Calcium-based inorganic substrate coloring composition and method for coloring calcium-based inorganic substrate therewith

Abstract

To provide a composition for coloring a calcium-based inorganic substrate capable of clearly coloring a calcium-based inorganic substrate and capable of imparting excellent light resistance and a method for coloring the calcium-based inorganic substrate therewith.SOLUTION: The coloring composition for calcium-based inorganic substrates of the present invention contains a dye, water, alcohol, and pigments. A content of the pigments is between 0.2 pt.mass to 6 pts.mass relative to a total of 100 pts.mass of the composition. According to the present invention, it is possible to provide a colored inorganic substrate that has excellent light resistance. Moreover, since the coloring is achieved by impregnation into the inorganic substrate, the colored state is maintained even if the surface of the substrate is worn.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a composition for coloring a calcium-based inorganic substrate and a method for coloring a calcium-based inorganic substrate using the same.

Background Art

[0002] When coloring calcium-based inorganic substrates such as concrete, cement, gypsum, and stone, in many cases, a method of forming a coating film using a paint containing a pigment on the surface is adopted.

[0003] However, such pigments generally have a larger particle diameter than the pores of the calcium-based inorganic substrate. For this reason, it has been pointed out that the pigments stay on the surface of the calcium-based inorganic material, and the colored layer is lost due to peeling or friction, and the substrate is relatively easily exposed.

[0004] Furthermore, in recent years, due to the improvement of the performance of admixtures contained in fresh concrete and the improvement of concrete placing technology and curing technology, the pore voids formed on the surface of calcium-based inorganic substrates (for example, concrete substrates) tend to be smaller and fewer. Although an improvement in coloring performance for such pore voids is desired, there is a reality that satisfactory results have not yet been obtained.

[0005] On the other hand, for coloring the calcium-based inorganic substrate, an approach using dyes has also been considered. For example, Patent Document 1 proposes a technique of applying a coating liquid containing a disperse dye or the like to an inorganic substrate such as concrete and impregnating the surface layer of the inorganic substrate up to about 1 mm to color the surface of the inorganic substrate. Patent Document 2 proposes a technique of coloring a calcium-based inorganic substrate using a first liquid containing a dye soluble in water or an organic solvent and a second liquid containing a surface strengthening agent composed of a water-soluble alkali silicate compound and / or a reinforcing resin.

[0006] However, in the technologies described in Patent Documents 1 and 2, it has been pointed out that the dyes used are liable to fade by ultraviolet rays, so the resulting colored substrate is inferior in light resistance. Further, since the inorganic substrate is not sufficiently impregnated with the dye, it has been pointed out that clear coloring tends to be lost also due to the abrasion of the colored substrate.

[0007] In recent years, for example, in stores or facilities such as retail stores, shopping malls, and designer mansions, there has been a demand for interior design with a predetermined coloration along with the texture of concrete.

[0008] However, it is extremely difficult to realize such a demand with paints. This is because even if the desired color can be realized by the resulting paint film, the texture is easily lost when the paint film covers the concrete surface. Although a paint presenting the texture of concrete has been dramatically improved and commercialized, the texture is due to the paint film and is merely pseudo.

Prior Art Documents

Patent Documents

[0009]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0010] The present invention aims to solve the above problems, and an object thereof is to provide a composition for coloring a calcium-based inorganic substrate that can clearly color the calcium-based inorganic substrate and can impart excellent light resistance, and a method for coloring a calcium-based inorganic substrate using the same.

Means for Solving the Problems

[0011] The present invention relates to a composition for coloring a calcium-based inorganic substrate, which contains a dye, water, alcohol, and a pigment, and the content of the pigment is 0.2 parts by mass to 6 parts by mass with respect to 100 parts by mass of the total mass of the composition.

[0012] In one embodiment, the composition for coloring a calcium-based inorganic substrate of the present invention further contains a surfactant.

[0013] In one embodiment, the above dye is at least one selected from the group consisting of a direct dye, a reactive dye, an acid dye, an acid mordant dye, a metal complex acid dye, and a basic dye.

[0014] In one embodiment, the above alcohol is a primary alcohol having 1 to 3 carbon atoms.

[0015] In one embodiment, the above surfactant is a nonionic surfactant.

[0016] In one embodiment, the composition for coloring a calcium-based inorganic substrate of the present invention further contains an aqueous polymer emulsion.

[0017] The present invention also relates to a method for coloring a calcium-based inorganic substrate, which includes a step of impregnating the surface of the calcium-based inorganic substrate with the above coloring composition to form an impregnated surface and is a method including this step.

[0018] In one embodiment, the coloring method of the present invention further includes a step of applying a protective coating solution containing at least one compound selected from the group consisting of an acrylic resin, an epoxy resin, a urethane resin, a resin having a silanol group or a group convertible to a silanol group, and a water-soluble alkali metal silicate compound to the impregnated surface.

Advantages of the Invention

[0019] According to the present invention, a colored inorganic substrate having excellent light resistance can be provided. Further, since the coloring is achieved by impregnation into the inorganic substrate, the colored state is maintained even when the surface of the substrate is worn.

Brief Description of the Drawings

[0020]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Modes for Carrying Out the Invention

[0021] Hereinafter, the present invention will be described in detail.

[0022] (Composition for Coloring Calcium-Based Inorganic Substrate) The composition for coloring a calcium-based inorganic substrate of the present invention is used for coloring a calcium-based inorganic substrate.

