JP2001239517A - Method for producing inorganic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an inorganic material in which a sealer film improved in weatherability and flexibility without deteriorating water and moisture barrier properties and toughness is formed. SOLUTION: In the method in which the inorganic material, after being molded and cured, is coated with a water base sealer, a water base coating composition containing (I) an epoxy resin emulsion obtained by dispersing an acryl-modified epoxy resin (B) in water with the use of a modified epoxy resin (A) obtained by the reaction of a polyethylene glycol (a) 400-20,000 in number average molecular weight, a bisphenol type epoxy resin (b), a compound (c) having an active hydrogen group in a molecule, and a compound (d) having at least two active isocyanate groups in a molecule as a dispersion stabilizing resin and (II) an amine curing agent is used as the water base sealer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an inorganic material by forming a sealer film having improved weather resistance and flexibility without impairing water resistance, moisture resistance and toughness.

[0002]

2. Description of the Related Art In recent years, an inorganic material has been formed into a plate shape as an outer wall material and a tile material of a building, and then primary curing, application of a sealer before autoclave, drying, autoclave curing,
After performing cutting and preheating, a sealer plate is manufactured by performing autoclave curing and then drying, and then a sealer plate is manufactured by performing the autoclave curing and then drying. ing.

[0003] As the above-mentioned sealer after curing in an autoclave, an organic solvent-based sealer has been widely used.
Water-based sealers have been replaced for pollution, health and safety. As such an aqueous sealer, an acrylic emulsion sealer and an epoxy emulsion sealer are mainly used.However, an acrylic emulsion sealer is inferior to organic solvent sealers in terms of barrier properties such as water permeability and is inferior to epoxy emulsion sealers. When shipped as a sealer plate, the sealer may have problems such as discoloration and poor adhesion of the top coat when exposed to sunlight outdoors due to poor weather resistance.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that an epoxy resin obtained by dispersing an acrylic modified epoxy resin in water using an epoxy resin modified with polyethylene glycol as a dispersion-stable resin. By using a water-based paint containing a resin-based emulsion as a sealer after curing in an autoclave, a sealer film with improved weather resistance and flexibility can be formed without impairing the water resistance and toughness, which are the characteristics of epoxy resins. The invention has been completed.

That is, the present invention relates to a method for producing an inorganic material, comprising forming and curing an inorganic material, and then coating an aqueous sealer, wherein the aqueous sealer comprises (I) a number average molecular weight of 4
100 to 20,000 polyethylene glycol (a)
A bisphenol-type epoxy resin (b), a compound (c) having one active hydrogen in one molecule, and a compound (c) having one active hydrogen in one molecule.
Compound (d) having at least two active isocyanate groups
An epoxy resin emulsion obtained by dispersing an acrylic modified epoxy resin (B) in water using the modified epoxy resin (A) obtained by the reaction of
I) A method for producing an inorganic material, characterized by using an aqueous coating composition containing an amine curing agent.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The modified epoxy resin (A) used in the present invention comprises a polyethylene glycol (a), a bisphenol type epoxy resin (b) and one active hydrogen in one molecule. A resin obtained by reacting the compound (c) with the compound (d) having two or more active isocyanate groups in one molecule.

The polyethylene glycol (a) is a polyetherdiol having a number average molecular weight of 400 to 20,000 and represented by the following formula: HO (C ₂ H ₄ O) _n H (n = 13 to 714) It is. When the number average molecular weight is less than 400, the hydrophilicity is inferior and the water dispersibility of the resin (A) decreases, while when it exceeds 20,000, the crystallinity of the resin (A) increases, which is not preferable.

The above-mentioned bisphenol type epoxy resin (b)
Is a compound having at least two epoxy groups in one molecule. In particular, diglycidyl ether of bisphenol obtained by a condensation reaction of a bisphenol compound with an epihalohydrin, for example, epichlorohydrin, has flexibility and anticorrosion properties. It is preferable from the point of view.

The bisphenol compounds include, for example, bis (4-hydroxyphenyl) -2,2-propane, bis (4-hydroxyphenyl) -1,1-ethane, bis (4-hydroxyphenyl) methane, 4,4 '
-Dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylsulfone, bis (4-hydroxyphenyl) -1,1-isobutane, bis (4-hydroxy-
3-t-butylphenyl) -2,2-propane and the like.

