JPH083472A - Production of colorant particle for dot coloring - Google Patents

Abstract

PURPOSE:To obtain the colorant particles which can be produced at a low cost by a simple treatment and can stably give the excellent visual effects characteristic of dot coloring. CONSTITUTION:A water-base liq. essentially contg. a thermoplastic resin, at least one thermosetting resin, and a pigment is spray dried to give particles with an average particle size of 5-500mum.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing colored particles for pointillistic coloring and a colored particle for pointillistic coloring obtained by the method.

[0002]

2. Description of the Related Art Conventionally, in the field of products in which color is important such as fibers, efforts have been made to give higher commercial value to products by enhancing the color effect. Various coloring materials and coloring methods have been investigated. One of such coloring methods is a method called stippling coloring. This method is intended to obtain a special visual effect such as a frost effect, a multicolor effect, a three-dimensional effect, etc., which cannot be obtained by ordinary uniform coloring, by forming a colored portion with innumerable small dots of one color or two or more colors. To do.

As a method for producing colored particles used for pointillistic coloring, a pigment and a thermoplastic substance are dispersed in an aqueous paste solution,
Next, a method is known in which an aqueous solution containing another paste that is incompatible with the paste in the solution is added to cause a two-phase separation into a sea-island texture, and then an electrolyte is added to gel the island component. (Japanese Patent Publication No. 50-34151). However, in such a method, since the particle size of the colored particles is determined mainly by adjusting the stirring speed, various factors such as the type and properties of the paste used, working conditions, and the like affect each other, It is very difficult to control the particle size with good reproducibility, and the manufacturing process itself is extremely complicated, resulting in poor production efficiency and inevitably high production cost. Further, since the obtained particles are a gelled product of a paste, the strength under actual use conditions is insufficient, and there is a major drawback that the particles are easily destroyed by the coating pressure during colored coating, for example. . Furthermore, when such particles are used as an aqueous printing paste or the like, the gelled product takes in water and swells, and as a result, the binding force is relatively lowered and a deflocculation state occurs, and the pigment is redispersed in the paste. Inconvenience also occurs. When such coloring particles are destroyed or re-dispersed, the colored product obtained using such colored particles has no difference from the visual effect in the case of ordinary uniform coating, and the visual effect peculiar to pointillistic coloring is obtained. I can't show it to the full.

Further, after dispersing the epoxy resin, urethane resin or the like and the pigment in water, a curing agent is added to cure the pigment, or the pigment is dispersed in an aqueous solution of a water-soluble condensation resin such as methylolmelamine. Heating with stirring
A method of obtaining colored particles by condensing by adjusting pH is also known. However, in these methods as well, it is difficult to control the particle size and classification is indispensable. Moreover, since it takes a long time to complete the reaction, the productivity is poor and the obtained colored particles are very expensive, which is inferior in practicality. It was a thing.

A method in which a pigment is dispersed in an aqueous solution using a thermoplastic resin or a paste whose solubility in water changes depending on pH, and the resin or paste is insolubilized by adjusting the pH with stirring to obtain particles. It is also known that, even in these methods, the particle size control depends only on the stirring speed, and it is difficult to obtain particles having a desired particle size. Moreover, the obtained particles were very unstable, and for example, even when prepared in an ink or the like, the particles swelled with time to give a colorless appearance.

Further, a method is known in which a pigment having an opposite potential and a resin or a paste are granulated by ion adsorption.
Since both particles are simply ionically adsorbed in the obtained particles and the binding force is extremely weak and they are easily broken during the coloring step, the effect of pointillistic coloring cannot be sufficiently exhibited.

As another method, a pulverizable melt mixture of various natural resins, synthetic resins, modified products thereof and pigments is mechanically pulverized and classified,
Although a method for obtaining colored particles is also known, it is essentially impossible to produce a large amount of crushed pieces having a certain particle size by such a method, and fine powder adheres to the surface of the obtained crushed pieces. Inevitably, there is a big problem that the fine powder greatly reduces the stippling effect.

