JP6952502B2 - Aqueous multi-pattern paint composition and multi-pattern coating - Google Patents

Description

The present invention relates to a novel water-based multi-pattern coating composition that does not require undercoating, and a multi-pattern coating film that is a dry-cured product thereof.

Various highly-designed multicolored pattern coatings have been proposed, which can give a plurality of color patterns to the exterior and interior of a building or the like by one coating. As the multicolored pattern paint used for the multicolored pattern coating, various forms of paint such as underwater oil type and underwater water type have been proposed, but in recent years, in terms of the environment, underwater water that basically does not use an organic solvent has been proposed. A type of water-based multi-pattern paint is attracting attention.

Patent Document 1 discloses a water-in-water multi-pattern paint composition in which flat colored gel particles are dispersed in a paint containing an aqueous resin and an extender pigment having a refractive index of 1.4 to 1.7. The multicolored pattern paint composition of Patent Document 1 is capable of forming a matte coating film having excellent smoothness and vividness by dispersing flat colored gel particles in a transparent matte paint. It is characterized by.

Patent Document 2 includes a colored paint particle component (A), a coating film forming component (B), and resin beads (C) having an average particle size of 1 to 40 μm, and the functions (A) and (B) can react with each other. A water-based multicolored pattern paint containing a group is disclosed. The water-based multi-pattern paint of Patent Document 2 is characterized in that by containing (C) in a specific amount, it is possible to form a matte multi-pattern coating film having excellent water resistance and weather resistance and having a variety of design feelings. ..

Patent Document 3 includes colored particles in which an emulsion paint is encapsulated with a gelled film, and the colored particles are specific translucent colored particles, so that the formed coating film is subjected to specific total light rays under specific conditions. Water-based coating compositions exhibiting transmittance are disclosed. Since the water-based coating composition of Patent Document 3 contains specific translucent colored particles, not only the color tone of the colored particles used but also the base can be seen through, and a pattern having a complex sense of depth is applied. It is characterized in that a film can be formed.

Japanese Unexamined Patent Publication No. 2005-15645 JP-A-2009-173770 Japanese Unexamined Patent Publication No. 2013-139585

However, the conventional water-based water-based multicolored pattern paint has relatively high transparency in the coating film portion where the colored paint does not exist in order to enhance the design of the multicolored pattern, and therefore, it is rational in terms of appearance, cost, etc. There is a problem that the base can be seen through in the coating with a standard coating film thickness.
Therefore, usually, the undercoat coating is performed to cover the base, and then the water-based colorful pattern paint is applied. Alternatively, as disclosed in Patent Document 3, a technique is adopted in which the base is intentionally made a part of the pattern.
When the undercoat coating is carried out, there is a problem that the coating process is increased by one process, the coating cost is increased by that amount, and the construction period is lengthened. Further, when the base is used as a part of the pattern, there is a problem that the selection and combination of the base and the multi-pattern paint are considerably limited in terms of the harmony between the multi-pattern paint and the color of the base.

Therefore, according to the present invention, it is possible to form a coating film that expresses a variety of design feelings without requiring an undercoat coating because the see-through of the base is highly suppressed even if the coating film has a reasonable coating thickness. An object of the present invention is to provide a water-based water-based multicolored pattern coating composition that can be produced. Another object of the present invention is to provide a multi-pattern coating film which is a dry-cured product of an aqueous multi-pattern paint composition.
Further, the multi-pattern coating film made of the water-based water-based multi-pattern paint composition has a drawback of low weather resistance. Therefore, it is also an object to provide an aqueous multi-pattern coating composition capable of obtaining a multi-pattern coating film having good weather resistance.

As a result of diligent studies to solve the above problems, the present inventors have made a coating film without the need for undercoating by blending a colored gel which is a main component for forming a multicolored pattern and water-insoluble colored particles. We have developed a water-based, water-based, multi-pattern paint composition with high weather resistance that can give a variety of design feelings to the product, and have completed the present invention.

That is, according to the present invention, (A) a colored gel containing a hydrogel in which water is retained in a hydrogel-forming substance, a coloring pigment and a resin, and the coloring pigment and the resin being dispersed in the hydrogel, It has (B) a gel insolubilizer, (C) a water-dispersible resin, (D) water-insoluble colored particles, and (E) water, and the component (B) is dissolved in water which is the component (E). , And the components (A), (C) and (D) are dispersed, the gel average particle size of the colored gel which is the component (A) is 0.15 to 5.0 mm, and the average of the components (D). A water-based multicolored pattern coating composition having a particle size of 5 to 300 μm and smaller than the gel average particle size is provided.

Further, according to the present invention from another viewpoint, there is provided a multi-pattern coating film which is a dry-cured product of the water-based multi-pattern coating composition of the present invention.

Since the water-based multicolored pattern coating composition of the present invention has a characteristic composition in which a specific coloring gel and water-insoluble colored particles are combined, it is used as an undercoat when applied to an object to be coated such as a surface of a building or the like. It is possible to prevent see-through of the base without performing painting, and it is possible to form a highly weather-resistant coating film having a vivid and diverse design feeling. Further, since the undercoating is not required, it is effective in shortening the construction period and reducing the coating cost.
Further, since the multi-pattern coating film of the present invention has a high effect of concealing the base even without the undercoat layer, it is possible to express a vivid and various design feeling on any base. Further, since the water-insoluble colored particles are present in the coating film, the coating film exhibits good weather resistance.
Examples of the surface of the building or the like include the outer wall and the inner wall of the building, and the surface of a wall, a gate, a signboard, a pillar, a bridge, a three-dimensional art, and the like. The material of the object to be painted is not particularly limited as long as it can be painted, and examples thereof include cement mortar, concrete, plaster, wood, resin, and paper.

It is a figure which shows the photograph of the concealment rate test paper. It is a figure which shows the photograph of the coating film of Example 1 formed on the concealment rate test paper. It is a figure which shows the photograph of the coating film of Example 2 formed on the concealment rate test paper. It is a figure which shows the photograph of the coating film of Comparative Example 1 formed on the concealment rate test paper. It is a figure which shows the photograph of the coating film of Comparative Example 2 formed on the concealment rate test paper.

