JPH023716B2 - - Google Patents

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention uses colored particles that have high tinting power, extremely vivid colors, and excellent durability, and is used to apply various small particles onto a colored object. The present invention relates to a novel pointillist printing method that makes a pattern formed by a collection of points as constituent elements appear, and allows the printing pattern to exhibit marbling effects, multicolor effects, three-dimensional effects, color change effects, etc. in the visual sense.

[Prior Art] Conventionally, a colored surface printed with colored paste used in a normal textile printing method visually appears as one uniform color having at least an area.

In order to print marbling or colorful dotted patterns on the colored surface, several types of printing paste are prepared according to the desired number of colors, and a special mold prepared for each dotted pattern is applied. It is necessary to prepare the same number of prints as the number of colors and print each print, and there are significant restrictions on pattern repeat and dot size.

In contrast, the present inventors have already disclosed a method for easily obtaining any pointillist pattern without requiring such complicated operations in Japanese Patent Publications No. 50-19670 and Japanese Patent Publication No. 51-1969.
Publication No. 28755, Publication No. 50-29551, and Publication No. 29551
This was disclosed in Publication No. 50-34151, etc.

[Problems to be Solved by the Invention] Among these new pointillist printing methods mentioned above, the invention disclosed in Japanese Patent Publication No. 50-34151 uses a pigment as the color component of the colored particles, and uses the so-called pigment resin printing method. It is characterized in that it can be used for fabrics etc. in accordance with the above, and is extremely useful in that it is easy to operate and that any object to be colored can be selected. However, although the invention has excellent durability because the color is pigment-based, there are some dissatisfaction with the sharpness and coloring power.

Therefore, in order to improve these color problems, the present inventors have developed a method for using so-called leuco dyes, that is, acidic substances, which have been commonly used in pressure-sensitive and thermal copying paper as dye components. If a mixture consisting of a colorless or light-colored poorly water-soluble dye that develops color in water, and a mixture consisting of the poorly water-soluble dye, an acidic substance as a coloring agent, and a solvent that dissolves both is made into suitable water-insoluble granules, We have found that this objective can be achieved very effectively.

By the way, the above coloring mechanism is well known as the principle of the copying method. However, in conventional copying methods, the object to be colored is paper, and the dye and coloring agent are prepared separately, and not only do they come into contact only on the paper, but the colored material itself has almost no property other than light resistance. Furthermore, while the component particulate materials used in these copying methods only require pressure destruction or thermal destruction, the particulate materials of the present invention can be used on any coloring object. It must have strong non-destructive performance at least semi-permanently.

The problems that must be solved in order to use the coloring mechanism conventionally used in copying methods for pointillist printing include the above-mentioned problems.

[Means for solving problems] Next, the configuration of the present invention will be described.

The present invention emulsifies in water a mixture consisting of a poorly water-soluble dye that develops color with an acidic substance, an acidic substance as a coloring agent for the poorly water-soluble dye, and a poorly water-soluble solvent with a boiling point of 150°C or higher, and then forms a film from the emulsion. By blending one or more colors of water-insoluble colored particles obtained by coating with a synthetic resin and crosslinking and curing into a printing paste made of synthetic resin, etc., and applying it on the object to be colored. , a pointillist printing method characterized by making a pointillist pattern of clear, deep and solid color appear on the object to be colored.

[Example] Examples of poorly water-soluble dyes that develop color with acidic substances used in the present invention include so-called proton-sensitive dyes.
For example, 3.3'dimethoxyfluorane (yellow in acid, hereinafter "in acid" will be omitted), 3 chlor.6
Phenylaminofluorane (orange), 3-diethylamino, 6-methyl, 7-chlorofluoran (vermilion), 3
Diethyl 7.8 benzofluorane (peach), 3.
3′・3″ tris(P dimethylaminophenyl) phthalide (dark blue), 3・3′ bis(P dimethylaminophenyl) phthalide (green), 3-diethylamino・6-methyl・7-phenylaminofluoran (black) Examples include colorless to light-colored dye bases selected from phenyl-substituted methane derivatives, fluorans, various indolylphthalides, spiropyrans, coumarins, etc. In the present invention, these dyes can be arbitrarily selected. However, the colors of these dyes are superior to those of ordinary pigments in terms of coloring power, sharpness, hue selectivity, etc.

