JPH0794622B2 - Coating composition for forming uneven surface - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Use) The coating composition of the present invention is excellent in decorativeness and moisture permeability, and therefore, is useful for beautifying and protecting buildings and articles.

(Prior Art) A film-forming composition, a so-called paint, is applied to a building or the like to enhance its aesthetic appearance, protects the body from deterioration over time, and protects leather, fiber, wood, paper, etc. It is applied to an article to improve its aesthetic value.

Conventionally, in order to enhance the aesthetic appearance, it has been made to form an uneven surface by using a paint, but the method is as follows, and each has drawbacks.

That is, in the method of applying a paint mixed with aggregates such as sand and perlite with a spray, roller, brush, etc., during storage, aggregates with a large specific gravity such as sand will settle during storage. However, if the specific gravity is small, such as perlite, it will float, so if the stirring before application is insufficient, the distribution of aggregate will be different at the beginning and the end of application, and a uniform uneven surface will be obtained. Instead, spray coating often causes clogging.

Further, when such a paint is used, a surface having a large number of recesses such as dimples on the surface of the golf ball cannot be obtained.

Further, there are drawbacks such as reduction in strength, elongation and adhesion of the coating film.

As another method, polyvinyl alcohol, a water-soluble resin such as methyl cellulose or a thickening agent such as pentonite is added to the coating, and there is a method of forming a rough surface by coating the coating with a structural viscosity with a roller. In addition to streaks in the direction in which the roller is rolled, the height of the convex portion or the depth of the concave portion is small, the shape becomes round and gentle, and a sharp uneven surface cannot be obtained.

As another method, there is also a method of applying a pattern by using a roller engraved with an uneven pattern, but in addition to the problem that such a special coating tool has to be used,
It has the drawback that the seams of the pattern are difficult to match.

In addition, JP-A-54-3842 proposes a multicolor paint in which a plurality of types of colored aqueous emulsions are each gelled and the gelled emulsion particles are dispersed in an emulsion for forming a coating film. Since these gel particles are non-uniform gels that are gelled from emulsions and are similar to the emulsion for forming a coating film, the drying speed of both is the same, so a coating film with a uniform surface is formed That cannot be formed.

In addition, Japanese Examined Patent Publication No. 51-8130 has a large amount of inorganic aggregate and a small amount of W /
It is proposed to form a worm-like pattern by rolling the gel particles with a trowel at the time of coating, which consists of gel particles having a larger particle size than the inorganic aggregate formed by removing some water from the W-shaped gel particles. However, if such a small amount of gel particles and a large amount of inorganic aggregate are used, the gap between the gel particles is filled with the inorganic aggregate and a smooth surface is formed, so a pattern cannot be formed unless the gel particles are rolled with a trowel. .

Further, in order to prevent deterioration of the skeleton, which is another purpose of the paint, it is also important to adjust the water content in the skeleton, and therefore it is also an important requirement that the coating film has moisture permeability.

When a non-moisture-permeable coating film is formed on a building, the water vapor contained inside the body is not released, so condensation occurs due to the temperature difference, and the water decomposes the wood in the body, etc., Mold or the like may occur. Especially, the water on the north side wall in winter freezes the water, destroying concrete and releasing internal water, causing blistering and peeling of the coating film, resulting in a problem that the body protection effect is lost. So, 100g / m ² , 24hr or more moisture permeability (JIS
Z0208) is required.

In addition to this, conventional coating films with moisture permeability have no gloss,
The glossy one lacked moisture permeability. For this reason, conventionally, clay, calcium carbonate, fillers such as silica powder have been blended in the paint, but not only the imparting of moisture permeability is insufficient, but the strength, elongation, adhesion of the coating film by blending the filler, It has a drawback that the gloss and the like are seriously deteriorated and that the storage stability is poor such that the filler is precipitated during the storage.

(Problems to be Solved by the Invention) It is an object of the present invention to provide a coating material which solves various drawbacks of conventional coating materials for forming an uneven surface and imparts moisture permeability to a coating film required as a protective coating material.

