JPH0625564A - Coating composition - Google Patents

Abstract

PURPOSE:To obtain a coating composition having a colorful pattern feeling of suede touch and a pepper-and-salt tone and excellent decoration free from sag during coating and coating unevenness, comprising a specific colored polymer powder or granule and specific short fibers. CONSTITUTION:This coating composition comprises (A) colored polymer powder or granule having 10-80mum average particle diameter obtained by covering the surface of particles of a synthetic resin such as vinyl chloride-based synthetic resin with a coating film of a synthetic resin containing colored pigment such as titanium dioxide and (B) short fibers such as rayon of 0.3-10mm length.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition, and its purpose is to provide a suede-like multi-colored pattern with a marbling effect on a coating film after coating, and to provide a light texture even if it is lightly colored. An object of the present invention is to provide a coating composition that does not lose the sense of multicolored pattern when viewed from above, can reveal a clear multicolored pattern, and does not cause sagging or uneven coating during coating.

[0002]

2. Description of the Related Art Color adjustment in a coating composition is performed by kneading a color pigment of each color with a varnish. As the color pigment used, the particle size is adjusted with particles of 10 μm or less so that there is no color unevenness and the dispersibility of the paint is high. Generally, the particle size of the color pigment should be as small as possible. Are required to maintain the color tone after coating. On the other hand, from the variety of consumers' preferences and changes in preferences,
In addition to a single color, there has been growing interest in paints that can express a wide variety of two or more colors.

Therefore, a "multicolored paint" has been proposed as a paint for forming a coating film containing two or more distinguishable colors by one coating. This "multicolored paint" is composed of a dispersion medium and a dispersion, and the two do not mix with each other, but are in a state in which they are dispersed or suspended in suitable particles, and are "scattered" by spraying or roller coating. It was a paint that brought out.

[0004] Such "multicolored paint" is a paint composition which gives a variety of colors different from the conventional single color paints. However, there are changes in the taste of consumers and variety of tastes. From the demand, there has been earnestly researched a coating composition that brings out a variety of colors, which is different from the "multicolored coating".

Therefore, it is possible to use two or more distinguishable colors.
Attention has come to be focused on paints that produce a "marbling" -like multicolored pattern in which two or more color particles are more finely dispersed, rather than a "scattering-like" pattern. In order not to show colorful patterns,
Even if pigments of different colors were mixed using particles with a particle size of 10 μm or less, the small dots of the pigments juxtaposed on the surface were completely melted together, and it was only visually recognizable as a single patternless color. . That is, even if an attempt is made to create a "marbled pattern" composed of a mixture of red and white using such fine particles, it can only be visually perceived as a pink coating film, and particles of two or more desired colors can be obtained. However, there was a problem that it was not possible to reveal a "Marbled" -like multicolored pattern that was more finely dispersed.

[0006] The inventors of the present invention have earnestly studied a paint composition having an excellent decorative property capable of showing a "marbling" -like multicolored pattern on a coating film.
If 200 μm colored particles are prepared and different colored particles are kneaded with an aqueous varnish to prepare a coating composition, the colored particles juxtaposed on the surface of the coating film will appear as a cloth or suede-like multicolored pattern. We have already found that That is, since it is impossible to make the color pigment large and uniformly disperse it, if the resin particles are formed to form a coating film on the surface of the particles, and the color particles are dispersed in a varnish to form a paint, the above phenomenon occurs. It is something that can be obtained.

[0007]

The above-mentioned coating composition, which has been found out by the present inventors, was an excellent technique that can be visually perceived as a suede-like "marbling" -like multicolored pattern, but it has a pale color tone. When adjusting the, there was a problem that it was not possible to see the colorful pattern feeling sufficiently when viewed from a distant position. Therefore, even if it is a light color tone, it can be clearly seen as a light colored marbling tone multicolored pattern when the ceiling surface or wall surface after painting is viewed from a distance, and there is no feeling of stiffness. However, it has been desired to create a coating composition that can express mottled accents and has no dripping or uneven coating during painting.

[0008]

According to the present invention, a colored polymer powder having an average particle size of 10 to 80 μm and a particle size of 0.3 to 10 mm formed by forming a coating film of a synthetic resin containing a coloring pigment on the surface of particles of a synthetic resin. By providing a coating composition characterized by containing long staple fibers as an essential component, the above-mentioned conventional problems are solved.