Next, in the present invention, examples of acidic substances that color the pigments include phthalic acid, benzoic acid, terephthalic acid, pyromellitic acid, trimellitic acid, toluic acid, oxystearic acid, oxalic acid, lauric acid, stearic acid, and tartaric acid. , carboxylic acids such as citric acid, anthranilic acid, and their ammonium salts or metal salts, phenol, P-phenylphenol, β-naphthol, resorcinol, phloroglycine, hydroquinone, dihydroxynaphthalene, bisphenol S, phenolphthalene, Phenols such as phenolic resin oligomers and their salts, oxycarboxylic acids such as salicylic acid, oxybenzoic acid, ethyl oxybenzoate, salomethyl, resorcinic acid, methylenebissalicylic acid, salicylic acid amide, methyl β-oxynaphthoate, etc. Salts, various thiophenols and their derivatives, triazoles, tetrazoles, mercapto group-containing heterocyclic compounds, thiourea derivatives, phosphoric acid esters, sulfonates, and inorganic compounds such as zinc chloride, tin chloride, antimony oxychloride, etc. In the present invention, one or more of these may be used.

In this case, the durability and sharpness of the coloring material are greatly affected by acidic substances, so
The selection is extremely important. Specifically, in order to avoid an adverse effect on the color of the pigments and to facilitate encapsulation, the acidic substance used in the present invention should be colorless or light-colored and water-insoluble or poorly water-soluble. Particularly preferred are those.

In the present invention, the poorly water-soluble solvent with a boiling point of 150°C or higher is one that can dissolve the acidic substance and pigments, that is, one that facilitates contact between the two and acts as a carrier for the coloring material. In the present invention, for example, mesitylene, tetralin, paraffin, squalane, naphthalene, diethylbenzene, dodecylbenzene,
Hydrocarbons such as bicyclohexyl, diphenyl, cyclohexylbenzene, etc., halogenated hydrocarbons such as dichlorobenzene, chlornaphthalene, diphenyl chloride, trichlorotoluene, etc., many vegetable oils, animal oils, mineral oils and waxes, benzyl alcohol, Alcohols such as octadecyl alcohol, nonyl alcohol, terpineol, etc., ethers such as benzyl ethyl ether, phenetol, butyl phenyl ether, ethylene glycol dibutyl ether, crown ether, β-naphthol methyl ether, dimethoxybenzene, etc., benzyl acetate, trichlorhydric Resyl phosphate, butyl stearate, lauryl stearate, phenyl benzoate, dibutyl phthalate and other esters, cabrylamide, stearylamide, N-methyl lauramide, acetanilide, urea, diphenyl urea, phthalimide, etc. Examples include amides, isophorone, ketones such as cyclohexanone, and in the present invention, these may be used alone or in combination of two or more. The reason why the boiling point of these poorly water-soluble solvents is limited to 150°C or higher in the present invention is that solvents with lower boiling points are generally water-soluble or highly volatile, and are difficult to mix with both the above-mentioned dye and acidic substance. This is because the stability of

Next, in the present invention, each of the above components, namely, a poorly water-soluble pigment that develops color with an acidic substance, an acidic substance, and a boiling point of 150
A mixture obtained by homogeneously mixing the three components of the solvent at a temperature of ℃ or higher, or by making a melt, or by making any of the components into a dispersion, is emulsified in water. In such a case, a known emulsifier may be used. A homogeneous emulsion is prepared using high-speed stirring or ultrasonic waves using a dispersant or protective colloid.

In the present invention, a film-forming resin having a desired function is further added to the emulsion to coat the mixture. Examples of the film-forming resin include acrylic ester resin, vinyl acetate resin, Ethylene copolymer resin, polyester resin, nylon resin, vinyl chloride resin, vinylidene chloride resin, styrene/maleic acid copolymer resin, ethylene/maleic acid copolymer resin, polyvinyl alcohol/vinyl acetate resin, polyolefin resin, urethane Examples include thermoplastic resins such as resins, thermosetting resins such as phenolic resins, epoxy resins, unsaturated polyester resins, etc., and emulsion particles coated with these film-forming resins may further include melamine resins, urea resins, etc. It is cross-linked and cured with resin, epoxy resin, etc., or formaldehyde, acid chloride, epichlorohydrin, isocyanate compound, acid, etc. The colored particles thus produced have a clear color with extremely strong coloring power, and are water-resistant. It is insoluble and strong, making it difficult to break during or after the printing process.

