KR940007778B1 - Photosensitive resin composition and color filter - Google Patents

Abstract

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Description

Photosensitive Resin Composition and Color Filter

Detailed description of the invention

[Industrial use]

The present invention relates to a photosensitive resin composition for easily dyeing a transparent substrate such as glass into an arbitrary color tone using an anionic dye, and a color filter obtained by using the resin composition.

In recent years, color filters obtained by coloring transparent substrates such as glass have been used in various display devices and the like. In particular, the color separation filter obtained by coloring transparent base materials, such as glass, is increasing demand for the purpose of colorization of a liquid crystal color TV set or a color TV camera.

The present invention has been carried out for the purpose of satisfying such a demand, and relates to a photosensitive resin composition for dyeing transparent substrates such as glass and a color filter obtained by using the resin composition.

Background Technology

In the prior art, protein-based natural polymer materials such as casein and gelatin have been mainly used. In the use of these substances, potassium dichromate or ammonium is added as a photocuring agent to a liquid obtained by dissolving casein, gelatin and the like in warm water, which is applied by spin coating to a glass plate, and then irradiated with active light through a mask to obtain a glass plate. The latent flaw of a salt soluble layer is formed in this, and it develops so that a salt soluble layer may appear. Next, a natural high molecular substance is used, such as dyeing with a dye.

In the case of using such casein, gelatin, etc., since they are natural products, they are susceptible to decay, or because their quality is not constant and varies widely depending on the raw materials, color reproducibility becomes extremely poor, and they are easily peeled off in hot water. In addition, there are drawbacks such that the deterioration of physical properties due to heat increases and the processing conditions are restricted. In addition, there are problems in dyeing, such as difficulty in obtaining a dark color because dyeing temperatures such as dyeing are restricted.

Moreover, in case of using casein or gelatin, ammonium bichromate or potassium dichromate is used together as a light curing agent, so there is a need to solve the pollution problem during work process and disposal, and chromium contained in gelatin is not completely removed. There is a problem that can be adversely affected.

The present inventors carried out examination of the synthetic polymer to solve this problem. First, a test was used to dye the surface of a substrate using a polymer having a basic group or a quaternary ammonium base having affinity for anionic dyes, in which case the polymer itself has an affinity with anionic dyes. Therefore, in the case of dyeing, the coating film is peeled off from the surface of the substrate in a salt bath, and the purpose of dyeing is obtained. It was also impossible. Furthermore, the present inventors produced a resin film with good dyeability without peeling off the film when the photosensitive resin composition obtained by adding an azide compound as a crosslinking agent to a salty polymer to a surface of a substrate such as a glass plate and irradiated with light. It is found that this is possible, and this finding is applied to practical use in the present invention. However, in recent years, it is required to further reduce the amount of light used for curing the photosensitive resin composition due to demands for high resolution quality, promotion of fixing efficiency, and energy saving. Generally, when the amount of light is insufficient with respect to the photosensitive resin composition, the film is weak and the film becomes rough during dyeing, and the dyeing film becomes opaque. Moreover, dyeing property and developability are also bad. Moreover, there also exists a problem that the dimensional stability of an image also worsens. In order to satisfy this requirement by increasing the photoreaction rate of the azide compound in the photosensitive resin composition, the addition effect of various known sensitizers on the increase of the photoreaction rate was studied, but none of the sensitizers provided a satisfactory effect.

[Initiation of invention]

The present inventors have reexamined in order to solve such a problem, and as a result, (a) anionic dye-shrinkable polymer (A), (b) azide photosensitive compound (B), and (c) acryloyl group in the same molecule And / or by using the photosensitive resin composition (D) containing the compound (C) which has two or more methacryloyl groups, the objective was achieved and came to complete this invention.

The photosensitive resin composition (D) used for this invention achieves the objective by performing hardening reaction with the light quantity of 1, compared with the case where only the azide photosensitive compound (B) is used. In general, compound (C), when used alone, requires a large amount of light corresponding to several times the azide photosensitive compound (B). By the way, by using azide photosensitive compound (B) and compound (C) simultaneously, the objective can be achieved with a small amount of light. It is assumed that the object is achieved with a small amount of light because some desirable interactions between the photosensitive compound (B) and the compound (C) work.

