JP2013040275A - Double-color amorphous colored particle and multicolored pattern coating material composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a double-color amorphous colored particle capable of giving excellent designability and three-dimensional depth to a coating film, and to provide a multicolored pattern coating material composition containing the same.SOLUTION: The double-color amorphous colored particle comprises a plurality of amorphous materials 11a and 11b, wherein the difference (ΔL*) of L* by L*a*b* color system between at least one pair of the amorphous materials 11a and 11b is 8 to 50. The multicolored pattern coating material composition containing the colored particle is also provided.

Description

  The present invention relates to multicolor amorphous colored particles and a multicolor pattern coating composition containing the multicolor amorphous colored particles.

The multicolored paint is a paint that can form a paint film having various patterns of two or more colors by a single painting, and is often used mainly for painting buildings such as outer walls and inner walls. As a colorful pattern paint, for example, a colorful pattern paint in which two or more colors of monochromatic colored particles encapsulated with a gelled film are dispersed in a dispersion medium has been proposed.
However, the coating film formed from the multicolored paint containing two or more colors of monochromatic colored particles does not always satisfy the design property sufficiently.

Therefore, for example, in Patent Document 1, an emulsion paint containing two or more large particles having an average particle diameter of 0.2 to 2.0 mm is encapsulated with a gelled film as a multicolored paint that takes into consideration design properties. A water-based multicolored paint composition containing various colored particles is disclosed.
Patent Document 2 discloses a water-in-water multicolored paint composition in which at least one flat colored gel particle is dispersed in a paint containing an extender having a refractive index of 1.4 to 1.7. Yes.

JP 2010-132747 A JP 2005-15645 A

However, in the case of the water-based multicolor coating composition described in Patent Document 1, it is possible to form a coating film having a complex and diverse hue by including two or more specific large powder particles, but has a depth that provides a three-dimensional effect. It is not easy to form a multicolored paint film.
On the other hand, in the case of the water-in-water multicolor pattern coating composition described in Patent Document 2, a matte coating film with excellent sharpness can be formed by containing a specific extender pigment, but it has excellent design and three-dimensional effect. It is not possible to form a coating film with a certain depth.

  The present invention has been made in view of the above circumstances, and is capable of imparting a depth such that the coating film has excellent design and three-dimensionality, and a multicolor pattern containing the multicolor amorphous colored particles. An object is to provide a coating composition.

The multicolor irregularly colored particles of the present invention are composed of a plurality of irregularly shaped particles, and at least one set of irregularly shaped particles has an L * difference (ΔL *) of 8 according to the L * a * b * color system. ˜50.
It is preferable that a * by L * a * b * colorimetric system is -2 or more and 2 or less and each b * is -3 or more and 3 or less.
The multicolored paint composition of the present invention is characterized by containing the above-mentioned multicolor irregularly colored particles.

  ADVANTAGE OF THE INVENTION According to this invention, the multicolor non-uniform colored particle | grains and multicolor pattern coating composition which can provide the depth which has the designability excellent in the coating film and a three-dimensional effect can be provided.

It is a schematic diagram which shows an example of the multicolor irregular-shaped colored particle of this invention. It is a figure which shows an example of the nozzle used for manufacture of the bicolor non-uniform colored particle | grains of this invention, (a) is a side view, (b) is a front view. It is a figure explaining the manufacturing method of the bicolor non-uniform colored particle | grains using the nozzle shown in FIG. It is a figure explaining the manufacturing method of the bicolor non-uniform colored particle | grains using the nozzle of another example, (a) is the state which the discharge ports of a nozzle are in contact, (b) is the discharge ports of a nozzle Is not touching. It is a figure explaining the manufacturing method of the bicolor non-uniform colored particle | grains using the nozzle of another example, (a) is a state in which the discharge port of a nozzle is not immersed in a dispersion medium, (b) is the state in which discharge of a nozzle is carried out. The outlet is immersed in the dispersion medium. It is a figure explaining the arrangement | positioning at the time of using three nozzles, (a) is a bottom view at the time of using three nozzles shown in FIG. 2, (b) is 3 nozzles shown in FIG. It is a bottom view at the time of using this.

