JPS62149988A - Dyeing of surface film on base material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a dyeing method for easily dyeing a transparent substrate such as glass into any desired color tone using an anionic dye.

In recent years, transparent substrates such as glass have been colored and used for various displays. In particular, the demand for transparent substrates such as glass as color separation filters for colorizing liquid crystal color televisions or cameras for color televisions is increasing.

The present invention relates to a method for dyeing transparent substrates such as glass, which has been developed to meet such demands.

(Prior art) Conventionally, in this field, protein-based natural polymer substances such as casein and gelatin have been mainly used. Potassium or ammonium dichromate is added and applied to a glass plate using a spin code method.The first step is to irradiate actinic light through a mask to form a latent image of a dyeable layer on the glass plate. The dyeable layer is revealed by development. The next step is to dye this with a dye.

(Problems to be solved by the invention) In the case of dyeing methods that use casein, gelatin, etc., since these are natural products, they are easily perishable, their quality is inconsistent, and there are large variations depending on the raw material source, resulting in poor color reproducibility. Ammonium dichromate or potassium dichromate are used as photocuring agents, so pollution problems must be solved during the work process and during disposal.
Furthermore, there is a problem that chromium incorporated into gelatin cannot be completely removed and the remaining chromium has an adverse effect.

The present inventors investigated synthetic polymers in order to solve these problems. First, an attempt was made to dye the surface of the substrate using a polymer having a basic group or a quaternary ammonium base that has an affinity for anionic dyes, but in this case, this polymer itself has an affinity for anionic dyes. Although dyeable.

Because it is water-soluble, if it is applied to a glass substrate, etc. and dyed after drying, the coating film will peel off from the substrate surface during the dye bath during the dyeing process, which will defeat the purpose of dyeing. It was not possible to obtain a dyed base material.

In order to solve these problems, the present inventors have developed a vinyl monomer that has a photosensitive group and a vinyl monomer that has a group (dyeable group) that has an affinity for an anionic dye that can be copolymerized with the photosensitive group. Patent application No. 59-240495 proposes that a copolymer is applied to the surface of a substrate to form a film, then irradiated with actinic rays to cause a reaction, and then the film is dyed with an anionic dye. In this method, a vinyl monomer having a dyeable group and a vinyl monomer having a photosensitive group are copolymerized to synthesize a polymer having a dyeable group and a photosensitive group in the same molecule. This is used for staining. In this method, the synthesis of dyeable polymers is by radical or ionic polymerization. However, photosensitive groups are generally unstable and easily react with heat, radicals, etc., and even in the synthesis of the above polymers, side reactions may occur due to heating during polymerization, heat of polymerization, radicals, ions, etc. generated during polymerization. It was necessary to control the polymerization operation very carefully because the photosensitive groups were likely to disappear and insoluble gel-like substances were likely to be generated.

(Means for solving the problems) The present inventors have conducted studies to solve these problems.

a) A polymer (A) having both a basic group and/or a quaternary ammonium base and an active hydrogen has a photosensitive group and
Polymer (C) obtained by esterification and/or amidation reaction of compound CB) having both x (x represents C1 or B) b) A photoreaction initiator (
D) and C) A photoreactive resin composition (1") containing the solvent Cl1f) is applied to the surface of the substrate to form a film, and then active light is irradiated to react. First, this film is treated with an anionic dye. It was found that the purpose could be achieved by dyeing with the method, and the present invention was completed.

That is, the patent application No. 59-2404 previously proposed by the present inventors
In the method of No. 95, a radical or ionic polymerization method was used to synthesize a dyeable polymer, so the photosensitive group was
Whereas it was easy to lose due to radicals, ions, etc., in the method of the present invention, polymer (C) is synthesized by esterification and/or amidation reaction between compound (B) and active hydrogen in polymer (A). Therefore, the reaction is completed at a low temperature, there is little loss of photosensitive groups, and therefore, there is little generation of gel-like substances in the polymer (C), and desirable dyed products can be obtained.