It is preferable that the anionic dye salt-containing polymer (A) used by this invention has a salt-containing monomer (a), a hydrophilic monomer (b), and a hydrophobic monomer (C) as a component. Moreover, a polymer (A) can be manufactured by using a conventionally well-known polymerization method.

Here, the following can be mentioned as a chlorinated monomer (a).

(N, N-dimethylamino) ethyl acrylate,

(N, N-dimethylamino) ethyl methacrylate,

(N, N-dimethylamino) ethyl acrylate,

(N, N-dimethylamino) ethyl methacrylate,

(N, N-dimethylamino) propyl acrylamide,

(N, N-dimethylamino) propyl methacrylamide,

(N, N-dimethylamino) ethyl vinyl ether,

(N, N-dimethylamino) propyl acrylate,

(N, N-dimethylamino) propyl methacrylate

4-vinylpyridine, diarylamine, 2-hydroxy-methacryloyloxypropyltrimethyl ammonium chloride, and methacryloyloxyethyltri methylammonium chloride.

As the hydrophilic monomer (b), the following may be mentioned:

Hydroxyethyl acrylate,

Hydroxyethyl methacrylate,

Acrylamide, methacrylamide,

Vinyl pyrrolidone,

Dimethylamino acrylamide,

Methylamino acrylamino,

As the hydrophobic monomer (c), the following may be mentioned:

Methyl acrylate, methyl methacrylate,

Ethyl acrylate, styrene, p-methylstyrene,

Butyl acrylate, butyl methacrylate,

2-ethylhexyl acrylate, 2-ethylhexyl methacrylate.

Each of such a salty monomer (a), a hydrophilic monomer (b), and a hydrophobic monomer (c) may use at least 1 type of monomer, and may use 2 or more types of monomers together.

Such salting monomer (a), hydrophilic monomer (b) and hydrophobic monomer (c) are preferably used in proportions of 10 to 80% by weight, 2 to 60% by weight and 5 to 50% by weight, respectively. The molecular weight of the polymer (A) thus prepared is preferably 5000 to 200,000, particularly preferably 10,000 to 100,000.

Examples of the azide photosensitive compound (B) used in the present invention include the following ones:

4, 4'-diazalcalcon,

2, 6-bis (4'-azidobenzal) cyclohexanone,

2, 6-bis (4'-azidobenzal) -4-methylcyclohexanone,

1, 3-bis (4'-azidobenzal) -2-propanone,

p-azidobenzaacetphenone,

p-azidobenzaacetone,

1, 3-bis (4'-azidobenzal) -2-propanone-2'-sulfonic acid,

4, 4'-diazidostilbene-2, 2'-disulfonic acid,

Sodium-4, 4'-diazidostilbene-2, 2'-disulfonate,

1, 3-bis (4'-azido-2'-sulfobenzal) -2-propanone,

1, 3-bis (4'-azido-2'-sodium sulfonatobenzal) -2-propanone,

2, 6-bis (4'-azido-2'-sulfobenzal) cyclohexanone,

2, 6-bis (4'-azido-2'-sulfobenzal) methylcyclohexanone,

2, 6-bis (4'-azido-2'-sodium sulfonatobenzal) -methylcyclohexanone, and

N, N'-diethyl-2, 2 'disulfonamide-4, 4'-diazidostilbene.

As an azide photosensitive compound (B), only 1 type of compound can be used or 2 or more types of compound can be used together.

The amount of the azide photosensitive compound (B) to be used is preferably 0.1 to 20 parts, particularly preferably 0.5 to 10 parts per 100 parts of the saltable polymer (A).