[Multicolored irregular colored particles]
FIG. 1 is a schematic view showing an example of the bicolor amorphous colored particles of the present invention. The multicolor irregular colored particles 10 of this example are composed of a plurality (two in this example) of irregularly shaped objects 11a and 11b having different colors, and the L of one irregularly shaped object 11a and the other irregularly shaped object 11b. * A * b * L * difference (ΔL *) by the color system is 8-50.

Here, “L * a * b * color system” is a color display method specified in JIS Z 8729, and each value of L *, a *, and b * is measured by a commercially available color difference meter. The
In the present invention, the L *, a *, and b * values for the indeterminate form are formed from an emulsion paint used to form the indeterminate form, and the color difference meter is used for the coat. It is a value measured by.
The color difference is measured with a sample coated with the coating thickness of the paint. The “hiding film thickness” in the present invention means that the desired paint is applied to the coated surface of the hiding rate test paper defined in JIS K 5600-4-1 and the black and white pattern cannot be visually observed through the coating film. It is the minimum film thickness.

Here, “indefinite shape” means that the shape is easily changed by a change in pressure or the like, and examples thereof include a gel shape.
Hereinafter, the case where the multicolor irregular colored particles 10 are gel colored particles will be described as an example.

  The bicolor amorphous colored particles 10 include, for example, two types of emulsion paints containing a resin emulsion, a hydrophilic colloid-forming substance, and a color pigment, and contain a gelling agent in a state where these emulsion paints are in contact with each other. It is obtained by dispersing in a dispersion medium.

<Emulsion paint>
(Resin emulsion)
As the resin emulsion, for example, commercially available resin emulsions such as polyvinyl acetate, acrylic resin, polystyrene, acrylonitrile, beova (branched fatty acid vinyl ester), natural or synthetic rubber, and emulsions of copolymers thereof are used. be able to. Among these, an acrylic resin is preferable.

(Hydrophilic colloid-forming substance)
When the emulsion paint contains a hydrophilic colloid-forming substance, the hydrophilic colloid-forming substance and a gelling agent described later can react to encapsulate the emulsion paint.
Examples of the hydrophilic colloid-forming substance include cellulose derivatives; polytylene oxide; polyvinyl alcohol; and aqueous solutions containing natural polymers such as casein, starch, galactomannone, guar gum, locust bean gum, and the like. Among them, an aqueous solution of guar gum is preferable, and the concentration of the aqueous solution is preferably 0.5 to 5% by mass, and more preferably 1.0 to 3% by mass.
A hydrophilic colloid-forming substance may be used alone or in combination of two or more.

The content (in terms of solid content) of the hydrophilic colloid-forming substance is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 3.0 parts by mass with respect to 100 parts by mass of the resin emulsion.
By setting the content of the hydrophilic colloid-forming substance within the above range, a stable gelled film can be obtained.

(Color pigment)
Examples of coloring pigments include inorganic pigments such as carbon black, titanium oxide, iron oxide, lead chromate, cadmium yellow, and cadmium red, and brilliant properties such as pearl pigments, mica pigments, mica-coated pearl pigments, aluminum powder, and stainless steel powder. Examples thereof include organic pigments such as pigments, phthalocyanine blue, phthalocyanine green, and quinacridone red.
A color pigment may be used individually by 1 type, and may use 2 or more types together.

  The content of the color pigment in the emulsion paint is preferably 15 to 40 parts by mass, more preferably 20 to 35 parts by mass with respect to 100 parts by mass of the resin emulsion.

(Optional component)
The emulsion paint may contain an extender pigment as an optional component, if necessary.
Examples of extender pigments include kaolin, barium sulfate, hydrous magnesium silicate, and calcium carbonate.
The extender pigments may be used alone or in combination of two or more.
As for content of an extender, 0-30 mass% is preferable in 100 mass% of emulsion paints, More preferably, it is 0-20 mass%.
The emulsion paint may contain a dispersing agent such as an anionic polymer dispersing agent for dispersing the color pigment.

(Preparation of emulsion paint)
The emulsion paint is obtained by adding a liquid mixture of a color pigment and water to a liquid obtained by adding a hydrophilic colloid-forming substance to the resin emulsion and stirring and mixing, and further stirring and mixing. In the case of using an optional component, it may be added to either of these two liquids.
The water content is preferably 100% by mass and 40 to 90% by mass, and more preferably 50 to 80% by mass, of the emulsion paint.

