JP2016098318A - Aqueous multicolor coating composition and coated article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous multicolor coating composition less in rebound during coating, easy to finish with uniformly and including an aggregate capable of expressing three-dimension sense and multicolor sense with shade.SOLUTION: There is provided an aqueous multicolor coating composition containing a dispersant and at least two color gelatinous coloring polymer particle dispersed with condition without dissolved in the dispersant and at least one color coloring polymer particle of the at least two color coloring polymer particle contains a light weight aggregate consisting of a synthetic resin. The light weight aggregate is preferably a foaming powder having bulk density of 0.5 g/cmor less. There is also preferably the aqueous multicolor coating composition where the light weight aggregate is contained at 0.1 to 40 pts.mass based on 100 pts.mass of the coloring polymer particle.SELECTED DRAWING: None

Description

  The present invention relates to an aqueous multicolored paint composition containing gel-like colored polymer particles, and a coated article on which the aqueous multicolored paint composition is formed.

  In recent years, there has been an increase in the demand for high design for exteriors (for example, walls and roofs) and interiors of buildings. As a finishing material, multi-color paints and stone-like paints are used in place of conventional single-color enamel paints. It has been increasingly used.

  Here, the multicolored paint is a paint in which particles of two or more colors in a gel form are suspended, and it has the feature that it is possible to create a color-scattering pattern with a single coating (a variety of colors can be expressed) (JIS K 5667). Such a multicolored paint is described in Patent Document 1 below, for example.

  On the other hand, a stone-like paint is a granite-like or marble-like paint that contains aggregates such as natural stone or ceramic, and a high-quality coating film can be obtained at a lower cost than using the stone itself. It has the characteristics.

Japanese Patent Laid-Open No. 2003-041196

  However, the conventional multicolored pattern paint as described in the above-mentioned Patent Document 1 is thin when forming a film because the water content of the gel-like colored polymer particles as a constituent material is increased due to the production method. It was easy to express the three-dimensional effect.

On the other hand, the conventional stone-like paints are easy to express a three-dimensional effect, but have many rebounds at the time of painting (particularly during spray painting), so that the coating efficiency is poor, and it takes time and effort to prevent scattering. Moreover, the aggregate that bounced off during painting felt pain when hitting hands and face.
Further, in the conventional stone-like paint, the aggregate is difficult to be uniformly distributed in the paint due to the difference in specific gravity of the aggregate, and for example, the finish is likely to be different between the first half and the second half of the painting.

  Here, it is thought that if the aggregate of the conventional stone-like paint is added to the conventional multi-color paint, it will be easy to express the three-dimensional effect in the multi-color paint, but the problems of the conventional stone-like paint remain. It was up to.

  The present invention has been made in consideration of the above-mentioned matters, and has a small amount of bounce at the time of painting, and is easy to finish uniformly. It aims at providing a coating composition etc.

  In order to solve the above-described problem, the at least two-colored colored polymer particles comprising a dispersion medium and at least two-colored gel-like colored polymer particles dispersed without being dissolved in the dispersion medium. Among these, at least one colored polymer particle was a water-based multicolored paint composition containing a lightweight aggregate made of a synthetic resin.

This water-based colorful pattern paint composition can express shaded three-dimensionality and versatility, and because it uses a lightweight aggregate made of synthetic resin, there is little rebound at the time of spray painting, it is difficult to feel pain, Aggregates tend to be evenly distributed in the paint and the finish is likely to be uniform.
In addition, the inclusion of a lightweight aggregate made of a synthetic resin in the colored polymer particles facilitates the familiarity with other paint components and can be evenly distributed, which contributes to construction stability.

  At this time, it is preferable that the lightweight aggregate is a water-based multicolor pattern coating composition, which is a foamed powder made of a synthetic resin.

The conventional stone-like paint uses hard mineral mineral aggregates, so the coated surface is rough and scratches on the human skin due to rubbing may cause the clothes to fray or tear. It was. Further, due to the peeling of the aggregate, a defect reaching the base or the undercoat may occur, which may impair the waterproof performance of the coating film.
However, since the above-mentioned water-based colorful pattern coating composition is a foamed powder made of a synthetic resin and a light aggregate, it is relatively soft, so that even when it is rubbed, the skin is hardly damaged and the clothes are not easily frayed or torn. Moreover, even if the aggregate is rubbed, it does not fall off entirely and the surface layer is only scraped. In other words, since it is difficult for defects to reach the base or near the undercoat, it is difficult to affect the waterproof performance due to coating film defects.
In addition, foams made of synthetic resin are easily yellowed and embrittled due to weathering deterioration, but the weathering deterioration is greatly delayed by encapsulating lightweight aggregate (foamed powder made of synthetic resin) in colored polymer particles. Can do.
Furthermore, since the foamed powder made of synthetic resin is rich in elasticity and flexibility, it can absorb the impact during spray coating and reduce the rebound, so that the coating efficiency and the ease of curing are improved.

