Composition for coloring calcium-based inorganic substrate, and method for coloring calcium-based inorganic substrate using same

Abstract

This composition for coloring a calcium-based inorganic substrate contains a dye, water, an alcohol and a pigment. Here, the content of the pigment is 0.2 parts by mass to 6 parts by mass relative to a total of 100 parts by mass of the composition. The present invention is capable of providing a colored inorganic substrate having excellent lightfastness. In addition, because this coloration is achieved by impregnation in an inorganic substrate, a colored state is maintained even if the substrate surface is abraded.

Description

Composition for coloring calcium-based inorganic substrates and method for coloring calcium-based inorganic substrates using the same

[0001] The present invention relates to a composition for coloring calcium-based inorganic substrates and a method for coloring calcium-based inorganic substrates using the same, and more particularly to a composition and method for coloring calcium-based inorganic substrates by impregnation.

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

[0003] However, these pigments generally have particle sizes larger than the pores of the calcium-based inorganic substrate, and therefore tend to remain on the surface of the calcium-based inorganic material, and the colored layer is easily lost due to peeling or friction, resulting in the substrate being exposed relatively easily.

[0004] Furthermore, in recent years, due to improvements in the performance of admixtures contained in ready-mixed concrete and improvements in concrete pouring and curing techniques, the pores and voids formed on the surface of calcium-based inorganic substrates (e.g., concrete substrates) tend to become smaller and fewer. Although there is a demand for improved coloring performance for such pores and voids, the reality is that no satisfactory solution has yet been achieved.

[0005] On the other hand, dye-based approaches have also been considered for coloring calcium-based inorganic substrates. For example, Patent Document 1 proposes a technique for coloring the surface of an inorganic substrate such as concrete by using a coating liquid containing a disperse dye or the like to impregnate the inorganic substrate to a surface layer of about 1 mm. Patent Document 2 proposes a technique for 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 strengthening resin.

[0006] However, it has been pointed out that the dyes used in the techniques described in Patent Documents 1 and 2 are prone to fading due to ultraviolet light, resulting in poor lightfastness of the resulting colored substrate. It has also been pointed out that the dye is not sufficiently impregnated into the inorganic substrate, so the vivid color tends to be lost due to wear of the colored substrate.

[0007] Recently, there has been a demand for interior designs that combine the texture of concrete with a predetermined coloring in stores or facilities such as retail stores, shopping malls, and designer apartments.

[0008] However, it is extremely difficult to achieve these goals with paint. This is because, even if the desired color can be achieved with the resulting paint film, the texture is easily lost when the paint film covers the concrete surface. Dramatic improvements have been made to paints that give the texture of concrete, and although these have been commercialized, this texture is only an imitation, as it is due to the paint film.

[0009] Japanese Patent Application Laid-Open No. 2002-187787 Japanese Patent Application Laid-Open No. 2002-282781

[0010] The present invention is intended to solve the above problems, and its object is to provide a composition for coloring calcium-based inorganic substrates that can vividly color calcium-based inorganic substrates and impart excellent light resistance, and a method for coloring calcium-based inorganic substrates using the same.

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

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

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

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

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

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

[0017] The present invention also provides a method for coloring a calcium-based inorganic substrate, which comprises the step of impregnating the surface of the calcium-based inorganic substrate with the coloring composition to form an impregnated surface.

[0018] In one embodiment, the coloring method of the present invention further includes a step of applying to the impregnated surface 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.

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

[0020] Photographs showing an overall cross-sectional view and a partially enlarged cross-sectional view of the colored mortar (SE3) produced in Example 3. Photographs showing an overall cross-sectional view and a partially enlarged cross-sectional view of the colored mortar (SE4) produced in Example 4. Photographs showing an overall cross-sectional view and a partially enlarged cross-sectional view of the colored mortar (SC2) produced in Comparative Example 2. Photographs showing an overall cross-sectional view and a partially enlarged cross-sectional view of the colored mortar (SC3) produced in Comparative Example 3. Photographs showing an overall cross-sectional view and a partially enlarged cross-sectional view of the colored mortar (SC4) produced in Comparative Example 4.

[0021] The present invention will be described in detail below.

