JP6970168B2 - Film formation method - Google Patents

Description

The present invention relates to a novel film forming method for inorganic materials such as concrete and cement mortar.

Permeable water absorption preventive material is applied to inorganic materials such as concrete and cement mortar, which have been conventionally used as base materials for buildings and civil engineering structures, as a method of imparting water absorption prevention and improving durability. The method of doing is widely used.

The permeable water absorption preventive material penetrates into the inorganic material to form a water repellent layer. Therefore, by applying such a permeable water absorption preventive material, the infiltration of water, carbon dioxide, etc. from the outside into the base material is blocked, the strength is prevented from being lowered due to the neutralization of the base material, and the base material is further protected. It can exert the effect of suppressing the corrosion of the steel frame or the reinforcing bar existing inside. In addition, it is possible to prevent the generation of efflorescence on the surface layer of the base material due to the migration of the calcium component inside the base material.

As such a permeable water absorption preventing material, a material containing a silane compound as a main component (for example, Patent Document 1) is known. However, it may not be possible to obtain sufficient water repellency, water absorption prevention property, etc. only by applying such a permeable water absorption prevention material, and there is room for improvement in practical use.

In Patent Document 2, a solvent-based water-repellent waterproof material (undercoat material) is applied to the concrete surface, and a waterproof material (intermediate coat material) made of an emulsion-based transparent synthetic resin is applied to the surface thereof, and another waterproof material. The method of applying (topcoat material) is described. According to such a method, it is expected that the water absorption prevention property of the concrete surface is improved and the durability is enhanced.

However, in the method of Patent Document 2, the adhesion of the emulsion-based waterproof material becomes insufficient, and there is a possibility that the desired effect cannot be obtained in terms of water absorption prevention property, durability and the like. Further, in the method of the above patent document, when defects such as contamination occur on the surface of the inorganic material, these defects may become conspicuous.

Japanese Unexamined Patent Publication No. 63-256581 Japanese Unexamined Patent Publication No. 2002-89006

The present invention has been made in view of such problems, and an object of the present invention is to provide a film forming method capable of imparting excellent water absorption prevention property, durability, aesthetics, etc. to an inorganic material. ..

To solve such problems, the present inventors have conducted extensive studies results, after subjecting the coating permeable water absorption preventing agent, a specific coating material as the second step (I) was with a coating as a first step, As a third step, he came up with a method of applying a covering material (II) with a specific instrument to give a pattern, and completed the present invention.

That is, the film forming method of the present invention has the following features.
1. 1. It is a film forming method for inorganic materials.
For the surface of inorganic materials
After applying a silane-based permeable water absorption inhibitor as the first step,
As a second step, a coating material (I) containing a synthetic resin emulsion and a pigment and having a hiding ratio of 90% or more of the formed film is applied.
As a third step, a coating material (II) containing a synthetic resin and a pigment and having a color tone different from that of the coating material (I) is applied to give a pattern.
The silane-based permeable water absorption inhibitor contains an alkylalkoxysilane compound having an alkyl group having 1 to 18 carbon atoms and does not contain a silicon-based resin.
The synthetic resin emulsion of the coating material (I) contains (meth) acrylic acid alkyl ester as a monomer constituting the synthetic resin, in which the glass transition temperature of the homopolymer is 50 ° C. or higher and the solubility parameter is 9.5 or lower. ,
The coating material (II) is a film forming method, characterized in that at least two or more kinds of liquid absorbing materials having different hardness and / or density are applied by a roller brush mixed on the outer peripheral surface of a cylinder.
2. 2. The synthetic resin emulsion of the coating material (I) is characterized by having a glass transition temperature of 10 to 60 ° C. The film forming method according to the above.
3. 3. The synthetic resin emulsion of the coating material (I) is characterized by having an average particle size of 120 nm or less. Or 2. The film forming method according to the above.
4. The synthetic resin emulsion of the coating material (I) is characterized by being a silicon-modified acrylic resin emulsion. ~ 3. The film forming method according to any one of.

In the film forming method of the present invention, a permeable water absorption inhibitor is applied to the surface of the inorganic material as a first step, and then a coating material (I) containing a specific synthetic resin emulsion and a pigment is applied as a second step. and with a coating, as a third step, the covering material with a specific instrument of (II) are given a coating by Rukoto to impart patterns, imparts excellent water-preventing property to the inorganic material, durability, aesthetics, etc. It is possible to form a film.

FIG. 1 is a cross-sectional view of the roller brush used in the present invention.

1. 1. Liquid absorbing material (1a-1e)
2. 2. Cylinder outer peripheral surface 3. Cylinder outer diameter direction

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

Film forming method of the present invention, the surface of the inorganic material, after subjecting the coating permeable water-preventing member as a first step, certain of the dressing (I) was with a coating as a second step, a third step The coating material (II) is applied with a specific instrument to form a film.
<Inorganic material>
Inorganic materials constitute the surface of buildings, civil engineering structures, and the like. Examples of such a base material include concrete, mortar, siding board, extruded board, gypsum board, pearlite board, brick, tile and the like. These base materials may have a coating film already formed on the surface thereof. The present invention is particularly preferably applied to a concrete surface such as a concrete wall surface. Such a concrete surface is usually obtained by mixing cement, water, aggregate, and an admixture in an appropriate ratio and kneading the concrete, and then pouring it into a formwork or a predetermined place to harden and demold it. It is obtained by doing so. The present invention can be applied to either a newly constructed concrete surface or a concrete surface that has deteriorated over time.

In the present invention, it is also possible to perform a treatment such as cleaning on the inorganic material prior to the first step. As the cleaning treatment, a method of applying various cleaning agents to the inorganic material and then washing with water may be adopted.