Particularly, as the bisphenol type epoxy resin (b), bisphenol A type epoxy resin, bisphenol F type epoxy resin and the like can be suitably used. The bisphenol-type epoxy resin (b) has an epoxy equivalent of about 150 to 5000, preferably about 160 to 1.
000 is desirable.

The compound (c) having one active hydrogen in one molecule is used for blocking an isocyanate group in the modified epoxy resin (A). Examples of the compound (c) include monohydric alcohols such as methanol, ethanol and diethylene glycol monobutyl ether; monovalent carboxylic acids such as acetic acid and propionic acid; and monovalent thiols such as ethyl mercaptan. A secondary amine such as diethylamine; a ketone to a primary amino group of an amine compound containing one secondary amino group or a hydroxyl group and one or more primary amino groups such as diethylenetriamine and monoethanolamine; Compounds modified to aldimine, ketimine, oxazoline or imidazoline by reacting with aldehyde or carboxylic acid at a temperature of, for example, 100 to 230 ° C .; oximes such as methyl ethyl ketoxime; phenol, nonylphenol-
And phenols such as phenol. These active hydrogen group-containing compounds (c) generally have a molecular weight of about 30 to 2,000, preferably about 30 to 200.

The compound (d) having two or more isocyanate groups in one molecule includes a conventionally known aliphatic compound,
Alicyclic or aromatic polyisocyanate compounds can be used. For example, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated 4,4'-diphenylmethane Examples thereof include diisocyanate, tolylene diisocyanate, xylylene diisocyanate, and biuret compounds and isocyanurate compounds thereof. These can be used alone or in combination of two or more.

It is generally appropriate that the reaction ratio of each of the components (a) to (d) be within the following range. The equivalent ratio of the hydroxyl group of (a) to the isocyanate group of (d) is 1 /
1.2 to 1/10, preferably 1 / 1.5 to 1/5, more preferably 1 / 1.5 to 1/3, equivalent of the hydroxyl group of (c) and the isocyanate group of (d). The ratio is 1/2 to 1 /
100, preferably 1/3 to 1/50, more preferably 1/3 to 1/20, of the total amount of the hydroxyl groups of (a), (b) and (c) and the isocyanate group of (d) The equivalence ratio is
1 / 1.5 or less, preferably 1 / 0.1 to 1 / 1.5,
More preferably, the ratio is set to 1 / 0.1 to 1 / 1.1.

The modified epoxy resin (A) is produced by mixing the components (a) to (d) and reacting them until substantially no unreacted isocyanate groups are present.

The acrylic modified epoxy resin (B) used in the present invention is mainly composed of a resin (B-B) obtained by reacting an epoxy resin with a carboxyl group-containing acrylic resin.
1) A resin (B-2) obtained by reacting an epoxy resin with an acid anhydride group-containing acrylic resin, and a resin (B-3) obtained by graft-polymerizing or copolymerizing a polymerizable unsaturated monomer with an epoxy resin. At least one selected from acrylic-modified epoxy resins.

The epoxy resin used in the acrylic modified epoxy resin (B) has two or more epoxy groups in one molecule and has an average epoxy equivalent of about 150 to about 1,2.
000, preferably in the range of about 150 to about 500. Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, epoxy ester resin obtained by modifying the above epoxy resin with dibasic acid, etc., alicyclic epoxy resin, and polyglycol type. Epoxy resins, epoxy group-containing acrylic resins and the like can be mentioned. Specifically, DER-331J (manufactured by Dow Chemical Company), EPON # 828,834,806H (manufactured by Yuka Shell Co., Ltd.), GY # 260 (Asahi Chiba) Epomic R # 140P (Mitsui Petrochemical Co., Ltd.), Epototo YD128 (Toto Kasei Co., Ltd.), ERL-4221, 42
29 (manufactured by Union Carbide), Denacol EX-8
Commercial products such as No. 30 (manufactured by Nagase Kasei Kogyo) can be used. Incidentally, the epoxy resin, the average epoxy equivalent is preferably in the range of about 150 to about 1,000,
For example, even when an epoxy resin having an epoxy equivalent of about 1,500 is used in combination, the average epoxy equivalent is about 150 to
Mixtures of epoxy resins in the range of about 1,000 can be used.