Among these azide photosensitive compounds (B), those having a sulfone group are water-soluble, and therefore have good developability, and have an advantage that they can be developed at a low temperature for a short time. Moreover, as a compound (C) used by this invention, the following are mentioned, for example:

Spiroglycol diacrylate [3, 9-bis (2-acryloyloxy-1, 1-dimethyl) -2, 4, 8, 10-tetraoxaspiro (5.5) undecane],

Cyclohexanedimethylol diacrylate,

Ethylene glycol diacrylate,

Diethylene glycol diacrylate,

Triethylene glycol diacrylate,

Polyethylene glycol diacrylate,

Polypropylene glycol diacrylate,

Butylene glycol diacrylate,

Neopentyl glycol diacrylate,

1, 4-butanediol diacrylate,

1, 6-hexanediol diacrylate,

Pentaerythritol diacrylate,

Pentaerythritol triacrylate,

Trimethylolpropane triacrylate,

Noblock Epoxy Acrylate

Bisphenol A epoxy acrylate,

Alkylene glycol diepoxy acrylate,

Glycidyl ester acrylate,

Polyester diacrylate,

Bisphenol A diacrylate,

Urethane diacrylate,

Methylenebis acrylamide,

Ethylene glycol dimethacrylate,

Diethylene glycol dimethacrylate,

Triethylene glycol dimethacrylate,

Polyethylene glycol dimethacrylate,

Propylene glycol dimethacrylate,

Butylene glycol dimethacrylate,

Neopentyl glycol dimethacrylate,

1, 4-butanediol dimethacrylate,

1, 6-hexanediol dimethacrylate, and

Trimethylolpropane trimethacrylate.

As compound (C), only one compound may be used, or two or more compounds may be used together.

The amount of the compound (C) used is preferably 0.1 to 20 parts, particularly preferably 0.5 to 10 parts per 100 parts of the saltable polymer (A).

The photosensitive resin composition having the composition described above is usually used after dilution with an organic solvent or the like. As an organic solvent, methyl cellosolve, ethyl cellosolve, toluene, xylene, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, methyl isobutyl ketone, methyl ethyl ketone, etc. are mentioned, for example. These solvents can be used favorably with one kind or a mixture of two or more kinds. Since the ratio of the organic solvent in the heat-sensitive photosensitive resin liquid is different depending on the composition of the photosensitive resin composition, it cannot be specified in detail, but it is preferable to select the ratio of the organic solvent which makes the resin liquid at a viscosity applicable to the substrate surface. desirable.

Furthermore, in order to improve the adhesiveness of a salty resin film and a glass plate, a silane coupling agent is normally added to the photosensitive resin composition. The addition ratio is preferably 0.1 to 20 parts, more preferably 0.5 to 10 parts per 100 parts of the saltable polymer (A).

Substrate, such as glass which apply | coated this chlorinated resin liquid, is normally exposed to ultraviolet rays through a mask. The unexposed portion is developed by an aqueous solution.

The development is preferably carried out at room temperature to 60 ℃ (for example 10 to 60 ℃) range. The film thickness of the resin thus developed can be produced, for example, at any thickness of 0.2 to 10 mu. Substrates such as glass and plastic having a predetermined pattern developed are dyed with anionic dyes.

As anionic dyes, acid dyes described as C.I.Acid in the Color Index, published by the Society of Dyers and Colorists, and C.I. Direct dyes described as Direct and C.I. Reactive dyes etc. which are described as Reactive are mentioned, Especially an acid dye is preferable. As the acid dyes, CIAcid Yellow 17, 49, East 67, East 72, East 127, East 110, East 135, East 161, CIAcid Red 37, East 50, East 111, East 114, East 257, East 266, East 317, CI Acid Blue 41, East 83, East 90, East 113, East 129, East 182, East 125, C.I. Acid Orange 7, copper 56, C.I. Acid Green 25, copper 41, C.I. Acid Violet 97, copper 27, copper 28, copper 48 and the like.

The dyeing method using these is dissolved 0.01 to 200 parts by weight of the dye in 1000 parts by weight of water. At this time, the pH of the liquid is good in the range of about alkali to acidic. The dye solution is used to perform dyeing in a temperature range of room temperature to 100 ° C., but dyeing at a high temperature makes it possible to obtain a dye in a short time, so it is preferable to perform at a high temperature. After dyeing, the dyeing material is collected and dried to obtain a substrate (color filter) on which the surface coating is dyed.