[0023] The above calcium-based inorganic substrate is a substrate composed of an inorganic material containing calcium in its constituent components. For example, it refers to indoor and outdoor buildings or structures constituting a building (such as wall surfaces, floor surfaces, passageways, roads, columns, and fences), monuments that can be placed outdoors or indoors (such as memorial monuments; memorial towers; and statues modeled after people, gods, Buddhas, animals, etc.), as well as their constituent parts (such as flat parts, curved parts, square columns, circular columns, spheres, ellipsoids, blocks, and flat plates); and combinations thereof.

[0024] The constituent materials of the calcium-based inorganic substrate are not particularly limited, but examples include concrete, cement, gypsum, and stone materials (such as those containing a calcium component), as well as combinations thereof.

[0025] The composition for coloring the calcium-based inorganic substrate of the present invention contains a dye, water, alcohol, and a pigment.

[0026] The dye constituting the composition of the present invention is preferably a dye soluble in water and / or an organic solvent. Here, the "organic solvent" preferably includes an organic solvent miscible with water. Examples of the dye include direct dyes, reactive dyes, acid dyes, acid mordant dyes, metal complex acid dyes, basic dyes, building dyes, and sulfur dyes, as well as combinations thereof.

[0027] Examples of direct dyes include those of the Color Index (CI), Direct Yellow 46, Direct Yellow 8, Direct Yellow 27, Direct Yellow 28, Direct Yellow 30, Direct Yellow 83, Direct Yellow 50, Direct Yellow 11, Direct Yellow 12, Direct Orange 26, Direct Red 23, Direct Red 28, Direct Red 80, Direct Red 31, Direct Violet 1, Direct Blue 86, Direct Blue 106, Direct Blue 1, Direct Blue 15, Direct Blue 80, Direct Blue 71, Direct Blue 151, Direct Green 6, Direct Green 1, Direct Brown 2, Direct Black 56, Direct Black 17, Direct Black 9, Direct Black 38, Direct Black 19, Direct Black 22, Direct Black 154, Direct Red 83:1, Direct Blue 6, Direct Red 13, Direct Red 220, Direct Violet 51, Direct Red 81, Direct Yellow 6, Direct Yellow 26, Direct Yellow 44, Direct Red 75, Direct Red 79, Direct Red 224, Direct Red 227, Direct Green 26, Direct Blue 199, Direct Yellow 106, Direct Orange 39, Direct Violet 66, Direct Orange 34, Direct Yellow 132, Direct Yellow 86, Direct Violet 9, Direct Red 243, Direct Yellow 142, Direct Yellow 161, Direct Blue 70, Direct Blue 78, Direct Blue 108, Direct Blue 200, Direct Blue 201, Direct Brown 1, Direct Black 168, Direct Brown 210, Direct Brown 115, and combinations thereof.

[0028] Examples of reactive dyes include those of the Color Index (CI), Reactive Yellow 145, Reactive Red 195, Reactive Blue 221, Procion, Mikacion, Cibacron, Drimarene, Reactone, and Remazol; and combinations thereof.

[0029] Examples of acid dyes include Acid Yellow 49, Acid Red 249, Acid Blue 40, Rosealin, Azorubin, Acid Orange, Metanil Yellow, Brilliant Milling Green BC, Acid Brown R, Acid Blue Black 10B, Acid Violet 5B, and Nigrosin BHL, as well as combinations thereof in the Color Index (CI).

[0030] An example of an acid mordant dye is Eriochrome Black T.

[0031] Examples of metal complex acid dyes include Acid Black 52 and the like.

[0032] Examples of basic dyes include magenta, rhodamine, safranine, chrysoidine, auramine, malachite green, Bismarck green, methylene blue, Victoria blue, methyl violet, Janus black, and Orange II, as well as combinations thereof.

[0033] Examples of vat dyes include indigo (Vat Blue 1), Vat Red 10, Vat Violet 13, and Vat Orange 1, as well as combinations thereof.

[0034] Examples of sulfur dyes include Sulfur Yellow 16, Sulfur Orange 1, Sulfur Red 6, Sulfur Blue 7, Sulfur Blue 15, and Sulfur Black 11 in the Color Index (CI), as well as combinations thereof.

[0035] In the present invention, direct dyes, reactive dyes, acid dyes, acid mordant dyes, metal complex acid dyes, and basic dyes, as well as combinations thereof, are preferred because, in combination with the components described later, it is possible to provide a colored substrate excellent in impregnation properties into the substrate, light resistance, and water resistance.

[0036] The content of the dye contained in the composition of the present invention is preferably 0.1 part by mass to 10 parts by mass, more preferably 0.2 part by mass to 8 parts by mass, and even more preferably 0.3 part by mass to 6 parts by mass with respect to 100 parts by mass of the total mass of the composition. When the content of the dye is less than 0.1 part by mass, the color obtained by coloring may be dilute and lack practicality. When the content of the dye exceeds 10 parts by mass, it may become a dark color (close to black) where color discrimination is difficult, lacking in color, or although color discrimination is possible, it will only increase the manufacturing cost without becoming any darker.

[0037] The water constituting the composition of the present invention serves to uniformly dissolve the above dye and promote the impregnation of the dye into the calcium-based inorganic substrate. The water may be any of pure water, ion-exchanged water, RO water, and tap water.