(Means for Solving the Problem) The present invention provides "1. coating a W / O type dispersion liquid in which water-containing gel particles having a water content of 50 to 99% by weight and a particle size of 1 to 500 µm are dispersed in an organic solvent. A coating composition for forming an uneven surface, which is blended in a forming composition, wherein the content of hydrous gel particles is 5 to 500% by weight, which is a leather-like, matte, or suede-like coating composition for forming an uneven surface.

2. The particle size of the hydrogel particles is 1 to 100 μm.
The leather-like, matte or suede-like uneven surface forming coating composition described in 1. Regarding

This coating composition can be applied by an ordinary spray, roller, brush or the like, and a surface having a large number of concave portions which is extremely sharp is obtained, and a coating film having excellent moisture permeability can be formed.

(Function) Examples of the coating-forming composition used in the present invention include casein paints, water-based paints such as urea resin-based water-based paints, synthetic resin emulsion paints, boil oil-based oil-based paints, natural resin-based oil-based paints and melamine resins. Oil-based paints such as paints, polyvinyl-based paints, polyester-based paints, synthetic resin-based oil-based paints such as silicon resin-based paints, lacquers, and fibrin-based oil-based paints such as acetyl cellulose paints.

Water-containing gel particles include agar gel, carrageenan gel,
Calcium alginate gel, gelatin gel, polyvinyl alcohol, cetoacetylated polyvinyl alcohol, acetoacetylated starch, acetoacetylated hydroxyethyl cellulose, polyacrylamide and its derivatives,
Water-containing gel fine particles in which polyacrylic acid, polyvinylpyrrolidone, an isobutylene-maleic anhydride copolymer and its derivative, a vinyl ether-maleic anhydride copolymer, etc. are dispersed in a W / O type are effective. It is a water-in-oil type water-in-oil type (W / O type) after emulsifying the aqueous gel-forming resin as described above, and then a gelation treatment such as adding a cross-linking agent to obtain water-containing gel fine particle W / O type dispersion liquid. Alternatively, a water-containing gel fine particle W / O type dispersion liquid can be obtained by emulsion-polymerizing a water-soluble monomer that becomes a water-soluble gel-forming resin to be polymerized with a crosslinking agent in a water-in-oil type and internally crosslinking. .

The particle size of the W / O type dispersed hydrogel fine particles thus obtained is 1 μm to 500 μm, and those having a particle size of 100 μm or less are particularly suitable for making a moisture permeable coating. Also, the particle size is 5 to 50
A material having a thickness of 0 μm is suitable for forming an uneven surface, but especially 5
Those with ~ 100μm are suitable for suede, and those with 50 ~ 500μm are suitable for leather-like uneven surface formation.

The coating composition for forming an uneven surface of the present invention may be prepared by mixing 5 to 500 parts by weight of the water-containing gel fine particles dispersed in the W / O type in the above-mentioned water-based paint or oil-based paint and stirring them uniformly. it can.

In addition, the water-based gel-forming resin aqueous solution and W / O
The uneven surface forming coating composition of the present invention can also be prepared by adding a mold emulsifier and a crosslinking agent, stirring and emulsifying and crosslinking.

By thus preliminarily containing the hydrogel particles in the film-forming composition, a good coating composition for forming an uneven surface can be obtained. However, both should be packaged separately and mixed at the time of use. A liquid type coating composition for forming an uneven surface can also be used.

In order to form an uneven surface using the uneven surface forming coating composition of the present invention, a suitable coating substrate using a coating tool such as spray, roller or brush, for example, wood, concrete, cement mortar, slate, ALC, metal,
When applied to the surface of plastics, woven fabrics, non-woven fabrics, paper, leather, etc., the water content in the hydrogel particles evaporates and shrinks after drying, so that an uneven surface having a large number of recesses is formed.

When the particle size is relatively large, it becomes a crater-like or ricin-like surface in which the convex parts of the sand wall pattern are reversed and become concave parts, and as the particle size decreases, it becomes a leather-like, matte, or suede-like surface. , When it becomes the thinnest, even if it is glossy to the naked eye, it forms a microscopic uneven surface. Therefore, it is necessary that the hydrogel particles have a particle size of 1 to 500 μm.

It is a feature of the present invention that the shape of the recess is extremely sharp.

This is because the water-containing gel particles having a water content of 50 to 99% by weight are used, so that they are sharply depressed due to evaporation of water. Therefore, such an effect is not exhibited with hydrous gel particles having a water content of less than 50% by weight.

