JPS63148261A - Coloring post-processing method - Google Patents

Abstract

PURPOSE:To prevent the generation of a fault by bleeding of a dye by dyeing a resin molding formed by using a photosetting compsn. with an acidic dye then subjecting the resin molding to an immersing treatment in an aq. soln. dissolved with a water soluble metal compd. CONSTITUTION:The resin molding formed by using the photosetting compsn. is dyed with the acidic dye and is then subjected to the immersion treatment in the aq. soln. dissolved with the water soluble metal compd. There is a compsn. consisting of an ethylenic unsatd. compd., photopolymn. initiator and thermopolymn. prohibitor as the photosetting compsn. The ethylenic unsatd. compd. includes an unsatd. polymer having an ethylenic unsatd. group, photopolymerizable ethylenic unsatd. monomer and the mixture composed thereof. Various compds. known as the photopolymn. initiator, for example, benzoin, benzoin methyl ether, etc., are used as the photopolymn. initiator. The thermopolymn. prohibitor is exemplified by hydroquinone, monotertiary butyl hydroquinone, etc. The resin molding which obviates bleeding of the dye, has excellent resistance to staining and has an extremely low color fading property is obtd.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention has low bleeding of colorant from colored resin moldings, excellent stain resistance even when used in high temperature and high humidity conditions, and low discoloration. The present invention relates to a post-coloring treatment method for improving coloring properties.

[Conventional technology and its problems]

Conventionally, it is known to photocure a photocurable composition without using a mold or the like to obtain a resin molded article using a three-dimensional method. It is used in the production of signboards, cut letters, three-dimensional maps, name plates, etc., as well as in the production of molded objects with fine nosoturns that are difficult to process using other molding methods such as molds.

Some of the molded articles obtained by such methods must be colored depending on the intended use. To color a resin molded article, a coloring agent such as a dye or a pigment is usually added to a raw material mixture in advance and the mixture is then molded. However, in the case of photocurable compositions, if the raw material composition is colored, the transmittance of actinic rays will decrease and sufficient photocuring will not take place. A method of coloring using

However, in the colored resin moldings obtained by this method, the dye is only fixed mainly through physical adsorption, and the bond between the dye and the resin is not sufficient, so if you touch the molding, your hands will be irritated. Problems often occur such as staining, dye bleeding and transfer to other objects, or easy fading. In particular, when the molded body is used for various display devices, such as CRTs, dials of instruments, and luminescent display boards, to improve clarity and contrast, or to control the direction of light emitted from display devices. When used in light-shielding screens to adjust the viewing angle, the reduction in transmittance due to dye breathing is a major obstacle.

On the other hand, Japanese Patent Application No. 60-134382 describes a method of coloring with an acid dye using a photocurable composition containing an ethylenically unsaturated compound having a basic group. However, especially when used in various display devices for automobiles, testing is required under extremely harsh conditions, and if left in a heated state for a long time, problems may occur due to dye breathing.

[Means and methods for solving the problem] As a result of extensive research, the present inventors have found that a resin molded article formed using a photocurable composition is colored with an acid dye and then treated with a water-soluble metal compound. It has been discovered that the object can be achieved by immersion treatment in an aqueous solution in which .

The photocurable composition used in the present invention can be arbitrarily selected from known photosensitive resins that can be cured by irradiation with light, and is not particularly limited. Examples of such photocurable compositions include compositions comprising a captive ethylenically unsaturated compound, (B) a photopolymerization initiator, and (C) a thermal polymerization inhibitor.

The recovered ethylenically unsaturated compounds include unsaturated polymers having ethylenically unsaturated groups, photopolymerizable ethylenically unsaturated monomers, and mixtures thereof. Examples of the unsaturated polymer include unsaturated polyester, unsaturated polyurethane, oligoester acrylate, oligoester methacrylate, unsaturated polyamide, unsaturated polyimide, unsaturated polyether, unsaturated polyacrylate,
Examples include unsaturated polymethacrylates and various modified products thereof. These polymers usually have an average molecular weight of substantially 500 or more.