Hereinafter, the present invention will be described in more detail.
The aqueous multi-pattern paint composition of the present invention contains (A) a hydrogel in which water is retained in a hydrogel-forming substance, a coloring pigment and a resin, and the coloring pigment and the resin are dispersed in the hydrogel. Water having (hereinafter, may be simply referred to as a colored gel), (B) a gel insolubilizer, (C) a water-dispersible resin, (D) water-insoluble colored particles, and (E) water. Is a suspension-like or paste-like composition using the above as a dispersion medium. Hereinafter, the water-based multicolored pattern coating composition of the present invention may be simply referred to as the coating composition of the present invention.
Specifically, the colored gel [component (A)] is dispersed as a hydrogel in water [component (E)], the gel insolubilizer [component (B)] is dissolved, and the water-dispersible resin [component (C)] is dissolved. )] And water-insoluble colored particles [component (D)] are suspended and dispersed. If necessary, components other than the components (A) to (D) that are generally used as paint components may be optionally contained.

[Colored gel; component (A)]
The colored gel is a hydrogel (hydrogel) containing a colored pigment and a resin dispersed in a system, and is a component that imparts various colors to a coating film. The hydrogel for the colored gel is not particularly limited as long as it is a hydrogel, and it is sufficient that water is retained in the hydrogel-forming substance to form the gel.
The hydrogel-forming substance is a dispersoid having a network structure for retaining water in the gel, and the substance that is the main part of the network structure reacts with or binds to the gelling agent that is the joint part of the network structure. Is formed.

In the hydrogel-forming substance, the substance that is the main part of the network structure (hereinafter referred to as the gel main raw material) is not particularly limited as long as it can form a hydrogel, and may be an inorganic compound or an organic compound. Well, both may be mixed and used.
As the inorganic compound, a water-swellable silicate compound is preferable, and examples thereof include water-swellable clay minerals such as hectorite, montmorillonite, bentonite, and attapulsite. These water-swellable silicate compounds may be synthetics as well as natural minerals. Hectorite is preferable because it can form a good hydrogel that is difficult to dissolve in water, and synthetic hectorite is preferable because it has a stable composition.
As the organic compound, a hydroxyl group-containing organic polymer is preferable, and examples thereof include polyvinyl alcohol, guar gum, carrageenan, xanthan gum, methyl cellulose, hydroxymethyl cellulose, and derivatives thereof. Polyvinyl alcohol, guar gum, and guar gum derivatives (modification such as hydroxypropylation) are preferable because the coloring pigment and the resin are well dispersed and a colored gel having excellent stability can be obtained. The polyvinyl alcohol may be a completely saponified product or a partially saponified product, and the range of the degree of saponification is not particularly limited as long as it is soluble in water within the following content range.

Examples of the gelling agent that reacts with or binds to the gel main raw material and serves as a joint portion of the network structure include phosphates, borates, silicates and the like. Phosphates and borates are preferred because they can form good hydrogels that are difficult to dissolve in water. Phosphate is particularly preferable when the gel main raw material is a water-swellable silicate compound such as hectorite, and borate is particularly preferable when the gel main raw material is a hydroxyl group-containing organic polymer such as polyvinyl alcohol or guar gum. This is because a stable hydrogel can be formed in water.
Examples of the phosphate include sodium phosphates such as sodium pyrophosphate and potassium phosphates such as potassium pyrophosphate, and examples of the borate include ammonium borates such as ammonium pentaborate and borosand. It can be exemplified.

When the gel main raw material and the gelling agent react or combine to form a network structure of a hydrogel-forming substance, both may be simply added or additively bonded, and some of their atoms are removed by dehydration or the like. It may be a condensation that binds apart. However, the desorbed molecules and the like remain in the formed colored gel.
Although hydrogel has been described with a network structure of a gel main raw material and a gelling agent, hydrogel may be formed by an action different from that of network structure formation.

Since the hydrogel-forming substance may be formed by condensation as described above, its content in the colored gel shall be specified by the amount of the gel main raw material and the gelling agent used as the raw materials.
The content of the gel main raw material in the colored gel is preferably 0.1 to 5% by mass, more preferably 0.2 to 4.0% by mass in both the inorganic compound and the organic compound. This is because a good hydrogel can be formed within this range. When the inorganic compound and the organic compound are used in combination, they may be blended in an arbitrary ratio as long as the total amount is within the range.

The content of the gelling agent in the colored gel is preferably 0.003 to 0.5% by mass, more preferably 0.005 to 0.4% by mass. This is because a good hydrogel can be formed within this range. When a gelling agent having hydrated water is used, the content range is the range of the compound portion excluding the hydrated water.

The amount of water for forming the hydrogel is preferably 20 to 80% by mass as the content in the colored gel. This is because a good hydrogel can be formed within this range. The water includes water as a dispersion medium when an emulsion resin described later is used, in addition to the water added as water during the production of the colored gel. As the water to be added, clean water, ion-exchanged water, purified water, pure water and the like can be used, and clean water is preferable.

The coloring pigment determines the color of the coloring gel, and ordinary paint pigments can be used. Examples thereof include inorganic pigments such as titanium oxide, iron oxide, chromium oxide and carbon black, and organic pigments such as azo-based, phthalocyanine-based and quinacridone-based pigments. As the color, a desired color may be selected for the multi-pattern coating film of the present invention, and a commercially available product having the desired color can be used.
The coloring pigment contained in the coloring gel of a certain color may be one kind or a mixture of two or more kinds. That is, the color of the colored gel may be a color produced by one type of pigment or a color adjusted by a plurality of types of pigments.
The particle size of the coloring pigment is preferably in the range of 0.05 to 1.0 μm as an average particle size regardless of the color and type. This is because the dispersibility is good. The average particle size can be measured by a dynamic light scattering method or the like, but it may be determined by the average particle size disclosed in commercially available pigments.
The content of the coloring pigment in the coloring gel is preferably in the range of 0.1 to 30% by mass, more preferably 1 to 20% by mass. This is because if it is less than the lower limit, the color of the colored gel may be light and the design may be poor. This is because if the upper limit is exceeded, the stability of the colored gel may decrease.

