JP2001342420A - Dispersion of enamel particle and coating composition for multicolored pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a dispersion of enamel particles in which the difference between hues of each color particle is not so clear, and the hues continuously and delicately change, capable of providing a design with moderate and deep feeling, having a multicolored pattern, hardly causing the change of the formed pattern even under various coating conditions, and excellent in preservation stability, and further to provide the coating composition for the multicolored pattern. SOLUTION: This dispersion of the enamel particles obtained by dispersing an enamel composition in an aqueous dispersion medium capable of forming a coating film having 0.05-0.60 contrast ratio and regulated so as to have 0.2-15 Pa.s viscosity and 1.0-8.0 TI value, contains (E) an aqueous solution of a polyvinyl alcohol, and (F) a cross-linking agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an enamel particle dispersion and a multi-color paint composition.

[0002]

2. Description of the Related Art Conventionally, there are various types of coating compositions for forming a colorful coating film on the wall of a building. Among such paint compositions, paints that form a multi-colored paint film by one application are called multi-color paints, and are JISK 5
667. According to this rule, the multicolor paint has a structure in which particles of two or more colors in a liquid or gel state are suspended.

[0003] In recent years, the use of these colorful paints has been diversified, and the design of the formed coating film has been diversified as required for each use. In particular, there has been a growing demand for a wall surface of a building, which has a relatively unclear colorful pattern and is a modest pattern that does not make the wall conscious, yet creates a deep and luxurious atmosphere.

[0004]

However, in the case of a multicolor paint, two or more color particles in a liquid or gel form in the composition are crushed to form a pattern, so that a large difference in hue between the color particles appears. However, since the contrast is increased, it is difficult to form such a modest and deep pattern.

On the other hand, these various colorful paints have a problem that, in the storage state, each color particle is settled or the color particles are united. In order to prevent these, a dispersant is used on the surface of the color particles, or a specific gelled film is formed, but neither is sufficient, and if painting is performed after long-term storage, the spread of the pattern and In some cases, a desired colorful pattern design cannot be expressed, for example, a large difference occurs in the degree of unevenness (smoothness).

Further, during spray coating, the partition walls on the surface of the color particles are easily broken due to fluctuations in conditions such as the air pressure of the coating equipment to be used and the diameter of the tip of the gun tip, and the contents are scattered. There are cases. The coating film thus formed has a string-like pattern, and it is difficult to obtain a colorful pattern with high aesthetics. Therefore,
Such multicolored paints must be applied under extremely limited coating conditions, and the degree of freedom in selecting coating equipment is low.

The present invention has been made in view of the above problems, and the difference in hue between each color particle is not so clear, the hue changes continuously and subtly, and a conservative and deep multicolored pattern design is provided. In the coating, the pattern formed is hardly changed by various conditions when the coating equipment is changed, furthermore, the storage stability of the coating is excellent, and even after coating for a long time, the coating is performed. An object of the present invention is to obtain an enamel particle dispersion liquid and a multi-color pattern coating composition that do not impair the design property.

[0008]

Means for Solving the Problems In order to solve such a problem, the present inventors have made intensive studies and found that an aqueous dispersion medium having a specific composition for forming a film having a specific concealment ratio is enameled with an enamel composition having a specific viscosity. It has been found that an enamel particle dispersion in which the substance is dispersed is effective.

