JPH0241371A - Production of colored high polymer powder and molding method and coating using colored high polymer powder - Google Patents

Abstract

PURPOSE:To obtain the title powder having appearance with marbled and multicolored pattern and flexibility and roughness by blending a mixture of dispersed and stabilized colored pigment and emulsion resin with vinyl chloride based resin particle and adding a metal salt thereto. CONSTITUTION:(A) Mixture of dispersed, stabilized and colored pigment (e.g., titanium dioxide) and emulsion resin (e.g., acryric resin) is blended with (B) particle of vinyl chloride based synthetic resin containing 4.7-50wt.% plasticizer and (C) a metal salt is added to the blend system to form colored high polymer powder having 10-200mu average particle size and provide the aimed powder particle unit.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a method for producing colored polymer powder, a molding method using the colored polymer powder, and a paint. Colored polymer powder that can be used to create coatings and coatings on resin sheets, etc., for fabrics, suede-like marbled appearance, supple and rough texture, and coatings and coatings with colored patterns. The present invention provides a method for producing granules, a molding method using the colored polymer powder, and a coating material.

(Prior Art and its Problems) Conventionally, the color of a coating composition has been adjusted by kneading color pigments of various colors into a varnish.

However, the coloring pigments used in such coating compositions have a particle size of 10 to eliminate color unevenness, improve dispersibility, and adjust color tone.
The smaller the particle size is, the more desirable it is for ordinary paints. For example, even if you try to create a marbling pattern by mixing red and white paints, the paint composition In the paint film of an object, the small dots of colored pigments of different colors arranged on the surface are completely fused together and can only be visually perceived as a single color with no pattern, that is, a pink paint film, and it has decorative properties. There was a lack of

Therefore, as a result of intensive research into paint compositions with excellent decorative properties in the form of multicolored patterns, the inventors found that
If a paint composition is prepared by adjusting 0 μm colored particles and kneading different colored particles with an aqueous face, the colored particles arranged in parallel on the surface of the coating film will be visually visible as a multicolored pattern similar to cloth or suede. I found out that I can capture it.

In other words, it is impossible to increase the size of colored pigments and disperse them uniformly, so if you make resin particles, form a coating on the surface of these particles, and disperse these colored particles on a surface to make a paint, the above phenomenon can be avoided. The reason is that it can be obtained.

First, in order to obtain these colored particles, the inventors attempted pearl polymerization by mixing sulfur and colored pigments in water, but the colored pigments inhibited the polymerization, or only the monomers were polymerized and the colored pigments were not produced. Polymerization in a wrapped state was difficult.

Next, there is an emulsion polymerization method in which seven polymers, an emulsifier, and a coloring pigment are mixed in water, an interfacial polymerization method in which polymerization is performed at the interface between an oil phase and an aqueous phase, and a method in which a coloring pigment and a polymer are dissolved in a good solvent. We tried a phase separation method in which a poor solvent was mixed into the paint, but in both cases it was difficult to control the particle size, resulting in a wide particle size distribution, uneven coating patterns, and poor yields of colored particles. .

In particular, in the interfacial polymerization method, colored particles sometimes harden while remaining in a fluid state, resulting in hollow interiors, resulting in poor particle strength against nail scratches and the like.

In addition, the inventors have already disclosed (Japanese Unexamined Patent Publication No. 63-14
5378), the small dots of colored pigments arranged in parallel on the surface of the coating film form a cloth-like, suede-like multicolored pattern, which has excellent decorative properties.
It was developed with the aim of obtaining a coating composition that does not cause uneven patterns on the coating film and has excellent coating film fastness.

However, although this method of producing a coating composition is superior to conventional ones, in reality it is difficult to cover 100% of the emulsion resin containing colored pigments on the surface of synthetic resin particles, resulting in an increase in yield. There was a drawback.

(Means for solving the problem) In the present invention, a mixture of a dispersion-stabilized colored pigment and an emulsion resin, and particles of a vinyl chloride synthetic resin containing 4.7 to 50 weight percent of a plasticizer are used. Mix and add metal salt to this mixed system to obtain an average particle size of 10 to 200 μm.
All of the above problems are solved by providing a method for producing colored polymer powder, which is characterized by obtaining colored polymer powder.

(Structure of the Invention) In the present invention, the emulsion resin is one whose emulsion stability is inhibited by the presence of metal ions, and which aggregates or adheres in the form of a gel to the surface of vinyl chloride synthetic resin particles containing a plasticizer, which will be described later. For example, synthetic resins such as acrylic, styrene-acrylic, polyester, polyurethane, vinyl chloride-vinyl acetate copolymer, vinyl chloride-acrylic copolymer, mastic, acaroid, benzoin, dragon plad, elemi, Examples include natural resins such as Sandarasoku.