[0022] (Composition for Coloring Calcium-Based Inorganic Substrates) The composition for coloring calcium-based inorganic substrates of the present invention is used to color calcium-based inorganic substrates.

[0023] The calcium-based inorganic substrate is a substrate made of an inorganic material containing calcium as a constituent component, and refers to, for example, structures that make up indoor and outdoor buildings or structures (e.g., walls, floors, walkways, roads, pillars, and fences), monuments that can be placed outdoors or indoors (e.g., memorials; memorial towers; and statues of people, gods, Buddhas, animals, etc.), and their constituent parts (e.g., flat parts, curved parts, prisms, cylinders, spheres, ellipsoids, blocks, and flat plates); and combinations thereof.

[0024] The constituent material of the calcium-based inorganic substrate is not particularly limited, but examples thereof include concrete, cement, gypsum, and stone (for example, containing calcium components), as well as combinations thereof.

[0025] The composition for coloring calcium-based inorganic substrates 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, "organic solvent" preferably includes an organic solvent miscible with water. Examples of dyes include direct dyes, reactive dyes, acid dyes, acid mordant dyes, metal complex acid dyes, basic dyes, vat dyes, sulfur dyes, and combinations thereof.

[0027] Examples of direct dyes include those listed in the Color Index (CI) as 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 Red 84:1, Direct Red 85:1, Direct Red 86:1, Direct Red 87:1, Direct Red 88:1, Direct Red 89:1, Direct Red 90:1, Direct Red 91:1, Direct Red 92:1, Direct Red 93:1, Direct Red 94:1, Direct Red 95:1, Direct Red 96:1, Direct Red 97:1, Direct Red 98:1, Direct Red 9 ... 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, by Color Index (CI), Reactive Yellow 145, Reactive Red 195, Reactive Blue 221, Procion, Mikacion, Cibacron, Drimaren, Reacton, and Remazol; and combinations thereof.

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

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

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

[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, and combinations thereof.

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

[0035] In the present invention, direct dyes, reactive dyes, acid dyes, acid mordant dyes, metal complex acid dyes, basic dyes, and combinations thereof are preferred because, when combined with the components described below, they can provide a colored substrate that is excellent in impregnation into the substrate and in light fastness and water fastness.

[0036] The content of the dye in the composition of the present invention is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 8 parts by weight, and even more preferably 0.3 to 6 parts by weight, per 100 parts by weight of the total weight of the composition. If the content of the dye is less than 0.1 part by weight, the color obtained by coloring may be weak and may lack practicality. If the content of the dye is more than 10 parts by weight, the color may become dark (close to black) and difficult to distinguish, resulting in a lack of color, or, although the color may be distinguishable, it may not become darker and only increase the production cost.

[0037] The water contained in the composition of the present invention serves to dissolve the dye uniformly 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 water in the composition of the present invention is preferably 20 to 90 parts by mass, more preferably 30 to 70 parts by mass, per 100 parts by mass of the total mass of the composition. If the water content is less than 20 parts by mass, the alcohol content will be relatively high, which may increase the volatility of the resulting composition as a whole, thereby impairing safety and workability. If the water content exceeds 90 parts by mass, the alcohol content will be relatively low, which may decrease the impregnation ability of the resulting composition into calcium-based inorganic substrates.

[0039] The alcohol constituting the composition of the present invention is miscible with the water and serves to appropriately dissolve the coloring components (molecules) constituting the dye and allow them to penetrate deep into the fine pores on the surface of the calcium-based inorganic substrate. In the present invention, the alcohol is preferably a primary alcohol, a secondary alcohol, or a tertiary alcohol 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] The alcohol is preferably a primary alcohol having 1 to 3 carbon atoms because it has excellent miscibility with water and can more effectively impregnate the calcium-based inorganic substrate with the dye. For example, isopropyl alcohol is more preferred because its inherent odor can be utilized to determine the dry state of the composition applied to the calcium-based inorganic substrate through olfaction.