[0038] The content of the water contained in the composition of the present invention is preferably 20 parts by mass to 90 parts by mass, more preferably 30 parts by mass to 70 parts by mass with respect to 100 parts by mass of the total mass of the composition. When the content of the water is less than 20 parts by mass, the relative alcohol content increases, so the volatility of the entire resulting composition increases, and safety and workability may be impaired. When the content of the water exceeds 90 parts by mass, the relative alcohol content decreases, and the impregnability of the resulting composition into the calcium-based inorganic substrate may decrease.

[0039] The alcohol constituting the composition of the present invention has the property of being miscible with the above water and serves to appropriately dissolve the coloring component (molecule) constituting the above dye and impregnate it deep into the fine pores on the surface of the calcium-based inorganic substrate. In the present invention, the alcohol preferably includes primary alcohols, secondary alcohols, and tertiary alcohols having 1 to 5 carbon atoms.

[0040] Examples of such alcohols include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, s-butyl alcohol, t-butyl alcohol, ethylene glycol, and glycerin, and combinations thereof.

[0041] For the reasons that it has excellent miscibility with the above water and can more effectively impregnate the above dye into the calcium-based inorganic substrate, the alcohol is preferably a primary alcohol having 1 to 3 carbon atoms. For example, isopropyl alcohol is more preferable because the dry state of the composition imparted to the calcium-based inorganic substrate using its unique odor can be grasped through the sense of smell.

[0042] Alternatively, among the primary alcohols having 1 to 3 carbon atoms, for example, methanol has a property of being highly volatile compared to ethanol and isopropyl alcohol in that its boiling point is 65°C and its vapor pressure is 12.9 kPa (20°C). Therefore, when methanol is used as the alcohol in the present invention, a more quickly drying coloring composition can be obtained. However, due to this quick drying property, the operator is forced to perform the coloring operation in an extremely short time. Therefore, in the present invention, the alcohol is preferably isopropyl alcohol, ethanol, or a combination thereof because a coloring composition having a somewhat milder quick drying property compared to methanol can be provided.

[0043] The content of the alcohol contained in the composition of the present invention is preferably 10 to 80 parts by mass, more preferably 20 to 70 parts by mass, based on 100 parts by mass of the total mass of the composition. When the content of the alcohol is less than 10 parts by mass, the effect of promoting impregnation deep into the fine pores on the surface of the calcium-based inorganic substrate may be reduced. When the content of the alcohol exceeds 80 parts by mass, the volatility of the entire resulting composition increases, drying becomes extremely fast, and workability may deteriorate.

[0044] The pigment constituting the composition of the present invention serves to supplement the coloring of the calcium-based inorganic substrate by the above dye.

[0045] In the present invention, examples of the pigment include inorganic pigments, organic pigments, and combinations thereof.

[0046] Examples of the inorganic pigment include titanium oxide, iron oxide, cobalt oxide, chromium oxide, carbon black, and their composite oxides, and combinations thereof.

[0047] Examples of the organic pigment include copper phthalocyanine (blue pigment), quinophthalone-based pigment (yellow pigment), and azo-based pigment (red pigment), and combinations thereof.

[0048] The size of the pigment is not particularly limited, but it is preferably 0.1 μm to 2 μm, more preferably 0.2 μm to 1 μm in average particle diameter, because it can enhance the filling efficiency into pores (for example, diameter 0.05 μm to 5 μm) formed in the calcium-based inorganic substrate and enhance the light-shielding effect from external light on the above dye impregnated inside. When the average particle diameter of the pigment is less than 0.1 μm, it is likely to aggregate, and there is a risk that uniform dispersion becomes difficult in the coexistence of the above water, alcohol, and surfactant. Also, manufacturing such a pigment having such a fine average particle diameter itself requires advanced technology and may reduce productivity. When the average particle diameter of the pigment exceeds 2 μm, it may not be filled into the pores formed in the calcium-based inorganic substrate, and it may be difficult to supplement the coloring by the above dye.

[0049] The content of the pigment contained in the composition of the present invention is 0.2 parts by mass to 6 parts by mass, preferably 0.3 parts by mass to 5 parts by mass, more preferably 0.5 parts by mass to 4 parts by mass with respect to 100 parts by mass of the total mass of the composition. When the content of the pigment is less than 0.2 parts by mass, the light resistance of the resulting composition may be insufficient. When the content of the pigment exceeds 6 parts by mass, the color of the dye as a constituent component may be concealed.

[0050] The composition of the present invention may further contain a surfactant.

[0051] The surfactant constituting the composition of the present invention plays a role of reducing the surface tension of the coloring component (molecule) of the dye in the coexistence of the above water and alcohol, making it easier to conform to the surface of the calcium-based inorganic substrate, and as a result, enhancing the impregnation property.

[0052] Examples of the surfactant are not particularly limited, and any of nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants may be used.

[0053] Examples of the nonionic surfactant are not necessarily limited, and include, for example, ester-type nonionic surfactants, ether-type nonionic surfactants, ester-ether-type nonionic surfactants, and combinations thereof. Due to the reason of low foaming property, the nonionic surfactant is preferably an ether-type nonionic surfactant.

[0054] Examples of the anionic surfactant are not necessarily limited, and include, for example, anionic surfactants of carboxylates, anionic surfactants of sulfonates, and anionic surfactants of sulfuric esters, and combinations thereof. Due to the reason of good solubility in water, the anionic surfactant is preferably an anionic surfactant of sulfonates.