By the way, these colored particles have a diameter of approximately 0.001
It is produced as spherical bodies with a size of 0.2 mm to 0.2 mm, but the particle size of such spherical bodies can generally be easily controlled by adjusting the stirring speed and the amount of emulsifier.

The colored particles according to the present invention are then filtered from water, and in the form of a water-containing wet cake or dry powder, one or more colors thereof are blended into a printing paste made of synthetic resin or the like. The synthetic resin that holds the colored particles in the glue may be an emulsion, a solvent solution, a plastisol, or a similar emulsion selected from the above-mentioned film-forming resins and cross-linking resins.
UV curable compositions and the like can optionally be used. In the present invention, in addition to the above-mentioned synthetic resin, the printing paste may contain various chemicals, such as surfactants, if necessary.
Thickeners, drying regulators, catalysts, crosslinking materials, solvents, ultraviolet absorbers, antioxidants, anti-aging agents, antifoaming agents, oils and fats, preservatives, extenders, dyes and pigments,
Fluorescent brighteners, metal powders, glitter pigments, glass bulbs, fragrances,
Although a foaming agent or the like may be added, such a case does not depart from the gist of the present invention.

The printing paste obtained in this manner is applied onto the object to be colored by a conventional printing method such as roll printing, gravure printing, screen printing, spraying, flexo printing, offset printing, coating, and padding. .

The object to be colored in the present invention is as follows:
Woven or knitted fabrics of natural fibers such as cotton, hemp, silk, and wool, recycled or semi-synthetic fibers such as rayon, kyupra, and acetate, and synthetic fibers such as polyolefin, polyamide, polyurethane, polyester, polyacrylic, and polyvinyl halide. mixtures thereof, films thereof, laminates thereof, non-woven fabrics, papers, etc.

Next, the printed colored body is subjected to treatments such as dry heat, steam heat, and UV irradiation as necessary, thereby revealing a pointillist pattern consisting of clear and rich colors.

Next, specific examples of the present invention will be shown.

Example 1 30 parts by weight of parafine wax (hereinafter, parts by weight are simply referred to as parts), 10 parts of stearamide, 4 parts of crystal violet lactone, 6 parts of zinc salicylate, Epicote 828 (trade name: manufactured by Yuka Ciel Co., Ltd.) , epoxy resin) 15 parts, Super Bethcamine J
-820 (trade name: Japan Reichhold Co., Ltd., butylated melamine) 4 parts of a homogeneous hot solution was poured into 150 parts of a 20% polyvinyl alcohol aqueous solution heated to 85°C under stirring, and the stirring speed was adjusted to give an average Particle size 50μ
Then, 6 parts of Epicure U (trade name: manufactured by Yuka Ciel Co., Ltd., curing agent) was added, and the mixture was heated and stirred at 85°C for 3 hours to form microcapsule particles onto a screen gauze. By filtering, washing with water, and dehydrating, 80 parts of blue-purple colored particles containing about 20% water were obtained. Such colored particles
Mix 80 parts with 2 parts of Demol SS (trade name, manufactured by Kao Soap Co., Ltd., dispersant) in 200 parts of water and stir.
℃ and added 5 parts of Denacol EX313 (product name: Nagase Biochemical Co., Ltd., water-soluble epoxy resin).
Then add 0.1 part of triethyltetramine, 85℃
If heated continuously for 2 hours, the epoxy resin will harden and become extremely robust colored particles.If these are filtered out, washed with water, and dried, 67 parts of blue-purple colored powder particles with a particle size of 50 μm will be obtained. . 10 parts of the colored particles thus obtained were added to a mixture of 15 parts of an acrylic acid ester emulsion copolymer (solid content 33%) and 75 parts of an oil-in-water emulsion containing 1% of methyl cellulose to form a printing paste. Obtained.

