JPH1112532A - Aqueous coating for stone-like finish - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject aqueous coating giving coating films not cracked with time and capable of realizing high grade durability and water resistance by including an aggregate and a crosslinking type aqueous emulsion composition comprising a specific semicarbazide derivative composition and an acrylic emulsion into which specific carbonyl groups are introduced. SOLUTION: This aqueous coating comprises 5-80% of an aggregate (e.g. feldspar, marble, a flaky pigment) containing >=5 wt.%, preferably >=20 wt.%, of an aggregate having a granule diameter of 0.05-8.0 mm, preferably 0.1-5.0 mm, and a crosslinkable aqueous emulsion composition comprising an acrylic emulsion having aldo groups or keto groups as carbonyl groups (e.g. an acrolein- acrylic acid-acrylic ester terpolymer emulsion) and a semicabazide derivative composition having an average semicarbazide residue number of >=2.5, preferably 3-20%, as a curing agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-based paint for finishing stones capable of forming a transparent natural stone pattern such as marble or granite on a surface of a base material such as a building material, a building, furniture or an ornament. About. Such paints include:
Also included are so-called ringing coating materials, skin-based coating materials, and multi-colored pattern coating materials.

In particular, a cross-linked aqueous emulsion composition containing an acrylic emulsion into which a specific carbonyl group has been introduced and a specific semicarbazide derivative composition, and a stone finish capable of forming a natural stone pattern containing an aggregate Water-based paint.

[0003]

2. Description of the Related Art As a resin for an aqueous finish coating material, a synthetic resin emulsion obtained by an emulsion polymerization method is often used because it forms a film at room temperature or under heating and drying to form a relatively durable coating film. Used. For example, Japanese Patent Publication No. 2-40702 and Japanese Patent Application Laid-Open No. 57-27177 propose a stone finish coating material comprising a synthetic resin emulsion and an aggregate. The coating films obtained from the coating materials described above have a drawback in that the coating film is whitened or fragile due to rain or dew, which causes cracks over time or cannot maintain sufficient adhesion strength. .

[0004] Also, since relatively large aggregates are used, the effect of filling with fine pigments for expressing the strength of the coating film or the adhesive strength cannot be expected, and the coating film inherent to the resin cannot be expected. Depends heavily on strength. Therefore, when exposed outdoors, the coating film tends to crack when trying to maintain the adhesive strength due to light, heat, rain, etc. However, there was a drawback that it could not be obtained.

Further, Japanese Patent Publication No. Sho 58-20991 discloses a binder for a surface covering agent made of a combination of a carbonyl group-introduced emulsion and a water-soluble acid hydrazine compound. Sex was not enough.

[0006]

SUMMARY OF THE INVENTION An aqueous paint for stone preparation which can give a natural stone pattern, wherein a coating film obtained from the paint does not crack with time and has a sufficient adhesion strength. It is an object of the present invention to propose a paint capable of exhibiting high durability and water resistance capable of maintaining the above-mentioned properties. In particular,
An object of the present invention is to provide a high-performance water-based paint for stone preparation, which contains a synthetic resin emulsion composition obtained by an emulsion polymerization method, a crosslinking agent, and an aggregate.

[0007]

Means for Solving the Problems The present inventors have made intensive studies in order to solve the above-mentioned problems, and as a result,
The present inventors have found that a specific stone-based finishing water-based paint exhibits excellent performance in a coating film obtained therefrom and can solve the above-mentioned problems, and have completed the invention. The aqueous paint for stone preparation of the present invention needs to contain an acrylic emulsion (A) having an ald group or a keto group. The excellent water resistance and the like of the water-based paint of the present invention is that when the aqueous medium in the paint evaporates to form a coating film, the ald group or keto group in the component (A) and the This is because the semicarbazide group is presumed to form a complex crosslinked polymer by forming a semicarbazone bond.

The method for producing the acrylic emulsion (A) having an ald group or a keto group can be a known emulsion polymerization method, and is not particularly limited. Examples of the production method include an ethylenically unsaturated carbonyl group-containing monomer (a) having at least one ald group or keto group in the molecule, an ethylenically unsaturated carboxylic acid monomer (b), and A method of emulsion-polymerizing a monomer system comprising another unsaturated monomer (c) copolymerizable with the above-mentioned monomer in an aqueous medium.

