Paint

Abstract

To provide a paint which enables intentional expression of separation of a color.SOLUTION: A paint contains a first coloring material as colored resin beads having a particle diameter of 1.0 μm or more, a second coloring material as a coloring pigment having a particle diameter of 0.5 μm or less, and an extender pigment, wherein the second coloring material exhibits a hue different from that of the first coloring material.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a paint that easily expresses color separation.

Background Art

[0002] Patent Document 1 discloses a paint composition including a coloring pigment and an extender pigment, wherein the extender pigment is particles having a uniform shape. In this paint composition, lightweight calcium carbonate having a uniform shape is used as the extender pigment. In this paint composition, unlike the case where amorphous heavy calcium carbonate is used as the extender pigment, the coating film applied to painting paper or the like can be thickened, so that the covering power is enhanced, and it is described in Patent Document 1 that the hiding power of the coloring pigment can be effectively enhanced.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] On the other hand, when developing a paint, in order to adjust the hue exhibited by the paint, there are cases where two or more color materials are mixed to prototype one paint. However, conventionally, it has been desired that one paint exhibits a uniform hue without unevenness. For this reason, a paint with unevenness is determined to have a quality defect. If the criterion for this determination is reversed, rather, if a paint that can easily express color separation intentionally can be developed, the paint developed in this way will be, for example, a new means that can easily express various colors in a painting or the like, and is considered desirable.

[0005] Therefore, an object of the present invention is to provide a paint that can easily express color separation intentionally.

Means for Solving the Problems

[0006] In order to solve the above problems, a paint according to one embodiment includes a first coloring material that is colored resin beads having a particle diameter of 1.0 μm or more, a second coloring material that is a coloring pigment having a particle diameter of 0.5 μm or less, and a extender pigment, and the second coloring material exhibits a hue different from that of the first coloring material.

[0007] According to such a paint, when the paint is applied to paper in a state containing water, the particles of the coloring pigment, which is the second coloring material, have a relatively small particle diameter, so they are likely to penetrate and diffuse into the gaps between the fibers constituting the paper together with water. On the other hand, the colored resin beads, which are the first coloring material, have a relatively large particle diameter, so they are likely to be blocked by interference from the particles of the extender pigment and are less likely to penetrate and diffuse into the gaps between the fibers constituting the paper. That is, in the paper coated with the paint, the particles of the coloring pigment, which is the second coloring material, are more likely to diffuse over a wider range of the paper than the colored resin beads, which are the first coloring material. For this reason, on the paper coated with the paint, a portion where the hue exhibited by the first coloring material is relatively dark and a portion where the hue exhibited by the second coloring material is relatively dark are likely to appear separately.

Advantages of the Invention

[0008] As described above, according to the present invention, it is possible to provide a paint that can easily express intentional color separation.

Brief Description of the Drawings

[0009]

Figure 1

Embodiments for Carrying Out the Invention

[0010] A paint according to one embodiment (hereinafter also referred to as "this paint") is a watercolor paint (a paint composition for watercolor painting) including a first coloring material, a second coloring material, and an extender pigment.

[0011] Generally, when watercolor paints are used, they are applied to paper together with water. Paper is a material containing a large number of cellulose-based fibers (fibers mainly composed of cellulose). When it comes into contact with water, water penetrates into the gaps between the hydrophilic cellulose-based fibers, or the porous cellulose-based fibers absorb water by capillary action, causing the paper to become soggy. At this time, the particles of the coloring material contained in the paint are more likely to diffuse over a wide area of the paper together with water, and are more likely to spread in a soggy manner until the paper dries. On the other hand, particles with a large particle diameter are less likely to be diffused over a wide area of the paper and will remain at the site where the paint is applied on the paper surface.

[0012] The first coloring material is resin beads colored with a dye or a coloring pigment (hereinafter also referred to as "colored resin beads"), and those that can generally be used for coloring. Examples of the colored resin beads colored with a dye include a polymer fine particle aqueous dispersion obtained by emulsion polymerization using, as a raw material, a resin such as a styrene resin, an acrylic resin, an acrylonitrile resin, or a copolymer resin having these resins as a main component, and dyed with an arbitrary dye. The dye here may be a non-fluorescent dye or a dye containing a fluorescent dye. When a dye containing a fluorescent dye is used, the obtained colored resin beads exhibit a fluorescent color. Further, the dye is fixed to the colored resin beads and is in a state of being substantially insoluble in water. Alternatively, examples of the colored resin beads colored with a coloring pigment include those obtained by mixing a resin such as an acrylic resin, a urethane resin, or a polyester resin with a coloring pigment and encapsulating the coloring pigment in the solidified resin beads by a resin bead formation method. Examples of the coloring pigment encapsulated in the resin beads here include the coloring pigments exemplified in the description of the second coloring material described later. Also, various products of colored resin beads are commercially available. The first coloring material may be commercially available colored resin beads.

[0013] From the perspective of preventing the colored resin beads from diffusing over a wide area of the paper together with water, the particle size of the colored resin beads in the first colorant is 1.0 μm or more. From the same perspective, the particle size of the colored resin beads in the first colorant may be, for example, 2.0 μm or more or 3.0 μm or more, preferably 4.0 μm or more, and more preferably 5.0 μm or more. On the other hand, the larger the particle size of the particles, the more difficult it is for them to adhere to the paper after the paint is applied, and the easier it is for them to fall off the paper. From the perspective of avoiding falling off, the particle size of the colored resin beads in the first colorant may be, for example, 20 μm or less or 15 μm or less, preferably 10 μm or less, and more preferably 8.0 μm or less. Therefore, the particle size of the colored resin beads in the first colorant may be, for example, 1.0 μm or more and 20 μm or less or 2.0 μm or more and 20 μm or less, preferably 4.0 μm or more and 10 μm or less, and more preferably 5.0 μm or more and 8.0 μm or less.

