JP6362823B2 - Grain-tone pattern coating film forming method and painted article coated in stone-tone - Google Patents

Description

  The present invention relates to a method for forming a stone-patterned coating film and a coated article coated in a stone-tone pattern.

  In recent years, stone-like patterns that have the appearance of natural stone such as granite (also called granite) are widely preferred as interior and exterior materials for buildings. Granite is generally a relatively coarse-grained rock, and there are various colors such as black, brown, white, maroon, or green.

  In the past, many coating compositions and coating methods capable of forming a coating with a stone-like appearance have been proposed in order to perform a stone-like pattern by painting.

  For example, in Patent Document 1, an undercoat containing an aggregate having a specific average particle diameter is applied to a synthetic resin emulsion paint, and a natural stone tone containing a synthetic resin emulsion, a colored aggregate, and natural stones thereon. The construction method of the natural stone tone coating material which applies a coating material is described.

  According to this invention, the texture of natural stone can be reproduced even with a roller brush, but the paint described in this document and containing a large amount of aggregate and natural stone cannot be said to have good workability and can be used for painting. It requires skill, and is not suitable for reproducing a stone pattern having a spotted pattern such as granite.

  As a technique for solving such a problem, for example, a method of forming a stone pattern using a multicolored paint is proposed. The multicolored paint is a paint in which particles of liquid or gel color are suspended and can form a scattered pattern with a single coating, and is defined in JIS K 5667 (2003).

  For example, Patent Document 2 discloses a water-based stone-like multicolor pattern paint composition mainly composed of water-soluble resin and / or water-dispersed resin, colored particles, and colored flakes. Things are disclosed.

  Further, Patent Document 3 discloses a natural stone-like paint composition comprising pattern color dispersed phase particles and a transparent dispersion medium as main components, and a natural composition characterized by coating the paint composition on various undercoat layers. A stone-like coating method is disclosed.

  According to these documents, it is possible to form a stone-like coating film using a multicolored paint, but since the dispersion of the color particles is uniform, it cannot be denied that it is monotonous and artificial, granite It is still insufficient to reproduce a design with a natural appearance close to.

  Further, the present applicant has proposed a method for forming a coating film using a water-based colorful pattern paint in Patent Documents 4 to 5 and the like.

  In Patent Document 4, a colored coating film (I) having a water absorption rate of 20% or less is formed on a surface to be coated to form a colored coating film. A method for forming a multicolored paint film is described in which II) is applied to form a multicolored paint film.

  Patent Document 5 discloses a design coating film in which a multicolored paint film (II) is applied to a bright paint film formed by painting a paint (I) containing a bright pigment. A forming method is described.

  Patent Documents 4 and 5 describe that it is possible to form a coating film with a unique design that gives a strong impression to the user, but a coating film that reproduces a stone-tone pattern such as granite. There is no description of the formation method.

Japanese Patent Laid-Open No. 10-238062 JP 2000-86942 A JP 2003-154308 A JP 2008-155119 A JP 2008-114112 A

  The objective of this invention is providing the coating-film formation method which reproduces the stone-tone pattern which has the spot as seen in granite using a coating composition.

  As a result of intensive studies on the above-mentioned problems, the inventors of the present invention have a texture close to that of granite by overlapping two different types of spotted pattern coating films in which the color difference between the upper layer and the lower layer is within a specific range. The present inventors have found that a coating film having a tone pattern can be easily formed, and have reached the present invention.

That is, the present invention
On the surface to be coated, (1) the coating composition (I) containing the colored paint particle component (IA) is applied, and the average particle diameter of different colors contained in the colored paint particle component (IA) is 0.15 to 0.15. A step of forming a first spotted pattern coating film in which a plurality of colored spotted patterns are dispersed by a group of colored paint particles stabilized with a 10 mm polysaccharide metal salt gel;
(2) The coating composition (II) containing the colored paint particle component (IIA) is applied over the first spotted pattern coating film obtained in the step (1), and the colored paint particle component (IIA) is applied. A second spotted pattern coating film in which dot patterns of multiple colors are dispersed by a group of colored paint particles stabilized with a polysaccharide metal salt gel having an average particle diameter of different colors of 0.15 to 10 mm. Comprising the steps of:
The colored paint particle component (IA) and the colored paint particle component (IIA) have different compositions,
At least one dot pattern included in the first spotted pattern coating film obtained in the step (1) and at least one included in the second spotted pattern coating film obtained in the step (2). The color difference ΔE of the seed-like dot pattern is at least 15,
A stone-like pattern coating film, characterized in that a difference in average value of the brightness of each spot-like pattern is 1.0 or more between the first spot-like pattern coating film and the second spot- like pattern coating film Forming method,
About.

  According to the method of the present invention, after a coating composition containing a colored paint particle component containing a single or a plurality of colored paint particle groups is applied to form a spotted pattern coating film, a spot pattern by the colored paint particle groups is formed. By providing a speckled pattern coating film having a dot pattern with a color difference of 15 or more different from the above, the lower spotted pattern coating film and the upper spotted pattern coating film interact with each other to finally obtain a stone-like tone In the pattern coating film, the presence of each dot pattern due to the colored paint particles is more conspicuous, and the texture and depth of granite can be produced.

  In addition, by selecting the composition and blending amount of the upper and lower colored paint particle components, it is possible to widen the diversity of the stone-patterned coating film that is formed, and various stone-grained patterns that are rich in variations. Can be easily formed.

<Coating surface>
Examples of the coated surface to which the method of the present invention is applied include, for example, metal substrates of iron, stainless steel, aluminum and the like and surface treated products thereof, cement-based substrates such as cements, limes, gypsum, porcelain tiles, and the like. Base materials such as plastic base materials such as vinyl chlorides, polyesters, polycarbonates, acrylics, wood surfaces such as plywood, wallpaper surfaces such as polyvinyl chloride, polyolefins, paper, cloth, etc. And structures.

