JPH07103256B2 - Colored polymer powder and method for producing the same, molded product and coating composition comprising colored polymer powder - Google Patents

Description

TECHNICAL FIELD The present invention relates to a colored polymer powder and a method for producing the same, a method for producing a molded product using the colored polymer powder and a coating composition, and The purpose is fine colored particles with an average particle size of 10 to 200 μm, and by making them an essential component of a coating composition, the appearance of a colorful pattern that should be called a variety of marbling, such as fabric or suede, and suppleness and roughness. A coating having a feeling of touch, a colored polymer powder capable of developing a coating film, a method for efficiently producing the colored polymer powder, and an automobile interior sheet or wallpaper A method that can easily obtain a molded product having excellent decorative properties, and further, the appearance of the multicolored pattern,
It is an object of the present invention to provide a coating composition having an excellent decorative property, which can provide a coating film having flexibility and texture having a texture.

(Prior Art) Conventionally, a coating composition is color-adjusted by kneading a color pigment of each color with a varnish.

However, the color pigment used in such a coating composition has a particle size of 10 μm in order to eliminate color unevenness, enhance dispersibility, and adjust color tone.
It is adjusted with particles of m or less.

In a normal paint, the smaller the particle size is, the more desirable it is.Therefore, even if an attempt is made to mix a red paint and a white paint to create a marbling pattern, the coating film of this paint composition has It was only visually perceived as a patternless single color in which small dots of differently colored coloring pigments juxtaposed completely melted together, that is, as a pink coating film, and the decorativeness was poor.

Therefore, as a result of intensive studies on the coating composition excellent in decorativeness as a multicolor pattern, the inventors of the present invention have disclosed Japanese Patent Application Laid-Open No. 63-145378, "Method for producing a multicolor pattern finish coating composition". Was obtained. With this method, small dots of colored pigments arranged in parallel on the surface of the coating film are excellent in decorativeness as a colorful pattern such as fabric and suede, and nonuniform pattern unevenness does not occur in the coating film. Has also been developed for the purpose of obtaining an excellent coating composition.

On the other hand, in JP-A-52-150444, a bulk specific gravity of about 0.1-
0.8 thermoplastic synthetic resin low foam particles (diameter 0.2 ~ 5.0m
m) and a synthetic resin emulsion paint containing aggregate, which is composed of a flexible synthetic resin emulsion, have been disclosed.

Further, in Japanese Examined Patent Publication No. 52-46970, 100 to 100 parts by weight of the inorganic fine particle powder, 10 to 100 parts by weight of polyvinyl chloride powder, an appropriate amount of a pigment are mixed, and the inorganic fine particle powder is added to the total amount thereof. 15-35% by weight of a resin solution consisting of a sticky solvent capable of sticking the polyvinyl chloride to a stick and a resin soluble in the solvent.
There has been disclosed a method for producing granules for coating, which is kneaded and granulated with a granulator.

However, the above-mentioned Japanese Patent Laid-Open No.
In the manufacturing method disclosed in 63-145378, it is difficult to coat the surface of the synthetic resin particles with an emulsion resin containing a coloring pigment by 100%, yield problems and problems regarding color development, and further increasing the particle size makes it excessive. There was the drawback of being rough.

Further, the technology disclosed in JP-A-52-150444 is an emulsion resin with aggregate having excellent physical properties,
There has been a problem that it is impossible to obtain particles having a particle size of 10 to 200 μm by coating the surface of the resin particles with a color pigment.

Moreover, in the thermoplastic synthetic resin low-foam particles disclosed herein, even when blended in a paint, the appearance of a multi-colored pattern that should be called a fabric or suede-like various marbling in the resulting coating film, There was a problem in that it was not possible to develop suppleness and a tactile sensation with a texture.

Furthermore, although the technique disclosed in Japanese Patent Publication No. 52-46970 can provide colored particles having the beauty of inorganic particles,
There was a problem that particles with a particle size of 200 μm could not be obtained.

Moreover, such inorganic particles have a problem in that they cannot exhibit the appearance of a marbling-like multicolored pattern as described above and the suppleness and texture of texture.

