JP6026195B2 - Inorganic substrate modification method - Google Patents

Description

The present invention relates to a novel method for modifying an inorganic base material.

Conventionally, inorganic base materials such as mortar and concrete used for flooring materials, non-combustible boards, tunnel interior boards, exposed surfaces, and the like may deteriorate over time due to load, friction, chemical erosion, and the like. In addition, since the inorganic base material has high water permeability, moisture or the like penetrates into the inside, and there is a possibility that deterioration such as cracks may occur due to freezing or expansion.
As a method for preventing such deterioration, a method of applying a silicate such as water glass to a substrate is known. In this method, silicate penetrates into the base material and reacts with polyvalent metal ions such as free calcium, magnesium and aluminum to form an insoluble gel and harden (form a cured body of silicate). It is integrated with the base material, and problems such as peeling are less likely to occur.

  On the other hand, in recent years, it has been attempted to color an inorganic base material in order to improve aesthetics. However, only by mixing and applying a pigment or the like to the silicate as described above, only the silicate penetrates into the base material, and most of the pigment remains on the base material surface, so the pigment is difficult to be fixed, Easily detached. As a method for solving such a problem, Patent Document 1 discloses that a base material is coated with a first coating liquid containing a pigment and a silanol group or a resin having a group that can be converted into a silanol group, and then water-soluble. A method for applying a second coating solution containing an alkali silicate compound is described.

  However, in the case of Patent Document 1, it is difficult for the silicate of the second coating solution to penetrate into the base material by the coating formed by the first coating solution, and the formation of a cured silicate body integrated with the base material is possible. May be insufficient. As a result, the abrasion resistance is inferior, and the pigment is liable to be detached, which may reduce the aesthetics.

JP 2010-37168 A

  This invention is made | formed in view of such a point, and it aims at obtaining the modification | reformation method of an inorganic base material effective in the improvement of the aesthetics (colorability) and abrasion resistance of an inorganic base material. Is.

As a result of intensive studies to achieve the above object, the inventor has applied a specific primer including a synthetic resin emulsion, colloidal silica, and a colorant on an inorganic base material, and then at least The present invention has been completed by conceiving a method for modifying an inorganic base material, including a step of applying a top coat obtained by mixing alkali metal silicate and water.

That is, the method for modifying an inorganic base material of the present invention has the following characteristics.
1. Inorganic substrate
A first step of applying a primer comprising a synthetic resin emulsion, colloidal silica , a colorant , and water ;
Next, a second step of applying a top coat obtained by mixing at least an alkali metal silicate and water,
Only including,
The amount of water in the primer is 70 to 99% by weight with respect to the entire primer.
The method for modifying an inorganic base material, wherein the amount of water in the top coating material is 50 to 98% by weight relative to the whole top coating material .
2. Inorganic substrate
A first step of applying a colloidal silica composite emulsion , a colorant , and a primer containing water ;
Next, a second step of applying a top coat obtained by mixing at least an alkali metal silicate and water,
Only including,
The amount of water in the primer is 70 to 99% by weight with respect to the entire primer.
The method for modifying an inorganic base material, wherein the amount of water in the top coating material is 50 to 98% by weight relative to the whole top coating material .
3. 1. The alkali metal silicate of the top coating material contains at least sodium silicate. Or 2. The method for modifying an inorganic base material as described in 1.
4). 1. The above coating material is obtained by mixing at least alkali metal silicate, alkylalkoxysilane, phosphoric acid or phosphate, and water. ~ 3. The method for modifying an inorganic base material according to any one of the above.
5). 3. The alkylalkoxysilane of the top coating material contains a trifunctional alkylalkoxysilane. The method for modifying an inorganic base material as described in 1.

  The present invention is a method for modifying the surface of an inorganic substrate including a step of applying a primer containing a specific component on the inorganic substrate, and a step of applying a primer containing a specific component. As a result, the water permeability of the inorganic base material can be lowered to increase the water repellency, and the aesthetics (colorability) and wear resistance can be improved.