At this time, it is also preferable that the lightweight aggregate be an aqueous multicolor pattern coating composition having a bulk density of 0.5 g / cm ³ or less.

In this water-based multicolor pattern coating composition, when the bulk density of the lightweight aggregate is 0.5 g / cm ³ or less, the rebound at the time of painting is further reduced, and the skin is hardly damaged even when it is rubbed. The bulk density of the lightweight aggregate is more preferably 0.2 g / cm ³ or less. The lower limit of the bulk density of the lightweight aggregate is not particularly limited, but is preferably 0.01 g / cm ³ or more.

  At this time, it is also preferable that the lightweight aggregate be an aqueous multicolored paint composition having an average particle diameter of 0.05 to 5 mm.

  This water-based colorful pattern coating composition is excellent in three-dimensional effect when formed into a film. The average particle size of the lightweight aggregate is more preferably in the range of 0.1 to 3 mm, and most preferably in the range of 0.2 to 1 mm.

  At this time, it is also preferable that the light-weight aggregate is a water-based multicolor pattern coating composition in which 0.1 to 40 parts by weight is contained in 100 parts by weight of the colored polymer particles.

  This water-based colorful pattern coating composition is excellent in three-dimensional effect when formed into a film.

  At this time, it is also preferable to use an aqueous multicolor pattern coating composition containing an aqueous synthetic resin emulsion-based clear coating.

  An aqueous multicolor paint composition can be obtained by blending two or more kinds of colored polymer particles having different color tones with the aqueous synthetic resin emulsion clear paint.

  In addition, a coated article on which the water-based colorful pattern paint composition described above is formed has a shaded three-dimensional effect and multicolored feeling, and the surface condition differs between the first half and the second half of painting. Less is.

  According to the present invention, it is possible to provide a water-based multicolored paint composition containing aggregates which can express a three-dimensional effect and a variety of shades with little rebound at the time of painting and easy to finish uniformly.

Hereinafter, an aqueous colorful pattern coating composition will be described by way of example. The aqueous multicolor pattern coating composition includes a dispersion medium, and at least two colors of gel-like colored polymer particles dispersed in a state not dissolved in the dispersion medium, and the at least two-color colored polymer particles Among them, the colored polymer particles of at least one color contain a lightweight aggregate made of a synthetic resin.
The present invention is not limited to the following embodiments and examples.

1. Colored polymer particles Colored polymer particles are gel-like particles that are dispersed without being dissolved in a dispersion medium (aqueous medium). The aqueous multicolored paint composition contains at least two colored polymer particles. The colored polymer particles of at least one color contain a lightweight aggregate made of a synthetic resin.

  The colored polymer particles containing lightweight aggregates are composed of (i) an aqueous synthetic resin emulsion, (ii) a heat-sensitive gelling agent, (iii) a colorant, and (iv) a light-weight aggregate-containing heat-sensitive material. The gelled emulsion composition can be obtained, for example, by dropping it into water having a temperature equal to or higher than the temperature at which the composition is gelled and heat-gelling.

  On the other hand, the colored polymer particles that do not contain lightweight aggregates are (i) an aqueous synthetic resin emulsion, (ii) a thermosensitive gelling agent, and (iii) a thermosensitive gelling emulsion that does not contain any lightweight aggregates. The composition can be obtained, for example, by dropping it into water having a temperature equal to or higher than the temperature at which the composition is gelled and heating to gel.

  Hereinafter, in the description of the method for producing the colored polymer particles, the case of the one containing a lightweight aggregate will be described as an example, but the colored polymer particles not containing the lightweight aggregate are also (iv) a lightweight aggregate. Except for not blending, it is possible to produce in the same procedure, so detailed description is omitted.

(I) Aqueous synthetic resin emulsion The aqueous synthetic resin emulsion is not particularly limited as long as it is usually used in the field of multicolored paints. Among these, emulsions used for interiors and exteriors of buildings, which are excellent in water resistance, alkali resistance and weather resistance, and have good adhesion to an object to be coated are preferable.

  More specifically, examples of such an aqueous synthetic resin emulsion include an acrylic resin emulsion and a silicone-modified acrylic resin emulsion.

  As the acrylic resin emulsion, for example, an emulsion obtained by emulsion polymerization of an acrylic monomer and, if necessary, other monomers according to a conventional method can be used.

  Examples of acrylic monomers include hydroxyl group-containing acrylic monomers such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate; carboxyl group-containing acrylic monomers such as acrylic acid and methacrylic acid; methacrylic acid Examples thereof include alkyl methacrylates or cycloalkyl esters such as methyl, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate and stearyl methacrylate.