[0009]

The constitution of the coating composition according to the present invention will be described below. In the present invention, a colored polymer powder having an average particle diameter of 10 to 80 μm formed by forming a coating film of a synthetic resin containing a coloring pigment on the surface of the synthetic resin particles is blended as one of the essential components. This colored polymer powder is
(a) A metal salt is added to a mixed system obtained by mixing a mixture of a dispersion-stabilized color pigment and an emulsion resin with synthetic resin particles containing a plasticizer, or (b) dispersion-stabilized A mixed system obtained by mixing particles of a synthetic resin in a paint having a coloring pigment and containing an alkali-neutralized polyvalent carboxylic acid resin and having an acid value of 5 or more in the solid content is a metal. It can be obtained by adding salt.

Known pigments are preferably used as the above-mentioned coloring pigments, for example, inorganic pigments such as titanium dioxide, amber, red iron oxide, yellow lead, dark blue, carbon black, ultramarine blue, manganese purple, Hansa Yellow, Benzidine Yellow and Toluidine. Organic pigments such as red, phthalocyanine blue, phthalocyanine green, and dioxazine violet are listed. Further, extender pigments such as barite, calcium carbonate, clay and talc can also be used in combination with the above color pigments. The addition amount of such a color pigment is preferably 2 to 300 parts by weight with respect to 100 parts by weight of the solid content of the emulsion resin or the solid content of the polycarboxylic acid resin, but is not particularly limited.

The metal salt added to the above-mentioned mixed system 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 preferable. Used for. The reason for using the metal salt is that the metal salt inhibits the stability of the emulsion resin or polyvalent carboxylic acid resin containing the color pigment, and the emulsion resin or polyvalent carboxylic acid resin containing the pigment is coagulated on the particle surface of the synthetic resin. This is to cause the analysis. The addition amount of this metal salt is preferably an appropriate amount by determining the amount of the metal salt at which the emulsion resin or the polyvalent carboxylic acid resin and the metal salt are mixed and gelled. Incidentally, it is also possible to add water to the metal salt and mix it as an aqueous metal salt solution,
In this case, the weight ratio of the emulsion resin solution or polyvalent carboxylic acid resin solution containing the color pigment and the aqueous metal salt solution is 7: 3 to 3: 7, preferably 6: 4, in consideration of particle stability.
It is preferable to set the ratio to 5: 5, but it is not particularly limited.
Although the metal salt has been described in detail above, calcium hydroxide can be used instead of this metal salt.

In the case of using an emulsion resin, it is preferable to use an emulsion resin whose emulsion stability is impeded by the presence of metal ions and which is agglomerated or gelled on the surface of particles of a synthetic resin containing a plasticizer described later. , For example, acrylic, styrene acrylic, polyester, polyurethane,
Preferred examples include synthetic resins such as vinyl chloride-vinyl acetate copolymers and vinyl chloride-acrylic copolymers, and natural resins such as mastics, acaloids, benzoins, dragon blood, elemi, and sandalac. The surfactant used is not particularly limited, and a cation,
Anionic, nonionic, amphoteric and other surfactants are preferably used, and in order to destabilize the emulsion with respect to metal ions, the addition amount thereof is 1% by weight based on the addition amount of the emulsion resin. The particle size of the emulsion resin is preferably 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.

As the synthetic resin, vinyl chloride synthetic resin and other synthetic resins can be suitably used without limitation.
The vinyl chloride-based 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, chlorinated vinyl chloride / vinyl chloride copolymer, etc.
It is possible to use those formed by a suspension polymerization method or an emulsion polymerization method. Polyethylene, polyacrylonitrile, polymethylmethacrylate, and the like can be preferably used as the synthetic resin other than the vinyl chloride resin. It should be noted that it is desirable to select those synthetic resins in which the average particle size of the colored polymer powder particles finally obtained is from 10 to 80 μm, which is somewhat affected by the plasticizer addition rate, etc. A synthetic resin having an average particle size of 20 to 50 μm is preferably used.