Hereinafter, modes for carrying out the present invention will be described.

The present invention relates to a modification method including a step of applying a specific primer on an inorganic base material and a step of applying a specific primer. Mainly, the primer is for coloring the inorganic base material. Moreover, the top coating material increases the surface strength of the inorganic base material and improves the wear resistance and the like. In particular, the undercoating material containing a specific component can be colored without inhibiting the permeation of the overcoating material into the inorganic substrate. As a result, the inorganic base material and the top coating material can form an integrated cured body of silicate, increase the surface strength of the inorganic base material, and suppress the detachment of the coloring material.

(Inorganic substrate)
Examples of the inorganic base material (hereinafter, also referred to as “base material”) of the present invention include inorganic porous base materials that are produced mainly from inorganic materials such as cement-based materials, calcium silicate-based materials, and gypsum-based materials. . For example, calcium silicate board, wood chip cement board, pulp cement board, lightweight cellular concrete board, mortar board, gypsum board, slate board, etc. can be mentioned.

(Priming material)
The primer of the present invention comprises (A) a synthetic resin emulsion (hereinafter also referred to as “component (A)”), (B) colloidal silica (hereinafter also referred to as “component (B)”), and (C) a coloring material. (Hereinafter also referred to as “component (C)”), which mainly colors the substrate.

The (A) synthetic resin emulsion of this invention is a component which plays the role which fixes a coloring material. As such (A) component, if it does not impair the effect of this invention, it can be used suitably. Specifically, vinyl acetate resin, vinyl chloride resin, epoxy resin, acrylic resin, urethane resin, acrylic silicon resin, fluorine resin, etc., or a composite system thereof can be used, and one or more of these are used. can do. These may have crosslinking reactivity.

  The component (A) is preferably capable of reacting with the component (B). As such (A) component, it is preferable that it is an emulsion which has functional groups, such as a hydroxyl group, a hydrolysable silyl group, and a carboxyl group, which can react with the silanol group which exists in (B) component, for example.

The colloidal silica (B) of the present invention is a compound having a silanol group on the surface thereof, a role of increasing the permeability of the coating material described later, and a role of forming a cured product by reacting with the alkali silicate in the coating material. Is responsible for. Such a component (B) can be produced using, for example, sodium silicate, lithium silicate, potassium silicate, or a silicate compound, and water and / or a water-soluble solvent can be used as a medium.

(B) It is preferable that the average primary particle diameter of a component is 1-200 nm (more preferably 5-100 nm, more preferably 5-100 nm). In such a range, it is possible to enhance the permeability of the later-described topcoat material without inhibiting the hue of the later-described component (C). The particle diameter of the component (B) is a value measured by a light scattering method.

The component (A) and the component (B) are (A) :( B) = 95: 5 to 40:60 (more preferably 90:10 to 50:50) in terms of solid content weight ratio. preferable. In such a range, the coloring material can be firmly fixed, and the top coating material can be efficiently infiltrated into the base material, so that a stronger cured body can be formed.

Further, as the undercoat material of the present invention, a colloidal silica composite emulsion (AB) (hereinafter, also referred to as “(AB) component”) in which a synthetic resin emulsion and colloidal silica are chemically bonded can be used. Such a component (AB) is obtained by complexing colloidal silica during the polymerization of the synthetic resin emulsion.
As the synthetic resin emulsion in the component (AB), the same component as the component (A) can be used, and in particular, one or more functional groups selected from a hydroxyl group, a hydrolyzable silyl group, and a carboxyl group are used. What has is preferable. Moreover, as colloidal silica, the same thing as said (B) component can be used.

Such (AB) component can form a film in which synthetic resin and colloidal silica are uniformly dispersed, so that the coloring material is uniformly fixed to the base material and the coating material described later penetrates evenly. Thus, a hardened body is formed. As a result, it is possible to exhibit an effect that is more excellent in aesthetics and wear resistance.