<First step>
The permeable water absorption preventive material of the first step in the present invention can be used without particular limitation as long as it is a material capable of exhibiting the water absorption preventive effect, and for example, silicone resin, acrylic resin, urethane resin, unsaturated polyester resin and the like are mainly used. Resin-based permeable water absorption inhibitor contained as a component; silicate-based permeable water absorption inhibitor containing an alkyl silicate compound as a main component; silane-based permeable water absorption prevention material containing a hydrolyzable silane compound and / or a condensate thereof as a main component Materials, etc. may be mentioned. In the present invention, a silane-based permeable water absorption inhibitor can be preferably used. Examples of the silane-based permeable water absorption inhibitor include an organoalkoxysilane compound, an organoacetoxysilane compound, an organohalogensilane compound, an organodissilane compound, an organosilanecarboxylic acid compound, an organosilanethiol compound, an organosilicon isocyanato compound, and an organosilicon. Examples thereof include isothianate compounds and those containing one or more selected from these condensates.

The permeable water absorption inhibitor is a solution in which the above-mentioned components are dissolved or dispersed in a medium, and may be dispersed by an emulsifier or the like. The medium of the permeable water absorption preventive material is not particularly limited, and is mainly composed of a strong solvent system containing an aromatic hydrocarbon solvent as a main component, a weak solvent system containing an aliphatic hydrocarbon solvent as a main component, and water as a main component. Although various forms such as an aqueous system can be used, a weak solvent system can be particularly preferably used in the present invention. The solvent as the main component may be contained in each medium in an amount of 50% by weight or more (preferably 70% by weight or more).

In such a permeable water absorption inhibitor, the content ratio of the compound as the main component thereof is preferably 0.1 to 50% by weight (more preferably 1 to 30% by weight, still more preferably 2 to 20% by weight). be. In such a range, a sufficient water absorption prevention effect can be exhibited.

In particular, in the present invention, an alkylalkoxysilane compound having an alkyl group having 1 to 18 carbon atoms as a main component compound is used in an amount of 0.1 to 50% by weight (more preferably 1 to 30% by weight, still more preferably 2 to 20% by weight). Weight%) is preferable. Such an alkylalkoxysilane compound is a compound in which an alkyl group and an alkoxysilyl group are bonded to a silicon atom, and for example, a compound represented by the following formula (1) and / or a condensate thereof can be used.
R ^1- Si (OR ² ) ₃ (1)
(In the formula, R ¹ and R ² represent an alkyl group ^{. R 1} has 1 to 18 carbon atoms.)

Specifically, examples of the alkylalkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, and butyltrimethoxy. Silane, Butyltriethoxysilane, Pentilt Remethoxysilane, Pentilt Riethoxysilane, Hexiltrimethoxysilane, Hexiltriethoxysilane, Heptiltrimethoxysilane, Heptiltriethoxysilane, Octiltrimethoxysilane, Octiltriethoxysilane, Nonyltrimethoxysilane Silane, nonyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, undecyltrimethoxysilane, undecyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, tridecyltrimethoxysilane, tridecyltriethoxysilane , Tetradecyltrimethoxysilane, tetradecyltriethoxysilane, pentadecyltrimethoxysilane, pentadecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, heptadecyltrimethoxysilane, heptadecyltriethoxysilane, octadecyl Examples thereof include trimethoxysilane and octadecyltriethoxysilane. As these condensates, those having an average degree of condensation of about 1 to 10 can be used. These can be used in one type or two or more types.

As the alkylalkoxysilane compound, a compound having an alkyl group R1 having ¹ to 18 carbon atoms (preferably 3 to 12, more preferably 5 to 8) is used. The alkyl group may be partially substituted with a halogen or the like. When the number of carbon atoms of the alkyl group is within such a range, it is possible to enhance the water absorption prevention property. As the alkoxyl group in the alkylalkoxysilane compound, one having 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms, more preferably 1 to ^{2 carbon atoms) may be used.}

In such a permeable water absorption inhibitor, in order to fully exert the action of the alkylalkoxysilane compound, it is desirable not to mix too much resin component, and it is desirable that the content ratio is lower than that of the alkylalkoxysilane compound. The content ratio of the resin component (solid content) in the permeable water absorption inhibitor is preferably less than 20% by weight (more preferably 10% by weight or less), and a form containing no resin component is also suitable.

The permeable water absorption inhibitor is, for example, a colorant, a thickener, a wetting agent, an antifreeze agent, a preservative, a fungicide, an algae-proofing agent, an antibacterial agent, and a dispersant, as long as the effect of the present invention is not significantly impaired. , Antifoaming agent, resin, ultraviolet absorber, antioxidant, catalyst and the like may be contained. The permeable water absorption inhibitor can be produced by uniformly mixing each of the above-mentioned components by a conventional method.

In the first step, such a permeable water absorption inhibitor is uniformly applied to the base material. The application device is not particularly limited, and a known application device such as a brush, a spray, a roller, and a coater can be used. The required amount for applying the permeable water absorption inhibitor may be appropriately set in consideration of the type and condition of the base material, but is preferably 30 to 500 g / m ² (more preferably 80 to 400 g / m). ² ) About. The permeable water absorption inhibitor may be applied and dried preferably at room temperature (0 to 40 ° C.). In the present invention, after the permeable water absorption preventive material is dried, the coating in the next step can be performed. The interval between steps is usually 1 hour or more and 10 days or less, preferably 3 hours or more and 7 days or less.

<Second step>
As the coating material (I) in the second step, a material containing a specific synthetic resin emulsion and pigment is used. The synthetic resin emulsion in this coating material has a homopolymer glass transition temperature (hereinafter also referred to as “Tg”) of 50 ° C. or higher (preferably 60 to 120 ° C.) and solubility parameters (hereinafter referred to as “solubility parameters”) as the monomers constituting the synthetic resin. It contains a (meth) acrylic acid alkyl ester (A) (hereinafter, also referred to as “component (A)”) having a “sp value”) of 9.5 or less (preferably 6 to 9.5). By applying a coating material containing such a component, it is possible to exhibit excellent performance in adhesion to the above-mentioned permeable water absorption preventing material and enhance the durability of the inorganic material. In the present invention, the acrylic acid alkyl ester and the methacrylic acid alkyl ester are collectively referred to as a (meth) acrylic acid alkyl ester.