The plasticizer to be mixed with the synthetic resin is not particularly limited, and it is 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 ratio of this plasticizer is 4.7 to 50% by weight, preferably 23 to 44% by weight, based on the weight of the synthetic resin after the addition of the plasticizer. In the case of resin, 33 to 44% by weight is preferable, and in the case of the emulsion polymerization method, it is desirable to be 23 to 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 color pigments cannot efficiently coat the surface of the synthetic resin particles.
If the plasticizer is added in an amount of more than wt%, the particles of the synthetic resin will become soft, sufficient coating strength will not be obtained, and adhesive force will occur between the particles, making it difficult to finally take out as particles. This is because. As a method of mixing the synthetic resin and the plasticizer, there is a method of using a Henschel mixer or the like. At this time, if necessary, a stabilizer of the synthetic resin, a modifier or the like may be mixed. Is also possible.

The amount of emulsion resin used (solid content) is
When the amount of the synthetic resin containing the plasticizer used is 1 (parts by weight), it is 0.05 to 2.0, preferably 0.1 to 1. The reason is that if it is less than 0.05, the particles of the synthetic resin containing the plasticizer cannot be sufficiently covered, and the particles have poor colorability, and if it exceeds 2.0, a gelled product in which only the particles of the emulsion resin are aggregated is obtained, This is because the particle strength becomes weak. If the amount of the synthetic resin is large, the fluidity becomes low. Therefore, water may be added as necessary to secure the fluidity.

The emulsion resin containing the coloring pigment and the particles of the synthetic resin containing the plasticizer as described above are mixed and stirred, and the mixture and the metal salt are mixed to form the synthetic resin on the surface of the particles of the synthetic resin. It is possible to obtain a dispersion liquid of colored polymer powder particles on which a coating film of emulsion paint is formed. The colored polymer powder and granules can be obtained by separating the colored polymer powder and the dispersion medium from the dispersion liquid.

On the other hand, when the polyvalent carboxylic acid resin is used, polyvalent carboxylic acid resins such as acrylic resin, styrene-butadiene resin, styrene-maleic acid resin, alkyd resin, and alginic acid can be preferably used. As a neutralizing agent for solubilizing such a polyvalent carboxylic acid resin, ammonia water, triethylamine, dimethylethanolamine, potassium hydroxide, sodium hydroxide and the like are preferably used. In addition, you may add a defoaming agent, a film-forming auxiliary agent, etc. as needed.

Further, as the synthetic resin particles mixed with the above-mentioned polyvalent carboxylic acid resin and mixed in the paint in which the acid value in the solid content is 5 or more, other than the vinyl chloride type synthetic resin as described above. In addition, acrylic resins, polyester resins, and others formed by emulsion polymerization, suspension polymerization, mechanical milling, or the like are preferably used. The synthetic resin particles had an average particle diameter of 10 in the finally obtained colored polymer powder.
It is desired to select a material having a thickness of from 80 to 80 μm, preferably from 20 to 50 μm.

The amount of the colored coating material (in terms of solid content) used is 0.05 to 2.0 when the amount of the synthetic resin particles used is 1 (part by weight).
, Preferably 0.1 to 1. The reason is that if it is less than 0.05, the particles of the synthetic resin cannot be sufficiently covered and particles with poor coloring properties are obtained, and if it exceeds 2.0, a gelled product in which only the excess particles of the polycarboxylic acid resin are aggregated is obtained. The reason is that these gelled products have a small particle size and are unlikely to form a suede-like pattern when made into a coating material, which is not desirable in any case.

In the present invention, as the colored polymer granules, those obtained by the above-mentioned method are preferably used. In addition to the above-mentioned method, a coating film is provided from a paint containing a color pigment and a vehicle resin, Colored polymer powder particles obtained by crushing this coating film are also suitably used.
In this case, as the vehicle resin used, those having a glass transition temperature Tg of 20 ° C. or higher and synthetic resins such as acrylic, styrene-acrylic, polyester, vinyl chloride and acrylic copolymer are suitable. Such paint,
A coating film is formed by coating the surface of the releasable material so as to have a uniform thickness between 2000 μm and 5000 μm. A colored polymer powder having an average particle size of 10 to 80 μm, which is obtained by drying the coating film, peeling the coating film from the base material, and pulverizing with a fine pulverizer such as a fine ball mill, is also available. It can be preferably used.