  Examples of other monomers that are copolymerized with acrylic monomers include aromatic vinyl monomers such as styrene, methylstyrene, and vinyltoluene.

The silicone-modified acrylic resin emulsion is prepared by, for example, adding an organic silicone (for example, an organic silicone having —SiOCH ₃ or —SiOH as a functional group) to the acrylic resin emulsion as described above, and reacting the acrylic resin and the organic silicone according to a conventional method. Can be obtained.

  As the aqueous synthetic resin emulsion, an emulsion prepared as described above may be used, or a commercially available aqueous synthetic resin emulsion may be used.

  The physical properties of the synthetic resin contained in the emulsion are not particularly limited, but those having a Tg (glass transition point) of about −40 to + 60 ° C. are preferably used, and those having about −30 to + 50 ° C. are used. Is more preferable.

  The solid content concentration of the aqueous synthetic resin emulsion can be appropriately selected from a wide range, but is preferably about 10 to 60% by weight, and more preferably about 30 to 50% by weight.

  Further, the content converted to the solid content of the synthetic resin emulsion in the heat-sensitive gelled emulsion composition is about 5 to 40% by weight, particularly about 10 to 35% by weight, based on the total solid content. Is preferred.

  The heat-sensitive gelling emulsion composition is prepared by mixing the above-described aqueous synthetic resin emulsion with a heat-sensitive gelling agent, a colorant, and a lightweight aggregate (only when a lightweight aggregate is included).

(Ii) Thermosensitive gelling agent The thermosensitive gelling agent is a thermogelling agent that has a temperature exceeding room temperature, preferably about 40 ° C or higher, more preferably about 60 ° C or higher, and even more preferably about 70 ° C or higher. There is no particular limitation as long as the gel is obtained so that the gel state is maintained even when the gel is cooled to room temperature, and both organic and inorganic materials can be used.

  Examples of organic heat-sensitive gelling agents include starch and derivatives thereof, nonionic surfactant system, alkylene oxide adduct of organopolysiloxane, alkylphenol formalin condensate of organopolysiloxane, alkylene oxide adduct of alkylphenol-formalin condensate, A polyvinyl methyl ether, an organopolysiloxane polyether copolymer, etc. can be mentioned, These 1 type can be used individually or in combination of 2 or more types. As the nonionic surfactant, those having a cloud point of about 30 to 80 ° C. are preferably used.

  The organic heat-sensitive gelling agent can also be used as a mixture with water, and the concentration of the heat-sensitive gelling agent in the mixture is preferably about 10 to 100% by weight, more preferably about 40 to 100% by weight. preferable.

  On the other hand, as the inorganic heat-sensitive gelling agent, for example, a solution in which a zinc compound is dissolved in ammonia water (hereinafter sometimes referred to as “ammonia aqueous solution of zinc compound”), ammonium nitrate, ammonium chloride, sodium carbonate, potassium carbonate, sulfuric acid. Sodium, potassium chloride, calcium chloride, calcium sulfate, magnesium sulfate, zinc ammonium complex salt, sodium nitrate, lead nitrate, sodium acetate and the like can be mentioned, and these can be used alone or in combination of two or more.

  Specific examples of the zinc compound include zinc hydroxide.

  The concentration of the zinc compound in the solution in which the zinc compound is dissolved in aqueous ammonia is not particularly limited, and is preferably about 5 to 15% by weight, particularly about 2 to 10% by weight. The concentration of ammonia water for dissolving the zinc compound is not particularly limited, and is preferably about 5 to 10% by weight.

  Among these, as the heat-sensitive gelling agent used in the present invention, organopolysiloxane alkylene oxide adduct, organopolysiloxane alkylphenol formalin condensate, organopolysiloxane polyether copolymer, etc. organopolysiloxane and zinc compound ammonia An aqueous solution is preferred.

  Since the hardness of the resulting colored polymer particles is proportional to the blending amount of the thermosensitive gelling agent in the thermosensitive gelling emulsion composition, the blending amount can be appropriately set according to the desired degree of gelation. . The amount of the heat-sensitive gelling agent (the amount of the organic heat-sensitive gelling agent is the amount of the mixture with water, or the amount of the aqueous solution in the case of using an aqueous ammonia solution of zinc compound) is usually 100 parts by weight of the aqueous synthetic resin emulsion. On the other hand, it is about 20-40 weight part.

(iii) Colorant As the colorant, those generally used in the field of multicolored paints can be used.

  Examples thereof include inorganic coloring pigments such as titanium oxide (titanium dioxide), carbon black, and iron oxide.

  Examples also include organic dyes such as quinacridone compounds such as quinacridone, azo dyes such as pigment red, and phthalocyanine dyes such as phthalocyanine blue and phthalocyanine green.

  In the present invention, an inorganic pigment is preferably used as the colorant from the viewpoint of weather resistance.