[0014] The "particle size" in this specification is the particle size (median diameter D 50 (median diameter)) at which the cumulative value in the volume-based cumulative particle size distribution reaches 50% by the method in accordance with the method described in JIS Z 8825:2013 (Particle Size Analysis - Laser Diffraction / Scattering Method). Using a colored resin bead or pigment as a sample, the particle size can be measured using a laser diffraction / scattering particle size distribution measuring device or the like. Also, in a composition containing one or more colored resin beads and multiple types of pigments such as this paint, to measure the particle size of a certain type of colored resin bead or pigment particle, the composition is centrifuged, and the particles of the colored resin beads and pigment particles are fractionated according to their specific gravity from the composition. The particles contained in each obtained fraction are collected and used as a sample for the above method. When observing each particle contained in a certain fraction obtained by centrifugation with the naked eye or an optical microscope, if two or more types of particles are observed (for example, when particles of red colored resin beads and particles of blue colored pigment are observed in a certain fraction), further centrifugation is performed for further separation so that the two or more types of particles are separated according to the specific gravity of the material, and the colored resin beads or pigment collected from the fraction after fractionation are used as a sample for measurement.

[0015] The specific gravity of the first colorant at 25°C may be, for example, 2.5 or less, or may be 2.0 or less. On the other hand, the smaller the specific gravity of the particles, the easier it is for them to float in the coating film formed by applying this paint together with water onto paper, and the longer it takes for them to settle in the coating film. For this reason, it is considered that the particles with a small specific gravity will settle after the particles of the extender pigment described later have settled. As a result, the particles with a small specific gravity settle on the particles of the extender pigment that have settled first and are blocked by the particles of the extender pigment, making it difficult to penetrate into the gaps between the paper fibers, and it is considered that the spread over a wide area of the paper is suppressed. Thus, from the viewpoint of making it easier to stop the first colorant on the paper surface, the specific gravity of the first colorant at 25°C is preferably 1.5 or less, more preferably 1.3 or less. The specific gravity of the first colorant at 25°C may be greater than 1.0, for example.

[0016] The "specific gravity" in this specification is the measured value of the true specific gravity at 25°C of the colored resin beads or pigments by a method conforming to the method described in JIS K 0061:2001 (Methods for Measuring the Density and Specific Gravity of Chemical Products). Using a commercially available specific gravity bottle with a Gay-Lussac thermometer, the true specific gravity at 25°C of the colored resin beads or pigments can be measured by the specific gravity bottle method. In a composition containing colored resin beads and multiple types of pigments such as this paint, to measure the specific gravity of a certain colored resin bead or a certain pigment, fractionation can be performed by centrifugation as described above for the particle size measurement method, and the specific gravity can be measured using the colored resin beads or pigments collected from the obtained fraction as a sample.

[0017] In terms of clearly showing the state of color separation on the paper coated with this paint, the first colorant may be colored resin beads containing an inorganic fluorescent pigment. Examples of the inorganic fluorescent pigment include metal oxides doped with rare earth elements. Or, from the perspective that it is easy to be blocked due to its low specific gravity and the state of color separation is clearer, it is more preferable that the first colorant is colored resin beads containing an organic fluorescent dye. The fluorescent dye is a dye that mainly exhibits color by photoluminescence, which emits light when returning from an excited state due to light absorption to the ground state. Examples of the organic fluorescent dye include, but are not limited to, merocyanine, perylene, acridine, luciferin, pyranine, stilbene, rhodamine, coumarin, fluorescein, or umbelliferone, etc.

[0018] The first colorant may consist of only one kind of colored resin beads with a particle size of 1.0 μm or more, or may be a combination of two or more kinds of colored resin beads each with a particle size of 1.0 μm or more. From the perspective of making the hue presented by the first colorant in this paint appear prominently on the paper surface, the content of the first colorant in this paint may be, for example, 5% by mass or more, or 10% by mass or more, preferably 15% by mass or more, or 20% by mass or more, and more preferably 25% by mass or more. Also, from the perspective of avoiding a situation where the hue presented by the first colorant on the paper surface is too prominent and the hue presented by the second colorant becomes relatively less prominent, the content of the first colorant in this paint may be, for example, 40% by mass or less, or 35% by mass or less, preferably 32% by mass or less, and more preferably 30% by mass or less. Therefore, the content of the first colorant in this paint may be, for example, 5% by mass or more and 40% by mass or less, preferably 15% by mass or more and 32% by mass or less, and more preferably 25% by mass or more and 30% by mass or less.

[0019] As used herein, the "content" means the content in terms of solid content (i.e., the content in dry mass excluding water), except when there is a description related to water (such as Tables 1 and 3 described later). In other words, unless otherwise specified with respect to water, the numerical value of the content of each component in this paint can also be said to be the numerical value of the content of each component in this paint when gently dried at room temperature until it is uniformly dried in a dry atmosphere and maintained at a constant weight. "Room temperature" as used herein is a constant temperature within the range of 5°C or higher and 35°C or lower. Also, the "content" as used herein means the "total content" of two or more components when two or more components are included as the components for which the content is indicated in this paint. For example, when two or more colored resin beads corresponding to the first colorant are included in this paint, the description of the "content of the first colorant" means the total content of those two or more colored resin beads.