Specific examples of such polymers include unsaturated polyesters and alkyds such as unsaturated dibasic acids such as maleic acid, fumaric acid, and itaconic acid, or their acid anhydrides, and ethylene glycol, zoropylene glycol, and diethylene glycol. , triethylene glycol, glycerin, trimethylolpropane, pentaerythritol,
Polyesters with polyhydric alcohols such as 1,4-polybutadiene having terminal hydroxyl groups, hydrogenated or non-hydrogenated 1,2-polybutadiene-acrylonitrile copolymers, some of the acid components being succinic acid, adipic acid, Examples of unsaturated polyurethanes include polyesters substituted with saturated polybasic acids such as phthalic acid, isophthalic acid, phthalic anhydride, and trimellitic acid, or polyesters modified with drying oil fatty acids or semi-drying oil fatty acids. A polyol having a terminal hydroxyl group and a compound in which an ethylenically unsaturated group is introduced using the terminal incyanate group or hydroxyl group of a compound linked via a urethane group derived from a polyisocyanate, such as the above-mentioned polyhydric alcohols and polyesters. Polyols, polyols such as polyether polyols, 1,4-polybutadiene with terminal hydroxyl groups,
Hydrogenated or non-aqueous 6'A 1 *2-polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, etc. and polyisocyanate such as tolylene diisocyanate, diphenylmethane-4,4-diincyanate, hexamethylene diisocyanate, etc. Isocyanates with terminal incyanates of polyurethanes or those into which unsaturated groups have been introduced using the reactivity of hydroxyl groups, or compounds having active hydrogen such as hydroxyl groups, carxyl groups, and amine groups among the unsaturated carboxylic acids or their esters mentioned above. Examples include compounds in which an unsaturated group is introduced by a reaction with a carzexyl group, a compound in which an unsaturated group is introduced by a reaction between a carzexyl group and a hydroxyl group, or a compound in which the above-mentioned unsaturated polyester is linked with a polyincyanate. In addition, oligoester acrylates include those in which acrylic acid or methacrylic acid coexists with an ester reaction system of polybasic acid and polyhydric alcohol, and are co-condensed to adjust the molar ratio of each to about 1,200 to 5,000 molecules; For example, adipic acid, phthalic acid, isophthalic acid or acid anhydride, ethylene glycol, phthalene gelicol, diethylene glycol, triethylene glycol, etc.
Condensation of an ester reaction system with a polyhydric alcohol such as chrycerin, trimethylolpronozone, or pentaerythritol in the coexistence of acrylic acid or methacrylic acid;
Epoxy acrylates, such as esters of acrylic acid or methacrylic acid and epoxy group-containing compounds obtained by polycondensation reaction of polyhydric alcohols, polyhydric phenols, or polyphenols with engineered chlorohydrin or alkylene oxide, with ethylenically unsaturated side chains. A compound obtained by reacting a polymer having a group such as polyvinyl alcohol or cellulose with an unsaturated carzenic acid or its acid anhydride, or a polymer or copolymer of acrylic acid or methacrylic acid. Reactions of copolymers containing cardaxyl groups with unsaturated alcohols, glycidyl acrylates, methacrylates, etc., and copolymers containing maleic anhydride with allyl alcohol, hydroxyalkyl acrylates, methacrylates, etc. Examples include a reaction product of a copolymer containing glycidyl acrylate or methacrylate as a copolymerization component and acrylic acid or methacrylic acid.

