JPH06229B2 - Substrate surface coating dyeing method - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a dyeing method for dyeing a transparent substrate such as glass with a dye in a plurality of colors in a stripe or mosaic pattern.

In recent years, transparent substrates such as glass have been colored and are being used for various displays and the like. In particular, there is an increasing demand for coloring a transparent base material such as glass to color a liquid crystal television or a television camera as a color separation filter. The present invention relates to a method of dyeing a transparent substrate such as glass, which has been made to meet such demands, with a plurality of colors in a stripe or mosaic pattern.

(Prior Art) Conventionally, in this field, as a dyeable resin, a protein type natural polymer substance such as casein or gelatin or a synthetic polymer type dyeable photosensitive resin has been mainly used. There are mainly the following two methods of using the dyeable resin.

1) A solution obtained by diluting a dyeable resin to an appropriate concentration is applied to a glass plate or the like to form a film, and then exposed through a mask,
Development is performed to form a dyeable resin film (cured film) having a first color stripe or mosaic, and this is dyed with a dye having a predetermined spectral characteristic. Next, this dyed film is coated with a dye-proof film or treated with a dye fixing agent, a dyeable resin film is again formed on a glass plate or the like in the same manner, and dyed with a second color dye. This operation is sequentially repeated to form a desired color filter.

Or, 2) A dyeable resin film (cured film) is provided on the surface of a substrate such as glass using a dyeable photosensitive resin, and then a dye-proof photosensitive resin film is formed and exposed using a mask. Then, after development, a stain-proof mask from which the stripes or mosaic portions of the first color have been removed is provided, then the dye-resin is dyed with a dye having predetermined spectral characteristics, and the dyeable resin is again removed without removing or removing the stain-proof mask. Form a dye-proof photosensitive resin film on the film, and similarly expose and develop it.
An operation of forming a dye-proof mask from which color stripes or mosaic portions are removed and dyeing is repeated to form a desired color filter.

(Problems to be solved by the invention) The method 1) of forming and dyeing a dyeable resin film in a stripe or mosaic shape as described above includes forming a dyeable resin film in a stripe or mosaic shape, dyeing, Since the coating operation of the dye-proof film is repeated, layers of the dye-proof film are overlapped with each other, resulting in a thick dye film of the whole product. If the dyed film becomes thicker, there arise problems such as a narrow viewing angle and a decrease in transparency as a color filter for liquid crystal TVs in which these dyed products are about to be used. Further, it has a drawback that the number of steps is extremely large and complicated.

Alternatively, even in the method using a dye fixing agent, there is a problem that an expensive dyeable photosensitive resin must be coated for the number of dyeing times.

Further, in the method 2), there is an advantage that a thin color filter can be formed by coating the dyeable resin once, but there is a problem that an expensive dye-proof photosensitive resin film must be coated a number of times. There is.

(Means for Solving Problems) As a result of studies to solve these problems, the present inventors have found that a dyeable photosensitive resin is used to form a dyeable resin film on the surface of a substrate such as glass. A dye-proof photosensitive resin film was formed on the (cured film), exposed using a mask, and developed to provide a dye-proof mask in which dyed portions such as stripes or mosaic portions of the first color were removed. After that, it is dyed with a dye having a predetermined spectral characteristic, then treated with a dye fixing agent, and then the unexposed portion of the dye-proof photosensitive resin film is exposed and developed using a mask as in the case of the first color, and the second color After removing the dyed parts such as stripes or mosaic parts, dye a second color with a dye having a predetermined spectral characteristic, and repeat this operation to dye the dyeable resin film in stripes or mosaics. The dyeing method for the surface coating of the substrate is characterized by It was found that the object could be achieved by the above, and the present invention was completed.

That is, according to the method of the present invention, the base material surface film (dyeable resin film) is formed only once, and the dye-proof photosensitive resin film is also formed only once. It is extremely labor-saving in two times and economical.

As the dyeable photosensitive resin (A) used in the present invention, various ones can be used. For example, (1) a composition obtained by imparting photosensitivity to gelatin, casein or the like, or (2) (a) a dyeable monomer. (B) 10-80% by weight (b) Hydrophilic monomer (C) 5-60% by weight (c) Hydrophobic monomer (D) Copolymer (J) consisting of 5-60% by weight and sensitizer (G) Or a dyeable photosensitive resin (A) obtained by reacting the photosensitive compound (E) with a pendant and (3) (a) a dyeable monomer (B) 10 to 80% by weight ( b) Hydrophilic monomer (C) 5 to 60% by weight (c) Hydrophobic monomer (D) 5 to 60% by weight (d) Dye having a photosensitive group (F) 0.1 to 30% by weight Photosensitive resin (A) and the like.