[0020] The second colorant is one kind of coloring pigment or a mixture of two or more coloring pigments that are insoluble in water and oil and are generally used for coloring. From the viewpoint of making the second colorant more likely to diffuse over a wider range of paper than the first colorant described above, the particle diameter of the second colorant is 0.50 μm or less, for example, it may be 0.40 μm or less, preferably 0.30 μm or less, and more preferably 0.25 μm or less. The particle diameter of the second colorant may be, for example, 0.05 μm or more, preferably 0.10 μm or more, and more preferably 0.15 μm or more. Therefore, the particle diameter of the second colorant may be, for example, 0.05 μm or more and 0.50 μm or less or 0.05 μm or more and 0.40 μm or less, preferably 0.10 μm or more and 0.30 μm or less, and more preferably 0.15 μm or more and 0.25 μm or less.

[0021] From the perspective of highlighting the state where the portion with a strong hue presented by the first colorant and the portion with a strong hue presented by the second colorant appear separately on the paper surface, the ratio of the particle diameter of the colored resin beads in the first colorant to the particle diameter of the colored pigment in the second colorant (particle diameter of the colored resin beads in the first colorant (μm) / particle diameter of the colored pigment in the second colorant (μm)) may be, for example, 5.0 or more, preferably 10 or more, more preferably 20 or more, and even more preferably 30 or more.

[0022] The specific gravity of the second colorant at 25°C may be, for example, 2.6 or less, 2.4 or less, or 2.3 or less, and may also be 1.6 or more, 1.8 or more, or 2.0 or more. From the perspective that the colored pigment in the second colorant is more likely to further diffuse over a wide range of the paper, it is preferable that the specific gravity of the second colorant at 25°C is greater than the specific gravity of the first colorant at 25°C. When the specific gravity of the second colorant is large, in the coating film formed by applying this paint on the paper, the particles of the colored pigment in the second colorant settle on the paper surface earlier than the particles of the colored resin beads in the first colorant, and penetrate into the gaps between the constituent fibers of the paper together with water. Thus, it is considered that the particles of the colored pigment in the second colorant are more likely to further diffuse over a wide range of the paper. From the same perspective, it is more preferable that the specific gravity of the second colorant at 25°C is 1.3 times or more of the specific gravity of the first colorant at 25°C, and even more preferably 1.6 times or more.

[0023] The second colorant may be a non-fluorescent and colored inorganic pigment. The non-fluorescent and colored inorganic pigment is preferable from the viewpoints of having high hiding power, excellent light resistance and heat resistance, and relatively large specific gravity as compared with the non-fluorescent and colored organic pigment described later. Examples of the material of the white inorganic pigment include titanium oxide, lead white (basic lead carbonate), zinc white (zinc oxide), or lithopone (barium sulfate / zinc sulfide). Examples of the material of the red inorganic pigment include red iron oxide (iron(III) oxide), red lead (lead oxide), vermilion (mercury sulfide), or molybdenum red. Examples of the material of the yellow inorganic pigment include chrome yellow (lead chromate), cadmium yellow (cadmium sulfide), zinc chromate, or litharge (lead monoxide). Examples of the material of the blue inorganic pigment include ultramarine, Prussian blue (iron(III) ferrocyanide), or cobalt aluminate. Examples of the material of the black inorganic pigment include iron black (iron(II,III) oxide) or carbon black.

[0024] The second colorant may be a non-fluorescent and colored organic pigment. The non-fluorescent and colored organic pigment is preferable from the viewpoint of being often vivid in color as compared with the non-fluorescent and colored inorganic pigment described above. Examples of the material of the colored organic pigment include polycyclic pigments, azo pigments, lake pigments, and the like. Examples of the material of the yellow polycyclic pigment include isoindolinone, isoindoline, azomethine, anthraquinone, anthrone, or xanthene. Examples of the material of the orange polycyclic pigment include diketopyrrolopyrrole, anthrone, perinone, or quinacridone. Examples of the material of the red polycyclic pigment include pigments such as quinacridone, diketopyrrolopyrrole, anthraquinone, perinone, or indigoid. Examples of the purple polycyclic pigment include dioxazine, quinacridone, anthrone, or xanthene. Examples of the material of the blue polycyclic pigment include phthalocyanine, anthraquinone, or indigoid. Examples of the material of the green polycyclic pigment include azomethine.

[0025] The second coloring material may be, for example, one coloring pigment selected from non-fluorescent and colored inorganic pigments, non-fluorescent and colored organic pigments, and fluorescent and colored organic pigments, or a combination of two or more coloring pigments. From the viewpoint of making it more visually distinguishable that the hue presented by the first coloring material and the hue presented by the second coloring material appear separately, it is preferable that the first coloring material is colored resin beads containing a fluorescent dye, and the second coloring material is a non-fluorescent coloring pigment. In this specification, "non-fluorescent" means that no color development by photoluminescence is observed, that is, it means that the coloring pigment presents a hue by light absorption and reflection. In other words, a "non-fluorescent coloring pigment" can also be said to be a coloring pigment that does not contain a fluorescent dye.

[0026] From the viewpoint of making it visually distinguishable that the hue presented by the first coloring material and the hue presented by the second coloring material appear separately on the paper coated with this paint, the second coloring material is a coloring pigment that presents a hue different from that of the first coloring material. When designing this paint, it is advisable to select a coloring pigment that presents a hue different from that of the first coloring material as the second coloring material. Here, the "different hue" means that a healthy person without color vision abnormality visually observes a part where the hue presented by the first coloring material is dark and a part where the hue presented by the second coloring material is dark formed by applying this paint on paper, and it is sufficient that the hues presented by both parts are different to such an extent that they can be recognized as different.