(Problems to be solved by the invention) In view of the above situation, the industry has an average particle size of 10 to 200 μm, which has a good yield and color development, and the appearance of a marbling-like multicolored pattern, suppleness and moderate roughness during use. It has been desired to create colored polymer powder and granules capable of exhibiting a feeling of touch, a method for producing the same, and a molded product and a coating composition comprising the colored polymer powder and granules.

(Means for Solving the Problem) The invention according to claim 1 has an average particle size of 10 consisting of 4.7 to 50% by weight of a plasticizer and 95.3 to 50% by weight of a vinyl chloride-based synthetic resin feed resin. A colored polymer powder having an average particle size of 10 to 200 μm, which has a coating film made of an emulsion resin containing a coloring pigment on the surface of particles of vinyl chloride synthetic resin having a particle size of ˜170 μm.

The invention described in claim 2 is a powder of vinyl chloride synthetic resin having an average particle size of 10 to 170 μm, which comprises 4.7 to 50% by weight of a plasticizer and 95.3 to 50% by weight of a vinyl chloride synthetic resin. , A mixture of a dispersion-stabilized mixture of a coloring pigment and an emulsion resin in an amount of 0.1 to 1.0 times the weight of the vinyl chloride-based synthetic resin, a metal salt is added to the mixed system, and particles of the vinyl chloride-based synthetic resin are mixed. Colored polymer powder having a mean particle size of 10 to 200 μm obtained by coagulating an emulsion resin containing a color pigment on the surface to form a film made of the emulsion resin. Is a manufacturing method.

The invention as set forth in claim 3, wherein the surface of the particles made of vinyl chloride synthetic resin having an average particle diameter of 10 to 170 μm, which comprises 4.7 to 50% by weight of a plasticizer and 95.3 to 50% by weight of a vinyl chloride synthetic resin. In addition, a colored polymer powder having an average particle diameter of 10 to 200 μm having a coating film made of an emulsion resin containing a color pigment, and comprising a mixture of different colored polymer powder particles. Is a molded product made of colored polymer powder particles.

A fourth aspect of the present invention is the surface of a particle made of vinyl chloride synthetic resin having an average particle diameter of 10 to 170 μm, which comprises 4.7 to 50% by weight of a plasticizer and 95.3 to 50% by weight of a vinyl chloride synthetic resin. In addition, for colored polymer powder having an average particle diameter of 10 to 200 μm having a coating film made of an emulsion resin containing a color pigment, a mixture of different colored polymer powder particles is contained as an essential component. It is a coating composition characterized by the following.

(Operation of the Invention) The operation of the invention described in claim 1 will be described.

The colored polymer powder of the present invention has an average particle size of 10 to 170 μm.
The vinyl chloride-based synthetic resin (2) contains 4.7 to 50% by weight of a plasticizer, so that it is softened, has a good feel, and has a good coloring property. If the plasticizer content is less than 4.7% by weight, the color developability deteriorates, and if the content exceeds 50% by weight, the vinyl chloride-based synthetic resin becomes too soft and causes adhesion between particles, so it is suitable for use. It's inconvenient.

The operation of the invention described in claim 2 will be described.

The plasticizer of 4.7 to 50% by weight of the present invention prevents the coloring pigment from adhering to the surface of the vinyl chloride-based synthetic resin powder and causes most of the particles to have a film made of an emulsion resin containing the coloring pigment. . Plasticizer content 4.7
If the content is less than 50% by weight, the emulsion resin cannot be efficiently coated on the surface of the vinyl chloride-based synthetic resin particles, and if the content exceeds 50% by weight, an adhesive force is generated between the particles and the particles are finally taken out as particles. Will be difficult.

The operation of the invention described in claims 3 and 4 will be described.

The plasticizer of 4.7 to 50% by weight contained in the present invention softens the particles to give a more supple feel, and prevents excessive graininess even if the particle size is increased. When the content of the plasticizer is less than 4.7% by weight, the particles become excessively rough when the particle size is increased, and when the content exceeds 50% by weight, the particles become too soft and the strength of the molded product and the coating film cannot be obtained.

(Example) Hereinafter, the Example of this invention is described.

First, examples of claims 1 and 2 will be described.

The colored polymer powder of the present invention is a fine particle colored product in which a film made of emulsion resin containing a coloring pigment is formed on the surface of vinyl chloride-based synthetic resin particles, and the average particle size is in the range of 10 to 200 μm. It is a polymer powder.

