JPH02283744A - Production of colored polymer powder or granule and coating material containing same - Google Patents

Abstract

PURPOSE:To prevent the formation of an unevenness in the pattern on a coating film by kneading a plasticizer with a colorant, adding a vinyl chloride resin of a specified particle diameter to the mixture, and agitating the resulting mixture under heating. CONSTITUTION:10-100 pts.wt. plasticizer (e.g. di-2-ethylhexyl phthalate) is kneaded with 2-10 pts.wt., per 100 pts.wt. plasticizer, colorant (e.g. carbon black), and 100 pts.wt. vinyl chloride resin powder with a mean particle diameter of 30-100mum is added to the above obtained mixture. The resulting mixture is stirred under heating to 80-150 deg.C to obtain a colored polymer powder or granule. This polymer powder or granule is kneaded with a water-based varnish, and an antifoamer, a thickener, etc., are optionally added to the mixture to obtain a coating material.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for producing colored polymer powder and a paint using this colored polymer powder, and its purpose is to produce wallpaper, synthetic resin sheets, etc. Colored polymer powder and granules that can be used to create fabrics, coatings and coatings with a suede-like appearance with a variety of marbling patterns, a supple and rough texture, and a visual appearance of colored patterns. The manufacturing method and the paint using this colored polymer powder are photographed.

(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 case of paint films on objects, small dots of colored pigments of different colors lined up on the surface were completely fused together, and could only be visually perceived as a patternless, single color, that is, a pink paint film, and lacked decorative properties. .

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 preparing colored particles of 0 μm and kneading different colored colored particles with water-based varnish, 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 uniformly disperse colored pigments by making them large, so if you make resin particles, form a coating film on the surface of these particles, and disperse these colored particles in varnish 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 monomers and colored pigments in water, but the colored pigments inhibited the polymerization, or only the monomers were polymerized, enveloping the colored pigments. Polymerization under these conditions was difficult.

Next, there are emulsion polymerization methods in which monomers, emulsifiers, and color pigments are mixed in water, interfacial polymerization methods in which polymerization is performed at the interface between the oil phase and the water phase, and polymerization methods in which color pigments and polymers are dissolved in a good solvent. Attempts were made to use a phase separation method in which a solvent was mixed, but in either case 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 surface of synthetic resin particles with an emulsion resin containing a colored pigment, and the yield is reduced. There was a drawback.

(Means for solving the problem) In the present invention, after kneading 10 to 100 parts by weight of a plasticizer and a colorant, 100 parts by weight of vinyl chloride resin powder having an average particle size of 30 to 100 μm is blended. All of the above problems are solved by providing a method for producing colored polymer powder, which is characterized by heating and stirring at 80 to 150°C, and a paint using this colored polymer powder.

(Structure of the Invention) In this invention, first, a plasticizer and a colorant are kneaded.

The plasticizer used in this invention is not particularly limited, and includes di-2-ethylhexyl phthalate, dihebutyl phthalate, di-n-octyl phthalate, dinonyl phthalate, dibutyl phthalate, butylbenzyl phthalate, diisodecyl acid, di-2-ethylhexyl tetrahydrophthalate, di-2-ethylhexyl adipate, diisodecyl adipate, di-2-ethylhexyl sepatate, 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.

The amount of plasticizer added is as follows: vinyl chloride resin powder 10
10 to 100 parts by weight, preferably 30 parts by weight
It is desirable that the amount be 80 parts by weight, particularly 30 to 6 parts by weight for vinyl chloride resin powder obtained by suspension polymerization.
It is desirable to use 1 part by weight, or 50 to 79 parts by weight if emulsion polymerization is used.

The reason for this is that if the blending amount of the plasticizer is less than 10 parts by weight per 100 parts by weight of the vinyl chloride resin powder, the particle surface of the vinyl chloride resin powder cannot be efficiently coated; If more than 1 part by weight of plasticizer is added, the vinyl chloride resin powder will become soft and sufficient coating strength will not be obtained, and adhesive force will develop between the particles, making it difficult to finally take them out as particles. This is because it becomes difficult.

Known colorants are preferably used, for example,
Examples include inorganic pigments such as titanium dioxide, amber, red iron, yellow lead, navy blue, carbon black, ultramarine, and manganese violet, and organic pigments such as Hansa yellow, benzidine erotic toluidine red, phthalocyanine blue, phthalocyanine green, and dioxazine violet.

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

The amount of colorant added is 2 to 100 parts by weight of the plasticizer.
The amount is preferably 100 parts by weight, particularly 20 to 100 parts by weight when the colorant is an inorganic pigment, and 2 to 10 parts by weight when the colorant is an organic pigment.