[0055] Examples of the cationic surfactant are not necessarily limited, and include, for example, amine salt-type cationic surfactants and quaternary ammonium salt-type cationic surfactants, and combinations thereof.

[0056] Examples of the amphoteric surfactant are not necessarily limited, and include, for example, carboxylate-type amphoteric surfactants.

[0057] In the present invention, since the surfactant does not ionize when dissolved in water and there is no need to consider its influence on the charging characteristics of the calcium-based inorganic substrate, the surfactant is preferably a nonionic surfactant.

[0058] The content of the surfactant contained in the composition of the present invention is preferably 0.1 part by mass to 5 parts by mass, more preferably 0.3 part by mass to 2 parts by mass, based on 100 parts by mass of the total mass of the composition. If the content of the surfactant is less than 0.1 part by mass, the impregnation property of the resulting composition into the calcium-based inorganic substrate may be reduced. If the content of the surfactant exceeds 5 parts by mass, the resulting composition is likely to foam, resulting in a decrease in workability and difficulty in obtaining uniform coloring.

[0059] The composition of the present invention may further contain an aqueous polymer emulsion.

[0060] The aqueous polymer emulsion is an aqueous emulsion containing a predetermined polymer used in paints, adhesives, adhesives, building materials for housing, etc., and is used to impart pigment fixing properties to the calcium-based inorganic substrate. The aqueous polymer emulsion also serves to impart the fixing property of the dye, which is a constituent component when the resulting composition is applied to the calcium-based inorganic substrate.

[0061] Examples of the aqueous polymer emulsion include acrylic emulsions, acrylic-silicone emulsions, styrene-acrylic emulsions, urethane emulsions, epoxy emulsions, ethylene-vinyl acetate emulsions, and vinyl acetate emulsions, as well as combinations thereof. Acrylic emulsions, acrylic-silicone emulsions, styrene-acrylic emulsions and combinations thereof are preferred, and acrylic emulsions are more preferred, because there are many of the above general-purpose products and the viscosity can be easily adjusted through the addition of water and / or thickeners.

[0062] Among the above aqueous polymer emulsions, for example, acrylic emulsions contain acrylic resins, methacrylic resins, acrylic copolymers, methacrylic copolymers, etc. as resin components. These resins are obtained by polymerizing acrylic monomers by known methods such as emulsion polymerization and solution polymerization.

[0063] The acrylic monomers constituting the above resin component are not particularly limited. For example, styrene, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, hexyl methacrylate, lauryl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, acrylamide, methacrylamide, glycidyl acrylate, and glycidyl methacrylate, and combinations thereof can be mentioned.

[0064] In the present invention, the aqueous polymer emulsion is preferably milky white or colorless itself in order to avoid the color development by the above dye being impaired. The aqueous polymer emulsion may be, for example, a commercially available clear paint.

[0065] The pH of the aqueous polymer emulsion is preferably 6.5 to 9.5, more preferably 7 to 9. When the aqueous polymer emulsion has a pH within such a range, it can be safely handled without eroding the applied calcium-based inorganic substrate.

[0066] The solid content of the aqueous polymer emulsion contained in the composition of the present invention is 0.5 parts by mass to 10 parts by mass, preferably 1 part by mass to 5 parts by mass, based on 100 parts by mass of the total mass of the composition. When the solid content of the aqueous polymer emulsion is less than 0.5 parts by mass, the fixing property of the pigment and the dye, which are the constituent components, may be insufficient when applied to the calcium-based inorganic substrate, resulting in easy color fading. When the solid content of the aqueous polymer emulsion exceeds 10, the impregnation property of the resulting composition may be reduced by blocking the pore spaces of the calcium-based inorganic substrate.

[0067] In addition, it is preferable that the above aqueous polymer emulsion has a viscosity of 1000 mPa·s or less.

[0068] The composition for coloring a calcium-based inorganic substrate of the present invention may also contain an ultraviolet absorber and / or an ultraviolet scattering agent in order to improve light resistance.

[0069] Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, and combinations thereof. Benzotriazole-based ultraviolet absorbers are preferred because of their high versatility and excellent absorption of near ultraviolet light (for example, wavelengths of 340 nm to 360 nm).

[0070] Examples of the ultraviolet scattering agent include zinc oxide, titanium oxide, and combinations thereof.

[0071] The contents of the ultraviolet absorber and the ultraviolet scattering agent in the present invention are not particularly limited, and those skilled in the art can select appropriate contents within a range that does not inhibit the effects exhibited by the composition of the present invention.

[0072] Furthermore, the composition for coloring calcium-based inorganic substrates of the present invention may contain other additives. Examples of other additives include defoamers, preservatives, and antibacterial agents, as well as combinations thereof. The content of other additives in the present invention is not particularly limited, and those skilled in the art can select an appropriate content within the range that does not inhibit the effects exhibited by the composition of the present invention.

[0073] (Composition for Coloring Calcium-Based Inorganic Substrates) Next, a method for coloring a calcium-based inorganic substrate using the composition for coloring a calcium-based inorganic substrate of the present invention will be described.

[0074] In the present invention, the surface of the calcium-based inorganic substrate is impregnated with the above-described composition for coloring a calcium-based inorganic substrate to form an impregnated surface.

[0075] For impregnating the composition for coloring a calcium-based inorganic substrate onto the surface of the calcium-based inorganic substrate, coating means well-known in the art such as a brush, a roll coater, and spraying are employed, for example.