Various known compounds can be used as the copolymerizable ethylenically unsaturated monomer, and examples of such compounds include esters of unsaturated carzene acids such as acrylic acid and methacrylic acid, such as alkyl- , cycloalkyl-,
Mono- or di-halogenated alkyl-, alkoxyalkyl-, hydroxyalkyl-, aminoalkyl-, tetrahydrofurfuryl-, allyl, cydyl-, benzyl-, phenoxy-acrylate and methacrylate, alkylene glycol, polyoxyalkylene glycol. Acrylates and methacrylates, trimesterolpronotriacrylates and methacrylates, pentaerythritoltetraacrylates and methacrylates, acrylamide, methacrylamide or derivatives thereof, such as acrylamides N-substituted or N,N'-substituted with alkyl or hydroxyalkyl groups. and methacrylamide, diacetone acrylamide and methacrylamide, N,N'-alkylene bisacrylamide and methacrylamide, allyl compounds such as allyl alcohol, allyl incyanate, diallyl phthalate, triallyl cyanurate, etc., maleic acid, maleic anhydride. Acids, esters of fumaric acid, such as mono- or dimaleates and fumarates of alkyl, alkyl halides, alkoxyalkyl, other unsaturated compounds such as styrene, vinyltoluene, divinylbenzene, N-
Examples include vinylcarnozole and N-vinylpyrrolidone. In addition, some of these monomers may be converted into azide compounds such as 4,4'-diazidostilbene, p-
4.4'-diazidebenzophenone, 4.4'-diazidophenylmethane, 4.
4'-Diazidochalcone, 2,6-di(4'-diazidobenzal)-cyclohexanone, 4,4'-diazidostilbene-α-carzenic acid, 4,4'-thia cytodiphenyl, 4,47-dia Cydostilbene-2.2'-,
9 Sodium sulfonate may also be used instead.

When used in combination with an unsaturated polymer, these monomers are added in an amount of 200 parts by weight or less per 100 parts by weight of the polymer.

On the other hand, as the photopolymerization initiator used as component (B),
Various known compounds generally known as photopolymerization initiators, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether,
Benzoin isopropyl ether, benzoin butyl ether, benzoin isobutyl ether, 2,2-dihydroxy-2-phenylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-jethoxy-2-phenylacetophenone, 2,2-jethoxy Acetophenone, benzophenone, 4,4'-bisdialkylamino-4-benzophenone, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid alkyl ester, 2-ethylanthraquinone, xanthone, thioxanthone, 2-chlorothioxanthone, benzyl, tetramethylthiuram Monosulfide, 1-phenyl-1,2
-propane dione-2-(o-ethoxycarzenyl)
Oxime, 2-methyl-[4-(methylthio)phenyl-2-morpholino-1-propanone, etc. can be used. These photopolymerization initiators are usually used in an amount of o, ooi to 10 by weight based on the composition.

In addition, as the thermal polymerization inhibitor used as component (C),
For example, hydroquinone, mono-tert-butylhydroquinone, benzoquinone, 2,5-diphenyl-p-penzoquinone,
Picric acid, di-p-fluorophenylamine, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, β-naphthoA/, N-nitrosodiphenylamine, aryl phosphite, arylalkyl phosphite, etc. can be mentioned.

The photocurable composition in the present invention includes the above (4) to (C
) In addition to the component, it is preferable to further add an ethylenically unsaturated compound having a basic group. As a basic group,
Examples include an amine group, a quaternary ammonium group, and a nitrogen atom-containing heterocyclic group.

Examples of such basic unsaturated compounds include the general formula (in the formula, R1 is a hydrogen atom or a methyl group, R2 and R3 are alkyl groups having 1 to 12 carbon atoms, and nl is an integer of 1 to 6). A compound represented by the general formula (in the formula, R4 is a hydrogen atom or a methyl group, R5 + R6 and R7 are alkyl groups having 1 to 12 carbon atoms, X is an anion, R
(2 is an integer of 1 to 6) Compounds having an ammonium group such as the compound represented by the following can be mentioned. Examples of these compounds include diethylamine ethyl acrylate or methacrylate, dimethylaminoethyl acrylate or methacrylate, dibutylaminoethyl acrylate or methacrylate, dibutylaminopropyl acrylate or methacrylate, diethylamine ethyl acrylate or methacrylate, and halogenated ammonium salts thereof. be.

Examples of other basic unsaturated compounds include vinylpyridine, alkylvinylpyridine, vinylpyrazine, vinylquinoline, vinyloxazole, vinylimidazole, and vinylbenzoxazole.