Here, as the dyeable monomer (B), for example, (N, N-dimethylamino) ethyl acrylate (N, N-dimethylamino) ethyl methacrylate (N, N-diethylamino) ethyl acrylate (N, N-diethylamino) 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-3-methacryloyloxypropyltrimethylammonium chloride methacryloyloxyethyltrimethylammonium chloride and the like can be mentioned.

Examples of the hydrophilic monomer (C) include the following.

Hydroxyethyl acrylate Hydroxyethyl methacrylate acrylamide, methacrylamide Vinylpyrrolidone dimethylaminoacrylamide Examples of the hydrophobic monomer (D) used in the present invention include methyl acrylate, methyl methacrylate ethyl acrylate, styrene p-methylstyrene, butyl acrylate butyl methacrylate. 2-Ethylhexyl acrylate 2-Ethylhexyl methacrylate etc. are mentioned.

Further, examples of the monomer (F) having a photosensitive group include the following.

p-Cinnamoyloxystyrene β-Cinnamoyloxyethyl vinyl ether β-Cinnamoyloxyethyl acrylate or methacrylate p- (Cinnamoyloxymethyl) styrene p-Cinnamylidene acetoxystyrene β- (furfuryl acryloyloxy) ethyl acrylate or methacrylate 7-Acryloyloxycoumarin 7-Methacryloyloxycoumarin 6-Hydroxymethylcoumarin acrylate and methacrylate β- (p-cinnamoylphenoxyethyl) vinyl ether p- (β-styrylphenyl) acrylate or methacrylate p-phenylmaleimidoacetoxystyrene 4'-methacryloyloxy-4-stilbazole 1-methyl-4- (p-methacryloyloxystyryl) pyridini Examples of ummethosulfate and the photosensitizer (G) are as follows.

4,4'-diazidochalcone 2,6-bis (4'-azidobenzal) cyclohexanone 2,6-bis (4'-azidobenzal) 4-methylcyclohexanone 1,3-bis (4'-azidobenzal) -2-propanone 1,3-bis (4'-azidocinnamylidene) -2-propanone 1,3-bis (4'-azidobenzal) -2-propanone
2'-sulfonic acid 4,4'-diazidostilbene-2,2'-disulfonic acid 1,3-bis (4'-azidobenzal) -2-propanone 2,6-bis (4'-azidobenzal) cyclohexanone-2 , 2'-Disulfonic acid 2,6-bis (4'-azidobenzal) -4-methylcyclohexanone diazo resin The photosensitizer (G) is preferably used in an amount of 0.1 to 30% by weight based on the copolymer (J).

Examples of the photosensitive compound (E) include the following.

β-chloroethyl cinnamic acid ester β-bromoethyl cinnamic acid ester β-bromoethyl cinnamylidene acetic acid ester β-bromoethylfuryl acrylate p-β-bromoethyloxycarbonyl benzalacetophenone 4-chloroacetoxystilbene β-chloroethyl ester -P-azidobenzoate β-bromoethyl-p-azidobenzoate p-azidobenzoic acid chloride cinnamic acid chloride cinnamylidene acid chloride β-furylacrylic acid chloride p-chlorocarbonylstilbazole m-sulfonylazidobenzoic acid chloride p-azidocinnamic acid Chloride p- (β-chlorocarbonylethoxy) stilbazole These photosensitive compounds (E) are used by pendant to the copolymer (J) by a quaternization or esterification reaction.

The photosensitive compound (E) is preferably used in an amount of 0.1 to 30% by weight based on the copolymer (J).

In the present invention, the dyeable photosensitive resin is applied to the surface of a substrate such as glass or plastic. In this case, the dyeable photosensitive resin is dissolved in a solvent, and if necessary, a known photoreaction initiator is added and applied. Examples of the solvent include dioxane,
2-Methoxyethanol, 2-ethoxyethanol, toluene, xylene, N-methylpyrrolidone and the like can be used. It is preferable to use the solvent in an amount that provides an appropriate viscosity.

When the dyeable photosensitive resin solution is applied to the base material, the solvent volatilizes after application and a film is formed on the surface of the base material. The thickness of the coating can be any thickness, for example 0.2-100 microns.

The film formed on the surface of the base material becomes a dyeable resin film (cured film) by irradiating and reacting with actinic rays. Examples of the actinic rays include visible rays, ultraviolet rays, electron beams and X-rays.

A dye-resisting photosensitive resin film is formed on the dyeable resin film obtained by irradiating with actinic rays, exposed using a mask, and developed to remove the dyed portion such as the stripe or mosaic portion of the first color. After the removed resist mask is provided, it is dyed with a dye having a predetermined spectral characteristic. Here, the formation of the dye-proof photosensitive resin film, the exposure through the mask, and the development may be performed by conventionally known methods.