The present invention has been made to solve the above-mentioned problems, and its main purpose is to produce colored particles for pointillistic coloring at low cost by a simple treatment operation,
Moreover, it is an object of the present invention to provide a method for producing colored particles for pointillistic coloring, in which the obtained colored particles can stably exhibit an excellent visual effect peculiar to pointillistic coloring.

[0009]

As a result of intensive studies to solve the above-mentioned problems, the present inventor has used a resin component composed of at least one of a thermoplastic resin and a thermosetting resin, and uses this together with a pigment. It has been found that the above object can be achieved by the method of spray-drying as an aqueous liquid, and the present invention has been completed here.

That is, in the present invention, an aqueous liquid containing at least one of a thermoplastic resin and a thermosetting resin and a pigment as an essential component is spray-dried to have an average particle size of 5 to 50.
The present invention relates to a method for producing colored particles for pointillistic coloring, wherein the particles are 0 μm in size, and the colored particles for pointillistic coloring obtained by the method.

In the present invention, it is necessary to produce a composite granulated product by using an aqueous liquid containing a pigment and a resin component by a specific means called spray drying. According to such a method, a composite granulated product containing a pigment can be produced by a very simple means, and the particle size of the granulated product can be easily adjusted with good reproducibility. The colored particles for pointillistic coloring obtained by this method are composite granules of a pigment and a resin, so are not easily broken, and even when used as an aqueous paste or the like, no inconvenient redispersion of the pigment occurs, and bleeding, etc. It is possible to provide a colored product which is free from the above problem and exhibits a clear and excellent visual effect. In the present invention, as the pigment, any conventionally known pigment can be used without particular limitation. Examples thereof include Hansa yellow, benzidine yellow, benzidine orange, pyrazolone orange, quinacridone red, various azo red organic pigments, dioxazine violet, anthraquinone yellow, phthalocyanine blue, indanthrene blue, and phthalocyanine green. Pigment; Fluorescent organic pigment obtained by coloring resin with fluorescent cationic dye or disperse dye; Commonly used such as chrome yellow, cadmium yellow, chrome orange, red pattern, cadmium red, cobalt purple, ultramarine blue, navy blue, viridian, emerald green Colored inorganic pigments; black inorganic pigments such as carbon black and iron black; body pigments or white inorganic pigments such as barium carbonate, talc, zinc white, titanium oxide, calcium carbonate, precipitated barium sulfate; zinc sulfide, calcium sulfide, zinc silicate , Zinc cadmium and the like alone or their copper, silver, manganese, bismuth, mesothorium, tritium activator, fluorescent pigments, phosphorescent pigments or night-light pigments composed of mixed sinters of metal oxides and rare earth elements; gold powder, silver powder, Metal powder pigments such as bronze powder, copper powder, aluminum powder; mica, M.I. I. O. , Glass spheres or the like or nickel, cobalt, copper, gold,
A metallic luster pigment coated with silver, palladium, titanium oxide, iron oxide, etc., a pearl pigment or a reflection type pigment; a microcapsule containing a thermochromic dye, a photochromic dye, etc., a reversible color change pigment such as solid solution particles or matrix particles, etc. Can be mentioned.

Further, as a special one which can be used as a pigment in the present invention, a disperse dye not containing a dispersant and a water-insoluble pigment such as oil color can be mentioned. In the granulation step, the dyes are dyed with the resin, so that the obtained colored particles for pointillistic coloring have properties similar to those of the fluorescent organic pigment.

The above-mentioned pigments may be used alone or in combination of two or more kinds.

In the present invention, it is necessary to use the above pigment in combination with a resin component composed of at least one of a thermoplastic resin and a thermosetting resin, and such a resin component is used to form a composite granule. As a result, it is possible to obtain colored particles for pointillistic coloring, in which breakage due to coating pressure during coloring coating hardly occurs, and redispersion of the pigment does not occur even when used as an aqueous paste or the like.