The ethylenically unsaturated carbonyl group-containing monomer (a) having an ald group or a keto group includes acrolein, diacetone acrylamide, diacetone methacrylamide, vinyl methyl ketone, vinyl ethyl ketone, acetoacetoxyethyl methacrylate, Examples include acetoacetoxyethyl acrylate, formylstyrene, and the like, and combinations thereof.

[0010] Ethylenically unsaturated carboxylic acid monomer (b)
The same type or a plurality of types may be used. Specific examples include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, maleic anhydride, maleic acid half ester, crotonic acid, and the like. As the other ethylenically unsaturated monomer (c) copolymerizable with these monomers, the same type may be used, or a plurality of types may be used. Specifically, it is an ethylenically unsaturated monomer having no carboxyl group, ald group, or keto group, and is a monomer copolymerizable with the monomer (a) and / or the monomer (b). .

Examples thereof include acrylates, methacrylates, acrylamide-based monomers, methacrylamide-based monomers, and vinyl cyanides.
Examples of (meth) acrylates include alkyl (meth) acrylates having 1 to 18 carbon atoms in the alkyl portion, hydroxyalkyl (meth) acrylates having 1 to 18 carbon atoms in the alkyl portion, and ethylene oxide. The number of groups is 1 to 100 (poly) oxyethylene (meth) acrylate, the number of propylene oxide groups is 1 to
Examples include 100 (poly) oxypropylene (meth) acrylates and (poly) oxyethylene di (meth) acrylates having 1 to 100 ethylene oxide groups. Specific examples of (meth) acrylates include:
Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, (meth) And dodecyl acrylate. Specific examples of (meth) acrylic acid hydroxyalkyl esters include:
Examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxycyclohexyl (meth) acrylate, and dodecyl (meth) acrylate. Specific examples of (poly) oxyethylene (meth) acrylate include ethylene glycol (meth) acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, diethylene glycol methoxy (meth) acrylate, and (meth) acrylate. Examples include tetraethylene glycol acrylate, tetraethylene glycol methoxy (meth) acrylate, and the like. Specific examples of (poly) oxypropylene (meth) acrylate include propylene glycol (meth) acrylate, propylene glycol methoxy (meth) acrylate, dipropylene glycol (meth) acrylate, and dipropylene glycol methoxy (meth) acrylate. And tetrapropylene glycol (meth) acrylate, tetrapropylene glycol methoxy (meth) acrylate, and the like. Specific examples of (poly) oxyethylene di (meth) acrylate include di (meth)
Examples include ethylene glycol acrylate, diethylene glycol di (meth) acrylate, diethylene glycol methoxy (meth) acrylate, and tetraethylene glycol di (meth) acrylate. Examples of (meth) acrylamide monomers include (meth) acrylamide, N-methylol (meth) acrylamide, and N-butoxymethyl (meth) acrylamide, and examples of vinyl cyanides include (meth) acrylonitrile and so on. Specific examples other than the above, for example, olefins such as ethylene, propylene, isobutylene,
Dienes such as butadiene, haloolefins such as vinyl chloride and vinylidene chloride, vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl benzoate, vinyl pt-butyl benzoate, vinyl pivalate, 2-ethylhexane Vinyl carboxylate esters such as vinyl acrylate, vinyl versatate and vinyl laurate; carboxylic acid isopropenyl esters such as isopropenyl acetate and isopropenyl propionate; ethyl vinyl ether, isobutyl vinyl ether; vinyl ethers such as cyclohexyl vinyl ether; styrene; Aromatic vinyl compounds such as vinyltoluene, allyl esters such as allyl acetate and allyl benzoate, allyl ethers such as allyl ethyl ether, allyl glycidyl ether and allyl phenyl ether, and further γ- ( Data) acryloxy propyl trimethoxy silane, 4- (meth) acryloyloxy -2,
2,6,6-tetramethylpiperidine, 4- (meth)
Acryloyloxy-1,2,2,6,6-pentamethylpiperidine, perfluoromethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluoropropyromethyl (meth) acrylate, vinylpyrrolidone, trimethylolpropane Tri (meth) acrylate, glycidyl (meth) acrylate, (meth)
Examples thereof include 2,3-cyclohexene acrylate, allyl (meth) acrylate, and the like, and combinations thereof.

