JPS60221755A - Method for dyeing surface film of base - Google Patents

Abstract

PURPOSE:To enable a transparent base, such as a glass plate, to be-dyed to an optional color tone by coating the surface of the base with a specified photoreactive compsn. to form a coat film, irradiating the film with actinic rays to cause photoreaction, and dyeing the film with an anionic dye. CONSTITUTION:The surface of the base is coated with (E) the photoreactive compsn. contg. (A) a polymer having photoreactive unsatd. groups and quaternary ammonium on the side chains, (B) a compd. having >=2 photoreactive unsatd. groups in one molecule, as an optional component, (C) a photopolymn. initiator, and (D) a solvent. The coat film thus formed is irradiated with actinic rays, to cause reaction, and this film is dyed with an anionic dye. the polymer (A) used for the compsn. (E) is dyeable itself, and moreover, since it is cross-linkable, an insoluble film is formed on the surface of the base, such as glass, and it is not easily dropped out at the time of dyeing. The coat film of the compsn. (A) is nonsticky before the irradiation of the actinic rays and easy to handle, and easily dyeable with the anionic dye after the irradiation. It can be used for various kinds of display devices, and liquid display color televisions.

Description

DETAILED DESCRIPTION OF THE INVENTION 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.

'If W f4+ / @ 6g81118 needle a)
A polymer (A) having both a photoreactive unsaturated group and a quaternary ammonium base in its side chain.

b) A compound (B) having two or more photoreactive unsaturated groups in one molecule as an optional component, C) A photoreaction initiator (C) as an optional component, and d) A solvent (D). A method of producing a coating on the surface of a substrate, which is characterized in that the adhesive resin composition (X) is applied to the surface of the substrate to form a coating, and then irradiated with actinic rays to react, and first, the coating is dyed with an anionic dye. This is related to dyeing methods.

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

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

In the conventional field, protein-based natural polymer substances such as casein and gelatin are mainly used, but these are used by adding dichromic acid as a photocuring agent to a solution of casein, gelatin, etc. dissolved in warm water. Potassium or ammonium is added and applied to a glass plate using a spin code method, and then active light is irradiated through a mask to form a latent image of a dyeable layer on the glass plate, followed by development. Reveals the dyeable layer. The next step is to dye this with a dye. In the case of dyeing methods that use casein, gelatin, etc., since these are natural products, they are easily perishable, their quality is not consistent, and there are large variations depending on the raw material source, and color reproducibility is extremely poor, and they may peel off in hot water. There are drawbacks such as easy processing, large deterioration of physical properties due to heat, and restrictions on processing conditions. Furthermore, there are problems in dyeing, such as difficulty in obtaining deep colors because the temperature of the dye bath during dyeing is restricted.

Furthermore, when using casein, gelatin, etc., ammonium dichromate or potassium dichromate is used as a photohardening agent, so it is necessary to solve the problem of pollution during these work processes and when disposing of the wood. Furthermore, there are other problems such as the chromium incorporated into gelatin cannot be completely removed and the remaining chromium may have an adverse effect.

The present inventors conducted studies to solve these problems and found that a) a polymer (A) having both a photoreactive unsaturated group and a quaternary ammonium base in the side chain; b) as an optional component. , a compound (B) having two or more photoreactive unsaturated groups in one molecule, c) a photoreactive resin composition containing a photoreaction initiator (C) as an optional component, and d) a solvent (D) ( E) was applied to the surface of the substrate, irradiated with actinic rays, reacted, and then dyed with an anionic dye to achieve the purpose of the present invention. It was completed. In other words, when using a polymer containing a quaternary ammonium base, this polymer itself has an affinity with anionic dyes and is dyeable, but since it is water-soluble, it must be applied to a glass substrate and dried. When post-dying is performed, the coating film peels off from the surface of the substrate during the dyeing bath during the dyeing process, making it impossible to achieve the purpose of dyeing.

In order to prevent this resin from falling off from the dye bath after coating, the present inventors added a compound (B
) as a crosslinking agent, but in this case, if the proportion of the crosslinking agent was small, the water resistance of the coating film was poor and the coating film peeled off. On the other hand, if a large amount is added, the water resistance improves, but since the compound (B) is inherently difficult to dye, there is a problem in that the dyeability decreases and a dark color tone cannot be obtained.

Furthermore, since Compound (B) contains many of the low molecular weight compounds 1 and is sticky, a coating film containing a large amount of this component is sticky before irradiation with actinic rays, making it difficult to handle and impractical.