In order to produce such finely divided colored polymer powder, a mixture of a dispersion-stabilized coloring pigment and an emulsion resin, 4.7 to 50% by weight of a plasticizer and 95.3% to 50% by weight of Average particle size of vinyl chloride 10-170 μm
Mix the powder of vinyl chloride synthetic resin.

Here, as the emulsion resin, any emulsion resin is preferable as long as the emulsion stability is hindered by the presence of metal ions and the vinyl chloride-based synthetic resin particles containing a plasticizer described below adhere to the surface in the form of agglomerates or gels. For example, synthetic resins such as acrylic, styrene acrylic, polyester, polyurethane, vinyl chloride vinyl acetate copolymer, vinyl chloride acrylic copolymer and natural resins such as mastic, acaloid, benzoin, dragon blood, elemi, thunderac, etc. Is mentioned. There is no particular limitation on the surfactant, and cationic, anionic, nonionic, amphoteric, etc. surfactants are preferably used, and the amount added in order to destabilize the emulsion with respect to metal ions. Is preferably 1% by weight or less with respect to the amount of the emulsion resin added and the particle size of the emulsion resin is 0.1 μm or less, but is not particularly limited.

In addition, you may add a defoaming agent, a film-forming aid, etc. to emulsion resin as needed.

Known ones are preferably used as the color pigment, for example, titanium dioxide, amber, red iron oxide, yellow lead, navy blue,
Inorganic pigments such as carbon black, ultramarine blue, manganese purple,
Hansa Yellow, Benzidine Yellow, Toluidine Red,
Examples include organic pigments such as phthalocyanine blue, phthalocyanine green, and diosazine violet.

Further, extender pigments such as barite, calcium carbonate, clay and talc can also be used in combination with the above color pigments.

The amount of color pigment added is the solid content of the emulsion resin.
The amount is preferably 2 to 300 parts by weight with respect to 100 parts by weight, but is not particularly limited.

The vinyl chloride synthetic resin is not particularly limited, and examples thereof include vinyl chloride homopolymer, vinyl chloride vinyl acetate copolymer, ethylene vinyl chloride copolymer, ethylene vinyl acetate vinyl chloride copolymer, urethane vinyl chloride copolymer. It is possible to use a chlorinated vinyl chloride copolymer or the like formed by a suspension polymerization method or an emulsion polymerization method.

It should be noted that it is desirable to select a vinyl chloride-based synthetic resin in which the average particle size of the colored polymer powder to be finally obtained is 10 to 200 μm, and it may be somewhat affected by the plasticizer addition rate and the like. However, a vinyl chloride-based synthetic resin having an average particle size of 10 to 170 μm is used.

The plasticizer to be mixed with the vinyl chloride-based synthetic resin is not particularly limited, and includes di-2-ethylhexyl phthalate, diheptyl phthalate, di-n-octyl phthalate, dinonyl phthalate, dibutyl phthalate, butylbenzyl phthalate. , Diisodecyl phthalate, tetrahydrophthalic acid di-
2-ethylhexyl, di-2-ethylhexyl adipate, diisodecyl adipate, di-2-ethylhexyl sebacate, tricresyl phosphate, trioctyl phosphate, acetyltributyl citrate, trioctyl trimellitate, tridecyl trimellitate, butylphthalyl. Butyl glycolate, epoxidized soybean oil, diallyl phthalate, polyethylene glycol dimethacrylate and the like are preferably used.

It is desirable that the addition rate of the plasticizer is 4.7 to 50% by weight, preferably 23 to 44% by weight, based on the weight of the vinyl chloride-based synthetic resin after the addition of the plasticizer, and particularly, it is obtained by the suspension polymerization method. 33 to 44 for vinyl chloride synthetic resin
%, Preferably 23 to 38% by weight in the case of the emulsion polymerization method.

The reason for this is that if the plasticizer addition rate is less than 4.7% by weight, the emulsion resin containing the coloring pigment cannot be efficiently coated on the surface of the vinyl chloride-based synthetic resin particles, resulting in 50% by weight.
If a plasticizer is added in excess of the above, the particles of the vinyl chloride-based synthetic resin become soft and sufficient coating film strength cannot be obtained, and the adhesive force between the particles makes it difficult to finally take out the particles. This is because

As a method of mixing the vinyl chloride-based synthetic resin and the plasticizer, there is a method of using a Henschel mixer or the like. At this time, if necessary, a stabilizer and a modifier of the vinyl chloride-based synthetic resin are used. It is also possible to mix agents and the like.