  In the case of using the method for forming a stone-tone pattern coating film of the present invention as a refurbishing method such as repainting, a single layer or multiple layers of an old coating film that has already been formed can be used as it is.

  The surface to be coated may have been previously treated with a sealer or a primer in order to improve the adhesion between the coating film and the surface to be coated.

<Step (1)>
In the present invention, the step (1) comprises: (1) a coating composition (I) containing a colored paint particle component (IA) and a single or a plurality of colored paint particle groups contained in the colored paint particle component (IA) It is the process of forming the 1st spotted pattern coating film in which the spotted pattern by was scattered.

  In the present invention, the colored paint particle component (IA) used for forming the first spotted pattern coating film may be a component containing a single colored paint particle group, or different colored paints of a plurality of colors. The component containing a particle group may be sufficient.

  The color type and the number of colors of the colored paint particle group contained in the colored paint particle component (IA) can be appropriately selected according to the target stone-tone appearance.

  The colored paint particle group is not particularly limited in terms of materials, production methods, and the like, and known ones conventionally known as the colored paint particle group contained in the multicolor paint composition can be used.

  The multicolor pattern paint composition is defined in JIS K5667 (2003) “Multicolor pattern paint”, and it is an oil-in-water type (O / W type) or water-in-oil type depending on the combination of the dispersion medium and the colored paint particle group constituting the paint. It is classified into four types: a type (W / O type), an oil-in-oil type (O / O type), and a water-in-water type (W / W type).

  In the present invention, examples of the colored paint particle group contained in the colored paint particle component (IA) include a particle group containing a colored paint containing an aqueous resin and a colorant in a polysaccharide metal salt gel. it can.

  As the aqueous resin contained in the colored paint, a resin that can be dissolved or dispersed in water is used. The resin type is not particularly limited. Specifically, for example, acrylic resin, polyolefin resin, silicon resin, polyurethane resin, epoxy resin, phenol resin, polyester resin, alkyd resin, polycarbonate These resins may be used alone or in combination of two or more, and two or more of these resins may be modified or graft polymerized.

  When the aqueous resin is in the form of dispersed particles, it can be a single layer or a multilayer such as a core / shell type.

  Examples of the colorant that can be included in the colored paint include color pigments, glitter pigments, and dyes. Among these, for example, white pigments such as titanium dioxide; black pigments such as carbon black, acetylene black, lamp black, bone black, graphite, iron black, and aniline black; yellow iron oxide, titanium yellow, and monoazo yellow , Condensed azo yellow, azomethine yellow, bismuth vanadate, benzimidazolone, isoindolinone, isoindoline, quinophthalone, benzidine yellow, permanent yellow and other yellow pigments; permanent orange and other orange pigments; red iron oxide, naphthol AS azo red Red pigments such as Ansanthrone, Anthraquinonyl Red, Perylene Maroon, Quinacridone Red Pigment, Diketopyrrolopyrrole, Watching Red, Permanent Red, etc .; Cobalt Purple, Quinacridone Biore Violet pigments such as dioxazine violet; blue pigments such as cobalt blue, phthalocyanine blue, and selenium blue; green pigments such as phthalocyanine green; and the bright pigments include aluminum powder, bronze powder, copper powder, Metallic pigments such as tin powder, iron phosphide, and zinc powder; mica, metal oxide-coated mica powder, pearlescent pigments such as mica-like iron oxide, and the like can be mentioned alone or in combination of two or more. These colorants can be used alone or in combination of two or more according to the color of the target colored paint particle group.

  The type and amount of the colorant are appropriately adjusted according to the transparency of the target colored paint particle group, and are generally in the range of 0.01 to 500% by mass based on the mass of the aqueous resin, preferably It can exist in the range of 0.05-400 mass%.

  In the colored paint, extender pigments can be used together with the colorant. Specific examples include barita powder, precipitated barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, white carbon, diatomaceous earth, talc, magnesium carbonate, alumina white, gloss white, quartz sand, quartz powder and the like. Or in combination of two or more.

  If necessary, the colored paint further comprises a specific gravity adjusting material such as balloon particles, an antifoaming agent, a curing catalyst, a pigment dispersant, an aromatic, a deodorant, an antibacterial agent, a neutralizing agent, a surfactant, a water repellent. Water solution, dispersant, antiseptic, antifungal agent, antifreezing agent, UV absorber, light stabilizer, film-forming aid, zinc whisker, formaldehyde adsorbent, antimony trioxide, antimony pentoxide, aluminum hydroxide, etc. Flame retardants and the like.

  The colored paint particle group used in the method of the present invention can be produced, for example, by bringing the composition containing the colored paint and water-soluble polysaccharide into contact with an aqueous medium containing a metal compound, and stirring as necessary. Thereby, a colored paint particle group comprising the colored paint in a polysaccharide metal salt gel can be formed.

  The water-soluble polysaccharide is a polysaccharide capable of changing to a water-insoluble or hardly soluble gel when contacted with a monovalent or polyvalent metal ion in an aqueous medium. Specifically, for example, Examples thereof include alginic acid or an alkali metal salt thereof, gellan gum, carrageenan and the like, and these can be used alone or in combination of two or more.

  The metal compound is a compound capable of forming a monovalent or polyvalent metal ion capable of forming a water-insoluble or hardly soluble salt with a water-soluble polysaccharide in an aqueous medium, and as a metal species in the metal compound, Periodic table group 2 elements such as magnesium, calcium, strontium, barium; periodic table group 6 elements such as chromium and molybdenum; periodic table group 7 elements such as manganese; periodic table group 8 elements such as iron and ruthenium; cobalt, rhodium, etc. Periodic table group 9 elements; nickel, palladium and other periodic table group 10 elements; copper, silver and other periodic table group 11 elements; zinc and cadmium and other periodic table group 12 elements; aluminum and other periodic table group 13 elements; cerium The group 16 element of the periodic table etc. can be mentioned, Among them, the group 2 element of the periodic table, especially calcium is preferable.