That is, the present invention provides the following enamel particle dispersion and multicolored paint composition. 1. JIS K 5660 "Shiny synthetic resin emulsion paint" 4.8 (A) Acid value is 0 to 30 with respect to aqueous dispersion medium forming a coating film having a hiding factor of 0.05 to 0.60.
Containing (B) a coloring material, (C) an organic solvent, and (D) a viscosity modifier at a temperature of 20 ° C.
The viscosity at 20 rpm (the guide value at the fourth rotation) measured by a BH type viscometer was adjusted to 0.2 to 15 Pa · s, and the TI value obtained by the following was adjusted to a range of 1.0 to 8.0. An enamel particle dispersion in which an enamel composition is dispersed, wherein the aqueous dispersion medium comprises (E) a weight average molecular weight of 1
000-100,000, a degree of saponification of 80-100, and an aqueous solution of polyvinyl alcohol having a concentration of 0.01-5% by weight,
An enamel particle dispersion comprising (F) a crosslinking agent. <TI value> TI value: a value obtained by using a BH-type viscometer according to Equation 1. TI value = η1 / η2 (Equation 1) (However, apparent viscosity at η1: 2 rpm (Pa ·
s: guide value at the second rotation), η2: apparent viscosity at 20 rpm (Pa · s: guide value at the fourth rotation)) The polyvinyl alcohol is a cationic polyvinyl alcohol. 3. The enamel particle dispersion according to 1. 3. The enamel composition comprises (A) a vinyl-based synthetic resin having an acid value of 0 to 30 and a solid content of 100 parts by weight, (B) 10 to 100 parts by weight of a coloring material, and (C) 100 parts by weight of an organic solvent.
(D) 1 to 10 parts by weight of a viscosity modifier. Or 2.
3. The enamel particle dispersion according to 1. 4.1. ~ 3. A multicolor paint composition comprising two or more of the enamel particle dispersions described in any one of the above.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS [Enamel Composition] First, the enamel composition contains (A) a vinyl synthetic resin having an acid value of 0 to 30 as an essential component. Examples of the monomer constituting the component (A) include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, and the like. Acrylic acid and methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate,
Hydroxyl-containing vinyl compounds such as 2-hydroxypropyl methacrylate and 2-hydroxyvinyl ether, carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid and fumaric acid, and acid anhydrides such as maleic anhydride, glycidyl acrylate and glycidyl methacrylate Epoxy compounds such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate, amino compounds such as aminoethyl vinyl ether, acrylamide, methacrylamide, itaconamide, α-ethylacrylamide, crotonamide, fumaric diamide, maleic diamide, N-butoxymethyl Amide compounds such as acrylamide, N-butoxymethylacrylamide, N-butoxymethylmethacrylamide, acrylonitrile, styrene, α-methyl Styrene, vinyl chloride, vinyl acetate, vinyl propionate and the like can be mentioned. The component (A) can be obtained by polymerizing one or more of these by a known method. Acrylic silicone resin is preferably used from the viewpoint of weather resistance when a multi-pattern film is formed.

The acrylic silicone resin is, for example,

Embedded image (In the formula, X represents a hydrolyzable group, R ¹ and R ² represent hydrogen or an alkyl group, an aryl group or an aralkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 3.)

A molecule having at least one hydrolyzable silyl group represented by the following formula and having a molecular weight of 10,000
~ 200000 vinyl resins. Such a vinyl resin is

[0013]

Embedded image (Wherein, R ³ is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group, and an aralkyl group, and X is a halogen, alkoxy, acyloxy, aminoxy, phenoxy, thioalkoxy, amino group A group selected, n is an integer from 1 to 3), a method of causing a hydrosilylation reaction of a hydrosilane compound and a vinyl polymer having a carbon-carbon double bond with a catalyst,

[0014]

Embedded image (Wherein, R ⁴ is a monovalent hydrocarbon group selected from alkyl, aryl, and aralkyl groups having 1 to 10 carbon atoms, R ⁵ is an organic residue having a polymerizable double bond, X is halogen, A group selected from alkoxy, acyloxy, aminoxy, phenoxy, thioalkoxy and amino, n is 1
Is an integer from 1 to 3. ) And various vinyl compounds by radical polymerization.