Furthermore, when the method of the present invention is used, there is no need to worry about spoilage as with natural products such as gelatin and casein.

The method for preparing the polymer (C) used in the present invention is to first prepare a basic group (primary, secondary or tertiary amine group) and/or a quaternary
A polymer (A) having both an ammonium base and an active hydrogen is prepared and then mixed with this polymer.

It is obtained by carrying out an esterification and/or amidation reaction using a compound (g) having both a photosensitive group and -COX.

Furthermore, the method for producing the polymer (A) having both a basic group and/or a quaternary ammonium base and an active hydrogen is generally a vinyl monomer having a basic group and/or a vinyl monomer having a quaternary ammonium base. and a vinyl monomer having active hydrogen.

Examples of the vinyl monomer having a basic group include the following.

(N,N-dimethylamino)ethyl acrylate.

(N,N-dimethylamine)ethyl methacrylate.

(N,N-diethylamino)ethyl acrylate.

(N,N-diethylamino)ethyl methacrylate.

(N,N-dimethylamino)propylacrylamide,
(N,N-dimethylamino)propyl methacrylamide, (N,N-diethylamino)ethyl vinyl ether,
(N,N-dimethylamino)propyl acrylate, (
N,N-dimethylamino)propyl methacrylate, 4
-Vinyl pyridine, diallylamine, allylamine Examples of vinyl monomers having a quaternary ammonium base include the following.

methacryloyloxyethyltrimethylammonium chloride, acryloyloxyethyltrimethylammonium chloride, 2-hydroxy-3-methacryloyloxypropyltrimethylammonium chloride,
Methacryloylaminopropyltrimethylammonium chloride.

Acryloylaminopropyltrimethylammonium chloride Furthermore, as a vinyl monomer having active hydrogen, 2-
Hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, hydroxyethyl methacrylamide,
Examples include hydroxyethyl acrylamide, methylol acrylamide, allylamine, diallylamine, and the like.

Polymer (A) uses the vinyl monomers mentioned above, but if desired, other copolymerizable monomers such as methyl methacrylate, methyl acrylate, ethyl acrylate, ethyl methacrylate, acrylamide, methacrylamide are used.

Styrene or the like may also be used as a copolymerization component.

The proportion of the monomer having a basic group and/or quaternary ammonium salt structure in the polymer (A) is preferably 5 to 90 mol.

The proportion of the vinyl monomer having active hydrogen in the polymer (A) is preferably 0.5 to 60 mol. Polymer (A) is synthesized by mixing the above monomers in appropriate proportions and using a solvent (for example, toluene) if necessary.

The polymer may be diluted with benzene, dioxane, alcohol (%) and polymerized in a conventional manner using conventional polymerization techniques in the absence of actinic rays.

The polymer (A) preferably has a molecular weight of about 1,000 to 500,000.

Further, as the compound CB), the following may be mentioned.

p-Azidobenzoic acid chloride CI GO+N3 Cinnamic acid chloride + J Co-CH=C< β-furyl acrylic acid chloride CI Co CHS:CIII 2 N-(chlorocarbonylmethyl)phenylmaleimide iris p-chlorocarbonylstilbazole CI COeC肚CH◇ m-Sulfonylazide benzoic acid chloride p-azido cinnamic acid chloride CI COCL: Cm+x3 p-(β-chlorocarbonylethoxy) stilbazole CI Co CH2CH2O+C肚CH<[Phase] These are all carboxylic acid chlorides, but these may also be used as carboxylic acid bromide.

The amount of these compounds CB) to be used cannot be unconditionally determined depending on the required physical properties of the desired polymer (C), the reactivity of the compound CB), and the reactivity of active hydrogen occupying in the polymer (A). ) It is preferable to use 10 to 100 mole based on the active hydrogen occupied in the active hydrogen.

The esterification and/or amidation reaction is carried out by diluting the compound (B) with an inert solvent such as benzene or toluene. The reaction temperature is preferably room temperature to 70°C.

