JP2017074578A - Method of forming coating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of forming a coating film which can provide excellent water absorption inhibiting property, durability, and aesthetic appearance or the like to an inorganic material.SOLUTION: In a method of forming a coating film, a permeable water absorption inhibitor is applied to a surface of an inorganic material as a first process. Then, as a second process, a coating material (I), which contains synthetic resin emulsion and pigment and of which a contrast ratio a formed film is 90% or higher, is applied. The synthetic resin emulsion contains (meth)acrylic acid alkyl ester of which a glass transition temperature is 50°C or higher and a solubility parameter is 9.5 or less as a monomer for constituting a synthetic resin.SELECTED DRAWING: None

Description

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

  As a method of imparting water absorption prevention and improving durability to inorganic materials such as concrete and cement mortar, which are conventionally used as base materials for buildings and civil engineering structures, a permeable water absorption prevention material is applied. This method is widely used.

  The permeable water absorption preventing material penetrates into an inorganic material to form a water repellent layer. Therefore, by applying such a permeable water absorption preventive material, the intrusion of water, carbon dioxide, etc. from the outside to the base material is blocked, and the strength reduction due to the neutralization of the base material is prevented. An effect of suppressing corrosion of steel frames or reinforcing bars existing inside can be exhibited. It is also possible to prevent the occurrence of efflorescence on the surface 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, there are cases where sufficient water repellency, water absorption preventing property, etc. cannot be obtained only by applying such a permeable water absorption preventing material, and there is room for practical improvement.

  In Patent Document 2, a solvent-based water-repellent waterproofing material (priming material) is applied to the concrete surface, and a waterproofing material (intermediate coating material) made of an emulsion-based transparent synthetic resin is applied to the surface. A method of applying (overcoating material) is described. According to such a method, it is expected that the water absorption preventing property on the concrete surface is improved and the durability is enhanced.

  However, in the method of Patent Document 2, the adhesion of the emulsion waterproof material becomes insufficient, and there is a possibility that desired effects cannot be obtained in terms of water absorption prevention and durability. Moreover, in the method of the said patent document, when malfunctions, such as contamination, have arisen on the inorganic material surface, there exists a possibility that these malfunctions may become conspicuous.

JP-A 63-256581 JP 2002-89006 A

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

  In order to solve such problems, the present inventors have intensively studied and have come up with a method of applying a specific covering material as the second step after applying the permeable water absorption preventing material as the first step. The present invention has been completed.

That is, the film forming method of the present invention has the following characteristics.
1. A method of forming a film on an inorganic material,
For the surface of inorganic material,
After applying the permeable water absorption prevention material as the first step,
As a second step, a coating material (I) containing a synthetic resin emulsion and a pigment, and having a concealment rate of the formed film of 90% or more, is applied,
The synthetic resin emulsion is a monomer constituting the synthetic resin,
A method for forming a film, comprising a (meth) acrylic acid alkyl ester having a glass transition temperature of a homopolymer of 50 ° C. or more and a solubility parameter of 9.5 or less.
2. The synthetic resin emulsion has a glass transition temperature of 10 to 60 ° C. The film formation method of description.
3. The synthetic resin emulsion has an average particle size of 120 nm or less. Or 2. The film formation method of description.
4). The synthetic resin emulsion is a silicon-modified acrylic resin emulsion. ~ 3. The film forming method according to any one of the above.
5). As a third step, a pattern is imparted by applying a coating material (II) containing a synthetic resin and a pigment, having a concealment rate of the formed coating of 90% or more and having a color tone different from that of the coating material in the second step. Features 1. ~ 4. The film forming method according to any one of the above.

  In the film forming method of the present invention, a coating material (I) containing a specific synthetic resin emulsion and a pigment is applied as the second step after applying the permeable water absorption preventing material as the first step on the surface of the inorganic material. By coating, it is possible to form a film that imparts excellent water absorption prevention, durability, aesthetics and the like to the inorganic material.

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

1. Liquid absorbing material (1a to 1e)
2. 2. Cylindrical outer peripheral surface Cylindrical outer diameter direction

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

The film forming method of the present invention forms a film by applying a specific coating material (I) as a second step after applying a permeable water absorption preventing material as a first step on the surface of an inorganic material. It is.
<Inorganic material>
Inorganic materials constitute surfaces of buildings, civil engineering structures, and the like. Examples of such a substrate include concrete, mortar, siding board, extruded board, gypsum board, pearlite board, brick, and tile. These substrates may be those having a 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 hardened and demolded by pouring the concrete, which is obtained by mixing and mixing cement, water, aggregates, and admixtures in an appropriate ratio, into the formwork or at a predetermined place. It is obtained by this. The present invention can be applied to either a newly provided concrete surface or a concrete surface that has deteriorated over time.