The above acrylic-modified epoxy resin (B-1)
The carboxyl group-containing acrylic resin used for the resin generally has a weight average molecular weight in the range of 3,000 to 50,000, preferably 5,000 to 20,000, and a resin acid value of 3 to 300, preferably 10 to 10. It is in the range of 100 mgKOH / g, and is obtained by copolymerizing a carboxyl group-containing monomer and other polymerizable unsaturated monomers by an ordinary method.

Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 5- Carboxypentyl (meth) acrylate and the like can be mentioned.

Other polymerizable unsaturated monomers include:
For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate,
I-butyl (meth) acrylate, t- (meth) acrylate
-Butyl, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, decyl acrylate, stearyl (meth) acrylate, lauryl acrylate, cyclohexyl (meth) acrylate, etc. Acrylic acid or methacrylic acid having 1 to 1 carbon atoms
24 alkyl or cycloalkyl esters;
C2-C18 alkoxyalkyl esters of acrylic acid or methacrylic acid such as methoxybutyl (meth) acrylate, methoxyethyl (meth) acrylate, and ethoxybutyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate; 3-hydroxypropyl (meth) acrylate, hydroxyalkyl (meth) acrylate and the like, hydroxyalkyl esters of acrylic acid or methacrylic acid having 2 to 8 carbon atoms; vinyl ethers such as ethyl vinyl ether, butyl vinyl ether and cyclohexyl vinyl ether; vinyl trimethoxysilane; Alkoxysilyl group-containing monomers such as vinyltriethoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane, and γ- (meth) acryloyloxypropyltriethoxysilane; Styrene, α-methylstyrene, vinyl chloride, butadiene and the like can be mentioned. These can be used alone or in combination of two or more.

The acrylic-modified epoxy resin (B-1) is
The epoxy resin and the carboxyl group-containing acrylic resin, the epoxy resin in the epoxy resin and the carboxyl group in the carboxyl group-containing acrylic resin has an equivalent ratio of 1:
It is obtained by mixing with a blending amount in the range of 0.05 to 1: 0.5 and, for example, usually reacting for about 1 to 10 hours in the presence of an epoxy group / carboxyl group reaction catalyst. Examples of the epoxy group / carboxyl group reaction catalyst include quaternary salt catalysts such as tetraethylammonium bromide, tetrabutylammonium bromide, tetraethylammonium chloride, tetrabutylphosphonium bromide, and triphenylbenzylphosphonium chloride; triethylamine, tributylamine And the like. The reaction temperature is 120 to
About 150 ° C. is appropriate.

The above acrylic-modified epoxy resin (B-2)
Examples of the polymerizable unsaturated monomer used in the above include carboxyl group-containing monomers and other polymerizable unsaturated monomers listed in the description of the carboxyl group-containing acrylic resin used in the acrylic-modified epoxy resin (B-1). It can be appropriately selected and used.

The acrylic-modified epoxy resin (B-2)
Is mixed with the polymerizable unsaturated monomer in a ratio of 10 to 2,000 parts by weight with respect to 100 parts by weight of the epoxy resin, and a polymerization initiator such as azobisisobutyronitrile and benzoyl peroxide is mixed. , Preferably in the presence of a peroxide-based polymerization initiator such as benzoyl peroxide to promote grafting efficiently,
The reaction may be carried out at a temperature of about 1 ° C. for about 1 to 10 hours.

In particular, the acrylic-modified epoxy resin (B-
As 2), a polymerizable unsaturated monomer containing a carboxyl group-containing monomer, and a product obtained by reacting a carboxyl group with an epoxy group after graft polymerization or copolymerization onto an epoxy resin is preferable. The reaction between the carboxyl group and the epoxy group has an equivalent ratio of 1: 0.05 to
1: within a range of 0.5, for example, usually 1 to 10 in the presence of the epoxy group / carboxyl group reaction catalyst.
It is obtained by a heating reaction for about an hour. The reaction temperature is 120
About 150 ° C. is appropriate.