A positive type is used as the dye-proof photosensitive resin.
As the positive type, for example, AZ111S (Hoechst Japan Co.), OFPR77 (Tokyo Ohka Kogyo Co., Ltd.), O
EBR1010 (Tokyo Ohka Kogyo Co., Ltd.), PBS (Mea
Company d) etc.

An anionic dye is used as a dye having a specific spectral characteristic.

Color Index (Society
of Dyers and Colorists) acid dyes described as CI Acid, direct dyes also described as CI Direct, reactive dyes also described as CI Reactive, etc., but acid dyes are particularly preferred. . CI Acid Yellow 17 and 4 as acid dyes
9, 67, 72, 127, 110, 135,
161, CI Acid Red 37, 50, 111, 1
14, 257, 266, 317, CI Acid Blue
41, 83, 90, 113, 129, 18
2, 125, CI Acid Orange 7, 56, CI Acid
Green 25, 41, CI Acid Violet 97, 27, 28, 48 and the like.

The dyeing method using these is to dissolve 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 may be in the range of weak alkali to acidic. Room temperature to 10 with this dye solution
Although the dyeing is carried out in the temperature range of 0 ° C., dyeing at a high temperature makes it possible to obtain a dyed product in a short time, and therefore it is preferably carried out at a high temperature.

After dyeing the first color in this manner, the dyed product is treated with a dye fixing agent.

Examples of the dye fixing agent used in the present invention include tannic acid type Fick agents [for example, Hifix SL (manufactured by Dainippon Pharmaceutical Co., Ltd.)]. The method of fixing the dye using the dye fixing agent is performed by a conventionally known method, for example, Hifix
1 to 5 g of SL and 1 to 5 g of organic acid (eg acetic acid) in water 1
It is preferable to dissolve it in the solution and treat with this solution at 50 to 80 ° C. for 0.5 to 10 minutes. On the other hand, if the treatment is carried out at a high temperature or the treatment time becomes long, the dye may drop off, which is not preferable.

Thereafter, exposure and development, dyeing and dye fixing agent treatment are repeated in the same manner to obtain a final dyed product.

(Example) Examples 1-4 A liquid having the formulation shown in Table 1 was subjected to a polymerization reaction at 75 to 80 ° C. for 5 hours in a nitrogen atmosphere, and then 6 parts of β-bromoethyl-p-azidobenzoate was added to each of the polymerization solutions.
The reaction was carried out at ℃ for 2 hours. To this reaction solution, 250 parts of ethyl cellosolve and 10 parts of Kayacure DETX (a thioxanthone photoreaction initiator manufactured by Nippon Kayaku Co., Ltd.) were added to prepare a dyeable photosensitive resin liquid. This dyeable photosensitive resin liquid is applied to a glass plate, and then this glass plate is coated with 100
After drying at ℃ for 20 minutes and UV curing,
Post baking was performed at 0 ° C. for 30 minutes.

The dyeable resin film had a thickness of 0.7 to 1.0 μm. The resin film was immersed in water for 5 minutes and then air-dried, and OEBR1010 (Tokyo Ohka Co., Ltd.) was further formed on the resin film.
(Made of) (dye-proof photosensitive resin) with a spinner at 3000 rp
It was applied for 20 seconds. Next, this glass plate is heated at 150 ° C. for 2
After drying for 0 minutes, electron beam irradiation is carried out through a mosaic mask, development is carried out for 2 minutes with a dedicated developing solution, and after drying, Blue 5P
When dyed with a 0.1% solution (manufactured by Nippon Kayaku Co., Ltd., a color filter) at 65 ° C. for 3 minutes, a glass plate was obtained in which only the exposed portion was dyed in blue in a mosaic pattern.

Furthermore, 7 g of this glass plate was added to a solution prepared by diluting 3 g of Hifix SL (Dainippon Pharmaceutical Co., Ltd.) and 2 g of acetic acid with water 1.
It was immersed at 0 ° C. for 2.5 minutes with stirring, washed with water, and dried.

Next, OEBR1010 was applied to this glass plate with a spinner at 3000 rpm for 20 seconds and dried at 150 ° C. for 20 minutes, and then a part of the undyed portion was irradiated with an electron beam through a mosaic-like mask. 14P (Nippon Kayaku Co., Ltd., color filter dye) 65% with 0.1% solution
When dyed at 5 ° C. for 5 minutes, a glass plate dyed in a mosaic shape in which red as well as blue was mixed was obtained. Further, after fixing the dye on this glass plate by the above-mentioned prescription, the undyed portion was similarly subjected to electron beam irradiation, development and drying, and then Green 1P (manufactured by Nippon Kayaku Co., dye for color filter) 0.1.
% Solution was dyed at 65 ° C. for 10 minutes and fixed.