Next, in the above formulation, the so-called proton-sensitive dye, crystal violet lactone, was changed to 3-diethylaminobenzo-7,8-fluorane and malachite green lactone, and all else was carried out in the same manner to produce each print containing pink and green colored particles, respectively. Got the paste.

The blue-purple, pink, and green printing pastes obtained in this way were mixed in a weight ratio of 40:40:20, and the colored particles of the three colors were individually scattered in their original particle shapes. A mixed printing paste was obtained. Using the mixed printing paste, mechanical printing was performed on broad cotton fabric using a full-surface engraving roll, and after drying,
Dry heat treatment was performed at 140°C for 3 minutes. When the printed fabric thus obtained is viewed from a distance of 0.5 m, it can be observed as a colorful pointillist pattern made up of aggregations of small dots in three colors: bluish-purple, peach, and green.
When viewed from a distance of 10 meters, it could be observed as a marble-like plain color with a reddish-brown three-dimensional effect. Furthermore, the colored particles were not destroyed during the printing process, and the hue was clearer and the coloring power was better than that of conventional pointillist printed fabrics using pigments, and the washing fastness and abrasion fastness were also good. .

Example 2 25 parts of behenyl alcohol, 12 parts of lauryl stearate, 5 parts of 3-diethylamino-6-methyl-7-chlorofluoran, 3 parts of 5(6)chlor 1, 2, 3 benzotriazole, 3 parts of bisphenol S, Coronate T100 (product Heat and dissolve 10 parts of polyvalent isocyanate (manufactured by Nippon Polyurethane Co., Ltd.) in advance, and add 5 parts of this to Fuji Chemi HEC K-150 (product name: hydroxyethyl cellulose, manufactured by Fuji Chemical Co., Ltd.).
% aqueous solution under stirring, and adjust the stirring speed to form a fine particle suspension with an average particle size of 20μ. Furthermore, 20 parts of Nitsuporan 1066 (product name: manufactured by Nippon Polyurethane Co., Ltd., polyol) was gradually dropped there, and 45
Microcapsule particles produced by stirring at ~55°C for 8 hours were filtered through a screen gauze, washed with water, and dehydrated. Thus, the average particle size of the vermilion color containing about 20% water.
96 parts of 25μ colored particles were obtained. Furthermore, the colored particles 96
of Sumitekus Resin 260 (trade name: Sumitomo Chemical Co., Ltd., urea resin) was mixed with 2 parts of Demol N (product name: Kao Soap Co., Ltd., dispersant) in 250 g of water and heated to 85°C with stirring. ), then add 0.2 parts of Sumitex Accelerator (trade name: manufactured by Sumitomo Chemical Co., Ltd., curing agent), and continue heating for 3 hours to harden the urea resin, creating extremely durable colorant-containing capsules. becomes. Filter these out, wash with water,
It was dried to obtain 73 parts of vermilion particle powder with an average particle size of 25 μm. 10 parts of the colored particles thus obtained were mixed into 62 parts of an oil-in-water emulsion containing 25 parts of an acrylic acid ester emulsion copolymer (solid content 33%) and 1% of methyl cellulose.
1 part, 2 parts of Sumitex Resin M-3 (trade name: manufactured by Sumitomo Chemical Co., Ltd., modified methylolmelamine), and 1 part of a 30% magnesium chloride aqueous solution were added and mixed to obtain a printing paste.

Next, in the above recipe, the so-called proton-sensitive dye, 3-diethylamino-6-methyl-7-chlorofluorane, was changed to crystal violet lactone, and everything else was done in the same manner to obtain a printing paste with blue-purple colored particles scattered therein. Ta.

The vermilion and blue-purple printing pastes thus obtained were mixed at a weight ratio of 3:7, and the colored particles of the two colors were individually scattered in their original particle shapes. A mixed printing paste was obtained. 80 mesh screen pattern (polka dot pattern) on polyester taffeta fabric using the mixed printing paste
After drying, dry heat treatment was performed at 150° C. for 5 minutes to obtain a pointillist printed cloth. In this way, this printed cloth is
When viewed from a distance of 0.5m, it can be observed as a colorful polka dot pattern made up of clusters of small dots of two colors, vermilion and blue-purple, and when viewed from a distance of 10m, It could be observed as a polka dot pattern with a reddish-purple three-dimensional effect due to color mixing. still,
The colored particles are not destroyed during the printing process, and the pointillist printed fabric has a clearer hue and better coloring power than conventional pointillist printed fabrics using pigments,
Moreover, the washing fastness and abrasion fastness were also good.