In the present invention, prior to the first step, the inorganic material can be subjected to a treatment such as washing. For the cleaning treatment, a method of washing with water after applying various cleaning agents to the inorganic material may be employed.

<First step>
The permeable water absorption preventive material in the first step in the present invention can be used without particular limitation as long as it is a material capable of exhibiting a water absorption preventive effect. For example, silicone resin, acrylic resin, urethane resin, unsaturated polyester resin, etc. are mainly used. Resin-based water-absorbing material containing resin as a component; Silicone-based water-absorbing material containing an alkylsiliconate compound as a main component; Silane-based water-absorbing material containing a hydrolyzable silane compound and / or its condensate as a main component Materials, etc. In the present invention, a silane-based water-absorbing material can be preferably used. Examples of the silane-based permeable water absorption preventing material include organoalkoxysilane compounds, organoacetoxysilane compounds, organohalogensilane compounds, organodisilane compounds, organosilanecarboxylic acid compounds, organosilanethiol compounds, organosilicon isocyanate compounds, and organosilicones. The thing containing 1 or more types chosen from an isothianate compound or these condensates is mentioned.

The permeable water absorption preventing material is a solution in which the above-described components are dissolved or dispersed in a medium, and may be dispersed by an emulsifier or the like. The medium in the permeable water absorption preventing material is not particularly limited, and is a strong solvent system mainly containing an aromatic hydrocarbon solvent, a weak solvent system mainly containing an aliphatic hydrocarbon solvent, and water as a main ingredient. Various forms such as an aqueous system can be used, but a weak solvent system can be preferably used in the present invention. In addition, the solvent used as a main component should just be contained 50weight% or more (preferably 70 weight% or more) in each medium.

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

Particularly in the present invention, 0.1 to 50% by weight (more preferably 1 to 30% by weight, still more preferably 2 to 20%) of an alkylalkoxysilane compound having 1 to 18 carbon atoms in the alkyl group as the main component compound. (% By weight) are preferred. Such an alkylalkoxysilane compound is a compound in which an alkyl group and an alkoxysilyl group are bonded to a silicon atom. 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, pentyltrimethoxysilane, pentyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, nonyltrimethoxy Silane, nonyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, undecyltrimethoxysilane, undecyltrie Xysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, tridecyltrimethoxysilane, tridecyltriethoxysilane, tetradecyltrimethoxysilane, tetradecyltriethoxysilane, pentadecyltrimethoxysilane, pentadecyltriethoxysilane, hexadecyl Examples include trimethoxysilane, hexadecyltriethoxysilane, heptadecyltrimethoxysilane, heptadecyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, and the like. As these condensates, those having an average degree of condensation of about 1 to 10 can be used. These can be used alone or in combination of two or more.

As the alkylalkoxysilane compound, those having ¹ to 18 carbon atoms (preferably 3 to 12, more preferably 5 to 8) of the alkyl group R ¹ are used. The alkyl group may be partially substituted with halogen or the like. If the carbon number of the alkyl group is within such a range, it is possible to improve water absorption prevention. The alkoxyl group in the alkoxysilane compound, the number of carbon atoms (number of carbon atoms in the R ²⁾ may be used those having 1 to 8 (preferably 1 to 4, more preferably 1 to 2).

  In such a permeable water absorption preventive material, it is desirable that the resin component is not mixed so much and the content ratio is lower than that of the alkylalkoxysilane compound in order to sufficiently exert the action of the alkylalkoxysilane compound. The content ratio of the resin component (solid content) in the permeable water absorption preventing material is preferably less than 20% by weight (more preferably 10% by weight or less), and a form not including the resin component is also suitable.

  The osmotic water absorption preventive material is, for example, a colorant, a thickener, a wetting agent, an antifreezing agent, an antiseptic agent, an antifungal agent, an antialgae agent, an antibacterial agent, and a dispersant, as long as the effects of the present invention are not significantly impaired. , An antifoaming agent, a resin, an ultraviolet absorber, an antioxidant, a catalyst, and the like may be included. The permeable water absorption preventing material can be produced by uniformly mixing the above-described components by a conventional method.