In order to advance the reaction smoothly, it is preferable to add a basic compound 1 without active hydrogen, such as pyridine, trimethylamine, triethylamine, etc., depending on the case.

Further, the photoreaction initiator (D) that initiates a reaction by irradiation with actinic rays used in the present invention includes the following.

Nitrobenzene p-nitrodiphenyl m-nitroaniline p-nitroaniline 2.4-dinitroaniline biclamide 2-chloro-4-nitroaniline 2.6-sinitro 4-nitroaniline p-nitrophenol? -Anthraldehyde acetophenone benzophenone dibenzalacetone benzyl p,p'-dimethylaminobenzophenone prl" -tetramethyldiaminobenzophenone (Michler's ketone) 1.4-naphthoquinone anthraquinone 1.2-benzoanthraquinone 1.9-benzoanthrone 2-keto- 3-aza-1,9-benzaanthrone 3-methyl-1,3-diaza-1,9-benzoanthrone 2-nitrofluorene 2.7-dinitrofluorene 2.5-dinitrofluorene 1.8-phthaloylnaphthalene 2 -Chloro-1,8-phthaloylnaphthalene 4-chloro-1,8-phthaloylnaphthalene 4-bromo-1,8-
Phthaloylnaphthalene 5.6-Sinitroacenaphthene 5-Benzoylacenaphtheneacenaphthenepyrene acridone α-naphthoquinone 5-nitroacenaphthene 2-nitrofluorene 1-nitropylenechloro-1,2-benzoantho2quinone 1.8- Phthaloylnaphthalene 9-Fluorenone Diphenyl disphite p-Nitrobenzaldehyde Drobenzoquinone Phenolacetophenone Anthrone Benzaldehyde Benzophenone Phenanthrene Naphthalene 2-Nitrofluorene 5-Nitroacenaphthene Chrysene p-Nitroaniline 2-Benzoylmethylene-1-methylnaphthothiazoline Benzyl N-aceteru 4-nitro-1-naphthylamine benzoquinone 4-nitro-1-naphthylamine anthracenethoxanthone compound These may be used alone or as a mixture of two or more, and the amount used is 30 parts by weight per 100 parts by weight of the polymer (C). % or less, preferably 10 parts by weight or less.

The solvent (E) used in the present invention is preferably one that dissolves the polymer (C) and the photoreaction initiator (D) well, and examples thereof include 2-methoxyethanol, 2-ethoxyethanol, toluene, and xylene. . These are 1
A species or a mixture of two or more kinds may be used, and the proportion of the solvent (K) in the photoreactive resin composition (F') varies depending on the properties of the polymer (C) and the photoinitiator (D). However, the viscosity of the photoreactive resin composition CF) is 1000 Qp8
It is preferable to include the following.

In the present invention, a polymer (C) containing a photoreaction initiator (D) and a solvent CB) as optional components is used as a photoreactive resin composition, and this photoreactive resin composition CI') In addition, other copolymerizable monomers, viscosity modifiers, defoamers, etc. may be included depending on the case. When such a photoreactive resin composition (F) is applied to a substrate, the solvent evaporates after application, and a resin film is subsequently formed.

According to the method of the present invention, a film having an arbitrary thickness of, for example, 0.5 to 100 microns can be formed.

Further, examples of the substrate to which the photoreactive resin composition (y) is applied include glass, plastic, and the like.

Examples of active rays include visible rays and ultraviolet rays.

Examples include X-rays and electron beams.

Next, the cured cut pieces are dyed with an anionic dye. Color index (SOcie) is an anionic dye.
Acid dyes listed as C Ac1d in t7 of Dyere and Co1ourie, published 8), direct dyes listed as i roc t from the same <C,
Examples include reactive dyes described as
Acidic dyes are particularly preferred. As an acid dye, C1 Engineering Ac
1d Yellow 17.