On the other hand, from the viewpoint of moisture permeability, when the water-containing gel particles evaporate the water contained therein, the film thickness of the recesses formed in the coating film becomes thin, and the water contained in the body becomes water vapor,
It is thought that it passes through this thin bottom membrane and diffuses to the outside.

Therefore, the amount of hydrous gel particles contained in the paint is 5% by weight.
The above is preferable, and if it is less than 5% by weight, excellent uneven surface and moisture permeability cannot be obtained, and if it exceeds 500% by weight, coating film performance is remarkably deteriorated, which is not practical.

In the case of the two-component coating composition for forming an uneven surface described above, for example, first, the film-forming composition is applied to a substrate, and the surface of the powder after drying is sprayed with hydrous gel particles. It is also possible to form an uneven surface by applying it by coating.

EXAMPLES Next, the present invention will be described with reference to production examples, examples and comparative examples.

Production Example 1 W / O of 70 parts by weight of a 10% by weight aqueous solution of polyvinyl alcohol
After emulsifying and dispersing in 30 parts by weight of xylene using a type emulsifier, 2 parts by weight of 10% by weight aqueous solution of glutaraldehyde was added dropwise with stirring, and stirring was continued at room temperature for 3 hours after the addition.
Hydrogel fine particles in which 70% by weight of polyvinyl alcohol hydrogel particles having a particle size of 5 to 50 μm and a water content of 90% by weight are contained in xylene by cross-linking the emulsified and dispersed particles.
A W / O type dispersion was obtained.

Production Example 2 W / O of 60 parts by weight of a 15% by weight aqueous solution of polyvinyl alcohol
After emulsifying and dispersing in 40 parts by weight of toluene using a type emulsifier, 3 parts by weight of a 10% by weight aqueous solution of glutaraldehyde was added dropwise with stirring, and stirring was continued at room temperature for 5 hours after the addition.
The emulsified and dispersed fine particles were cross-linked and gelled to obtain a water-containing gel fine particle W / O type dispersion containing 60 wt% of polyvinyl alcohol water-containing gel fine particles having a particle size of 100 to 500 μm and a water content of 85 wt%.

Production Example 3 In the same manner as in Production Example 1, except that a 10% by weight aqueous solution of polyvinyl alcohol was replaced with a 10% by weight aqueous solution of acetoacetylated polyvinyl alcohol and a thinner for paint was used instead of xylene. As a result, a water-containing gel fine particle W / O type dispersion containing 70 wt% of acetoacetylated polyvinyl alcohol hydrogel fine particles having a particle diameter of 5 to 30 μm and a water content of 90 wt% in a paint thinner was obtained.

Production Example 4 A 4% by weight aqueous solution of carrageenan was prepared at 70 ° C, and the mixture was added dropwise to xylene at 70 ° C using a W / O type emulsifier to emulsify and disperse, and then gradually cooled to room temperature to obtain a particle size in xylene. 5-30
Micro particles of water-containing carrageenan gel with a water content of 96% by weight
A water-containing gel fine particle W / O type dispersion liquid containing 40% by weight was obtained.

Production Example 5 10% by weight of acrylamide, methylenebisacrylamide
A petroleum hydrocarbon with a boiling point of 190 ° C in which a W / O type emulsifier was dissolved in 50 parts by weight of a mixed aqueous solution containing 0.5% by weight and 89.5% by weight of water.
The mixture was dropped and dispersed in 150 parts by weight, the temperature was raised to 70 ° C. after the dispersion, and a 10% by weight aqueous solution of ammonium persulfate was added to carry out a polymerization reaction for 3 hours. Then, cool to room temperature, particle size 1 ~ 30μ
m, a water-containing gel microparticle W / O type dispersion containing 25% by weight of hydrous polyacrylamide gel microparticles having a water content of 90% by weight in a solvent was obtained.

Example 1 30 parts by weight of the water-containing gel fine particle W / O type dispersion prepared in Production Example 1 (21 parts by weight as gel particles) was added to 100 parts by weight of an elastic thick film paint using an acrylic polymer emulsion as a film forming material. A coating material for forming an uneven surface was prepared by mixing.