In the first step, such a permeable water absorption preventing material is uniformly applied to the substrate. The applicator is not particularly limited, and known applicators such as brushes, sprays, rollers, and coaters can be used. The required amount when applying the permeable water absorption preventing material may be appropriately set in consideration of the type and state of the base material, but is preferably 30 to 500 g / m ² (more preferably 80 to 400 g / m). ² ) About. Application and drying of the permeable water absorption preventing material are preferably performed at room temperature (0 to 40 ° C.). In the present invention, after the permeable water absorption preventing material is dried, the next coating can be performed. The interval between the 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 more (preferably 60 to 120 ° C.) as a monomer constituting the synthetic resin, and a solubility parameter (hereinafter referred to as “Tg”). (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-described permeable water absorption preventing material, and to improve 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 (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, for example, 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). The glass transition temperature of the homopolymer can be measured by DSC (differential scanning calorimeter). Further, the solubility parameter is described in “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) is 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. When it is in such a range, the performance which was excellent in adhesiveness with the above-mentioned permeable water absorption preventive material can be exhibited, and durability etc. of an inorganic material can be improved.

Moreover, the glass transition temperature of a synthetic resin emulsion can be adjusted by selecting the kind of monomer, a mixing ratio, etc. The glass transition temperature may be appropriately set in consideration of 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. In addition, the glass transition temperature of a synthetic resin emulsion can be calculated | required with the formula of Fox.

  Furthermore, 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 diameter 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. For example, an acrylic resin emulsion, an epoxy-modified acrylic resin emulsion, a urethane-modified acrylic resin emulsion, a silicon-modified acrylic resin emulsion, a fluorine-modified acrylic resin An emulsion, etc., or these composite systems etc. are mentioned, These 1 type (s) or 2 or more types 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 using a reactive silyl group-containing compound as an essential component. By using a silicone-modified acrylic resin emulsion, adhesion, durability, etc. can be improved, and furthermore, a coating film with good contamination resistance, weather resistance, yellowing resistance, water resistance, chemical resistance, etc. can be formed. Can do.

In the present invention, as the silicone-modified acrylic resin emulsion, for example, one containing the above component (A) as a monomer component and further satisfying any one of the following conditions (1) to (4) is preferable.
(1) Synthetic resin emulsion containing a reactive silyl group-containing monomer as a monomer component (2) As a monomer component, at least one monomer selected from a reactive silyl group-containing monomer, a hydroxyl group-containing monomer, and a carboxyl group-containing monomer is included A synthetic resin emulsion obtained 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) 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, and the like.

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

The reactive silyl group-containing monomer in the above (1) and (2) is a compound containing a reactive silyl group and a polymerizable double bond. 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 Methoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, vinylmethyldimethoxysilane, methyldimethoxysilyl ester Vinyl ether, and methyl dimethoxy silyl propyl vinyl ether and the like, can be used one or two or more thereof.

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. These 1 type (s) or 2 or more types 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, one or two of these. The above can be used.

As the silane compounds in the above (2) and (4), those having two or more reactive silyl groups in one molecule are used. For example, tetrafunctional alkoxy such as tetraethoxysilane, tetramethoxysilane, tetrabutoxysilane, etc. Silanes: methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltributoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltri Trifunctional alkoxysilanes such as ethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, and phenyltributoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldibutoxysilane, and diethyl Dimethoxysilane, diethyldiethoxysilane, dipropyldimethoxysilane, dipropyldiethoxysilane, dibutyldimethoxysilane, dibutyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldibutoxysilane, methylphenyldimethoxysilane, methylphenyldi Bifunctional alkoxysilanes such as ethoxysilane; tetrachlorosilane, methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, phenyltrichlorosilane, vinyltrichlorosilane, dimethyldichlorosilane, diethyldichlorosilane, diphenyldichlorosilane, methylphenyldichlorosilane, etc. Chlorosilanes: tetraacetoxysilane, methyltriacetoxysilane, phenyltriacetate Shishiran, dimethyldiacetoxysilane, acetoxy silanes such as diphenyl diacetoxy silane and the like, can be used one or two or more thereof. Moreover, the compound which has one reactive silyl group in 1 molecule can also be used together.

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-epoxycyclohexyl) 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:
Amino 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 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 ethylenically unsaturated double bond-containing ultraviolet absorber, an ethylenically unsaturated double bond-containing light stabilizer, and the like can also be used.