49. Same 67, Same 72, Same 127. Same 110° Same, 3
5. 161, C1 Engineering Ac1d Red 37, 5
0° 111. 114, 257. 266, 31
7゜C1 Engineering Ac1d Blue 41. 83, 90
, 113°, 129. Same 182. 125, C, I
Ac1d Orange7, 56. C, engineering Ac1d
Green 25, 41. C, lAc1d Vi
olet, 97, 271, 28. 48 etc. are mentioned.

The dyeing method using these dyes involves dissolving 0.01 to 200 parts by weight of the dye in 1000 parts by weight of water.

The pH of this liquid removal may be in the weakly alkaline to acidic range.

Dyeing is carried out with this dye solution at a temperature ranging from room temperature to 100°C, and dyeing at a high temperature is preferable because a dyed product can be obtained in a short time. After dyeing in this manner, the dyed product is taken out and dried to obtain a dyed base material with a dyed surface coating.

(Example) Example 1 Toluene 200 parts (N,
N-dimethylamino)ethyl methacrylate
451 (N,N-dimethylamino)ethyl acrylate 4512-Hydroxyethyl methacrylate 10'α,α'-azobis(imbutyronitrile) 11 The liquid of the above formulation was heated in a nitrogen atmosphere at 60°C for 2 hours and at 80°C for 5 hours. When the polymerization reaction took place, the entire mixture became a viscous liquid. Next, 5 parts of p-azidobenzoic acid chloride was added to this solution and the reaction was carried out at 60° C. for 2 hours, whereby most of the p-azidobenzoic acid chloride reacted. This reaction solution was poured into inglovir ether to precipitate the polymer. The precipitated polymer was dried under vacuum. Next, 15 parts of the obtained polymer were mixed and dissolved in 85 parts of 2-ethoxyethanol to obtain a photoreactive resin composition.

Next, silane coupling agent KBM503 (
A 10% ethanol solution (Shin-Etsu Chemical Co., Ltd. #) was applied, air-dried and then heated at 110°C for 7 minutes, and the surface was further washed and dried with acetone to obtain a glass plate for coating.

The photoreactive resin composition was applied to the surface of this coating glass plate, and after heat treatment at 80° C. for 30 minutes, ultraviolet rays were irradiated through a mask having a predetermined pattern to cure the coating film. Next, this glass plate was immersed in pure water for 2 minutes for development. The film thickness was 0.7 μm. Next, this glass plate was dyed with Red 141) (color filter dye manufactured by Nippon Kayaku ■) at a concentration of 0.2% and dyed at 60°C for 5 minutes. A glass plate with a pattern was obtained. The pH of the dyeing bath was 7.5. Green 1p instead of red 14p.

When the same operation was carried out using Blue SP (all dyes for color filters manufactured by Nippon Kayaku ■), glass plates dyed deep green and blue were obtained, respectively.

For comparison, as Reference Example 1, a coating film was prepared using a resin composition using 2-ethoxyethanol as a solvent according to the recipe of Example 1 using a polymer that did not react with the p-azidobenzoic acid chloride.

When operations such as ultraviolet irradiation and dyeing were performed, only an opaque glass plate with some of the dyed film peeled off was obtained.

Example 2 200 parts of ethanol (N, N
-dimethylamino)propyl methacrylamide 50
#2-Hydroxyethyl methacrylate 5
0Iα,α'-Azobis(isobutyronitrile) TI Polymerization was carried out in the same manner as in Example 1 using the liquid with the above formulation. Next, this polymerization solution was poured into isopropyl ether to precipitate the revolimer. After drying this polymer, 15 parts of the dry polymer was dissolved in 85 parts of N-methylpyrrolidone. Next, 0.75 parts of cinnamic acid chloride was added and dissolved in this solution, and the reaction was carried out at 60°C for 2 hours. Most responded. This solution was further poured into isopropyl ether to precipitate the polymer. Next, after drying this polymer, 5 parts of the dry polymer, 0 and 2 parts of 4,4'-bis(diethylamino)benzophenone (photoreaction initiator) were mixed and dissolved in 20 parts of 2-ethquin ethanol to form a photoreactive resin. It became a thing.