The amount of these basic unsaturated compounds added is selected within the range of 0.5 to 25% by weight, preferably 1 to 10% by weight based on the composition.

In addition, in order to make coloring with an acid dye more effective after photocuring, the photocurable composition is added in an amount within a range that does not significantly reduce the transmittance of actinic rays to the composition, that is, the total amount of the composition. 1% by weight or less, preferably Vio, 5
Color improvers, such as inorganic pigments such as Carzen Black and Ingara, and various organic pigments or dyes, can also be added in amounts below - by weight.

Furthermore, the photocurable composition may contain various additives as desired, such as extender pigments such as silica, alumina, clay, talc, and calcium carbonate, polymethyl methacrylate,
Polymers soluble in the composition such as polyamide, polystyrene, cellulose acetate, cellulose acetate butyrate, cellulose acetate peropione-1-, polyvinyl acetate, etc. can be added.

In order to produce the colored resin molded article of the present invention using the photocurable composition prepared in this way, first, a layer of the composition is provided on a support, and then a desired mask is applied to this layer. Actinic light is irradiated through the pattern to photocure it, and then the uncured portion of the non-irradiated area is removed by means such as washing and development to form a desired pattern on the support. Next, the pattern is colored in an arbitrary tone using an acid dye. In this case, if desired, the support may be colored at the same time, or only the /e turn formed by photocuring the composition without using the support may be colored. Furthermore, after coloring the nosoturn, the support can be removed to obtain a molded product with only a colored pattern.

Examples of acidic dyes used here include acidic azo dyes,
Any known acid dyes such as acidic anthraquinone dyes and metal complex azo dyes can be used.
Specifically, for example, those described in "Dye Handbook" (Maruzen Publishing, Organic Synthetic Chemistry Association 84) can be used.

In particular, metal complex azo dyes are advantageous because they have good fastness after coloring.

Further, dyeing of Nosoturn is carried out in an acidic or neutral dye bath according to a conventional method. If desired, commonly used pHM stabilizer side base agents and various other auxiliary agents may be added to this dye bath.

The pattern was provided on a support because it could be dyed in relatively low temperature dyebaths. When dyeing the e-turn, only the pattern can be dyed without dyeing the support. For example, if the support is a plastic sheet,
By dyeing at a temperature of 80° C. or lower, preferably 60° C. or lower, it is possible to dye only the pattern.

Therefore, such a dyeing method is convenient when the molded article of the present invention is used for a light-shielding screen or the like that requires the nosoturn to be light-opaque and the support to be transparent. At this time, by using black acid dye, 1. The e-turn can be easily made light-opaque so that its blackening density [D] is a value of 3 or more.

In the present invention, metal compounds such as aluminum, copper, chromium, and zinc are suitable as water-soluble metal compounds.

These metal compounds include aluminum acetate, aluminum sulfate, aluminum chloride, potassium alum, ammonium alum, acetate steel, sulfate steel, chloride steel,
Examples include chromium sulfate, chromium chloride, chromium potassium, chromium ammonium, zinc acetate, zinc sulfate, and zinc chloride. Among these, aluminum compounds are suitable because they are easy to treat wastewater, and potassium alum and ammonium alum are particularly preferred.

The concentration of the aqueous solution of these water-soluble metal compounds is 0.
．． It is selected in the range of 5 to 15% by weight, preferably 1 to 10% by weight. In addition, the immersion treatment conditions include placing a resin molded body colored with an acid dye in an aqueous solution of a water-soluble metal compound for 30 minutes.
It is only necessary to soak for 10 to 60 minutes at a temperature of 0 to 80 °C.

In the present invention, active light sources used for photocuring include light sources that generate ultraviolet rays, such as arc lamps, mercury lamps, xenon lamps, metal halide lamps, fluorescent lamps for ultraviolet rays,
Alternatively, sunlight, laser light, etc. can be used.