The resin in the colored gel is the main material of the coating film, and plays a role of forming a film adhered to the substrate by applying the coating composition of the present invention to the substrate and drying it.
Examples of the resin include water-insoluble acrylic resins, vinegar-based resins, vinyl chloride-based resins, ethylene-based resins, fluorine-based resins, epoxy-based resins, and urethane-based resins. As these resins, those commonly called "emulsion resins" in which fine particles of the resin are dispersed in water, which are usually used as a raw material for paints, can be used. Among these, acrylic silicone resins, fluororesins and the like are preferable in terms of improving the design, weather resistance and durability of the multi-pattern coating film of the present invention, and examples thereof include acrylic silicone emulsion resins. Emulsion-form resins are preferred in terms of ease of blending for the production of colored gels. The resin concentration of the emulsion resin is preferably 10 to 70% by mass from the viewpoint of hydrogel formation, and more preferably 30 to 60% by mass of the emulsion resin preferably used in the coating field.
The main dispersion medium of the emulsion resin is water, which is also a raw material for hydrogel when preparing a colored gel.
The content of the resin in the colored gel is preferably in the range of 5 to 50% by mass, more preferably 10 to 30% by mass as the resin solid content. This is because if it is less than the lower limit value, a good multicolored pattern coating film may not be obtained, and if it exceeds the upper limit value, the resin content may be too large and it may be difficult to produce a colored gel.

The colored gel may further contain an extender pigment as a gel volume improver, if desired. If the coating cost does not need to be considered, it is not necessary to add the extender pigment.
As the extender pigment, calcium carbonate, precipitated barium sulfate, aluminum silicate, magnesium silicate (talc) and the like can be used.
The content of the extender pigment in the coloring gel is preferably 30% by mass or less. If it exceeds 30% by mass, the design of the multicolored pattern coating film formed may be deteriorated. Further, in order to exert an effective gel volume improving effect, it is preferable to add 10% by mass or more.

The colored gel is atomized into particles and dispersed in the aqueous colorful pattern coating composition at the time of producing the aqueous colorful pattern coating composition described later. The gel average particle size of the colored gel particles is 0.15 to 5.0 mm. This is because if the value is less than the lower limit, a clear colorful pattern is not obtained, and if the value exceeds the upper limit, the reproducibility of the colorful pattern is deteriorated due to deformation of the colored gel during painting.
For the average gel particle size, 20 gel particles are randomly selected by putting colored gel in a petri dish with a diameter of 30 mm and observing with a stand microscope (manufactured by Tokai Sangyo Co., Ltd.) or a peak scale loupe (manufactured by Tokai Sangyo Co., Ltd.). Then, the longest part of the gel particles in the visual field is measured as the particle size (particle size), and the average value of the 20 particles is used.

The colored gel may contain a thickener, a settling inhibitor, a preservative, an antifoaming agent, etc., which are usually used in paints, as optional components as long as the object of the present invention is not impaired. The content of these optional components in the colored gel is preferably 5% by mass or less. The optional component in this case does not include the above-mentioned extender pigment.

Next, an embodiment of a method for producing a colored gel will be described.
A colored pigment, an extender pigment and an optional component are added to water, and the mixture is stirred until uniformly dissolved or dispersed to prepare a colored pigment dispersion liquid. The stirring temperature is preferably 10 to 50 ° C., and the stirring may be performed at room temperature. The stirring time is not particularly limited as long as it is uniformly dissolved or dispersed, and may be about 5 minutes to 2 hours. As the stirrer, a stirrer or the like using a stirrer blade such as a homodisper or a paddle blade can be used.
Subsequently, a resin, a gel main raw material, and a gelling agent are added to the colored pigment dispersion liquid and stirred to produce a colored gel. The stirring temperature is preferably 10 to 50 ° C., and the stirring may be performed at room temperature. The stirring time is not particularly limited as long as the hydrogel is formed and the colored pigment is uniformly dispersed in the hydrogel, and the stirring time may be about 5 minutes to 2 hours. As the stirrer, a stirrer using a stirrer blade such as a paddle blade or an anchor blade, a planetary mixer or the like can be used.

After the stirring is completed, it is desirable to leave the mixture at room temperature for 1 hour or longer, preferably 5 hours or longer, in order to form a stable gel. About 24 hours is sufficient as the upper limit of the standing time at the point where the formed gel reaches an equilibrium state.
By the above production method, a gel-forming substance having a network structure or the like is formed, and water in which a coloring pigment, a resin or the like is dispersed is retained in the network structure or the like to form a hydrogel.

As described above, a colored gel having a desired color can be produced. Further, a plurality of types of colored gels having different colors can be prepared as the component (A) by the same production method.
However, even if the component (A) composed of one color gel is used and the components (B) to (E) described later are blended to produce a water-based multicolored pattern coating composition in which the color gel is one color. good. Since an object of the present invention is a multicolored pattern paint, a plurality of "one-color water-based multicolored pattern paint compositions" having different colors are blended to form a "water-based multicolored pattern paint composition containing a plurality of colored gels". May be good.
The content of the colored gel in the coating composition of the present invention is preferably in the range of 5 to 70% by mass, more preferably 20 to 50% by mass. This is because a good multicolored pattern coating film can be obtained within this range. The content is the content of the total amount of the colored gel regardless of whether the colored gel is a single gel of one color or a mixed gel of a plurality of colors.

[Gel insolubilizer; component (B)]
The gel insolubilizer has a role in preventing the colored gel from gradually dissolving in water over time in the coating composition of the present invention.
As the gel insolubilizer, the same gelling agent as that used for producing a colored gel can be used, and phosphates, borates, silicates and the like can be mentioned. When a water-swellable silicate compound such as Hectrite is used as the main raw material for the gel, it is preferable to use a phosphate, and when a hydroxyl group-containing organic polymer such as polyvinyl alcohol or guar gum is used, borate is used. It is preferable to use salt. When both are used, it is preferable to use phosphate and borate in combination. This is because a good hydrogel that is difficult to dissolve in water can be formed.
Examples of the phosphate include sodium phosphates such as sodium pyrophosphate and potassium phosphates such as potassium pyrophosphate, and examples of the borate include ammonium borates such as ammonium pentaborate and borosand. It can be exemplified.
The content of the gel insolubilizer in the coating composition of the present invention is preferably 0.001 to 1% by mass, more preferably 0.005 to 0.5% by mass. This is because a good hydrogel can be maintained within this range. When a phosphate and a borate are used in combination, the mixing ratio of the phosphate and the borate should be adjusted to the mixing ratio of the water-swellable silicate compound which is the main raw material of the gel and the hydroxyl group-containing organic polymer. good.