Example 3 25 parts of cetyl alcohol, 3 parts of Crystoll 205 (trade name: liquid paraffin, manufactured by Etsuso Standard Oil Co., Ltd.), 15 parts of diphenyl, 3 parts of diethylamino.
4 parts of 6-methyl/7-phenylaminofluorane, 5 parts of bisphenol A, Uvinal 400 (product name:
Manufactured by BASF, UV absorber) 2 parts, Rigoratsuku
2063 (trade name: Showa Kobunshi Co., Ltd., unsaturated polyester) 13 parts was heated and dissolved in advance, and this was poured into 200 parts of a 6% gelatin aqueous solution under stirring.
Adjust the stirring speed to disperse into oil droplets with an average particle size of 70μ, then add 0.3 parts of 50% benzoyl peroxide and 0.15 parts of cobalt naphthenate and continue heating and stirring at 80°C for 10 hours to produce microcapsule particles. The mixture was filtered, washed with water, and dried to obtain 62.5 parts of black granules.

62.5 parts of the colored particles were dissolved in 200 parts of water.
Mix and stir with 2 parts of N, heat to 80°C, and add 3 parts of Sumitekus Resin A-1 (trade name: Polyacrylamide resin manufactured by Sumitomo Chemical Co., Ltd.), Sumitekus Resin.
Add 2 parts of 501 (trade name: manufactured by Sumitomo Chemical Co., Ltd., urea-melamine-formaldehyde initial condensate), then add 0.2 parts of Sumitex Accelerator MX (trade name: manufactured by Sumitomo Chemical Co., Ltd., curing agent) for 3 hours. When heating and stirring were continued, extremely strong colorant-containing capsules were obtained, which were collected by filtration, washed with water, and dried to obtain 64.7 parts of black particles with an average particle size of 70 μm. Adding and mixing 20 parts of the black particles to a mixture of 30 parts of an acrylic acid ester emulsion copolymer (solid content 33%) and 50 parts of an oil-in-water emulsion containing 1% of methyl cellulose,
A printing paste was obtained.

Next, in the above formulation, the so-called proton-sensitive dye 3-diethylamino-6-methyl-7-phenylaminofluorane was replaced with 3-diethylamino-6-methoxyfluorane and malachite green lactone.
Otherwise, printing pastes with yellow and green colored particles scattered therein were obtained using the same method. The black, yellow, and green printing pastes obtained in this way were adjusted to a weight ratio of 10:20:70, and
A mixed printing paste was obtained in which colored particles were individually powdered while maintaining their original particle shapes. Using this mixed printing paste, a polyester/cotton mixed broadcloth fabric was printed in the same manner as in Example 1. The thus obtained printed fabric had the same effect as in Example 1, and could be observed as a marble-like plain color with a three-dimensional effect consisting of small dots of three colors, black, yellow, and green.
In addition, the colored particles are not destroyed during or after the printing process, and compared to conventional pointillist printed fabrics using pigments, the colored particles have a clearer hue and excellent coloring power, and also have excellent washing fastness and friction resistance. The fastness was also good.