[0027] From the viewpoint of making it more visually distinguishable that the hue presented by the first coloring material and the hue presented by the second coloring material appear separately, it is preferable that the hue presented by the first coloring material and the hue presented by the second coloring material are separated by 90° or more and 270° or less in the hue circle of the Munsell color system, more preferably 120° or more and 240° or less, and even more preferably 150° or more and 210° or less. The hue circle of the Munsell color system may conform to JIS Z 8721-1993 (Color display method - Display by three attributes), and for example, it may be divided into any of 10 hues, 24 hues, or 100 hues.

[0028] As combinations of the hues exhibited by the first colorant and the hues exhibited by the second colorant, from the perspective of making the color separation prominent by expressing a contrastive color combination of warm colors and cool colors, for example, combinations of red (R) and blue-green (BG), yellow-red (YR) and blue (B), yellow (Y) and purple-blue (PB), yellow-green (GY) and purple (P), green (G) and red-purple (RP), blue-green (BG) and red (R), blue (B) and yellow-red (YR), purple-blue (PB) and yellow (Y), purple (P) and yellow-green (GY), or red-purple (RP) and green (G) are preferably mentioned. Further, from the perspective of making the color separation more prominent, in the case of a combination where the first colorant exhibits a fluorescent warm-color hue and the second colorant exhibits a non-fluorescent cool-color hue, a combination where the first colorant is a colored resin bead containing an organic fluorescent dye selected from red (R), yellow-red (YR), and yellow (Y), and the second colorant is a non-fluorescent colored pigment selected from blue-green (BG), blue (B), and purple-blue (PB) is even more preferable. The specific combinations of hues are not limited to the examples given here.

[0029] From the perspective of making the hue exhibited by the second colorant appear prominent on the paper surface, the content of the second colorant in this paint may be, for example, 1.0% by mass or more, preferably 2.0% by mass or more, and more preferably 3.0% by mass or more. Also, from the perspective of avoiding a situation where the hue exhibited by the second colorant is too prominent and the hue exhibited by the first colorant becomes relatively less prominent, the content of the second colorant in this paint may be, for example, 30% by mass or less or 20% by mass or less, preferably 15% by mass or less or 10% by mass or less, and more preferably 5.0% by mass or less. Therefore, the content of the second colorant in this paint may be, for example, 1.0% by mass or more and 30% by mass or less, preferably 2.0% by mass or more and 15% by mass or less, and more preferably 3.0% by mass or more and 5.0% by mass or less.

[0030] From the perspective of making the hue presented by the first coloring material appear prominent on the paper surface, the ratio of the content of the first coloring material to the second coloring material in this paint (content of the first coloring material / content of the second coloring material) may be, for example, 1.0 or more, 2.0 or more, or 3.0 or more, preferably 4.0 or more or 5.0 or more, and more preferably 6.0 or more or 7.0 or more. From the perspective of making the hue presented by the second coloring material appear prominent on the paper surface, the ratio of the content of the first coloring material to the second coloring material in this paint (content of the first coloring material / content of the second coloring material) may be, for example, 10.0 or less or 9.0 or less, preferably 8.0 or less. From the perspective of making both the hue presented by the first coloring material and the hue presented by the second coloring material prominent, the ratio of the content of the first coloring material to the second coloring material in this paint (content of the first coloring material / content of the second coloring material) is preferably 4.0 or more and 10.0 or less, and more preferably 6.0 or more and 8.0 or less.

[0031] Extender pigments have high transparency, so they have low hiding power and are pigments with properties that are difficult to use as coloring pigments. Generally, extender pigments are incorporated into paints for purposes such as bulking, dilution, or strengthening of the coating film. The aforementioned colored resin beads and coloring pigments do not correspond to the extender pigments in this paint. Examples of the material of the extender pigment include barite (barium sulfate), precipitated barium sulfate, gypsum (calcium sulfate dihydrate), kaolin, silica (silicon dioxide), white carbon (precipitated silica), talc, barium carbonate, or calcium carbonate, etc.

[0032] From the perspective of making it easy to stop the particles of the colored resin beads in the first coloring material on the paper surface, the particle diameter of the extender pigment in this paint may be, for example, 3.0 μm or more, preferably 4.0 μm or more, and more preferably 5.0 μm or more. From the perspective of avoiding falling off from the paper surface, the particle diameter of the extender pigment may be, for example, 20 μm or less or 15 μm or less, preferably 10 μm or less or 8.0 μm or less, and more preferably 6.0 μm or less. Therefore, the particle diameter of the extender pigment may be, for example, 3.0 μm or more and 20 μm or less, preferably 4.0 μm or more and 10 μm or less, and more preferably 5.0 μm or more and 6.0 μm or less.

[0033] The specific gravity of the extender pigment in this paint at 25°C is not particularly limited as long as it does not conflict with the object of the present invention. For example, it may be 4.0 or less, 3.5 or less, 3.0 or less, or 2.8 or less, and may also be 1.8 or more, 2.0 or more, 2.2 or more, or 2.4 or more. From the viewpoint of easily plugging the first coloring material on the paper surface, the extender pigment in this paint is preferably a pigment having a specific gravity at 25°C greater than that of the first coloring material. From the same viewpoint, the specific gravity of the extender pigment at 25°C is more preferably 1.5 times or more, and even more preferably 2.0 times or more, the specific gravity of the first coloring material at 25°C.