<Dispersion medium>
The dispersion medium is obtained by adding water and diluting an aqueous solution containing a gelling agent, a dispersion containing an extender pigment, and an aqueous solution containing a water-soluble polymer compound with stirring.
As for content of water, 20-80 mass% is preferable in 100 mass% of dispersion media, More preferably, it is 30-70 mass%.

(Gelling agent)
Examples of the gelling agent include an aqueous solution containing magnesium montmorillonite clay, sodium pentachlorophenol, borate, tannic acid, titanium lactate, calcium chloride, and the like. Among these, an aqueous solution of borate is preferable, and the concentration of the aqueous solution is preferably 0.05 to 10% by mass, and more preferably 0.5 to 8% by mass.
A gelling agent may be used individually by 1 type, and may use 2 or more types together.

  The content (in terms of solid content) of the gelling agent is preferably 0.05 to 5% by mass, more preferably 0.1 to 3% by mass in 100% by mass of the dispersion medium. By setting the content of the gelling agent within the above range, a stable gelled film can be obtained.

(Optional component)
The dispersion medium may contain extender pigments and water-soluble polymer compounds as optional components as necessary.
Examples of extender pigments include dispersions containing kaolin, barium sulfate, hydrous magnesium silicate, calcium carbonate, and the like. Among them, a dispersion of hydrous magnesium silicate is preferable, and the concentration of the dispersion is preferably 0.05 to 20% by mass, more preferably 2 to 10% by mass.
The extender pigments may be used alone or in combination of two or more.
The content of the extender pigment (in terms of solid content) is preferably 0.05 to 10% by mass and more preferably 0.1 to 5% by mass in 100% by mass of the dispersion medium.

Examples of the water-soluble polymer compound include aqueous solutions containing hydroxyethyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, and the like. Among them, an aqueous solution of carboxymethyl cellulose is preferable, and the concentration of the aqueous solution is preferably 0.1 to 5% by mass, and more preferably 0.5 to 3% by mass.
A water-soluble high molecular compound may be used individually by 1 type, and may use 2 or more types together.
The content of the water-soluble polymer compound (in terms of solid content) is preferably 0.05 to 3% by mass, more preferably 0.1 to 2% by mass in 100% by mass of the dispersion medium.

<Manufacture of multicolor irregular colored particles>
The multicolor irregular colored particles 10 are formed by charging a plurality of emulsion paints having different colors into a stirred dispersion medium and dispersing (subdividing) in the dispersion medium.
In the case of using two types of emulsion paints, specifically, two nozzles 20 having the tip of the discharge port 21 cut obliquely as shown in FIGS. 2A and 2B are used. As shown, the nozzles 20a and 20b are bundled so that the cut surfaces of the discharge ports 21a and 21b of the two nozzles 20a and 20b face each other. Then, one type of emulsion paint is discharged from each of the nozzles 20a and 20b above the dispersion tank 30 containing the dispersion medium 31, and the emulsion paint is put into the dispersion medium 31 in contact with the emulsion paint. The dispersion medium 31 is stirred with a disperser (not shown) such as a dissolver.

  Here, the two types of emulsion paints are selected so that each emulsion paint is formed into a coating film, and the difference (ΔL *) in L * measured for the obtained coating film is in the range of 8-50.

  As described above, when the emulsion paints are put into the dispersion medium 31 in contact with each other, the hydrophilic colloid-forming substance contained in the emulsion paint and the gelation contained in the dispersion medium are brought into contact with each emulsion paint. The emulsion paints are individually confined in a three-dimensional network formed by the action of the agent. Further, when this is subdivided, as shown in FIG. 1, double-colored irregularly colored particles (multicolored gel-like colored particles) composed of irregularly shaped (gel-like) 11a and 11b encapsulated with a gelled film. 10 is formed. Each of the indefinite shapes 11a and 11b is formed based on two types of emulsion paints in contact with each other.

  The discharge port 21 of the nozzle 20 is cut so that the angle θ1 formed by the cut surfaces when the two nozzles 20a and 20b are bundled so that the cut surfaces face each other as shown in FIG. 3 is 45 to 120 °. Preferably, it is 60 to 90 °. When the angle θ1 is 45 ° or more, the discharge amount of each emulsion paint discharged from the discharge ports 21a and 21b can be set to a sufficient amount. On the other hand, when the angle θ1 is 120 ° or less, the emulsion paints to be discharged are easily brought into contact with each other, and can be easily put into the dispersion medium 31 in a contacted state.