  The metal compound is not particularly limited as long as it is a compound having the above metal species. For example, formic acid, acetic acid, propionic acid, butyric acid, lactic acid, oxalic acid, fumaric acid, succinic acid, phosphoric acid, citric acid, gluconic acid, etc. Metal salts of organic acids; hydroxides, metal oxides; metal carbonates, and the like. These can be used alone or in combination of two or more.

  An aqueous medium containing metal ions can be prepared by dissolving at least a part of the metal compound in an aqueous medium such as water. At that time, the metal compound does not need to be completely dissolved in the aqueous medium, and may be partially dissolved.

  The colored paint particle component (IA) can be obtained, for example, by bringing a composition containing a colored paint and a water-soluble polysaccharide into contact with an aqueous medium containing a metal compound and stirring. The stirring speed can be, for example, in the range of 500 to 4000 rpm, preferably 700 to 3000 rpm.

  The average particle diameter of the colored paint particle component (IA) containing the single color paint particle group or the multiple color paint particle group thus obtained is adjusted according to the production conditions of the color paint particle group and the material used. In general, however, it is preferably in the range of 0.15 to 10 mm, preferably 0.2 to 5 mm.

  Since the particle size distribution of the colored paint particle component (IA) is as described above, there is an effect that the presence of each dot pattern is more conspicuous while it is a natural stone-tone pattern.

  In this specification, the average particle diameter of the colored paint particle component (IA) is calculated by randomly selecting 30 colored paint particles and observing them with an optical microscope.

  Further, in the present invention, it is suitable that the colored paint particle component (IA) includes a colored paint particle group that forms a dot-like pattern having a saturation by the Munsell display system of 10 or less, preferably 6 or less.

  In the present invention, the saturation by the Munsell display system is a single spot-like pattern intended for colorimetry in the spot-like pattern coating film formed by the coating composition (I) for forming the first spot-like pattern. Using a tristimulus direct-reading color difference meter “CR400” (trade name, manufactured by Konica Minolta Co., Ltd.), using D65 as a light source, colorimetry was performed with a viewing angle of 2 ° and a diffuse illumination light receiving method (d / 0). .

  Further, when it is difficult to measure the color of the dot pattern, the value obtained by measuring the saturation of the coating film obtained by coating the composition before the granulation of the colored paint particle group up to the concealed film thickness as described above is used. Thus, the saturation of the target dot pattern can be obtained.

  The coating composition (I) used in the method of the present invention is added to the colored coating particle component (IA) from the viewpoint that the film forming property of the spotted pattern coating film to be formed and the manner of scattering of the spotted pattern are appropriate. A coating film forming component (IB) can be contained. The coating film-forming component (IB) itself has film-forming properties, and is an aqueous resin from the viewpoints of affinity with the colored coating particle component (IA) and storage stability as the coating composition (I). It is desirable that it is an aqueous composition comprising

  As the water-based resin contained in the coating film-forming component (IB), those generally used as a resin binder in the water-based paint field can be used. For example, as described above as the water-based resin in the colored paint particle component (IA) It can be used by appropriately selecting from those. Moreover, the form of aqueous resin is not specifically limited, Either 1 liquid type or 2 liquid type may be sufficient.

  The blending ratio of the colored paint particle component (IA) and the coating film forming component (IB) is 1/99 to 60/40 in terms of the solid content mass ratio of the colored paint particle component (IA) / coated film forming component (IB). The range of 10/90 to 50/50, particularly 20/80 to 45/55 is preferred.

  Further, from the viewpoint of film physical properties such as durability of the first spotted pattern coating film, the colored paint particle component (IA) and the coating film forming component (IB) each contain a functional group capable of reacting with each other. It is desirable.

  The combination of reactive functional groups contained in the colored paint particle component (IA) and the coating film forming component (IB) is not particularly limited as long as it is a combination that can react with each other under the drying conditions of the coating film. Specifically, for example, hydroxyl group and isocyanate group, hydroxyl group and alkyl ether group, hydroxyl group and imino group, carboxyl group and epoxy group, amino group and epoxy group, amide group and epoxy group, carbonyl group and hydrazine group, carbonyl group Examples thereof include a combination of a group and a hydrazide group, a carbonyl group and a semicarbazide group, a carbonyl group and a bisacetyldihydrazone group, self-condensation of hydrolyzable silyl groups, and oxidative curing with an unsaturated fatty acid group.

  The coating composition (I) contains a resin in which both the colored coating particle component (IA) and the coating film forming component (IB) have a reactive functional group, and the colored coating particle component (A) and / or The coating film forming component (IB) can also be in a form containing a crosslinking agent having a reactive functional group capable of reacting with the reactive functional group.

  The coating composition (I) can contain extender pigments, glitter pigments, transparent coating particle groups and coating additives as necessary.

  Among these, examples of the transparent paint particle group include a particle group obtained by granulating a transparent paint substantially not containing a colorant as the colored paint particle group.

  Examples of the paint additive include a neutralizer, a viscosity modifier, an anti-settling agent, an antistatic agent, a softener, an antibacterial agent, a fragrance, a curing catalyst, a pH adjuster, a humidity control agent, a dispersant, an antifoaming agent, Preservatives, fungicides, antifreezing agents, UV absorbers, light stabilizers, film-forming aids, aldehyde adsorbents, waxes, antimony trioxide, antimony pentoxide, aluminum hydroxide and other flame retardants Can be mentioned.

The coating amount of the coating composition (I) can be changed according to the composition of the coating composition to be used, the kind of the substrate to be coated, etc., but is 10 to 500 g / m ^{2 in} dry mass, preferably A range of ^{20 to} 300 g / m ² is preferable. The coating composition (I) may be applied a plurality of times so that the coating amount falls within the above range. In addition, the coating means can be performed using a coating means known per se, for example, appropriately selected according to the use of the substrate such as a roller, air spray, airless spray, lysine gun, universal gun, brush, roll coater, etc. can do.