Example 4 15 parts of oleic acid amide, stearyl alcohol
25 parts of malachite green lactone, 3 parts of zinc benzoate, 3 parts of resorcinol, and 10 parts of Epicote 802 (trade name: manufactured by Yuka Ciel Co., Ltd., epoxy resin) were heated and dissolved in advance, and this was heated to 85°C. The mixture was poured into 150 parts of a 20% polyvinyl alcohol aqueous solution with stirring, and the stirring speed was adjusted until the average particle size was 20μ.
Then, 4 parts of Epicure T (trade name: manufactured by Yuka Ciel Co., Ltd., curing agent) was added, and the mixture was heated at 85°C.
The mixture was heated and stirred for 3 hours, and the resulting microcapsule particles were separated by filtration, washed with water, and dried to obtain 57 parts of green spherical particles. Add 57 parts of the colored particles to water.
Mix and stir 2 parts of Demol N (trade name: Kao Soap Co., Ltd., dispersant) into 200 parts, heat to 80°C, add 5 parts of benzoguanamine formaldehyde initial condensate, and then add 0.2 parts of a 20% ammonium chloride aqueous solution.
When the benzoguanamine resin is added and heated and stirred for 4 hours, the benzoguanamine resin hardens and becomes an extremely strong colorant-containing capsule. This was collected by filtration, washed with water, and dried to obtain 59.5 parts of green spherical particles with an average particle size of 20 μm. 10 parts of the green particles thus obtained were mixed with 90 parts of Okuno UV Color AL (trade name: photosensitive resin, manufactured by Okuno Pharmaceutical Co., Ltd.) to obtain a green printing paste. After coating the entire surface of the PP film with the paste using a knife coater, a high-pressure mercury lamp of 1KW (80W/cm) was irradiated at a distance.
A film was formed by irradiating at 10 cm for 10 seconds. The colored particles were not destroyed during or after printing, and exhibited a clear green color with great tinting power over the entire surface of the PP film, and could be observed as a three-dimensional marbling tone.

Example 5 15 parts of green spherical particles with an average particle size of 20 μ obtained in Example 4, 2 parts of Glow Yellow MF2G (trade name: Fluorescent pigment, manufactured by Matsui Shiki Kagaku Kogyo Co., Ltd.), acrylic acid ester emulsion copolymer (solid content 33%) and 65 parts of an oil-in-water emulsion containing 1% of methyl cellulose were mixed to obtain a printing paste. Using the printing paste, a screen type (80 meshes) with a large number of flower silhouette patterns was printed on a cotton broadcloth fabric, and after drying, a dry heat treatment was performed at 140°C for 3 minutes to obtain a cotton fabric with a pointillist pattern. Ta. The printed fabric is
When viewed from a distance of more than 0.5 m, it could be observed as a pointillist pattern with countless green dots arranged on a yellow ground, and when viewed from a distance of 10 m, it could be observed as a yellow-green flower pattern with a three-dimensional effect. . Also,
The colored particles are not destroyed during or after the printing process, and the hue is clearer and the coloring power is better than that of conventional pointillist printed fabrics using pigments, and the color fastness to washing and rubbing is also good. It was hot.

[Effect of the invention] Next, the effects of the present invention will be listed.

(1) The colored object obtained by the present invention has a pattern manifested by a collection of various small dots as constituent elements, and the marbling effect, multicolor effect, three-dimensional effect, discoloration effect, etc. of the pattern are noticeable. Demonstrate.

(2) The printing paste used in the present invention contains two
If colored particles of more than one color are individually scattered as they are, even if printed with one printing plate, the resulting colored object will be composed of aggregations consisting of dots of two or more colors. It is a manifestation of a pattern, and microscopically it has a multicolored effect due to the overlapping colors due to the adjacency of small dots, while macroscopically it exhibits the effect of a mixed color that has a three-dimensional effect by mixing colors in the visual area. do.

(3) The colored particles used in the present invention are hard granules with a uniform particle size, and depending on the manufacturing conditions, 0.001
Particles of arbitrary size within the range of 0.2mm to 0.2mm can be obtained, and the individual colored particles in the printing paste are individually scattered while maintaining their original particle shape, and the colored particles are separated in the printing paste. The particles will not be broken and become uniformly finely dispersed, and the components in the particles will not ooze out. Moreover, the storage stability of the printing paste is also good.

(4) The colored bodies obtained by the present invention have extremely clear, deep, and durable colors compared to conventional pigments.

Claims (1)

[Scope of Claims] 1. A mixture consisting of a poorly water-soluble dye that develops color with an acidic substance, an acidic substance serving as a coloring agent for the poorly water-soluble dye, and a poorly water-soluble solvent with a boiling point of 150°C or higher is emulsified in water, and then the emulsion is obtained. One or more colors of water-insoluble colored particles obtained by coating with a film-forming resin and cross-linking and curing are blended into a printing paste made of a synthetic resin or the like, and the printing paste is coated. A pointillist printing method characterized by printing on a colored object to reveal a pointillist pattern. 2. The pointillist printing method according to claim 1, wherein the acidic substance is colorless or light-colored and insoluble or poorly soluble in water.