As described above, the modified epoxy resin (A) is used as a dispersion-stable resin, and the acrylic modified epoxy resin (B) is dispersed in water in an aqueous medium by a method known per se to obtain an epoxy resin emulsion (I). Is obtained. In this case, the ratio of the resins (A) and (B) used is 10/90 to 90/10, preferably 1 in terms of solid content ratio.
A range of 5/85 to 50/50 is preferred. If the amount of the resin (A) is less than the usage ratio range, the dispersibility becomes poor, which is not preferable.

In the present invention, the aqueous coating composition containing the epoxy resin emulsion (I) obtained as described above and the amine curing agent (II) is used as an aqueous sealer.

As the amine curing agent (II), a conventionally known curing agent for epoxy resin which is a curing agent having an active hydrogen equivalent in the range of 40 to 300 can be used.
Specifically, for example, polyamines such as metaxylenediamine, diaminodiphenylmethane, isophoronediamine, 1,3-bisaminocyclohexylamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, dimethylethanolamine, and polyoxypropylenepolyamine; Examples thereof include polyamine epoxy resin adducts, ketimine compounds, polyamidoamines, and polyamide resins. These can be used alone or in combination of two or more.

In order to facilitate emulsification and workability,
An amine-added modified epoxy resin obtained by reacting the modified epoxy resin (A) with an amine compound having active hydrogen to such an extent that an epoxy group is not substantially detected is used as a dispersion-stable resin. Dispersed in aqueous medium to obtain amine curing agent (II)
May be used.

Examples of the amine compound having active hydrogen include diethylamine and diethanolamine.
Secondary monoamines; compounds in which a primary amino group such as diethylene triamine, ethyl eminoethyl emine and monoethanolamine are modified with ketimine; salts of tertiary amines such as dimethylethanolamine and triethylamine with organic acids; .

In the aqueous coating composition, the epoxy resin emulsion (I) and the amine curing agent (II) are usually used in a molar ratio of 10 to the active hydrogen in the amine and the epoxy group in the epoxy resin. / 90-70 / 30, preferably 20 / 80-60 / 40.

The aqueous coating composition may further contain, if necessary, pigments such as coloring pigments, extenders, anticorrosion pigments, etc .; curing catalysts, surfactants, defoamers, pigment dispersants, anti-settling agents, thickeners. Paint additives such as an agent, an organic solvent, a film-forming aid, a coating surface adjusting agent, a plasticizer, and a preservative; and a water-soluble resin other than the above (I), a colloidal dispersion, and the like.

The water-based paint composition obtained as described above is a two-pack paint comprising a paint base containing an epoxy resin emulsion (I) and an amine curing agent (II). Is what is done.

The method of the present invention is a method for producing an inorganic material, which comprises forming and curing an inorganic material, and then applying an aqueous sealer, wherein the aqueous coating composition is used as the aqueous sealer.

In the method of the present invention, the inorganic material refers to a composition comprising cement as a main component, a reinforcing fiber such as pulp or rock wool, a siliceous material such as silica sand, and an inorganic filler. Alternatively, an inorganic hardening material (for example, a calcium silicate plate, an asbestos cement plate, a wood chip cement plate, a pulp cement plate, a lightweight cellular concrete plate) formed by press molding or the like and water-hardened is used.

The curing of the inorganic material may or may not be performed in an autoclave, but if the autoclave is not cured, then after the primary curing, if the autoclave is cured, the coating is performed after the autoclave curing. Is desirable. The autoclave curing can be performed under the conditions employed for the ceramic substrate without any particular limitation. When the autoclave curing is not performed, the aqueous coating composition may be applied after applying a treating agent such as an acrylic emulsion or an epoxy emulsion as a base treatment. When performing autoclave curing, usually
Since the pre-autoclave sealer is applied in order to suppress the generation of efro during autoclave curing, the aqueous coating composition is applied onto the pre-autoclave sealer film after autoclave curing. A conventionally known sealer before autoclave can be used.