  The formed coating film can be dried by any of heat drying, forced drying, or room temperature drying depending on the composition of the coating composition used.

<Step (2)>
In the present invention, in the step (2), the coating composition (II) containing the colored coating particle component (IIA) is repeatedly applied onto the first spotted pattern coating film obtained in the step (1), and the colored coating composition is applied. This is a step of forming a second spotted pattern coating film in which a spotted pattern formed by a group of colored paint particles of a single color or a plurality of colors contained in the particle component (IIA) is scattered.

  The colored paint particle component (IIA) used in the step (2) is a component containing a single color or a plurality of colored paint particle groups.

  In the present invention, the colored paint particle component (IIA) is different from the colored paint particle component (IA) in the composition of the colored paint particle group.

  In the present specification, the case of “different compositions” means not only the case where the colors of the colored paint particle group contained in the colored paint particle component (IA) and the colored paint particle component (IIA) are all different from each other, but also the colored paint particle component Even when (IA) or the colored paint particle component (IIA) has a plurality of colors, the colored paint particle component (IA) and the colored paint particle component (IIA) include both colored paint particle groups of the same color. A case where the mass ratio of the colored paint particle group of the same color is different between the colored paint particle component (IA) and the colored paint particle component (IIA) is also included as a case where the composition is different.

  The average particle diameter of the colored paint particle component (IIA) is visually recognized through the colored paint particle component (IIA), for example, in the range of 0.15 to 10 mm, preferably 0.2 to 5 mm. The presence of a spotted pattern due to the colored paint particle component (IA) is favorable and preferable.

  In the present invention, the colored paint particle component (IIA) includes a colored paint particle group that forms a dot-like pattern having a saturation of 10 or less, preferably 6 or less, and has a grainy texture like a granite. This is preferable.

  The average particle diameter and saturation of the colored paint particle component (IIA) can be measured by the same method as that for the colored paint particle component (IA).

  In the present invention, at least one kind of spotted pattern contained in the first spotted pattern coating film obtained in the step (1) and the second spotted pattern coating film obtained in the step (2) It is characterized in that the color difference ΔE of at least one kind of dotted pattern included is at least 15, and is included in each of the colored paint particle component (IA) and the colored paint particle component (IIA) so as to have this relationship The color and combination of the colored paint particle groups to be selected are selected.

  If the maximum value of the color difference ΔE of the dot pattern between the first and second spotted pattern coating films is less than 15, the texture and texture of the finally obtained stone pattern coating film may be sufficient. It is not preferable because it becomes artificial.

  Moreover, as a preferable range of the maximum value of the color difference ΔE of the dot pattern between the first and second spotted pattern coating films, it is 50 to 80, preferably 55 to 75.

  In this specification, the color difference ΔE by the Munsell display system is determined by using a tristimulus value direct-reading color difference meter “CR400” (trade name, manufactured by Konica Minolta), using D65 as a light source, a viewing angle of 2 °, and a diffuse illumination receiving system ( d / 0).

  Further, in the present invention, when it is difficult to measure the color of one point-like pattern for the purpose of color measurement, the colored paint particle component (IA) and the composition before granulation of the colored paint particle component (IIA) are concealed. The color difference ΔE between the first and second punctiform patterns can be obtained by the color difference obtained by measuring the color of the coating film obtained by coating up to the film thickness.

  In the present invention, the colored paint particle component (IA) and / or the colored paint particle component (IIA) may each be a single colored paint particle group or a colored paint particle group consisting of a plurality of colors. However, when any one includes a plurality of colored paint particle groups, the color difference ΔE between the dot pattern included in the first spotted pattern coating film and the dot pattern included in the second spotted pattern coating film is It is preferable that the ratio of the colored paint particle group involved in at least 15 relationships is in the range of 20% or more, preferably 30% or more, more preferably 60% or more.

  The ratio of the colored paint particle group in which the color difference ΔE between the dot pattern included in the first spotted pattern coating film and the dot pattern included in the second spotted pattern coating film is at least 15 is in the above range. Therefore, the texture and depth of the resulting stone-tone pattern stand out more.

  In this specification, the ratio N (%) of the colored paint particle group in which the color difference contained in the colored paint particle component (IA) and the colored paint particle component (IIA) is 15 or more is calculated as follows.

  N (%) = [(of the colored paint particle group contained in the colored paint particle component (IA), solid content mass of the colored paint particle group having a color difference of 15 or more with the colored paint particle group (IIA1) × colored paint particle component) (Proportion of the colored paint particle group (IIA1) in (IIA)) + (of the colored paint particle group (IIA2) included in the colored paint particle component (IA), a colored paint having a color difference of 15 or more with the colored paint particle group (IIA2) Solid content mass of the particle group × the proportion of the colored paint particle group (IIA2) in the colored paint particle component (IIA)) + (of the colored paint particle group contained in the colored paint particle component (IA)) (IIAn) and the solid content mass of the colored paint particle group having a color difference of 15 or more × the proportion of the colored paint particle group (IIAn) in the colored paint particle group (IIA)] × 100 / colored paint particle component (IA) Solid mass.

  Here, the colored paint particle component (IA) includes the colored paint particle group (IA1), the colored paint particle group (IA2),... The colored paint particle group (IAn), the colored paint particle group (IA1), and the colored paint particles. Group (IA2), ... Colored paint particle group (IAn) is a colored paint particle group having different colors, and Colored paint particle component (IIA) is colored paint particle group (IIA1), Colored paint particle group (IIA2) ... containing colored paint particles (IIAn), colored paint particles (IIA1), colored paint particles (IIA2), ... colored paint particles (IIAn) are colored paint particles having different colors. is there.