[0034] From the viewpoint of making the color separation appear clearly on the paper coated with this paint, the extender pigment in this paint is preferably a pigment obtained by pulverizing a mineral or a shell. Examples of the extender pigment obtained by pulverizing a mineral include kaolin. Examples of the extender pigment obtained by pulverizing a shell include chalk. The particles of such a pigment (for example, chalk) are relatively large in particle diameter, amorphous, and different in shape for each particle as compared with the particles of a chemically synthesized extender pigment (for example, light calcium carbonate). Although the mechanism by which color separation easily appears by using an extender pigment whose particle shapes are not uniform is unclear, it is considered as follows. In the coating film formed by applying this paint on the paper, in the layer where the particles of the extender pigment with non-uniform shapes settle and accumulate on the paper surface, there are gaps of a size through which the particles of the coloring resin beads in the first coloring material with a relatively large particle diameter hardly pass, but gaps of a size through which the particles of the coloring pigment in the second coloring material with a relatively small particle diameter easily pass are likely to be formed. For this reason, the first coloring material is plugged on the paper surface by the layer of the extender pigment and does not diffuse over a wide range of the paper, whereas the second coloring material passes through the gaps formed in the layer of the extender pigment and migrates into the gaps between the fibers constituting the paper, and is likely to diffuse over a wide range of the paper together with water through the gaps between the fibers.

[0035] From the same perspective, it is more preferable that the extender pigment in this paint is lead white. The particle size of lead white may be, for example, 3.0 μm or more and 20 μm or less, or 4.0 μm or more and 15 μm or less, preferably 5.0 μm or more and 10 μm or less. From the perspective of easily causing color separation, it is more preferable that lead white contains scaly particles when observed under a microscope. In other words, it can also be said that it is more preferable that the extender pigment in this paint contains calcium carbonate particles that are scaly. From the same perspective, the aspect ratio (length of the long side (μm) on the surface / length of the short side (μm) orthogonal to the long side on the surface) of the substantially rectangular surface formed on the scaly particles of lead white may be, for example, greater than 1.5, preferably 2.0 or more, and more preferably 3.0 or more. Lead white containing such scaly particles is suitable for blocking the particles of the colored resin beads of the first colorant on the paper surface by the layer of lead white according to the mechanism described above. On the other hand, for the particles of the colored pigment of the second colorant, it is considered that the shape is such that the particles of the colored pigment can easily pass through the gaps formed in the layer of lead white, and it is considered that the particles of the colored pigment of the second colorant are likely to diffuse over a wide range of the paper together with water.

[0036] In this paint, only one kind of extender pigment may be contained, or two or more kinds may be contained. From the perspective of highlighting color separation by efficiently blocking the first colorant on the paper surface, the content of the extender pigment in this paint may be, for example, 5.0% by mass or more, preferably 10% by mass or more, and more preferably 15% by mass or more. Also, from the perspective of avoiding the situation where the extender pigment falls off the paper surface, the content of the extender pigment in this paint may be, for example, 30% by mass or less, preferably 25% by mass or less, and more preferably 20% by mass or less. Therefore, the content of the extender pigment in this paint may be, for example, 5.0% by mass or more and 30% by mass or less, preferably 10% by mass or more and 25% by mass or less, and more preferably 15% by mass or more and 20% by mass or less.

[0037] In addition to the first coloring material, the second coloring material, and the extender pigment, this paint may further contain one or more selected from a water-soluble polymer compound, an amphiphilic polymer compound, a wetting agent, an antiseptic and antifungal agent, a drying accelerator, a surfactant, a dispersant, an antifoaming agent, and water, as necessary.

[0038] The water-soluble polymer compound and the amphiphilic polymer compound impart dispersibility of the pigment and fixability to the paper surface to this paint. Examples of the water-soluble polymer compound include gum arabic, dextrin, carboxymethyl cellulose, etc. Examples of the amphiphilic polymer compound include vinyl acetate-acrylic copolymer, etc. These polymer compounds may be used alone or in combination of two or more. From the viewpoint of more easily imparting dispersibility of the pigment and fixability to the paper surface in this paint, the content of one or more polymer compounds selected from the water-soluble polymer compound and the amphiphilic polymer compound may be, for example, 5% by mass or 10% by mass or more, preferably 20% by mass or more. Also, in the case of this paint in a solid form as described later, the content of one or more polymer compounds selected from the water-soluble polymer compound and the amphiphilic polymer compound is more preferably 35% by mass or more, and even more preferably 40% by mass or more. Also, from the viewpoint of avoiding the situation where this paint becomes excessively high in viscosity, the content of one or more polymer compounds selected from the water-soluble polymer compound and the amphiphilic polymer compound in this paint may be, for example, 60% by mass or less, preferably 55% by mass or less, and more preferably 50% by mass or less. Therefore, the content of one or more polymer compounds selected from the water-soluble polymer compound and the amphiphilic polymer compound in this paint may be, for example, 5% by mass or more and 60% by mass or less, preferably 20% by mass or more and 55% by mass or less, more preferably 35% by mass or more and 50% by mass or less, and even more preferably 40% by mass or more and 50% by mass or less.