[0076] The composition for coloring a calcium-based inorganic substrate of the present invention enables the dye, which is a constituent component, to dissolve more uniformly in the composition and to lower the interfacial tension, making it easier to conform to the surface of the calcium-based inorganic substrate. As a result, the impregnability of the composition to the calcium-based inorganic substrate is enhanced, and the composition can penetrate deeper from the surface of the calcium-based inorganic substrate.

[0077] In the present invention, after the surface of the calcium-based inorganic substrate is impregnated with the above-described coloring composition, a protective coating liquid may be applied to the resulting impregnated surface.

[0078] The protective coating liquid contains an acrylic resin, an epoxy resin, a urethane resin, a resin having a silanol group or a group convertible to a silanol group, and / or a water-soluble alkali silicate compound, and is prepared, for example, in the form of an aqueous solution. In the present invention, a plurality of protective coating liquids having different content components may be used and laminated on an impregnated surface impregnating the composition of the calcium-based inorganic substrate in the form of two or more layers.

[0079] When the protective coating liquid contains an acrylic resin, an epoxy resin, and / or a urethane resin, it is preferable that these resins are contained in the protective coating liquid in the form of an emulsion.

[0080] The resin having a silanol group or a group convertible to a silanol group is, for example, a resin having a silanol group (including an isolated silanol group, a vicinal silanol group, and a geminal silanol group) or a group convertible to the silanol group on the main chain and / or branched chain constituting a thermoplastic resin such as an acrylic resin or a styrene-acrylic resin.

[0081] The "group convertible to a silanol group" refers to a group in which the OH moiety constituting the silanol group is substituted by an alkoxy group, a halogen atom, or the like. The group convertible to a silanol group can be converted to a silanol group through hydrolysis.

[0082] The resin having a silanol group or a group convertible to a silanol group is commercially available in the form of an emulsion (for example, an aqueous emulsion) or in a form dissolved or dispersed in a predetermined solvent. In the present invention, the resin having a silanol group or a group convertible to a silanol group can be used alone or in combination of two or more in the protective coating liquid.

[0083] The water-soluble alkali silicate compound is a silicate compound represented by the general formula M2O·nSiO2 (where M is an alkali metal and n is an integer from 2 to 4). Examples of the water-soluble alkali silicate compound include sodium silicate (such as sodium orthosilicate, sodium sesquisilicate, sodium metasilicate, etc.), lithium silicate, potassium silicate, and combinations thereof. Lithium silicate is preferred because it is highly versatile and can better protect the colored layer of the calcium-based inorganic substrate colored with the composition of the present invention and provide excellent water resistance.

[0084] The water-soluble alkali silicate compound forms a water-insoluble silicate compound by reacting with polyvalent metal ions present in the surroundings or by removing the alkali metal component (M) constituting the compound from the silica network of the compound. An aqueous solution of the water-soluble alkali silicate compound is generally called water glass. In the present invention, the water-soluble alkali silicate compound can be used alone or in combination of multiple types in the protective coating liquid.

[0085] The content of the acrylic resin, epoxy resin, urethane resin, resin having a silanol group or a group convertible to a silanol group, and / or water-soluble alkali silicate compound contained in the protective coating liquid is not particularly limited, and an appropriate content can be selected by those skilled in the art.

[0086] Alternatively, instead of applying the above protective coating liquid or after applying the above protective coating liquid, a solution containing a water repellent may be applied to the impregnated surface of the coloring composition or the surface to which the protective coating liquid is applied. By applying such a water repellent, water resistance can be provided to the impregnated surface or the surface to which the protective coating liquid is applied.

[0087] For the application of the above protective coating liquid and the solution containing the water repellent, coating means well-known in the art such as a brush, a roll coater, spraying, etc. are also employed.

[0088] In this way, the surface of the calcium-based inorganic substrate can be colored.

[0089] The calcium-based inorganic substrate (colored substrate) colored by the method of the present invention can be impregnated with the dye contained in the composition for coloring the calcium-based inorganic substrate from its surface to a predetermined depth (hereinafter, also referred to as "impregnation depth"). The impregnation depth is not particularly limited, and examples thereof include a depth of up to 1 mm from the surface and a depth of up to 2 mm from the surface. Therefore, even if the obtained colored substrate is worn to near the impregnation depth, the colored state of its surface is hardly impaired, and the colored state can be maintained for a long time.

Examples

[0090] Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples.

[0091] 1. Preparation of Coloring Composition and Evaluation of Light Resistance (Example 1: Preparation and Evaluation of Coloring Composition (E1)) 2.5 parts by mass of a blue reactive dye (Sumifix Supra Blue BRF manufactured by Iwase Shoten Co., Ltd.), 52.5 parts by mass of ion-exchanged water, 40 parts by mass of isopropyl alcohol, 1 part by mass of a surfactant (nonionic surfactant; SN Wet 366 manufactured by Sannopco Ltd.), 0.5 part by mass of a blue pigment (LBS manufactured by Lancex Co., Ltd.; average particle diameter 0.3 μm), 2.5 parts by mass of a polymer acrylic emulsion (Acrylic Emulsion GD89 manufactured by Henkel Japan Co., Ltd.) (the solid content of the emulsion is about 1 part by mass), and 1 part by mass of an ultraviolet absorber (Antifade MC-500 manufactured by Meisei Chemical Industry Co., Ltd.) were mixed to obtain a coloring composition (hereinafter, sometimes simply referred to as "composition") (E1) (total amount 100 parts by mass).