In the emulsion polymerization step of the acrylic emulsion (A) having an ald group or a keto group, the pH (hydrogen ion concentration) in the polymerization tank is preferably carried out at 1.5 to 4.0. More preferably, it is carried out at 0.5 to 3.0. This is because a paint that gives a coating film having excellent water resistance can be obtained. It is also possible to add various polymerization regulators within the above range if desired. For example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium monohydrogen phosphate, sodium dihydrogen phosphate And a chain transfer agent for controlling the molecular weight such as dodecyl mercaptan.

[0013] The radical polymerization catalyst, which is capable of radically decomposing by heat or a reducing substance to cause addition polymerization of a monomer, such as water-soluble or oil-soluble persulfate, peroxide, azobis compound, etc. Is used. Examples thereof include potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2,2
-Azobisisobutyronitrile, 2,2-azobis (2
-Diaminopropane) hydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile) and the like.
The amount is usually 0.01 to 2% by weight based on the monomer.
Be blended. When it is desired to accelerate the polymerization rate and further perform polymerization at a low temperature, a reducing agent such as sodium bisulfite, ferrous chloride, ascorbate, or Rongalite is used in combination with a radical polymerization catalyst.

Further, a usual surfactant can be used in combination as an emulsifier. For example, anionic surfactants such as fatty acid soaps, alkyl sulfonates, alkyl sulfosuccinates, polyoxyethylene alkyl sulfates, polyoxyethylene alkyl aryl sulfates, polyoxyethylene alkyl aryl ethers, and polyoxyethylene sorbitan fatty acid esters , Nonionic surfactants such as oxyethyleneoxypropylene block copolymer, and α- [1-[(allyloxy) methyl] -2
-(Nonylphenoxy) ethyl] -ω-hydroxypolyoxyethylene (trade name: Adecaria Soap NE-2)
0, NE-30, NE-40, etc., Asahi Denka Kogyo Co., Ltd.
Co., Ltd.), polyoxyethylene alkylpropenyl phenyl ether (trade names: Aqualon RN-10, RN-2)
0, RN-30, RN-50, etc., Daiichi Pharmaceutical Co., Ltd.
Nonionic surfactants which are copolymerized with an ethylenically unsaturated monomer, which is called a reactive nonionic surfactant such as a nonionic surfactant described above. However, the amount used is preferably 1 part by weight or less per 100 parts by weight of all monomers. Use in this range improves the water resistance and adhesion of the coating film.

When the above requirements of the present invention are satisfied,
During the emulsion polymerization, the formation of aggregates is small, and the result is excellent in water resistance. Acrylic emulsion having an ald group or keto group produced by the present invention (A)
In order to maintain the long-term dispersion stability of the emulsion, after the polymerization is completed, p is adjusted using amines such as ammonia, sodium hydroxide, potassium hydroxide, and dimethylaminoethanol.
It is preferable to adjust to a range of H5 to 10.

In the present invention, the acrylic emulsion (A) having an ald group or a keto group preferably contains at least two kinds of emulsion polymerization type polymers in the same particle. This is the invention of claim 2. In order to include at least two types of emulsion polymerization type polymers in the same particle, after the emulsion polymerization step of seed particles using the monomer system [1] is completed in an aqueous medium as a first step, In the second step, it is necessary to obtain a carbonyl group-containing emulsion by emulsion-polymerizing a monomer system [2] different from the monomer system [1] in the presence of particles. In addition, the emulsion polymerization of the second stage can be further divided into two or more stages within the range satisfying the above requirements.

In the invention of claim 2, in the emulsion polymerization in the first step, the monomer (a) containing an ethylenically unsaturated carbonyl group having at least one ald group or keto group in the molecule is 0.5%. % By weight, preferably 0.5 to 20% by weight, and the amount of the ethylenically unsaturated carboxylic acid monomer (b) is 0.1% by weight.
1 to 20% by weight, preferably 1 to 15% by weight, more preferably 4 to 15% by weight, and 99.4% by weight of another unsaturated monomer (c) copolymerizable with these monomers. The reaction is carried out in an aqueous medium by supplying the monomer system [1] in an amount of preferably 98.5% by weight or less, more preferably 95.5% by weight or less.