[Water-dispersible resin; component (C)]
The water-dispersible resin in the coating composition of the present invention is the main material of the coating film like the resin in the colored gel, and is adhered to the substrate by applying the coating composition of the present invention to the substrate and drying it. It plays a role in forming a film.
Examples of the water-dispersible resin include water-insoluble acrylic resins, vinegar-based resins, vinyl chloride-based resins, ethylene-based resins, fluorine-based resins, epoxy-based resins, and urethane-based resins. As these resins, those commonly called "emulsion resins" in which fine particles of the resin are dispersed in water, which are usually used as a raw material for paints, can be used. Among these, acrylic silicone resins, fluororesins and the like are preferable in terms of improving the design, weather resistance and durability of the multi-pattern coating film of the present invention, and examples thereof include acrylic silicone emulsion resins. Further, the water-dispersible resin may be the same as or different from the resin used for the colored gel.
Emulsion resins are preferable in terms of ease of blending for producing the coating composition of the present invention. The resin concentration of the emulsion resin is preferably 15 to 65% by mass, and more preferably 30 to 60% by mass, which is preferably used in the coating field, in terms of the design of the multi-pattern coating film.

The main dispersion medium of the emulsion resin is water, and the water becomes a part of the water of the component (E) which is the dispersion medium of the aqueous multi-pattern coating composition of the present invention.
The content of the water-dispersible resin in the coating composition of the present invention is preferably in the range of 2 to 50% by mass, more preferably in the range of 10 to 30% by mass, as the resin solid content. This is because if it is less than the lower limit value, a good multicolored pattern coating film may not be obtained, and if it exceeds the upper limit value, the resin content may be too large and it may be difficult to produce a colored gel.

[Water-insoluble colored particles; component (D)]
The water-insoluble colored particles in the coating composition of the present invention are components that play a major role in preventing see-through of the substrate. By combining the colored gel and the water-insoluble colored particles, it is possible to prevent see-through of the base and form a colorful pattern coating film having a vivid and colorful design feeling. Further, it is considered that the coating film is formed so that a part of the water-insoluble colored particles covers at least a part of the colored gel, thereby suppressing the deterioration of the colored gel due to environmental exposure, thereby various. It is considered to contribute to the improvement of weather resistance of the pattern coating film.
Examples of the water-insoluble colored particles include colored inorganic particles obtained by coloring silica sand, ceramic particles, etc. with a pigment, so-called colored sand, and colored ceramic aggregate, and colored organic resin particles such as colored acrylic resin particles and colored non-acrylic resin particles. It can be exemplified. Examples of the non-acrylic resin include polyalkylene resins, polystyrene resins, polyurethane resins and the like. As the color, a desired color may be selected for the multi-pattern coating film of the present invention. Further, one color of water-insoluble colored particles may be used, or a plurality of types of water-insoluble colored particles having different colors may be used. Further, as long as the following average particle size and function are satisfied, commercially available colored inorganic particles and colored organic resin particles can be used as the water-insoluble colored particles of the present invention.

The particle size of the water-insoluble colored particles is 5 to 300 μm as an average particle size regardless of the color and type, which is smaller than the gel average particle size of the colored gel. The average particle size is more preferably 10 to 150 μm. By satisfying this condition, water-insoluble colored particles can be present in a well-balanced manner between the gaps between the gel particles of the colored gel particles and the surface of the colored gel when the coating film is formed. Thereby, a multi-pattern coating film having excellent hiding property and weather resistance can be formed.
The average particle size can be measured by, for example, a laser diffraction method, but the average particle size may be determined by the average particle size disclosed in commercially available colored resin particles.

The content of the water-insoluble colored particles in the coating composition of the present invention is preferably 1 to 40% by mass, more preferably 2 to 15% by mass. This is because if it is less than the lower limit, the concealing property of the base may be insufficient. This is because if the value exceeds the upper limit, the stability of the coating composition of the present invention may decrease, and the design of the multi-pattern coating film may decrease.

The color of the water-insoluble colored particles used as a component of the coating composition of the present invention (when a plurality of colors are used in combination, the toning color thereof) is not particularly limited, and a desired color may be used. In the formed coating film, when it is desired to utilize a colorful pattern by the colors of a plurality of colored gels, a color similar to the color of the colored gel may be selected.

[Water; component (E)]
The water as the component (E) is water other than the water that forms the hydrogel of the component (A) and serves as a dispersion medium for the coating composition of the present invention. Since the water-dispersible resin of the component (C) represents only the resin solid content, when, for example, an emulsion resin is used as the raw material of the component (C), the water as the dispersion medium of the emulsion resin is the component (E). ). Similarly, when a substance containing water is used as a raw material for the components (B) and (D), the water is included in the component (E).
In addition to the water that can be contained in the raw materials of the components (B) to (D), as the water to be added as water, clean water, ion-exchanged water, purified water, pure water and the like can be used, and clean water is preferable.
The content of water as the component (E) in the coating composition of the present invention is preferably in the range of 20 to 90% by mass, more preferably 30 to 70% by mass. This is because if it is less than the lower limit, the components (A), (C) and (D) may not be well dispersed. This is because if the upper limit is exceeded, the concealing property of the base may be insufficient.

The coating composition of the present invention may contain any thickener, anti-settling agent, antiseptic agent, antifoaming agent, antifungal agent, antifungal agent, etc., which are usually used for paints, as long as the object of the present invention is not impaired. It may be contained as an ingredient. When these optional components are contained in the colored gel, the content of these optional components in the coating composition of the present invention is preferably 10% by mass or less including them.

Examples of the thickener include fibrin derivatives and nonionic surfactants. Examples of preservatives include benzisothiazolinone-based, benzisothiazolinone-based composite agents, and methylisothiazolinone-based preservatives. Examples of the defoaming agent include polyether type, mineral oil type, silicone type and the like. Examples of the algae-proofing agent and the fungicide-proofing agent include triazine-based compounds and isothiazolin-based compounds. When these optional components are contained, a colored gel and a raw material that does not affect the stability of the coating composition of the present invention may be selected.