Furthermore, regarding the method of removing the uncured part of the non-irradiated part,
For example, the photocurable composition may be washed and removed by spraying a developing solution such as an aqueous alkaline solution, an aqueous surfactant solution, or various organic solvents, or by rubbing it with a brush, or if the photocurable composition is in a liquid state, it may be removed using compressed air. It may be removed by blowing it off.

The photocurable molded article of the present invention may be provided on the support from the beginning as described above, or a molded article may be formed separately and mounted on the support. In this case, various plastic sheets such as polyethylene terephthalate, polymethacrylate, polycarbonate, polyvinyl chloride, polyamide, polystyrene, polypropylene, polyethylene, polyester, polyimide,
A sheet of polysulfone, cellulose acetate, etc., a metal sheet, such as a sheet of aluminum, iron, copper, zinc, etc., or paper, a wooden board, a ceramic board, a stone board, a glass board, etc. can be used. When using these supports, the support may be treated with a primer or coated with an adhesive, if necessary, in order to improve adhesion to the molded body.

〔Effect of the invention〕

The post-treated colored resin molded article of the present invention not only combines the resin and the dye, but also has no bleeding of the dye due to the formation of a complex salt between the dye and the metal, has excellent stain resistance, and is resistant to fading. This is extremely rare. Therefore, when the molded body is used in combination with a special holiday as described above, the dye does not transfer from the colored nosoturn to the support,
Furthermore, even when the molded article is used by being attached to another sheet, there is no bleeding of the dye into the adhesive layer.

Therefore, the molded product of the present invention can be used in combination with various display devices that have colored JR turns in the form of fine stripes or square or hexagonal lattices on a transparent support to control the direction of display light and to reduce external light. It is suitable for use in light-shielding screens, etc., which are used to prevent effects and improve contrast.

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.

Example 1 Propylene glycol, diethylene glycol adivic acid, and fumaric acid at a molar ratio of 0.1510.3510.35
To 100 parts by weight of an unsaturated polyester resin (acid value 30) obtained by condensation at a ratio of 10.15, 12 parts by weight of diethylene glycol dimethacrylate, 20 parts by weight of tetraethylene glycol, dimethacrylate, and 18 parts by weight of 2-hydroxyethyl methacrylate. 10 parts by weight of diethylaminoethyl methacrylate, 2 parts by weight of benzoin isobutyl ether, 0 parts by weight of 4-tert-butylcatechol
．． A photocurable composition was prepared by blending 0.3 parts by weight, and then, using this composition, a colored resin molded article was formed by the following operations.

That is, a negative film having a striped pattern with a pitch of 50 μm in the transparent part and 150 μm in the non-transparent part and a polypropylene film with a thickness of 20 μm are superimposed on a transparent glass plate, and the basic unsaturated film prepared as described above is placed on top of the negative film having a striped pattern with a pitch of 50 μm in the transparent part and 150 μm in the non-transparent part. After providing a layer of the compound-containing photocurable composition, an adhesive (Atocoat AD-335A + curing agent ADFJ) is applied on this composition layer.
A PET film having a thickness of 200 μm coated with PET film (manufactured by Toyo Morton Co., Ltd.) was covered so that the adhesive layer was in contact with the composition layer. At this time, the thickness of the core composition layer was adjusted to 150 μm using a spacer. From the negative film side of the thus assembled assembly, the negative film was exposed for 80 seconds using a 3 KW ultra-high pressure mercury lamp to photocure it into a striped pattern. After exposure, remove the negative film and polypropylene film, and then lower the liquid temperature to 40-45℃.
The resin composition in the non-exposed areas was removed by spraying a weak alkaline solution of . After removing this unexposed area, the plate was washed with water and post-exposed (irradiation amount: 1000 m J 7 m
”) and drying (50°C, 10 minutes).

Then, 1% by weight of acid dye (Kayakalan Blue Black RL) adjusted to pH 3.5 with acetic acid was added.
Using a dye bath manufactured by Nippon Kayaku Co., Ltd., dyeing was carried out at 50°C for 60 minutes, and only the image area made of the photocured composition was dyed black.
A light-shielding screen having striped stereoscopic images with a height of 150μ and a pitch of 150μ was created.