Examples of the component (A) of the present invention include tert-butyl methacrylate (Tg: 107 ° C., sp value: 9.07), cyclohexyl methacrylate (Tg: 83 ° C., sp value: 7.44), and the like. .. Examples of the (meth) acrylic acid alkyl ester other than the component (A) include methyl methacrylate (Tg: 105 ° C., sp value: 9.93), ethyl acrylate (-20 ° C., sp value: 10.2), n. -Butyl acrylate (Tg: -56 ° C, sp value: 9.77), n-butyl methacrylate (Tg: 20 ° C, sp value: 9.45), 2-ethylhexyl acrylate (Tg: -70 ° C, sp value: 9.22) and the like. The glass transition temperature of the homopolymer can be measured by a DSC (differential scanning calorimetry device). In addition, the solubility parameter is "Polymer Engineering and Science (POLYMER ENGINEERING AND SCIENCE)", 1974, VoL. 14, No. 2, P.I. It is a value calculated by the method described in 147-154.

The content of the component (A) may be 3 to 70% by weight (more preferably 5 to 50% by weight, still more preferably 8 to 40% by weight) in the solid content of the synthetic resin emulsion of the present invention. preferable. Within such a range, excellent performance can be exhibited in the adhesion with the above-mentioned permeable water absorption preventing material, and the durability of the inorganic material can be improved.

Further, the glass transition temperature of the synthetic resin emulsion can be adjusted by selecting the type of monomer, the mixing ratio, and the like. The glass transition temperature may be appropriately set in consideration of the final required performance and the like, but in the present invention, it is preferably 10 to 60 ° C. (more preferably 15 to 55 ° C.). In such a case, the effect of the present invention can be further enhanced. The glass transition temperature of the synthetic resin emulsion can be obtained by the Fox calculation formula.

Further, the synthetic resin emulsion preferably has an average particle size of 120 nm or less (more preferably 30 nm or more and 100 nm or less). In such a case, the effect of the present invention can be further enhanced. The average particle size can be measured by a dynamic light scattering method.

The synthetic resin emulsion of the present invention is not particularly limited as long as it satisfies the above conditions, and is, for example, an acrylic resin emulsion, an epoxy-modified acrylic resin emulsion, a urethane-modified acrylic resin emulsion, a silicon-modified acrylic resin emulsion, or a fluorine-modified acrylic resin. Emulsions, etc., or composite systems thereof and the like can be mentioned, and one or more of these can be used.

The synthetic resin emulsion of the present invention is preferably a silicon-modified acrylic resin emulsion. The silicon-modified acrylic resin emulsion is obtained by using a reactive silyl group-containing compound as an essential component. By using a silicon-modified acrylic resin emulsion, adhesion, durability, etc. can be improved, and a coating film having good stain resistance, weather resistance, yellowing resistance, water resistance, chemical resistance, etc. can be formed. Can be done.

In the present invention, the silicon-modified acrylic resin emulsion preferably contains, for example, the component (A) as a monomer component and further satisfies any of the following conditions (1) to (4).
(1) Synthetic resin emulsion containing a reactive silyl group-containing monomer as a monomer component (2) Containing at least one or more monomers selected from a reactive silyl group-containing monomer, a hydroxyl group-containing monomer, and a carboxyl group-containing monomer as a monomer component. Synthetic resin emulsion made by adding a silane compound to a resin,
(3) A synthetic resin emulsion obtained by reacting a functional group in a resin with a silane coupling agent having a functional group capable of reacting with the functional group.
(4) Examples thereof include a synthetic resin emulsion obtained by reacting a functional group in a resin with a silane coupling agent having a functional group capable of reacting with the functional group, and further adding a silane compound.

Examples of the reactive silyl group include those in which an alkoxyl group, a phenoxy group, a mercapto group, an amino group, a halogen and the like are bonded to a silicon atom. In the present invention, an alkoxysilyl group in which an alkoxyl group is bonded to a silicon atom is suitable.

The reactive silyl group-containing monomer in (1) and (2) above is a compound containing a reactive silyl group and a polymerizable double bond, and is, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-. Butoxysilane, vinyltris (β-methoxyethoxy) silane, allyltrimethoxysilane, trimethoxysilylethyl vinyl ether, triethoxysilylethyl vinyl ether, trimethoxysilylpropyl vinyl ether, triethoxysilylpropyl vinyl ether, γ- (meth) acryloyloxypropyltri Examples thereof include methoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, vinylmethyldimethoxysilane, methyldimethoxysilylethyl vinyl ether, methyldimethoxysilylpropylvinyl ether and the like. One kind or two or more kinds can be used.

Examples of the hydroxyl group-containing monomer in (2) above include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxyethyl vinyl ether and the like. One or more of these can be used. Examples of the carboxyl group-containing monomer in (2) include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, maleic anhydride, itaconic anhydride and the like, and one or two of these. The above can be used.

As the silane compound in the above (2) and (4), those having two or more reactive silyl groups in one molecule are used, and for example, tetrafunctional alkoxy such as tetraethoxysilane, tetramethoxysilane, and tetrabutoxysilane. Silanes; methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltri Trifunctional alkoxysilanes such as ethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, dipropyl Bifunctional alkoxysilanes such as dimethoxysilane, dipropyldiethoxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldibutoxysilane, methylphenyldimethoxysilane, and methylphenyldiethoxysilane; Chlorosilanes such as tetrachlorosilane, methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane, diphenyldichlorosilane, methylphenyldichlorosilane; tetraacetoxysilane, methyltri Examples thereof include acetoxysilanes such as acetoxysilane, phenyltriacetoxysilane, dimethyldiacetoxysilane, and diphenyldiacetoxysilane, and one or more of these can be used. Further, a compound having one reactive silyl group in one molecule can also be used in combination.

Examples of the combination of the functional groups in the above (3) and (4) include a hydroxyl group and an isocyanate group, an amino group and an isocyanate group, a carboxyl group and an epoxy group, an amino group and an epoxy group, and an alkoxysilyl group. The silane coupling agent is, for example, a compound having at least one reactive silyl group and other substituents in one molecule, and specifically, β- (3,4 epylcyclohexyl) ethyltrimethoxy. Silane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ -Aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, isocyanate functional silane and the like can be mentioned, and one or more of these can be used.