In the method of the present invention, the aqueous coating composition is suitably used at a concentration of 1 to 50% by weight, preferably 3 to 45% by weight, of the solid content of the coating. When the solid content of the coating is less than 1% by weight, the number of coatings is increased to secure a coating film thickness, and the coating workability is deteriorated. On the other hand, when it exceeds 50% by weight, the permeability to the substrate is inferior. If the front sealer is applied, the adhesion to the pre-autoclave sealer film is unfavorably deteriorated.

In the method of the present invention, the coating amount (in terms of solid content) of the aqueous coating composition is suitably in the range of 1 to 200 g / m ² , preferably 5 to 150 g / m ² . If the coating amount is less than 1 g / m ^{2, the} water resistance and moisture permeability decrease, whereas if it exceeds 200 g / m ² , the blocking resistance and the like decrease, which is not preferable.

The method of applying the aqueous coating composition is not particularly limited, and conventionally known methods such as spray coating, roller coating, brush coating, dip coating, and flow coater (such as curtain flow coater) can be employed. Ambient temperature of 50 to 2 with a normal drying oven, hot air drying oven, jet heater, etc.
00 ° C, preferably at 70 to 150 ° C for 10 seconds to 30 minutes,
Preferably 20 seconds to 20 minutes, more preferably 30 seconds to
It is preferable to dry for about 10 minutes.

In the method of the present invention, after forming and curing an inorganic material, the above-mentioned aqueous coating composition is applied as an aqueous sealer to obtain a sealer-coated inorganic material. It can also be a material.

As the top coat, there can be used, without any particular limitation, conventionally known top coats such as aqueous, organic solvent type and solventless types, such as acrylic resin type, urethane resin type, vinyl chloride resin type and cellulose resin type. , A silicone resin, a polyester resin, an alkyd resin, a fluororesin, and a binder resin containing two or more kinds of modified resins and blend resins. The topcoat can be used either in a lacquer type or a crosslinked type. Further, as the top coat, the above resin-based paint may be an enamel paint containing a pigment or a clear paint containing no pigment.

[0040]

According to the present invention, an aqueous coating containing an epoxy resin emulsion obtained by dispersing an acrylic modified epoxy resin in water using an epoxy resin modified with polyethylene glycol as a dispersion-stable resin is used as a sealer after curing in an autoclave. Thereby, an inorganic building material can be obtained in which a sealer film having improved weather resistance and flexibility is formed without impairing the water resistance and toughness, which are features of the epoxy resin.

[0041]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. “Parts” and “%” mean “parts by weight” and “% by weight”, respectively.

Production Example 1 of Epoxy Resin Emulsion Polyethylene glycol 600 having a number average molecular weight of 4000
0 parts, propylene glycol monomethyl ether 135
And 3800 parts of “Epicoat 828” (manufactured by Yuka Shell Epoxy Co., Ltd., bisphenol A type epoxy resin, epoxy equivalent: 184 to 194), and after homogenizing at 100 ° C., 522 parts of triene diisocyanate was added and 2 After reacting for an hour, the temperature was raised to 120 ° C.
Allowed to react for hours. After confirming that the isocyanate value had become 0.5 or less, 1170 parts of propylene glycol monomethyl ether was added for dilution. The obtained dispersion stable resin (A) has a nonvolatile content of 90% and an epoxy equivalent of 498.
(Solid content).

Next, 400 parts of ethylene glycol monobutyl ether and “Epicoat 828” were placed in another reaction vessel.
(Bisphenol A type epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent: 184 to 194) 500 parts were charged, heated to 130 ° C. under a nitrogen stream, and the following vinyl monomer and polymerization initiator were added dropwise in 3 hours. After dropping, the mixture was aged for 2 hours. Next, 0.3 g of tetraethylammonium bromide was charged and reacted for about 2 hours. When the acid value of the resin became 0.3 mgKOH / g or less, 278 parts of the dispersion stable resin (A) obtained as described above was added. Further, 1422 parts of water was added with stirring to obtain an acrylic-modified epoxy resin emulsion (B-1). The resulting acrylic-modified epoxy resin emulsion (B-1)
The nonvolatile content was 40%, and the epoxy equivalent was 501 (solid content).