The amount of the mixture of the emulsion resin and the color pigment used is 0 with respect to the weight of the vinyl chloride synthetic resin containing the plasticizer.
It is desirable to use 1 to 1 times the amount. The reason is that if the amount is less than 0.1 times, the particles of the vinyl chloride-based synthetic resin containing the plasticizer cannot be sufficiently covered, and the particles have poor colorability, and if the amount exceeds 1.0 times, only the particles of the emulsion resin are aggregated. This is because the gelled product is obtained and the particle strength is weakened.

If the amount of vinyl chloride-based synthetic resin is large, the fluidity becomes low. Therefore, water may be added to secure the fluidity, if necessary.

A metal salt is added to a mixed system of a mixture of such a coloring pigment and an emulsion resin and particles of a vinyl chloride resin to coagulate an emulsion resin containing a coloring pigment on the vinyl chloride resin particle surface, A film made of emulsion resin is formed.

The metal salt is not particularly limited, and for example, calcium chloride, barium chloride, aluminum sulfate, cuprous sulfate, ferric chloride, silver nitrate, lead acetate and the like are preferably used.

The reason why the metal salt is used is that the metal salt inhibits the stability of the emulsion resin containing the color pigment and causes the emulsion resin containing the pigment to coagulate on the particle surface of the vinyl chloride-based synthetic resin.

The addition amount of the metal salt is preferably an appropriate amount by determining the amount of the metal salt at the time of mixing the emulsion resin and the metal salt to cause aggregation and gelation.

Incidentally, it is also possible to add water to the metal salt and mix it as an aqueous metal salt solution, in which case the weight ratio of the emulsion resin solution containing the color pigment and the aqueous metal salt solution is 7 in consideration of the stability of the particles. : 3 to 3: 7 Preferably, it is set to 6: 4 to 5: 5, but it is not particularly limited.

In the present invention, a mixture of the color pigment and the emulsion resin as described above and particles of a vinyl chloride-based synthetic resin composed of a plasticizer and vinyl chloride are mixed and stirred, and the mixture and a metal salt are mixed to obtain a vinyl chloride-based resin. A dispersion liquid of colored polymer powder is obtained by forming a film of synthetic resin emulsion paint on the surface of synthetic resin particles.

The average particle size of the colored polymer granules obtained as described above is
It is desirable that the thickness is 10 to 200 μm, preferably 30 to 100 μm.

The reason is that when kneading colored polymer powder particles of different colors,
If the particle size is less than 10 μm, they cannot be visually identified, so particles of multiple colors cannot be visually perceived as a multicolored pattern, and if it exceeds 200 μm, the color distribution of the multicolored pattern becomes rough and decorative. This is because the excellent fabric, a suede-like multicolored pattern does not appear, and the touch is rough and a soft touch cannot be obtained.

When the particle size is 30 to 100 μm, the texture is good, and the texture of cloth or suede is most noticeable.

Next, an embodiment of the invention described in claim 3 will be described.

In this example, a colored polymer powder and a dispersion medium are separated from the dispersion liquid to obtain a colored polymer powder, and a molded product of the colored polymer powder is obtained by a molding method such as a fluidized-bed method. .

A fluidized dipping method as one of molding methods using the colored polymer powder is described with reference to the drawings.

FIG. 1 is a schematic diagram illustrating this molding method.

In the figure, (1) is a colored polymer powder, (2) is a container for containing the colored polymer powder, and (3) is a mold material.

The colored polymer particles (1) are placed in a container (2), the heated mold material (3) is immersed in the container (2), and the colored polymer powder particles (1) are placed on the outer surface of the mold material (2). ) Is fused to form a thin film.

Then, the mold material (3) is taken out of the container, cooled with water or air, and the molded product (4) is peeled from the mold material (3).

FIG. 2 is a vertical cross-sectional view showing a state in which the molding material (3) is covered with the molded product (4) of the colored polymer powder particles (1).