Examples of other copolymerizable monomers copolymerizable with these monomers include, for example.
Amine group-containing monomers such as dimethylaminoethyl (meth) acrylate and dimethylaminopropyl (meth) acrylate;
Amide group-containing monomers such as (meth) acrylamide and ethyl (meth) acrylamide; nitrile group-containing monomers such as acrylonitrile;
Epoxy group-containing monomers such as glycidyl (meth) acrylate;
Aromatic vinyl monomers such as styrene, methylstyrene, chlorostyrene, vinyltoluene;
Sulfonic acid-containing vinyl monomers such as styrene sulfonic acid and vinyl sulfonic acid;
Acid anhydrides such as maleic anhydride and itaconic anhydride; chlorine-containing monomers such as vinyl chloride, vinylidene chloride and chloroprene;
Alkylene glycol monoallyl ethers such as ethylene glycol monoallyl ether, propylene glycol monoallyl ether, diethylene glycol monoallyl ether;
Vinyl ester-based monomers such as vinyl acetate and vinyl propionate;
Ethylene, propylene, isobutylene and the like can be used. These can be used alone or in combination of two or more. In addition, an ultraviolet absorber containing an ethylenically unsaturated double bond, a light stabilizer containing an ethylenically unsaturated double bond, and the like can also be used.

The amount of the silicon component in the silicon-modified acrylic resin emulsion is preferably 0.1 to 30% by weight (more preferably 0.2 to 10% by weight) in terms of _{SiO 2 in the solid content of the emulsion.} When the amount of the silicon component is in such a range, excellent performance is exhibited in the adhesion with the above-mentioned permeable water absorption preventing material, and the durability of the inorganic material can be enhanced.

The SiO ₂ conversion is expressed by the weight of the compound having a Si—O bond remaining _{as silica (SiO 2) when it is completely hydrolyzed and then calcined at 900 ° C.} In general, alkoxysilanes, silicates, etc. have the property of reacting with water to undergo a hydrolysis reaction to form silanol, and further causing a condensation reaction between silanols or silanol and alkoxy. When this reaction is carried out to the ultimate, it becomes _{silica (SiO 2).} These reactions are in the general formula,
RO (Si (OR) ₂ O) _n R + (n + 1) H ₂ O → nSiO ₂ + (2n + 2) ROH
It is expressed by the reaction formula. In the present invention, the amount of silicon component is converted based on this reaction formula.

Examples of the pigment include a pigment (a) having a refractive index of 2 or more, an average particle size of 0.1 to 2 μm, and a whiteness of 95 or more (hereinafter, also referred to as “component (a)”), a refractive index of less than 2, and an average particle size. Pigments (b) with a whiteness of 0.5 to 50 μm and a whiteness of 50 or more and less than 95 (hereinafter, also referred to as “component (b)”), pigments (c) other than the above (a) and (b) (hereinafter, “component (c)”). It is also called.).
Examples of the component (a) include titanium oxide, zinc oxide, aluminum oxide, magnesium oxide, hollow resin particles and the like.
Examples of the component (b) include extender pigments such as heavy calcium carbonate, precipitated calcium carbonate, kaolin, talc, clay, pottery clay, China clay, barium sulfate, barium carbonate, silica stone powder, and diatomaceous earth.

Examples of the component (c) include carbon black, lamp black, bone black, graphite, black iron oxide, copper chrome black, cobalt black, copper manganese iron black, red pepper, molybdate orange, permanent red, permanent carmine, and anthraquinone. Red, Perylene Red, Kinacridon Red, Yellow Iron Oxide, Titanium Yellow, First Yellow, Benzimidazolone Yellow, Chrome Green, Cobalt Green, Phthalocyanine Green, Ultramarine, Navy Blue, Cobalt Blue, Phthalocyanine Blue, Kinacridone Violet, Dioxazine Violet, etc. Color pigments are mentioned, and these particle sizes are preferably less than 50 μm (more preferably 40 μm or less, still more preferably 0.01 to 20 μm). In the present invention, one kind or two or more kinds selected from the above-mentioned component (a), component (b), and component (c) can be used.

The "refractive index" referred to here is a value measured using an Abbe refractometer. The "whiteness" is a comparison value by a white meter (Ket type phototube white clock) when the whiteness of magnesium oxide is 100 and the dark state is 0.

The covering material (I) is characterized in that the hiding rate of the formed film is 90% or more (preferably 93% or more, more preferably 95% or more). When the concealment rate is 90% or more, it is possible to easily and stably obtain the desired finish. In addition, it is possible to alleviate defects and contamination on the surface of the base material and enhance the aesthetic appearance. In this case, the color is preferably set to, for example, gray similar to concrete.

The reflectance of the formed coating film is determined by applying the covering material to the reflectance test paper with a film applicator (gap 150 μm), and in an environment of temperature 23 ° C. and humidity 50% (hereinafter referred to as “standard state”) for 24 hours. It is a value calculated by the following formula after measuring the visual reflectance of the test piece obtained by drying.
<Formula>
Concealment rate (%) = (visual reflectance of the coating film on the black ground) / (visual reflectance of the coating film on the white ground) × 100

Further, as the coating material (I), a material that forms a matte film is preferable. In this case, it is possible to easily form an exposed concrete-like pattern having excellent aesthetics.
The term "matte" as used herein includes not only what is generally called matte, but also what is called 3-minute gloss, 5-minute gloss, and the like. Specifically, in the present invention, the gloss can be defined by the mirror surface gloss. The mirror glossiness of the covering material (I) is preferably 40 or less (more preferably 20 or less, still more preferably 0.1 or more and 10 or less).

The "mirror glossiness" is a value measured according to JIS K5600-4-7 "mirror glossiness". Specifically, a coating material is applied to one side of a glass plate using a film applicator with a clearance of 150 μm, and the coated surface is placed horizontally and dried for 48 hours in a standard state. Mirror gloss (measurement angle 60 degrees) It is a value obtained by measuring.