[0042] Alternatively, among the primary alcohols having 1 to 3 carbon atoms, for example, methanol has a boiling point of 65°C and a vapor pressure of 12.9 kPa (20°C), making it more volatile than ethanol or isopropyl alcohol. Therefore, using methanol as the alcohol in the present invention can produce a faster-drying coloring composition. However, this quick-drying property forces the worker to complete the coloring work in an extremely short time. Therefore, the present invention provides a coloring composition with a somewhat milder quick-drying property than methanol, and therefore, the alcohol is preferably isopropyl alcohol, ethanol, or a combination thereof.

[0043] The content of 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, per 100 parts by mass of the total mass of the composition. If the content of alcohol is less than 10 parts by mass, the effect of promoting deep impregnation into fine pores on the surface of the calcium-based inorganic substrate may be reduced. If the content of alcohol exceeds 80 parts by mass, the volatility of the entire obtained composition may increase, drying may become significantly faster, and workability may be reduced.

[0044] The pigment constituting the composition of the present invention plays a role in complementing the coloring of the calcium-based inorganic substrate by the dye.

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

[0046] Examples of inorganic pigments include titanium oxide, iron oxide, cobalt oxide, chromium oxide, carbon black, and composite oxides thereof, as well as combinations thereof.

[0047] Examples of organic pigments include copper phthalocyanine (a blue pigment), quinophthalone pigments (yellow pigments), and azo pigments (red pigments), as well as combinations thereof.

[0048] The size of the pigment is not particularly limited, but the average particle diameter is preferably 0.1 μm to 2 μm, more preferably 0.2 μm to 1 μm, to increase the filling efficiency into pores (e.g., diameters of 0.05 μm to 5 μm) formed in the calcium-based inorganic substrate and enhance the light-shielding effect of the dye impregnated therein from external light. If the average particle diameter of the pigment is less than 0.1 μm, it may be prone to aggregation, making it difficult to uniformly disperse in the presence of water, alcohol, and surfactant. Furthermore, producing a pigment with such a fine average particle diameter requires advanced technology, which may reduce productivity. If the average particle diameter of the pigment exceeds 2 μm, it may not fill the pores formed in the calcium-based inorganic substrate, making it difficult to complement the coloring by the dye.

[0049] The content of the pigment in the composition of the present invention is 0.2 to 6 parts by mass, preferably 0.3 to 5 parts by mass, and more preferably 0.5 to 4 parts by mass, relative to 100 parts by mass of the total mass of the composition. If the content of the pigment is less than 0.2 parts by mass, the lightfastness of the resulting composition may be insufficient. If the content of the pigment is more than 6 parts by mass, the color of the dye, which is 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 reduces the interfacial tension of the coloring components (molecules) of the dye in the presence of the water and alcohol, thereby making them more compatible with the surface of the calcium-based inorganic substrate, and as a result, plays a role in enhancing impregnation.

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

[0053] The nonionic surfactant is not necessarily limited, but examples thereof include ester-type nonionic surfactants, ether-type nonionic surfactants, ester-ether-type nonionic surfactants, and combinations thereof. Because of their low foaming properties, the nonionic surfactant is preferably an ether-type nonionic surfactant.

[0054] The anionic surfactant is not necessarily limited, but may be, for example, a carboxylate anionic surfactant, a sulfonate anionic surfactant, a sulfate anionic surfactant, or a combination thereof. Because of its good solubility in water, the anionic surfactant is preferably a sulfonate anionic surfactant.

[0055] The cationic surfactant is not necessarily limited to, but includes, for example, an amine salt type cationic surfactant, a quaternary ammonium salt type cationic surfactant, and a combination thereof.

[0056] The amphoteric surfactant is not necessarily limited, but examples thereof include carboxylate-type amphoteric surfactants.

[0057] In the present invention, the surfactant is preferably a nonionic surfactant, since it is not ionized when dissolved in water and there is no need to consider the effect on the charging properties of the calcium-based inorganic substrate.

[0058] The content of the surfactant in the composition of the present invention is preferably 0.1 to 5 parts by mass, more preferably 0.3 to 2 parts by mass, per 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 ability of the resulting composition into calcium-based inorganic substrates may be reduced. If the content of the surfactant is more than 5 parts by mass, the resulting composition may be prone to foaming, reducing workability and making it difficult to achieve uniform coloring.