The viscosity of the coating composition of the present invention is not particularly limited as long as it can be applied to the object to be coated. For example, the viscosity at room temperature by a Brookfield type (B type) viscometer is 2 to 30 Pa · s. Is preferable. When applied by spray coating, 10 Pa · s or less is more preferable. When applied with a trowel, 10 to 30 Pa · s is more preferable. This is because if it is within this range, it is easy to paint and it is difficult for leaning to occur when it is applied to a vertical surface.

Next, a method for producing the coating composition of the present invention will be described.
The coating composition of the present invention is produced by adding the components (A) to (E) and, if desired, the above-mentioned optional components in an arbitrary order or collectively into a stirring (mixing) device and stirring and mixing them. Can be done. Preferably, a part of the components (A), (B) and (E) is first placed in a stirrer and stirred to atomize the colored gel which is the component (A) into particles. This is because it is easier to granulate than stirring after adding all the components. The amount of water of the component (E) added at this time is preferably 5 to 30 parts by mass with respect to 100 parts by mass of the component (A). This is because it is easy to granulate.
The stirring device for atomizing the colored gel is not particularly limited, but an anchor blade agitator and a planetary mixer are preferable in terms of ease of atomization. The rotation speed, stirring time, etc. may be appropriately selected in a suitable range depending on the capacity of the stirrer, the charging amount, etc. For example, stirring may be performed at several tens of rpm for several minutes to 2 hours.

More specifically, for example, the following manufacturing method can be exemplified. A part of the components (A), (B) and (E) is first put into a stirring device and stirred to atomize the colored gel which is the component (A) into particles. Next, the emulsion resin which is the raw material of the component (C) is added and further stirred, and the finely divided colored gel and the water-dispersible resin are uniformly dispersed in the system to obtain a dispersion liquid. It is preferable that the dispersion liquid is passed through a sieve having a predetermined opening so that the particle size of the colored gel is within a predetermined range. This is because the design of the multi-pattern coating film becomes better. However, in the present application, "sieving" means that the finely divided colored gel is squeezed through the mesh of the sieve using a rubber spatula or the like, rather than the meaning of classification. That is, it means that the finely divided colored gel is further made finer than the opening of the sieve.
As the sieve to be used, a sieve having an opening of 3.5 mesh (opening; 5.6 mm) or less is preferable. However, if it is smaller than 60 mesh (opening; 0.25 mm), it is difficult to rub the colored gel. Therefore, the minimum opening of the sieve used is preferably 60 mesh (opening; 0.25 mm). The mesh shall be JIS standard.

The sieved dispersion is placed in the stirring device again, and water-insoluble colored particles as the component (D), water as a part of the component (E) if necessary, and optionally an optional component are added and mixed by stirring. do. Preferably, the component (D) dispersed in water is added. This is because the component (D) can be well dispersed in the system. Therefore, the concentration of the emulsion resin which is the raw material of the component (C) is adjusted so that water for dispersing the component (D) can be secured, and the amount of water which is the component (E) in the coating composition of the present invention. Is preferably within a suitable range.

As the stirring device used for mixing each component after the colored gel is granulated, for example, a stirrer using a stirring blade such as a paddle blade or an anchor blade, a planetary mixer, or the like can be used.
Further, in the production of the coating composition of the present invention by the stirring device, it is preferable to appropriately perform a defoaming operation. This is because the coating composition of the present invention and the intermediate obtained during the manufacturing process have a high viscosity and are easily entangled with bubbles.
The stirring temperature is preferably 10 to 50 ° C., and the stirring may be performed at room temperature. The stirring time may be a time suitable for obtaining a uniform coating composition, and may be, for example, about 5 minutes to 1 hour. The rotation speed may be appropriately selected in a suitable range depending on the capacity of the stirrer, the amount of charge, and the like, and may be, for example, several rpm to several tens of rpm.

As described above, the water-based colorful pattern coating composition of the present invention can be produced. However, the above manufacturing method is an example and is not limited to the manufacturing method.

Subsequently, a method for coating the coating composition of the present invention will be described. However, the coating method shown below is an example, and the coating method is not limited to the following method as long as the multi-pattern coating film of the present invention can be formed.

The coating composition of the present invention can be coated, for example, by spray coating. As the gun used for spray painting, a universal gun, a ricin gun, a mortar gun and the like can be used. The blowing pressure is preferably 0.1 to 0.6 MPa, more preferably 0.1 to 0.3 MPa. This is because if the spray pressure is less than the lower limit value, spray coating may not be performed properly, and if it exceeds the upper limit value, the design of the multicolored pattern coating film may be deteriorated.
The caliber of the gun is preferably 2.0 to 8.0 mm, more preferably 4.0 to 6.0 mm. This is because if the diameter is less than the lower limit, the design of the multicolored pattern coating film may be deteriorated, and if it exceeds the upper limit, the spray dispersibility of the paint may be deteriorated and uniform coating may not be possible.
Roller coating is also possible. In this case, a coating roller may be used to apply the coating according to a conventional method. It is preferable to use a sand bone roller in that a multi-pattern coating film having a better design can be obtained. The coating composition of the present invention may be applied as it is, or may be appropriately diluted with water and applied. Further, it may be painted using a trowel.

Examples of the object to be painted to which the coating composition of the present invention is applied include surfaces such as outer walls, inner walls, walls, gates, signboards, pillars, bridges, and three-dimensional arts of buildings. The material of the object to be painted is not particularly limited as long as it can be painted, and examples thereof include cement mortar, concrete, plaster, wood, resin, and paper.
By coating these objects with the water-based multi-pattern coating composition of the present invention as described above and drying it, the multi-pattern coating of the present invention having high design, excellent sharpness, and good weather resistance A film can be obtained.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In this example, the water-based multicolored pattern coating composition of each example and the coating composition of each comparative example are simply referred to as coating compositions. Further, the multicolored pattern coating film of each example and the coating film of each comparative example are simply referred to as coating films.