  The blending amount of the colorant is not particularly limited, but is usually about 1 to 70 parts by weight, preferably about 10 to 40 parts by weight with respect to 100 parts by weight of the aqueous synthetic resin emulsion (i) component. is there.

(iv) Lightweight aggregate Lightweight aggregate is made of synthetic resin. A known resin can be used for the lightweight aggregate, and examples thereof include ethylene vinyl acetate, polyacrylonitrile, polyurethane, polystyrene, polypropylene, phenol, polyvinyl chloride, urea, polyimide, and synthetic rubber. In particular, ethylene vinyl acetate, which is rich in flexibility and elasticity and excellent in weather resistance, is preferable. These may be used alone or in combination of two or more.

  The lightweight aggregate is preferably a foamed powder made of a synthetic resin (foamed synthetic resin powder). At this time, the type of gas filling the pores is not limited. The lightweight aggregate is a foamed powder made of a synthetic resin, and may be a hollow balloon. Specifically, a heat-expandable microsphere (thermal expansion microcapsule) encapsulating a low-boiling hydrocarbon (core) in a thermoplastic polymer cell is heated to expand the encapsulated low-boiling hydrocarbon and heat You may use what was expanded by softening a plastic shell and became a hollow balloon. Further, the lightweight aggregate is a foamed powder made of a synthetic resin, and preferably has closed cells.

The bulk density of the lightweight aggregate is preferably 0.5 g / cm ³ or less in consideration of the bounceability and scratching property, because the flexibility obtained by the material and the expansion ratio varies. More preferably, it is ³ or less.

  The average particle size of the lightweight aggregate can be set as appropriate according to the target design. In a normal case, it may be about 0.05 to 5 mm. When the average particle size of the lightweight aggregate is 0.05 mm or more, the three-dimensional effect when the film is formed is excellent. Further, if the average particle size of the lightweight aggregate is 5 mm or less, the aggregate is difficult to drop off during painting. However, depending on the bulk density, if the particle size is too small, it tends to be windy and difficult to handle, and depending on the amount added, if the particle size is too large, the contact area with the coating surface may be reduced and it may easily fall off during painting. There is sex. Therefore, the average particle size of the lightweight aggregate is desirably in the range of 0.1 to 3 mm, and more preferably in the range of 0.2 to 1 mm.

  The blending amount of the lightweight aggregate is not particularly limited, but it is preferably blended so that 0.1 to 40 parts by weight of the lightweight aggregate is contained in 100 parts by weight of the colored polymer particles.

  In addition to the above-described components, additives such as extender pigments, dispersants, thickeners, antifoaming agents and the like can be appropriately blended in the heat-sensitive gelling emulsion composition as necessary.

  Water may be further added to the thermosensitive gelled emulsion composition to adjust the viscosity and solid content concentration.

  The heat-sensitive gelled emulsion composition comprises (i) an aqueous synthetic resin emulsion, (ii) a heat-sensitive gelling agent, (iii) a colorant, and (iv) a lightweight aggregate (with a lightweight aggregate only) It is prepared by mixing the additives as described above if necessary. The heat-sensitive gelled emulsion composition thus obtained preferably has a solid content concentration of about 10 to 40% by weight.

(V) Production of colored polymer particles containing light-weight aggregate The colored polymer particles containing light-weight aggregate are prepared as described above, for example, a lightweight aggregate-containing thermosensitive gelled emulsion composition, It can be obtained by dropping into water having a temperature equal to or higher than the temperature at which the composition gels and gelling. The dropping is preferably performed while stirring.

  Water may be used as it is, or may contain an antifoaming agent, a dispersing agent, a thickener and other additives (for example, a film-forming aid) as exemplified above. In the following description, water itself or water containing additives is referred to as an “aqueous medium”.

  The aqueous medium is heated to a temperature at which the heat-sensitive gelling emulsion composition is gelled by the heat-sensitive gelling agent, usually about 40 ° C. or higher, preferably about 60 ° C. or higher, more preferably 70 ° C. or higher. The upper limit of the temperature is not particularly limited, but is preferably a temperature at which the aqueous medium does not boil, for example, about 98 ° C. or less in the case of water itself.

  The ratio of the heat-sensitive gelling emulsion composition (C) and the aqueous medium (M) is not particularly limited and can be appropriately set, but is (C) :( M) = 1: 1 to 1 by weight ratio. The ratio is preferably about 1:10, particularly about 1: 1.5 to 1: 7.

  The dropping speed of the heat-sensitive gelling emulsion composition can be appropriately set according to the size of the desired colored polymer particles and the like, to the extent that the temperature of the aqueous medium does not drop significantly, that is, below the set gelling temperature. It is sufficient that the speed does not become.