The average particle size of the colored polymer powder particles obtained by the above method is 10 to 80 μm, preferably 20 to 50 μm. The reason for this is that when different colored colored polymer powders are kneaded, particles with a particle size of less than 10 μm cannot be visually identified individually, so particles of multiple colors can be visually perceived as a multicolored pattern. Not possible, meanwhile 80 μm
If it exceeds the range, the color distribution of the multicolored pattern becomes rough, and the cloth with excellent decorative properties, the suede-like multicolored pattern does not appear, and the feeling of touch is rough and a soft tactile sensation cannot be obtained. . Particle size 20 to 50
At μm, the texture is good, and the texture of fabric or suede is most noticeable.

Next, the short fiber having a length of 0.3 to 10 mm, which is another essential component of the coating composition according to the present invention, will be described. Examples of suitable materials for this short fiber include rayon, nylon, vinylon, and cellophane, but are not particularly limited. Such short fibers having a length of 0.3 to 10 mm, more preferably about 0.5 mm, are mixed in 0.05 to 4.0 parts by weight with respect to 100 parts by weight of the coating composition. The reason for this is that if the length of the short fibers is less than 0.3 mm, it will be difficult to cut the fibers, and the blending amount of the short fibers will be
If it is less than 0.05 parts by weight, it is not possible to express an appropriate colorfulness with a "marbling" -like colorful pattern in the coating film after coating which is the object of the present invention, while if the length exceeds 10 mm, it will be after coating. This is because the suede feeling does not appear in the coating film, and when the blending amount exceeds 4.0 parts by weight, the fluidity of the coating material is lost and the coating becomes difficult, which is not preferable in any case. In addition, by mixing 0.6 parts by weight of short fibers with a length of about 0.5 mm, it is possible to produce a suede-like multi-colored pattern, and to produce a conspicuous pattern even if it is a light color and it is appropriate. It is possible to effectively give a nice feeling to the coating film, and it is possible to almost prevent sagging and uneven coating at the time of coating.

Short fibers are directly mixed into the dispersion liquid of the colored polymer powder particles as described above, or the colored polymer powder particles are taken out from the dispersion liquid and kneaded in an aqueous varnish together with the short fibers, and if necessary. A coating composition can be obtained by adding an antifoaming agent or a thickener. Alternatively, the short fibers may be blended after adjusting the coating material, and there is no particular limitation. 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. By changing the hardness and flexibility of the above-mentioned aqueous varnish or colored polymer powder, it is possible to obtain coatings having various tactile sensations.
It is also possible to obtain a multicolor finish paint by kneading various types of colored polymer powder particles of different colors and kneading them together with short fibers in an aqueous varnish.

[0024]

EXAMPLES Next, the effects of the coating composition according to the present invention will be made clearer by giving examples.

(Example 1) Styrene acrylic emulsion containing 47% non-volatile components as an emulsion synthetic resin (trade name: ACRONAL YJ1210D Mitsubishi Yuka Birdiche Co., Ltd.)
80 parts by weight of titanium dioxide 40 as a coloring pigment
Parts by weight were mixed. Next, as a vinyl chloride-based synthetic resin, a vinyl chloride polymer with an average particle size of 40 μm (trade name ZEON 10
3ZXA Nippon Zeon Co., Ltd.) and mixed so as to contain di-n-octyl phthalate as a plasticizer in an amount of 29% by weight.
50 parts by weight were prepared. Mix the emulsion resin containing the color pigment and the vinyl chloride synthetic resin containing the plasticizer, add an appropriate amount of water, and then add calcium chloride as the metal salt to 1.1.
The mixture was mixed in parts by weight to obtain a dispersion of colored polymer powder having an average particle diameter of 42 μm. Prepared in exactly the same manner, except that 99 parts by weight of the white colored polymer powder taken out from the obtained dispersion liquid and 4.4 parts by weight of the pigment were mixed in place of carbon black,
After mixing 1 part by weight of each of the black colored polymer powder particles taken out, 50 parts by weight of an aqueous varnish containing 55% of non-volatile components and 0.6 parts by weight of rayon short fibers (average length 0.5 mm) are kneaded to produce a multicolored color. A coating composition of was obtained.