1. 1. Raw material components used in the production of paint compositions 1-1. Raw material for component (A) [colored gel] (1) Gel main raw material A1; Hectorite [Na _0.3 (Mg, Li) ₃ Si ₄ O ₁₀ (OH) ₂ ]
A2; PP-135 (polyvinyl alcohol, manufactured by Isono Chemical Co., Ltd.)
(2) Gelling agent A3; Potassium pyrophosphate (K ₄ P ₂ O ₇ )
A4; pentaborate ammonium tetrahydrate _{[NH 4 B 5 O 8 ·} 4H 2 O]
(3) Color pigment A5; JRNC (titanium dioxide, white, average particle size 0.27 μm, manufactured by TAYCA CORPORATION)
A6; TAROX BL-100 (black iron oxide, average particle size 0.17 μm, manufactured by Titan Kogyo Co., Ltd.)
A7; TAROX LEMON (yellow iron oxide, average particle size 0.09 μm, manufactured by Titan Kogyo Co., Ltd.)
A8; 120R (red iron oxide, average particle size 0.15 μm, manufactured by Toda Pigment Co., Ltd.)
(4) Resin A9; Boncoat SA-6340 (Acrylic silicone emulsion resin, resin solid content 50% by mass, manufactured by DIC Corporation)
(5) Constituent pigment A10; μ-POWDER 3N (heavy calcium carbonate, average particle size 1.3 μm, manufactured by Bikita Powder Industry Co., Ltd.)
A11; Precipitated barium sulfate (Fuhei) (average particle size 0.72 μm, manufactured by Kawazu Sangyo Co., Ltd.)
(6) Water (represents only those added as water, does not include water from other raw material components)
A12; clean water

1-2. Ingredient (B) [Gel insolubilizer]
B1; Potassium pyrophosphate (K ₄ P ₂ O ₇ )
B2; pentaborate ammonium tetrahydrate _{[NH 4 B 5 O 8 ·} 4H 2 O]

1-3. Ingredient (C) [Water-dispersible resin]
C1; Boncoat SA-6340 (Acrylic silicone emulsion resin, resin solid content 50% by mass, manufactured by DIC Corporation)

1-4. Component (D) [Water-insoluble colored particles]
D5 to D12 are components corresponding to the component (D) having an average particle size outside the average particle size range of the water-insoluble colored particles of the present invention.
D1; Tuftic (registered trademark) AR650M-W [Colored acrylic fine particles (polymethylmethacrylate fine particles), white, average particle size 30 μm, manufactured by Toyobo Co., Ltd.)
D2; Tuftic AR650M-C [Colored acrylic fine particles (same as above), black, average particle size 30 μm, manufactured by Toyobo Co., Ltd.]
D3; Tuftic AR650M-Y [Colored acrylic fine particles (same as above), yellow, average particle size 30 μm, manufactured by Toyobo Co., Ltd.]
D4; Tuftic AR650M-R [colored acrylic fine particles (same as above), red, average particle size 30 μm, manufactured by Toyobo Co., Ltd.]
D5; Bucella Color Sand S White [Fired colored aggregate, white, average particle size 500 μm, manufactured by Keimu Bucella Co., Ltd.]
D6; Bucella Color Sand KS Black [Fired colored aggregate, black, average particle size 500 μm, manufactured by Keimu Bucella Co., Ltd.]
D7; Bucella Color Sand S Yellow [Fired colored aggregate, yellow, average particle size 500 μm, manufactured by Keimu Bucella Co., Ltd.]
D8; Bucella Color Sand S Red [Fired colored aggregate, red, average particle size 500 μm, manufactured by Keimu Bucella Co., Ltd.]
D9; JRNC (titanium dioxide, white, average particle size 0.27 μm, manufactured by TAYCA CORPORATION)
D10; TAROX BL-100 (black iron oxide, average particle size 0.17 μm, manufactured by Titan Kogyo Co., Ltd.)
D11; TAROX LEMON (yellow iron oxide, average particle size 0.09 μm, manufactured by Titan Kogyo Co., Ltd.)
D12; 120R (red iron oxide, average particle size 0.15 μm, manufactured by Toda Pigment Co., Ltd.)

1-5. Ingredient (E) [water]
E1; Clean water (E1 represents only water added as water, and does not include water from other raw material components)

2. Preparation of colored gel as component (A) 2-1. Colored gel 1
Put 29.65 g of A12 (water), 6.1 g of A5 (titanium dioxide), 3.2 g of A10 (heavy calcium carbonate), and 18.1 g of A11 (precipitated barium sulfate) in a mixing container and batch. Using a formula tabletop sand mill (manufactured by Kampe Home Paint Co., Ltd.), a colored pigment dispersion liquid in which each component was dispersed was prepared by stirring at room temperature for 15 minutes. Next, 41.7 g of A9 (acrylic silicone emulsion resin, 20.9 g as the resin solid content) was added to the dispersion and stirred to obtain a colored pigment-resin dispersion. The color pigment-resin dispersion is placed in a planetary mixer (universal mixing stirrer, manufactured by Dalton Corporation), and 0.4 g of A1 (hectrite) and 0.8 g of A2 (polyvinyl alcohol) are further added at room temperature. After stirring for 15 minutes, 0.04 g of A3 (potassium pyrophosphate) and 0.01 g of A4 (ammonium borate) were added, and the mixture was stirred at room temperature for 20 minutes to obtain a precursor of colored gel 1 (white). Got Stirring with a planetary mixer was carried out under reduced pressure (-0.1 MPa; gauge pressure) to defoam the air mixed by foam entanglement.
The precursor was allowed to stand at room temperature for 12 hours to obtain a stable gel, colored gel 1.
2-2. Colored gels 2-24
Colored gels 2 to 24 were prepared in the same manner as colored gel 1 except that the composition of each colored gel was as shown in Tables 1 to 3 and the finished amount was adjusted to be substantially the same as that of colored gel 1. bottom. That is, for each colored gel, first, a colored pigment dispersion liquid in which the colored pigment and the extender pigment are dispersed in water is prepared by using a batch type tabletop sand mill, and then an emulsion resin is added to prepare a colored pigment-resin dispersion liquid. Prepared. Next, a precursor of each colored gel was prepared by mixing and stirring the colored pigment-resin dispersion liquid, the gel main raw material and the gelling agent using a planetary mixer.