As another molding method, a method of sprinkling the colored polymer powder particles (1) on the surface of the heating mold material (3) and performing sexual formation can also be adopted.

The shape of the mold material (3) is not limited to the shape shown in the drawings, and the container (2) can be formed without heating the mold material (3).
It is also possible to melt the colored polymer powder particles (1) therein and form a thin film on the mold material (3).

Further, it is possible to add a plasticizer and a stabilizer to the colored polymer powder and obtain a molded product by a known molding method such as extrusion molding or injection molding.

The molded product thus obtained can be provided with a matte, multicolored pattern finish, and is a molded product with excellent decorative properties that can be suitably used for automobile interior sheets, wallpaper, and the like.

Next, an embodiment of the invention described in claim 4 will be described.

The dispersion of the colored polymer powder obtained as described above is used as it is, or the colored polymer powder is taken out and kneaded into an aqueous varnish, and an antifoaming agent or a thickener is added as necessary. To obtain a coating composition.

The water-based varnish is not particularly limited, and emulsion resins and water-soluble resins such as acrylic resins and vinyl acetate resins are preferably used.

It is possible to obtain a coating film having various tactile sensations by changing the hardness, flexibility or change of the above-mentioned aqueous varnish or colored polymer powder.

It is also possible to obtain a multicolor finish paint by appropriately combining various types of colored polymer powder particles of different colors and kneading them in an aqueous varnish.

Next, specific examples, comparative examples and test examples of the present invention will be listed.

Example 1 80 parts by weight of a styrene acrylic emulsion having a nonvolatile content of 47% as a synthetic synthetic resin (trade name: ACRONAL YJ1210D manufactured by Mitsubishi Yuka Perdishe Co., Ltd.) was mixed with 40 parts by weight of titanium dioxide as a color pigment.

Next, a vinyl chloride polymer having a mean particle size of 40 μm (trade name ZEON 103ZXA Nippon Zeon Co., Ltd.) as a vinyl chloride-based synthetic resin contains 29% by weight of di-n-octyl phthalate as a plasticizer. And mixed to prepare 150 parts by weight.

Emulsion resin containing color pigment and vinyl chloride synthetic resin containing plasticizer are mixed, and after adding an appropriate amount of water, 1.1 parts by weight of calcium chloride is mixed as a metal salt to obtain a colored polymer having an average particle diameter of 42 μm. A dispersion liquid of powder and granules was obtained.

(Comparative Examples 1 to 3) The addition rate of di-n-octyl phthalate as a plasticizer was 0.
% (Comparative Example 1), 3.9% (Comparative Example 2) and 52% (Comparative Example 3), except that they were mixed in the same manner as in Example 1 and having an average particle diameter of 42 μm. Dispersion of powder and granules (Comparative Example 1), dispersion of colored polymer powder having an average particle diameter of 43 μm (Comparative Example 2) and dispersion of colored polymer powder having an average particle diameter of 48 μm (Comparison) Example 3) was obtained respectively.

(Example 2) A dispersion of colored polymer powder having an average particle diameter of 45 µm was obtained in the same manner as in Example 1 except that aluminum sulfate was used as the metal salt.

(Example 3) As an emulsion resin, 40 parts by weight of titanium dioxide as a color pigment was mixed with 80 parts by weight of an acrylic emulsion having a nonvolatile content of 50% (trade name, Nicazole RX876, manufactured by Nippon Carbide Industry Co., Ltd.).

Next, the vinyl chloride synthetic resin has an average particle size of 130 μm.
Vinyl chloride polymer (trade name: Summit SX-D Sumitomo Chemical Co., Ltd.) with dibutyl phthalate as a plasticizer
400 parts by weight were prepared by mixing so as to contain 38% by weight.

Emulsion resin containing coloring pigment and vinyl chloride synthetic resin containing plasticizer are mixed, water is added in an appropriate amount, and then 0.6 parts by weight of calcium chloride is mixed as a metal salt to obtain a colored polymer having an average particle diameter of 145 μm. A dispersion liquid of powder and granules was obtained.

(Example 4) As an emulsion resin, 40 parts by weight of titanium dioxide as a color pigment was mixed with 80 parts by weight of an acrylic emulsion having a nonvolatile content of 50% (trade name, Nicazole RX876, manufactured by Nippon Carbide Industry Co., Ltd.).