The vinyl compound used herein includes methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, and the like. Acrylic acid and methacrylic acid ester, 2-hydroxyethyl acrylate, 2
-Hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, hydroxyl-containing vinyl compounds such as 2-hydroxyvinyl ether, acrylic acid, methacrylic acid, itaconic acid, carboxylic acids such as fumaric acid, and maleic anhydride. Such acid anhydrides, glycidyl acrylate, epoxy compounds such as glycidyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, amino compounds such as aminoethyl vinyl ether, acrylamide, methacrylamide, itaconic amide,
α-ethylacrylamide, crotonamide, fumaric diamide, maleic diamide, N-butoxymethylacrylamide, N-butoxymethylacrylamide, N
Amide compounds such as butoxymethyl methacrylamide,
Examples thereof include acrylonitrile, styrene, α-methylstyrene, vinyl chloride, vinyl acetate, and vinyl propionate. The vinyl polymer is obtained by polymerizing one or more of these.

Even if the acid value of the vinyl synthetic resin is 0,
The enamel particles are prevented from coalescing due to the protective colloid effect of the polyvinyl alcohol adsorbed on the surface of the enamel particles, but if the acid value is larger than 30, it is difficult to form particles when mixing the enamel composition with the aqueous polyvinyl alcohol solution. Becomes

Next, (B) coloring materials include titanium oxide, zinc white, graphite, yellow iron oxide, oka, titanium yellow, carbon black, graphite, chrome green, cobalt green, ultramarine blue, cobalt blue, cobalt violet, Molybdate Orange, Bengal, Permanent Red, Brilliant Carmine, Lake Red, Anthraquinone Red, Perylene Red, First Yellow,
Organics such as permanent yellow, isosindrinone yellow, quinophthalone yellow, phthalocyanine green, phthalocyanine blue, and quinacridone violet;
And inorganic coloring pigments.

(C) Organic solvents include petroleum hydrocarbons such as petroleum benzene, mineral spirits and terpenes, aromatic hydrocarbons such as benzene, toluene and xylene, alicyclic hydrocarbons such as cyclohexane, dichloroethane and tricrene. Or a mixture of solvents such as chlorinated hydrocarbons such as perchrene or the like.

(D) Viscosity modifiers include bentonite, sericite, ultrafine powdered silica, inorganic materials such as surface-treated calcium carbonate, amide wax, hydrogenated castor oil wax, benzylidene sorbitol, metal soap, polyethylene oxide,
Organic compounds such as sulfate ester anion activators can be used.

In the present invention, it is necessary that the enamel composition containing the components (A) to (D) has a specific viscosity. The specific viscosity means that the viscosity at 20 rpm measured at 20 ° C. with a BH type viscometer (the guide value at the fourth rotation) is 0.2 to 15 Pa · s, and the TI value is 1.0 to 1.0.
Although it is in the range of 8.0, when such a value is satisfied, the enamel particles are not destroyed even by shear stress at the time of coating, and a desired colorful pattern can be formed. In particular, when the viscosity is 0.3 to 10 Pa · s and the TI value is 2.0 to 6.0, the effects described above are stably exhibited, which is preferable.

If the viscosity at 20 rpm (the guide value at the fourth rotation) is lower than 0.2 Pa · s, the enamel particles are greatly deformed by shear stress, or the pattern formed on the surface to be coated flows. As a result, the design is impaired. On the other hand, when it is higher than 15 Pa · s, it becomes difficult to disperse the enamel composition in the aqueous polyvinyl alcohol solution.

On the other hand, if the TI value is smaller than 1.0, the pattern formed on the surface to be coated tends to flow even if the viscosity is 0.2 to 15 Pa · s. Enamel particles are crushed and scattered due to shear stress at the time of painting.

Here, the enamel composition is not particularly limited as long as it contains the above components and satisfies the above viscosity, but the ratio of the components is as follows:
(A) A vinyl synthetic resin having an acid value of 0 to 30 as solid content of 1
100 parts by weight, (B) 10 to 100 parts by weight of the coloring material, (C) 100 to 1000 parts by weight of the organic solvent,
(D) It is desirable from the point of design that the viscosity modifier is in a ratio of 1 to 10 parts by weight.

In the present invention, a fibrous substance or a filler may be added to such an enamel composition to such an extent that the viscosity is not impaired. As such a fibrous substance, pulp fiber, cellulose fiber, sepiolite, wollastonite, etc., as a filler, calcium carbonate, talc,
Clay, white carbon, gypsum, barium sulfate,
Mica and the like.