As a result of repeated studies in order to improve these drawbacks, the present inventors found that when a polymer (A) having both a photoreactive unsaturated group and a quaternary ammonium base in the side chain is used, the polymer (A) In addition to being dyeable itself, it has crosslinking properties, so after irradiation with actinic rays, it forms an insoluble film on the surface of the substrate such as glass, which easily falls off into the dyeing bath during dyeing. It turned out to be difficult. Furthermore, in the present invention, the coating film before irradiation with actinic rays is non-adhesive and easy to handle, and furthermore, it is extremely easily dyed with an anionic dye after irradiating with actinic rays.

Furthermore, by using the method of the present invention, there is no need to worry about spoilage, products of constant quality can be obtained, and in addition, there is no need to worry about the effects of hexavalent Romu.

The side chain used in the present invention has a photoreactive unsaturated group and a quaternary
The polymer (A) having a class ammonium base can be prepared by various methods.

For example, a method in which a homopolymer or copolymer obtained by polymerizing a monomer having a tertiary amine group is reacted with a compound having an active halogen atom and a carbon-carbon unsaturated bond, or a method in which a monomer having a halogen atom is polymerized. Examples include a method of reacting a homopolymer or copolymer obtained by using a compound having a tertiary amino group and a carbon-carbon unsaturated bond.

Examples of the monomer having a tertiary amino group or a compound having a tertiary amine group and a carbon-carbon unsaturated bond include (N,N-dimethylamino)ethyl acrylate, (N
, N-dimethylamine)ethyl methacrylate, (N,
N-diethylamino)ethyl acrylate, (N,N-
diethylamino)ethyl methacrylate, (NIN-dimethylamino)propyl methacrylate, 4-vinylpyridine.

Diarylamines, etc. may be used, but these may be used alone or as a mixture of two or more, and if preferred, other copolymerizable monomers such as methyl methacrylate, methyl acrylate, ethyl acrylate, ether methacrylate, styrene, etc. It may also be used as a component for polymerization.

In addition, active...compounds having a rogen atom and a carbon-carbon unsaturated bond, or monomers having a rogen atom include, for example, allyl chloride, allyl bromide, l5-
Chloro-2-methylpropene, 6-chloro-1-methylpropene, a-furomo-1-butene, chloroacetic acid vinyl ester, r-chloro-iso-butene, m-
Examples include chloromethylstyrene, p-chloromethylstyrene, crotylproma(de,3-chloro-2-hydroxypropyl methacrylate).
It may be used as a seed or a mixture of two or more.

In the method for producing the polymer (A), the proportions of the raw materials used are preferably as follows.

That is, when a homopolymer or a copolymer obtained by polymerizing a monomer having a 5th-class amino group is reacted with a compound having an active rogen atom and a carbon-carbon unsaturated bond, the monomer 100 having a 5th-class amino group It is preferable to use 20 to 300 moles of the compound having an active halogen atom and a carbon-carbon unsaturated bond. or,·
- When a homopolymer or copolymer obtained by polymerizing a heptamer having a rogene atom is reacted with a compound having a tertiary amine group and a carbon-carbon unsaturated bond.

Tilt 100 moles of monomer with a herogen atom,
It is preferable to use 20 to 500 moles of the compound having a 5th class amino group and a carbon-carbon unsaturated bond.

The polymer (A) synthesized by the above method undergoes various steps after the coating film dries and before photocuring as described above, so the coating film before photocuring is non-tacky at room temperature. It is preferable that there be. Therefore, when synthesizing the polymer (A), it is preferable to adjust the synthesis components and degree of polymerization so that the synthesized polymer (A) is non-tacky at room temperature.

Preferably, the polymer (A) separation device is 500μ or higher. In addition, as mentioned above, since the polymer (A) itself is photocurable, the coating after photocuring becomes difficult to peel off in the dyeing bath, but if you want to further improve the strength or transparency of the coating, is a compound having two or more photoreactive unsaturated groups in one molecule (B
) is preferably added and mixed in an appropriate number.

Examples of the above compound (B) include the following.

Ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, butylene glycol diacrylate, butylene glycol dimethacrylate, neopentyl glycol diacrylate , neopentyl glycol dimethacrylate, 1,4-butanediol diacrylate, i, 6-hexanethiol diacrylate L/-), i,
6-hexanethiol dimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, novolak epoxy acrylate, bisphenol A-based epoxy acrylate, alkylene glycol gepoxy acrylate, glycidyl ester acrylate.

Polyester diacrylate, bisphenol A diacrylate, urethane diacrylate.