The silicon component amount 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, it is possible to exhibit excellent performance in adhesion with the above-described permeable water absorption preventing material, and to improve the durability and the like of the inorganic material.

The term “SiO ₂ conversion” refers to the weight remaining as silica (SiO ₂ ) when the compound having a Si—O bond is completely hydrolyzed and then baked at 900 ° C. In general, alkoxysilanes, silicates, and the like have the property of reacting with water to cause hydrolysis reaction to form silanol, and further causing condensation reaction between silanols or silanol and alkoxy. When this reaction is performed to the ultimate, silica (SiO ₂ ) is obtained. These reactions have 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 equation.

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. Pigment (b) having a whiteness of 50 to less than 95 (hereinafter also referred to as “component (b)”), pigment (c) other than the above (a) and (b) (hereinafter referred to as “component (c)”) ")").
Examples of the component (a) include titanium oxide, zinc oxide, aluminum oxide, magnesium oxide, and hollow resin particles.
Examples of the component (b) include heavy pigments such as heavy calcium carbonate, precipitated calcium carbonate, kaolin, talc, clay, porcelain clay, china clay, barium sulfate, barium carbonate, quartzite 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, brown, molybdate orange, permanent red, permanent carmine, anthraquinone. Red, perylene red, quinacridone red, yellow iron oxide, titanium yellow, first yellow, benzimidazolone yellow, chrome green, cobalt green, phthalocyanine green, ultramarine, bitumen, cobalt blue, phthalocyanine blue, quinacridone violet, dioxazine violet, etc. A color pigment is mentioned, These particle diameters are preferably less than 50 micrometers (more preferably 40 micrometers or less, still more preferably 0.01-20 micrometers). In this invention, the 1 type (s) or 2 or more types chosen from the said (a) component, (b) component, (c) component can be used.

Here, the “refractive index” is a value measured using an Abbe refractometer. The “whiteness” is a comparison value obtained 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 formed film has a concealment ratio of 90% or more (preferably 93% or more, more preferably 95% or more). When the concealment rate is 90% or more, it is possible to obtain a desired finish easily and stably. In addition, it is possible to alleviate defects on the surface of the base material, contamination, etc., and improve aesthetics. The color in this case is preferably set to, for example, gray that approximates concrete.

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

Further, as the covering material (I), a material that forms a matte film is preferable. In this case, it is possible to easily form a concrete exposed tone pattern with excellent aesthetics.
The “matte” referred to here includes not only what is generally called matte but also what is called three-minute gloss, five-minute gloss, and the like. Specifically, in the present invention, the gloss can be defined by the specular gloss. The specular glossiness in the coating material (I) is preferably 40 or less (more preferably 20 or less, still more preferably 0.1 or more and 10 or less).

  The “specular gloss” is a value measured according to JIS K5600-4-7 “specular gloss”. 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 specular gloss when the coated surface is horizontally placed and dried for 48 hours in a standard state (measurement angle 60 degrees). Is a value obtained by measuring.

The concealment rate and gloss in the coating material (I) can be appropriately adjusted depending on the type, particle diameter, mixing ratio, and the like of the pigment to be blended in the coating material. In covering material (I), what contains said (a) component, (b) component, and (c) component is preferable. As a preferable aspect of the pigment ratio in the coating material (I), 10 to 500 parts by weight (more preferably 30 to 300 parts by weight, more preferably 50 parts by weight) of the component (a) 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 (more preferably 30 to 300 parts by weight, more preferably 50 to 250 parts by weight) of the component (b), and 0.1 to 50 parts by weight of the component (c). Part (more preferably 0.5 to 20 parts by weight). In such a case, it is easy to obtain a concrete texture.

  In addition to the above components, the coating material (I) of the present invention is, for example, a thickener, a wetting agent, an antifreezing agent, a film-forming aid, a preservative, and an antifungal agent within a range that does not significantly impair the effects of the present invention. , An algae inhibitor, an antibacterial agent, a dispersant, an antifoaming agent, a resin, an ultraviolet absorber, a light stabilizer, an antioxidant, a catalyst, and the like. Moreover, as long as the effect of this invention is not impaired remarkably, synthetic resin emulsions other than the above can also be included as a synthetic resin emulsion. Coating | covering material (I) can be manufactured by mixing each above-mentioned component uniformly by a conventional method.