Acrylic acid 45 parts Styrene 50 parts Methyl methacrylate 305 parts Hydroxyethyl acrylate 100 parts t-butyl peroxy-2-ethylhexanoate 25 parts Production Example 2 Ethylene glycol monobutyl ether 40 is added to a reaction vessel.
0 parts and 500 parts of “Epicoat 1001” (manufactured by Yuka Shell Epoxy Co., Ltd., bisphenol A type epoxy resin, epoxy equivalent: 450 to 500), and heated to 130 ° C. under a nitrogen stream to obtain the following vinyl monomer and polymerization The initiator was added dropwise in 3 hours, and the mixture was aged for 2 hours after the addition. Then
0.3 g of tetraethylammonium bromide was charged and reacted for about 2 hours to obtain a resin acid value of 0.3 mgKOH /
g, 278 parts of the dispersion stable resin (A) prepared in Production Example 1 was added. Further, 1422 parts of water was added with stirring to obtain an acrylic-modified epoxy resin emulsion (B-2). The obtained acrylic-modified epoxy resin emulsion (B-2) had a nonvolatile content of 40% and an epoxy equivalent of 980 (solid content).

Acrylic acid 20 parts Styrene 50 parts Methyl methacrylate 330 parts Hydroxyethyl acrylate 100 parts t-butyl peroxy-2-ethylhexanoate 25 parts Production Example 3 A container was charged with 400 parts of ethylene glycol monobutyl ether, and “Epicoat 1001” was charged. 1000 parts (Bisphenol A type epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent: 450 to 500) were dissolved. Next, 278 parts of the dispersion-stable resin (A) obtained in Production Example 1 was added thereto, and 1447 parts of water was further added with stirring.
An epoxy resin emulsion (B-3) was obtained. The obtained epoxy resin emulsion (B-3) has a nonvolatile content of 40%.
%, Epoxy equivalent was 476 (solid content).

Preparation Example 1 of Water- based Coating Composition Preparation 50 parts of water, 50 parts of titanium white (“CR-97”, trade name, manufactured by Ishihara Sangyo Co., Ltd.), talc (“S talc”, trade name, Japan) Talc Co., Ltd.) 50 parts, "Nopco Santo K" (trade name, San Nopco Co., Ltd., dispersant) 2 parts,
"Nopco Spas 44C" (trade name, San Nopco Co., Ltd.)
(Manufactured by a company, dispersant) were mixed and dispersed with a paint shaker to produce a pigment paste.

In 200 parts of the emulsion (B-1),
150 parts of the pigment paste and "Eporsion EB-1"
35 parts (trade name, manufactured by Nippon NS Co., Ltd., amine curing agent) were mixed and stirred and mixed to prepare an aqueous paint.

Preparation Examples 2 and 3 The same procedures as in Preparation Example 1 were repeated except that emulsions (B-2) and (B-3) were used instead of emulsion (B-1). Paint, created.

Preparation Example 4 Butyl cellosolve 15 was added to 200 parts of "Polytron J1351" (trade name, manufactured by Asahi Kasei Corporation, 50% non-volatile content acrylic emulsion) (emulsion a).
And 150 parts of the above-mentioned pigment paste were mixed and stirred and mixed to prepare an aqueous paint.

Preparation Example 5 150 parts of the above-mentioned pigment paste were added to 200 parts of "Eporsion EA-3" (trade name, epoxy resin emulsion manufactured by NSC Japan Ltd.) (hereinafter referred to as emulsion b).
60 parts of "Eporsion EB-1" (trade name, amine curing agent, manufactured by Nippon NS Co., Ltd.) were blended and mixed by stirring to prepare an aqueous paint.