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

[0060] Aqueous polymer emulsions are water-based emulsions containing specific polymers used in paints, adhesives, pressure-sensitive adhesives, housing construction materials, etc., and are used to impart fixability to pigments on calcium-based inorganic substrates. The aqueous polymer emulsions also play a role in imparting fixability to dyes, which are components of the resulting compositions, when applied to calcium-based inorganic substrates.

[0061] Examples of aqueous polymer emulsions 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. Because many of the above general-purpose products are available and the viscosity can be easily adjusted by adding water and / or a thickener, acrylic emulsions, acrylic-silicone emulsions, styrene-acrylic emulsions, and combinations thereof are preferred, with acrylic emulsions being more preferred.

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

[0063] The acrylic monomer constituting the resin component is not particularly limited, but examples thereof include 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.

[0064] In the present invention, the aqueous polymer emulsion itself is preferably milky white or colorless in order to avoid impairing the color development by the dye. 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 this range, it can be handled safely without corroding the calcium-based inorganic substrate to which it is applied.

[0066] The solid content of the aqueous polymer emulsion contained in the composition of the present invention is 0.5 to 10 parts by mass, preferably 1 to 5 parts by mass, per 100 parts by mass of the total mass of the composition. If the solid content of the aqueous polymer emulsion is less than 0.5 parts by mass, the fixation of the constituent pigments and dyes when applied to a calcium-based inorganic substrate may be insufficient, resulting in a tendency to discoloration. If the solid content of the aqueous polymer emulsion exceeds 10 parts by mass, the pores and voids of the calcium-based inorganic substrate may be blocked, thereby reducing the impregnation ability of the resulting composition.

[0067] The aqueous polymer emulsion preferably has a viscosity of 1000 mPa·sec or less.

[0068] The composition for coloring calcium-based inorganic substrates 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 they are versatile and have excellent absorption properties for near-ultraviolet rays (e.g., wavelengths of 340 nm to 360 nm).

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

[0071] The contents of the ultraviolet absorber and ultraviolet scattering agent in the present invention are not particularly limited, and an appropriate content can be selected by a person skilled in the art within a range that does not inhibit the effects of 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 antifoaming agents, preservatives, antibacterial agents, and combinations thereof. The content of other additives in the present invention is not particularly limited, and an appropriate content can be selected by a person skilled in the art as long as it does not inhibit the effects of 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 a calcium-based inorganic substrate is impregnated with the above-mentioned composition for coloring calcium-based inorganic substrates to form an impregnated surface.

[0075] To impregnate the surface of the calcium-based inorganic substrate with the composition for coloring a calcium-based inorganic substrate, coating means well known in the art, such as brush, roll coater, spray, etc., are employed.

[0076] The composition for coloring calcium-based inorganic substrates of the present invention allows the dye, which is a constituent, to dissolve more uniformly in the composition and lowers the interfacial tension, making it easier to blend with the surface of the calcium-based inorganic substrate, thereby increasing the impregnation ability of the composition into the calcium-based inorganic substrate and allowing the composition to penetrate deeper into the calcium-based inorganic substrate from the surface.

[0077] In the present invention, after the surface of the calcium-based inorganic substrate is impregnated with the 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 components may be used, and may be laminated in the form of two or more layers on the surface of the calcium-based inorganic substrate impregnated with the above composition.

[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] Resins having silanol groups or groups convertible to silanol groups are resins having silanol groups (including isolated silanol groups, vicinal silanol groups, and geminal silanol groups) or groups convertible to such silanol groups on the main chain and / or branched chains constituting thermoplastic resins such as acrylic resins and styrene-acrylic resins.

[0081] The term "group convertible to a silanol group" refers to a group in which the OH moiety constituting a silanol group is substituted with an alkoxy group, a halogen atom, etc. The group convertible to a silanol group can be converted to a silanol group via hydrolysis.

[0082] Resins having silanol groups or groups convertible to silanol groups are commercially available in the form of emulsions (e.g., aqueous emulsions) or in the form dissolved or dispersed in a predetermined solvent. In the present invention, resins having silanol groups or groups convertible to silanol groups can be used alone or in combination in the protective coating solution.