[0092] This composition (E1) was applied to a mortar flat plate (manufactured by Kyoei Concrete Industry Co., Ltd.; size 60 mm × 60 mm × 10 mm) at an application amount of 150 g / m 2It was applied by brush painting three times so as to obtain the desired result, and then placed indoors at 25°C for 2 hours for curing. During this curing process, it was confirmed that the odor of isopropyl alcohol completely disappeared. As a result, colored mortar (SE1) was obtained.

[0093] For the obtained colored mortar (SE1), a lightfastness test (blue scale level 3 irradiation; exposure time approximately 6 hours) was conducted in accordance with JIS L 0842 and judged on a gray scale. The results are shown in Table 1.

[0094] (Example 2: Preparation and evaluation of coloring composition (E2)) A coloring composition (E2) (total amount 100 parts by mass) was obtained in the same manner as in Example 1, except that the content of the blue pigment was changed to 1.0 part by mass and the content of ion-exchanged water was changed to 52.0 parts by mass. A colored mortar (SE2) was prepared in the same manner as in Example 1, except that this composition (E2) was used, and the same lightfastness test as in Example 1 was conducted on the obtained colored mortar (SE2). The results are shown in Table 1.

[0095] (Comparative Example 1: Preparation and evaluation of coloring composition (C1)) A coloring composition (C1) was obtained in the same manner as in Example 1, except that no blue pigment was added (i.e., the content was 0 part by mass) and the content of ion-exchanged water was changed to 53.0 parts by mass. A colored mortar (SC1) was prepared in the same manner as in Example 1, except that this composition (C1) was used, and the same lightfastness test as in Example 1 was conducted on the obtained colored mortar (SC1). The results are shown in Table 1.

[0096]

Table 1

[0097] As shown in Table 1, the colored substrates (SE1) and (SE2) obtained in Examples 1 and 2 had increased numerical values in the grayscale determination results and improved light resistance compared to the colored substrate (SC1) of Comparative Example 1. From this, it can be seen that the compositions (E1) and (E2) obtained in Examples 1 and 2, compared to the composition (C1) of Comparative Example 1, contained a predetermined amount of pigment in the composition, thereby improving the light resistance of the colored substrate obtained by applying the composition.

[0098] 2. Preparation and Evaluation of Inkjet Ink (Example 3: Preparation and Evaluation of Coloring Composition (E3)) 2.5 parts by mass of a blue acid dye (Suminol Fast Blue PR manufactured by Iwase Shoten Co., Ltd.), 52.5 parts by mass of ion-exchanged water, 40 parts by mass of isopropyl alcohol, 1.0 part by mass of a surfactant (nonionic surfactant; SN Wet 366 manufactured by Sannopco Ltd.), 0.5 part by mass of a blue pigment (LBS manufactured by Ranksess Co., Ltd.; average particle diameter 0.3 μm), 2.5 parts by mass of a polymer acrylic emulsion (Acrylic Emulsion GD89 manufactured by Henkel Japan Co., Ltd.), and 1.0 part by mass of an ultraviolet absorber (Antifade MC-500 manufactured by Meisei Chemical Industry Co., Ltd.) were mixed to obtain a coloring composition (E3) (total amount 100 parts by mass).

[0099] This composition (E3) was applied to a mortar flat plate (manufactured by Kyoei Concrete Industry Co., Ltd.; size 60 mm × 60 mm × 10 mm) by brushing back and forth 3 times so that the coating amount was 150 g / m 2 and cured by placing it indoors at 25°C for 2 hours. It was confirmed that the odor of isopropyl alcohol completely disappeared during this curing. Thereby, a colored mortar (SE3) was obtained.

[0100] The obtained colored mortar (SE3) was cut along the thickness direction, the depth to which the acid dye constituting the composition (E3) was impregnated from the surface of the colored mortar was measured with a caliper, and the state in which the acid dye constituting the composition (E3) was impregnated in this cross-section was photographed. The results are shown in Table 2 and Figure 1.

[0101] (Example 4: Preparation and Evaluation of Coloring Composition (E4)) A coloring composition (E4) (total amount: 100 parts by mass) was obtained in the same manner as in Example 3, except that no surfactant was added (i.e., the content was 0 part by mass) and the content of ion-exchanged water was changed to 53.5 parts by mass. A colored mortar (SE4) was prepared and cut in the same manner as in Example 3, except that the composition (E4) was used. The depth of impregnation of the acid dye constituting the composition (E4) from the surface of the colored mortar was measured with a caliper, and the state of impregnation of the acid dye constituting the composition (E4) in this cross-section was photographed. The results are shown in Table 2 and Figure 2.

[0102] (Comparative Example 2: Preparation and Evaluation of Coloring Composition (C2)) A coloring composition (C2) (total amount: 100 parts by mass) was obtained in the same manner as in Example 3, except that no surfactant was added (i.e., the content was 0 part by mass), the content of isopropyl alcohol was changed to 20 parts by mass, and the content of ion-exchanged water was changed to 73.5 parts by mass. A colored mortar (SC2) was prepared and cut in the same manner as in Example 3, except that the composition (C2) was used. The depth of impregnation of the acid dye constituting the composition (C2) from the surface of the colored mortar was measured with a caliper, and the state of impregnation of the acid dye constituting the composition (C2) in this cross-section was photographed. The results are shown in Table 2 and Figure 3.