In the present invention, the thermoplastic resin is not particularly limited, and any conventionally known thermoplastic resin can be used. Examples thereof include polyethylene resin, polystyrene resin, polypropylene resin, polyester resin, polyamide resin, vinyl chloride resin, vinylidene chloride resin, vinyl acetate resin, acrylic ester resin, methacrylic ester resin, acrylonitrile resin, acrylamide resin, urethane resin. , Phenoxy resin, butadiene resin, polycarbonate resin, EVA
Resin, ethylene-vinyl chloride copolymer resin, EVA-vinyl chloride graft polymer resin, AAS resin, AES resin, A
S resin, ABS resin, ACS resin, MBS resin, chlorinated vinyl chloride resin, chlorinated polyethylene resin, chlorinated polypropylene resin, polyacetal resin, thermoplastic polyimide resin, polyetherimide resin, polyether resin, polyetheretherketone resin , Polyphenylene ether resin, polyphenylene sulfide resin, polymethylpentene resin, polyparamethylstyrene resin, polyethylene oxide resin, polyvinyl formal resin, polyamideimide resin, fluororesin, ketone resin,
Examples thereof include various homopolymers and copolymers such as coumarone resin, vinyl propionate resin, ionomer resin, cellulosic resin, and various liquid crystal polymers.

The thermosetting resin usable in the present invention is not particularly limited, and any conventionally known thermosetting resin can be used. Examples thereof include epoxy resin, phenol resin, melamine resin, guanamine resin, urea resin, urethane resin, alkyd resin, xylene resin, silicone resin, polyimide resin, crosslinkable acrylic resin, maleic acid resin, diallyl phthalate resin, DFK resin. , Vinyl ester resin, unsaturated polyester resin, polyoxybenzoyl resin, furan resin, and the like, and these are preferably used in a prepolymer state where curing is not completed as described later.

The above-mentioned thermoplastic resin and thermosetting resin may be used alone or in combination of two or more kinds.

When the above-mentioned thermoplastic resin is used in the present invention, the thermoplastic resin not only acts as a binder for fusion-bonding the pigments to each other, but also acts as an adhesive to the article to be colored. In the ink or paint containing the colored particles for pointillistic coloring, it is possible to obtain a colored product having excellent adhesive strength even if the amount of the adhesive component such as the binder is reduced or even if it is unused.

When a thermosetting resin is used, since the resin itself is excellent in hardness and heat resistance, the particles obtained are excellent in shape retention (breakage resistance) during the coloring process. Therefore, more vivid stippling coloring can be performed. However, since the thermosetting resin may not be able to provide a sufficient binding force between the pigments under the heating conditions during spray drying described below, in this case, a polymer protective colloid is used in combination or a spray drying step is performed. It is preferable to subject the particles to secondary drying (heat treatment).

Examples of the polymer protective colloid that can be used in combination with the thermosetting resin include various pastes, water-soluble polymers, and the like. Examples thereof include starches, agar, fungi, sodium alginate, tragacanth gum, gum arabic, Locust bean rubber, naphtha crystal rubber, dextran,
Natural polymers such as levan, glue, casein, gelatin, collagen; semi-synthetic cellulosic polymers such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose; synthetic polymers such as polyvinyl alcohol, sodium polyacrylate, polyethylene oxide, etc. Can be used. The amount of the polymeric protective colloid used is not particularly limited, but is usually about 0.001 to 1 part by weight with respect to 1 part by weight of the thermosetting resin.

In the present invention, considering the respective characteristics of the thermoplastic resin and the thermosetting resin as described above,
A resin may be arbitrarily selected and used according to the purpose, application, etc., and a thermoplastic resin and a thermosetting resin may be used together to synergistically utilize the characteristics of each resin. At that time, the blending ratio of the thermoplastic resin and the thermosetting resin may be arbitrarily adjusted in consideration of respective characteristics.

Next, a method for producing the colored particles for pointillistic coloring according to the present invention will be described.