[0083] The water-soluble alkali silicate compound is represented by the general formula M ２ O.nSiO ２ (wherein M is an alkali metal and n is an integer of 2 to 4). Examples of water-soluble alkali silicate compounds include sodium silicate (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 a 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 surrounding polyvalent metal ions or by removing the alkali metal component (M) constituting the compound from the silica network of the compound. Aqueous solutions of water-soluble alkali silicate compounds are generally called water glass. In the present invention, the water-soluble alkali silicate compounds can be used alone or in combination 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 a person skilled in the art.

[0086] Alternatively, instead of or after applying the 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] The solution containing the protective coating liquid and the water repellent agent can also be applied by any coating means known in the art, such as by brush, roll coater, or spray.

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

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

[0090] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples.

[0091] 1. Preparation of Coloring Composition and Evaluation of Lightfastness (Example 1: Preparation and Evaluation of Coloring Composition (E1)) A coloring composition (hereinafter sometimes simply referred to as "composition") (E1) (total amount 100 parts by mass) was obtained by mixing 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 San Nopco Ltd.), 0.5 parts by mass of a blue pigment (LBS manufactured by Lanxess K.K.; average particle size 0.3 μm), 2.5 parts by mass of a polymer acrylic emulsion (acrylic emulsion GD89 manufactured by Henkel Japan Ltd.) (solid content of the emulsion was approximately 1 part by mass), and 1 part by mass of an ultraviolet absorber (Anti-Fade MC-500 manufactured by Meisei Chemical Industry Co., Ltd.).

[0092] This composition (E1) was applied to a mortar plate (manufactured by Kyoei Concrete Industry Co., Ltd.; size: 60 mm x 60 mm x 10 mm) in an amount of 150 g / m ２The mixture was applied with a brush three times so that the color was 100%. The mixture was then placed in a room at 25°C for 2 hours to cure. It was confirmed that the odor of isopropyl alcohol had completely disappeared during this curing. This gave a colored mortar (SE1).

[0093] The obtained colored mortar (SE1) was subjected to a light fastness test (blue scale grade 3 irradiation; exposure time: approximately 6 hours) in accordance with JIS L 0842, and evaluated using 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 obtained colored mortar (SE2) was subjected to a light fastness test in the same manner as in Example 1. 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 parts 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 obtained colored mortar (SC1) was subjected to a light fastness test in the same manner as in Example 1. The results are shown in Table 1.

[0096]

[0097] As shown in Table 1, the colored substrates (SE1) and (SE2) obtained in Examples 1 and 2 had increased grayscale evaluation results and improved lightfastness compared to the colored substrate (SC1) of Comparative Example 1. This shows that the compositions (E1) and (E2) obtained in Examples 1 and 2 contained a predetermined amount of pigment, which improved the lightfastness of the colored substrate obtained by applying the composition, compared to the composition (C1) of Comparative Example 1.

[0098] 2. Preparation of coloring composition and evaluation of impregnation property (Example 3: Preparation and evaluation of coloring composition (E3)) A blue acid dye (Suminol Fast Blue PR manufactured by Iwase Shoten Co., Ltd.) 2.5 parts by mass, ion-exchanged water 52.5 parts by mass, isopropyl alcohol 40 parts by mass, surfactant (nonionic surfactant; SN Wet 366 manufactured by San Nopco Ltd.) 1.0 part by mass, blue pigment (LBS manufactured by Lanxess K.K.; average particle size 0.3 μm) 0.5 parts by mass, polymer acrylic emulsion (acrylic emulsion GD89 manufactured by Henkel Japan Ltd.) 2.5 parts by mass, and ultraviolet absorber (Anti-fade MC-500 manufactured by Meisei Chemical Industry Co., Ltd.) 1.0 part by mass were mixed to obtain a coloring composition (E3) (total amount 100 parts by mass).

[0099] This composition (E3) was applied to a mortar plate (manufactured by Kyoei Concrete Industry Co., Ltd.; size: 60 mm x 60 mm x 10 mm) in an amount of 150 g / m ２ The mixture was applied with a brush three times so that the color was 100%. The mixture was then placed in a room at 25°C for 2 hours to cure. It was confirmed that the odor of isopropyl alcohol had completely disappeared during this curing. This gave a colored mortar (SE3).