Next, vinyl chloride synthetic resin with an average particle size of 100 μm
Vinyl chloride vinyl acetate polymer (trade name: Denka Vinyl
MM-90 Denki Kagaku Co., Ltd.) and mixed so as to contain 33% by weight of di-n-octyl phthalate as a plasticizer.
Parts by weight were prepared.

Emulsion resin containing coloring pigment and vinyl chloride synthetic resin containing plasticizer are mixed, and after adding an appropriate amount of water, 1.2 parts by weight of calcium chloride is mixed as a metal salt to obtain a colored polymer powder having an average particle diameter of 115 μm. A dispersion of granules was obtained.

(Comparative Examples 4 to 5) Prepared in the same manner as in Example 4 except that the mixing amount of the vinyl chloride-based synthetic resin containing the plasticizer was 2000 parts by weight (Comparative Example 4) and 15 parts by weight (Comparative Example 5). Then, a dispersion liquid of colored polymer powder having an average particle diameter of 115 μm was obtained.

(Example 5) As an emulsion resin, 40 parts by weight of titanium dioxide as a color pigment was mixed with 80 parts by weight of a styrene acrylic emulsion having a nonvolatile content of 47% (trade name: Acronal YJ1210D manufactured by Mitsubishi Yuka Birdish Co., Ltd.). .

Next, the average particle size of the vinyl chloride synthetic resin is 150 μm.
Ethylene vinyl chloride copolymer
1050 Tosoh Corp.) with phthalic acid di-n as a plasticizer
75 parts by weight were prepared by mixing so as to contain 9.1% by weight of octyl.

Emulsion resin containing color pigment and vinyl chloride synthetic resin containing plasticizer are mixed, and after adding an appropriate amount of water, 0.37 parts by weight of calcium chloride as a metal salt is mixed to give a colored polymer powder having an average particle diameter of 155 μm. A dispersion of granules was obtained.

(Example 6) As an emulsion resin, 80 parts by weight of a vinyl chloride vinyl acetate emulsion (trade name: Vinibrand 601, manufactured by Nisshin Chemical Co., Ltd.) having a non-volatile content of 43% was used, and titanium dioxide was used as a coloring pigment.
40 parts by weight were mixed.

Next, a vinyl chloride polymer (trade name ZEON 103ZXA Nippon Zeon Co., Ltd.) having a mean particle size of 40 μm as a vinyl chloride-based synthetic resin, and diisodecyl adipate as a plasticizer were used.
172 parts by weight were prepared by mixing so as to contain 29% by weight.

Emulsion resin containing color pigment and vinyl chloride synthetic resin containing plasticizer are mixed, and after adding an appropriate amount of water, 0.34 parts by weight of aluminum sulfate as a metal salt is mixed to give a colored polymer powder with an average particle diameter of 45 μm. A dispersion of granules was obtained.

(Comparative Example 6) As an emulsion resin, 40 parts by weight of titanium dioxide as a color pigment was mixed with 80 parts by weight of a styrene acrylic emulsion having a nonvolatile content of 47% (trade name: Acronal YJ1210D manufactured by Mitsubishi Petrochemical Pardische Co., Ltd.).

Next, as a vinyl chloride-based synthetic resin, a vinyl chloride polymer having an average particle size of 1 μm (trade name: Zeon 121 Nippon Zeon Co., Ltd.)
150 parts by weight was prepared by mixing di-n-octyl phthalate as a plasticizer in an amount of 29% by weight.

Emulsion resin containing color pigment and vinyl chloride synthetic resin containing plasticizer are mixed, and after adding an appropriate amount of water, 1.1 parts by weight of calcium chloride is mixed as a metal salt to give a colored polymer powder having an average particle diameter of 2 μm. A dispersion of granules was obtained.

(Comparative Example 7) A vinyl chloride-based synthetic resin was prepared in the same manner as Comparative Example 6 except that a vinyl chloride vinyl acetate polymer having an average particle size of 220 µm (trade name: Grafmer Nippon Zeon Co., Ltd.) was used. A dispersion liquid of colored polymer powder having an average particle diameter of 250 μm was obtained.