Best Mode for Carrying Out the Invention

Example 1

Dimethylaminopropyl acrylamide 31 parts

2-hydroxyethyl methacrylate 14 parts

Vinyl Pyrrolidone Part 15

Methyl methacrylate 15 parts

Methyl acrylate 13 parts

Dimethylamino acrylamide 10 parts

200 parts Dioxane

,

'-아조비스(이소부티로니트릴) 1부

,

1 part of azobis (isobutyronitrile)

The polymerization is carried out for 5 hours at 80 ° C. in a nitrogen atmosphere using the liquid of the above formulation. The polymerization solution is poured into a large amount of isopropyl ether, the polymer component is precipitated and the polymer is taken out and dried. 0.63 parts of 4,4'-diazidocalcon, 0.57 parts of spiroglycol diacrylate, 88 parts of ethyl cellosolve, 27 parts of diethylene glycol dimethyl ethylene and a silane coupling agent KBM 603 (Shinetsu Chemical Co., Ltd)) 0.6 part mixed solution was used as the saltable photosensitive resin liquid.

Next, the chlorinated photosensitive resin solution was applied to a glass plate by spin coating, dried at 80 ° C. for 30 minutes, and then irradiated with UV light having a surface roughness of 8 mW / cm 2 through a mask having a resolution test pattern on the dried resin coating. For 5 seconds. UV-irradiated resin coating was used a developer at 60 ° C. containing 2 parts of emulsion 913 (polyoxyethylene nonylphenylene ether type nonionic surfactant (manufactured by Caothorco Co., Ltd.)) with respect to 1000 parts of water. By developing for 5 minutes under stirring to obtain a glass substrate having a salt film only in the irradiated portion. After the glass plate was post-baked at 160 DEG C for 30 minutes, the film thickness was 0.5 mu. The glass plate thus treated was dyed at 60 ° C. for 10 minutes using a 0.2% aqueous solution of Blue 43P (color filter dye, Nippon Kayaku Co., Limited) to obtain a glass plate dyed in a dark blue pattern. . The resolution of the pattern of this glass plate was 5 micrometers, and both the transparency of a dyeing film and the dimensional stability of an image were satisfactory.

Example 2

The operation was carried out in the same manner as in Example 1, except that 0.59 parts of SU-4100 (polyacrylate oligomer, Mercury Yucca Fine Chemicals Co., Limited) was used instead of 0.57 parts of spiroglycol diacrylate used in Example 1. Repeat. The UV irradiation time required to obtain the same resolution as in Example 1, the transparency of the dye film and the dimensional stability of the image was 7 seconds.

Example 3

The operation is carried out in the same manner as in Example 1, except that 0.67 parts of cyclohexanedimethylol diacrylate is used instead of 0.57 parts of spiroglycol diacrylate used in Example 1. The UV irradiation time required to obtain the same resolution as in Example 1, the transparency of the dye film and the dimensional stability of the image was 5 seconds.

Example 4

0.2 parts of 1,3-bis (4'-azidobenzal) -2-propanone and 0.4 parts of 4,4'-azidocalcon were used instead of 0.63 parts of 4,4'-diazidochalcon used in Example 1. The operation is carried out in the same manner as in Example 1 except that. The UV irradiation time required to obtain the same resolution as in Example 1, the transparency of the dye film and the dimensional stability of the image was 5 seconds.

Example 5

The operation is carried out in the same manner as in Example 1, except that 0.3 parts of ethylene glycol dimethacrylate and 0.3 parts of spiroglycol diacrylate are used instead of 0.57 parts of spiroglycol diacrylate used in Example 1. The UV irradiation time required to obtain the same resolution as in Example 1, the transparency of the dye film and the dimensional stability of the image was 5 seconds.

Example 6

The operation is carried out in the same manner as in Example 1, except that 0.65 parts of p-azidobenzalacetophenone is used instead of 0.63 parts of 4,4'-diazidochalcon used in Example 1. The UV irradiation time required to obtain the same resolution as in Example 1, the transparency of the dye film and the dimensional stability of the image was 5 seconds.