In the component (AB), the synthetic resin emulsion and the colloidal silica are preferably 95: 5 to 40:60 (more preferably 90:10 to 50:50) in terms of solid content weight ratio. In such a range, the coloring material can be firmly fixed, and the top coating material can be efficiently infiltrated into the base material, so that a stronger cured body can be formed.

As the colorant (C) of the present invention, a color pigment and / or a dye can be used. Specifically, examples of the color pigment include titanium oxide, zinc oxide, alumina, carbon black, ferric oxide (valve), yellow iron oxide, iron oxide, ultramarine, cobalt green, and other inorganic color pigments, azo series Organic pigments such as naphthol, pyrazolone, anthraquinone, perylene, quinacridone, disazo, isoindolinone, benzimidazole, phthalocyanine, quinophthalone, pearl pigment, aluminum pigment, fluorescent pigment, etc. It is done. A desired color tone can be prepared by combining one or more of these color pigments.
In addition to the above color pigments, extender pigments can also be used. Examples of extender pigments include calcium carbonate, barium sulfate, clay, kaolin, porcelain clay, talc, quartzite powder, and diatomaceous earth.

  The average particle diameter of the color pigment is not particularly limited, but is preferably 0.005 to 5 μm (more preferably 0.01 to 3 μm). The content of the component (C) is preferably 5 to 100 weights with respect to 100 parts by weight of the total amount (solid content) of the component (A) and the component (B) / or the component (AB) (solid content). Parts (more preferably 10 to 50 parts by weight). In such a range, the effect of the present invention is easily obtained because it is difficult to inhibit the permeation of the overcoat material into the base material.

  Examples of the dye include acid dyes, basic dyes, cationic dyes, direct dyes, soluble vat dyes, acid mordant dyes, spirit bath dyes, and reactive dyes. The content of the dye is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the total amount (solid content) of the component (A) and the component (B) / or the component (AB) (solid content). More preferably, it is 0.5 to 10 parts by weight. In such a range, the effect of the present invention is easily obtained because it is difficult to inhibit the permeation of the overcoat material into the base material.

The undercoat material of the present invention preferably contains water in addition to the component (A), the component (B) and the component (C) / or the component (AB) and the component (C). The amount of water in the primer of the present invention is preferably 50 to 99% by weight, more preferably 70 to 97% by weight, based on the entire primer. By being in such a range, the effect of the present invention can be sufficiently exhibited.
In addition, the water in this invention contains the water used as a medium of the said (A) component, the said (B) component, the said (C) component, or the said (AB) component.

The undercoat material of the present invention can contain a known additive as required, as long as the effects of the present invention are not significantly impaired. Examples of such additives include thickeners, film-forming aids, leveling agents, wetting agents, plasticizers, antifreezing agents, antiseptics, antifungal agents, antialgae agents, antibacterial agents, deodorants, Examples thereof include a dispersant, an antifoaming agent, an adsorbent, a flame retardant, a water repellent, a crosslinking agent, an ultraviolet absorber, an antioxidant, and a catalyst.

(Coating material)
The topcoat material of the present invention is obtained by mixing at least (D) alkali metal silicate (hereinafter also referred to as “component (D)”) and water, and increases the surface strength of the inorganic base material, It improves wear and the like.

The (D) alkali metal silicate of the present invention is a water-soluble alkali represented by the general formula: M ₂ O.nSiO ₂ (M is at least one alkali metal selected from Li, K, Na, and Cs). Any metal silicate (also referred to as “water glass”) can be used. Examples of such component (D) include sodium silicate, sodium orthosilicate, sodium metasilicate, lithium silicate, and potassium silicate. Moreover, the water glass marketed as an aqueous solution of an alkali metal silicate can also be used. Said alkali metal silicate may be used independently, or 2 or more types may be mixed and used for it.