[0039] The wetting agent is for properly maintaining the moisture content of the paint and enhancing its dispersibility in water during use. Examples of the wetting agent include compounds such as glycerin, ethylene glycol, propylene glycol, or polyethylene glycol. These compounds may be used alone or in combination of two or more. From the viewpoint of maintaining the moisture content and enhancing redissolubility, the content of the wetting agent in this paint may be, for example, 3.0% by mass or more, preferably 4.0% by mass or more. Also, from the viewpoint of avoiding the situation where the drying of this paint becomes too slow, the content of the wetting agent in this paint may be, for example, 40% by mass or less or 30% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less. Therefore, the content of the wetting agent in this paint may be, for example, 3.0% by mass or more and 40% by mass or less, preferably 4.0% by mass or more and 20% by mass or less, more preferably 4.0% by mass or more and 10% by mass or less.

[0040] The antiseptic and antifungal agent may be one conventionally used in paints. Examples of the antiseptic and antifungal agent include compounds such as phenol, xylenol, formaldehyde, potassium sorbate, sodium dehydroacetate, methyl benzoate, dithio-2,2'-bis(benzylmethylamide), 2-methylisothiazolin-3-one, 2-(4-thiazolyl)benzimidazole, or 2-thiocyanomethylthiobenzothiazole. These compounds may be used alone or in combination of two or more. The content of the antiseptic and antifungal agent in this paint may be, for example, 0.01% by mass or more or 0.05% by mass or more, and may also be, for example, 5.0% by mass or less or 1.0% by mass or less.

[0041] Drying accelerators, surfactants, dispersants, and antifoaming agents that have been conventionally used in paints may be contained in this paint in the amounts conventionally contained in paints. Water may be contained in some amount in this paint when it is manufactured in a form contained in a tube. However, this paint in the form of a low-viscosity tube containing a large amount of water may have a problem that each pigment has settled and separated by specific gravity at a stage before being mixed with water for use. From the viewpoint of solving this problem, this paint is preferably in the form of a solid paint. The water content in the solid paint is not particularly limited as long as it does not conflict with the object of the present invention. For example, it may be 10% by mass or less, or may be 5% by mass or more and 9% by mass or less. The solid paint is a solid watercolor paint, also referred to as a solid watercolor paint or gouache. The user can utilize the property that the solid paint dissolves in water to express the shade of color, bleeding, blurring, etc. on the paper surface according to the amount of water added to the solid paint.

[0042] When manufacturing this paint in the form of a solid paint, it is preferable to gently dry the paint in the form of a high-viscosity liquid at room temperature to remove most of the water. When drying at room temperature, from the viewpoint of avoiding a situation where various pigments contained in the liquid paint settle and separate by specific gravity before the liquid paint solidifies, it is preferable to dry the liquid paint in the form where the content of one or more selected from the above-mentioned water-soluble polymer compounds and amphiphilic polymer compounds is 35% by mass or more at room temperature to manufacture this paint in the form of a solid paint. Also, from the viewpoint of avoiding a situation where unnatural depressions occur on the surface of the obtained solid paint, it is preferable to heat-dry the liquid paint in the form where the content of one or more selected from the above-mentioned water-soluble polymer compounds and amphiphilic polymer compounds is 40% by mass or more to manufacture a solid paint.

[0043] This paint may further contain other colorants, which are coloring pigments having a particle size larger than 0.5 μm, as long as they do not conflict with the object of the present invention. The upper limit value of the particle size of the other colorants may be the same as the upper limit value of the particle size described above in the description of the first colorant. However, from the viewpoint of making the separation between the hue exhibited by the first colorant and the hue exhibited by the second colorant more clearly appear on the paper surface, the content of the other colorants in this paint may be, for example, 10% by mass or less, 5% by mass or less, 2% or less, or 1% by mass or less. From the same viewpoint, this paint is preferably a composition that substantially does not contain colorants other than the first colorant and the second colorant.

[0044] The object to which this paint is applied is not particularly limited as long as it can be drawn on the surface using a brush and watercolor paint, but it is preferably paper. Examples of paper include drawing paper, watercolor paper, Japanese paper, Kent paper, or imitation paper (fine paper). Japanese paper is paper made by draining a slurry-like raw material mainly composed of fibers obtained by pounding raw material plants such as kozo, mitsumata, ganpi, hemp, coniferous trees, broad-leaved trees, or bamboo. The basis weight of the paper is not particularly limited as long as the second colorant can diffuse together with water on the paper surface when this paint is applied to the paper. For example, it may be 5 g / m 2 or more and 200 g / m 2 or less, or 30 g / m 2 or more and 130 g / m 2 or less. From the viewpoint of making the color separation prominent, the paper is preferably one that has not been sized (stopping water bleeding) on the surface.

[0045] The matters disclosed by this specification include the following. (1) A first colorant that is a colored resin bead having a particle size of 1.0 μm or more, A second colorant that is a coloring pigment having a particle size of 0.5 μm or less, An extender pigment, and A paint in which the second colorant exhibits a hue different from that of the first colorant. (2) The extender pigment has a specific gravity at 25°C greater than that of the first colorant, and the paint according to (1) above. (3) The paint according to (1) or (2) above, wherein the extender pigment contains lead white. (4) The paint according to any one of (1) to (3) above, wherein the first coloring material is the colored resin beads containing a fluorescent dye, and the second coloring material is the non-fluorescent colored pigment. (5) The paint according to any one of (1) to (4) above, wherein the hue presented by the first coloring material and the hue presented by the second coloring material are separated by 90° or more and 270° or less in the hue circle of the Munsell color system. (6) The paint according to any one of (1) to (5) above, which is a solid paint.

[0046] In the present invention, it is not limited to the embodiments described above, etc., and it can also be implemented in various improved, modified or deformed forms based on the knowledge of those skilled in the art without departing from the gist of the present invention. In the present invention, within the range where the same action or effect is produced, it may be implemented in a form in which any specific matter is replaced with another technique.