Next, the photoreactive resin composition was applied to a silane coupling agent-treated glass plate prepared by performing the same operation as in Example 1, and after heat treatment at 120°C for 10 minutes, through a mask having a predetermined pattern, The coating film was cured by UV irradiation. Next, this glass plate was immersed in pure water for 2 minutes for development. This film thickness was 0.9 μm. Next, this glass plate was dyed with Green 1P1% solution at 60° C. for 10 minutes to obtain a dark green colored transparent glass plate having a predetermined pattern. The pH of the dyeing bath was 7.4.

For comparison, Example 2 was prepared using a polymer that had been reacted with the cinnamic acid chloride as Reference Example 2. A resin composition containing 4,4'-bis(diethylamino)benzophenone and 2-ethoxyethanol was prepared according to the recipe, and operations such as coating, ultraviolet irradiation, and dyeing were performed using this in the same manner as in Example 2. When this process was carried out, only an opaque glass plate with some of the dyed film peeled off was obtained.

Examples 3, 4.5 In the table, numbers indicate parts.

Polymerization was carried out in the same manner as in Example 1 using the liquid of the above formulation. Next, 7 parts of p-azidobenzoic acid chloride was added to this polymerization solution, and the reaction was carried out at 60° C. for 2 hours, whereby most of the p-azidobenzoic acid chloride reacted. This reaction solution was poured into inpropyl ether to precipitate the polymer. The precipitated polymer was dried, and 18 parts of the dry polymer, 1.8 parts of Kayacure DETX (manufactured by Nippon Kayaku ■, thioxanthone-based photoreaction initiator) were mixed with 8 parts of 2-ethoxyethanol.
Two parts were mixed and dissolved to obtain a photoreactive resin composition.

Next, the photoreactive resin composition was applied to a silane coupling agent-treated glass plate prepared in the same manner as in Example 1, and then heat-treated at 80° C. for 30 minutes.

The coating film was cured by UV irradiation. The film thickness of this coating film was 1.0 μm. Next, this glass plate is red j4p
When dyed with a 0.1% solution at 60° C. for 5 minutes, a glass plate having a transparent thin film dyed deep red was obtained in all Examples. The pH of the dyeing bath was 7.2.

For comparison, as Reference Examples 3 and 4.5, a resin containing 2-ethoxyethanol and Kayacure DETX was prepared according to the recipe of Examples 3 and 4.5 using a polymer that was not reacted with the p-azidobenzoic acid chloride. A composition was prepared, and operations such as coating, ultraviolet irradiation, and dyeing were performed using this in the same manner as in Example 3.4.5. In each case, a glass plate with partially peeled opaque dyed film was obtained. I could only get it.

(Effects of the Invention) The present invention does not have the problems of being easily putrefied or having large variations depending on the raw materials compared to conventional natural products such as gelatin or casein-dichromate photosensitive resins, and also There is no problem of chromium pollution.

Furthermore, polymer CC) is synthesized not by a polymerization reaction using radicals, but by an esterification reaction, etc., and the reaction can be completed in a short time at low temperatures, and there is no generation of gel-like substances due to side reactions, resulting in good reproducibility. Polymer CC) is obtained.

Therefore, when this is used to dye a substrate such as glass, a high-quality dyed product can be obtained.

This is suitable for use in liquid crystal color televisions, displays, etc.

Claims (1)

[Claims] 1.a) A photosensitive group and -COX (X represents Cl or Br) are added to the polymer (A) having both a basic group and/or a quaternary ammonium base and active hydrogen. A polymer (C) obtained by esterification and/or amidation reaction using the compound (B) b) a photoreaction initiator (D) as an optional component and c) a solvent (
The photoreactive resin composition (F) containing E) is applied to the surface of the substrate to form a film, and then irradiated with actinic rays to react, and then this film is dyed with an anionic dye. A method for dyeing the surface film of a substrate.