3. 3. Performance evaluation of coating film Each performance evaluation of the coating film formed by the method described later was carried out as follows.
3-1. Designability The appearance of the coating film was visually observed and judged according to the following criteria.
〇: Clear colorful patterns are observed.
Δ: A colorful pattern is observed, but a portion where the colorful pattern portion derived from the colored gel is excessively covered with insoluble colored particles and the colorful pattern disappears is observed.
X: Many of the colorful patterns derived from the colored gel are excessively covered with insoluble colored particles, and almost no colorful patterns are observed.

3-2. Concealment rate The concealment rate was evaluated using the concealment rate test paper (manufactured by TP Giken Co., Ltd.) shown in FIG. 1 in accordance with JIS K5600. The concealment rate test paper has a black background part and a white background part, and the paint is applied to both parts almost uniformly and dried to form a coating film. When the hiding property is good, the ground portion cannot be seen through, and a coating film having a uniform appearance is formed. On the other hand, when the hiding property is poor, the ground portion is transparent, and a coating film having a different appearance is formed on the black ground and the white ground.
After forming a coating film on the concealment rate test paper, the tristimulus values Y of each of the coating film on black and the coating film on white are measured at 4 points each with a color difference meter CR-300 (manufactured by Minolta Co., Ltd.). The average value was obtained, and the concealment rate (%) was calculated by the following formula [1]. The higher the concealment rate, the higher the concealment. The amount of the coating composition applied to the hiding ratio test paper was 800 g / m ² .
Concealment rate (%) = (Y _B / Y _W ) x 100 (Formula [1])
[Y _B ; 4-point average value of the tristimulus values of the coating film on the black background; Y _W ; 4-point average value of the tristimulus values of the coating film on the white background]

3-3. Weather resistance The weather resistance was evaluated using an eye super UV tester SUV-W261 (manufactured by Iwasaki Electric Co., Ltd.). Specifically, the weather resistance was evaluated by comparing the glossiness and color difference (ΔE) of the coating film before and after UV (ultraviolet) irradiation by the method shown below.
[UV irradiation test]
Two coating films were prepared by uniformly applying the coating composition to a slate plate of 4 cm × 4 cm × 0.3 cm (length × width × thickness) so that the application amount was 800 g / m ^2. One sheet was stored as a reference coating film for color difference measurement, and the remaining one sheet was subjected to a UV irradiation test under the following conditions.
<UV irradiation conditions>
UV intensity: 150mW / cm ²
Irradiation environment: temperature 63 ° C, humidity 50%
(A) UV irradiation time: 6 hours (b) Shower cleaning: After UV irradiation for 6 hours, shower wash with pure water for 10 seconds according to the conventional method, and then stand still for 2 hours in an environment of temperature 35 ° C. and humidity 90%. Then, shower washing with pure water again for 10 seconds "(a)->(b)" was repeated as one cycle, and 3 after 300 hours, 500 hours and 600 hours (all total time) after the start of the test. In terms of points, the following gloss retention and color difference (ΔE) were measured and evaluated.

[Gloss retention rate]
The glossiness of the coating film before and after UV irradiation was measured with a gloss meter VG-2000 (manufactured by Nippon Denshoku Industries Co., Ltd.), and the gloss retention rate was calculated by the following mathematical formula [2]. The glossiness of the coating film after UV irradiation after each elapsed time was measured, and the gloss retention rate after each elapsed time was calculated. It can be judged that the higher the gloss retention rate, the better the weather resistance.
Gloss retention rate (%) = (glossiness of coating film after UV irradiation / glossiness of coating film before UV irradiation) × 100
(Formula [2])

[Color difference (ΔE)]
^{The L *} a ^* b ^* values were measured by CR-300 at any five points of the reference coating film not irradiated with UV, and the average value was used as a reference (reference L ^* a ^* b ^* value). ^{Next, the L *} a ^* b ^* values of the UV-irradiated coating film were similarly measured with CR-300 at any five locations, and the average value was calculated. ^{From the difference between the average L *} a ^* b ^* value of the coating film after UV irradiation and the above-mentioned reference L ^* a ^* b ^* value, the color difference (ΔE) represented by the following mathematical formula [3] was obtained. ^{That is, the L *} a ^* b ^* values of the coating film after UV irradiation after each elapsed time were measured, and ΔE after each elapsed time was calculated. It can be judged that the smaller the value of ΔE, the smaller the change in color before and after UV irradiation, and the better the weather resistance.
ΔE = [(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ] ^1/2 (Formula [3])

(Example 1; paint composition 1)
25.37 g of E1 (water), 43.3 g of colored gel 1 and 0.01 g of B1 and 0.22 g of B2 (gel insolubilizer) are placed in a mixing container at room temperature for about 10 minutes with a planetary mixer. The mixture was stirred and the colored gel 1 was atomized into particles. Then, 31.1 g of C1 (acrylic silicone emulsion resin, 15.55 g as resin solid content) was further added to the mixing container, and the mixture was stirred at room temperature for about 10 minutes to make the colored gel 1 finely divided and dispersed in water. The sex resin was uniformly dispersed in the system to obtain a gel dispersion. The gel dispersion was strained with a 12-mesh (1.4 mm mesh) sieve using a rubber spatula to prepare a gel dispersion of colored gel 1 with a 12-mesh pass.
As for the colored gel 4, the colored gel 7, and the colored gel 13, a 12-mesh pass gel dispersion was obtained by the same preparation method as described above.
74.4 g, 5.4 g, 5.4 g, 5.4 g, and a total of 90.6 g of the gel dispersions of the colored gels 1, 4, 7, and 13 were placed in a mixing container, and 5.4 g of D1 (coloring) was added. 9.4 g of a water-insoluble colored particle dispersion liquid in which 4.0 g of E1 (clean water) was dispersed (acrylic fine particles, white) was added, and the mixture was stirred at room temperature for 10 minutes to obtain a coating composition 1. As a stirrer, an anchor type low-speed stirrer was used, and the stirring force was adjusted so that each colored gel, water-insoluble colored particles, and the like were uniformly dispersed.
The composition of the coating composition 1 is shown in Table 4.
The gel average particle size of the colored gel in the coating composition 1 was measured by the above method using a peak scale loupe and found to be 1.16 mm.