In addition, various additives which are usually added to the paint, for example, a thickener, a plasticizer, a preservative, a drying regulator, a dispersant, an ultraviolet absorber and the like are appropriately added to such an extent that the effects of the present invention are not impaired. You may.

[Aqueous Dispersion Medium] The aqueous dispersion medium in the present invention must form a coating film having a opacity of 0.05 to 0.60 in 4.8 of JIS K 5660 “Shiny synthetic resin emulsion paint”. For this reason, a coloring material is contained in the aqueous dispersion medium. As the coloring material, the same coloring material as the above-mentioned enamel particles can be used. The compounding amount is appropriately determined so that the coating formed by the aqueous dispersion medium falls within the above-mentioned hiding ratio. Further, among the coloring materials, those having a particle diameter of 1 μm or less can be used more preferably, since the enamel particles have a deep and luxurious atmosphere with a deep hue. Concealment rate is 0.0
When it is smaller than 5, the composite effect of the hue of the dispersion medium and the hue of the enamel particles is not obtained, and only the spotted pattern of the enamel particles is formed. If the concealment ratio is larger than 0.60,
The hue of the enamel particles becomes unclear, and a monochromatic coating of the hue of the dispersion medium is formed.

(Aqueous solution of polyvinyl alcohol) The aqueous dispersion medium contains, as the component (E), a 0.01 to 5% by weight aqueous solution of polyvinyl alcohol. Thereby, the above-mentioned enamel composition can form enamel particles using polyvinyl alcohol as a protective colloid. The polyvinyl alcohol in the aqueous polyvinyl alcohol solution has a weight average molecular weight of 10,000 to 100,000 and a saponification degree of 80 to 1
00 is used. Weight average molecular weight of 100
If it is lower than 00, the strength of the partition walls due to crosslinking of polyvinyl alcohol on the surface of the enamel particles is too weak,
During storage, the enamel particles coalesce. When the weight average molecular weight is higher than 100,000, the adsorption on the surface of the enamel particles becomes insufficient, and as a result, the strength of the partition walls becomes weak. Further, when the degree of saponification of polyvinyl alcohol is smaller than 80, the crosslinking density of the partition walls formed by crosslinking is too low, the strength of the partition walls is weakened, and each enamel particle is united with each other at the time of storage, or painted. On the way, the enamel particles are crushed apart. When the concentration of the aqueous polyvinyl alcohol solution is lower than 0.01% by weight, the enamel particles cannot be stably dispersed, and the storage stability decreases. If the content is higher than 5% by weight, the particle size of the enamel particles becomes too small, and the colorful feeling of the formed film is not so much expressed.

If cationic polyvinyl alcohol is used as the polyvinyl alcohol used in the aqueous polyvinyl alcohol solution, the storage stability can be further improved. Such a cationic polyvinyl alcohol is not particularly limited, but, for example, for each production method, firstly, as a method for post-modifying a polyvinyl alcohol polymer, an aminoacetal described in JP-B-30-5563 is disclosed. Of amino group by conversion, No. 57-3
Japanese Patent No. 4842 describes a method for producing a cationic polyvinyl alcohol containing a quaternary ammonium salt by reacting glycidyltrimethylammonium chloride with polyvinyl alcohol in the presence of an alkali catalyst, and a second method for copolymerization. JP-A-56-14504, JP-A-56-88113, JP-A-56-118997
In each of the publications, a method of saponifying a copolymer of aminoalkyl (meth) acrylamide, aminoalkyl (meth) acrylate (or a quaternary ammonium salt thereof) and vinyl acetate to obtain a cationic polyvinyl alcohol,
Further, as described in JP-A-59-135202, N- (3-allyloxy-2-hydroxypropyl)
Dimethylamine, N- (3-allyloxy-2-hydroxy-2-methylpropyl) dimethylamine, N- (4
(Allyloxy-3-hydroxybutyl) dimethylamine and those obtained by partially or completely saponifying a copolymer of a cationic monomer such as a quaternary ammonium salt thereof and an alkyl vinyl ester, etc. There is.