The hiding rate and luster of the covering material (I) can be appropriately adjusted depending on the type, particle size, mixing ratio and the like of the pigment to be blended in the covering material. The covering material (I) preferably contains the above-mentioned component (a), component (b), and component (c). As a preferred embodiment of the pigment ratio in the covering material (I), the component (a) is added in an amount of 10 to 500 parts by weight (more preferably 30 to 300 parts by weight, still more preferably 50 parts by weight) with respect to 100 parts by weight of the solid content of the synthetic resin. ~ 250 parts by weight), 10 to 500 parts by weight of the component (b) (more preferably 30 to 300 parts by weight, still more preferably 50 to 250 parts by weight), and 0.1 to 50 parts by weight of the component (c). Parts (more preferably 0.5 to 20 parts by weight). In such a case, the texture of concrete can be easily obtained.

In addition to the above components, the coating material (I) of the present invention is, for example, a thickener, a wetting agent, an antifreeze agent, a film-forming auxiliary, an antiseptic, and an antifungal agent within a range that does not significantly impair the effects of the present invention. , Antifungal agent, antibacterial agent, dispersant, defoaming agent, resin, ultraviolet absorber, light stabilizer, antioxidant, catalyst and the like. Further, a synthetic resin emulsion other than the above can be included as the synthetic resin emulsion as long as the effect of the present invention is not significantly impaired. The covering material (I) can be produced by uniformly mixing each of the above-mentioned components by a conventional method.

In the second step, such a coating material (I) is uniformly applied to the base material. The application device is not particularly limited, and a known application device such as a brush, a spray, or a roller can be used. The required amount for coating the covering material may be appropriately set in consideration of the type and condition of the base material, but is preferably about 30 to 500 g / m ² (more preferably 80 to 200 g / m ² ). be. The coating material may be applied and dried preferably at room temperature.

<Third step>
In the present invention, as a third step, a specific covering material (II) can be applied to give a pattern. As a result, a natural pattern with random and subtle color tone changes can be obtained. The coating material (II) in the third step contains a synthetic resin and a pigment as essential components, and contains various additives as necessary.

In the coating material (II), the synthetic resin is not particularly limited, and for example, vinyl acetate resin, vinyl chloride resin, epoxy resin, acrylic resin, urethane resin, acrylic silicon resin, fluororesin and the like, or a composite system thereof and the like can be used. One or more of these can be used. Examples of such synthetic resins include water-soluble resins, water-dispersible resins, NAD-type resins, solvent-soluble resins, solvent-free resin types, and the like, and are not particularly limited to one-component type, two-component type, and the like. Can be done. In the present invention, a one-component type of a water-soluble resin and / or a water-dispersible resin is particularly preferable. Further, as the synthetic resin, the same material as the above-mentioned covering material (I) can also be used. As the pigment, the same pigment as the coating material (I) can be used.

The covering material (II) is characterized in that the hiding rate of the forming film is 90% or more (preferably 93% or more, more preferably 95% or more), and the color tone is different from that of the covering material (I). In such a case, various patterns can be formed by combining the color tones of the covering material (I) and the covering material (II), and a pattern layer having excellent aesthetics can be formed. Further, in the present invention, the color of the covering material (II) is preferably darker than that of the covering material (I). In such a case, a more natural pattern can be added. For example, when forming an exposed concrete pattern, the color of the covering material (II) is preferably a darker color than that of the covering material (I), and further is a gray color that is darker than that of the covering material (I). Etc. are preferable. The term "dark" as used herein means that the brightness value L ^* (CIE L ^* a ^* b ^* color space) is lower than that of the first coating material.

Further, as the coating material (II) of the present invention, a material that forms a matte film is preferable. In this case, a more natural pattern can be added. In particular, it is possible to easily form an exposed concrete pattern with excellent aesthetics. The mirror glossiness of the covering material (II) is preferably 40 or less (more preferably 20 or less, still more preferably 0.1 or more and 10 or less).

The hiding rate and luster of the covering material (II) can be appropriately adjusted depending on the type, particle size, mixing ratio and the like of the pigment to be blended in the covering material. The covering material (II) preferably contains the above-mentioned component (a), component (b), and component (c). As a preferred embodiment of the pigment ratio in the covering material (II), the component (a) is added in an amount of 10 to 500 parts by weight (more preferably 30 to 300 parts by weight, still more preferably 50 parts by weight) with respect to 100 parts by weight of the solid content of the synthetic resin. ~ 250 parts by weight), 10 to 500 parts by weight of the component (b) (more preferably 30 to 300 parts by weight, still more preferably 50 to 250 parts by weight), and 0.1 to 50 parts by weight of the component (c). Parts (more preferably 0.5 to 20 parts by weight). In such a case, the texture of concrete can be easily obtained.

In the third step, such a covering material (II) is applied to give a pattern. The coating device is not particularly limited as long as a pattern can be applied, and a known coating device such as a brush, a spray, or a roller can be used. However, in the present invention, the hardness and / or the hardness as shown in FIG. 1 and / or It is preferable that at least two or more liquid absorbing materials (FIGS. 1: 1a to 1e) having different densities are formed by a roller brush mixed on the outer peripheral surface of the cylinder (FIG. 1: 2). By using such a specific roller brush, it is possible to impart a continuously and subtly changing pattern peculiar to a concrete surface. In particular, when the outer peripheral surface of the cylinder has an uneven shape, a more natural pattern can be imparted. In the present invention, the outer diameter (FIG. 1: R) of the roller brush may be appropriately set according to a desired pattern, but is preferably 20 to 60 mm (more preferably 30 to 50 mm).