In the present invention, the component (D) preferably contains at least sodium silicate having a SiO ₂ / Na ₂ O (molar ratio) of 5/1 to 2/1 (more preferably 4/1 to 3/1). In such a case, the component (D) can easily penetrate into the substrate, and a dense cured body can be formed. Furthermore, in the present invention, it is preferable to use SiO ₂ / K ₂ O (molar ratio) of 5 / 1-1 / 1 (more preferably 4 / 1-1 / 1) were mixed silicate of potassium. This makes it easier for the component (D) to penetrate into the substrate, and a dense cured body can be formed. Thereby, the surface strength of the base material can be increased, and the whitening of the surface of the base material and the peeling of the coloring material can be suppressed.

The mixing ratio of sodium silicate and potassium silicate is SiO ₂ / (Na ₂ O + K ₂ O) (molar ratio) of 5/1 to 1/1 (preferably 4/1 to 2/1), and the entire coating material On the other hand, the SiO ₂ content is preferably adjusted to 5 to 30% by weight (more preferably 10 to 20% by weight). In such a range, a dense cured body can be formed, and coating unevenness and the like are suppressed, resulting in a good finish.

The topcoat material of the present invention preferably contains (E) an alkylalkoxysilane (hereinafter also referred to as “component (E)”) in addition to the component (D). By including the component (E), the water repellency of the substrate can be increased. In the present invention, the water repellency refers to the ability to prevent moisture from being sucked into the inorganic base material, and the water repellency persistence refers to the above-mentioned water repellency being sustained over a long period of time.

Examples of such component (E) include tetraethoxysilane, tetramethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetraisobutoxysilane, tetrasec-butoxysilane, tetrat-butoxysilane, and tetraphenoxy. Tetrafunctional alkoxysilanes such as silane;
Methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, Trifunctional alkyl alkoxy such as propyltripropoxysilane, propyltributoxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltripropoxysilane, butyltributoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane Silanes;
Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldibutoxysilane, diethyldipropoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dibutyldimethoxysilane, dibutyldi And bifunctional alkylalkoxysilanes such as ethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldibutoxysilane, methylphenyldimethoxysilane, and methylphenyldiethoxysilane.
These may be used alone or in combination of two or more.

In the present invention, it is particularly preferable to include a trifunctional alkylalkoxysilane. Furthermore, an alkyl group having 1 to 3 carbon atoms is preferable. Examples of such component (E) include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, etc. Is mentioned.

  The topcoat material of the present invention preferably further contains (F) phosphoric acid or a phosphate (hereinafter also referred to as “component (F)”). By including the component (F), the water repellency of the substrate can be further enhanced. Examples of such component (F) include phosphoric acid, orthophosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, hydroxyammonium phosphate, and alkali metal phosphates. In the present invention, it is particularly preferable to include at least one selected from phosphoric acid, orthophosphoric acid, ammonium phosphate, and ammonium hydrogen phosphate. Further, it preferably contains ammonium phosphate.

  When the top coating material of the present invention is used in combination with the above component (D), the above component (E), and the above component (F), it can form a denser cured product, and the water permeability of the substrate. The water repellent durability and wear resistance can be further improved. Moreover, it can suppress that the water etc. which remain on the base-material surface become a strong base. The mechanism of action is not clear, but the (D) component and (E) component penetrate into the base material and react with polyvalent metal ions such as calcium, magnesium, and aluminum released from the base material, and are insoluble gels. When forming and forming a cured body, the (F) component increases the curability, and a dense cured body can be formed. As a result, the water permeability of the substrate can be lowered over a long period of time, and as a result, the water repellency persistence and the surface strengthening action can be enhanced, and the unreacted component (D) and the alkali metal remaining after the reaction It is thought that elution can be suppressed and the strong base of the accumulated water and running water on the substrate surface can be sufficiently reduced. Furthermore, the oil repellency of a base material can also be improved by using together said (D) component, said (E) component, and said (F) component.