  In the present invention, it is desirable that the first spotted pattern coating film and the second spotted pattern coating film be a combination of spotted patterns having different brightness. More specifically, the first spotted pattern coating film and the second spotted pattern coating film have a difference in average value of brightness of each spotted pattern of 1.0 or more, preferably 1.0 to 9. It is suitable to be in the range of 5. By adjusting the difference in the average value of the brightness of each spotted pattern between the first spotted pattern coating film and the second spotted pattern coating film as described above, the texture and depth feel more like granite. A stone-patterned coating film having the same is obtained.

  In the present specification, the average value of the brightness of each dot-like pattern formed by each colored paint particle group is the lightness of each dot-like pattern by the Munsell display system and the mass of the colored paint particle group forming the dot-like pattern. It is obtained by calculating the rate by the following formula.

  Average value of lightness of each dot pattern of the first spotted pattern coating film = lightness of dot pattern by colored paint particle group (IA1) × mass of colored paint particle group (IA1) / total weight of colored paint particle group + Lightness of dotted pattern by colored paint particle group (IA2) × Colored paint particle army (IA2) mass / total weight of colored paint particle group + ・ ・ ・ Lightness of dot pattern by colored paint particle group (IAn) / Colored paint particle group Total mass.

  Average value of lightness of each dot pattern of the second spotted pattern coating film = lightness of dot pattern by colored paint particle group (IIA1) × mass of colored paint particle group (IIA1) / total weight of colored paint particle group + Lightness of dotted pattern by colored paint particle group (IIA2) × Colored paint particle army (IIA2) mass / Total weight of colored paint particle group + ・ ・ ・ Lightness of dot pattern by colored paint particle group (IIAn) / Colored paint particle group Total mass.

  Here, the colored paint particle component (IA) includes the colored paint particle group (IA1), the colored paint particle group (IA2),... The colored paint particle group (IAn), the colored paint particle group (IA1), and the colored paint particles. Group (IA2), ... Colored paint particle group (IAn) is a colored paint particle group having different colors, and Colored paint particle component (IIA) is colored paint particle group (IIA1), Colored paint particle group (IIA2) ... containing colored paint particles (IIAn), colored paint particles (IIA1), colored paint particles (IIA2), ... colored paint particles (IIAn) are colored paint particles having different colors. is there.

  The brightness of each punctiform pattern using the Munsell display system was determined by using a tristimulus value direct-reading color difference meter “CR400” (trade name, manufactured by Konica Minolta Co., Ltd.) as a light source. The color was measured with a viewing angle of 2 ° and a diffuse illumination light receiving method (d / 0).

  In the present invention, when color measurement is difficult, for example, when the dot pattern is too small, the brightness of the coating film obtained by coating the composition before coloring of the colored paint particle component to the concealed film thickness is reduced. Thus, the brightness of the dot pattern by the colored paint particle component can be obtained.

  In the present invention, the coating composition (II) for forming the second spotted pattern coating film may contain a coating film forming component (IIB) in addition to the colored coating particle component (IIA).

  As the coating film-forming component (IIB) contained in the coating composition (II), it can be used by appropriately selecting from the description of the coating composition (I).

  The blending ratio of the colored coating particle component (IIA) and the coating film forming component (IIB) is 1/99 to 60/40 in terms of the solid content mass ratio of the colored coating particle (IIA) / coated film forming component (IIB). The range of 10/90 to 50/50, particularly 20/80 to 45/55 is preferred.

  Moreover, it is desirable that the colored paint particle component (IIA) and the coating film forming component (IIB) each contain functional groups that can react with each other.

  As the combination of the reactive functional groups contained in the colored paint particle component (IIA) and the coating film forming component (IIB), the reactive functional group contained in the colored paint particle component (IA) and the coating film forming component (IB). Combinations similar to those exemplified as the combinations can be mentioned.

  The coating composition (II) contains a resin in which both the colored coating particle component (IIA) and the coating film forming component (IIB) have a reactive functional group, and further the colored coating particle component (IIA) and / or coating. The film forming component (IIB) can also be in a form containing a crosslinking agent having a reactive functional group capable of reacting with the reactive functional group.

  In the present invention, the colored paint particle component (IA), the colored paint particle component (IIA), the coating film forming component (IB), and the coating film forming component (IIB) each have a reactive functional group that reacts with each other. Of course, the interlaminar adhesion of both layers can be improved as well as the physical properties of the first and second speckled coating films.

  The coating composition (II) may contain a known additive for coating materials as exemplified in the explanation of the extender pigment and the coating composition (I), if necessary.

The coating amount of the coating composition (II) can be changed according to the composition of the coating composition to be used, the kind of the substrate to be coated, etc., but is 10 to 500 g / m ^{2 in} dry mass, preferably A range of ^{20 to} 300 g / m ² is preferable. The coating composition (II) may be applied a plurality of times so that the coating amount falls within the above range. In addition, the coating means can be performed using a coating means known per se, for example, appropriately selected according to the use of the substrate such as a roller, air spray, airless spray, lysine gun, universal gun, brush, roll coater, etc. can do.

  The formed coating film can be dried by any of heat drying, forced drying, or room temperature drying depending on the composition of the coating composition used.

<Undercoating process>
In the method of the present invention, before the step (1), the surface to be coated is protected, and an undercoat coloring paint is applied if necessary for the purpose of concealing the surface to be coated with an appropriate hue, and then dried to form the undercoat coloring coating. A step of forming a film may be included.

  Such undercoat colored paint is not particularly limited, and can be appropriately selected according to the type and state of the surface to be coated, or the target graininess, etc. In addition, a normal topcoat colored paint is used as a base forming paint. It is also possible to paint.

  As the above-mentioned undercoat coloring paint, conventionally known ones can be used without limitation, but can be appropriately selected according to the type and state of the surface to be coated, for example, acrylic resin, acrylic silicon resin, polyolefin resin, Water-based or solvent-based resins consisting of resin types such as silicone resin, polyurethane resin, epoxy resin, phenol resin, polyester resin, alkyd resin, biodegradable resin, etc. It is preferable to use a paint containing a water-based resin.