(Crosslinking Agent) In the present invention, the crosslinking agent used for dispersing the enamel composition in an aqueous solution of polyvinyl alcohol is not particularly limited as long as it is a compound which causes a crosslinking reaction with the hydroxyl group of polyvinyl alcohol. , Organic titanate compounds, alkoxysilane compounds, aluminum chelate compounds, aluminum alkoxide compounds and the like.

Among them, the organic titanate compound is an organic compound having titanium as a central metal.
Alkoxide type such as i-propoxytitanium and tetra-n-butoxytitanium; acylate type such as di-i-propoxybis (acetylacetonato) titanium;
A chelate type such as n-butoxybis (triethanolaminato) titanium can be used.
Chelate types such as butoxybis (triethanolaminat) titanium are preferably used because they are gradually hydrolyzed in an aqueous dispersion medium.

The amount of the crosslinking agent to be added is not particularly limited as long as the crosslinking reaction with polyvinyl alcohol is sufficiently performed.
The amount is preferably about 0.01 to 10 parts by weight with respect to 0 parts by weight.

In addition, in the aqueous dispersion medium, various additives usually added to the paint, for example, a thickener, a plasticizer, a preservative, a drying regulator, a dispersant, an ultraviolet absorber and the like can be used. May be appropriately added to such an extent that does not impair.

[Production Method] As a method for producing the enamel particle dispersion of the present invention, a method of adding a crosslinking agent while dispersing the enamel composition while stirring the aqueous polyvinyl alcohol solution, or a method of adding the enamel composition to the aqueous polyvinyl alcohol solution Is dispersed and a crosslinking agent is further added.

The particle diameter of the enamel particles is adjusted by appropriately setting the peripheral speed of the stirring blade and the blending time of the enamel composition, but is preferably 0.01 to 10.0 mm. When the enamel particle size is smaller than 0.01 mm, the colorfulness of the formed film is not so much expressed.
Conversely, when the enamel particle size is larger than 10.0 mm, problems such as a decrease in storage stability and the occurrence of uneven coating are likely to occur,
It lacks practicality.

The mixing ratio of the aqueous polyvinyl alcohol solution to the enamel composition is preferably about 1: 0.5 to 3 for the aqueous polyvinyl alcohol: enamel composition.

As described above, a monochromatic enamel dispersion is produced, and the enamel particle dispersions of the respective colors produced by the same method are mixed to obtain a multi-color paint.

[Coating method] The site to which the composition of the present invention is applied is not particularly limited. For example, metal, glass, porcelain tile, concrete, mortar, siding board, ALC board, extruded board, plastic board It can be used as a surface finishing material for various substrates.

The composition of the present invention is subjected to a surface treatment as needed on the substrate and then coated. The coating amount is usually about 0.2 to 1.0 kg / m ² .

The composition of the present invention can be coated using various coating equipment, but is mainly applied by spraying using a spray gun. The spray gun is not limited to a specific gun, and for example, ordinary coating equipment such as a ricin gun, a tile gun, and a universal gun can be used.

After the composition of the present invention has been applied, a clear coating may be further applied. The clear paint is not particularly limited, and a known paint can be used. A slightly colored one can also be used. Examples of the type of resin include acrylic resin, urethane resin, acrylic silicon, and fluorine. Considering weather resistance,
Acrylic silicon type, fluorine type and the like are desirable. The coating with the clear coating may be performed by a known coating, and can be performed by various coating methods such as spray coating, roller coating, and brush coating. The application amount of the clear paint may be appropriately set according to the application site and the like, and is usually about 0.1 to 0.4 kg / m ² .

[0041]

EXAMPLES In order to clarify the effects of the present invention, examples and comparative examples will be described below.

* Production of aqueous solution of polyvinyl alcohol Using the raw materials shown in Table 1, each aqueous solution of polyvinyl alcohol was produced according to the formulation shown in Table 2. The numbers in Table 2 are shown in parts by weight except for the concentration.