The component (E) is preferably 2 to 50 parts by weight (more preferably 5 to 40 parts by weight) with respect to 100 parts by weight of the solid content of SiO ₂ contained in the component (D), and the component (F) is , Preferably 0.1 to 10 parts by weight (more preferably 0.2 to 5 parts by weight). By using together in such a range, the water / oil repellency and surface strengthening action of the substrate can be further enhanced, and elution of the unreacted component (D) can be suppressed. It is possible to further reduce the strong base of the accumulated water.

The topcoat material of the present invention preferably further contains a silane coupling agent (G). By containing (G) component, the water permeability of a base material can be reduced and water-repellent durability and abrasion resistance can be improved further. Examples of such component (G) include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylethoxysilane, γ -Glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylsilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyltrimethoxysilane, isocyanate functional silane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxyproopylmethyldiethoxysilane, γ-mercaptopropyltrimethoxy Silane N- mentioned [2- (vinyl benzylamino) ethyl] -3-aminopropyl trimethoxysilane, may be used alone or two or more of these.

  In the present invention, an epoxy group-containing silane coupling agent such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and γ-glycidoxypropylsilane is preferably used in combination. In this case, the effect of the present invention can be further enhanced.

The component (G) is preferably 1 to 50 parts by weight (more preferably 2 to 25 parts by weight) with respect to 100 parts by weight of the solid content of SiO ₂ contained in the component (D). By using together in such a range, since adhesiveness with undercoat material can be improved further, water-repellent sustainability and abrasion resistance can be improved further.

The topcoat material of the present invention is obtained by mixing water with the component (D). Moreover, it is a thing obtained by mixing the said (E) component, the said (F) component, and the said (G) component as needed. The amount of water in the top coating material of the present invention is preferably 50 to 98% by weight, more preferably 70 to 95% by weight, based on the whole top coating material. By being in such a range, it is excellent in the permeability to a base material, and the effect of the present invention can be further enhanced.
In addition, the water in this invention contains the water used as a medium of (D) component, (F) component, (G) component, etc.

The manufacturing method of the topcoat material of this invention is not specifically limited, What is necessary is just to mix (D) component and water by a well-known method. Moreover, although it does not specifically limit in the case of the aspect containing (D) component, (E) component, (F) component, and (G) component, For example, it can manufacture with the following method.
(1) After mixing component (D), component (E), component (G) and water to obtain mixed solution (I), component (F) is then added to mixed solution (I). How to stir.
(2) (E) component, (F) component, (G) component and water are mixed to obtain a mixed solution (II), and then (D) component is added to the mixed solution (II). How to stir.
(3) The component (D), the component (F) and water are mixed to obtain a mixed solution (III), and then the component (E) and the component (G) are added to the mixed solution (III). How to stir.
In addition, in said (1)-(3), (E) component, (F) component, (G) component are mixed as needed.

    In the above (1) to (3), when the (D) component or the mixed solution containing the (D) component and the mixed solution containing the (F) component or (F) component are mixed, the latter has a pH of 4 or more (preferably It is preferably adjusted to pH 5 or more and 11 or less. As a result, the top coating material of the present invention can be stably produced, and the effects of the present invention can be sufficiently exhibited.

For example,
In said (1), it is preferable to add (F) component adjusted to pH 4 or more to mixed solution (I).
In (2) above, (F) component adjusted to pH 4 or higher is added to (E) component to obtain mixed solution (II), or (E) component, (F) component not adjusted to pH And after obtaining mixed solution (II) containing water, it is preferable to adjust to pH 4 or more.

Further, in (3) above, the mixed solution (III) is obtained by mixing the (F) component adjusted to pH 4 or higher with the solution obtained by previously mixing the (D) component and water, or by previously mixing the (F) component and water. It is preferable to obtain the mixture obtained by mixing the component (D) with a solution adjusted to pH 5 or higher.