  Examples of the pigment contained in the undercoat colored paint include conventionally known pigments such as colored pigments, extender pigments, luster pigments, and rust preventive pigments, and are appropriately selected according to the target texture. be able to.

  In the method of the present invention, when an undercoat step is provided before the step (1), the Munsell of the undercoat colored coating film and at least one kind of spotted pattern contained in the first and / or second spotted pattern coating film. The color difference due to the display system is preferably 30 or less.

  In the method of the present invention, since the undercoat colored coating film and the spotted pattern are in the above-described relationship, there is an effect of improving the texture and texture of the stone texture.

  The above-mentioned undercoat coloring paint can be applied using a known coating means, for example, depending on the use of a substrate such as a roller, air spray, airless spray, lysine gun, universal gun, brush, roll coater, etc. It can be selected appropriately.

  The formed undercoat coating film can be dried by any of heat drying, forced drying or room temperature drying depending on the type of the undercoat coloring paint used.

<Clear painting process>
In the method of the present invention, after the step (2) is completed, a step of applying a topcoat clear paint may be provided as necessary.

  By applying the top coat clear, the texture and depth of the textured coating film can be improved.

  Examples of such a top coat clear coating include acrylic resins, acrylic silicon resins, polyolefin resins, silicon resins, polyurethane resins, epoxy resins, phenol resins, polyester resins, alkyd resins, bio-resins, and the like. Examples thereof include water-based or solvent-based paints containing a water-based or solvent-based resin composed of a resin type such as a degradable resin as a resin binder, and it is preferable to use a water-based paint containing a water-based resin. Such a topcoat clear paint may contain a colorant or extender pigment as exemplified for the color paint particle component (IA) to the extent that the transparency of the coating film is not impaired.

  The top coat clear paint can be applied by using a coating means known per se, for example, roller, air spray, airless spray, lysing gun, universal gun, brush, roll coater, etc. It can be appropriately selected and used accordingly. The clear coating film to be formed can be dried by any of heat drying, forced drying or room temperature drying depending on the type of clear coating used.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to only these examples. In the following examples, “part” and “%” mean “part by mass” and “% by mass”, respectively.

[Coating board]
On a slate plate (600 × 900 × 3 mm), “EP sealer transparent” (manufactured by Kansai Paint Co., Ltd., water-based acrylic emulsion sealer) is applied by roller coating so that the coating amount is 100 g / m ² and dried. A coated plate was used.

[Undercoating paint]
Undercoat paint (X-1): “Ares Aqua Gloss White” (manufactured by Kansai Paint Co., Ltd., acrylic resin-based water-based paint).

[Paint with colored paint particles]
<Manufacture of emulsion for colored paint particles>
Production Example 1
285 parts of deionized water and 1 part of “New Coal 707SF” (Note 1) were added to a 4-liter flask having a volume of 2 liters, and maintained at 85 ° C. after purging with nitrogen. 41 parts of an initiator aqueous solution obtained by dissolving 3 parts of a pre-emulsion obtained by emulsifying the components of the following composition therein and 3 parts of ammonium persulfate in 120 parts of deionized water are added and added. 20 minutes after completion, the remaining pre-emulsion and ammonium persulfate aqueous solution were dropped into the flask over 4 hours.
Deionized water 368 parts Styrene 150 parts Methyl methacrylate 410 parts n-Butyl acrylate 240 parts 2-Ethylhexyl acrylate 150 parts Diacetone acrylamide 20 parts 2-hydroxyethyl acrylate 25 parts Acrylic acid 5 parts "Newcol 707SF" (Note 1) 66 After completion of the dropwise addition, this was further maintained at 85 ° C. for 2 hours, and then the temperature was lowered. When the temperature reached 40 to 60 ° C., the pH was adjusted with ammonia water to obtain an emulsion (a1) having a solid content of 55%. . The average particle size of the emulsion (a1) was 175 nm, and the pH was 8.3.
(Note 1) “New Coal 707SF”: trade name, manufactured by Nippon Emulsifier Co., Ltd., an anionic surfactant having a polyoxyethylene chain, non-volatile content of 30%.

<Manufacture of emulsion for coating film forming component>
Production Example 2
285 parts of deionized water and 1 part of “New Coal 707SF” (Note 1) were added to a 4-liter flask having a volume of 2 liters, and maintained at 85 ° C. after purging with nitrogen. 41 parts of an initiator aqueous solution obtained by dissolving 3 parts of a pre-emulsion obtained by emulsifying the components of the following composition therein and 3 parts of ammonium persulfate in 120 parts of deionized water are added and added. 20 minutes after completion, the remaining pre-emulsion and ammonium persulfate aqueous solution were dropped into the flask over 4 hours.
Deionized water 368 parts Styrene 150 parts Methyl methacrylate 400 parts n-Butyl acrylate 360 parts 2-Ethylhexyl acrylate 67 parts Diacetone acrylamide 10 parts 2-hydroxyethyl acrylate 10 parts Acrylic acid 3 parts "Newcol 707SF" (Note 1) 66 After completion of the dropwise addition, this was further maintained at 85 ° C. for 2 hours, and then cooled to 40-60 ° C. Subsequently, pH was adjusted with aqueous ammonia to obtain an emulsion (a2) having a solid content of 55%. The average particle size of the emulsion (a2) was 180 nm, and the pH was 8.0.