Next, the vinyl chloride resin powder is blended with the plasticizer mixed with the colorant, and the vinyl chloride resin powder is impregnated with the plasticizer by heating and stirring using a Hensel mixer or the like. .

The vinyl chloride resin powder used in this invention is not particularly limited, and examples include vinyl chloride homopolymer,
Vinyl chloride vinyl acetate copolymer, ethylene vinyl chloride copolymer, ethylene vinyl acetate vinyl chloride copolymer, urethane vinyl chloride copolymer, chlorinated vinyl chloride copolymer, etc., are produced by suspension polymerization method, emulsion polymerization method, etc. It is possible to use one formed by

The average particle size of this vinyl chloride resin powder is 30 to 1
00 μm, preferably 40 to 60 μm.

The reason is that when kneading different colored polymer powders,
Particles with a diameter of less than 30 μm 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.On the other hand, if the particle size exceeds 100 μm, the color distribution of the multicolored pattern becomes rough, resulting in a highly decorative fabric or a suede-like multicolored pattern. This is because not only does it not emit moisture, but it also feels rough to the touch, making it impossible to obtain a soft texture.

In particular, when the particle size is 40 to 60 μm, the texture is good and the fabric
The suede-like texture is most noticeable.

In this invention, the temperature conditions for heating and stirring are preferably 80 to 150°C.

The reason for stirring at a temperature of 80 to 150'C is that if the temperature is less than 8°C, the vinyl chloride resin powder cannot be impregnated with the plasticizer kneaded with the colorant, and as a result, the chloride The vinyl resin powder will not be colored, and 150'
This is because if it exceeds C, the vinyl chloride resin powder particles will soften and melt, resulting in large variations in particle size, which may cause uneven patterns in the coating film when applied to paints.

In this invention, organic tin compounds, metal soaps, stabilizers for vinyl chloride resins such as lead-based inorganic salts, phenol-based, organic sulfide-based, organic phosphite-based antioxidants, etc. are mixed. It is also possible to do so.

Through the above operations, the colorant is kneaded with the plasticizer, and this plasticizer is impregnated into the inside of the vinyl chloride resin powder, thereby substantially coloring the vinyl chloride resin powder and making it a colored polymer. Obtain granular material.

Next, a paint containing this colored polymer powder will be explained.

The colored polymer powder obtained as described above is kneaded into an aqueous varnish, and if necessary, an antifoaming agent, a thickener, etc. are 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.

(Effect of the invention) The method for producing colored polymer powder according to the present invention mainly involves kneading 10 to 100 parts by weight of a plasticizer and a coloring agent, and then kneading the colorant.
This is a method for producing colored polymer powder, which is characterized by blending 100 parts by weight of vinyl chloride resin powder with an average particle size of 30=100 μm and heating and stirring at 80 to 150°C, resulting in the following effects: play.

In other words, the plasticizer mixed with the coloring agent is impregnated inside the vinyl chloride resin powder particles, which have a size that can be discerned with the naked eye, so different colored polymer powder particles are prepared and mixed. By adjusting the color by adjusting the color, the small dots of colored particles arranged on the surface of the coating film can be visually perceived as a multicolored pattern similar to cloth or suede, which has excellent decorative properties.

Since the colored particles have a core of vinyl chloride resin powder 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.

Since paints using this colored polymer powder can have a matte multi-colored pattern finish, the hardness of the powder or varnish, By appropriately changing the flexibility, coatings with various tactile sensations can be obtained, and can be used for walls, 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) 50 parts by weight of di-π-octyl phthalate as a plasticizer,
After adding 40 parts by weight of titanium dioxide as a coloring agent, the mixture is kneaded.

Furthermore, the average particle size of the vinyl chloride resin powder is 40μ.
100 parts by weight of a vinyl chloride polymer (trade name: Zeon 103ZXA manufactured by Nippon Zeon (Kiki)) was blended and stirred using a Hensel mixer at a temperature of 105°C. Through the above operations, the average particle size was A colored polymer powder with a diameter of 42 μm was obtained.

(Example 2.3) The amount of di-n-octyl phthalate added as a plasticizer was 1
0 parts by weight (Example 2) and 8 parts by weight and 10 parts by weight of titanium dioxide.
It was prepared in the same manner as in Example 1 except that 0 parts by weight (Example 3) and 40 parts by weight of titanium dioxide were used, and the average particle size was 40 μm.
colored polymer powder (Example 2) and an average particle size of 48
Colored polymer powder (Example 3) of μm size was obtained.