  Ammonia, alkylamine, alkanolamine, alkali metal hydroxide, etc. can be used for pH adjustment of each solution in the above. In the present invention, it is particularly preferable to use one or more selected from ammonia, alkylamine, and alkanolamine. In this case, the water repellency can be further enhanced. Among these, examples of the alkylamine include monoethylamine, diethylamine, triethylamine, isopropylamine, diisopropylamine and the like. Examples of the alkanolamine include aminoethanol, aminopropanol, N, N-dimethylethanolamine, N, N-diethylethanolamine, N-methylethanolamine, N-methyldiethanolamine and the like.

In the case where ammonium phosphate, ammonium hydrogen phosphate, hydroxyammonium phosphate, or an alkali metal phosphate is used as the component (F), the pH can be adjusted to 4 or more without using the pH adjuster.

  The topcoat material of the present invention can contain a known additive as required, as long as the effects of the present invention are not significantly impaired. Examples of such additives include thickeners, film-forming aids, leveling agents, wetting agents, plasticizers, antifreezing agents, antiseptics, antifungal agents, antialgae agents, antibacterial agents, deodorants, Examples thereof include a dispersant, an antifoaming agent, an adsorbent, a flame retardant, a color pigment, an extender pigment, a fiber, a water repellent, a crosslinking agent, an ultraviolet absorber, an antioxidant, and a catalyst.

The present invention is a method for modifying an inorganic base material, which includes a first step of applying the primer to the inorganic base material, and then a second step of applying the top coat material.

In the first step and the second step, the undercoating material and the overcoating material can be applied by a known coating method, and the coating device is not particularly limited, and a coating device such as a spray, coater, roller, or brush is used. can do.

In the first step, the coating amount of the primer is preferably about 0.005 to 0.2 kg / m ² (more preferably 0.01 to 0.15 kg / m ² ). In such a range, the effect of the present invention is easily obtained because it is difficult to inhibit the permeation of the overcoat material into the base material. Moreover, the undercoating material may be dried and cured at room temperature.

The second step can be performed in a state where the undercoat layer of the first step is semi-cured or cured. The coating amount of the top coating material is preferably about 0.01 to 0.4 kg / m ² (more preferably 0.05 to 0.3 kg / m ² ). In such a range, the water permeability of the base material can be sufficiently reduced and the surface strength can be improved, so that the effects of the present invention are easily obtained. Moreover, the top coating material may be dried and cured at room temperature.

  Examples are given below to clarify the features of the present invention.

(Priming material)
(Primer 1)
200 parts by weight of acrylic resin emulsion (solid content 50% by weight), colloidal silica aqueous dispersion (average primary particle size 20 nm, solid content 20% by weight) 252 parts by weight, color pigment (quinacridone red (average particle size 0.4 μm) 100 parts by weight of an aqueous dispersion (solid content: 35% by weight) were mixed, and water was added and stirred so that the amount was 95% by weight with respect to the whole primer, whereby primer 1 was obtained.

(Prime material 2)
Colloidal silica composite acrylic resin emulsion (solid content 45%, acrylic resin: colloidal silica (weight ratio) = 65: 35, colloidal silica average primary particle diameter 20 nm) 345 parts by weight, coloring pigment (quinacridone red (average particle diameter 0. 4 μm) aqueous dispersion, solid content 35 wt%) 100 parts by weight were mixed, and water was further added and stirred to 95 wt% with respect to the entire undercoat material to obtain undercoat 2.

(Primer 3)
200 parts by weight of an acrylic resin emulsion (solid content 50% by weight), 100 parts by weight of a color pigment (quinacridone red (average particle size 0.4 μm) aqueous dispersion, solid content 35% by weight), and 84 parts by weight of water are mixed. Furthermore, water was added and stirred so as to be 95% by weight with respect to the entire undercoat material to obtain an undercoat material 3.

(Priming material 4)
200 parts by weight of acrylic silicone resin emulsion (solid content 50% by weight), 100 parts by weight of coloring pigment (quinacridone red (average particle size 0.4 μm) aqueous dispersion, solid content 35% by weight), and 84 parts by weight of water are mixed. Further, undercoat material 4 was obtained by adding and stirring water so as to be 95% by weight with respect to the entire undercoat material.