[0051] Each water-based paint-a prepared in Example 1-6 and create as Comparative Examples 1 to 3 the inorganic material, as shown in Table 1, slate (substrate A), calcium silicate plate (substrate B) And a cement composition comprising Portland cement, silica sand powder, and pulp, cured in an autoclave at 180 ° C. for 8 hours at 10 atm, an inorganic material having a substrate density of 1.3 (substrate C)
Each of the substrates was coated so as to have a solid content of 60 g / m ² to obtain each coated plate. Each of the obtained coated plates was subjected to the following performance evaluation test. Table 1 shows the results. (* 1) Water resistance: The water resistance of each coated plate was evaluated by the funnel method of JIS K 5400. Permeability is 1ml / 24h
The following were evaluated as ○, those exceeding 1 ml / 24h and 3 ml / 24h or less, and evaluated as × when exceeding 3 ml / 24h. (* 2) Substrate adhesion: A 5 × 5 grid was cut into each coated plate at 4 mm intervals with a cutter knife, and a peeling test was performed with Cellotape (registered trademark). If all 25 squares were left without peeling, the sample was evaluated as ○, 20 to 24 squares remained, Δ, and 19 or less squares were left without peeling. (* 3) Weather resistance: Each coated plate was tested with a sunshine weatherometer for 500 hours. If the appearance of this test plate is not different from that before the test, ◎; if there is a change in color but the color difference is 0.5 or less, ○; if there is a change in color, but the color difference exceeds 0.5 and 1 or less The sample having an abnormal appearance such as choking or weak was evaluated as x, and the sample having an abnormal appearance such as chalking was evaluated as x.

Examples 7 to 10 and Comparative Examples 4 to 6 Each of the aqueous paints prepared as described above was coated on a slate plate (substrate A) in an amount of 60 g as shown in Table 2 by applying a solid content.
/ M ² , and then (a) an acrylic top coat (“IM Coat 5111”, manufactured by Kansai Paint Co.) or (b) an acrylic silicon top coat (“IM Coat 5315”, manufactured by Kansai Paint Co.) ) Was applied so that the applied amount of the solid content was 60 g / m 2 to obtain each coated plate. Each of the obtained coated plates was evaluated in the same manner as in the above-mentioned (* 2) substrate adhesion test. Table 2 shows the results.

[0053]

[Table 1]

[0054]

[Table 2]

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 171/00 C09D 171/00 Z (72) Inventor Masaaki Shinohara 4-171-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture Inside Kansai Paint Co., Ltd. (72) Inventor Sumio Noda 4-171-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture Inside Kansai Paint Co., Ltd. (72) Inventor Reijiro Nishida 4-171-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa F-term in Nishi Paint Co., Ltd. DB222 DB381 DB382 DB392 DB471 DB472 DF041 DF042 DG161 DG162 DH002 GA07 JB04 JB05 JB07 JB09 JB18 K A03 MA08 MA10 NA01 NA03 NA04 NA07 NA12 NA24 PA07 PA14 PB05 PC03 PC04

Claims (6)

[Claims] 1. A method for producing an inorganic material, comprising forming and curing an inorganic material and then coating an aqueous sealer, wherein the aqueous sealer comprises (I) a number average molecular weight of 400 to 20,000.
00 polyethylene glycol (a) and bisphenol-
(B), a compound obtained by reacting a compound (c) having one active hydrogen in one molecule and a compound (d) having two or more active isocyanate groups in one molecule. An inorganic material characterized by using an epoxy resin emulsion obtained by dispersing an acryl-modified epoxy resin (B) in water, using an epoxy resin (A) as a dispersion-stable resin, and an aqueous coating composition containing (II) an amine curing agent. The method of manufacturing the material. 2. The method for producing an inorganic material according to claim 1, wherein the acrylic-modified epoxy resin (B) is a resin (B-1) obtained by reacting an epoxy resin with a carboxyl group-containing acrylic resin. 3. The method for producing an inorganic material according to claim 1, wherein the acrylic-modified epoxy resin (B) is a resin (B-2) obtained by graft-polymerizing or copolymerizing an epoxy resin with a polymerizable unsaturated monomer. . 4. The method for producing an inorganic material according to claim 3, wherein the polymerizable unsaturated monomer contains a carboxyl group-containing monomer, and the carboxyl group and the epoxy group are reacted after graft polymerization or copolymerization. 5. The method for producing an inorganic material according to claim 1, wherein the use ratio of the resins (A) and (B) is in the range of 10/90 to 90/10 in terms of solid content ratio. 6. The method for producing an inorganic material according to claim 1, wherein a top coat is continuously applied after the aqueous sealer is applied.