There are no particular limitations on the surfactant, and cationic, anionic, nonionic, amphoteric, and other surfactants are preferably used, and the amount added is important in order to destabilize the emulsion against metal ions. It is desirable that the amount of the emulsion resin be 1% by weight or less based on the amount of the emulsion resin added and the particle size of the emulsion resin be 0.1 μm or less, but there are no particular limitations.

In addition, an antifoaming agent, a film-forming aid, etc. may be added to the emulsion resin as necessary.

Known coloring pigments are preferably used, such as inorganic pigments such as titanium dioxide, amber, red iron, yellow lead, navy blue, carbon black, ultramarine blue, manganese purple, Hansa yellow, penzidine erotic toluidine red, and phthalocyanine blue. Examples include organic pigments such as phthalocyanine green and diosazine violet.

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

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

The vinyl chloride-based synthetic resin is not particularly limited, and includes, for example, vinyl chloride homopolymer, vinyl chloride vinyl acetate copolymer, ethylene vinyl chloride copolymer, ethylene vinyl acetate vinyl chloride copolymer, and urethane vinyl chloride copolymer. , a chlorinated vinyl chloride copolymer, etc. formed by a suspension polymerization method, an emulsion polymerization method, or the like can be used.

It is desirable to select this vinyl chloride-based synthetic resin so that the average particle size of the final colored polymer powder is 10 to 200 μm, and this may vary depending on the addition rate of plasticizer, etc. However, a vinyl chloride synthetic resin having an average particle size of 10 to 170 μm is preferably used.

The plasticizer to be mixed with the vinyl chloride 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, di-2 tetrahydrophthalate
-ethylhexyl, di-2-ethylhexyl adipate, diisodecyl adipate, di-2-ethylhexyl sepatate, tricresyl phosphate, trioctyl phosphate,
Acetyl tributyl citrate, trioctyl trimellitate, tridecyl trimellitate, butylphthalyl butyl glycolate, epoxidized soybean oil, diallyl phthalate, polyethylene glycol dimethacrylate, and the like are preferably used.

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

The reason for this is that if the plasticizer addition rate is less than 4.7% by weight, the emulsion resin containing the colored pigment cannot efficiently coat the particle surface of the vinyl chloride synthetic resin, and if the plasticizer addition rate exceeds 50% by weight, the plasticizer This is because, if added, the particles of vinyl chloride synthetic resin become soft, making it impossible to obtain sufficient coating strength, and also creating adhesion between the particles, making it difficult to finally take them out as particles. .

In addition, as a method of mixing the vinyl chloride-based synthetic resin and the plasticizer, there is a method using a Hensel mixer, etc. At this time, if necessary, a stabilizer or a modifying agent for the vinyl chloride-based synthetic resin may be mixed. It is also possible to mix agents, etc.

The amount of emulsion resin used is 0.0 when the amount of vinyl chloride synthetic resin containing plasticizer is 1 (part by weight).
5-2. O1 is preferably 0.1 to 1.

The reason for this is that if it is less than 0.05, it will not be possible to sufficiently cover the particles of vinyl chloride synthetic resin containing a plasticizer, resulting in particles with poor coloring properties, and if it exceeds 2.0, only the emulsion resin particles will aggregate. This is because a gelled product is obtained and the particle strength becomes weak.

Note that if the amount of the vinyl chloride synthetic resin is large, the fluidity will be low, so water may be added as necessary to ensure fluidity.

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

The reason for using the metal salt is that the metal salt inhibits the stability of the emulsion resin containing the colored pigment and causes the emulsion resin containing the pigment to coagulate on the particle surface of the vinyl chloride synthetic resin.

The amount of the metal salt to be added is preferably determined by mixing the emulsion resin and the metal salt and determining the amount of the metal salt that will coagulate into a gel.

In addition, it is also possible to add water to the metal salt and mix it as a metal salt aqueous solution. In this case, the layer ratio of the emulsion resin solution containing the colored pigment and the metal salt aqueous solution is set to 7 in consideration of the stability of the particles. :3 to 3 near, preferably 6:4 to 5:5
Although it is preferable to set the value to 1, it is not particularly limited.

In this invention, an emulsion resin containing a color pigment as described above and particles of a vinyl chloride synthetic resin containing a plasticizer are mixed and stirred, and this mixture is mixed with a metal salt.
A dispersion of colored polymer powder is obtained in which a coating of a synthetic resin emulsion paint is formed on the surface of vinyl chloride synthetic resin particles.