(Coating material)
The following were used as raw materials.
(D1) Sodium silicate solution (active ingredients: SiO ₂ 26%, Na ₂ O 7.0%, SiO ₂ / Na ₂ O (molar ratio) = 3.83)
(D2) Potassium silicate solution (active ingredients: SiO ₂ 28%, K ₂ O 22.0%, SiO ₂ / K ₂ O (molar ratio) = 1.99)
(D3) lithium silicate solution (active _{ingredient: SiO 2 20.4%, Li 2} O2.9%, SiO 2 / Li 2 O ( molar ratio) = 3.50)
(E1) Methyltriethoxysilane (E2) Propyltrimethoxysilane (E3) Dimethyldimethoxysilane (F1) Ammonium phosphate aqueous solution (concentration 16.7%, pH = 7.0)
(F2) phosphoric acid aqueous solution (concentration 5%, pH = 1.0)
(F3) Sodium phosphate aqueous solution (concentration 8.4%, pH = 11.5)
(G1) γ-Glycidoxypropyltrimethoxysilane

(Coating material 1)
According to the formulation shown in Table 1, (D1) sodium silicate was mixed with water to obtain a top coating material 1.

(Coating material 2)
According to the composition shown in Table 1, (F1) after mixing ammonium phosphate aqueous solution and water, (D1) sodium silicate was added and stirred, and then (E1) methyltriethoxysilane was added and stirred. Got.

(Coating materials 3-7, 10, 12-15)
According to the formulation shown in Table 1, topcoat materials 3 to 7, 10, and 12 to 15 were obtained in the same manner as topcoat material 2.

(Coating material 8)
According to the formulation shown in Table 1, a mixed solution in which (E1) methyltriethoxysilane, (F2) phosphoric acid aqueous solution, and water were mixed was adjusted to pH 7 using aqueous ammonia. Next, (D1) sodium silicate was added and stirred to obtain a top coating material 8.

(Coating material 9)
According to the formulation shown in Table 1, a mixed solution of (E1) methyltriethoxysilane, (F2) phosphoric acid aqueous solution, and water was adjusted to pH 7 using 2 amino-1 propanol. Next, (D1) sodium silicate was added and stirred to obtain a top coating material 9.

(Coating material 11)
According to the formulation shown in Table 1, (F1) ammonium phosphate aqueous solution and water were mixed, (D1) sodium silicate was added and stirred, then (E1) methyltriethoxysilane, (G1)) γ-glycidoxy Topcoat material 11 was obtained by adding and stirring propyltrimethoxysilane.

<Preparation of specimen>
Using each undercoat material and each topcoat material shown in Table 2, the following test body A and test body B were prepared.
Specimen A: A base material (slate plate: L100 × W100 × T3 mm) was brushed with a coating amount of 0.1 kg / m ² and dried and cured at room temperature (23 ° C., humidity 50% lower) for 24 hours. Then, the top coating material was brushed at a coating amount of 0.2 kg / m ² and allowed to stand for 30 minutes. After leaving still, after removing the surplus of the top coating material, it was wiped with water, and was cured for 7 days at room temperature (23 ° C., humidity 50% lower).
Specimen B: Specimen B was prepared in the same manner as Specimen A, except that standard mortar: L75 × W75 × T20 mm was used as the base material.