Compound (B) assists in the crosslinking of polymer (A) and makes the coating film stronger, so the type of compound to be used varies depending on the crosslinkability of polymer (A) and the object to be created, so it cannot be absolutely specified. However, it is preferable that the tackiness of the coating film before photocuring is non-adhesive to the extent that it does not adversely affect workability, and it is added to the extent that the dyeability of the coating film after curing is not inhibited. When compound (B) is used, the equipment used is 200 parts of compound (B) per 100 parts of polymer (A).
It is preferable to set the amount below that of heavy mold.

The photoreaction initiator (C) that initiates polymerization by irradiation with actinic rays used in the present invention includes anthraquinones such as 2-ethylanthraquinone and 2-butylanthraquinone, and acyloin such as benzoin and its alkyl ether derivatives. kind.

Examples include benzophenones such as benzophenone and Michler's ketone, and ketoaldonyl compounds such as benzyl and diacetyl.

These may be used alone or in a mixed system of two or more, and the grade used is a total of 100% of the polymer (A) and compound (B).
The content is preferably 200 parts by weight or less.

The solvent (D) used in the present invention is preferably one that can dissolve the polymer (A), the photoreaction initiator (C), and the compound (B) well, such as 2-methoxyethanol, 2-
Examples include ethoxyethanol, toluene, xylene, and the like. These may be used alone or in combination of two or more, and the proportion of the solvent (D) in the photoreactive resin composition (E) is the proportion of the polymer (A), the photoinitiator (C), and the compound. Although it varies depending on the properties of (B), the photoreactive resin composition (
The viscosity of E) is less than or equal to 200 cp, preferably 200
It is preferable to include it so that the viscosity is less than cps.

The present invention comprises a polymer (A) and a compound (B) as an optional component.
A photoreactive resin composition containing a photoreaction initiator (C) and a solvent (D) as optional components is used as a photoreactive resin composition. Other polymerizable viscosity modifiers, defoamers, etc. may also be included. When such a photocurable resin composition (E) is applied to a substrate, the solvent evaporates after application, and the resin film is formed afterwards. I can do it.

Since this resin film is non-adhesive, it is not easily deformed before being irradiated with actinic light, making it easy to handle. After coating, it is irradiated with actinic rays and cured.

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.

Examples of active light include visible light, ultraviolet light, X-rays, and electron beams.

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

Next, the cured resin is dyed with an anionic dye. Color index (Socie) is an anionic dye.
Acidic dyes described as C.I Ac1d in ty of Dyers and Co1ouris 78), direct dyes described as C.
Examples include reactive dyes listed as e.
Acidic dyes are particularly preferred. As an acid dye, C0 engineering Ac
l Yellow 17.

Same 49, same 67% same 72, same 127, same 110° same 13
5, 161. C0 engineering ACia Red S 7, same 50° same 111, same 114. 257. 266, 3
17, C1 engineering Ac1dBlue 41, same 83% same 9
0° 113, 129. Same 182, Same 125, C, Engineering Ac1d Orange 7, Same 56%C, Engineering Ac1
d Green25, 41, C1 Engineering Acl Viol
Examples include e7q'7, 27, 28%, and 48.

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 way, the dyed product is taken out and dried.

Next, examples of the present invention will be described.

All numbers in the middle part of the example indicate parts by weight.

Example 1 Toluene 69 parts (N, 11-dimethylamino) ether methacrylate
50 parts azoisobutyronitrile 1 part The above-prescribed liquid was subjected to a polymerization reaction at 80° C. for 8 hours in a nitrogen atmosphere to obtain 100 parts of a poly(N,N-dimethylamino)ethyl methacrylate solution.

Next, when 15 parts of chloromethylstyrene (M, P mixture) is mixed and reacted with the dissolved iso part of Nico at room temperature, the whole is solidified after 16 hours.

This was taken out and dissolved in 260 parts of 2-ethoxyethanol, and 16 parts of Irgacure 651 (sensitizer manufactured by Nano 5 Geigy) was added and dissolved to obtain a dyeable photoreactive resin composition.

Next, silane coupling agent KBM503 (
Shin-Etsu Chemical @10 After applying ethanol solution and air drying 1
Heat and dry at 10°C for 5 minutes.

Further, this surface was washed with acetone and dried to be used as a coating base material.

The resin composition was applied to the surface of this coating substrate to a thickness of 1 micron by a spin cord method. The coating film was not sticky. Next, ultraviolet rays B o Watt/cm 4
The coating film was cured by irradiation for seconds.