[0043]

[Table 1]

[0044]

[Table 2]

* Production of Enamel Compositions Using the raw materials shown in Table 1, each enamel composition was produced according to the formulation examples shown in Table 3. The numbers in Table 3 indicate the viscosity,
Except for the TI value, all parts are shown in parts by weight.

[0046]

[Table 3]

* Manufacture of multi-pattern paints Using the respective formulation examples shown in Tables 2 and 3, enamel particle dispersions were manufactured in combinations shown in Table 4. As a production procedure, after each enamel composition was dispersed while stirring the aqueous polyvinyl alcohol solution, a crosslinking agent was mixed. At this time, the crosslinking agent was mixed at a ratio of 0.5% by weight based on the solid content of polyvinyl alcohol. Thereafter, the pH was adjusted to about 9 using aminomethylpropanol as a pH adjuster. The aqueous polyvinyl alcohol solution and each of the enamel compositions were mixed at a weight ratio of 1: 1.5. As described above, after the mono-colored enamel particle dispersions were produced, the mono-colored enamel particle dispersions were finally mixed in each of the combinations shown in Table 4 to produce a multicolor paint composition. In addition, Formulation Example 15 could not produce an enamel particle dispersion.

[0048]

[Table 4]

* Test method (Initial state of paint) Immediately after producing a colorful paint, JISK 5
According to 667 "Colorful paint" 5.3 "State in container", the state of the paint when stirred slowly was visually checked. The evaluation was ○: no abnormality, ×: abnormal (lumps, gelation, abnormal thickening, etc.). (Storage Stability Test) After the multicolor paint was left in a thermostat at 50 ° C. for one month, the state of the paint when slowly stirred as described above was visually checked. The evaluation was ○: no abnormality, ×: abnormal (lumps, gelation, abnormal thickening, etc.). (Appearance of coating film) The multi-colored coating composition before and after storage was spray-coated on a slate plate at a coating amount of 0.3 kg / m ² , dried and cured at room temperature, and the appearance of the coating film was visually observed. Was evaluated. Evaluation: ○: appearance in which the color tone changes continuously and slightly, ×: appearance in which the contrast of the color particles is clear,
Or, the appearance was monochromatic and monotonous.

* Test results

[0051]

[Table 5]

(Examples 1 and 2) White enamel particles
The multi-color paint composition was dispersed in a black aqueous dispersion medium, and the formed coating film had an appearance in which the gray color tone changed continuously and slightly. It was also excellent in storage stability, and a coating film having the same appearance as in the initial stage could be obtained even after coating after storage.

Example 3 A multicolor paint composition in which white enamel particles and gray enamel particles are dispersed in a yellow aqueous dispersion medium, and the formed coating film has a continuous beige color tone. And the appearance changed slightly. It was also excellent in storage stability, and a coating film having the same appearance as in the initial stage could be obtained even after coating after storage.

Example 4 A multicolor paint composition in which gray enamel particles are dispersed in a white aqueous dispersion medium, and the formed coating film has a continuous and subtle change in gray color tone. It became the appearance. It was also excellent in storage stability, and a coating film having the same appearance as in the initial stage could be obtained even after coating after storage.

(Comparative Example 1) A multi-color paint composition in which gray enamel particles are dispersed in a white aqueous dispersion medium. The concealing rate of the aqueous dispersion medium is high.
It has a white, monotonous appearance.

(Comparative Example 2) A multicolor paint composition in which white enamel particles and gray enamel particles were dispersed in an aqueous dispersion medium containing no pigment.
The appearance of the contrast between the white grains and the gray grains was clear.

Comparative Example 3 As a result of using an aqueous dispersion medium in which the concentration of polyvinyl alcohol was lower than the concentration specified in the present invention, a slight increase in viscosity was observed immediately after the production of the colorful paint. Sedimented and coalesced after storage stability test.