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

<Third step>
In the present invention, as the third step, a specific coating material (II) can be applied to give a pattern. As a result, a natural pattern having a random and subtle color change 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 covering material (II), the synthetic resin is not particularly limited, and examples thereof include vinyl acetate resin, vinyl chloride resin, epoxy resin, acrylic resin, urethane resin, acrylic silicon resin, fluororesin, or a composite system thereof. And 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. Can do. In the present invention, a one-component type of a water-soluble resin and / or a water-dispersible resin is particularly preferable. In addition, the same synthetic resin as the coating material (I) can be used. As the pigment, those similar to the above-mentioned coating material (I) can be used.

The covering material (II) has a concealment ratio of the formed film of 90% or more (preferably 93% or more, more preferably 95% or more), and has a color tone different from that of the covering material (I). In such a case, various patterns can be formed by combining the color tone of the coating material (I) and the coating material (II), and a pattern layer having excellent aesthetics can be formed. In the present invention, the color of the covering material (II) is preferably darker than the covering material (I). In such a case, a more natural pattern can be given. For example, in the case of forming a concrete exposed tone pattern, the color of the covering material (II) is preferably darker than the covering material (I), and further, the gray color is darker than the covering material (I). Etc. are preferably set. Here, “dark” means that the lightness value L ^* (CIE L ^* a ^* b ^* color space) is lower than that of the first covering 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 given. In particular, it is possible to easily form a concrete exposed tone pattern with excellent aesthetics. The specular gloss in the coating material (II) is preferably 40 or less (more preferably 20 or less, still more preferably 0.1 or more and 10 or less).

The concealment rate and gloss in the coating material (II) can be appropriately adjusted depending on the type of pigment to be blended in the coating material, the particle diameter, the mixing ratio and the like. In covering material (II), what contains said (a) component, (b) component, and (c) component is preferable. As a preferable aspect of the pigment ratio in the coating material (II), 10 to 500 parts by weight (more preferably 30 to 300 parts by weight, more preferably 50 parts by weight) of the component (a) 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 (more preferably 30 to 300 parts by weight, more preferably 50 to 250 parts by weight) of the component (b), and 0.1 to 50 parts by weight of the component (c). Part (more preferably 0.5 to 20 parts by weight). In such a case, it is easy to obtain a concrete texture.

  In the third step, such a covering material (II) is applied to give a pattern. The applicator is not particularly limited as long as it can give a pattern, and a known applicator such as a brush, a spray, or a roller can be used. In the present invention, hardness and / or as shown in FIG. It is preferable that at least two or more types of liquid-absorbing materials (FIGS. 1: 1a to 1e) having different densities are formed by a roller brush mixed on the cylindrical outer peripheral surface (FIG. 1: 2). By using such a specific roller brush, it is possible to impart a continuous and subtly changing pattern peculiar to the concrete surface. In particular, when the cylindrical outer peripheral surface has an uneven shape, a more natural pattern can be given. In the present invention, the outer diameter of the roller brush (FIG. 1: R) may be appropriately set according to the 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 of these having different hardness or density (preferably 3 Mix more than seed). In the present invention, it is preferable to use a combination of two or more (preferably three or more) sponge materials. The hardness of each liquid absorbing material is preferably 10 to 3000 N (more preferably 20 to 2000 N, 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, it is 5 to 150 kg / m ³ ). By using a roller brush combined with such a liquid absorbing material, it is possible to form a pattern corresponding to the deformation of each liquid absorbing material, the transferability of the covering material, and the like. “Hardness” as used herein refers to the value of hardness (Method C) measured from the force when the specimen is compressed to a thickness of 40% according to JIS K6400-2. The “density” is an apparent density value calculated from the weight and dimensions of the test piece in accordance with JIS K7222.

In addition, the liquid absorbing material is preferably fixed so as to cover the outer peripheral surface of the cylinder, and at least two kinds (preferably three kinds or more) of liquid absorbing materials having different hardness and / or density are arranged in the cylinder outer diameter direction ( The form fixed so that it may be piled up on FIG. 1: 3) is more preferable. Furthermore, it is more preferable that the liquid-absorbing material is compression-molded so that a large number of liquid-absorbing materials are randomly mixed in the outer circumferential direction and the outer radial direction. The effect of this invention can be heightened by using the roller brush which has such a liquid absorbing material.