[0100] The resulting colored mortar (SE3) was cut along the thickness direction, and the depth of the impregnation of the acid dye constituting the composition (E3) from the surface of the colored mortar was measured with a vernier caliper, and the state of the impregnation of the acid dye constituting the composition (E3) at 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 parts 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 this 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 vernier caliper, and the state of impregnation of the acid dye constituting the composition (E4) at this cross section was photographed. The results are shown in Table 2 and FIG. 2.

[0102] (Comparative Example 2: Preparation and Evaluation of Coloring Composition (C2)) No surfactant was added (i.e., content 0 parts 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 coloring composition (C2) was obtained in the same manner as in Example 3 (total amount 100 parts by mass). Except for using this composition (C2), a colored mortar (SC2) was prepared and cut in the same manner as in Example 3, and the depth of impregnation of the acid dye constituting the composition (C2) from the surface of the colored mortar was measured with a vernier caliper, and the state of impregnation of the acid dye constituting the composition (C2) at this cross section was photographed. The results are shown in Table 2 and FIG. 3.

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

[0104] (Comparative Example 4: Preparation and Evaluation of Coloring Composition (C4)) No isopropyl alcohol was added (i.e., content 0 parts by mass), 1.0 parts by mass of a surfactant (nonionic surfactant; SN Wet 366 manufactured by San Nopco Co., Ltd.) was added, and the content of ion-exchanged water was changed to 92.5 parts by mass. A coloring composition (C4) was obtained in the same manner as in Example 3 (total amount 100 parts by mass). Except for using this composition (C4), a colored mortar (SC4) was prepared and cut in the same manner as in Example 3, and the depth of impregnation of the acid dye constituting the composition (C4) from the surface of the colored mortar was measured with a vernier caliper, and the state of impregnation of the acid dye constituting the composition (C4) at this cross section was photographed. The results are shown in Table 2 and FIG. 5.

[0105]

[0106] As shown in Table 2 and Figures 1 to 5, the dye impregnated into the colored substrates (SE3) and (SE4) obtained in Examples 3 and 4 was greater in depth from the surface of the colored substrate than the colored substrates (SC2) to (SC4) of Comparative Examples 2 to 4. In particular, it can be seen that the impregnation of the dye, which is a constituent component, is further improved in the composition (E3) obtained in Example 3 by containing a 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 colored composition) A flexible board (Flexible Board FB manufactured by Nippon Test Panel Co., Ltd.) and a glass plate were prepared as test pieces. Next, 1 g of each of the colored compositions (E3) and (E5) obtained in Examples 3 and 5, and the colored composition (C4) obtained in Comparative Example 4, was dropped onto the test piece. After dropping, the flexible board was pressed into a thin circular shape to a diameter of 55 mm, and the glass plate was pressed into a thin circular shape to a diameter of 40 mm, and the time until each dropped colored composition dried on the test piece was measured. The results are shown in Table 3.

[0109]

[0110] As shown in Table 3, the colored compositions (E3) and (E5) obtained in Examples 3 and 5 both contain isopropyl alcohol, and therefore, compared to the colored composition (C4) of Comparative Example 4, which does not contain isopropyl alcohol, it was possible to shorten the drying time on substrates such as flexible boards and glass flat plates. It was also confirmed that the odor of isopropyl alcohol that was present in the colored compositions (E3) and (E5) obtained in Examples 3 and 5 immediately after coloring completely disappeared after drying. From this, it can be seen that the colored 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 plate (manufactured by Kyoei Concrete Industry Co., Ltd.; size 60 mm × 60 mm × 10 mm) in an amount of 150 g / m ２ The mixture was applied with a brush three times so that the color was 100%. The mixture was then placed in a room at 25°C for 2 hours to cure. It was confirmed that the odor of isopropyl alcohol had completely disappeared during this curing. This gave a colored mortar (SE6).

[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 Paint Mortar (SC5)) Instead of the coloring composition (E2) obtained in Example 2, a commercially available water-based paint (Exterior Colors, manufactured by Cainz Co., Ltd.) was used as an outdoor paint for concrete, etc., and the applied amount was 130 mL / m ２ A coating mortar (SC5) was obtained in the same manner as in Example 6, except that the coating was carried out by brushing three times in a row so that the coating amount was 100%.