Next, add Kayanol to an acetic acid acidic (pHL3) aqueous solution.
0.04% Floxine NK (Nippon Kakami)
When the solution was dissolved and dyed at 90° C. for 20 minutes, a glass substrate dyed in vivid red was obtained.

For comparison, as Reference Example 1, a toluene solution of polydimethylaminoether methacrylate, which had not been reacted with the chloromethylstyrene, was used to prepare 2-ethoxyethanol and Irgacure 6 according to the recipe of 11[NflJl].
Using a resin composition added with 51, coating film, ultraviolet irradiation,
Examples 2 to 5 Glass substrates were dyed to an opaque level of staining after similar operations such as dyeing Example 2 in which coating films prepared in the same manner as in Example 1 and Reference Example τ were dyed The results of .3 and its reference example 2% 3 are shown in Table 1.

1st Shishi Example 4 Bo+) (N,N-dimethylamino)ethyl methacrylate prepared according to the recipe of Example 1, toluene solution 50
10 parts of allyl chloride are mixed with the mixture and reacted at room temperature for 40 hours to solidify the whole.

This was dissolved in 240 parts of 2-ethoxyethanonyl, and further 24 parts of R-166 (epoxy diac, IJ rate manufactured by Nippon Kayaku ■) and 10 parts of Irgacure 651% were mixed to obtain a photoreactive resin composition.

This photoreactive resin composition was applied to a glass plate in a film thickness of 2 μm according to the recipe of Example 1.

This coating film had low tackiness and good workability.

Next, this was irradiated with ultraviolet light at 80 Walt/c for 1.4 seconds to cure the coating film. Next, Kay according to the procedure of Example 1.
arusTurquei'ee Blue GL (f
9
When dyeing was carried out for a.degree. C. es minutes, a glass plate with a transparent coating film dyed on a deep back was obtained. The pH of the dyeing bath is 8.
It was 5.

For comparison, as Reference Example 4, a toluene solution of poly(N,N-dimethylamino)ethyl methacrylate that did not react with the allyl chloride was used, and 2-ethoxyethanol and Irgacure 651 were prepared according to the recipe of Example 4.
When similar operations such as coating, ultraviolet irradiation, and dyeing were carried out using a resin composition containing the same, only a glass plate that was stained without staining was obtained.

Example 516 The results of Examples 5 and 6 and Reference Examples 5 and 6, in which paint films prepared in the same manner as in Example 4 and Reference Example 4 were dyed, are shown in Table 2.

2nd Shishi Example 7.8 5 parts of 4-vinyl pyridine polymer (molecule 112,000) was dissolved in 45 parts of 2-ethoxyethanol, 8 parts of chloromethylstyrene (m, p mixture) was mixed therewith, and the mixture was heated to room temperature. After 20 hours of reaction, Irgacure 651
% 1 part was added and dissolved to obtain a dyeable photoreactive resin composition. Next, using this in the same manner as in Example 1, a coating film having a thickness of 2 μm was formed on a glass plate. This coating film had no stickiness and had good workability. Next, apply this to ultraviolet B 0W
Table 3 shows the results of staining in the same manner as in Example 1 by irradiating at /r, m for 5 seconds.

For comparison, as Reference Examples 7 and 8, the 2-
Table 3 shows the results of applying a resin composition to which Irgacure 651 was added using an ethoxyethanol solution according to the formulations of Examples 7 and 8, applying ultraviolet rays, and dyeing.

Table 5 Example 9 Toluene 69.5 parts (N,N-dimethylamino)ethyl acrylate 30
Part azoisobutyronitrile 0.5 parts The liquid of the above formulation was subjected to a polymerization reaction at 80°C for 8 hours in a nitrogen atmosphere using a conventional method to obtain poly('Ni1-dimethylamino).
100 parts of ethyl acrylate solution are obtained. Next, when 50 parts of this solution is mixed with 15 parts of 4-promo-1-butene at room temperature, the entire mixture is solidified after 70 hours. This was taken out and dissolved in 260 parts of 2-ethoxyethanol, and 14 parts of Irgacure 651 was further added and dissolved to obtain a dyeable photoreactive resin composition. Next, this photoreactive resin composition was applied to a glass plate in a film thickness of 1 μm according to the recipe of Example 1. This coating film had low tackiness and good workability. Next, apply this to ultraviolet rays 80wa 7t/cm%
The coating film was cured by irradiation for 6 seconds.