  The liquid-absorbing material has a three-dimensional shape with an indeterminate outer shape, and the individual size thereof 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, since the liquid absorbing materials having different sizes in addition to the hardness and / or density are randomly mixed on the outer peripheral surface of the cylinder, the effect of the present invention can be further enhanced. Since irregular irregular shapes are easily formed between the liquid-absorbing materials, the effect of the present invention can be further enhanced. Here, the “size” is the longest axis of the outer shape, and is measured, for example, by sieving with a sieve having one side of a predetermined dimension. Moreover, although the thickness of the liquid absorption fixed to the cylinder outer peripheral surface is based also on the magnitude | size of each liquid absorption, Preferably it is 50 mm or less (more preferably 1-30 mm, More preferably, 2-15 mm). Furthermore, in this invention, it is preferable to provide an uneven | corrugated pattern according to a desired pattern in the outer peripheral surface of a liquid absorption. Examples of the method for providing the uneven shape include a method of embossing at the time of compression molding of the liquid absorbent material, a method of partially removing the liquid absorbent material that has been compression molded, and the like. Thereby, the effect of the present invention can be further enhanced. In the case of partially removing the compression-molded liquid-absorbing material, a random uneven shape can be easily obtained according to a known method such as picking and turning.

In the third step of the present invention, the coating material (II) is preferably applied after the coating material (I) is dried. Thereby, the finish with high aesthetics can be obtained stably. In this case, the roller brush is preferably rolled and applied to the entire surface of a layer formed of 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) It is. It is also possible to paint in a plurality of times within the range of the required amount. 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 aesthetics.
The coating and drying of the coating material (II) are preferably performed at room temperature.

  In the film forming method of the present invention, after the second step or the third step, a recess due to a cone mark (hereinafter referred to as “a recess”) can be repaired. Repair the dent by applying a coating material that is darker than the color tone of the coating material (I) (preferably a coating material that is darker than the color tone of the coating material (I) and the coating material (II)) with a brush or the like. Is desirable. Thereby, a shading feeling is given to the depression.

In the film forming method of the present invention, a clear layer can be provided as necessary after the third step. By providing a clear layer, not only the weather resistance and the like are improved, but also the color tone of the shade by the coating material (I) and the coating material (II) is more harmonized, and the color tone (and light and dark) changed continuously and slightly. It is possible to enhance the texture specific to the concrete surface having the. Such a clear layer can be formed of, for example, a clear coating material using an acrylic resin, a urethane resin, an epoxy resin, an acrylic silicon resin, a fluorine resin, or the like as a binder. The clear coating material may be either water-based or solvent-based, matte type or glossy type. The clear coating material is preferably a low contamination type. Furthermore, coloring is possible as long as the effects of the present invention are not impaired. The clear coating material is preferably applied to the entire surface. As a coating method, various methods such as brush coating, spray coating, and roller coating can be employed. The coating amount is preferably 0.01 to 0.5 kg / m ² (more preferably 0.05 to 0.4 kg / m ² ). It is also possible to divide and apply a plurality of times within the range of the application amount.

Examples are given below to clarify the features of the present invention.
[Osmotic water absorption prevention material]
-Permeable water absorption preventing material A (mixture of hexyltrimethoxysilane and aliphatic hydrocarbon solvent, weight ratio 3:97)
-Permeable water absorption preventing material B (mixture of hexyltrimethoxysilane and aliphatic hydrocarbon solvent, weight ratio 12:88)
-Permeable water absorption preventing material C (hexyltrimethoxysilane, soluble acrylic resin, mixture of aliphatic hydrocarbon solvent, weight ratio 3:25:72)

[Coating material (I)]
・ Coating 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 an antifoaming agent and 10 parts by weight of water.

・ Coating materials (IB) to (IP)
Based on the formulation shown in Table 1 and Table 2, coating materials (IB) to (IP) were produced by the same method as the coating material (IA).

[Coating material (II)]
・ Coating material (II-A)
70 parts by weight of white pigment A, 20 parts by weight of extender pigment B, 30 parts by weight of extender pigment B, 0.8 parts by weight of coloring pigment, 4 parts by weight of a film-forming aid, 0.2 wt. Part, 0.1 part by weight of antifoaming agent, and 10 parts by weight of water were mixed and stirred by a conventional method to produce a coating material (II-A) (gray, L ^* = 71, glossiness 1.8). .