The two nozzles 20a and 20b shown in FIG. 3 have the same cutting angle, but the cutting angle may not be the same as long as the angle θ1 is within the above range. If two nozzles 20a and 20b having different cutting angles are used, multicolor amorphous colored particles having different proportions of irregular shapes can be obtained.
If there is a difference in the discharge flow rate and discharge flow rate of each emulsion paint, even if the cutting angles of the two nozzles 20a and 20b are the same as shown in FIG. Particles are obtained.

  The two nozzles 20a and 20b are preferably installed at a position where the distance d1 from the contact point 22 of the discharge ports 21a and 21b to the water surface 32 of the dispersion medium 31 is 10 cm or less, more preferably 5 cm or less. is there. If the distance d1 is 10 cm or less, it can be put into the dispersion medium 31 before the two emulsion paints in contact with each other are mixed. If the emulsion paint is mixed and put into the dispersion medium, the resulting irregular colored particles may be monochromatic irregular colored particles having a hue formed by mixing two types of emulsion paint.

  In this way, by encapsulating the emulsion paint with a gelled film, the bicolor amorphous colored particles can be stably dispersed in the dispersion medium. In addition, the multicolor amorphous colored particles generated in the dispersion medium are usually in a state of being dispersed in the dispersion medium, that is, a state of “colored particle dispersion” in which the multicolor amorphous colored particles are dispersed in the dispersion medium. It is used for multi-pattern paint compositions. Therefore, the ratio of the emulsion paint and the dispersion medium is preferably 100 to 500 parts by weight, more preferably 150 parts by weight, when the total of all emulsion paints charged into the dispersion medium is 100 parts by weight. It is -400 mass parts. By setting the ratio of the emulsion paint and the dispersion medium within the above range, encapsulated multicolor irregularly colored particles having a uniform shape are formed.

  Such multicolor amorphous colored particles are composed of a plurality of amorphous materials having different colors, and the difference in L * due to the L * a * b * color system between an arbitrary amorphous material and another amorphous material. Since (ΔL *) is 8 to 50, it seems that a deep shadow is formed on each multicolor irregular colored particle. Therefore, the coating film can be provided with such a depth that there is a three-dimensional feeling (depth feeling) as well as excellent design properties. Preferred ΔL * is 15 to 40, and more preferred ΔL * is 20 to 30. When ΔL * is less than the lower limit or exceeds the upper limit of the above range, the design property is lowered and it is difficult to obtain a depth with a three-dimensional effect. Specifically, the shadow becomes difficult to recognize and the depth is not felt. Further, in the case of monochromatic irregularly colored particles, it is difficult to appear as if a shadow is formed, and it is not easy to impart a depth that gives the coating film a three-dimensional effect.

  Further, each of the amorphous materials constituting the multicolor irregular colored particles has an a * of −2 or more and 2 or less according to the L * a * b * color system, and ab * of −3 or more. It is preferable that it is 3 or less. If each amorphous object is within such a range, it becomes an approximate color not only in lightness (L *) but also in color, so that it can be felt as if a shadow has been made more reliably.

  In addition, in the case where the multicolor irregular colored particles are composed of two kinds of irregularly shaped (i) and irregularly shaped (ii) having different colors as in the above example, the irregularly colored (i) and irregularly shaped (i) ΔL * is obtained from the value of L * for each of the shaped objects (ii), and this value ΔL * may be 8 to 50. In addition, when the multicolor irregular colored particles are composed of three types of irregularly shaped (i), irregularly shaped (ii), and irregularly shaped (iii) having different colors, ΔL * determined for at least one of the three combinations of the shaped product (ii), the amorphous product (ii) and the amorphous product (iii), and the amorphous product (iii) and the amorphous product (i) The value of may be 8-50. Preferably, it is an aspect in which the value of ΔL * obtained is 8 to 50 for all three combinations. As described above, in the present invention, L * a * b between at least one set of irregular shapes (at least two irregular shapes) among a plurality of types of irregular shapes contained in the multicolor irregular shaped colored particles. * The difference in L * (ΔL *) depending on the color system may be 8 to 50, but preferably, the arbitrarily selected amorphous material is ΔL * between all other amorphous materials. Satisfies the relationship of 8 to 50.