Example

[0047] The present invention will be described below with reference to examples and the like, but the present invention is not limited to the examples.

[0048] As the first coloring material, which is colored resin beads having a particle diameter of 1.0 μm or more, the following commercially available products were prepared. SX-103 (manufactured by Shinroihi Co., Ltd., colored resin beads containing a red organic fluorescent dye) SX-104 (manufactured by Shinroihi Co., Ltd., colored resin beads containing an orange organic fluorescent dye) SX-105 (manufactured by Shinroihi Co., Ltd., colored resin beads containing a yellow organic fluorescent dye) SX-117 (manufactured by Shinroihi Co., Ltd., colored resin beads containing a pink organic fluorescent dye) In addition, the product series of the colored resin beads containing these organic fluorescent dyes are described in the product description as having an average particle size of 4 μm to 6 μm. Further, when the present inventors measured the particle size of the colored resin beads containing these organic fluorescent dyes by the aforementioned method, for example, the 10% diameter D 10 was 3.65 μm, and the median diameter D 50 (median diameter) was 6.67 μm, and the 90% diameter D 90 was 11.6 μm. Also, all of SX-103, SX-104, SX-105, and SX-117 had a specific gravity of 1.2 at 25°C measured by the aforementioned method.

[0049] As the second colorant, which is a colored pigment with a particle size of 0.50 μm or less, the following commercially available products were prepared. SA Blue DY-12K (manufactured by Mikuni Shikiso Co., Ltd., blue non-fluorescent organic pigment) SA Green DY-4K (manufactured by Mikuni Shikiso Co., Ltd., green non-fluorescent organic pigment) High Micron Red #7356NB (manufactured by Mikuni Shikiso Co., Ltd., red non-fluorescent organic pigment) Blue FLGB Conc (manufactured by Dainichi Seika Chemicals Co., Ltd., blue non-fluorescent organic pigment) Green FLB Conc (manufactured by Dainichi Seika Chemicals Co., Ltd., green non-fluorescent organic pigment) Golden yellow FL4G Conc (manufactured by Dainichi Seika Chemicals Co., Ltd., yellow non-fluorescent organic pigment) In addition, SA Blue DY-12K had a particle size of 0.17 μm measured by the aforementioned method and a specific gravity of 1.62 at 25°C measured by the aforementioned method. SA Green DY-4K, when measured in the same way, had a particle size of 0.14 μm and a specific gravity of 2.1 at 25°C.

[0050] As other colorants, the following commercially available products were prepared. Note that "Bayferrox" is a registered trademark. Rose #13FD: manufactured by Nomura Chemical Industry Co., Ltd., rose-colored non-fluorescent organic pigment) Bayferrox 3920 (manufactured by Lanxess Co., Ltd., yellowish-brown non-fluorescent inorganic pigment) Bayferrox 110M (manufactured by Lanxess Co., Ltd., brown non-fluorescent inorganic pigment) Ultramarine Blue 82 (manufactured by Veneta, blue non-fluorescent inorganic pigment) In addition, all of the other color materials prepared here were not colored resin beads, and the particle size measured by the method described above was larger than at least 0.5 μm and generally 2.0 μm or more.

[0051] The following commercially available products were prepared as extender pigments. Generally, the particle size of lithopone is about 2 μm to 6 μm. Tokka Shirogane (manufactured by Nakagawa Shirogane Manufacturing Co., Ltd., powder obtained by pulverizing naturally occurring scallop shells) Barium Sulfate P-30 (manufactured by Takehara Chemical Industry Co., Ltd., barium sulfate powder) When observed with an optical microscope, Tokka Shirogane contained many scaly calcium carbonate particles. Also, when the particle size of Tokka Shirogane was measured by the method described above, the 10% diameter D 10 was 1.55 μm, the median diameter D 50 (median diameter) was 5.42 μm, and the 90% diameter D 90 was 11.2 μm. Also, when the specific gravity of Tokka Shirogane at 25°C was measured by the method described above, it was 2.71.

[0052] The following commercially available products were prepared as water-soluble polymer compounds. Note that "Amicol" is a registered trademark. Arabic Col SS (manufactured by Sanei Pharmaceutical Trading Co., Ltd., gum arabic) Red Jade Dextrin (manufactured by Nisshoku Chemical Co., Ltd., dextrin) In addition, glycerin manufactured by Kao Corporation was prepared as a wetting agent. A preservative and an antifoaming agent, which are generally commercially available for use in paints, were prepared. As water, the tap water in Nara City, Nara Prefecture was used as it was.

[0053] [Examples 1 to 8] First, a medium composition containing lithopone as an extender pigment was prepared according to the formulation shown in Table 1 below.

Table 1

[0054] Next, according to the formulation shown in Table 2 below, a medium composition containing chalk (Table 1), a first colorant containing a fluorescent dye, and a non-fluorescent second colorant were mixed. The obtained mixture was filled into a plastic container, and the container was gently dried at room temperature to trial-produce solid watercolor paints (dry pigments) according to each of Examples 1 to 8. When the water content in these solid watercolor paints was measured, the water content was about 8% by mass.

Table 2

[0055] [Examples 9 to 16] First, a medium composition containing barium sulfate as an extender pigment was prepared according to the formulation shown in Table 3 below.

Table 3

[0056] Next, according to the formulation shown in Table 4 below, a medium composition containing barium sulfate (Table 3), a first colorant containing a fluorescent dye, and a non-fluorescent second colorant were mixed. The obtained mixture was filled into a plastic container, and the container was gently dried at room temperature to trial-produce solid watercolor paints (dry pigments) according to each of Examples 9 to 16. When the water content in these solid watercolor paints was measured, the water content was about 8% by mass.

Table 4

[0057] [Comparative Examples 17 to 23] According to the formulation shown in Table 5 below, a barium sulfate-containing magnesium composition (Table 3), other non-fluorescent colorants, and a non-fluorescent second colorant were mixed. The obtained mixture was filled into a plastic container, and the obtained mixture was gently dried at room temperature together with the container to trial-produce solid watercolor paints (dry pigments) according to each of Comparative Examples 17 to 23. When the water content in these solid watercolor paints was measured, the water content was about 8% by mass.

Table 5

[0058] [Evaluation Test] For each of the solid watercolor paints trial-produced as described above, in the container, the surface part of the solid watercolor paint was gradually dissolved in water little by little with a water-containing brush tip to take a small amount of the paint, and after mixing the paint with a small amount of water and spreading it on a plastic palette for painting, a sufficient amount was placed on commercially available watercolor paper with the brush tip of a painting brush and written. Thereafter, the hue presented by the first colorant or the hue presented by other colorants appeared at the site written with the brush tip on the watercolor paper. Also, at a site slightly separated from the sites where these hues appeared on the watercolor paper, the hue presented by the second colorant appeared together with the water spreading diffusively. The watercolor paper was visually observed in a bright room, and the three items of the beauty of the color combination, the ease of understanding color separation, and the ease of color separation were evaluated in four grades according to the following criteria respectively. The evaluation results are shown in Tables 6 to 8 described later.

[0059] Beauty of color combination: Evaluation criteria AA The difference in the color combination of two colors is prominent and easy to understand, and the appearance is particularly beautiful. A The difference in the color combination of two colors is easy to understand, and the appearance is beautiful. B Although it is a similar color combination, the difference in the color combination of two colors can be seen at a glance in appearance. C The colors are so similar that the difference in the color combination cannot be understood without staring, and the appearance is dirty.

[0060] Ease of understanding color separation: Evaluation criteria When there are two colors as vivid as the pigments blended in the AA paints, they leave a strong impression. A One can tell at a glance that there are two colors. B Upon closer inspection, one can tell that there are two colors. C Even upon closer inspection, one cannot tell that there are two colors.

[0061] Ease of color separation: Evaluation criteria AA The areas where the two colors are each showing through are clearly separated on the watercolor paper. A The areas where the two colors are each showing through are adjacent, but the boundary is easy to distinguish. B The areas where the two colors are each showing through are adjacent, and the boundary is difficult to distinguish. C The two colors are each showing through in substantially the same area on the watercolor paper, and the boundary is indistinguishable.

[0062] [Table 6]

[0063] [Table 7]

[0064] [Table 8]

[0065] In the paints according to Examples 1 to 8, the hue of the fluorescent color presented by the first colorant and the hue of the non-fluorescent color presented by the second colorant appeared on the watercolor paper in a clearly separated state, and a drawing with a visually appealing aurora-like contrast was obtained. Figure 1 shows the drawing that appeared on the watercolor paper using the paint according to Example 2. Around the area where the hue presented by the first colorant (fluorescent red in Figure 1) appeared on the watercolor paper, an area where the hue presented by the second colorant (non-fluorescent blue in Figure 1) appeared oozed out from that area.

[0066] In addition, compared with Examples 9 to 16 using barium sulfate as the extender pigment, in Examples 1 to 8 using lead white as the extender pigment, visually, the hue of the fluorescent color exhibited by the first colorant and the hue of the non-fluorescent color exhibited by the second colorant were clearly separated. Further, compared with Comparative Examples 17 to 23 using non-fluorescent coloring pigments as other colorants, in Examples 1 to 16 using colored resin beads containing a fluorescent dye as the first colorant, the beauty of the color combination was prominent, showing a particularly beautiful appearance and receiving high evaluation.

[0067] In addition, compared with Examples 1 to 8 described above, a solid watercolor paint (dry watercolor) according to Comparative Example 24 was also prototyped under the same formulation and prototyping conditions, except that commercially available colored resin beads with a particle diameter of about 0.4 μm were used instead of the first colorant used in Examples 1 to 8. However, even when the paint according to this Comparative Example 24 was applied to watercolor paper together with water, no particular color separation was observed on the paper surface of the watercolor paper. Therefore, it was suggested that in the case of a paint using colored resin beads with a particle diameter of about 0.4 μm instead of the first colorant, the particle diameter was too small for the colored resin beads to be easily blocked on the paper surface, and it was difficult to intentionally express color separation in relation to the coloring pigment of the second colorant.

Claims

1. a first coloring material that is a colored resin bead having a particle diameter of 1.0 μm or more; a second coloring material that is a coloring pigment having a particle diameter of 0.5 μm or less; an extender pigment; A paint wherein the second colorant exhibits a different hue than the first colorant.

2. 2. The paint according to claim 1, wherein the extender pigment has a specific gravity at 25°C greater than that of the first coloring material.

3. 3. A paint according to claim 1 or claim 2, wherein the extender pigment comprises chalk.

4. 3. The paint according to claim 1, wherein the first coloring material is the colored resin beads containing a fluorescent dye, and the second coloring material is the non-fluorescent colored pigment.

5. 3. The paint according to claim 1, wherein the hue exhibited by the first coloring material and the hue exhibited by the second coloring material are separated by an angle of 90° or more and 270° or less on the Munsell hue circle.

6. 3. The paint according to claim 1 or claim 2, which is a solid paint.

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