<Production of aqueous clear emulsion for top coat>
Production Example 3
285 parts of deionized water and 1 part of “New Coal 707SF” (Note 1) were added to a 4-liter flask having a volume of 2 liters, and maintained at 85 ° C. after purging with nitrogen. 41 parts of an initiator aqueous solution obtained by dissolving 3 parts of a pre-emulsion obtained by emulsifying the components of the following composition therein and 3 parts of ammonium persulfate in 120 parts of deionized water are added and added. 20 minutes after completion, the remaining pre-emulsion and ammonium persulfate aqueous solution were dropped into the flask over 4 hours.
Deionized water 368 parts Styrene 100 parts Methyl methacrylate 410 parts n-Butyl acrylate 350 parts 2-Ethylhexyl acrylate 120 parts Vinyltriethoxysilane 5 parts 2-Hydroxyethyl acrylate 10 parts Acrylic acid 5 parts "Newcol 707SF" (Note 1) After the completion of dropping 66 parts, this was further maintained at 85 ° C. for 2 hours, and then cooled to 40-60 ° C. Subsequently, pH was adjusted with aqueous ammonia to obtain an emulsion (a3) having a solid content of 55%. The average particle size of the emulsion (a3) was 185 nm, and the pH was 8.2.

<Manufacture of enamel clear for colored paint particles>
Production Example 4
The following components were charged in a 1 liter stainless steel container, and stirred and mixed with a stirrer for 30 minutes to obtain an enamel clear (b1) for colored paint particle groups.
55% emulsion obtained in Production Example 1 (a1) 450 parts “TEXANOL” (Note 2) 30 parts “DISPER BYK-190” (Note 3) 7 parts “BYK-028” (Note 4) 3 parts “Adecanol UH- 420 "(Note 5) 3 parts (Note 2)" TEXANOL ": trade name, manufactured by Eastman Chemical Company, 2,2,4-trimethylpentanediol monoisobutyrate, film-forming aid,
(Note 3) “DISPER BYK-190”: trade name, manufactured by BYK Chemie, pigment dispersant,
(Note 4) “BYK-028”: trade name, manufactured by BYK Chemie, antifoaming agent,
(Note 5) “Adecanol UH-420”: trade name, manufactured by Adeka, urethane-modified thickener.

<Manufacture of white paint for colored paint particles>
Production Example 5
Into a 1 liter stainless steel container, 500 parts of the enamel clear (b1) obtained in Production Example 4 above was charged, and then 125 parts of titanium dioxide was blended, followed by stirring and mixing with a stirrer for 30 minutes to obtain a white paint (b2) Got.

<Manufacture of aqueous coating composition for colored coating particle group>
Production Example 6
Enamel clear (b1) obtained in Production Example 4 above, white paint (b2) obtained in Production Example 5 above, and color paste for water-based paint (manufactured by Yokohama Chemical Co., Ltd.) 88) is added to 300 parts of a water-based paint toned with the standard color EN-85 for the 2009 edition E paint issued by the Japan Paint Industry Association, and then 300 parts of a 2% aqueous sodium alginate solution is added to make it uniform. Thus, the water-based coating composition (A-1) for colored coating particle groups was obtained by stirring and mixing for 10 minutes.

Production Examples 7-9
In the above Production Example 6, water-based paint compositions (A-2) to (A-4) for colored paint particle groups were obtained in the same manner as in Production Example 6 except that the standard colors were as shown in Table 1 below. .

Production Example 10
The following components were sequentially blended in a container and stirred and mixed so as to be uniform to obtain a translucent colored paint particle group aqueous paint composition (A-5).
Enamel clear (b1) 300 parts Carbon black 0.5 part 2% Sodium alginate aqueous solution 280 parts.

<Manufacture of aqueous medium>
Production Example 11
After mixing 2000 parts of deionized water in a 4 liter stainless steel container, 3 parts of calcium propionate and 3 parts of calcium hydroxide were added and stirred until uniform to obtain an aqueous medium (B-1).

<Manufacture of colored paint particles>
Production Example 12
Into a 4 liter stainless steel container, 1,300 parts of the aqueous medium (B-1) for producing the colored paint particle group obtained in Production Example 11 was charged, and the rotational speed was 2,000 rpm using a stirring blade having a diameter of 75 mm. 650 parts of the aqueous coating composition (A-1) obtained in Production Example 6 was gradually dropped into the container while stirring at, thereby generating a light gray colored coating particle group. Next, the liquid in the container was further stirred for 15 minutes at the same rotation speed, and then filtered using a 200-mesh wire mesh to obtain a colored paint particle liquid (C-1). The obtained colored paint particle liquid (C-1) had a solid content of 20%.

Production Examples 13-16
In the above Production Example 12, the colored paint particle liquids (C-2) to (C-4) and the same as in Production Example 12 except that the formulation of the aqueous medium and the aqueous coating composition to be dropped is as shown in Table 2. A translucent colored paint particle liquid (C-5) was produced.

<Manufacture of colored paint particle liquid (C-6)>
Production Example 17
Into a 4 liter stainless steel container, 1,300 parts of the aqueous medium (B-1) for producing the colored paint particle group obtained in Production Example 11 was charged, and the rotating speed was 1,000 rpm using a stirring blade having a diameter of 75 mm. 650 parts of the aqueous coating composition (A-1) obtained in Production Example 6 was gradually dropped into the container while stirring at, thereby generating a light gray colored coating particle group. Next, the liquid in the container was further stirred for 10 minutes at the same rotation speed, and then filtered using a 200 mesh wire net to obtain a colored paint particle liquid (C-6) having a slightly larger average particle diameter. The resulting colored paint particle liquid (C-6) had a solid content of 20%.

In Table 2, Munsell hue, Munsell lightness, Munsell saturation are values obtained by coating the composition before granulation to the concealed film thickness, and the average particle diameter is a value measured according to the description.

<Production of water-based clear paint for coating film forming component>
Production Example 18
The following components were sequentially charged into a 2 liter stainless steel container and stirred and mixed with a stirrer until uniform for 30 minutes to obtain an aqueous clear paint (D-1).
55% emulsion (a2) obtained in Production Example 2 825 parts “TEXANOL” (Note 6) 50 parts “BYK-028” (Note 8) 10 parts “Primal ASE 60” (Note 9) 3 parts Calcium propionate 0.7 (Note 9) “Primal ASE60”: trade name, manufactured by Rohm and Haas, polyacrylic acid viscosity modifier.