[0103] (Comparative Example 3: Preparation and Evaluation of Coloring Composition (C3)) A coloring composition (C3) (total amount: 100 parts by mass) was obtained in the same manner as in Example 3, except that neither a surfactant nor isopropyl alcohol was added (i.e., the content of both was 0 part by mass) and the content of ion-exchanged water was changed to 93.5 parts by mass. A colored mortar (SC3) was prepared and cut in the same manner as in Example 3, except that the composition (C3) was used. The depth of impregnation of the acid dye constituting the composition (C3) from the surface of the colored mortar was measured with a caliper, and the state of impregnation of the acid dye constituting the composition (C3) in this cross-section was photographed. The results are shown in Table 2 and Figure 4.

[0104] (Comparative Example 4: Preparation and Evaluation of Coloring Composition (C4)) A coloring composition (C4) (total amount 100 parts by mass) was obtained in the same manner as in Example 3, except that isopropyl alcohol was not added (i.e., the content was 0 part by mass), 1.0 part by mass of a surfactant (nonionic surfactant; SN Wet 366 manufactured by Sannopco Ltd.) was added, and the content of ion-exchanged water was changed to 92.5 parts by mass. A colored mortar (SC4) was prepared and cut in the same manner as in Example 3 except that this composition (C4) was used. The depth to which the acid dye constituting the composition (C4) was impregnated from the surface of the colored mortar was measured with a caliper, and the state in which the acid dye constituting the composition (C4) was impregnated in this cross-section was photographed. The results are shown in Table 2 and Figure 5.

[0105]

Table 2

[0106] As shown in Table 2 and Figures 1 to 5, the colored substrates (SE3) and (SE4) obtained in Examples 3 and 4 had a greater depth of the impregnated dye from the surface of the colored substrate compared to the colored substrates (SC2) to (SC4) of Comparative Examples 2 to 4. In particular, it can be seen that the composition (E3) obtained in Example 3 further improved the impregnation property of the dye, which is a constituent component, by the inclusion of the surfactant.

[0107] 3. Preparation of Coloring Composition and Evaluation of Drying Performance (Example 5: Preparation of Coloring Composition (E5)) A coloring composition (E5) (total amount 100 parts by mass) was obtained in the same manner as in Example 3, except that the content of isopropyl alcohol was changed to 10 parts by mass and the content of ion-exchanged water was changed to 82.5 parts by mass.

[0108] (Drying Performance of Coloring Composition) As test pieces, a flexible board (flexible board FB manufactured by Nippon Test Panel Co., Ltd.) and a glass plate were prepared. Next, 1 g each of the coloring compositions (E3) and (E5) obtained in Examples 3 and 5 and the coloring composition (C4) obtained in Comparative Example 4 were dropped onto these test pieces. After dropping, the flexible board was thinly spread circularly to a diameter of 55 mm, and the glass plate was thinly spread circularly to a diameter of 40 mm, and the time until each dropped coloring composition dried on the test piece was measured. The results are shown in Table 3.

[0109]

Table 3

[0110] As shown in Table 3, since both of the coloring compositions (E3) and (E5) obtained in Examples 3 and 5 contain isopropyl alcohol, compared with the coloring composition (C4) of Comparative Example 4 that does not contain isopropyl alcohol, the drying time on substrates such as flexible boards and glass flat plates could be shortened. Also, it was confirmed that the odor of isopropyl alcohol that the coloring compositions (E3) and (E5) obtained in Examples 3 and 5 had immediately after coloring completely disappeared after drying. From this, it can be seen that the coloring compositions (E3) and (E5) obtained in Examples 3 and 5 had excellent workability in that they could be dried in a shorter period of time.

[0111] 4. Preparation of Coloring Composition and Evaluation of Texture of Colored Mortar (Example 6: Preparation of Colored Mortar (SE6)) A coloring composition (E6) (total amount 100 parts by mass) was obtained in the same manner as in Example 1 except that the content of the blue pigment was changed to 3.0 parts by mass and the content of ion-exchanged water was changed to 50.0 parts by mass. This coloring composition (E6) was applied to a mortar flat plate (manufactured by Kyoei Concrete Industry Co., Ltd.; size 60 mm × 60 mm × 10 mm) at an application amount of 150 g / m 2It was applied by brush coating three times so as to obtain the desired result, and then left in the room at 25°C for 2 hours for curing. During this curing process, it was confirmed that the odor of isopropyl alcohol completely disappeared. As a result, colored mortar (SE6) was obtained.

[0112] (Example 7: Preparation of Colored Mortar (SE7)) A coloring composition (E7) (total amount 100 parts by mass) was obtained in the same manner as in Example 1, except that the content of the blue pigment was changed to 6.0 parts by mass and the content of ion-exchanged water was changed to 47.0 parts by mass. A colored mortar (SE7) was obtained in the same manner as in Example 6, except that this coloring composition (SE7) was used.

[0113] (Comparative Example 5: Preparation of Painted Mortar (SC5)) Instead of the coloring composition (E2) obtained in Example 2, an aqueous paint (Exterior Colors manufactured by Kains Co., Ltd.) commercially available as an outdoor paint for concrete etc. was used, and the application amount was 130 mL / m 2 A painted mortar (SC5) was obtained in the same manner as in Example 6, except that it was applied by brush coating three times so as to obtain the desired result.