First, an aqueous liquid containing a resin component consisting of at least one of a thermoplastic resin and a thermosetting resin and a pigment as essential components, and further containing the above-mentioned polymer protective colloid and the like, if necessary, is prepared. . The thermoplastic resin and the thermosetting resin can be added in the form of a solution, an emulsion, a suspension or the like using water or an organic solvent as a solvent or a dispersion medium, or can be added in a powder form as it is. Good. When a thermosetting resin is used, it is preferable to add it in the state of prepolymer which is not completely cured.

The ratio of the pigment and the resin which are the essential components in the aqueous liquid, that is, the ratio of the pigment and the resin in the obtained particles depends on the kind of the pigment and the resin used and is not particularly limited. Usually, when the amount of the pigment used is about 10 parts by weight or less relative to 1 part by weight of the resin, good colored particles can be obtained, and when the ratio of the resin is too small,
The binding force between the pigments becomes weak and tends to be broken. Further, there is no problem in reducing the ratio of the pigment, and particles close to colorless can be produced. However, in the case of producing ordinary colored particles, the amount of the pigment used is 1 part by weight per 1 part by weight of the resin. It is preferably about 0001 parts by weight or more.

The proportion (concentration) of the essential components in the aqueous liquid may be arbitrarily selected according to the drying conditions and the intended particle size of the particles, and is not particularly limited. Usually, it is preferably about 5 to 50% by weight. The proportion of water in the total solvent or dispersion medium in the aqueous liquid is preferably 50% by weight or more.

Further, in the aqueous liquid, any additive may be used in combination, if necessary, as long as it is an additive that can be blended in, for example, a commonly-prepared ink or paint. Examples of such additives include organic solvents, surfactants,
Polymer protective colloid, oil, wax, catalyst, electrolyte,
Plasticizer, resin cross-linking agent, wetting agent, softening agent, ultraviolet absorber,
Antioxidants, antistatic agents, preservatives, deodorants, repellents, insect repellents, antibacterial agents, insecticides, fungicides, rust inhibitors, pH adjusters, viscosity modifiers, flame retardants, lubricants, various dyes , Extender pigment,
Examples thereof include a fluorescent whitening agent, an anti-bleaching agent, an ultraviolet emission type dye, a drying regulator, a foaming agent, an antifoaming agent, a water repellent, a perfume, and various other stabilizers. In particular, as a resin component,
When a thermosetting resin is used, it is preferable to add an appropriate resin crosslinking agent, if necessary.

Next, the above-mentioned aqueous liquid material is put into a spray dryer at a constant speed to carry out spray drying to volatilize volatile components in the liquid material to form a composite granulated product. Colored particles for pointillistic coloring can be obtained. The conditions for spray drying are not particularly limited, and spray drying may be performed according to a conventional method using various ordinary spray dryers. Temperature, disk rotation speed, liquid feed rate, etc. It may be appropriately adjusted so as to obtain the target composite granulated product according to the type of the above.
The average particle size of the colored particles is required to be 5 to 500 μm. By setting the average particle size within this range, a colored product excellent in visual effect and having good touch, feel, friction fastness, etc. can be obtained. be able to. When the average particle size of the colored particles is less than 5 μm, the visual effect as a pointillistic coloring is poor, while when it exceeds 500 μm, the touch, feel, friction fastness and the like of the colored product are deteriorated or reduced. It is not preferable. The particle size of the colored particles can be extremely easily controlled by adjusting the concentration of the essential components in the aqueous liquid, the disk rotation speed of the spray dryer, the feeding speed of the liquid, and the drying temperature (spray dry temperature). It can be adjusted with good reproducibility. As described above, according to the method of the present invention, since the particle size of the colored particles can be easily adjusted with good reproducibility, colored particles having an arbitrary particle size and good uniformity can be obtained. Therefore, the colored particles are extremely useful in pointillistic coloring in which the superiority or inferiority of the visual effect depends on the size and uniformity of the particle size.

When the curing of the resin does not proceed sufficiently under the heating conditions during the spray-drying and the bond strength between the pigments cannot be sufficiently provided, as described above, the spray-drying may be performed as necessary. Secondary drying (heat treatment) of particles that have undergone the process
Can be applied. The heating conditions in this case may be appropriately determined according to the type of resin used.