  According to this method, the shape of the colored polymer particles can be freely controlled. For example, when the viscosity of the thermosensitive gelled emulsion composition is increased, spherical particles can be obtained.

  When the thermosensitive gelled emulsion composition is made to flow on the plate and dripped so as to spread on the water surface, it gels into a disk shape. The colored polymer particles of the present invention include such disk-shaped particles.

  The stirring speed of the aqueous medium can also be set as appropriate according to the desired size of the gelled particles and the like, but is usually about 100 to 1000 rpm as the rotation speed of the stirrer. If the stirring is vigorous, the obtained colored polymer particles become smaller, and conversely, if the stirring is moderated, the obtained colored polymer particles become larger. Therefore, the dropping method and the stirring speed may be adjusted according to the desired shape and size.

  After dropping, the residence time in the aqueous medium is not particularly limited as long as desired particles can be obtained, but is usually about 20 to 90 minutes, preferably about 40 to 70 minutes.

  Moreover, after completion of dropping of the entire amount of the thermosensitive gelled emulsion composition, stirring may be continued for about 5 to 30 minutes, preferably for about 10 to 20 minutes while maintaining the temperature at the time of dropping.

  Thus, the resin in the aqueous synthetic resin emulsion is gelled by the heat-sensitive gelling agent, and colored polymer particles in which the colorant is uniformly dispersed in the gel are obtained.

  The colored polymer particles can be collected by filtration according to a conventional method. Moreover, you may exclude the thing of the particle size outside a predetermined range, when collect | recovering.

  For example, filter through a mesh with a large hole first to remove large particles, then remove the supernatant of the filtrate to obtain a particle solution of about 15% solids, and finally filter with a mesh with a small hole. The particles of the final object can be obtained on the net.

  The non-volatile content of the colored polymer particles is preferably about 15 to 40% by weight, particularly about 20 to 35% by weight.

When the gel thus obtained, that is, the colored polymer particles are disc-shaped, the thickness thereof is not particularly limited and includes various thicknesses, but is generally about 30 to 500 μm, preferably 50. Preferably, the outer diameter is not particularly limited and can be appropriately set depending on the application, but is usually about 0.05 to 5 mm, 0.1 About 2 mm is preferable. If the thickness and outer diameter of the particles are within the above ranges, coloring can be confirmed by visual observation, and the construction is excellent (especially in the case of spray coating). The thickness and outer diameter of the particles can be determined by observing randomly selected particles with a microscope or the like. For example, the obtained particles are mixed with an aqueous synthetic resin emulsion-based clear coating at a ratio of about 1:10 (weight), applied to an ABS plate of about 10 cm ² , dried, and observed with a microscope after drying. And can be sought. The thickness of the particles can be determined, for example, by cutting the coating film, observing the cut surface with a microscope and observing the thickness of the particles. Here, the “outer diameter” means the diameter if it is a perfect circle, the long diameter if it is elliptical, and the longest diameter if it is indefinite.

  The hardness of the gel can be adjusted freely within a wide range, and the type and amount of gelling agent can be adjusted according to the purpose of use to obtain the optimum hardness.

  For example, the hardness of the gel is such that it is not pulverized by mechanical stirring such as a mixer; the deformation of the particles is small during coating with a spray gun or roller, that is, unidirectional particles in brush or roller coating It is preferable to satisfy the following conditions: softness that does not cause deformation of the coating; softness that does not catch on the diameter of the spray gun; softness that does not cause roughness of the coated surface to be obtained.

2. Water-based multicolored paint composition The colored polymer particles obtained in this way and having two or more different color tones are blended in a water-based synthetic resin emulsion-based clear paint. Can be obtained. The water-based multicolored paint composition contains at least two colored polymer particles, and at least one of the colored polymer particles includes a lightweight aggregate made of a synthetic resin. Need to be. For the colored polymer particles not containing the lightweight aggregate, as described above, (iv) The same method as the method for producing the colored polymer particles containing the lightweight aggregate except that the lightweight aggregate is not blended. It can be produced by a procedure.

  As the water-based synthetic resin emulsion-based clear paint, a clear paint which is usually used for blending a colorant in the field of multi-pattern paints can be used.

  For example, (i) an aqueous synthetic resin emulsion used for preparing the above-mentioned heat-sensitive gelled emulsion composition, that is, a clear paint containing an acrylic resin emulsion, a silicone-modified acrylic resin emulsion, etc., in addition to a vinyl acetate resin Clear paints including emulsions, urethane resin emulsions, and alkyd resin emulsions can be used.

  The clear paint may be produced according to a conventional method, or a commercially available one may be used.

  As an aqueous synthetic resin emulsion-based clear coating, not only a transparent clear coating but also a colored clear coating (for example, a clear coating containing colored pigments, aluminum flakes, and pearl pigments) may be blended with colored polymer particles. Good.