Example 2 20 parts by weight of the water-containing gel fine particle W / O type dispersion prepared in Production Example 4 was mixed with 100 parts by weight of a solvent-type gloss coating material (a pigment volume concentration of 20%) using an acrylic resin as a coating forming material. A coating material for forming an uneven surface was prepared.

Example 3 The same as Example 2 except that the solvent type gloss coating material containing acrylic resin as the film forming material was replaced with the emulsion type coating material containing acrylic-styrene copolymer emulsion as the film forming material. A coating material for forming an uneven surface was prepared in the same manner.

Example 4 200 parts by weight of the water-containing gel fine particle W / O type dispersion prepared in Production Example 5 was mixed with a coating composition using a two-component curing type urethane resin as a film forming material to prepare a coating composition for forming an uneven surface.

The 60 ° glossiness of the coating film formed using this paint is 15, which is much lower than the glossiness 95 of the coating film formed using the original paint, and the gloss has completely disappeared. The appearance of the film was a leather-like pattern with a high-grade feeling and an excellent quantity.

Example 5 Paint 100 using solvent-based baking type melamine resin as a film forming material
150 parts by weight of the hydrogel fine particle W / O type dispersion prepared in Production Example 2 was mixed with parts by weight to prepare an uneven surface forming coating material. A coating film formed by baking this coating material on a steel plate at 150 ° C. for 30 minutes showed a pattern with fine craters dispersed in the melamine resin layer, which was excellent in high-class feeling and volume feeling.

Example 6 100 parts by weight of the acrylic solvent-based gloss paint used in Example 2 was added with 10% by weight of acetoacetylated polyvinyl alcohol.
Add 20 parts by weight of aqueous solution, 1 part by weight of W / O type emulsifier and 5% by weight aqueous solution of glutaraldehyde, stir and emulsify, and continue stirring at room temperature for 3 hours to emulsify and disperse acetoacetoacetylation. Fine particles of a polyvinyl alcohol aqueous solution were cross-linked and gelled, and a coating material for forming an uneven surface was directly prepared by dispersing about 17% by weight of hydrogel particles having a particle size of 5 to 50 μm and a water content of 90% by weight in a commercial coating material.

Comparative Tests Regarding Examples 1, 2, and 3, the moisture permeability, the gloss of the coating film, and the coating strength were compared with those of commercially available water-based and solvent-based moisture-permeable coatings.
Compared with gloss paint.

The results are shown in Table 1.

In this way, by adjusting the particle size and blending amount of the gel, it is possible to improve the moisture permeability without lowering the gloss of the coating film.

(Effect) When a coating film is formed by using the coating composition for forming an uneven surface of the present invention, the following excellent effects are exhibited.

An extremely sharp uneven surface with a large number of recesses is obtained, and depending on the size of the hydrogel particles contained, it changes from a sand wall with a large number of recesses to a leather-like, suede-like, or matte-like surface for pattern formation. Since no aggregate is used, the surface feels soft and does not cause scratches on the human body. The desired uneven surface can be formed only by applying with a normal coating tool such as a spray, a roller, or a brush, and the spray is not clogged.
Since the specific gravity of the water-containing gel particles can be close to or close to that of the coating material, the water-containing gel particles do not settle or float over time, and the coating can always be performed in a good condition.

The coating formed by using the coating composition for forming an uneven surface of the present invention has extremely good moisture permeability, and therefore, when applied to the surface of the skeleton of a building, it prevents dew condensation inside the skeleton so that mold formation or rot of the skeleton, or No damage to the body due to freezing occurs, and no blistering or peeling of the coating film occurs. A coating film that has both gloss and moisture permeability can be obtained.

Claims (2)

[Claims] 1. A water content of 50 to 99% by weight and a particle size of 1 to 500 μm.
A W / O type dispersion in which the water-containing gel particles are dispersed in an organic solvent is a coating composition for forming an uneven surface, the water-containing gel particles being 5 to 500% by weight. A coating composition for forming an uneven surface of a leather-like, matte or suede-like surface. 2. The leather-like tone, the matte tone according to claim 1, wherein the hydrogel particles have a particle size of 1 to 100 μm.
A coating composition for forming a suede-like uneven surface.