The colored particles for pointillistic coloring obtained by the method of the present invention may be prepared by using one kind or two or more kinds thereof, a coloring composition of ordinary formulation such as a printing ink, a printing paste, a paint, a spray coloring agent, a coating agent and the like. Is prepared. Then, by performing printing, printing, coating, dipping, spraying, brush coating, etc. using the coloring composition according to a conventional method, a unique frost effect, multicolor effect, three-dimensional effect,
It is possible to obtain a colored product that exhibits a visual effect such as a washing effect. For example, when a printing paste is prepared by using colored particles of two or more colors and a printing cloth is obtained by printing this on a cloth, the printing part does not have a uniform mixed color pattern,
The pattern is composed of innumerable small dots of two or more colors. Microscopically, in addition to the individual color that each small dot presents, there is also a multiple color in the adjoining part of these small dots, which produces a variety of effects However, macroscopically, the effect of mixed colors having a stereoscopic view is exhibited by color mixing in the visual sense. In addition, in addition to the resin binder and the adhesive as an adhesive component, various additives as described above can be added to the various colored compositions described above, if necessary. At this time,
The particles of the present invention can be secondarily aggregated and used by preparing a colored composition using a resin binder having an electric potential opposite to that of the particles of the present invention.

By using the colored particles obtained according to the present invention in combination with various ordinary dyes and pigments, the color effect of the colored product can be further varied. For example, a colored product obtained by using a coloring composition obtained by using the colored particles obtained by the present invention and a general organic pigment in combination exhibits microscopically defrosting with small dots scattered in a uniform background color, and macroscopically. As a result, the multi-color effect that the color of the small dots appears to stand out independently of the background color is exhibited. Also,
By using a metal powder pigment or a pearl pigment in combination, it is possible to freely obtain a pointillized colored product having metallic luster or pearl luster.

The object to be colored with the coloring composition containing the colored particles for pointillistic coloring obtained by the present invention is not particularly limited, and examples thereof include woven fabric, knitted fabric, non-woven fabric, paper, plastics and wood. , Metal, ceramics and the like, and cloths, sheets, films, boards, sewn products, molded products and the like made of these.

Further, for example, a printing ink or the like containing the colored particles for pointillistic coloring is prepared, a transfer sheet is produced therefrom, and the transfer sheet is transferred to an object to obtain a desired pointillized colored product. You can also

[0033]

According to the present invention, the following excellent effects are achieved.

(A) According to the production method of the present invention, the particle size of the obtained particles can be adjusted easily and with good reproducibility, and the frost effect, the multicolor effect, the three-dimensional effect, and the washing effect peculiar to the pointillistic coloring are obtained. It is possible to extremely easily manufacture colored particles for pointillistic coloring that can stably exhibit the visual effects such as. In addition, the obtained colored particles for pointillistic coloring are produced very efficiently, so that the production cost is low.

(B) The obtained colored particles for pointillistic coloring are composite granules obtained by spray-drying an aqueous liquid containing a pigment and a synthetic resin as essential components. Even when it is used as the coloring composition, the undesired redispersion of the pigment does not occur. Further, it is possible to provide a colored product which has a uniform particle size, is free from adhesion of fine powder, is clear and has no problem such as bleeding and which exhibits an excellent visual effect.

[0036]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.
In the following examples, "parts" and "%" mean "parts by weight" and "% by weight", respectively.

Example 1 Methacrylic acid 4.7%, acrylonitrile 42.9%,
48% aqueous emulsion 50 of acrylic resin (Tg 90 ° C.) obtained using a monomer component consisting of 42.9% methyl acrylate and 9.5% ethyl acrylate 50
To 50 parts of water, 20 parts of phthalocyanine blue having an average particle size of about 0.4 μm was added and mixed with 5 parts of a dispersion liquid in 100 parts of water, and 50 parts of water was further added and sufficiently stirred to form an aqueous liquid material. Prepared.