The average particle diameter of the colored polymer powder obtained as described above is preferably 10 to 200 μm, preferably 30 to 100 μm.

The reason is that when kneading different colored polymer powders,
Particles with a diameter of less than 108m cannot be individually identified with the naked eye, so
Visually, the particles of multiple colors melt together completely and cannot be perceived as a multicolored pattern, and if the particle size exceeds 200 μm, the color distribution of the multicolored pattern becomes rough, resulting in a suede-like multicolored pattern, which is a fabric with excellent decorative properties. This is because it is not smooth and the texture is rough when touched, making it impossible to obtain a soft texture.

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

The colored polymer powder and the dispersion medium are separated from the dispersion liquid, the colored polymer powder is taken out, and a molded product of the colored polymer powder is obtained by a molding method such as a fluidized dipping method.

The fluidized dipping method as one of the molding methods using this colored polymer powder will be explained based on 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 storing the colored polymer powder, and (3) is a mold material.

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

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

FIG. 2 is a longitudinal sectional view showing a state in which the mold material (3) is covered with a molded article (4) of the colored polymer powder (1).

Another molding method that can be used is to sprinkle the colored polymer powder (1) on the surface of the heated mold material (3) and mold it.

The shape of the mold material (3) is not limited to the shape shown in the drawings, and the shape of the mold material (3) is not limited to the container (2) without being heated.
It is also possible to melt the colored polymer powder (1) inside and form a thin film on the mold material (3).

Furthermore, it is also possible to add a plasticizer or a stabilizer to this colored polymer powder and obtain a molded product by known molding methods such as extrusion molding and injection molding.

Next, a paint containing this colored polymer powder as an essential component will be explained.

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 if necessary, an antifoaming agent or a thickener is added. to obtain a coating composition.

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

By changing the hardness and flexibility of the water-based varnish or colored polymer powder, it is possible to obtain coatings with various textures.

Note that it is also possible to obtain a multi-colored pattern finish paint by appropriately combining a wide variety of colored polymer powders of different colors and kneading them into an aqueous varnish.

(Effects of the Invention) This invention involves mixing a mixture of a dispersion-stabilized colored pigment and an emulsion resin with particles of a vinyl chloride synthetic resin containing 4.7 to 50% by weight of a plasticizer. This is a method for producing a colored polymer powder, which is characterized by adding a metal salt to a powder and obtaining a colored polymer powder having an average particle size of 10 to 200 μm.The method has the following effects.

In other words, the color is adjusted by mixing different colored colored particles on the surface of vinyl chloride synthetic resin particles whose size can be discerned with the naked eye. The dots are visually perceived as a multicolored pattern similar to cloth or suede, and are highly decorative.

Since the colored particles are cored with resin particles whose particle size has been adjusted in advance, the particle size distribution of the colored particles is narrow, and uneven patterns do not occur in the coating film.

Furthermore, since the colored particles have pre-cured resin particles as their core, the coating film has excellent fastness.

Furthermore, since the vinyl chloride synthetic resin contains a plasticizer, the emulsion resin containing the coloring pigment efficiently coats the particle surface of the vinyl chloride synthetic resin.

Molded products and paints using this colored polymer powder can be finished with a matte multi-colored pattern, so the molded products can be used for automobile interior sheets, wallpaper, etc. By appropriately changing the hardness and flexibility of the particles or varnish, coatings with various textures can be obtained.
It can be used in home appliances, electronic equipment, furniture, displays, etc.

Next, by listing examples, comparative examples, and test examples of this invention, the above effects will be made clearer.

(Example 1) Styrene acrylic emulsion with 47% non-volatile components as emulsion synthetic resin (trade name Acronal YJ12)
40 parts by weight of titanium dioxide as a coloring pigment was mixed with 80 parts by weight of 10D (manufactured by Mitsubishi Yuka Birdifsche).

Next, as a vinyl chloride-based synthetic resin, the average particle size is 40 μm.
A vinyl chloride polymer (trade name: Zeon 103ZXA, manufactured by Zeon Corporation) was mixed with di-n-octyl phthalate as a plasticizer in an amount of 29% by weight to prepare 150 parts by weight.

An emulsion resin containing a colored pigment and a vinyl chloride synthetic resin containing a plasticizer are mixed, an appropriate amount of water is added, and 1.1 parts by weight of calcium chloride as a metal salt is mixed to produce a colored product with an average particle size of 42 μm. A dispersion of polymer powder was obtained.