  The blending amount of the colored polymer particles can be appropriately set, but is preferably about 1 to 60% by weight, preferably about 5 to 55% by weight, based on the total amount of the aqueous multicolored paint composition. When the blending amount is not more than the above upper limit value, a sufficient clear coating film is easily formed, and when the blending amount is not less than the above lower limit value, it is possible to obtain a coating film having a particularly excellent multicolored design.

  The water-based colorful pattern coating composition of the present invention can be applied to a base material such as ALC, concrete, mortar, slate, ceramic, plastic, wood, stone, etc. It can be used for painting.

  The coating composition can be applied by an ordinary coating method such as brush, roller, spray gun coating or the like.

The above-mentioned water-based multicolor pattern paint composition is a multicolor pattern paint with an aggregate that can express a three-dimensional effect and a multi-colored feeling with a small amount of rebound at the time of painting and a uniform finish.
Hereinafter, the present invention will be described more specifically with reference to examples.

1. Preparation of colored polymer particles First, colored polymer particles necessary for an aqueous multicolor pattern coating composition were prepared. The aqueous multicolor pattern coating composition contains colored polymer particles of at least two colors. Formulation Examples 1, 2, 3, and 4 are gray colored polymer particles, and Formulation Examples 5 and 6 are white colored polymer particles. In addition, the blending example 3 uses an inorganic substance (calcium carbonate) instead of a synthetic resin as an aggregate, and is positioned as a comparative example.

[Formulation Example 1]
Formulation Example 1 is gray polymer particles containing ethylene vinyl acetate foam as a lightweight aggregate. The manufacturing method is as follows.
An aqueous medium having the composition shown in the following formulation b) in Table 1 and a heat-sensitive gelled emulsion composition having the composition shown in formulation a) were prepared by uniformly mixing the respective components. As the ethylene vinyl acetate foam as a lightweight aggregate, one having a bulk density of 0.2 g / cm ³ and an average particle size of 0.2 to 1 mm was used. Next, the heat-sensitive gelled emulsion composition was added dropwise over about 60 minutes while heating the aqueous medium to 70 ° C. and stirring (500 rpm). Stirring was continued while heating to maintain the temperature at 70 ° C. for 10 minutes after the completion of dropping, and stirring was stopped 30 minutes after the heating was completed and the mixture was allowed to cool. Subsequently, by filtering through a mesh of 5 mesh, particles of 4 mm or more were removed to obtain the desired product in the filtrate. Further, the supernatant of the filtrate is removed to obtain a mixture containing particles having a solid content of about 8%. Finally, the mixture is filtered through a 100-mesh net, and gray colored polymer particles (nonvolatile content: 16 as the final target) are formed on the net. %). The shape of the particles was a disk shape with protrusions. No problem occurred during production, and no segregation, aggregation or disintegration over time was confirmed (the same applies to all of Formulation Examples 1 to 6). Moreover, 5 to 6 parts by weight of ethylene vinyl acetate foam as a lightweight aggregate was contained in 100 parts by weight of the obtained gray colored polymer particles.

[Formulation Example 2]
Formulation Example 2 is gray polymer particles containing styrene foam as a lightweight aggregate. Specifically, gray colored polymer particles were prepared in the same manner as in Formulation Example 1 except that synthetic resin 2 (styrene foam) was used instead of synthetic resin 1 (ethylene vinyl acetate foam) in formulation a). Obtained. As the styrene foam as a lightweight aggregate, one having a bulk density of 0.2 g / cm ³ and an average particle size of 0.2 to 1 mm was used. Further, 100 parts by weight of the obtained gray colored polymer particles contained 5 to 6 parts by weight of styrene foam as a lightweight aggregate.

[Composition Example 3]
Formulation Example 3 is gray polymer particles containing calcium carbonate, which is an inorganic aggregate. Specifically, in Formulation a), the same method as Formulation Example 1 was used except that 100 parts by weight of an inorganic substance (3 parts of calcium carbonate) was used instead of 20 parts by weight of synthetic resin 1 (ethylene vinyl acetate foam). A gray colored polymer particle was obtained. In the present blending example 3, as described above, an inorganic material is used as an aggregate instead of a synthetic resin.

[Formulation Example 4]
Formulation Example 4 is gray polymer particles that do not contain lightweight aggregates. Specifically, gray colored polymer particles were obtained by the same method as Formulation Example 1 except that no aggregate was used in Formulation a).

[Formulation Example 5]
Formulation Example 5 is white polymer particles containing ethylene vinyl acetate foam as a lightweight aggregate. Specifically, white is used in the same manner as in Formulation Example 1 except that in addition to using 20 parts by weight of titanium oxide and 5 parts by weight of carbon black in Formulation a), 25 parts by weight of titanium oxide is used (carbon black is not added). Colored polymer particles were obtained.