Next, as in Example 1, dissolve Green 1P (a color filter dye manufactured by Nippon Kayakami Co., Ltd.) to a concentration of 0.048% and dye it at 60°C for 10 minutes. A glass plate having the following properties was obtained. In addition, p of the dyeing bath
H was 8.0.

For comparison, Example 9 was prepared using a toluene solution of poly(N,N-dimethylamino)ethyl acrylate that was not reacted with the 4-promo-1-butene as Reference Example 9.
When a 2-ethoxy-like operation was performed according to the recipe, the dyed film was opaque and some of the film fell off, making it impractical.

Example 10 Poly(N,N-dimethylamino)ethyl acrylate prepared according to the recipe of Example 9, 15 parts of allyl I:+acetate was mixed with 50 parts of toluene solution, and the mixture was reacted at room temperature for 20 hours to completely solidify. do.

This was dissolved in 240 parts of 2-ethoxyethanol, and 1.12 parts of Irgacure 6s was further mixed therein to obtain a photoreactive resin composition. This photoreactive resin composition was applied to a glass plate in a film thickness of 1 μm according to the recipe of Example 1. This coating film had low tackiness and good workability.

Next, this was irradiated with ultraviolet rays B OWatt:/rn for 6 seconds to cure the coating film, and this coating film was dyed using the recipe of Example 9 to obtain a glass plate having a transparent coating film dyed deep green. .

Patent Applicant: Nippon Kayaku Co., Ltd. Procedural Amendment February 2nd, 1981, Manabu Shiga, Commissioner of the Patent Office 2. Name of Invention: Dyeing Method for Substrate Surface Film 3. Relationship with the Person Who Makes the Amendment Case: Patent Applicant: Tokyo Metropolitan Government 11-2 Fujimi-chome, Chiyoda-ku (408) Nippon Kayarai Co., Ltd., Tsunekazu Sossakano, 4th agent, 11-2 Fujimi-chome, Chiyoda-ku, Tokyo (voluntary) 6. Inventions increased by amendment No number 7 Column 8 Detailed explanation of the invention of the specification subject to the amendment 8 Contents of the amendment.

Contents of the amendment 1. After "methacrylate" on page 8, line 5 of the specification, [β-chloroether cinnamic acid ester CI CH2CH20CO (JI=CH◇β-bromoether cinnamic acid ester Br CH2CH2OC0CH==CH-4CJ: )β
-Promoethylnamilitane acetate B r C
H2CH2OC0Ckl==CHQCH=CH◇β-bromoetherfuryl acrylic acid ester B r CH2C
H2OC0CH==CH-wa p-β-promoetheroxycarponylbenzalacetophenone Br CH2CH
20C0CH==CH-CO<n4-chloroacetoxy7
Insert "Sterben".

2. On page 11, line 10, the phrase "polymerization" is corrected to "reaction."

5. Insert the following sentence after line 19 on page 23.

“Example 11 Toluene 207 parts (N,N-dimethylamino)ethyl acrylate 45
(N,N-dimethylamino)ethel methacrylate
45 parts azoisobutyronitrile 3 parts The liquid of the above formulation was subjected to a polymerization reaction at 80°C for 8 hours in a nitrogen atmosphere to form a co-polymerization reaction of (N,N-dimethylamino)ether acrylate and (N,N-dimethylamino)ethyl methacrylate. 300 parts of a polymer solution was obtained.

Next, 25 parts of β-glomoethyl cinnamic acid ester was added to 50 parts of this copolymer solution at room temperature to obtain a B r CH2CH2OC0CH==Ha color precipitate. This was separated and the precipitate was dried under reduced pressure to obtain a dry solid.

Next, 20 parts of dry solid in 80 parts of 2-ethoxyethanol,
Two parts of Michler's ketone were mixed and dissolved and applied to a film thickness of 1 μm for photoreaction. This coating film had low tackiness and good workability. Next, apply ultraviolet light 80 Waet, 4m15
The coating film was cured by irradiation for seconds, and the coating film was dyed using the recipe of Example 9 to obtain a glass plate having a transparent coating film dyed deep green. ” JP-A-Sho GO-221755 (8)

Claims (1)

[Scope of Claims] a) A polymer (A) having both a photoreactive unsaturated group and a quaternary ammonium base in its side chain. b) A compound (B) having two or more photoreactive unsaturated groups in one molecule as an optional component, C) A photoreaction initiator as an optional component, and d) A solvent (D). Dyeing of a film on the surface of a substrate, characterized in that the resin composition (R) is applied to the surface of the substrate to form a film, irradiated with actinic rays to cause a reaction, and then this film is dyed with an anionic dye. Law.