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

In addition, the following were used as a raw material.
Synthetic resin emulsion A: Silicon-modified acrylic resin emulsion (cyclohexyl methacrylate, methyl methacrylate, 2-ethylhexyl acrylate, methyltrimethoxysilane adduct of γ-methacryloyloxypropyltrimethoxysilane copolymer, cyclohexyl methacrylate content in solid content 20% by weight, 2% by weight of silicon component in solids, 50% by weight of solids, 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 10% by weight in solid content, silicon content 2% by weight in solid content, solid content 50% by weight, Tg 38 ° C., average particle diameter 75 nm)
Synthetic resin emulsion C: Silicon-modified acrylic resin emulsion (cyclohexyl methacrylate, methyl methacrylate, 2-ethylhexyl acrylate, methyltrimethoxysilane adduct of γ-methacryloyloxypropyltrimethoxysilane copolymer, cyclohexyl methacrylate content in solid content 20% by weight, 2% by weight of silicon component in solids, 50% by weight of solids, Tg 50 ° C., average particle size 72 nm)

Synthetic resin emulsion D: Silicone modified acrylic resin emulsion (cyclohexyl methacrylate, methyl methacrylate, 2-ethylhexyl acrylate, methyltrimethoxysilane adduct of γ-methacryloyloxypropyltrimethoxysilane copolymer, cyclohexyl methacrylate content in solids 20% by weight, 8% by weight of silicon component in solid content, 50% by weight of solid content, Tg 36 ° C., average particle diameter 75 nm)
Synthetic resin emulsion E: Silicone modified acrylic resin emulsion (cyclohexyl methacrylate, methyl methacrylate, 2-ethylhexyl acrylate, methyltrimethoxysilane adduct of γ-methacryloyloxypropyltrimethoxysilane copolymer, cyclohexyl methacrylate content in solids 6% by weight, 2% by weight of silicon component in solids, 50% by weight of solids, Tg 32 ° C., average particle diameter 78 nm)
Synthetic resin emulsion F: Silicone modified acrylic resin emulsion (cyclohexyl methacrylate, methyl methacrylate, 2-ethylhexyl acrylate, methyltrimethoxysilane adduct of γ-methacryloyloxypropyltrimethoxysilane copolymer, cyclohexyl methacrylate content in solid content 20% by weight, 2% by weight of silicon component in solids, 50% by weight of solids, Tg 12 ° C., average particle size 72 nm)
Synthetic resin emulsion G: Silicone modified acrylic resin emulsion (cyclohexyl methacrylate, methyl methacrylate, 2-ethylhexyl acrylate, methyltrimethoxysilane adduct of γ-methacryloyloxypropyltrimethoxysilane copolymer, cyclohexyl methacrylate content in solid 20% by weight, 2% by weight of silicon component in solids, 50% by weight of solids, 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 20% by weight, solid content 50% by weight, Tg 32 ° C., average particle size 80 nm)
Synthetic resin emulsion I: acrylic resin emulsion (methyl methacrylate / 2-ethylhexyl acrylate copolymer, solid content 50% by weight, Tg 32 ° C., average particle diameter 80 nm)

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

(Concealment rate measurement)
Coating materials (IA) to (IP) and coating materials (II-A) to (II-G) were respectively applied to the concealment rate test paper with a film applicator (gap 150 μm), and the temperature was 23 A test piece obtained by drying for 24 hours in an environment of 50 ° C./humidity (hereinafter referred to as “standard state”) was subjected to black ground coating and white using a color difference meter “CR-300” (manufactured by Minolta Co., Ltd.). The luminous reflectance of the ground coating film was measured, and the concealment rate was calculated from these. The results are shown in Tables 1-3.

(Examples 1-16, Comparative Examples 1-3)
For concrete base material that has partially deteriorated, as a first step, brush the entire surface with a required amount of 200 g / m ² of a permeable water absorption prevention material, and in a standard state (temperature 23 ° C., relative humidity 50%) Dried for 16 hours. Next, as a second step, the coating material (I) is brushed on the entire surface at a required amount of 100 g / m ² , dried in a standard state for 24 hours, side-cured, and further dried for 14 days to prepare a test specimen. Was evaluated. Table 4 shows the combination of the permeable water absorption preventing material and the coating material (I), and the results.

-Water absorption prevention test The test body was fixed vertically, water was continuously sprayed on the test body using a hose for 60 minutes, and the color change at that time was observed. The evaluation criteria are “◎” when no color change was observed before and after the test, “◯” when almost no color change was observed, “△” when color change was observed, and significant color change. What was recognized was set as "x".