Further, this glass plate was immersed in methyl ethyl ketone at room temperature for 10 minutes with stirring to obtain an unstained portion of OEBR101.
When 0 was peeled off, a glass plate dyed in a mosaic shape was obtained by mixing green with blue and red. Example 1
Table-2 shows the dyeability of the mosaic pattern of these glass plates obtained in No. 5 and the result of microscopic observation.

As shown in Table 2, in Examples 1 to 5, the dyeability was good, there was no dye bleeding on the unexposed area, and the pattern was very clear.

Examples 6-10 The liquid of the formulation in Table 3 was subjected to a polymerization reaction at 75 to 80 ° C. for 5 hours in a nitrogen atmosphere, and then 150 parts of N-methylpyrrolidone, 100 parts of ethyl cellosolve, 1, and 1, were added to each polymerization solution.
1.5 parts of 3-bis (4'-azidobenzal) -2-propanone was added and dissolved to obtain a dyeable photosensitive resin liquid. This dyeable photosensitive resin liquid was applied to a glass plate, and then this glass plate was dried at 100 ° C. for 20 minutes, then UV-cured and post-baked at 140 ° C. for 30 minutes.

The dyeable resin film had a thickness of 0.7 to 1.0 μm. This resin film was immersed in water for 5 minutes and air-dried, and then OEBR1010 was further applied onto this resin film with a spinner at 3000 rpm for 20 seconds. Example 1 below
When the same operation as in ~ 5 was performed, a mosaic-dyed glass plate mixed with blue, red and green was obtained. Table 4 shows the dyeing properties of the mosaic patterns of these glass plates obtained in Examples 6 to 10 and the results of microscopic observation. Examples 11 and 12 The liquid having the formulation shown in Table 5 above was subjected to a polymerization reaction in a nitrogen atmosphere at 60 to 65 ° C. in the absence of actinic rays, and then 100 parts of N-methylpyrrolidone and 150 parts of ethyl cellosolve were added to each polymerization solution. , 4'-bis (dimethylamino) benzophenone was added and dissolved to obtain a dyeable photosensitive resin liquid.

Using this dyeable photosensitive resin liquid, dyed products were produced in exactly the same manner as in Examples 1 to 5. In all cases, the dyeability was good, and there was no bleeding of the dye on the unexposed areas and a very good pattern. A dyed product with clear and good resolution was obtained.

Example 13 To 300 parts of a polymerization solution prepared by the same formulation as in Example 1, 9 parts of p-azidobenzoic acid chloride was added and reacted at 60 ° C. for 2 hours.

Next, this reaction solution was purified by the reprecipitation method. To 10 parts of this polymer, 40 parts of ethyl cellosolve and Kayacure D
1 part of ETX was added to obtain a dyeable photosensitive resin liquid. When the same operation as in Example 1 was carried out using this dyeable photosensitive resin liquid, the dyeability was good, and a dyed product with good resolution was obtained without bleeding of the dye to the unexposed areas.

Example 14 Hifix SL in Example 1
In the same manner as in Example 1, except that 1 g of tannic acid was used instead of the above, the dyeing property was as good as in Example 1, no bleeding of the dye to the unexposed area, and a pattern A clear dyed product was obtained.

(Effects of the Invention) According to the present invention, the number of coats of the film in the step of producing a surface film dyeing substrate such as a color filter is two, and the use of an expensive dyeable photosensitive resin and dye-proof photosensitive resin The amount is extremely small and economical compared with the conventional method, the number of film curing operations is also small, and the labor can be saved in the process. Moreover, since the dyeable resin film is one layer, it is thin and the obtained dyed product has good transparency,
It has a wide viewing angle and is suitable as a color filter for liquid crystal TVs.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location G02B 5/20 101 7348-2K 5/22 7348-2K

Claims (1)

[Claims] 1. A first color obtained by forming a dye-resisting photosensitive resin film on a substrate surface using a dyeable photosensitive resin, exposing the same with a mask and developing the film. After providing a dye-proof mask from which the dyed part is removed, it is dyed with a dye having a predetermined spectral characteristic, and then treated with a dye fixing agent. The photosensitive resin film is exposed and developed, the second dyed part is removed, the second color is dyed with a dye having a predetermined spectral characteristic, and this operation is repeated to sequentially dye the dyeable resin film. A method for dyeing the surface coating of a substrate.