(Test Example) 50 parts by weight of white colored polymer powder particles taken out from the dispersions obtained in the above Examples and Comparative Examples, and 4.4 parts by weight in which the pigment was changed to carbon black in each Example and Comparative Example. Except for the above, it was prepared in exactly the same manner, and after mixing 50 parts by weight of the black colored polymer powder particles taken out, respectively, non-volatile components 55%
50 parts by weight of the above aqueous varnish was kneaded to obtain each coating composition.

The coating composition was applied twice to the surface of a slate plate test piece, and the appearance and touch of the coating film were examined.

The appearance was evaluated by visually observing the color clarity 2 hours after application.

The touch was evaluated 24 hours after application by touching with a fingertip and observing the presence or absence of roughness.

At the time of evaluation, panelists of 20 men and women were randomly selected, the best evaluation was 10 points, and the worst evaluation was 0 points, and the average score is shown in Table 1. .

Further, it was observed under a microscope whether or not the coating material sufficiently covered the particles, and Table 1 shows the coating property of each of those that are sufficiently coated and the coating property of each of which is not.

Further, as the particle strength, scratches were taken with a nail 30 days after application to examine whether or not the particles were crushed, and ◯ for uncrushed particles and × for crushed particles are also shown in Table 1.

As a result, in Examples 1 to 6, the appearance of a marbling-like multicolored pattern, the suppleness and the tactile sensation having an appropriate roughness are obtained,
Both fabrics and suede-like textures were obtained.

Particularly, Examples 1 and 2 were excellent.

On the other hand, Comparative Examples 1, 2, 4, and 5 have uneven appearance, particularly Comparative Example 1 is conspicuous of uncolored powder and granules, and Comparative Example 3 is highly tacky and sticky to the touch. In Comparative Example 6, only a single color pattern was visually perceived in appearance, and a multicolored pattern was not obtained.

Comparative Example 7 had a rough color distribution in appearance and was different from a fabric and a suede-like multicolored pattern, and further, it was too rough to the touch and had an unpleasant feeling.

From the above results, the average particle size of the colored polymer powder is 10 to 20.
0 μm (preferably 30 to 100 μm), plasticizer addition rate
It can be seen that 4.7 to 50% by weight (preferably 23 to 44% by weight) has excellent appearance and touch.

(Effect of the invention) The invention according to claim 1 is a vinyl chloride synthetic resin having an average particle size of 10 to 170 µm, which comprises 4.7 to 50% by weight of a plasticizer and 95.3 to 50% by weight of a vinyl chloride synthetic resin. Since it is a colored polymer powder having an average particle diameter of 10 to 200 μm and having a coating film made of an emulsion resin containing a coloring pigment on the surface of the manufactured particles, the following effects are exhibited.

That is, since this colored polymer powder contains 4.7 to 50% by weight of the plasticizer, vivid color development is obtained,
Moreover, the coating film can exhibit suppleness and a tactile sensation having an appropriate roughness.

Furthermore, since the colored polymer powder is made of resin particles whose particle size is adjusted in advance as a core (core) material, the particle size distribution of the colored particles is narrow, and uneven coating patterns do not occur in the coating film.

Further, since the colored particles have the particles of the resin which have been cured in advance as the core, the fastness of the coating film is excellent.

The invention according to claim 2 is a powder of vinyl chloride synthetic resin having an average particle size of 10 to 170 μm, which comprises 4.7 to 50% by weight of a plasticizer and 95.3 to 50% by weight of a vinyl chloride synthetic resin, The vinyl chloride-based synthetic resin is mixed with 0.1 to 1.0 times the weight of the coloring pigment and a dispersion-stabilized mixture of the emulsion resin, and a metal salt is added to the mixed system to obtain the vinyl chloride-based synthetic resin particle surface. A colored polymer powder having a mean particle size of 10 to 200 μm is obtained by coagulating an emulsion resin containing a colored pigment into a film to form a film made of the emulsion resin. Since it is a manufacturing method, the following excellent effects are exhibited.

That is, an average particle size of 10 to 10
The average particle size is obtained by forming a film of emulsion containing a color pigment on the surface of 170 μm vinyl chloride-based synthetic resin particles.
It is possible to efficiently obtain colored particles of 10 to 200 μm.