  Moreover, it is preferable that each quantity of the multiple types of emulsion coating material to be used is at least 20 mass% or more when these total mass is 100 mass%. When the amount of each emulsion paint is 20% by mass or more, the design properties of the formed coating film are further improved.

The multicolor irregular colored particles formed in this way are soft and contain a lot of moisture. The particle diameter can be freely controlled by the viscosity of the emulsion paint or dispersion medium, the number of revolutions of the disperser, the stirring time, the combination of the hydrophilic colloid-forming substance and the gelling agent, and the amount of the gelling agent. Usually, if the viscosity of the emulsion paint or the dispersion medium is increased, the particle diameter is increased, and if the rotational speed of the disperser is increased, the particle diameter is decreased.
The particle diameter of the bicolor amorphous colored particles is preferably 0.1 to 50 mm, more preferably 3 to 20 mm. By setting the particle diameter within the above range, when a plurality of multicolored irregular colored particles having different color tones are mixed, a three-dimensional effect is likely to occur in the coating film, and the design property is enhanced.

<Other embodiments>
The method for producing the bicolor amorphous colored particles is not limited to the above. For example, in the example described above, the two nozzles whose tip of the discharge port is cut obliquely are bundled so that the cut surfaces face each other, but if the two types of emulsion paints can be put into the dispersion medium in contact with each other, The cut surfaces may not face each other, for example, may face the opposite side.

Moreover, the nozzle used for manufacture of a multicolor irregular-shaped colored particle does not need to cut | disconnect the front-end | tip of a discharge outlet diagonally. In this case, as shown in FIG. 4A, the discharge ports 41a and 41b are in contact with each other so that the angle θ2 formed by the discharge ports 41a and 41b of the two nozzles 40a and 40b is 45 to 120 °. The angle is preferably 60 to 90 °. When the angle θ2 is 45 ° or more, the discharge amount of each emulsion paint discharged from the discharge ports 41a and 41b can be set to a sufficient amount. On the other hand, if the angle θ2 is 120 ° or less, the emulsion paints to be discharged are easily brought into contact with each other, and can be easily put into the dispersion medium 31 in a contacted state.
If two types of emulsion paints come into contact with each other before being put into the dispersion medium 31 of the dispersion tank 30 provided below the discharge ports 41a and 41b and can be put into the dispersion medium 31 in this state, FIG. As shown in FIG. 4, the discharge ports 41a and 41b of the two nozzles 40a and 40b may be separated from each other.

  Furthermore, as shown in FIG. 5A, multicolor irregular colored particles may be produced by using a nozzle 50 provided with a discharge port 51 at a point where two pipes 50a and 50b merge. In this case, two types of emulsion paints are brought into contact with each other at the junction 52 of the pipes 50 a and 50 b, and are discharged from the discharge port 51 in the contacted state and are put into the dispersion medium 31 of the dispersion tank 30. Accordingly, the distance d2 from the junction 52 of the pipes 50a and 50b to the discharge port 51 is preferably short. If the distance d2 is too long, the two-color emulsion paints in contact at the confluence 52 are mixed before being discharged, and it becomes easy to obtain monochromatic irregular colored particles. The distance d2 is preferably 3 cm or less, more preferably 1 cm or less. If the distance d2 is 3 cm or less, it can be put into the dispersion medium 31 before the two types of emulsion paints in contact with each other are mixed.

  In FIG. 5 (a), two types of emulsion paints are put into the dispersion medium 31 in contact with each other from a nozzle 50 installed above the dispersion tank 30, but for example, as shown in FIG. 5 (b). As described above, the discharge port 51 of the nozzle 50 may be immersed in the dispersion medium 31. In this case, the two-color emulsion paints contacted at the junction 52 of the pipes 50 a and 50 b are directly charged into the dispersion medium 31.

In addition, in the case of producing multicolor irregular colored particles composed of three or more irregular shapes, for example, a nozzle in which the tip of the discharge port 21 is cut obliquely as shown in FIGS. 2 (a) and 2 (b). It is preferable that three nozzles 20 are used and three nozzles are arranged as shown in FIG. 6A when viewed from the discharge port side. Further, in the case of using a nozzle whose tip of the discharge port is not cut obliquely as shown in FIG. 4, the three nozzles are arranged as shown in FIG. 6B when viewed from the discharge port side. Preferably it is done.
In FIGS. 6A and 6B, reference numerals 20a to 20c and 40a to 40c are nozzles, and reference numerals 21a to 21c and 41a to 41c are discharge ports corresponding to the respective nozzles.