[Test Example 1]
The following evaluation was implemented about each obtained test body (Test Example 1-1 to Test Example 1-5). The results are shown in Table 2.
<Aesthetic evaluation>
About each test body A and test body B, the aesthetics were evaluated visually. The results are shown in Table 2.
◎: Good ○: Slightly good △: Slightly poor (slightly whitened surface)
X: Defect (coloration defect or surface whitening)

<Abrasion resistance (surface strength) evaluation>
For specimen A, the weight loss after 500 revolutions was observed with a Taber tester, wear wheel CS-17, load 1000 g, according to JIS K5600 5.9 wear resistance (wear wheel method). Evaluation was made by comparing with wear reduction of an untreated slate plate. The criteria are shown below.
◎: better than untreated product ○: slightly better than untreated product △: equivalent to untreated product ×: untreated

<Evaluation of colorant detachability>
About the test body after the said abrasion resistance evaluation, the change of the hue was visually evaluated.
◎: No hue change ○: Slight hue change △: The substrate can be seen through (decrease in concealment)
×: Substrate exposed

<Water repellency evaluation>
30 μL of water was spotted on the specimen B and wiped off after 30 seconds. When there was no water inhalation (penetration) in the spot portion by visual observation, it was determined that there was water repellency. The evaluation criteria are shown below.
◎: No sucking ○: Almost no suction
Δ: Degree of stain remains ×: Inhalation

[Test Example 2]
Subsequently, using each undercoat material and each topcoat material shown in Table 3, a test body A and a test body B were prepared.
In addition to the evaluation in Test Example 1, the following evaluations were further performed (Test Example 2-1 to Test Example 2-15). The results are shown in Table 3.
<Oil repellency evaluation>
30 μL of liquid paraffin was spotted on the specimen B and wiped off after 30 seconds. When there was no oil absorption (penetration) in the spot portion by visual observation, it was determined that there was oil repellency. The evaluation criteria are shown below.
○: No suction
Δ: Degree of stain remains ×: Inhalation

<Evaluation of pH of accumulated water>
100 μL of water was spotted on the specimen B, and the pH of the spot solution was measured after 10 minutes.

  In Test Example 2-1 to Test Example 2-13 using the top coating materials 1 to 13, good results were obtained in aesthetics, abrasion resistance (surface strength), detachability, water repellency, and oil repellency. Moreover, in Test Example 2-2 to Test Example 2-12, the pH of the accumulated water was also good with neutral to weak basicity.

[Test Example 3]
Using each undercoat material and each topcoat material shown in Table 4, the produced test body B was evaluated for water repellency and oil repellency after immersion in water (Test Example 3-1 to Test Example 3-12). ).
<Evaluation of water and oil repellency after immersion in water>
The back side surface of the test body B was sealed with an epoxy resin, immersed in water for 1 day, dried, and the water repellency and oil repellency were confirmed in the same manner as in Test Example 1 and Test Example 2. Moreover, it evaluated similarly also after making it soak in water for 2 days. The results are shown in Table 4.

It was a favorable result in Test Example 3-1 to Test Example 3-10.

Claims (5)

Inorganic substrate
A first step of applying a primer comprising a synthetic resin emulsion, colloidal silica , a colorant , and water ;
Next, a second step of applying a top coat obtained by mixing at least an alkali metal silicate and water,
Only including,
The amount of water in the primer is 70 to 99% by weight with respect to the entire primer.
The method for modifying an inorganic base material, wherein the amount of water in the top coating material is 50 to 98% by weight relative to the whole top coating material . Inorganic substrate
A first step of applying a colloidal silica composite emulsion , a colorant , and a primer containing water ;
Next, a second step of applying a top coat obtained by mixing at least an alkali metal silicate and water,
Only including,
The amount of water in the primer is 70 to 99% by weight with respect to the entire primer.
The method for modifying an inorganic base material, wherein the amount of water in the top coating material is 50 to 98% by weight relative to the whole top coating material . The method for reforming an inorganic base material according to claim 1 or 2, wherein the alkali metal silicate of the top coating material contains at least sodium silicate. The said top coating material is a thing obtained by mixing at least alkali metal silicate, alkyl alkoxysilane, phosphoric acid or phosphate, and water, The Claim 1 characterized by the above-mentioned. A method for modifying an inorganic substrate. The method for modifying an inorganic base material according to claim 4, wherein the alkylalkoxysilane of the top coating material contains a trifunctional alkylalkoxysilane.