Moreover, since the vinyl chloride-based synthetic resin contains 4.7 to 50% by weight of the plasticizer, the particle surface of the vinyl chloride-based synthetic resin can be efficiently coated with the emulsion resin containing the color pigment. Further, since the colored particles obtained by this method contain a plasticizer, even if the particle size is increased, there is no excessive roughness.

The invention according to claim 3 is characterized in that the surface of particles made of vinyl chloride synthetic resin having an average particle diameter of 10 to 170 μm, which comprises 4.7 to 50% by weight of plasticizer and 95.3 to 50% by weight of vinyl chloride synthetic resin, Coloring, characterized in that the colored polymer powder having an average particle size of 10 to 200 μm and having a coating film made of an emulsion resin containing a color pigment, is a mixture of different colored polymer powder particles. Since it is a molded product made of polymer powder, it has the following excellent effects.

In other words, it is a molded product with a matte, colorful pattern finish,
It is a molded product with excellent decorative properties that can be used for automobile interior sheets and wallpaper.

The invention according to claim 4 is characterized in that the surface of particles made of vinyl chloride synthetic resin having an average particle size of 10 to 170 μm, which comprises 4.7 to 50% by weight of plasticizer and 95.3 to 50% by weight of vinyl chloride synthetic resin, A colored polymer powder having an average particle diameter of 10 to 200 μm having a coating film made of an emulsion resin containing a color pigment, containing a mixture of different colored polymer powders as an essential component. Since the coating composition is characterized by the following, the following excellent effects are exhibited.

That is, it is a coating composition having an excellent decorative property, which is capable of developing a coating film having a multi-colored appearance that should be called a variety of marbling like fabric or suede, and a suppleness and a texture having a texture.

Further, in this coating composition, a film having various tactile sensations can be obtained by appropriately changing the hardness and flexibility of the colored polymer powder or varnish, and the wall, home electric appliances, electronic devices, furniture, displays, etc. Can be used for.

[Brief description of drawings]

FIG. 1 is a schematic view for explaining a fluidized dipping method as one of the molding methods using the colored polymer powder particles according to the present invention, and FIG. 2 is a mold material coated on the molded product of the colored polymer powder particles. It is a longitudinal cross-sectional view showing a state. (1) …… Colored polymer powder (2) …… Container, (3) …… Molding material (4) …… Molded product

Claims (4)

[Claims] 1. An average particle size of 10 to 170 comprising 4.7 to 50% by weight of a plasticizer and 95.3 to 50% by weight of a vinyl chloride-based synthetic resin.
A colored polymer powder having an average particle size of 10 to 200 μm, which has a film made of an emulsion resin containing a coloring pigment on the surface of a vinyl chloride synthetic resin particle having a size of μm. 2. An average particle size of 10 to 170 consisting of 4.7 to 50% by weight of a plasticizer and 95.3 to 50% by weight of a vinyl chloride-based synthetic resin.
μm vinyl chloride synthetic resin powder and 0.1 to 1.0 times by weight of the vinyl chloride synthetic resin a dispersion-stabilized mixture of a coloring pigment and an emulsion resin are mixed, and a metal salt is added to this mixture system. Then, an emulsion resin containing a color pigment is coagulated on the surface of the particles of the vinyl chloride-based synthetic resin to form a coating film of the emulsion resin to obtain a colored polymer powder having an average particle diameter of 10 to 200 μm. A method for producing a colored polymer powder or granular material, comprising: 3. An average particle size of 10 to 170 comprising 4.7 to 50% by weight of a plasticizer and 95.3 to 50% by weight of a vinyl chloride-based synthetic resin.
Regarding a colored polymer powder having an average particle diameter of 10 to 200 μm, which has a film made of an emulsion resin containing a coloring pigment on the surface of a vinyl chloride synthetic resin particle having a particle size of 10 μm, A molded product composed of a colored polymer powder or granular material, characterized in that it is composed of a mixture of materials. 4. An average particle size of 10 to 170 comprising 4.7 to 50% by weight of a plasticizer and 95.3 to 50% by weight of a vinyl chloride synthetic resin.
Regarding a colored polymer powder having an average particle diameter of 10 to 200 μm, which has a film made of an emulsion resin containing a coloring pigment on the surface of a vinyl chloride synthetic resin particle having a particle size of 10 μm, A coating composition, which comprises a mixture of materials as an essential component.