Next, this aqueous liquid material was fed into an L-8 type spray dryer (manufactured by Okawara Kakoki Co., Ltd.) set at a spray dry temperature of 180 ° C. and a disk rotation speed of 15000 rpm to feed 1.0 l / h. Then, by spray-drying, about 24 parts of blue colored particles for pointillistic coloring, which are composite granules having an average particle diameter of about 50 μm, were obtained.

10 parts of the colored particles, 90 parts of an acrylic acid ester-based resin emulsion (printing binder, trade name: binder 350R; manufactured by Matsui Dye Chemical Industry Co., Ltd.) and 2 parts of an epoxy-based crosslinking agent are mixed to form a printing paste. Prepared,
Using the 80 mesh character pattern screen version,
The paste was printed on a cotton T-shirt and then heat-treated at 130 ° C. for 3 minutes.

The imprinted portion of the T-shirt was composed of clear blue dots when viewed from a close distance, but when viewed from a distance, it had a unique wash-out tone.
In addition, the printed part had almost the same touch feeling as the part other than the pattern, and was excellent in various fastnesses.

Example 2 40% aqueous emulsion of urethane resin (softening point 178.3 ° C.) (trade name: Sancure 861: manufactured by Suncore)
100 parts, 10 parts of a dispersion obtained by previously dispersing 10 parts of quinacridone red having an average particle size of about 0.2 μm in 40 parts of water, 50 parts of calcium carbonate having an average particle size of about 0.1 μm, 5 parts of ethylene glycol and 100 parts of water. Were mixed and stirred to prepare 265 parts of a uniform aqueous liquid.

The liquid material was spray-dried using the same spray dryer as in Example 1 at a spray dry temperature of 210 ° C., a disk rotation speed of 11000 rpm, and a feed speed of 1.5 liters / hour to obtain an average particle diameter of about 60 μm. About 90 parts of red colored particles for pointillistic coloring were obtained.

Next, 5 parts of the red colored particles, Example 1
A printing ink was prepared by mixing 5 parts of the blue colored particles obtained in 1 above and 90 parts of a urethane emulsion binder (trade name: AR binder GS; manufactured by Matsui Dye Chemical Industry Co., Ltd.), and one side was treated with a silicone resin. Screen plate with floral pattern (70 mesh) on a polyester film
Was used to print the ink. Next, when the ink printed surface is wet, hot-melt polyester resin powder (trade name:
Byron GM902, manufactured by Toyobo Co., Ltd.) is sprinkled on the entire surface of the film to a dry film thickness of about 200 μm, excess powder adhering to parts other than the pattern part is removed, and dried at 25 ° C. to form a floral pattern. A transfer printing sheet having the above was obtained.

The printed surface of the transfer printing sheet was brought into contact with the back surface of the cotton shirt, treated with a heat press machine at 160 ° C. for 5 seconds, and then the polyester film was peeled off to remove the flowers on the back surface of the shirt. The pattern was transferred.

The pattern portion of the obtained shirt is composed of small dots of red and blue when viewed from a close distance, but it is remarkable that it can be observed as a purple floral pattern having a stereoscopic view from a distance. The visual effect was great. Also,
The texture, feel and various fastnesses of the patterned portion were all good.

Example 3 55% of ethylene-vinyl acetate copolymer (Tg 0 ° C.)
70 parts of aqueous emulsion, 50 parts of chrome yellow having an average particle size of about 0.7 μm, 20 parts of cadmium red having an average particle size of about 0.3 μm, 8 parts of polyethylene glycol, 0.5 part of a silicone antifoaming agent and 200 parts of water are mixed. , And stirred to prepare an aqueous liquid.

Next, using the same spray dryer as in Example 1, a spray dry temperature of 130 ° C. and a disk rotation speed of 1 were used.
The liquid material obtained above was set at 8000 rpm, and was fed at a feed rate of 2.0 liters / hour and spray-dried to obtain orange stippling coloring particles having an average particle diameter of about 45 μm.