(Example 2) Nicazole RX291 (manufactured by Nippon Carbide Industries Co., Ltd .: trade name) acrylic styrene resin (acid value of 50% non-volatile component as polyvalent carboxylic acid synthetic resin)
20) Synthetic resin 75.2 parts by weight consisting of 22.6 parts by weight and Nicazole RX669 (trade name) (acid value 0, non-volatile content 50%) acrylic styrene resin 52.6 parts by weight, mixed with titanium dioxide 40 parts by weight as a coloring pigment. did. Next, as a synthetic resin powder, 150 parts by weight of a vinyl chloride polymer having an average particle diameter of 40 μm (trade name: ZEON 103ZXA, manufactured by Nippon Zeon Co., Ltd.) was prepared. The above-mentioned polycarboxylic acid resin containing a coloring pigment (acid value
After mixing the emulsion resin consisting of 6) with synthetic resin powder and adding water in an appropriate amount, mix 1.1 parts by weight of calcium chloride as a metal salt to obtain a colored polymer powder with an average particle diameter of 42 μm. A dispersion was obtained. Black colored polymer powder particles were prepared in exactly the same manner except that 99 parts by weight of the white colored polymer powder particles extracted from the obtained dispersion liquid and 4.4 parts by weight of the pigment were mixed in place of carbon black. After mixing with 1 part by weight of each body, 50 parts by weight of an aqueous varnish containing 55% of non-volatile components and 0.3 part by weight of nylon short fibers (average length 10 mm) were kneaded to obtain a light-colored coating composition.

(Example 3) Titanium dioxide as a color pigment, a paint made of acrylic resin without a film-forming aid as a vehicle resin (Pencit # 10 manufactured by Asahi Pen Co., Ltd.)
0 semi-gloss white (without film-forming auxiliary agent) was used, and a coating film of 4000 μm was applied on the surface of the peelable material in an amount of 20 m ² . After drying, the coating film was peeled off and pulverized with a ball mill to obtain a colored polymer powder having an average particle diameter of 80 μm. Obtained white colored polymer powder 99
1 part by weight of each of the black colored polymer powders obtained was prepared in exactly the same manner except that 4.4 parts by weight of the pigment was used instead of carbon black as the pigment.
50 parts by weight of 55% aqueous varnish and short vinylon fibers (average length)
1.0 mm) 4.0 parts by weight was kneaded to obtain a light-colored coating composition.

Comparative Example 1 A coating composition similar to that of Example 1 was obtained except that rayon short fibers were not mixed. (Comparative Example 2) A coating composition similar to that of Example 2 was obtained except that short nylon fibers were not mixed. (Comparative Example 3) A coating composition similar to that of Example 3 was obtained except that vinylon short fibers were not mixed.

(Test Example) The coating compositions obtained in Examples 1 to 3 and Comparative Example were applied twice to the surface of a slate plate test piece, and the appearance, touch and sagging state of the coating film were examined. It was
In each of the examples and comparative examples, the appearance was evaluated by visually observing the conspicuousness (suede feel) of the multicolored sensation of light colors when viewed 3 m after 2 hours from the application. The touch was evaluated 24 hours after application by touching with a fingertip and observing the presence or absence of roughness.
The sagging state of the paint was applied with a sag tester and evaluated by the sag wet film thickness. 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. .

[Table 1]

[0030]

As described above in detail, the present invention provides a colored polymer powder having an average particle size of 10 to 80 μm, which is obtained by forming a coating film of a synthetic resin containing a coloring pigment on the surface of a particle of the synthetic resin and 0.3. Since it is a coating composition characterized by containing a short fiber having a length of up to 10 mm as an essential component, as is apparent from the above examples, a suede-like, marbling-like multicolored pattern is formed on the coating film after coating. Along with giving a moderate feel, even if the coating film after painting is light-colored, it does not lose the colorful pattern feeling when viewed from a distance, and it is possible to express a unique and calm accent, and painting It is an excellent coating composition that does not cause sagging or uneven coating.

Claims (1)

[Claims] 1. An average particle diameter of 10 to 80 formed by forming a paint film of synthetic resin containing a coloring pigment on the surface of synthetic resin particles.
A coating composition comprising a colored polymer powder of μm and short fibers having a length of 0.3 to 10 mm as essential components.