In the roller brush, examples of the liquid absorbing material mixed on the outer peripheral surface of the cylinder include felt, non-woven fabric, sponge material, and the like, and at least two or more kinds (preferably 3) having different hardness, density, or both of them. Use a mixture of seeds and above). In the present invention, it is preferable to use two or more kinds (preferably three or more kinds) of sponge materials in combination. The hardness of each liquid absorbing material is preferably 10 to 3000 N (more preferably 20 to 2000 N, still more preferably 30 to 1500 N), and the density is preferably 1 to 300 kg / m ³ (more preferably 3 to 200 kg / m ^3). , More preferably 5 to 150 kg / m ³ ). By using a roller brush in which such a liquid absorbing material is combined, it is possible to form a pattern corresponding to the degree of deformation of each liquid absorbing material, the transferability of the covering material, and the like. The "hardness" referred to here is a value of hardness (method C) measured from the force when the test piece is compressed to a thickness of 40% according to JIS K6400-2. The "density" is a value of apparent density calculated from the weight and dimensions of the test piece according to JIS K7222.

Further, the liquid absorbing material is preferably fixed so as to cover the outer peripheral surface of the cylinder, and at least two or more types (preferably three or more types) of liquid absorbing materials having different hardness and / or density are formed in the outer diameter direction of the cylinder (preferably three or more types). A form fixed so as to be stacked in FIG. 1: 3) is more preferable. Further, it is more preferable that a large number of liquid absorbing materials are compression-molded so as to be randomly mixed in the outer peripheral direction and the outer diameter direction. By using a roller brush having such a liquid absorbing material, the effect of the present invention can be enhanced.

The liquid absorbing material has a three-dimensional shape having an irregular outer shape, and its individual size is preferably 1 to 30 mm (more preferably 2 to 20 mm). Such liquid absorbing materials gather to form a liquid absorbing material. In the present invention, it is preferable that a large number of liquid absorbing materials having different sizes are mixed. In such a case, liquid absorbing materials having different sizes in addition to hardness and / or density are randomly mixed on the outer peripheral surface of the cylinder, so that the effect of the present invention can be further enhanced. Since irregular irregular shapes are likely to be formed between the liquid absorbing materials, the effect of the present invention can be further enhanced. The "size" referred to here is the longest axis of the outer shape, and is measured by sieving with a sieve having squares having a predetermined dimension on one side, for example. The thickness of the liquid absorbing liquid fixed to the outer peripheral surface of the cylinder is preferably 50 mm or less (more preferably 1 to 30 mm, still more preferably 2 to 15 mm), although it depends on the size of each liquid absorbing liquid. Further, in the present invention, it is preferable to provide an uneven pattern on the outer peripheral surface of the liquid absorbing liquid according to a desired pattern. Examples of the method of providing the uneven shape include a method of embossing at the time of compression molding of the liquid absorbing material, a method of partially removing the compression molded liquid absorbing material, and the like. Thereby, the effect of the present invention can be further enhanced. When the compression-molded liquid absorbing material is partially removed, a random uneven shape can be easily obtained by a known method such as picking or crushing.

In the third step of the present invention, the coating material (II) is preferably applied after the coating material (I) is dried. As a result, a highly aesthetically pleasing finish can be stably obtained. Further, in this case, it is preferable to roll and apply the roller brush to the entire surface of the layer formed by the coating material (I) (hereinafter, also referred to as “coating layer (I)”). The coating with the amount, the coating material is preferably less than the coating with the amount (I), preferably 0.005~0.3kg / ^{m 2} (more preferably 0.01~0.2kg ^{/ m} 2) Is. Within such a required amount, it is possible to apply the coating in a plurality of times. In such a case, a natural pattern having a random and subtle color tone change can be formed while utilizing the color tone of the coating layer (I), which is advantageous in terms of improving the aesthetic appearance.
The coating material (II) may be applied and dried preferably at room temperature.

In the film forming method of the present invention, it is also possible to repair a dent (hereinafter referred to as a “dent”) due to a cone mark after the second step or the third step. The dents are repaired by applying a covering material darker than the color tone of the covering material (I) (preferably a covering material darker than the color tone of the covering material (I) and the covering material (II)) with a brush or the like. Is desirable. As a result, a feeling of shadow is given to the depression.

In the film forming method of the present invention, a clear layer can be provided after the third step, if necessary. By providing a clear layer, not only the weather resistance is improved, but also the color tones of the covering material (I) and the covering material (II) are more harmonized, and the color tones are continuously and slightly changed (further, the shades). It is possible to enhance the texture peculiar to the concrete surface having. Such a clear layer can be formed of, for example, a clear coating material having an acrylic resin, a urethane resin, an epoxy resin, an acrylic silicon resin, a fluororesin or the like as a binder. The clear coating material may be water-based or solvent-based, matte type or glossy type. Further, the clear coating material is preferably a low-contamination type. Furthermore, coloring is possible as long as the effect of the present invention is not impaired. The clear dressing is preferably applied to the entire surface. As the coating method, various methods such as brush coating, spray coating, and roller coating can be adopted. The coating amount is preferably 0.01 to 0.5 kg / m ² (more preferably 0.05 to 0.4 kg / m ² ). Within the range of such a coating amount, it is possible to apply the coating in a plurality of times.

A test example is shown below to clarify the features of the present invention.
[Permeable water absorption preventive material]
-Permeable water absorption inhibitor A (mixture of hexyltrimethoxysilane and aliphatic hydrocarbon solvent, weight ratio 3:97)
-Permeable water absorption inhibitor B (mixture of hexyltrimethoxysilane and aliphatic hydrocarbon solvent, weight ratio 12:88)
-Permeable water absorption inhibitor C (mixture of hexyltrimethoxysilane, soluble acrylic resin, aliphatic hydrocarbon solvent, weight ratio 3:25:72)

[Coating material (I)]
・ Covering material (IA)
Synthetic resin emulsion A 100 parts by weight, white pigment A 70 parts by weight, extender pigment A 20 parts by weight, extender pigment B 30 parts by weight, coloring pigment 0.8 parts by weight, film-forming aid 4 parts by weight, ultraviolet absorber 0.2 parts by weight, ^{A coating material (IA) (gray, L *} = 76, glossiness 1.8) was produced by uniformly mixing and stirring 0.1 part by weight of the defoaming agent and 10 parts by weight of water.