The obtained coating composition 1 was applied to the concealment rate test paper and the slate plate at 800 g / m ² by spray coating, and dried by natural drying for 24 hours to form a coating film for each test.
The design property, hiding rate, and weather resistance of the formed coating film were evaluated. The evaluation results are shown in Table 4. Further, a photograph of the coating film formed on the concealment rate test paper is shown in FIG. 2 as a figure.

(Examples 2 , 5 to 6 , Reference Examples 3 and 4 ; Paint Compositions 2 to 6)
Each Example and Reference Example are the same as in Example 1 except that the composition of each coating composition is as shown in Table 4 and the finished amount is adjusted to be substantially the same as that of the coating composition 1. The coating compositions 2 to 6 were prepared by blending the components (A) to (E) of the above and straining with a sieve. Table 4 shows the gel average particle size of the colored gel in each coating composition.
A coating film was formed on each of the obtained coating compositions in the same manner as in Example 1, and the design, hiding ratio, and weather resistance were evaluated. The evaluation results are shown in Table 4. Further, a photograph of the coating film of Example 2 formed on the concealment rate test paper is shown in FIG. 3 as a figure.

(Comparative Examples 1 to 3; Paint Compositions 7 to 9)
Except that the water-insoluble colored particles of the component (D) were not blended, the composition of each coating composition was as shown in Table 4, and the finished amount was adjusted to be substantially the same as that of the coating composition 1. In the same manner as in Example 1, the components (A) to (E) of each Comparative Example were blended, strained with a sieve, and the like to prepare coating compositions 7 to 9. Table 4 shows the gel average particle size of the colored gel in each coating composition.
A coating film was formed on each of the obtained coating compositions in the same manner as in Example 1, and the design, hiding ratio, and weather resistance were evaluated. The evaluation results are shown in Table 4. Further, photographs of the coating films of Comparative Examples 1 and 2 formed on the concealment rate test paper are shown in FIGS. 4 and 5 as figures.

(Comparative Examples 4 to 9; Paint Compositions 10 to 15)
Using water-insoluble colored particles whose average particle size is outside the average particle size range of the water-insoluble colored particles of the present invention, the composition of each coating composition is as shown in Table 4, and the finished amount is the coating composition 1. The coating compositions 10 to 15 were prepared in the same manner as in Example 1 except that the amounts were adjusted to be substantially the same as those of the above, and the components (A) to (E) of each Comparative Example were blended and strained with a sieve. Prepared. Table 4 shows the gel average particle size of the colored gel in each coating composition.
For each of the obtained coating compositions, a coating film was formed in the same manner as in Example 1, and its design and concealment ratio were evaluated. The evaluation results are shown in Table 4.

As is clear from Table 4, the coating films formed by the coating compositions 1 , 2, 5 and 6 of Examples 1, 2, 5 and 6 have a significantly superior hiding ratio as compared with Comparative Examples 1 to 6. It has a high effect of hiding the base. The difference in the hiding performance is clear from the comparison between Example 1 of FIG. 2 and Comparative Example 1 of FIG. 4 and the comparison of Example 2 of FIG. 3 and Comparative Example 2 of FIG. In Examples 1 and 2, the black portion of the hiding rate test paper is almost concealed by the formed coating film, whereas in Comparative Examples 1 and 2, the black portion of the hiding rate test paper by the coating film is almost concealed. The black part is visible through due to insufficient concealment.
In addition, the colorful pattern of the coating film is clear and very vivid, expressing a variety of design feelings. The coating films formed in Comparative Examples 7 to 9 had a high hiding rate as in Examples 1, 2, 5 and 6, but did not develop a colorful pattern, and were compared with the coating films of Examples 1, 2, 5 and 6. The design feeling is significantly inferior.
Further, the coating films formed by the coating compositions 1, 2, 5 and 6 of Examples 1, 2, 5 and 6 are formed by the coating compositions 7 to 9 of Comparative Examples 1 to 3 which do not contain water-insoluble colored particles. Compared with the coated film, the gloss retention rate is high, the color difference value is small, and the weather resistance is remarkably excellent.

Claims (6)

(A) A hydrogel, a coloring pigment and a resin in which water is retained in a hydrogel-forming substance which is a reaction product or a binder between a gel main raw material and a gelling agent is contained, and the coloring pigment and the resin are dispersed in the hydrogel. Colored gel and
(B) Gel insolubilizer and
(C) Water-dispersible resin and
(D) Water-insoluble colored particles and
(E) With water,
The gel main raw material is composed of a water-swellable silicate compound and a hydroxyl group-containing organic polymer.
The component (B) is dissolved in water which is the component (E), and the components (A), (C) and (D) are dispersed, and the gel average of the colored gel which is the component (A). The particle size is 0.15 to 5.0 mm, and the average particle size of the component (D) is 5 to 300 μm, which is smaller than the gel average particle size.
Aqueous multi-pattern paint composition. The gelling agent contains a phosphate and a borate.
The water-based multicolored pattern coating composition according to claim 1. (A) A hydrogel, a coloring pigment and a resin in which water is retained in a hydrogel-forming substance which is a reaction product or a binder between a gel main raw material and a gelling agent is contained, and the coloring pigment and the resin are dispersed in the hydrogel. Colored gel and
(B) Gel insolubilizer and
(C) Water-dispersible resin and
(D) Water-insoluble colored particles and
(E) With water,
The gel main raw material is a water-swellable silicate compound, and the gelling agent is a phosphate.
The component (B) is dissolved in water which is the component (E), and the components (A), (C) and (D) are dispersed, and the gel average of the colored gel which is the component (A). The particle size is 0.15 to 5.0 mm, and the average particle size of the component (D) is 5 to 300 μm, which is smaller than the gel average particle size.
Aqueous multi-pattern paint composition. The component (A) is composed of a plurality of types of colored gels having different colors.
The water-based multicolored pattern coating composition according to any one of claims 1 to 3. The component (D) is one or more water-insoluble colored particles selected from colored sand, colored ceramic aggregate, and colored organic resin particles.
The water-based multicolored pattern coating composition according to any one of claims 1 to 4. A dry-cured product of the water-based colorful pattern coating composition according to any one of claims 1 to 5.
Multi-pattern coating film.

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