Next, in a 5% by weight potassium aqueous solution, 6
It was immersed for 30 minutes at 5°C. When this screen was left at 110° C. for 72 hours, the increase in transmission density was measured and is shown in Table 1.

Example 2 An experiment was carried out in exactly the same manner as in Example 1, except that ammonium sulfur and chloride were used instead of potassium sulfur.

Example 3 An experiment was conducted in exactly the same manner as in Example 1, except that a photocurable composition containing no diethylaminoethyl methacrylate was used.

Comparative Example 1 An experiment was conducted in exactly the same manner as in Example 1, except that the immersion treatment in the potassium aqueous solution was omitted.

Comparative Example 2 An experiment was conducted in exactly the same manner as in Example 3, except that the immersion treatment in the potassium aqueous solution was omitted.

Example 4 Polyethylene adipate (diol, molecular weight 2000)
Add 35 parts by weight of tolylene diisocyanate and 0.5 parts by weight of dibutyltin lauray to 200 parts by weight, and heat at 70°C.
This was then reacted with ethylene oxide-propylene oxide copolymer (35 ethylene oxide units).
Weight% content, block copolymer diol, molecular weight 200
0) was added and reacted to obtain a block copolymer having incyanate groups at both ends.

To 300 parts by weight of this copolymer, 25 parts by weight of 2-hydroxyethyl methacrylate and 0.1 parts by weight of hydroquinone were added and reacted at 70°C for 2 hours to prepare a prepolymer. To 3003 parts of this prepolymer were added 70 parts by weight of 2-hydroxypropyl methacrylate, 10 parts by weight of 2-ethylhexyl acrylate, 15 parts by weight of n-butyl acrylate, and 15 parts by weight of dimethylaminoethyl methacrylate.
A photocurable composition was prepared by blending 25M parts and 6 parts by weight of benzoin ethyl ether.

Next, place the non-transparent part on a transparent glass plate with a side length of 3.
A negative film having a lattice pattern with a width of 50μ in the transparent part and a polypropylene film with a thickness of 20μ are stacked, a layer of the photocurable composition obtained as described above is provided on top of this, and a layer of the photocurable composition obtained as described above is provided on top of this. On this composition layer, the 200 μm thick polyester film used in Example 1 was covered so that the adhesive layer was in contact with the composition layer. At this time, the thickness of the composition layer was adjusted to 300 μm using a spacer.

From the negative film side of the assembly assembled in this way,
It was exposed for 70 seconds using a parallel light source consisting of a 3KW high-pressure mercury lamp, a reflective mirror, and a lens, and was photocured into a lattice pattern. After exposure, the first lath board, negative film, and polypropylene film of this assembly were removed, and development, washing, post-exposure, and dyeing were performed under the same conditions as in Example 1, except that an aqueous surfactant solution was used as the developer. , we created a light-shielding screen with a fine black stereoscopic image in a checkered pattern. Next, using double-sided adhesive tape on this screen, 200
A μ-thick polyester film was laminated as a protective sheet.

Then, in a 5% by weight potassium alum aqueous solution, 6
i9 for 30 minutes at 5°C. This screen is heated to 110℃
The increase in permeation density was measured after being left for 72 hours, and the results are shown in Table 1.
It was shown to.

Example 5 In Example 1, the dye was replaced with 1% by weight of the acid dye Lany.
l Black BG, extra cone, (
The experiment was carried out in exactly the same manner as in Example 1, except that the sample was changed to one containing [manufactured by Sumitomo Chemical Co., Ltd.].

Table 1 Each light-shielding screen was left at 100° C. for 72 hours, and the transmission density of the relief portion was measured.

Manufactured by Dainippon Screen Manufacturing Co., Ltd.

Claims (1)

[Claims] A post-coloring treatment method in which a resin molded article formed using a photocurable composition is colored with an acid dye and then immersed in an aqueous solution in which a water-soluble metal compound is dissolved.