-Coating material (IB) to (IP)
Based on the formulations shown in Tables 1 and 2, the covering materials (IB) to (IP) were produced by the same method as the covering material (IA).

[Coating material (II)]
・ Covering material (II-A)
70 parts by weight of white pigment A, 20 parts by weight of extender pigment A, 30 parts by weight of extender pigment B, 0.8 parts by weight of coloring pigment, 4 parts by weight of film-forming aid, 0.2 parts by weight of ultraviolet absorber with respect to 100 parts by weight of synthetic resin emulsion C. ^{A coating material (II-A) (gray, L *} = 71, glossiness 1.8) was produced by mixing and stirring a portion, 0.1 part by weight of a defoaming agent, and 10 parts by weight of water by a conventional method. ..

-Coating material (II-B) to (II-G)
Based on the formulation shown in Table 3, the covering materials (II-B) to (II-G) were produced by the same method as the covering material (II-A).

The following raw materials were used.
-Synthetic resin emulsion A: Silicon-modified acrylic resin emulsion (cyclohexylmethacrylate, methylmethacrylate, 2-ethylhexylacrylate, γ-methacryloyloxypropyltrimethoxysilane copolymer methyltrimethoxysilane adduct, cyclohexylmethacrylate content in solid content 20% by weight, silicon component amount in solid content 2% by weight, solid content 50% by weight, Tg 32 ° C., average particle diameter 78 nm)
-Synthetic resin emulsion B: Silicon-modified acrylic resin emulsion (t-butyl methacrylate, cyclohexyl methacrylate, methyl methacrylate, 2-ethylhexyl acrylate, γ-methacryloyloxypropyltrimethoxysilane copolymer methyltrimethoxysilane adduct, in solid content T-Butyl methacrylate content 10% by weight, cyclohexyl methacrylate content in solid content 10% by weight, silicon component content in solid content 2% by weight, solid content 50% by weight, Tg 38 ° C., average particle size 75 nm)
-Synthetic resin emulsion C: Silicon-modified acrylic resin emulsion (cyclohexylmethacrylate, methylmethacrylate, 2-ethylhexylacrylate, γ-methacryloyloxypropyltrimethoxysilane copolymer methyltrimethoxysilane adduct, cyclohexylmethacrylate content in solid content 20% by weight, silicon component amount in solid content 2% by weight, solid content 50% by weight, Tg 50 ° C., average particle size 72 nm)

-Synthetic resin emulsion D: Silicon-modified acrylic resin emulsion (cyclohexylmethacrylate, methylmethacrylate, 2-ethylhexylacrylate, γ-methacryloyloxypropyltrimethoxysilane copolymer methyltrimethoxysilane adduct, cyclohexylmethacrylate content in solid content 20% by weight, silicon component amount in solid content 8% by weight, solid content 50% by weight, Tg 36 ° C., average particle diameter 75 nm)
-Synthetic resin emulsion E: Silicon-modified acrylic resin emulsion (cyclohexylmethacrylate, methylmethacrylate, 2-ethylhexylacrylate, γ-methacryloyloxypropyltrimethoxysilane copolymer methyltrimethoxysilane adduct, cyclohexylmethacrylate content in solid content 6% by weight, silicon component amount in solid content 2% by weight, solid content 50% by weight, Tg 32 ° C., average particle diameter 78 nm)
-Synthetic resin emulsion F: Silicon-modified acrylic resin emulsion (cyclohexylmethacrylate, methylmethacrylate, 2-ethylhexylacrylate, γ-methacryloyloxypropyltrimethoxysilane copolymer methyltrimethoxysilane adduct, cyclohexylmethacrylate content in solid content 20% by weight, silicon component amount in solid content 2% by weight, solid content 50% by weight, Tg 12 ° C., average particle size 72 nm)
-Synthetic resin emulsion G: Silicon-modified acrylic resin emulsion (cyclohexylmethacrylate, methylmethacrylate, 2-ethylhexylacrylate, γ-methacryloyloxypropyltrimethoxysilane copolymer methyltrimethoxysilane adduct, cyclohexylmethacrylate content in solid content 20% by weight, silicon component amount in solid content 2% by weight, solid content 50% by weight, Tg 32 ° C., average particle size 130 nm)

-Synthetic resin emulsion H: Acrylic resin emulsion (cyclohexyl methacrylate, methyl methacrylate, 2-ethylhexyl acrylate copolymer, cyclohexyl methacrylate content in solid content 20% by weight, solid content 50% by weight, Tg 32 ° C., average particle diameter 80 nm)
-Synthetic resin emulsion I: Acrylic resin emulsion (methylmethacrylate / 2-ethylhexyl acrylate copolymer, solid content 50% by weight, Tg 32 ° C., average particle size 80 nm)

-White pigment A: titanium oxide (whiteness 97, refractive index 2.71, average particle diameter 0.3 μm)
-Constituent pigment A: talc (whiteness 60, refractive index 1.57, average particle size 4 μm)
-Constituent pigment B: Kaolin (whiteness 80, refractive index 1.56, average particle size 6 μm)
-Constituent pigment C: Heavy calcium carbonate (whiteness 89, refractive index 1.56, average particle size 36 μm)
-Constituent pigment D: clay (whiteness 92, refractive index 1.55, average particle size 4 μm)
-Constituent pigment E: Silica stone powder (whiteness 90, refractive index 1.54, average particle size 18 μm)
-Constituent pigment F: diatomaceous earth (whiteness 88, refractive index 1.46, average particle size 30 μm)
・ Color pigment: carbon black

(Measurement of concealment rate)
The covering materials (IA) to (IP) and the covering materials (II-A) to (II-G) are each applied to a reflectance test paper with a film applicator (gap 150 μm), and the temperature is 23. A black ground coating film and white were used for a test piece obtained by drying for 24 hours in an environment of 50% temperature and 50% humidity (hereinafter referred to as "standard state") using a color difference meter "CR-300" (manufactured by Minolta Co., Ltd.). The visual reflectance of the ground coating film was measured, and the concealment rate was calculated from these. The results are shown in Tables 1-3.