  In addition, when producing multicolored irregular colored particles using a nozzle having three or more nozzles or a nozzle provided with a discharge port at the end of three or more pipes, the number of nozzles or pipes and the type of emulsion paint May not necessarily match. That is, if emulsion paints of different colors are discharged from at least two nozzles or pipes, it is not always necessary to discharge emulsion paints of different colors from the remaining nozzles or pipes.

[Multicolored paint composition]
The multicolor pattern coating composition of the present invention contains the bicolor amorphous colored particles of the present invention and water, and is usually obtained by stirring and mixing the colored particle dispersion and water. In addition, the multicolor paint composition may contain two or more types of multicolor irregular colored particles having different color tones. By including two or more types of multicolor irregular shaped colored particles, a pattern having a more complicated depth can be obtained when a coating film is formed.

  The content of the colored particle dispersion is preferably 30 to 100% by mass and more preferably 40 to 80% by mass in 100% by mass of the multicolor pattern coating composition. When the content of the colored particle dispersion is 30% by mass or more, a more complicated and three-dimensional coating film is easily obtained.

Since the bicolor irregular colored particles have a binder function, it is not necessary to further add a binder resin in the production of the multicolor pattern coating composition of the present invention using this, but if necessary, the role of the binder You may mix | blend the resin emulsion which fulfill | performs.
As resin emulsions, polyvinyl acetate, acrylic resin, acrylic-silicone resin, polystyrene, acrylonitrile, beova (branched fatty acid vinyl ester), natural or synthetic rubber, and emulsions of copolymers thereof are generally commercially available resins. Emulsions can be used. Among these, an acrylic resin is preferable.
The amount of the resin emulsion blended when producing the multicolor pattern paint composition is preferably 0 to 50% by mass, more preferably 20 to 40% by mass in 100% by mass of the multicolor pattern paint composition. . By including the resin emulsion within the above range, it is possible to obtain a coating film having excellent coating workability and good durability.

  30-85 mass% is preferable in 100 mass% of colorful pattern coating compositions, and, as for the quantity of the water mixed at the time of manufacture of a colorful pattern coating composition, 40-80 mass% is more preferable.

  The multi-color paint composition of the present invention contains known additives such as thickeners, dispersants, antifoaming agents, preservatives, leveling agents and the like as optional components within the range not impairing the effects of the present invention. Also good.

There are no particular restrictions on the use of the thus obtained multicolor pattern coating composition, and it can be applied to various coating objects such as mortar, concrete, ceramic materials, plastic, metal, wood and paper. is there.
Although there is no restriction | limiting in particular in the application quantity of the colorful pattern coating composition at the time of application | coating, It is preferable to apply | coat so that it may become 300-600 g / m < ² > normally.
Moreover, there is no restriction | limiting also in the coating method, It can apply | coat by well-known application methods, such as a brush, a trowel, a roller, and a spray, and can dry at normal temperature and heat.

As described above, according to the multi-pattern paint composition containing multicolored irregularly colored particles having an L * difference (ΔL *) between at least one pair of irregularly shaped objects of 8 to 50, On the other hand, the depth which has the outstanding design property and a three-dimensional feeling can be provided. In addition, in the multicolor irregular colored particles, irregularly colored objects of different colors are necessarily adjacent to each other. Therefore, according to the multicolor pattern coating composition containing such multicolor irregular shaped colored particles, it cannot be obtained when a coating composition containing two or more kinds of monochromatic colored particles is used. The novelty in design such as “adjacent to a specific color” is exhibited.
Further, in the case of a coating composition containing two or more kinds of monochromatic colored particles, even if the same coating composition is used, the overlapping of the colored particles changes due to coating, thereby causing a difference in the appearance of the coating film. . Therefore, it is necessary to consider such a difference in appearance when painting. However, in the case of a multicolor pattern coating composition containing multicolored irregular colored particles, there are always different colors adjacent to each other in the multicolored irregular colored particles. Does not occur. Therefore, it is not necessary to paint while considering how the coating film looks.