(Comparative Examples 1 and 2) 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). A dispersion of polymer powder (Comparative Example 1), a dispersion of colored polymer powder with an average particle size of 43 μm (Comparative Example 2), and a dispersion of colored polymer powder with an average particle size of 48 μm (Comparative Example 3) were obtained.

(Example 2) A dispersion of colored polymer powder having an average particle size of 45 μm was obtained by preparing 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 coloring pigment was mixed with 80 parts by weight of an acrylic emulsion containing 50% non-volatile components (trade name Nikazol RX876 manufactured by Nippon Carbide Industries).

Next, as a vinyl chloride-based synthetic resin, the average particle size is 130 μm.
m vinyl chloride polymer (trade name Sumilift 5X-D
(manufactured by Sumitomo Chemical Co., Ltd.) and dibutyl phthalate as a plasticizer was mixed to contain 38% by weight to prepare 400 parts by weight.

An emulsion resin containing a colored pigment and a vinyl chloride synthetic resin containing a plasticizer are mixed, an appropriate amount of water is added, and 0.6 parts by weight of calcium chloride as a metal salt is mixed to produce a colored product with an average particle size of 145 μm. A dispersion of polymer powder was obtained.

(Example 4) As an emulsion resin, 40 parts by weight of titanium dioxide as a coloring pigment was mixed with 80 parts by weight of an acrylic emulsion containing 50% non-volatile components (trade name Nikazol RX876 manufactured by Nippon Carbide Industries ■).

Next, as a vinyl chloride-based synthetic resin, the average particle size is 100 μm.
M of vinyl chloride vinyl acetate polymer (trade name: Denka Vinyl 11M-90 manufactured by Electrochemical Co., Ltd.) was mixed with di-n-octyl phthalate as a plasticizer at a content of 33 mff1%, and 76 overlapping parts were prepared. Prepared.

An emulsion resin containing a colored pigment and a vinyl chloride synthetic resin containing a softening agent are mixed, an appropriate amount of water is added, and 1.2 parts by weight of calcium chloride as a metal salt is mixed to produce a colored product with an average particle size of 115 μm. A dispersion of polymer powder was obtained.

(Comparative Example 4..5) The amount of vinyl chloride synthetic resin containing a plasticizer was 100%.
It was prepared in the same manner as in Example 4, except that it was 0 parts by weight (Comparative Example 4) and 15 parts by weight (Comparative Example 5), and the average particle size was 11 parts by weight.
A dispersion liquid of 5 μm colored polymer powder was obtained.

(Example 5) As an emulsion resin, a styrene acrylic emulsion (trade name: Acronal YJ121) containing 47% nonvolatile components was used.
40 parts by weight of titanium dioxide as a coloring pigment was mixed with 80 parts by weight of OD (manufactured by Mitsubishi Yuka Birdifushie Co., Ltd.).

Next, as a vinyl chloride-based synthetic resin, the average particle size is 150 μm.
m ethylene vinyl chloride copolymer (trade name: Lyuron E)
-1050 (manufactured by Tosoh)), phthalate di-
75 parts by weight were prepared by mixing so that n-octyl was contained in an amount of 9.1% by weight.

An emulsion resin containing a colored pigment and a vinyl chloride synthetic resin containing a plasticizer are mixed, an appropriate amount of water is added, and 0.37 parts by weight of calcium chloride as a metal salt is mixed to obtain a highly colored material with an average particle size of 155 μm. A dispersion of molecular powder was obtained.

(Example 6) As an emulsion resin, 40 parts by weight of titanium dioxide as a coloring pigment was mixed with 80 parts by weight of a vinyl chloride vinyl acetate emulsion (trade name: Vinibluff 6o1 manufactured by Nissin Chemical Co., Ltd.) containing 43% non-volatile components.

Next, as a vinyl chloride-based synthetic resin, the average particle size is 40 μm.
A vinyl chloride polymer (trade name: Zeon 103ZXA manufactured by Nippon Zeon ■) was mixed with diisodecyl adipate as a plasticizer so as to contain 29% by weight to prepare 172 parts by weight.

An emulsion resin containing a colored pigment and a vinyl chloride synthetic resin containing a plasticizer are mixed, an appropriate amount of water is added, and 0.34 parts by weight of aluminum sulfate as a metal salt is mixed to obtain a highly colored material with an average particle size of 45 μm. A dispersion of molecular powder was obtained.

(Comparative Example 6) As an emulsion resin, a styrene acrylic emulsion containing 47% non-volatile components (trade name Acronal YJ121) was used.
80 parts by weight of 0D (manufactured by Mitsubishi Yuka Verdissier ■) was mixed with 0 parts by weight of titanium dioxide as a coloring pigment.