(Comparative Example 4) As a result of using an aqueous dispersion medium in which the concentration of polyvinyl alcohol was higher than the concentration specified in the present invention, a slight increase in viscosity was observed immediately after the production of the colorful pattern paint. After the storage stability test, the viscosity increased abnormally.

(Comparative Example 5) Since polyvinyl alcohol having a weight average molecular weight lower than the specified range of the present invention was used, storage stability was poor.

(Comparative Example 6) Since polyvinyl alcohol having a degree of saponification lower than the specified range of the present invention was used, storage stability was poor.

(Comparative Example 7) The white enamel particles (Formulation Example 16) had a 20 rpm viscosity lower than the range specified by the present invention. It has dropped.

(Comparative Example 8) Since the TI value of the white enamel particles (Formulation Example 17) was higher than the range specified in the present invention, the particles were pulverized into pieces at the time of spray coating, and the particles were finely dispersed and applied. , The design was reduced.

(Comparative Example 9) Since the TI value of the white enamel particles (Formulation Example 18) was lower than the range specified in the present invention, the white particles flowed on the surface to be coated, and the design was reduced. Was.

[0064]

According to the present invention, the difference in hue between each color particle is not so clear, the hue changes continuously and subtly, and it is possible to obtain a conservative, deep, colorful pattern design. It is difficult to change the pattern formed by various conditions when the coating equipment is changed, furthermore, the storage stability of the paint is excellent, and its design is not impaired even after painting after long-term storage An enamel particle dispersion and a multi-color pattern coating composition are obtained.

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 4D075 CA32 CB17 CB36 DA06 DB01 DB12 DB13 DB14 DB31 DC02 EA06 EA10 EB13 EB14 EB15 EB19 EB20 EB22 EB33 EB42 EB52 EB55 EB56 EC11 EC30 EC33 EC37 EC54 4J038 CC02 CG02 CF08 CG082 CG142 CG162 CG172 CH032 CH042 CH122 CH172 CH202 DL152 GA06 KA03 KA06 KA07 KA08 MA02 MA08 MA10 MA15 NA01 NA26 PB05 PC02 PC03 PC04 PC08

Claims (4)

[Claims] (1) JIS K 5660 "Shiny synthetic resin emulsion paint" 4.8 (A) Acid value is 0 with respect to an aqueous dispersion medium forming a film having a hiding factor of 0.05 to 0.60.
And (B) a coloring material, (C) an organic solvent, and (D) a viscosity modifier at a temperature of 20 ° C. and a viscosity at 20 rpm (measured with a BH type viscometer at the fourth rotation). The guideline value) is an enamel particle dispersion in which an enamel composition adjusted to be in a range of 0.2 to 15 Pa · s and a TI value obtained in the following range of 1.0 to 8.0 is dispersed. The aqueous dispersion medium comprises (E) a weight average molecular weight of 10,000 to 100,000 and a saponification degree of 80 to 10.
0. An enamel particle dispersion comprising: a polyvinyl alcohol aqueous solution having a concentration of 0.01 to 5% by weight; and (F) a crosslinking agent. <TI value> TI value: a value obtained by using a BH-type viscometer according to Equation 1. TI value = η1 / η2 (Equation 1) (However, apparent viscosity at η1: 2 rpm (Pa ·
s: guide value at the second rotation), η2: apparent viscosity at 20 rpm (Pa · s: guide value at the fourth rotation)) 2. The enamel particle dispersion according to claim 1, wherein the polyvinyl alcohol is a cationic polyvinyl alcohol. 3. An enamel composition comprising (A) an acid value of 0 to 30.
For 100 parts by weight of a vinyl-based synthetic resin as a solid content,
(B) 10 to 100 parts by weight of the coloring material, (C) 100 to 1000 parts by weight of the organic solvent, and (D) 1 to 1 part by weight of the viscosity modifier.
The enamel particle dispersion according to claim 1 or 2, which is contained in an amount of 0 part by weight. 4. A multicolor paint composition comprising two or more of the enamel particle dispersions according to claim 1.