  Although the coating film by the multicolored paint composition is provided on the surface of the object to be coated, it may be provided directly on the object to be coated or may be provided via a base coat layer. Moreover, the clear coating layer may be provided in the formed coating film as needed. Alternatively, the multicolor pattern coating composition may be used as a coating composition for forming the topcoat layer and applied onto a coating film formed from another coating material.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these. In the examples, “part” means “part by mass”, and “%” means “% by mass”.

[Manufacture of multicolored irregular colored particles]
<Preparation of emulsion paint G-1>
According to the composition shown in the component (a) in Table 1, 38 parts of an acrylic resin emulsion (manufactured by Nippon Acrylic Chemical Co., Ltd., “Primal AC38”) and 28.5 parts of a 1.5% aqueous solution of a nonionic guar rubber derivative (solid) Min. 0.43 parts) to prepare a mixed solution (a).
Separately, according to the composition shown in the component (b) of Table 1, 10 parts of titanium white (Ishihara Sangyo Co., Ltd., “Titanium R930”) and an anionic polymer dispersant (Nippon Acrylic Chemical Co., Ltd., “Orotan 731”) “) 1 part and 22.5 parts of water were mixed to prepare a mixed solution (b).
Subsequently, the mixed solution (a) and the mixed solution (b) were mixed and stirred to obtain an emulsion paint G-1 (white).

<Preparation of emulsion paint G-2>
Emulsion paint G-2 (black) was obtained in the same manner as emulsion paint G-1, except that the mixed solution (b) was prepared according to the composition shown in the component (b) of Table 1.
The iron oxide black shown in Table 1 was “Baiferox 318” manufactured by LANXESS.

<Preparation of emulsion paints F-1 to F-12>
In accordance with the formulation shown in Tables 2 and 3, emulsion paints G-1 and G-2 were mixed to obtain emulsion paints F-1 to F-12.
The obtained emulsion paints F-1 to F-12 are applied to the coated surface of the cover factor test paper defined in JIS K 5600-4-1 to form a coating film. L *, a *, and b * were measured using a colorimeter CM-2500d (manufactured by Konica Minolta Co., Ltd.). The results are shown in Tables 2 and 3.
Table 4 shows the difference in L * (ΔL *) between one emulsion paint and another emulsion paint for emulsion paints F-1 to F-12. For example, ΔL * between the emulsion paint F-1 and the emulsion paint F-2 is 2.75.

<Preparation of dispersion medium>
To 25 parts of a 4% dispersion of hydrous magnesium silicate in water (1 part solids), 5 parts of a 5% aqueous solution of ammonium biborate (solids 0.25 parts) and 25 parts of a 1% aqueous solution of sodium carboxymethylcellulose ( (0.25 part solid content) was added and stirred and mixed, and then 45 parts water was added and diluted to obtain a dispersion medium.

<Manufacture of Multicolor Amorphous Colored Particles A-1 to A-16, B-1 to B-4>
When the emulsion paints F-1 to F-12 are used in combination as shown in Tables 5 to 7 and two kinds of emulsion paints are used (A-1 to A-12, B-1 to B-2), As shown in FIG. 3, each emulsion paint is discharged from the discharge ports 21a and 21b of the nozzles 20a and 20b, and before reaching the liquid level of the dispersion medium 31, and is stirred by the dissolver in the contacted state. The dispersion medium 31 was charged to obtain a colored paint dispersion containing double-colored amorphous colored particles.
The ratio (mass basis) of the emulsion paint and the dispersion medium was set so that the total amount of all emulsion paints charged into the dispersion medium: the amount of dispersion medium = 60: 40.
The angle θ1 formed by the cut surfaces was 75 °, and the distance d1 from the contact 22 of the discharge ports 21a and 21b to the water surface 32 of the dispersion medium 31 was 5 cm.
Moreover, when three types of emulsion paints are used (A-13 to A-16, B-3 to B-4), three nozzles are equally arranged as shown in FIG. did.
In the table, for example, the description of “F-5: 50” means that 50 parts of the emulsion paint F-5 was used.

<Production of Monochromatic Amorphous Colored Particles C-1 to C-3>
As shown in Table 8, the emulsion paints F-1, F-6, and F-9 were used, respectively, and the emulsion paint was added to the dispersion medium in a ratio of the total amount of the emulsion paint: the amount of the dispersion medium = 60: 40, Stirring was performed with a dissolver to obtain monochromatic, irregularly colored particles C-1, C-2, and C-3.