( Test Examples 1 to 16, Comparative Examples 1 to 3)
As the first step, a permeable water absorption preventive material is brushed over the entire surface of a partially deteriorated concrete base material at a required amount of 200 g / m ² , and under standard conditions (temperature 23 ° C., relative humidity 50%). It was dried for 16 hours. Next, as a second step, the covering material (I) ^{was brushed over the entire surface at a required amount of 100 g / m 2} , dried in a standard state for 24 hours, side-cured, and then dried for another 14 days to prepare a test piece. Was evaluated. The combination of the permeable water absorption preventing material and the covering material (I) and the results are shown in Table 4.

-Water absorption prevention test The test piece was fixed vertically, and water was continuously sprinkled on the test piece for 60 minutes using a hose, and the color change at that time was observed. The evaluation criteria were "◎" for those with no color change before and after the test, "○" for those with almost no color change, "△" for those with almost no color change, and significant color change. Those recognized were marked as "x".

The adhesion of the test piece after the water absorption prevention test was evaluated by a cross-cut method according to JIS K 5600-5-6. The evaluation criteria are "◎" for those with a defect area of 5% or less, "○" for those with a defect area of more than 5% and 20% or less, and "△" for those with a defect area of more than 20% and within 35%. , Those with a defect area of more than 35% were marked with "x".

-Durability test The test piece was repeatedly heated and cooled in a cycle of 18 hours in water (20 ° C.) → 3 hours at -20 ° C. → 3 hours at 50 ° C. for a total of 10 cycles. Then, the adhesion was evaluated by a cross-cut method according to JIS K 5600-5-6. The evaluation criteria are "◎" for those with a defect area of 5% or less, "○" for those with a defect area of more than 5% and 20% or less, and "△" for those with a defect area of more than 20% and within 35%. , Those with a defect area of more than 35% were marked with "x".

-The appearance of the aesthetically formed coating film is "◎" if the deteriorated part of the concrete base material is not visible at all and has a finish (pattern) similar to the texture of the concrete surface, the deteriorated part of the concrete base material, etc. The one with excellent aesthetics that is not visible at all is marked with "○", and the one with visible deteriorated parts is marked with "×".

( Test Example 17)
After the coating material (IA) of Test Example 1 is dried, as a third step, the coating material (II-A) is applied in an amount of 70 g / m ² , and the hardness and / or density is different as shown in FIG. Roller brush 1 (outer diameter 45 mm, liquid absorption thickness 2) having a mixture of sponge materials 1 to 5 (each sponge material is an amorphous solid satisfying a size of 2 to 18 mm) and having a random uneven shape on the outer peripheral surface of the cylinder. 10 mm) was applied, dried in a standard state for 24 hours, side-cured, and then dried for another 14 days to prepare a test piece, and the same evaluation as in Test Example 1 was performed.
-Sponge material 1: Hardness 45-60N, density 50-100kg / m ³
-Sponge material 2: Hardness 75 to 110 N, density 15 to ^{30 kg / m 3}
-Sponge material 3: Hardness 110-140 N, density 15-50 kg / m ³
-Sponge material 4: hardness 110-300N, density 30-85kg / m ³
-Sponge material 5: hardness 10-12 kN, density 5-15 kg / m ³

( Test Example 18)
The covering material (II-A) of Test Example 17 is a mixture of three types of sponge materials 2 to 4 having different hardness and / or density (each sponge material is an amorphous solid having a size of 2 to 18 mm) and is cylindrical. A test piece was prepared in the same manner as in Test Example 17 except that the outer peripheral surface was coated with a roller brush 2 (outer diameter 45 mm, liquid absorbing liquid thickness 2 to 10 mm) having a random uneven shape, and the same evaluation was performed. .. The results are shown in Table 5.

( Test Example 19 to Test Example 23, Comparative Example 4)
Dressing of Test Example 17 (I-A), in place of the coating material (II-A), but using coating material shown in Table 5 (I) and the coating material of (II), in the same manner as in Test Example 17 A test piece was prepared and the same evaluation was performed. The results are shown in Table 5.

Appearance of film formed by Test Example 17 Test Example 23, as compared with Comparative Example 4, was a good finish that approximates the texture of the concrete surface. Among them, Test Examples 17 to 21 had an excellent finish.

( Test Example 24)
A clear coating material (water-based acrylic silicone resin clear, matte type) was further applied on the film formed by Test Example 17 with a wool roller so as to ^{have an application amount of 100 g / m 2, and a film was formed.} The appearance of the formed film was even better than that of Test Example 17.

Claims (4)

It is a film forming method for inorganic materials.
For the surface of inorganic materials
After applying a silane-based permeable water absorption inhibitor as the first step,
As a second step, a coating material (I) containing a synthetic resin emulsion and a pigment and having a hiding ratio of 90% or more of the formed film is applied.
As a third step, a coating material (II) containing a synthetic resin and a pigment and having a color tone different from that of the coating material (I) is applied to give a pattern.
The silane-based permeable water absorption inhibitor contains an alkylalkoxysilane compound having an alkyl group having 1 to 18 carbon atoms and does not contain a silicon-based resin.
The synthetic resin emulsion of the coating material (I) contains (meth) acrylic acid alkyl ester as a monomer constituting the synthetic resin, in which the glass transition temperature of the homopolymer is 50 ° C. or higher and the solubility parameter is 9.5 or lower. ,
The coating material (II) is a film forming method, characterized in that at least two or more kinds of liquid absorbing materials having different hardness and / or density are applied by a roller brush mixed on the outer peripheral surface of a cylinder. The film forming method according to claim 1, wherein the synthetic resin emulsion of the coating material (I) has a glass transition temperature of 10 to 60 ° C. The film forming method according to claim 1 or 2, wherein the synthetic resin emulsion of the coating material (I) has an average particle size of 120 nm or less. The film forming method according to any one of claims 1 to 3, wherein the synthetic resin emulsion of the coating material (I) is a silicon-modified acrylic resin emulsion.

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