In addition, 50 parts of chrome yellow and 20 parts of cadmium red in the above aqueous liquid are mixed with chrome yellow 7
An aqueous liquid which was replaced with 0 part was prepared, and similarly 50 parts of chrome yellow and cadmium red 2 in the above aqueous liquid were prepared.
Aqueous liquids were prepared in which 0 parts were replaced with 70 parts of cadmium red, and using these liquids, yellow pointillistic coloring particles and red pointillistic coloring particles were produced respectively.

Three parts each of the three colored particles thus obtained, 20 parts of vinyl chloride-vinyl acetate copolymer resin, 30 parts of methyl ethyl ketone, 60 parts of xylene and a polyoxyethylene alkyl ether type surfactant were used. 1
And a paint were prepared and uniformly sprayed onto a vinyl chloride table cloth by hand spraying.
The obtained table cloth had an orange color on the entire surface when viewed from a distance, but when viewed from a close distance, it was a beautiful one composed of the above-mentioned vivid dots of three colors and had good rubbing fastness.

Example 4 To 15 parts of melamine (trade name: Nicamin; manufactured by Nippon Carbide Co.), 29 parts of 37% aqueous formalin solution was added,
The pH was adjusted to 8 with a 10% aqueous sodium carbonate solution, and the mixture was reacted in a warm water bath at 90 ° C. for 30 minutes while stirring to give about 4 syrup-like methylol melamine aqueous solution.
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Next, in 200 parts of 10% aqueous solution of gum arabic, 5 parts of aluminum powder and 30% aqueous dispersion of photochromic microcapsules (trade name: Photopia Aquarite Ink Yellow AQ-G; manufactured by Matsui Pigment Chemicals Co., Ltd.) ) 150 parts was added and dispersed uniformly, 10 parts of the above methylol melamine aqueous solution was added thereto, and tartaric acid was gradually added while stirring to adjust the pH to 5 to prepare an aqueous liquid.

Subsequently, the same spray dryer as in Example 1 was set at a spray drying temperature of 190 ° C. and a disk rotation speed of 13000 rpm, and the above aqueous liquid material was charged at a feed rate of 1.2 liters / hour for spray drying. To obtain a composite granulated product,
After heat treatment at 0 ℃ for 10 minutes, average particle size is about 50μm
To obtain colored particles for pointillistic coloring.

On the other hand, 0.2 parts of phthalocyanine blue, 30 parts of precipitated barium sulfate and 1 part of water were added to an aqueous dispersion of photochromic microcapsules used in the above aqueous liquid material.
Colored particles for pointillistic coloring different from the above were produced in the same manner except that the amount was changed to 00 parts.

One particle each of the particles thus obtained is
A mixture of 0 part and 20 parts of ethyl cellulose and 150 parts of ethyl alcohol is used as a coating agent, and a clay coat paper (52 g / m ² ) is coated on one side with an air knife coater so as to have an adhesion amount of 50 g / m ² and dried. did.

The coated surface of the obtained coated paper can be observed as a set of blue dots having a metallic luster when viewed from a close place in a place not exposed to sunlight, and when viewed from a distance, the entire surface has a dull metallic luster. Although it could be observed as a plain marbled surface, it could be observed as small dots of blue and yellow with metallic luster when viewed from the sun in a place where it was exposed to sunlight, and a green stereoscopic view with a dull metallic luster when viewed from afar. It could be observed as a plain surface with a frosted surface. By cutting the coated paper into an appropriate size,
It can be used as wrapping paper or colored paper that exhibits such a unique visual effect.

Example 5 100 parts of water, 50% aqueous dispersion of pink fluorescent pigment (trade name: Glow Color Pink MIB; manufactured by Matsui Dye & Chemical Co., Ltd.) 1
After uniformly mixing 20 parts, 50 parts of the acrylic resin aqueous emulsion used in Example 1, and 3 parts of the methylolmelamine aqueous solution obtained in Example 4, tartaric acid was gradually added to adjust the pH to 5, An aqueous liquid was prepared.