Next, a vinyl chloride polymer (product name: Zeon 121 manufactured by Nippon Zeon ■) with an average particle size of 1 μm as a vinyl chloride-based synthetic resin was added to contain 29% by weight of di-n-octyl phthalate as a plasticizer. By mixing, 150 parts were prepared.

An emulsion resin containing a colored pigment and a vinyl chloride synthetic resin containing a plasticizer are mixed, an appropriate amount of water is added, and 1.1 parts by weight of calcium chloride as a metal salt is mixed to obtain a highly colored material with an average particle size of 2 μm. A dispersion of molecular powder was obtained.

(Comparative Example 7) The average particle size was A dispersion of colored polymer powder having a diameter of 250 μm was obtained.

(Test Example) 50 parts by weight of white colored polymer powder taken out from the dispersion obtained in each Example and Comparative Example and 4.4 parts by weight when the pigment was changed to carbon black in each Example and Comparative Example. 50 parts by weight of the black colored polymer powders were prepared in exactly the same manner except that they were mixed together, and then 50 parts by weight of an aqueous varnish containing 55% non-volatile components was kneaded to obtain each coating composition. I got something.

These coating compositions were applied twice to the surface of a slate board test piece to examine the appearance and feel of the coating film.

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

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

For the evaluation, 20 male and female panelists were randomly selected and evaluated in increments of 1 point, with the best evaluation being 10 points and the worst being 0 points, and the average scores for each are listed in Table 1. did.

Furthermore, it was observed with a microscope whether the particles were sufficiently coated with the paint, and the coatability was recorded in Table 1 as ○ if the paint was sufficiently coated, and × if it was not.

In addition, the particle strength was determined by scratching with a fingernail 30 days after application.
Check whether the particles can be soaked, and if they are not crushed, mark with ○.
Those that were crushed were also marked with an x in Table 1.

(The following is a blank space) As a result, Examples 1 to 6 had a marbled-like multicolored appearance, a supple texture and a moderately rough texture, and both had a cloth-like or suede-like texture.

In particular, Example 1.2 was excellent.

On the other hand, Comparative Examples 1, 2, and 4.5 had uneven appearance, and in particular, Comparative Example 1 had noticeable uncolored powder and granules.
Comparative Example 3 was highly sticky and sticky to the touch, and Comparative Example 6 was only visually perceived as a single color pattern, and no multicolored pattern appearance was obtained.

Comparative Example 7 had a coarse color distribution in appearance, unlike the multicolored pattern of cloth or suede, and was too rough to the touch, giving it an unpleasant feel.

From the above results, the average particle diameter of the colored polymer powder is 10 to 200 μm (preferably 30 to 100 μm), and the addition rate of plasticizer is 4.7 to 50% by weight (preferably 23 to 44% by weight). It can be seen that the product has excellent appearance and feel.

[Brief explanation of the drawing]

Fig. 1 is a schematic diagram illustrating the fluidized dipping method as one of the molding methods using colored polymer powder according to the present invention, and Fig. 2 shows a molded material coated with a molded material of colored polymer powder. It is a longitudinal cross-sectional view showing a state. (1) Colored polymer powder (2) Container (3) Mold material (4)
...Molded article procedure amendment 1986 Patent Application No. 191955 2, name of the invention Method for producing colored polymer powder and granule, molding method and paint using this colored polymer powder 3, amended Relationship with the Patent Case Patent Applicant Address 4-1-12 Tsurumi, Tsurumi-ku, Osaka Name Name Asahipen Co., Ltd. Representative Kuninaka
Kobun 4, agent address: 2-2-2 Dojima, Kita-ku, Osaka 8530
No. 6, No. 2 Eiwa Building Voluntary Issue 6. Subject of amendment: “Detailed explanation column of the invention in the specification” 7. Contents of amendment

Claims (3)

[Claims] (1) A mixture of a dispersion-stabilized colored pigment and an emulsion resin is mixed with particles of vinyl chloride synthetic resin containing 4.7 to 50% by weight of a plasticizer, and a metal salt is added to the mixed system. 1. A method for producing colored polymer powder, which comprises adding colored polymer powder to obtain colored polymer powder having an average particle size of 10 to 200 μm. (2) A method for molding colored polymer powder, which comprises fusion-forming a thin film of the colored polymer powder on the surface of a mold material, and then cooling and peeling it off to obtain a molded product. (3) A paint containing the colored polymer powder as an essential component.