[Composition Example 6]
Formulation Example 6 is white polymer particles that do not contain lightweight aggregates. Specifically, instead of using 20 parts by weight of titanium oxide and 5 parts by weight of carbon black in blend a), 25 parts by weight of titanium oxide is used (carbon black is not blended), and aggregate is used in blend a). Other than these, white colored polymer particles were obtained in the same manner as in Formulation Example 1.

  In Table 1 above, the numerical values of the components in the blending a) and the blending b) all indicate parts by weight. As the silicone-modified acrylic resin emulsion, Polydurex X1767 (trade name) manufactured by Asahi Kasei Chemicals Corporation was used. As an aqueous ammonia solution of a zinc compound, Hardener A12 (trade name) manufactured by Asahi Kasei Chemicals Corporation was used. The concentration of the zinc compound contained in the aqueous ammonia solution of the zinc compound was 9.6%.

2. Preparation of water-based multicolor pattern coating composition And, the colored polymer particles obtained by the formulation shown in Table 1 were used for coating. Specifically, white colored polymer particles and gray colored polymer particles were mixed to obtain a gray multicolor paint.

[Example 1]
Example 1 is a water-based multicolor pattern coating composition containing an ethylene vinyl acetate foam. Specifically, the colored polymer particles of Formulation Example 1 (aggregate: ethylene vinyl acetate foam, color tone: gray) and the colored polymer particles of Formulation Example 5 (aggregate: ethylene vinyl acetate foam, color tone: white) 150 parts by weight, and 300 parts by weight of a water-based synthetic resin emulsion-based clear are blended into this to obtain a water-based multicolor pattern coating composition.

[Example 2]
Example 2 is an aqueous multicolor pattern coating composition containing an ethylene vinyl acetate foam and a styrene foam. Specifically, the colored polymer particles of Formulation Example 2 (aggregate: styrene foam, color tone: gray) and the colored polymer particles of Formulation Example 5 (aggregate: ethylene vinyl acetate foam, color tone: white) are 150 weights. A water-based multicolored paint composition is obtained by mixing 300 parts by weight of the water-based synthetic resin emulsion clear.

[Example 3]
Example 3 is a water-based multicolor pattern coating composition containing an ethylene vinyl acetate foam. Specifically, 150 parts by weight of the colored polymer particles of Formulation Example 1 (aggregate: ethylene vinyl acetate foam, color tone: gray) and the colored polymer particles of Formulation Example 6 (aggregate: none, color tone: white) These were mixed one by one, and 300 parts by weight of an aqueous synthetic resin emulsion-based clear was added thereto to obtain an aqueous multicolor pattern coating composition.

[Comparative Example 1]
Comparative Example 1 is an aqueous multicolor pattern coating composition containing calcium carbonate. Specifically, the colored polymer particles of Formulation Example 3 (aggregate: calcium carbonate, color tone: gray) and the colored polymer particles of Formulation Example 6 (aggregate: none, color tone: white) are mixed by 150 parts by weight, An aqueous multicolor pattern coating composition was obtained by adding 300 parts by weight of an aqueous synthetic resin emulsion clear to this.

[Comparative Example 2]
Comparative Example 2 is an aqueous multicolor pattern coating composition that does not contain aggregate. Specifically, the colored polymer particles of Formulation Example 4 (aggregate: none, color tone: gray) and the colored polymer particles of Formulation Example 6 (aggregate: none, color tone: white) were mixed by 150 parts by weight. An aqueous multicolor pattern coating composition was obtained by blending 300 parts by weight of an aqueous synthetic resin emulsion clear.

[Comparative Example 3]
Comparative Example 3 is a water-based multicolor pattern paint composition in which ethylene vinyl acetate foam is mixed (after-applied) with a multicolor pattern paint that does not contain aggregate. Specifically, the colored polymer particles of Formulation Example 4 (aggregate: none, color tone: gray) and the colored polymer particles of Formulation Example 6 (aggregate: none, color tone: white) are mixed by 150 parts by weight, This was mixed with 300 parts by weight of an aqueous synthetic resin emulsion-based clear and 20 parts by weight of ethylene vinyl acetate foam to obtain an aqueous multicolor pattern coating composition.

[Comparative Example 4]
Comparative Example 4 is a water-based multicolor pattern coating composition in which calcium carbonate is mixed (after-applied) with a multicolor pattern paint that does not contain aggregate. Specifically, the colored polymer particles of Formulation Example 4 (aggregate: none, color tone: gray) and the colored polymer particles of Formulation Example 6 (aggregate: none, color tone: white) are mixed by 150 parts by weight, This was mixed with 300 parts by weight of an aqueous synthetic resin emulsion clear and 100 parts by weight of calcium carbonate to obtain an aqueous multicolor pattern coating composition.