Next, using the same spray dryer as in Example 1, a spray dry temperature of 170 ° C. and a disk rotation speed of 1 were used.
The mixture was set at 3000 rpm, the above-mentioned aqueous liquid was added at a feed rate of 1.3 liter / hour, and spray-dried to obtain a composite granulated product, which was further heat-treated at 150 ° C. for 5 minutes. Thus, colored particles for pointillistic coloring having an average particle diameter of about 55 μm and exhibiting a fluorescent pink color were obtained.

Further, in the same manner, an aqueous dispersion of the pink fluorescent pigment in the above aqueous liquid is added to 50% of the yellow fluorescent pigment.
Aqueous liquid (trade name: Glow Color Yellow MI2G; manufactured by Matsui Dye and Chemical Industry Co., Ltd.) was replaced with 120 parts of an aqueous dispersion, and an aqueous dispersion of a pink fluorescent pigment in the above-mentioned aqueous liquid was replaced with a blue fluorescent pigment. 50% aqueous dispersion (trade name: Glow
(Color Blue MIBR; manufactured by Matsui Pigment & Chemical Industry Co., Ltd.) Aqueous liquid materials were produced in place of 120 parts respectively, and these liquid materials were used in the same manner as described above to exhibit point yellow coloring particles and fluorescent blue particles. Each of the stippled coloring particles was produced.

With respect to the colored particles for fluorescent pointillistic coloring obtained above, 5 parts of pink, 70 parts of yellow and 15 parts of blue were used, and 120 parts of a 40% aqueous emulsion of a butadiene-styrene copolymer, 1 part of hydroxyethyl cellulose were used.
0 parts and 500 parts of water were mixed to obtain a printing paste.
The printing paste was printed on a nylon fabric using a screen plate (100 mesh) on which a silhouette pattern of flowers was arranged, dried and then heat-treated at 150 ° C. for 5 minutes.

The imprinted portion of the nylon woven fabric was observed as a colorful flower pattern composed of a set of small dots of fluorescent pink, fluorescent yellow and fluorescent blue when viewed from near, but when viewed from a distance, 3 It could be observed as a flower pattern having a three-dimensional view of fluorescent grass color with mixed colors. The various fastnesses and feel of the printed portion were good.

Example 6 10 parts of colored particles for stippling coloring obtained in Example 1 (anionic), 10 parts of 10% chitosan F (cationic paste), cationic acrylic ester emulsion (trademark: binder MRC, Matsui) 30 parts, water 20
Part, 27 parts of a turpentine and 3 parts of an emulsifier were printed on a white cotton broad cloth using an 80 mesh screen plate. In the obtained colored product, compared with the colored product obtained in Example 1, 2 due to the ion complex was used.
Due to the secondary aggregation, the colored particles are about 20% larger,
The stippling effect was more clear.

Comparative Example 1 Aqueous Emulsion 50 of Acrylic Resin Used in Example 1
Parts were used in the same manner as in Example 1 except that 24 parts of methyl cellulose and 76 parts of water were used instead of 50 parts of water and 50 parts of water.

A printing paste was prepared using the particles in the same manner as in Example 1. The pigment was redispersed in the paste to form a uniform blue paste, and the print obtained by using the paste was a uniform blue color. And the same as that of a printed material using a usual pigment, and no effect as a pointillistic coloring was obtained.

Comparative Example 2 500 parts of water was further added to the aqueous liquid material in Example 1 and the disk rotation speed of the spray dryer was 4000.
When spray drying was performed at 0 rpm in the same manner as in Example 1, blue particles having an average particle size of about 4 μm were obtained.

When printing was carried out using the particles in the same manner as in Example 1, the printed portion had an almost uniform blue colored surface, and the effect as pointillistic coloring was not obtained.

[0066]

Claims (2)

[Claims] 1. An aqueous liquid containing at least one of a thermoplastic resin and a thermosetting resin, and a pigment as an essential component is spray-dried to obtain a granular material having an average particle diameter of 5 to 500 μm. A method for producing colored particles for stippling coloring. 2. Colored particles for pointillistic coloring having an average particle size of 5 to 500 μm obtained by spray drying an aqueous liquid containing at least one of a thermoplastic resin and a thermosetting resin, and a pigment as an essential component.