Comparative Example 1

The operation is carried out in the same manner as in Example 1, except that 0.57 parts of spiroglycol diacrylate used in Example 1 is not added. The UV irradiation time required to obtain the same resolution as in Example 1, the transparency of the dye film and the dimensional stability of the image was 40 seconds.

Comparative Example 2

The operation is carried out in the same manner as in Example 4, except that 0.57 parts of spiroglycol diacrylate used in Example 4 is not added. The UV irradiation time required to obtain the same resolution as in Example 4, the transparency of the dye film and the dimensional stability of the image was 35 seconds.

Comparative Example 3

The operation is carried out in the same manner as in Example 6, except that 0.57 parts of spiroglycol diacrylate used in Example 6 is not added. The UV irradiation time required to obtain the same resolution as in Example 1, the transparency of the dye film and the dimensional stability of the image was 43 seconds.

Example 7

0.68 parts of sodium 4,4'-diazidostilbene-2,2'-disulfonate, instead of 0.63 parts of 4,4'-diazidochalcone used in Example 1, spiroglycol diacrylate used in Example 1 0.67 parts of cyclohexanedimethylol diacrylate was used instead of 0.57 parts, and development was carried out for 1 minute by stirring in a developer at 25 ° C. instead of developing for 5 minutes under stirring in a developer at 60 ° C. in Example 1. And all work in the same manner as in Example 1. The UV irradiation time required to obtain the same resolution as in Example 1, the transparency of the dye film and the dimensional stability of the image was 5 seconds.

Example 8

0.67 parts of 1,3-bis (4'-azidobenzal) -2-propanone-2'-sulfonic acid instead of 0.63 parts of 4,4'-diazidochalcon used in Example 1, used in Example 1 0.67 parts of cyclohexanedimethylol diacrylate was used instead of 0.57 parts of spiroglycol diacrylate, and in Example 1 was stirred in a developer at 25 ° C. instead of developing for 5 minutes under stirring in a developer at 60 ° C. All of the operations were performed in the same manner as in Example 1 except that development was performed for a minute. The UV irradiation time required to obtain the same resolution as in Example 1, the transparency of the dye film and the dimensional stability of the image was 20 seconds.

[Comparative Example 4]

The operation was carried out in the same manner as in Example 7, except that 0.67 parts of the cyclohexanedimethylol diacrylate used in Example 7 was not added. When UV irradiation was performed for 30 seconds, image formation was not satisfactory, and satisfactory results were not obtained.

[Comparative Example 5]

The operation is carried out in the same manner as in Example 8, except that 0.67 parts of the cyclohexanedimethylol diacrylate used in Example 8 is not added. Even when UV irradiation was performed for 60 seconds, image formation was not satisfactory, and satisfactory results were not obtained.

Example 9

0.15 parts of sodium 4,4'-diazidostilbene-2,2'-disulfonate and 0.48 parts of 4,4'-diazidochalcone instead of 0.63 parts of 4,4'-diazidochalcone used in Example 1, 0.67 parts of cyclohexanedimethylol diacrylate instead of 0.57 parts of spiroglycol diacrylate used in Example 1 and a developer at 40 ° C. instead of developing for 5 minutes under stirring in a developer at 60 ° C. in Example 1 All work was carried out in the same manner as in Example 1 except that the development was performed for 5 minutes under stirring. The UV irradiation time required to obtain the same resolution as in Example 1, the transparency of the dye film and the dimensional stability of the image was 8 seconds.

Comparative Example 6

The operation was carried out in the same manner as in Example 9, except that 0.67 parts of cyclohexanedimethylol diacrylate used in Example 9 was not added. The UV irradiation time required to obtain the same results as in Example 9 was 50 seconds.

[Examples 10 to 12]

The polymerization reaction was carried out using the liquid in the above formulation and the polymer obtained was dried by the same operation as in Example 1. A salty photosensitive resin liquid is manufactured by the method similar to Example 1 except using each polymer obtained in this way, and the resin liquid is processed by the method similar to Example 1. The UV irradiation time required to obtain the same resolution as in Example 1, the transparency of the dye film and the dimensional stability of the image was the same as in Example 1.