[Comparative Example 5]
Comparative Example 5 is a typical conventional stone-like paint. Specifically, acrylic emulsion resin (250 parts by weight), film-forming aid (25 parts by weight), thickener (5 parts by weight), black silica sand No. 4 (150 parts by weight), Color Sand Brown No. 6-7 This is a stone-like paint obtained by blending (200 parts by weight), 3 kg of calcium carbonate (400 parts by weight), and an antifoaming agent (3 parts by weight).

  The coating materials shown in Examples 1 to 3 and Comparative Examples 1 to 5 were applied to an ALC plate previously coated with an appropriate undercoat, and the rebound property and the coating efficiency were evaluated. Moreover, it applied also to the slate board which applied the same undercoat, and it cured at 23 degreeC for 2 weeks, and used for the abrasion property and a weather resistance test. The following procedures evaluated the rebound property at the time of coating, the coating efficiency, the abrasion property of a coating film, and the weather resistance.

<Rebound>
The paints shown in the Examples and Comparative Examples were sprayed on the ALC plate previously coated with the undercoat. At this time, the lower surface of the painted surface was cured, and the amount of aggregate bounced back and dropped was measured and evaluated by the ratio to the amount applied to the ALC plate.
<Coating efficiency>
The paints shown in the Examples and Comparative Examples were sprayed on the ALC plate previously coated with the undercoat. At this time, the ratio of the amount discharged from the sprayer to the amount applied to the ALC plate was evaluated.
<Abrasion (Eraser)>
This was carried out using a Gakushin Abrasion Tester (manufactured by Tester Sangyo Co., Ltd.). Evaluation was made by changing the weight of the eraser by reciprocating 100 times under a load of 100 g / cm ³ .
<Abrasion (cotton cloth)>
This was carried out using a Gakushin Abrasion Tester (manufactured by Tester Sangyo Co., Ltd.). Evaluation was made by the number of times until the fabric was torn under a load of 100 g / cm ³ .
<Weather resistance (color difference)>
Using a metal weather (manufactured by Daipura Wintes Co., Ltd.), a 500 h test was conducted at an illuminance of 80 mW / cm ² and the color difference from the initial stage was evaluated. For the color difference measurement, CR-400 (manufactured by Konica Minolta Co., Ltd.) was used.

  The test results are shown in Table 2.

As shown in Table 2 above, Comparative Example 1 including an inorganic substance (calcium carbonate) as a lightweight aggregate is more rebounding and coating than Examples 1 to 3 including a synthetic resin as a lightweight aggregate. The wearing efficiency and wearability were inferior, and the superiority of using a synthetic resin as a lightweight aggregate was found.
Further, in Comparative Example 3, although the raw material composition itself is almost the same as Example 1, Example 1 in which the lightweight aggregate is encapsulated in the colored polymer particles has a lighter aggregate added later. It was found that the aggregate holding ability of the coating film was superior to that of Comparative Example 3 containing. In other words, it is preferable that the dispersion medium does not contain a lightweight aggregate.

  The water-based multicolored paint composition of the present invention contains a lightweight aggregate in at least one of the colored polymer particles to be blended, so that it is difficult to pick up the roughness of the material with a single coating and has a three-dimensional effect with a shadow. A painted surface that expresses a variety of feelings. This painted surface enhances and attenuates the three-dimensional effect with shadows depending on the intensity of external light and the incident angle, so that it gives a variety of expressions in combination with a variety of feelings. Therefore, it is useful as a high-quality architectural finishing material required in the construction field.

  The present invention has been described above with reference to specific embodiments and examples. However, the present invention is not limited to the above-described embodiments, and is attached to the application for this application by those skilled in the art. Various changes and modifications can be made without departing from the scope of the appended claims.

Claims (7)

A dispersion medium;
Including at least two colors of gel-like colored polymer particles dispersed in a state not dissolved in the dispersion medium,
The colored polymer particles of at least one color among the colored polymer particles of at least two colors contain a lightweight aggregate made of a synthetic resin.
Water-based colorful pattern paint composition.
Lightweight aggregate
It is a foamed powder made of synthetic resin.
The water-based multicolored paint composition according to claim 1.
Lightweight aggregate
A bulk density of 0.5 g / cm ³ or less,
The water-based colorful pattern coating composition according to claim 1 or 2.
Lightweight aggregate
The average particle size is 0.05-5 mm,
The water-based colorful pattern coating composition according to any one of claims 1 to 3.
Lightweight aggregate
0.1 to 40 parts by weight are contained in 100 parts by weight of the colored polymer particles,
The water-based colorful pattern coating composition according to any one of claims 1 to 4.
Including water-based synthetic resin emulsion-based clear paint,
The water-based colorful pattern coating composition according to any one of claims 1 to 5.
The aqueous colorful pattern paint composition according to any one of claims 1 to 6 is formed into a film.
Painted article.