[0114] (1) Specular Glossiness The specular glossiness of the flat surfaces of the colored mortars (SE2) obtained in Example 2 above, the colored mortar (SE6) obtained in Example 6, the colored mortar (SE7) obtained in Example 7, and the painted mortar (SC5) obtained in Comparative Example 5, as well as a mortar flat plate (manufactured by Kyoei Concrete Industry Co., Ltd.; size 60 mm × 60 mm × 10 mm) (Reference Example 1) to which no coloring composition or paint was applied, was measured at an incident angle of 60° in accordance with JIS K5600-4-7. The results are shown in Table 4.

[0115]

Table 4

[0116] As shown in Table 4, the painted mortar (SC5) obtained in Comparative Example 5 exhibited specular glossiness due to the paint film formed on the mortar flat plate, showing a significant difference compared to the specular glossiness of the unpainted mortar flat plate (Reference Example 1). In contrast, the colored mortars (SE2), (SE6), and (SE7) obtained in Examples 2, 6, and 7 all had the same specular glossiness as the unpainted mortar flat plate (Reference Example 1). Although the mortar flat plate was colored as required, the glossiness of its surface was not significantly different from that of the unpainted mortar flat plate (Reference Example 1).

[0117] (2) Texture of concrete (sensory evaluation) Regarding the colored mortar (SE2) obtained in Example 2 above, the colored mortar (SE6) obtained in Example 6, the colored mortar (SE7) obtained in Example 7, the painted mortar (SC5) obtained in Comparative Example 5, and the mortar flat plate (Reference Example 1) to which no coloring composition or paint was applied, eight experts evaluated their appearance and touch according to the following criteria.

[0118] (2-1) Appearance 5 points: Except for the presence or absence of coloring, it was not inferior to the untreated mortar flat plate (Reference Example 1) at all. 4 points: Except for the presence or absence of coloring, when observing close to the surface (distance: about 30 cm) compared to the untreated mortar flat plate (Reference Example 1), it was confirmed that there was a slight difference. 3 points: Except for the presence or absence of coloring, when observing from a place about 1 m away compared to the untreated mortar flat plate (Reference Example 1), it was confirmed that there was a slight difference. 2 points: Except for the presence or absence of coloring, when observing from a place about 1 m away compared to the untreated mortar plate (Reference Example 1), it was confirmed that the surface state was clearly different. 1 point: Except for the presence or absence of coloring, when compared to the untreated mortar flat plate (Reference Example 1), it was confirmed that a paint film was clearly formed on it and it had a different texture.

[0119] (2-2) Touch When touching the surface at 5 points with a finger, it was no inferior to the untreated mortar plate (Reference Example 1). When touching the surface at 4 points with a finger, it was confirmed that there was a slight difference compared to the untreated mortar flat plate (Reference Example 1). When touching the surface at 3 points with a finger, there were differences compared to the untreated mortar flat plate (Reference Example 1), but all were recognized as being inherent to concrete. When touching the surface at 2 points with a finger, there were differences compared to the untreated mortar flat plate (Reference Example 1), and it was recognized that much of the texture of the concrete was lost. When touching the surface at 1 point with a finger, it was recognized that a clearly different coating film was formed compared to the untreated mortar flat plate (Reference Example 1), and almost all of the texture of the concrete was lost.

[0120] The results are shown in Tables 5 and 6.

[0121]

Table 5

[0122]

Table 6

[0123] As shown in Tables 5 and 6, the painted mortar (SC5) obtained in Comparative Example 5 had an appearance and touch that were clearly different from those of the uncolored mortar flat plate (Reference Example 1) due to the coating film formed on the mortar flat plate. In contrast, the colored mortars (SE2), (SE6), and (SE7) obtained in Examples 2, 6, and 7 all had the same appearance and touch as the uncolored mortar flat plate (Reference Example 1), and this tendency became more apparent as the content of the pigment contained in the colored composition decreased.

Industrial Applicability

[0124] The composition of the present invention can be used for coloring various calcium-based inorganic substrates, and is useful in technical fields such as the construction field, for example.

Claims

1. A composition for coloring a calcium-based inorganic substrate, containing a dye, water, alcohol, and a pigment, wherein the content of the pigment is 0.2 parts by mass to 6 parts by mass with respect to 100 parts by mass of the total mass of the composition.

2. The composition for coloring a calcium-based inorganic substrate according to Claim 1, further containing a surfactant.

3. The composition for coloring a calcium-based inorganic substrate according to Claim 1, wherein the dye is at least one selected from the group consisting of a direct dye, a reactive dye, an acid dye, an acid mordant dye, a metal complex acid dye, and a basic dye.

4. The composition for coloring a calcium-based inorganic substrate according to Claim 1, wherein the alcohol is a primary alcohol having 1 to 3 carbon atoms.

5. The composition for coloring a calcium-based inorganic substrate according to Claim 1, wherein the surfactant is a nonionic surfactant.

6. The composition for coloring a calcium-based inorganic substrate according to Claim 1, further containing an aqueous polymer emulsion.

7. A method for coloring a calcium-based inorganic substrate, comprising the step of impregnating the surface of the calcium-based inorganic substrate with the coloring composition according to any one of Claims 1 to 6 to form an impregnated surface. The method comprising this step.

8. The coloring method according to Claim 7, further comprising the step of applying a protective coating liquid containing at least one compound selected from the group consisting of an acrylic resin, an epoxy resin, a urethane resin, a resin having a silanol group or a group convertible to a silanol group, and a water-soluble alkali silicate compound to the impregnated surface.

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