[Comparative Examples 7 to 9]

The operation is carried out in the same manner as in Examples 10 to 12, except that 0.57 parts of spiroglycol diacrylate used in Examples 10 to 12 are not added. The UV irradiation time required to obtain the same resolution, transparency of the dye film and dimensional stability of the image as in Examples 10 to 12 was 35 seconds.

[Industry availability]

The present invention is free from problems such as gelatin or casein, which are conventional natural products, and a tendency to rot, and a large change in product quality due to raw materials. It also eliminates the problem of hexavalent chromium pollution from waste liquids. Furthermore, since the resin is cured by one light amount of water compared to the case where the compound (C) is not used, the saltable photosensitive resin composition (D) of the present invention contributes to energy saving, rationalization of the process, and cost reduction.

Claims (10)

A photosensitive resin composition containing (a) an anionic dye-salt polymer, (b) an azide photosensitive compound, and (c) a compound having two or more acryloyl groups and / or methacryloyl groups in the same molecule. The compound according to claim 1, wherein 0.1 to 20 parts of an azide photosensitive compound and 0.1 to 20 parts of a compound having two or more acryloyl groups and / or methacryloyl groups in the same molecule are used with respect to 100 parts of the anionic dye saltable polymer. Resin composition. The azide photosensitive compound according to claim 1 or 2, wherein the azide photosensitive compound is 4, 4'-diazidochalcone, 2, 6-bis (4'-azidobenzal) cyclohexanone, 2, 6-bis (4 '). -Azidobenzal) -4-methylcyclohexanone, 1, 3-bis (4'-azidobenzal) -2-propanone, p-azidobenzal acetophenone, p-azidobenzal acetone, 1, 3 -Bis (4'-azidobenzal) -2-propanone-2'-sulfonic acid, 4,4'-diazidostilben-2, 2'-disulfonic acid, sodium-4, 4'-diazidostilbene -2,2'-disulfonate, 1, 3-bis (4'-azido-2'-sulfobenzal) -2-propanone, 1, 3-bis (4'-azido-2'-sodium Sulfonatobenzal) -2-propanone, 2, 6-bis (4'-azido-2'-sulfobenzal) cyclohexanone, 2, 6-bis (4'-azido-2'-sulfobenzal ) Methylcyclohexanone, 2, 6-bis (4'-azido-2'-sodium sulfonatobenzal) -methylcyclohexanone, and N, N'-diethyl-2, 2'- disulfonamide A resin composition which is at least one compound selected from the group consisting of -4, 4'-diazidostilbene. The compound according to claim 1 or 2, wherein the compound having two or more acryloyl groups and / or methacryloyl groups in the same molecule is selected from spiroglycol diacrylate (3, 9-bis (2-acryloyloxy-). 1, 1-dimethyl) -2, 4, 8, 10-tetraoxaspiro (5.5) undecane), cyclohexanedimethylol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol di Acrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, butylene glycol diacrylate, neopentyl glycol diacrylate, 1, 4-butanediol diacrylate, 1, 6-hexanediol diacrylate, penta Erythritol diacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, noblock epoxy acrylate, bisphenol A epoxy acrylate, alkylene gly Cold diepoxy acrylate, glycidyl ester acrylate, polyester diacrylate, bisphenol A diacrylate, urethane diacrylate, methylenebisacrylamide, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, Triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, propylene glycol dimethacrylate, butylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1, A resin composition which is at least one compound selected from the group consisting of 6-hexanediol dimethacrylate, and dimethylolpropane trimethacrylate. The resin composition for producing a color filter according to claim 1 or 2. The resin composition for manufacturing a color filter according to claim 3. The resin composition for producing a color filter according to claim 4. The color filter obtained using the resin composition of Claim 1 or 2. The color filter obtained using the resin composition of Claim 3. The color filter obtained using the resin composition of Claim 4.