<Manufacture of paint with colored paint particles>
Production Examples 19-25
The components shown in Table 3 below were charged in a 500 ml stainless steel container while sequentially stirring, and then stirred until uniform to prepare paints (E-1) to (E-7) containing colored paint particles. .

Production Example 26
<Manufacture of water-based clear paint for top coat>
The following components were sequentially charged into a 2 liter stainless steel container, and stirred and mixed with a stirrer until uniform for 30 minutes to obtain an aqueous clear paint (D-2) for top coat.
55 parts emulsion (a3) obtained in Production Example 3 825 parts “TEXANOL” (Note 6) 50 parts “BYK-028” (Note 8) 10 parts “Adecanol UH-420” (Note 5) 3 parts.

<Manufacture of stone-tone pattern coating plate>
Example 1
Said to be coated plate, primer coating (X-1) as the "Ares Aqua Gloss white" (manufactured by Kansai Paint Co., Ltd., acrylic resin aqueous paint) and roller coating as the coating amount is 100 g / m ^2, temperature 20 ° C. The film was dried for 1 day under conditions of a relative humidity of 60%. Next, the paint (E-1) containing the colored paint particle liquid was applied on the undercoat coating film with a universal gun so that the coating amount was 250 g / m ² , and 1 under the conditions of an air temperature of 20 ° C. and a relative humidity of 60%. After drying for a day, paint (E-2) with colored paint particles is applied with a universal gun so that the coating amount is 250 g / m ^2, and dried for one day under conditions of an air temperature of 20 ° C. and a relative humidity of 60%. To obtain a stone-patterned coated plate.

Examples 2-3 and Comparative Examples 1-2
In Example 1 above, the same manner as in Example 1 above except that the undercoat paint, the first colored paint particle-containing paint, the second colored paint particle-containing paint type or presence / absence is as shown in Table 4 below. A stone-patterned coated plate was obtained.

Example 4
The clear paint (D-2) obtained in Production Example 26 is further roller-coated on the stone-patterned coated plate obtained in Example 1 and dried for 7 days under conditions of an air temperature of 20 ° C. and a relative humidity of 60%. To obtain a stone-patterned coated plate. Each coated plate obtained in Examples 1-4 and Comparative Examples 1-2 was visually evaluated according to the following criteria. The results are shown in Table 4.

(* 1) Visual particle feeling of colored paint particles ◎: The texture of the colored paint particles on the stone-tone coated plate is very good.
○: The grain feeling of the pattern by the colored paint particles is good on the stone-tone coated plate,
Δ: The graininess of the pattern due to the colored paint particles on the stone-tone coated plate is slightly poor,
X: The particle feeling of the pattern by a coloring paint particle is inferior on a stone-tone coating board.
(* 2) Deep feeling ◎: Deep feeling like granite is noticeable.
○: A deep feeling like granite is recognized,
Δ: Slight depth like granite is recognized,
X: A feeling of depth like granite is not recognized.
(* 3) Texture ◎: Excellent texture like granite,
○: Excellent texture like granite,
Δ: Slightly lacking texture like granite, pattern irregularity,
X: The texture like granite is insufficient and the pattern unevenness is large.

Claims (6)

On the surface to be coated, (1) the coating composition (I) containing the colored paint particle component (IA) is applied, and the average particle diameter of different colors contained in the colored paint particle component (IA) is 0.15 to 0.15. A step of forming a first spotted pattern coating film in which a plurality of colored spotted patterns are dispersed by a group of colored paint particles stabilized with a 10 mm polysaccharide metal salt gel;
(2) The coating composition (II) containing the colored paint particle component (IIA) is applied over the first spotted pattern coating film obtained in the step (1), and the colored paint particle component (IIA) is applied. A second spotted pattern coating film in which dot patterns of multiple colors are dispersed by a group of colored paint particles stabilized with a polysaccharide metal salt gel having an average particle diameter of different colors of 0.15 to 10 mm. Comprising the steps of:
The colored paint particle component (IA) and the colored paint particle component (IIA) have different compositions,
At least one dot pattern included in the first spotted pattern coating film obtained in the step (1) and at least one included in the second spotted pattern coating film obtained in the step (2). The color difference ΔE of the seed-like dot pattern is at least 15,
A stone-like pattern coating film, characterized in that a difference in average value of the brightness of each spot-like pattern is 1.0 or more between the first spot-like pattern coating film and the second spot- like pattern coating film Forming method. The colored paint particle component (IA) and the colored paint particle component (IIA) include a colored paint particle group that forms a dot-like pattern having a saturation of 10 or less according to the Munsell display system. Film forming method. The colored paint particle component (IA) and the colored paint particle component (IIA) include a plurality of colored paint particle groups, and a spot pattern and a second spot pattern included in the first spotted pattern coating film. The method for forming a stone-tone pattern coating film according to claim 1 or 2, wherein the proportion of the colored paint particle group involved in the relationship where the color difference ΔE of the dot-like pattern contained in the pattern coating film is at least 15 is 20% or more.   The coating composition (I) further comprises a coating film forming component (IB), and the coating composition (II) further comprises a coating film forming component (IIB). A method for forming a textured coating film. A coating film forming method further comprising a step of applying an undercoat colored paint to a surface to be coated and drying to form an undercoat colored paint film, the undercoat colored paint film and the first and second spotted patterns The method for forming a stone-tone pattern coating film according to any one of claims 1 to 4 , wherein a color difference from at least one kind of dot-like pattern contained in the coating film is 30 or less. The method for forming a stone-patterned coating film according to any one of claims 1 to 5 , wherein a clear paint is further applied as a top coat on the coating film obtained in step (2).