[0114] (1) Specular Gloss The specular gloss of the colored mortar (SE2) obtained in Example 2, 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 plate (manufactured by Kyoei Concrete Industry Co., Ltd.; size 60 mm × 60 mm × 10 mm) (Reference Example 1) that was not coated with any coloring composition or paint, was measured at an incident angle of 60 ° in accordance with JIS K5600-4-7. The results are shown in Table 4.

[0115]

[0116] As shown in Table 4, the coated mortar (SC5) obtained in Comparative Example 5 exhibited a specular gloss due to the coating film formed on the mortar slab, which was significantly different from the specular gloss of the uncolored mortar slab (Reference Example 1). In contrast, the colored mortars (SE2), (SE6), and (SE7) obtained in Examples 2, 6, and 7 all had a specular gloss equivalent to that of the uncolored mortar slab (Reference Example 1). Although the mortar slabs were colored to a certain extent, the surface gloss was not significantly different from that of the uncolored mortar slab (Reference Example 1).

[0117] (2) Texture of Concrete (Sensory Evaluation) Eight experts evaluated the appearance and texture of the colored mortar (SE2) obtained in Example 2, 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 a mortar slab (Reference Example 1) that was not coated with any coloring composition or paint, according to the following criteria.

[0118] (2-1) Appearance 5 points: Except for the presence or absence of coloring, it was comparable to the untreated mortar slab (Reference Example 1). 4 points: Except for the presence or absence of coloring, slight differences were observed when observing the untreated mortar slab (Reference Example 1) by bringing one's face close to the surface (distance: approximately 30 cm). 3 points: In addition to the presence or absence of coloring, slight differences were observed when observing the untreated mortar slab (Reference Example 1) from a distance of approximately 1 m. 2 points: In addition to the presence or absence of coloring, it was confirmed that the surface condition was clearly different from the untreated mortar slab (Reference Example 1) when observed from a distance of approximately 1 m. 1 point: In addition to the presence or absence of coloring, it was confirmed that a coating film had clearly formed on it, giving it a different texture compared to the untreated mortar slab (Reference Example 1).

[0119] (2-2) Touch 5 points: When the surface was touched with a finger, it was comparable to the untreated mortar board (Reference Example 1). 4 points: When the surface was touched with a finger, it was confirmed that there was a slight difference compared to the untreated mortar board (Reference Example 1). 3 points: When the surface was touched with a finger, there was a difference compared to the untreated mortar board (Reference Example 1), but it was possible to recognize that both were inherent to concrete. 2 points: When the surface was touched with a finger, there was a difference compared to the untreated mortar board (Reference Example 1), and it was possible to recognize that most of the texture of concrete had been lost. 1 point: When the surface was touched with a finger, it was confirmed that a different coating film had clearly formed compared to the untreated mortar board (Reference Example 1), and it was possible to recognize that the texture of concrete had almost completely been lost.

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

[0121]

[0122]

[0123] As shown in Tables 5 and 6, the coated mortar (SC5) obtained in Comparative Example 5 had a coating film formed on the mortar slab, which gave it an appearance and feel that was clearly different from that of the uncolored mortar slab (Reference Example 1). In contrast, the colored mortars (SE2), (SE6), and (SE7) obtained in Examples 2, 6, and 7 all had the same appearance and feel as the uncolored mortar slab (Reference Example 1), and this tendency became more apparent as the content of the pigment contained in the coloring composition decreased.

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

Claims

1. A composition for coloring by impregnating 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.

2. The composition according to claim 1, further containing a surfactant.

3. The composition 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 according to claim 1, wherein the alcohol is a primary alcohol having 1 to 3 carbon atoms.

5. The composition according to claim 2, wherein the surfactant is a nonionic surfactant.

6. The composition according to claim 1, further containing an aqueous polymer emulsion.

7. A method for coloring by impregnating a calcium-based inorganic substrate, which includes 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.

8. The method according to claim 7, further including the 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 silicate compound to the impregnated surface.

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