(Comparative Examples 1 and 2) The amount of di-π-octyl phthalate added as a plasticizer was 3
It was prepared in the same manner as in Example 1 except that 0 parts by weight (Comparative Example 1) and 1) 0 parts by weight (Comparative Example 2) were used, but in Comparative Example 1, the fluidity of the mixture of colorant and plasticizer was small and it was not possible to heat and stir. However, in Comparative Example 2, colored polymer powders with an average particle size of 48 μm were obtained.

(Example 4) 50 parts by weight of di-4-octyl phthalate as a plasticizer,
After adding 40 parts by weight of titanium dioxide as a coloring agent, the mixture is kneaded.

Furthermore, the average particle size of the vinyl chloride resin powder is 30μ.
Mixed with 100 parts by weight of vinyl chloride polymer of
The mixture was stirred using a Hensel mixer at a temperature of .

Through the above operations, a colored polymer powder having an average particle size of 32 μm was obtained.

(Comparative Examples 3 and 4) Prepared in the same manner as in Example 4 except that a vinyl chloride polymer with an average particle size of 20 μm and a vinyl chloride polymer with an average particle size of 130 μm were used as the vinyl chloride-based synthetic resin, and the average A colored polymer powder (Comparative Example 3) with a particle size of 23 μm and a colored polymer powder (Comparative Example 4) with an average particle size of 132 μm were obtained.

(Example 5) 50 parts by weight of diisodecyl adipate as a plasticizer and 40 parts by weight of titanium dioxide as a colorant are mixed and then kneaded.

Furthermore, the average particle size of the vinyl chloride resin powder is 100.
100 parts by weight of a μm vinyl chloride vinyl acetate polymer (trade name: Denka Vinyl MM-90 manufactured by Denki Kagaku ■) was blended and stirred using a Hensel mixer at a temperature of 105°C.

By the above operations, a colored polymer powder having an average particle size of 1) 5 μm was obtained.

(Examples 6 and 7) Example 5 except that the temperature conditions during stirring in Example 5 were 80°C (Example 6) and 150°C (Example 7).
Colored polymer powders (Examples 6 and 7) having an average particle size of 1) 5 μm were obtained in the same manner as above.

(Comparative Examples 5 and 6) Prepared in the same manner as in Example 5 except that the temperature conditions during stirring in Example 5 were 70'C (Comparative Example 5) and 160°C (Comparative Example 6). A colored polymer powder (Comparative Example 5) with an average particle size of 1) 0 μm and a colored polymer powder (Comparative Example 6) with an average particle size of 132 μm were obtained.

(Test Example) 50 white colored polymer powders obtained in each example and comparative example
parts by weight, and 50 parts by weight of a green colored polymer powder prepared in exactly the same manner as in each Example and Comparative Example except that 5 parts by weight of the coloring agent was changed to phthalocyanine green. After mixing, 50 parts by weight of an aqueous varnish containing 55% non-volatile components was kneaded to obtain each coating composition.

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 selected at random and evaluated in increments of 1 point, with the best evaluation being 10 points and the worst being 0 points.
It is listed in the table.

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 are crushed, and if they are not crushed, mark ○,
Those that were crushed were marked with an x in Table 1 below.

(Margins below) 1. Table 3 can only be visually perceived as a pattern of a single color, and the appearance of a multicolored pattern was not obtained.

Comparative Example 4 had a coarse color distribution in appearance (unlike the multicolored pattern of cloth or suede, it had a unpleasant feel).

In Comparative Example 6, the particles were fused together and could not be taken out as particles.

As a result, in Examples 1 to 7, an appearance with a marbling-like multicolored pattern and flexibility were obtained, and in both cases, products with a cloth-like or suede-like texture were obtained.

In particular, Example 1 was excellent.

Claims (4)

[Claims] (1) After kneading 10 to 100 parts by weight of a plasticizer and a colorant, 100 parts by weight of vinyl chloride resin powder having an average particle size of 30 to 100 μm is blended, and the mixture is heated and stirred at 80 to 150°C. A method for producing a colored polymer powder consisting of: (2) The method for producing a colored polymer powder according to claim (1), characterized in that 20 to 100 parts by weight of an inorganic pigment is blended as the colorant to 100 parts by weight of a plasticizer. (3) The method for producing a colored polymer powder according to claim (1), characterized in that 2 to 10 parts by weight of an organic pigment is blended as the colorant to 100 parts by weight of a plasticizer. (4) A paint characterized by containing the colored polymer powder produced according to claims (1) to (3).