[Example 1]
<Preparation of multi-color paint composition>
As shown in Table 9, in 25 parts of an acrylic resin emulsion ("Primal AC-33" manufactured by Nippon Acrylic Chemical Co., Ltd.), 70 parts of a colored particle dispersion containing bicolor amorphous colored particles A-1, and alkali-soluble 1 part of a mold thickener (SN thickener 636), 0.1 part of 25% aqueous ammonia and 3.9 parts of water were mixed and stirred with a dissolver to produce a multi-pattern coating composition.

(Appearance evaluation: Designability)
The obtained multicolor pattern coating composition was spray-coated on the surface of the slate plate so that the coating amount was 500 g / m ² and dried at room temperature to obtain a multicolored paint film. And the external appearance of the coating film was observed visually and evaluated by the following evaluation criteria. The results are shown in Table 9.
A: There is a complex depth where the shading is conspicuous and there is a stereoscopic effect.
○: There is a feeling of shading, and there is a depth that has a three-dimensional effect.
(Triangle | delta): A shading feeling is weak and there is a slight depth which has a three-dimensional feeling.
X: A shadow is not felt and there is no depth which has a three-dimensional feeling.

[Examples 2 to 16, Comparative Examples 1 to 4]
A multicolor paint composition was prepared in the same manner as in Example 1 except that the colored particle dispersion containing the bicolor amorphous colored particles shown in Tables 9 to 11 was used, and the appearance of the coating film was evaluated. The results are shown in Tables 9-11.

[Comparative Examples 5 to 7]
Instead of the colored particle dispersion containing the bicolor irregular colored particles, the colored particle dispersion containing the monochromatic irregular colored particles C-1 to C-3 was used in combination of two or three types as shown in Table 12. Except for the above, a multicolor pattern coating composition was prepared in the same manner as in Example 1, and the appearance of the coating film was evaluated. The results are shown in Table 12.

As is clear from the results shown in the table, the multicolored paint composition obtained in each example was able to form a deep multicolored paint film having a three-dimensional effect.
In particular, the multicolor pattern paints of Examples 2 to 9 and 11 to 14 including multicolored irregularly colored particles composed of a plurality of irregularly shaped products having a difference in values of L * (ΔL *) of 15 to 40 in all groups. From the composition, it was possible to form a multi-pattern coating film that felt a depth with a three-dimensional effect. Above all, from the multi-pattern paint compositions of Examples 4 to 7 where the difference in L * value (ΔL *) is 20 to 30, the coating film has a more pronounced shading, has a complex depth, and is excellent in design. Could be formed. In addition, although Example 11 satisfy | fills the conditions (deltaL *) of the value of L * of 20-30, since the ratio of the emulsion paint F-2 used for manufacture is small, compared with Examples 4-7. The design property of the coating film was slightly lowered.
Further, in the multicolor pattern paint composition of Example 16, one set of ΔL * is 10.18 and is in the range of 8 to 50, but the remaining two sets of ΔL * both exceed 50. For this reason, the designability was slightly lowered.
On the other hand, the multicolor pattern coating compositions of Comparative Examples 1 to 4 include those composed of a plurality of amorphous materials having a difference in value of L * (ΔL *) outside the preferred range as multicolor irregular colored particles. Therefore, it was not possible to form a coating film having a three-dimensional effect and depth like the coating film of the example.
Moreover, since the multicolored paint composition of Comparative Examples 5 to 7 contains two or more kinds of single-color irregularly shaped colored particles, the formed coating film did not have a shadow and did not have a depth such as a three-dimensional effect. .

10: Multicolor irregular shaped colored particles 11a, 11b: irregularly shaped particles

Claims (3)

It consists of a number of irregular shapes,
A multicolor irregularly colored particle having a difference in L * (ΔL *) of 8 to 50 according to the L * a * b * color system between at least one set of irregular shapes.   2. Each of the indefinite shapes has an a * of −2 or more and 2 or less and an b * of −3 or more and 3 or less according to the L * a * b * color system. Multicolor irregular colored particles.   A multi-color paint composition containing the multicolored irregular colored particles according to claim 1 or 2.

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