  About the test body after a water absorption preventive test, adhesiveness was evaluated by the cross-cut method according to JISK5600-5-6. The evaluation criteria are “◎” when the defect area is within 5%, “◯” when the defect area is over 5% and within 20%, and “△” when the defect area is over 20% and within 35%. “,” And “x” are those having a defect area of more than 35%.

-Durability test About the test body, the water-cooling repetition which made water immersion (20 degreeC) 18 hours->-20 degreeC 3 hours-> 50 degreeC 3 hours 1 cycle was performed in total 10 cycles. Then, according to JIS K 5600-5-6, adhesiveness was evaluated by the crosscut method. The evaluation criteria are “◎” when the defect area is within 5%, “◯” when the defect area is over 5% and within 20%, and “△” when the defect area is over 20% and within 35%. “,” And “x” are those having a defect area of more than 35%.

・ Appearance of the coating formed with aesthetic appearance is such that the deteriorated part of the concrete base material is not visible at all, and the finish (pattern) is similar to the texture of the concrete surface. Is not visually recognized at all, and “〇” is excellent in aesthetics, and “X” is that in which the deteriorated portion is visually recognized.

(Example 17)
After the coating material (IA) of Example 1 is dried, as a third step, the coating material (II-A) is applied at a coating amount of 70 g / m ² and has five different hardnesses and / or densities as shown in FIG. Sponge materials 1 to 5 (each sponge material is an irregular solid satisfying a size of 2 to 18 mm) and a roller brush 1 having a random irregular shape on the outer peripheral surface of the cylinder (outer diameter 45 mm, liquid absorption thickness 2 To 10 mm), dried in a standard state for 24 hours, side-cured, and further dried for 14 days to produce a test specimen, which was evaluated in the same manner as in Example 1.
-Sponge material 1: Hardness 45-60N, density 50-100kg / m < ³ >
-Sponge material 2: Hardness 75-110N, density 15-30kg / m ³
-Sponge material 3: Hardness 110-140N, density 15-50kg / 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

(Example 18)
The coating material (II-A) of Example 17 was mixed with three types of sponge materials 2 to 4 (each sponge material was an indefinite solid satisfying a size of 2 to 18 mm) having different hardness and / or density, and a cylinder. A test specimen was prepared in the same manner as in Example 17 except that the test piece was coated with a roller brush 2 having an irregular shape on the outer peripheral surface (outer diameter 45 mm, liquid absorption thickness 2 to 10 mm), and the same evaluation was performed. . The results are shown in Table 5.

(Examples 19 to 23, Comparative Example 4)
It replaced with the coating | covering material (IA) of Example 17, and coating | covering material (II-A), and except having used the coating | covering material (I) and coating | covering material (II) which are shown in Table 5, it is the same as that of Example 17. A specimen was prepared and evaluated in the same manner. The results are shown in Table 5.

The appearance of the films formed in Examples 17 to 23 was a good finish that approximated the texture of the concrete surface compared to Comparative Example 4. Especially, Examples 17-21 became the finishing which was excellent.

(Example 24)
A clear coating material (water-based acrylic silicone resin clear, matte type) was further applied on the coating film formed in Example 17 with a wool roller so that the coating amount was 100 g / m ² , thereby forming a coating film. The appearance of the formed film was even better than Example 17.

Claims (5)

A method of forming a film on an inorganic material,
For the surface of inorganic material,
After applying the permeable water absorption prevention material as the first step,
As a second step, a coating material (I) containing a synthetic resin emulsion and a pigment, and having a concealment rate of the formed film of 90% or more, is applied,
The synthetic resin emulsion is a monomer constituting the synthetic resin,
A method for forming a film, comprising a (meth) acrylic acid alkyl ester having a glass transition temperature of a homopolymer of 50 ° C. or more and a solubility parameter of 9.5 or less.   The film forming method according to claim 1, wherein the synthetic resin emulsion 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 has an average particle size of 120 nm or less.   The said synthetic resin emulsion is a silicon | silicone modified acrylic resin emulsion, The film formation method in any one of Claims 1-3 characterized by the above-mentioned. As a third step, a pattern is imparted by applying a coating material (II) containing a synthetic resin and a pigment, having a concealment rate of the formed coating of 90% or more and having a color tone different from that of the coating material in the second step. The film forming method according to claim 1, wherein: