outside. It is necessary to mount a circularly polarizing plate to prevent reflection.

In order to solve this problem, a method of preventing light reflection by using a black PDL (Pixel Defining Layer) colored black in the partition wall is being studied. If reflected light can be prevented without mounting a circularly polarizing plate, it will become possible to manufacture a foldable or bendable display.

As a photosensitive resin composition used as a material of the spacer with which a liquid crystal display panel is equipped, there exists the radiation-sensitive resin composition of patent document 1, for example.

Moreover, in patent document 2, the photosensitive composition used suitably as a resist for formation of a color filter, a black matrix, black column spacer, etc. is described.

Moreover, in patent document 3, the photosensitive resin composition for black column spacers containing alkali-soluble resin, a photopolymerizable monomer, a photoinitiator, and a light-shielding agent is described.

Japanese Patent Laid-Open No. 2001-302712 Japanese Patent Laid-Open No. 2011-170075 Japanese Patent Laid-Open No. 2013-134263

a black matrix, a color filter, a black column spacer, etc. which are forming a liquid crystal display element and a liquid crystal display element in recent years; Or in each member, such as black PDL which forms the organic electroluminescent display panel, stricter dimensional accuracy is calculated|required. For this reason, the more outstanding developability is calculated|required by the photosensitive resin composition which can be used as these materials. Moreover, in order to improve the display characteristic of a liquid crystal display element, the cured resin film which hardened the photosensitive resin composition used for the said use needs to have favorable colorant dispersibility. Moreover, in order to prevent deterioration of the liquid crystal display element with respect to the impact from the outside, it is calculated|required that the resin cured film which hardened the photosensitive resin composition used for the said use has a high elastic recovery factor.

This invention was made in view of the said circumstances, and it has excellent developability, and makes it a subject to provide the photosensitive resin composition from which the resin cured film which has favorable colorant dispersibility and has a high elastic recovery factor is obtained.

Moreover, this invention makes it a subject to provide the resin cured film of the photosensitive resin composition of this invention, and the image display apparatus provided with this.

The configuration of the present invention for solving the above problems is as follows.

[1] Resin (A);

a photopolymerization initiator (B);

A 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 an ethylenically unsaturated group-containing monocarboxylic acid (a2), and a structure derived from a polybasic acid (a3) ( a31),

The 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 a phenol resin (a4) and epihalohydrin,

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 component (a1) to (a3) in the resin (A) is the ethylenically unsaturated group-containing monocarr with respect to 1.00 mol of the site derived from the epoxy group of the epoxy resin (a1). The structural unit derived from the 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), the photoinitiator (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)

The photosensitive resin composition as described in [1] containing.

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

[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] Of [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 as 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 acid 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 cured resin film according to [8].

The photosensitive resin composition of this invention has the outstanding developability, dimensional precision is high, and the colorant dispersibility is favorable, and the cured resin film which has a high elastic recovery factor is obtained. Therefore, the photosensitive resin composition of this invention is suitable as a material of a black PDL, a black matrix, a color filter, and a black column spacer.

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

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of the photosensitive resin composition of this invention, its cured resin film, and an image display apparatus is demonstrated in detail. In addition, this invention is not limited only to embodiment described below.

[Photosensitive resin composition]

The photosensitive resin composition of this embodiment contains resin (A), a photoinitiator (B), a solvent (C), a coloring agent (D), and a reactive diluent (E).

[Resin (A)]

The resin (A) has a structure (a11) derived from the epoxy resin (a1), a structure (a21) derived from an ethylenically unsaturated group-containing monocarboxylic acid (a2), and a structure 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 a phenol resin (a4) and epihalohydrin, and the phenol resin (a4) is a condensate of a dihydric phenol compound and an aldehyde compound.

In the said resin (A), each structural unit ratio derived from the said (a1)-(a3) component is as follows. The structural unit derived from the said ethylenically unsaturated group containing monocarboxylic acid (a2) is 0.85-1.00 mol with respect to 1.00 mol of the site|part derived from the epoxy group of the said epoxy resin (a1). The structural unit derived from the said polybasic acid (a3) is 0.10-0.70 mol with respect to 1.00 mol of the site|part derived from the epoxy group of the said epoxy resin (a1).

Resin (A) may contain the structural unit derived from another arbitrary component in the range which does not impair the effect of this invention.

The said dihydric phenol compound is a compound containing two aromatic hydroxyl groups in 1 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;

dioxybenzenes such as hydroquinone and resorcin;

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 alicyclic structure-containing dihydric phenols such as (3,5-dimethyl-4-hydroxyphenyl)cyclohexane;

Other 4,4'-dihydroxybiphenyl-3,3',5,5'-tetramethylbiphenyl etc. are mentioned, However, It is not specifically limited. These may be used individually by 1 type, and may mix and use 2 or more types. Among these, compounds having two 4-hydroxyphenyl groups from the viewpoint of developability, dispersibility of colorant, and elastic recovery when used for the photosensitive resin composition are preferable, bisphenols are more preferable, and bisphenol A and bisphenol F are more preferably.

The aldehyde compound is not particularly limited as long as it is a compound having at least one formyl group in one molecule, and examples thereof include formaldehyde, acetaldehyde, benzaldehyde, crotonaldehyde, and hydroxybenzaldehyde. These may be used individually by 1 type, and may mix and use 2 or more types. Especially, formaldehyde is preferable from a viewpoint of developability at the time of using for the photosensitive resin composition, dispersibility of a coloring agent, and an elastic recovery factor.

As said epihalohydrin, epichlorohydrin, epiiodohydrin, epiblomhydrin, β-methylepichlorohydrin, etc. can be used. From a viewpoint of the reactivity with the condensate of a dihydric phenol compound and an aldehyde compound, epichlorohydrin is preferable. In addition, the reaction product of a phenol resin (a4) and epihalohydrin is not restrict|limited to what was obtained by making a phenol resin (a4) and epihalohydrin actually react. The structure of the reactant may be the same as that of the reactant. For example, after making the hydroxyl group of a phenol resin (a4) allyl-ether, it is good also as glycidyl ether by oxidizing an allyl group.

3000-30000 are preferable, as for the weight average molecular weight of a phenol resin (a4), 4000-20000 are more preferable, 5000-15000 are still more preferable.

4000-30000 are preferable, as for the weight average molecular weight of an epoxy resin (a1), 5000-20000 are more preferable, 6000-15000 are still more preferable.

Moreover, 100-5000 are preferable, as for epoxy equivalent, 150-1000 are more preferable, 200-600 are still more preferable.

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 (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 itaconic acid, and the like. These may be used independently and may use 2 or more types. Among these, (meth)acrylic acid and 2-(meth)acryloyloxyethyl succinic acid are preferable from the viewpoint of availability and reactivity with an 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 acid anhydride.

In resin (A) used for this embodiment, each structural unit ratio derived from (a1)-(a3) component is as follows.

The structural unit derived from an ethylenically unsaturated group containing monocarboxylic acid (a2) is 0.85-1.00 mol with respect to 1.00 mol of the site|part derived from the epoxy group of an epoxy resin (a1), It is preferable that it is 0.90-1.00 mol, and it is 0.95-1.00 It is more preferable that it is mole. Particularly preferably, the structural unit derived from the ethylenically unsaturated group-containing monocarboxylic acid (a2) is 0.99 to 1.00 moles, that is, it is preferable that the resin (A) does not contain substantially unreacted epoxy groups. . If the structural unit derived from an ethylenically unsaturated group containing monocarboxylic acid (a2) is 0.85 mol or more, an unsaturated group is fully contained in resin (A). Therefore, as a photosensitive resin composition, it has the outstanding sclerosis|hardenability and developability, and the resin cured film which has favorable colorant dispersibility and high hardness and elastic recovery factor is obtained.

Further, with respect to 1.00 mol of the site derived from the epoxy group of the epoxy resin (a1), 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, furthermore preferably 0.20 to 0.40 mol desirable. When the structural unit derived from a polybasic acid (a3) is 0.10 mol or more, the acid value of resin (A) becomes high enough, the residue of an unexposed part does not generate|occur|produce in the image development process, and favorable developability as a photosensitive resin composition is acquired. Moreover, favorable developability is acquired as the structural unit derived from a polybasic acid (a3) is 0.70 mol or less in an image development process without an exposure part running short.

In addition, "1.00 mol of site|part derived from an epoxy group" means the number of moles of an unreacted epoxy group before the ethylenically unsaturated group-containing carboxylic acid (a2) and polybasic acid (a3) are added.

It is preferable that it is 1000-20000, as for the weight average molecular weight of resin (A), it is more preferable that it is 3000-10000, It is still more preferable that it is 5000-7500. The image development process after apply|coating and exposing the photosensitive resin composition as a weight average molecular weight is 1000 or more WHEREIN: It is difficult to generate|occur|produce a notch in a developing pattern, and it is preferable. The image development process after apply|coating and exposing the photosensitive resin composition as a weight average molecular weight is 20000 or less WHEREIN: Since image development time can be adjusted in an appropriate range, it is preferable.

A weight average molecular weight is the value which measured under the following conditions using gel permeation chromatography (GPC), and carried out standard polystyrene conversion.

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

Column temperature: 40°C

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

Developing solvent: tetrahydrofuran

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

Flow rate: 1mL/min

Although the acid value (JIS K6901 5.3) of resin (A) is not restrict|limited as long as this invention exhibits the desired effect, 20-300KOHmg/g is preferable, 30-200KOHmg/g is more preferable, 40-125KOHmg/g This is more preferable. When an acid value is 20KOHmg/g or more, the developability of the photosensitive resin composition is favorable. On the other hand, since the photocured part becomes difficult to melt|dissolve with respect to a developing solution by apply|coating and exposing the photosensitive resin composition as an acid value is 300KOHmg/g or less, it is preferable.

Although the unsaturated group equivalent of resin (A) of this embodiment is not restrict|limited as long as this invention exhibits the desired effect, 100-4000 g/mol is preferable, 200-2000 g/mol is more preferable, 250-500 g/mol is further desirable. When an unsaturated group equivalent is 100 g/mol or more, the developability of the photosensitive resin composition will become favorable. On the other hand, the sensitivity of the photosensitive resin composition becomes it higher that an unsaturated group equivalent is 4000 g/mol or less, and a finer pattern can be formed. Moreover, it contributes to the hardened|cured material hardness improvement of the photosensitive resin composition, and the resin cured film which has a high elastic recovery factor is obtained.

In addition, an unsaturated group equivalent is the mass of resin (A) per 1 mol of unsaturated bonds (ethylenic carbon-carbon double bond) in resin (A). The unsaturated group equivalent can be calculated|required by dividing the mass of resin (A) by the number of moles of the unsaturated group in resin (A) (g/mol). In this specification, the unsaturated group equivalent of resin (A) is a theoretical value calculated from the input amount of the ethylenically unsaturated group containing monocarboxylic acid (a2) used in order to introduce|transduce an unsaturated group into resin (A).

[Method for producing resin (A)]

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

It is preferable to use the method shown below as a manufacturing method of resin (A) of this embodiment. First, the epoxy resin (a1) which is a reaction product of the condensate of a dihydric phenol compound and an aldehyde compound, and epihalohydrin is obtained using a catalyst as needed in a solvent. The obtained epoxy resin (a1) and ethylenically unsaturated group containing monocarboxylic acid (a2) are made to react, and a resin (A) precursor is synthesize|combined (1st process). In this step, with respect to the epoxy group of the epoxy resin (a1), the carboxyl group of the ethylenically unsaturated group-containing monocarboxylic acid (a2) is subjected to an addition reaction, and the resulting resin (A) precursor contains an ethylenically unsaturated group-containing monocarboxylic acid. An unsaturated group derived from the acid (a2) is introduced. And the epoxy group derived from an epoxy resin (a1) produces|generates a hydroxyl group by ring-opening addition. Next, the polybasic acid (a3) is reacted with the hydroxyl group of the resin (A) precursor to synthesize the resin (A) (second step).

The reaction conditions in the first step can be appropriately set according to a conventional method. For example, 50-150 degreeC is preferable and, as for the reaction temperature in a 1st process, 60-140 degreeC is more preferable. As for the reaction time in a 1st process, 1 to 10 hours are preferable, for example.

The mixing ratio of the epoxy resin (a1) and the ethylenically unsaturated group-containing monocarboxylic acid (a2) is the unsaturated group equivalent of the target resin (A) or the ethylenically unsaturated group-containing monocarboxylic acid with respect to the epoxy group in the epoxy resin (a1). It can set suitably according to the addition amount (introduction ratio of the unsaturated group with respect to an epoxy group) of carboxylic acid (a2). For example, 0.85-1.10 mol is preferable, as for the compounding ratio of an ethylenically unsaturated group containing monocarboxylic acid (a2) with respect to 1.00 mol of epoxy groups in an epoxy resin (a1), 0.90-1.00 mol is more preferable, 0.95-1.00 mole is more preferred. In particular, in order to produce the resin (A) precursor in which unreacted epoxy groups do not substantially remain, the blending ratio of the ethylenically unsaturated group-containing monocarboxylic acid (a2) is 1.00 mol or more. If the compounding ratio of ethylenically unsaturated group containing monocarboxylic acid (a2) is 0.85 mol or more, increase in molecular weight by reaction of the epoxy groups of an epoxy resin (a1) can be suppressed. When the blending ratio of the ethylenically unsaturated group-containing monocarboxylic acid (a2) is 1.10 mol or less, as a photosensitive resin composition, good colorant dispersibility, developability, and elastic recovery rate of the cured product can be ensured.

It does not specifically limit as a solvent used for a 1st process, A well-known thing can be used suitably. Specific examples of the solvent 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; 3-methyl ethoxypropionate, 3-ethoxy ethyl propionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 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-propionic acid 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;

Carboxylic acid amide compounds, such as N-methylpyrrolidone, N,N- dimethylformamide, and N,N- dimethylacetamide, etc. are mentioned. These solvents may be used independently and may mix and use 2 or more types.

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

Although the usage-amount of the solvent used for a 1st process is not specifically limited, When the sum total of the epoxy resin (a1) used as a raw material and ethylenically unsaturated group containing monocarboxylic acid (a2) is 100 mass parts, 30-1000 A mass part is preferable, and 50-800 mass parts is more preferable. Since the viscosity of the resin (A) precursor can be controlled in an appropriate range that the usage-amount of said solvent is 1000 mass parts or less, it is preferable. On the other hand, it is preferable that the usage-amount of the said solvent is 30 mass parts or more, since it can prevent that baking occurs at the time of reaction and can perform a synthesis reaction stably. Moreover, coloring and gelatinization of a resin (A) precursor can be prevented as said solvent usage-amount is 30 mass parts or more.

In this embodiment, in order to accelerate|stimulate reaction of an epoxy resin (a1) and an ethylenically unsaturated group containing monocarboxylic acid (a2), it is preferable to use a catalyst. It does not specifically limit as a catalyst used in this embodiment, It selects suitably according to the kind etc. of a raw material.

Examples of the catalyst used in the present embodiment include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, chromium chelate compounds, etc. can be heard These catalysts may be used independently and may mix and use 2 or more types.

Although the usage-amount of the catalyst used in this embodiment is not specifically limited, When the sum total of an epoxy resin (a1) and an ethylenically unsaturated group containing monocarboxylic acid (a2) is 100 mass parts, generally 0.01- It is 5 mass parts, Preferably it is 0.1-2 mass parts, More preferably, it is 0.2-1 mass part.

In a 1st process, in order to prevent gelatinization of resin, it is preferable to use a polymerization inhibitor. It does not specifically limit as a polymerization inhibitor used in a 1st process, According to the raw material of resin, etc., it selects suitably.

As a polymerization inhibitor used in a 1st process, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, butylhydroxytoluene, etc. are mentioned, for example. These polymerization inhibitors may be used independently and may use 2 or more types.

Although the usage-amount of a polymerization inhibitor is not specifically limited, When the sum total of an epoxy resin (a1) and an ethylenically unsaturated group containing monocarboxylic acid (a2) is 100 mass parts, it is generally 0.01-5 mass parts, Preferably it is 0.1-2 mass parts, More preferably, it is 0.2-1 mass part.

The reaction conditions in the second step can be appropriately set according to a conventional method. For example, 50-130 degreeC is preferable and, as for the reaction temperature in a 2nd process, 60-120 degreeC is more preferable. As for the reaction time in a 1st process, 1 to 10 hours are preferable, for example.

The blending ratio of the resin (A) precursor and the polybasic acid (a3) is a polybasic acid ( It is preferable that the compounding ratio of a3) is 0.10-0.70 mol, It is more preferable that it is 0.15-0.50 mol, It is still more preferable that it is 0.20-0.40 mol. If the compounding ratio of a polybasic acid (a3) is 0.10 mol or more, developability favorable as a photosensitive resin composition will be acquired. Since the side reaction at the time of a synthesis|combination can be suppressed as the compounding ratio of a polybasic acid (a3) is 0.70 mol or less, and developability as a photosensitive resin composition improves, a finer pattern can be formed.

As a blending ratio of the polybasic acid (a3) to 1.00 mol of the epoxy group-derived site of the epoxy resin (a1) in the resin (A) precursor, it is preferably 0.10 to 0.70 mol, more preferably 0.15 to 0.50 mol, and 0.20 to 0.40 More preferably, it is mole.

As a solvent used for a 2nd process, the thing similar to the solvent used by a 1st process can be used, and the solvent used by the 1st process may be contained. That is, after a 1st process is complete|finished, without removing the solvent used in a 1st process, you may perform a 2nd process continuously.

Although the usage-amount of the solvent used for a 2nd process is not specifically limited, When the sum total of an epoxy resin (a1), an ethylenically unsaturated group containing monocarboxylic acid (a2), and a polybasic acid (a3) is 100 mass parts, 30 - 1000 mass parts is preferable, and 50-800 mass parts is more preferable. Since the viscosity of resin (A) can be controlled in the usage-amount of said solvent being 1000 mass parts or less in an appropriate range, it is preferable. On the other hand, it is preferable that the usage-amount of the said solvent is 30 mass parts or more, since it can prevent that baking occurs at the time of reaction, and can perform a synthetic reaction stably. Moreover, coloring and gelatinization of resin (A) can be prevented as said solvent usage-amount is 30 mass parts or more.

In a 2nd process, the catalyst and polymerization inhibitor similar to what was used in the 1st process can be used. When performing a 2nd process continuously after a 1st process, it can use continuously, without removing the catalyst and polymerization inhibitor used at a 1st process, In a 2nd process, you may add newly.

[Photoinitiator (B)]

Although it will not specifically limit if it is a polymerization initiator which generate|occur|produces a radical by light irradiation as a photoinitiator (B), For example, Benzoin compounds, such as benzoin, benzoin methyl ether, benzoin ethyl ether, 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 ;

an acylphosphine oxide compound, 1.2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime)], etc. are mentioned. These photoinitiators (C) may be used independently and may use 2 or more types.

[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 according to the type of the resin (A) or the like. It is preferable that the solvent (C) has compatibility with the reactive diluent (E) mentioned later.

As a solvent (C), the thing similar to the solvent which can be used when manufacturing resin (A) can be used, It is preferable to use a glycol ether type 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 the solution containing any component other than a solvent (C) as a material of the photosensitive resin composition other than a solvent (C), you may use the solvent contained in the said solution as a solvent (C).

[Colorant (D)]

The coloring agent (D) should just melt|dissolve or disperse|distribute to the solvent (C), and is not specifically limited. As a coloring agent (D), dye and a pigment are mentioned, for example. As a coloring agent (D), only dye may be used, only a pigment may be used, and it may use it combining dye and a pigment. When using the cured resin film of the photosensitive resin composition of the present embodiment as any of black PDL, black matrix, color filter, and black column spacer, the colorant (D) is used according to the purpose of the member formed of the cured resin film, etc. It can be used individually or in combination of 2 or more types. For example, when a black thing is used as a coloring agent (D), the resin cured film of the photosensitive resin composition becomes a thing suitable as black PDL, a black matrix, and a black column spacer.

Examples of the dye 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, 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, and the like.

It is preferable to use the acid dye of an azo type, a xanthene type, an anthraquinone type, or a phthalocyanine type among these dyes.

These dyes may be used independently and may mix and use 2 or more types.

As an example of a pigment, 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 red 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, 38;

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

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

and black pigments such as aniline black, perylene black, titanium black, cyanine black, lignin black, lactam organic black, RGB black, carbon black, and iron oxide.

These pigments may be used independently and may mix and use 2 or more types.

As a black pigment, it is preferable to use an inorganic black pigment and an organic black pigment together from an optical density viewpoint of the image display apparatus provided with the resin cured film of the photosensitive resin composition of this embodiment, and carbon black and lactam type organic black together more preferably.

When a pigment is included as a coloring agent (D), from a viewpoint of improving the dispersibility of the pigment in the photosensitive resin composition, the photosensitive resin composition may contain the well-known dispersing agent. Content of a dispersing agent can be set suitably according to the kind of pigment etc. to be used.

As a dispersing agent, it is preferable to use a polymer dispersing agent from the point of being excellent in dispersion stability with time. The polymer dispersant can be arbitrarily selected, for example, a urethane-based dispersant, a polyethyleneimine-based dispersant, a polyoxyethylene alkyl ether-based dispersant, a polyoxyethylene glycol diester-based dispersant, a sorbitan aliphatic ester-based dispersant, an aliphatic modified ester-based dispersant and the like. As a polymer dispersing agent, brand names such as EFKA (registered trademark, manufactured by BASF Japan), Disperbyk (registered trademark, manufactured by Big Chemi Corporation), Dispalon (registered trademark, manufactured by Kusumoto Chemical Co., Ltd.), SOLSPERSE (registered trademark, manufactured by Zeneka Corporation) A commercially available one may be used.

<Reactive Diluent (E)>

The photosensitive resin composition of this embodiment contains a reactive diluent (E) other than resin (A), a photoinitiator (B), a solvent (C), and a coloring agent (D).

A reactive diluent (E) is a compound which has at least 1 ethylenically unsaturated group in a molecule|numerator, and it is preferable that it is a compound which has two or more 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. Moreover, when the resin cured film of the photosensitive resin composition containing a reactive diluent (E) is used as black PDL, a black matrix, a color filter, and a black column spacer, the intensity|strength of a cured resin film becomes favorable. Moreover, after apply|coating and exposing the photosensitive resin composition containing a reactive diluent (E) on the to-be-formed surface of a resin cured film, the resin cured film developed and formed has favorable adhesiveness with a to-be-formed surface.

As the monofunctional monomer (monomer having only one ethylenically unsaturated bond) used as the reactive diluent (E), for example, (meth)acrylamide, methylol (meth)acrylamide, 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 derivatives ( meth)acrylate compounds;

aromatic vinyl compounds such as styrene, α-methylstyrene, α-chloromethylstyrene, and vinyltoluene;

Carboxylic acid ester, such as vinyl acetate and a vinyl propionate, etc. are mentioned. These monofunctional monomers may be used independently and may use 2 or more types.

As the polyfunctional monomer (monomer having a plurality of ethylenically unsaturated bonds) used as the reactive diluent (E), for example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di (meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 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 diglycyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, phthalic acid diglycidyl ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycyl ether pole (meth) acrylate, urethane (meth) acrylate (ie, tolylene diisocyanate), (meth)acrylate compounds, such as a reaction product of trimethylhexamethylene diisocyanate and hexamethylene diisocyanate and 2-bedroxyethyl (meth)acrylate, and tri (meth)acrylate of tris(hydroxyethyl) isocyanurate;

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

dicarboxylic acid ester compounds such as divinyl adipate;

triallyl cyanurate;

(meth)acrylamide compounds, such as a condensate of methylenebis (meth)acrylamide, (meth)acrylamide methylene ether, and a polyhydric alcohol, and N-methylol (meth)acrylamide, etc. are mentioned. These polyfunctional monomers may be used independently and may use 2 or more types.

<Other ingredients>

Moreover, the photosensitive resin composition of this embodiment may contain well-known additives, such as a coupling agent, a leveling agent, and a thermal-polymerization inhibitor, in the range which does not impair the effect of this invention. As a coupling agent, KBM-403 (3-glycidoxypropyl triethoxysilane, the Shin-Etsu Silicone make) etc. are mentioned, for example. Content of these additives will not be specifically limited if it is a range which does not impair the effect of this invention.

The content of the resin (A) is preferably 1 to 50 parts by mass, when the total of the resin (A), the photoinitiator (B), the colorant (D), and the reactive diluent (E) of the photosensitive resin composition is 100 parts by mass, 10 -40 mass parts is more preferable, and 20-35 mass parts is still more preferable. The photosensitive resin composition which has favorable photocurability as content of resin (A) is 1 mass part or more will be obtained. It becomes the photosensitive resin composition which has favorable applicability|paintability as content of resin (A) is 50 mass parts or less.

If the content of the photoinitiator (B) is 100 parts by mass of the total of the resin (A), the photoinitiator (B), the colorant (D) and the reactive diluent (E) of the photosensitive resin composition, 0.01 to 10 parts by mass is preferable, A mass part is more preferable than 0.1-8 mass parts, and 1-5 mass parts is still more preferable. The photocurability of the photosensitive resin composition is favorable as content of a photoinitiator (B) is 0.01 mass part or more. The image development process after application|coating and exposure of the photosensitive resin composition as content of a photoinitiator (B) is 10 mass parts or less WHEREIN: A residue will not generate|occur|produce.

If the content of the solvent (C) is 100 parts by mass of the total of the resin (A), the photoinitiator (B), the colorant (D) and the reactive diluent (E) of the photosensitive resin composition, it is preferably 100 to 2000 parts by mass, It is more preferable that it is 150-1000 mass parts, and it is still more preferable that it is 200-500 mass parts. It becomes the photosensitive resin composition which has favorable applicability|paintability as content of a solvent (C) is 100 mass parts or more. When content of a solvent (C) is 2000 mass parts or less, the application|coating process of the photosensitive resin composition WHEREIN: A coating film which has sufficient film thickness will be obtained.

The content of the colorant (D) is preferably 1 to 50 parts by mass, when the total of the resin (A), the photoinitiator (B), the colorant (D), and the reactive diluent (E) of the photosensitive resin composition is 100 parts by mass, 10 -40 mass parts is more preferable, and 20-30 mass parts is still more preferable. If content of a coloring agent (D) is 1 mass part or more, the resin cured film of the photosensitive resin composition has sufficient color reproducibility. In addition, when a black thing is used as a coloring agent (D), a cured resin film will have sufficient light-shielding property. The image development process after apply|coating and exposing the photosensitive resin composition as content of a coloring agent (D) is 50 mass parts or less WHEREIN: A residue is hard to generate|occur|produce.

The content of the reactive diluent (E) is preferably 1 to 60 parts by mass, when the total of the resin (A), the photoinitiator (B), the colorant (D) and the reactive diluent (E) of the photosensitive resin composition is 100 parts by mass, 15-50 mass parts is more preferable, and 30-45 mass parts is still more preferable. If content of a reactive diluent (E) is 1 mass part or more, even if it contains a coloring agent (D) abundantly, the photosensitive resin composition which has favorable sclerosis|hardenability will be obtained. When content of a reactive diluent (E) is 60 mass parts or less, the image development process after apply|coating and exposing the photosensitive resin composition WHEREIN: A residue is hard to generate|occur|produce.

[Method for producing photosensitive resin composition]

Next, the method of manufacturing the photosensitive resin composition of this embodiment is demonstrated.

The photosensitive resin composition of this embodiment is any resin (A) of this embodiment, a photoinitiator (B), a solvent (C), a coloring agent (D), a reactive diluent (E), a dispersing agent, and an additive Any one or more components of can be manufactured by the method of mixing using a well-known mixing apparatus.

The photosensitive resin composition of this embodiment prepares beforehand the composition containing resin (A) and a solvent (C), and then, in said composition, a photoinitiator (B), a coloring agent (D), and a reactive diluent You may manufacture by the method of further adding and mixing (E) and any 1 or more types of components of a dispersing agent and an additive.

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

In the present embodiment, it is not always necessary to isolate the desired resin (A) from the resin solution in which the reaction for synthesizing the resin (A) is completed. Therefore, as a composition containing the resin (A) and the solvent (C), the solvent contained in the resin solution at the time when the reaction for synthesizing the resin (A) is completed is not separated from the resin solution, and after the reaction is completed You may use the resin solution as it is. Moreover, as a composition containing resin (A) and a solvent (C), you may use what added and mixed another solvent to the resin solution after completion|finish of reaction.

Since the photosensitive resin composition of this embodiment contains resin (A) of this embodiment, it has the outstanding developability, and the colorant dispersibility is favorable, and the cured resin film which has a high elastic recovery factor is obtained. Therefore, the photosensitive resin composition of this embodiment is suitable as a material of a black PDL, a black matrix, a color filter, and a black column spacer.

Moreover, the photosensitive resin composition of this embodiment has favorable colorant dispersibility, can fully satisfy general characteristics, such as developability, even if the colorant (D) is black, and is a cured resin 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, the adhesiveness with respect to a to-be-formed surface is favorable, and the black pattern which has sufficient light-shielding property can be formed.

[Cured Resin Film]

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

Since the cured resin film of this embodiment has favorable colorant dispersibility, solvent resistance, and elastic recovery factor, it is suitable as a black PDL, a black matrix, a color filter, and a black column spacer that are members of an image display device.

[Method for producing cured resin film]

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

First, the photosensitive resin composition is apply|coated on the to-be-formed surface of a resin cured film, and a resin layer (coating film) is formed. Next, the resin layer is exposed through a mask of a predetermined pattern, and the exposed portion is photocured. Next, the unexposed part of the resin layer is developed with a developing solution, and it is set as the resin cured film which has a predetermined|prescribed pattern. Then, as needed, a post-baking (heat treatment) of a cured resin film is performed.

When exposing a resin layer, you may use the halftone mask of a predetermined|prescribed pattern. In this case, an unexposed part and a semi-exposed part are developed with a developing solution, and it is set as the resin cured film which has a predetermined|prescribed pattern.

Although it does not specifically limit as a method of apply|coating the photosensitive resin composition, For example, the screen printing method, the roll coat method, the curtain coat method, the spray coat method, the spin coat method, etc. are mentioned.

After apply|coating the photosensitive resin composition, you may volatilize the solvent (C) contained in a resin layer by heating using heating means, such as a circulation type oven, an infrared heater, and a hotplate, as needed. The heating conditions after application|coating are not specifically limited, What is necessary is just to set suitably 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.

Although it does not specifically limit as a method of exposing a resin layer, For example, the method of irradiating active energy rays, such as an ultraviolet-ray and an excimer laser beam, is mentioned.

What is necessary is just to set the energy dose irradiated to a resin layer suitably according to the composition of the photosensitive resin composition. For example, although the energy dose irradiated to a resin layer can be 30-2000 mJ/cm<2>, it is not limited to this range.

Although it does not specifically limit as a light source used for exposure, 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 arbitrarily and can be used.

As a developing solution used for image development, since excellent developability is obtained, it is preferable to use an alkali developing solution. As an alkali developing solution, For example, aqueous solutions, such as sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, 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 -ethyl-N-β-methanesulfonamide ethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and aqueous solutions thereof such as sulfate, hydrochloride or p-toluenesulfonate; The aqueous solution of a p-phenylenediamine type compound, etc. are mentioned.

An antifoaming agent, surfactant, etc. may be contained in a developing solution as needed.

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

Moreover, after developing with a developing solution, it is preferable to perform post-baking (heat treatment) of the cured resin film which has a predetermined|prescribed pattern. By performing a post-baking, hardening of a cured resin film can be advanced more. It does not specifically limit as conditions of a post-baking, It can select arbitrarily, What is necessary is just to set suitably according to the composition of the photosensitive resin composition. For example, the heating temperature of the post-baking can be 130°C to 250°C. Moreover, it is preferable that the heating time of a post-baking is 10 minutes - 4 hours, More preferably, they are 20 minutes - 2 hours.

[Image display device]

The image display apparatus of this embodiment is equipped with the resin cured film of this embodiment. As a specific example of an image display apparatus, a liquid crystal display device, organic electroluminescent display, etc. are mentioned, for example.

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

Although it does not specifically limit as a material of the base material which forms the to-be-formed surface of a cured resin film, For example, Glass, silicone, polycarbonate, polyester, polyamide, polyamideimide, polyimide, aluminum, printed wiring A board|substrate, an array board|substrate, etc. in which the wiring pattern is formed in the surface, such as a board|substrate, are mentioned.

The manufacturing method of the image display apparatus of this embodiment should just include the process of forming the cured resin film of this embodiment by the manufacturing method mentioned above, About members other than the member formed with the cured resin film, it can be manufactured according to a conventional method. can

The cured resin film which hardened the photosensitive resin composition of this embodiment has the outstanding developability, the colorant dispersibility and solvent resistance are favorable, and has a high elastic recovery factor. For this reason, it is suitable as a material of black PDL, a black matrix, a color filter, and a black column spacer with which an image display apparatus is equipped.

Example

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

<Synthesis Example 1>

(Step 1)

In a flask equipped with a stirring device, dropping funnel, condenser, thermometer, and gas inlet tube, propylene glycol monomethyl ether acetate (86 g) as a solvent and bisphenol A novolac epoxy resin (Nanya Plastics Co., Ltd. product name NPPN-438, product name NPPN-438, epoxy) Equivalent 198) was added to 198 g, stirred and dissolved. Next, acrylic acid (72 g) as 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 are added, and the inside of the flask is stirred while blowing in air, 120 The temperature was raised to °C and the reaction was carried out for 2 hours.

(Second process)

Next, 32 g of succinic anhydride as an anhydride of the polybasic acid (a3) was added, followed by stirring at 120°C for 30 minutes to synthesize Resin (A) of Synthesis Example 1.

Propylene glycol monomethyl ether acetate was added and mixed as a solvent (C) to the resin (A) solution after completion|finish of reaction, and it was set as the preparation solution (solid content concentration 40 mass %) containing resin (A) and solvent (C). . In addition, solid content means the heating remainder when a composition is heated at 130 degreeC for 2 hours, and resin (A) becomes a main component as for solid content of a preparation solution.

<Synthesis Examples 2 to 7>

Resin (A) was synthesized in the same manner as in Synthesis Example 1 except for having the composition shown in Table 1, propylene glycol monomethyl ether acetate was added, and a preparation solution containing resin (A) and solvent (C) (solid content) concentration of 40% by mass).

As compounds in Table 1, the following were used.

NPPN-438: Bisphenol A novolac type epoxy resin (Nanya Plastics Co., Ltd. product name NPPN-438, epoxy equivalent 198)

AA: acrylic acid

MAA: methacrylic acid

HOMS: acryloyloxyethyl succinic acid

SA: succinic anhydride

THPA: tetrahydrophthalic anhydride

CHTC: 1,2,4-cyclohexanetricarboxylic acid

<Method for measuring acid value>

According to JIS K6901 5.3.2, it was measured using a mixture indicator of bromothymol blue and phenol red. The acid value means the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of the resin (A).

<Unsaturation group equivalent>

It is the mass of resin (A) per mole number of polymerizable unsaturated bonds, and is a calculated value computed based on the usage-amount of the component (a1) - (a3) which is a raw material.

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

It measured under the following conditions using gel permeation chromatography (GPC), and it converted into standard polystyrene.

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

Column temperature: 40°C

Sample: 0.2% tetrahydrofuran solution of resin (A)

Developing 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, dropping funnel, condenser, thermometer and gas inlet tube, 71 g of propylene glycol monomethyl ether acetate as a solvent, 210 g of cresol novolac epoxy (YDCN-704L, epoxy equivalent: 210), and 72 g of acrylic acid And 0.2 g of triphenylphosphine which is a catalyst, and 0.7 g of butylhydroxytoluene which is a polymerization inhibitor were added, the inside of a flask was stirred, blowing in air, and it heated up at 120 degreeC, and made it react for 2 hours.

Next, in the same flask, 28.6 g of tetrahydrophthalic anhydride was thrown in, and it stirred at 120 degreeC for 30 minutes, and synthesize|combined resin.

Propylene glycol monomethyl ether acetate was added and mixed to the resin solution after completion|finish of reaction as a solvent (C), and it was set as the preparation solution (solid content concentration 40 mass %) containing resin and a solvent (C).

About the resin synthesize|combined by the comparative synthesis example 1, it carried out similarly to the synthesis example 1, and measured the acid value of solid content, a weight average molecular weight, and the unsaturated group equivalent. As a result, the solid content acid value of the resin synthesize|combined by the 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 the flask provided with the stirring apparatus, the dropping funnel, a condenser, a thermometer, and a gas introduction tube, it stirred, nitrogen substitution, and heated up at 120 degreeC. Then, 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, 12 g of t-butylperoxy-2- What added ethylhexanoate (polymerization initiator, Nichiyo Co., Ltd. make, perbutyl (trademark) O) was dripped in the said flask over 2 hours from the dropping funnel. After completion of the dropwise addition, the mixture was further stirred at 120°C for 2 hours to carry out a copolymerization reaction. Then, 42 g of acrylic acid, 0.4 g of metoquinone as a polymerization inhibitor, and 0.5 g of triphenylphosphine as a catalyst were added to the reaction solution, and low oxygen air into which nitrogen gas was injected so that the oxygen concentration was 4% to 7% was blown while blowing 110 It was heated at ℃ for 10 hours.

Then, confirming that an acid value is 1.0KOHmg/g or less, tetrahydrophthalic anhydride is thrown in 55g, it is made to react at 110 degreeC for 2 hours, and the resin solution (solid content acid value 80.6KOHmg/g, weight average molecular weight 9500) of 50 mass % of solid content concentration. ) was obtained.

<Comparative Synthesis Examples 3 to 6>

Except having set it as the composition shown in Table 1, it carried out similarly to Synthesis Example 1, synthesize|combined resin, propylene glycol monomethyl ether acetate was added, and the preparation solution containing resin (A) and solvent (C) (solid content concentration 40 mass %).

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

Using the prepared solution containing the resin (A) and the solvent (C) of Synthesis Examples 1 to 7 and the resin solution described in Comparative Synthesis Examples 1, 2, 4 to 6, the composition (parts by mass) shown in Table 2 was carried out 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.

As the compounds described in Table 2, the following were used.

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

PGMEA: propylene glycol monomethyl ether acetate

DPHA: dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Kogyo Co., Ltd., product name A-DPH)

KBM-403: 3-glycidoxypropyltriethoxysilane (coupling agent, Shin-Etsu Silicone, product name KBM-403)

Black mill base: It was prepared by the following "adjustment of a mill base" method.

<Adjustment of the mill base>

0.6 g of carbon black, 3.6 g of lactam-based black (manufactured by BASF, Irgaphor Black S0100CF), 7.5 g of Azisper 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 with zirconia beads and shaken with a paint shaker for 5 hours to prepare a mill base.

About the photosensitive resin composition of Examples 1-7 and Comparative Examples 1-5, the following method evaluated optical density (OD value, colorant dispersibility), elastic recovery factor, image development form, and fine wire adhesiveness, respectively. The results are shown in Table 3.

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

The photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 5 were coated on a 10 cm × 10 cm IZO (In ₂ O ₃ -ZnO) substrate (a substrate on which a wiring pattern made of IZO is formed on the surface). was spin-coated to a thickness of 1.5 µm. Then, the solvent in a coating film was volatilized by heating an IZO board|substrate at 90 degreeC for 3 minute(s). Next, the entire surface of the coating film was exposed (exposure amount: 50 mJ/cm 2 ) and photocured using Multilite ML-251D/B manufactured by Ushio Electric Co., Ltd. and an irradiation optical unit PM25C-100. Then, the 1.0-micrometer-thick resin cured film made into the objective was obtained by developing for 120 second in 0.2 mass % potassium hydroxide aqueous solution, and also post-baking at 230 degreeC for 30 minute(s).

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

It can be said that it is excellent in colorant dispersibility, so that an optical density is high.

<Evaluation of elastic recovery rate>

About the resin cured film used for evaluation of optical density, the elastic recovery factor in 25 degreeC was measured using the elasticity measuring apparatus (DUH-W201S, Shimadzu Corporation) according to the following measurement conditions.

As the pressing body for pressing the cured resin film, a flat pressing body having a diameter of 50 µm was used. The elastic recovery rate was measured by a test in which a load of 300 mN was applied to obtain discriminable results between the groups compared. A load rate of 3 gf/sec and a holding time of 3 sec were kept constant. About elastic recovery factor, after loading a load of 300 mN for 3 second to a flat press body, it removed, and the elastic recovery factor of the cured resin film before and behind a load was measured by using a three-dimensional thickness measuring apparatus. The elastic recovery factor means the ratio of the distance (recovery distance) recovered after the lapse of the recovery time of 10 minutes to the compressed distance (compression displacement) when a load of 300 mN is applied, and is expressed by the following formula.

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

<Evaluation of developing form and fine wire adhesion>

The photosensitive resin compositions of Examples 1-7 and Comparative Examples 1-5 were spin-coated on a 10 cm x 10 cm glass substrate so that the thickness of a coating film might be set to 2.5 micrometers. Then, the solvent was volatilized by heating a glass substrate at 90 degreeC for 3 minute(s). Next, a pattern mask of dots having a diameter of 1 µm in intervals of 1 µm to 35, 30, 25, 20 to 3 µm was placed on the coating film, and from above the mask, Multilite ML-251D/B manufactured by Ushio Denki Co., Ltd. and an irradiation optical unit It was exposed using PM25C-100 (exposure amount 20mJ/cm<2> 80mJ/cm<2>), and was photocured. Then, thin wire|wire adhesiveness was evaluated by developing for 120 second with 0.2 mass % potassium hydroxide aqueous solution, and confirming the size of the developed minimum pattern.

At the time of development, the development form was also confirmed. The developing form is not peeling of a coating film but melt|dissolution, and developability is favorable.

As shown in Table 3, the photosensitive resin compositions of Examples 1-7 had high optical density (colorant dispersibility) and elastic recovery factor of a cured resin film, and evaluation of the image development form and fine wire adhesiveness was favorable.

On the other hand, compared with Examples 1-7, the resin cured film of the photosensitive resin composition of Comparative Examples 1-5 was especially inferior in fine wire adhesiveness and image development form.

Claims (9)

Resin (A) and
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 an ethylenically unsaturated group-containing monocarboxylic acid (a2), and a structure 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 ethylenically unsaturated group-containing monocarboxylic acid (a2),
The epoxy resin (a1) is a reaction product of a phenol resin (a4) and epihalohydrin,
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 component (a1) to (a3) in the resin (A) is the ethylenically unsaturated group-containing monocarr with respect to 1.00 mol of the site derived from the epoxy group of the epoxy resin (a1). The structural unit derived from the 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.
The photosensitive resin composition, characterized in that. According to claim 1,
When the total of the resin (A), the photoinitiator (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)
The photosensitive resin composition containing. 3. The method of claim 1 or 2,
The photosensitive resin composition wherein the resin (A) has an acid value of 20 to 300 KOHmg/g and an unsaturated group equivalent of 100 to 4000 g/mol. 4. The method according to any one of claims 1 to 3,
The photosensitive resin composition in which the said colorant (D) contains an inorganic black pigment and an organic black pigment. 5. The method according to any one of claims 1 to 4,
The photosensitive resin composition wherein the phenol resin (a4) is a condensate of bisphenol A and formaldehyde. 6. The method according to any one of claims 1 to 5,
The 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. 7. The method according to any one of claims 1 to 6,
The photosensitive resin composition wherein the polybasic acid (a3) is at least one selected from tetrahydrophthalic anhydride, succinic anhydride and 1,2,4-cyclohexanetricarboxylic acid anhydride. The cured resin film of the photosensitive resin composition in any one of Claims 1-7. An image display device comprising the cured resin film according to claim 8 .