In the second stage emulsion polymerization, the ethylenically unsaturated carboxylic acid monomer (b) is reduced to 0 or a monomer system [1] in the presence of the seed particles obtained by the first stage emulsion polymerization. Is supplied in an aqueous medium by supplying a monomer system [2] having a weight ratio smaller than that contained in [1].
Preferably, the emulsion polymerization of the second step is carried out in the presence of seed particles by using an ethylenically unsaturated carbonyl group-containing monomer (a) having at least one ald or keto group in the molecule.
Is 0 to 20% by weight, more preferably 0.5 to 20% by weight, the weight ratio of the ethylenically unsaturated carboxylic acid monomer (b) is 0 or less than the weight ratio contained in the monomer system [1], preferably Is less than 0 or 4% by weight, and is carried out in an aqueous medium by supplying a monomer system [2] containing another unsaturated monomer (c) copolymerizable with these monomers.

The weight ratio of the ethylenically unsaturated carboxylic acid monomer (b) contained in the monomer system [2] is changed to the ethylenically unsaturated carboxylic acid monomer (b) contained in the monomer system [1]. If the weight ratio is less than the above, the water resistance of the resulting coating film will be sufficient. The Tg (glass transition temperature) of the polymer obtained from the monomer system [1] for the purpose of achieving a highly compatible property of expressing the strength of the coating and developing the flexibility, and obtaining a coating having excellent water resistance. Can be higher than the Tg of the polymer obtained from the monomer system [2].

The ratio [1] / [2] of the monomer system [1] to the monomer [2] is preferably from 1/99 to 95/5, and is preferably 5 /
95-80 / 20 is more preferred. A coating film having excellent water resistance can be obtained at a ratio within this range. In the invention of claim 2, in order to obtain a coating film having excellent water resistance, in the emulsion polymerization step of the seed particles using the monomer system [1], the pH (hydrogen ion concentration) is set to 1.5 to 4.0. It is preferably carried out, and more preferably carried out at a pH of 1.5 to 3.0. Further, it is not preferable not only during the emulsion polymerization of the seed particles but also after the emulsion polymerization to partially solubilize with an alkali or the like from the viewpoint of water resistance. After the emulsion polymerization of the seed particles, the pH (hydrogen ion concentration) becomes 1. 5 to 4.0, preferably pH 1.5 to
More preferably, it is 3.0.

According to the third aspect of the present invention, the emulsifier used for the acrylic emulsion having an ald group or a keto group according to the first or second aspect is an ethylenically unsaturated monomer having a sulfonate group. It is preferable that the monomer is an ethylenically unsaturated monomer selected from the group consisting of a monomer, an ethylenically unsaturated monomer having a sulfate group, and a mixture thereof.

When these monomers are used as an emulsifier, it is necessary to use 0.05 to 20 parts by weight based on 100 parts by weight of the monomer system. When the emulsion polymerization process is a two-stage process, an ethylenically unsaturated monomer having a sulfonate group and ethylene having a sulfate group are used as emulsifiers with respect to 100 parts by weight of each of the monomer systems [1] and [2]. 0.1 to 5 parts by weight of an ethylenically unsaturated monomer selected from the group consisting of an ethylenically unsaturated monomer and a mixture thereof.

When used in these ranges, the resulting coating film has sufficient water resistance. The ethylenically unsaturated monomer having a sulfate group means a compound having a radical polymerizable double bond and a sulfate group in the molecule, and represented by the following general formulas (1), (2), and ( 3), (10)
And two or more of them can be used in combination.
Specifically, as a material represented by the general formula (1), for example, Adecaria Soap (trademark) SE102 manufactured by Asahi Denka Kogyo KK
5N and the like and represented by the general formula (2), for example, Aqualon (trademark) HS-10 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
Examples of the compound represented by the general formula (3) include Antox (trademark) -MS-60 manufactured by Nippon Emulsifier Co., Ltd., and examples of the compound represented by the general formula (10) include Sanyo Chemical Co., Ltd. And Ereminol (registered trademark) RS-30.

The ethylenically unsaturated monomer having a sulfonate group means a compound having a radical polymerizable double bond and a sulfonate group in the molecule, and represented by the following general formulas (4), (5), These are represented by (6), (7), (8), and (9), and two or more of them can be used in combination. Specifically, as those represented by the general formulas (4) and (5), for example, Eleminol (trademark) JS-2, J manufactured by Sanyo Chemical Industries, Ltd.
S-5, which is represented by the general formulas (6) and (7), for example, Latemul (trademark) S-120 manufactured by Kao Corporation,
S-180, S-180A and the like. Examples of the compound represented by the general formula (8) include sodium p-styrenesulfonate and potassium p-styrenesulfonate, and examples of the compound represented by the general formula (9) include acrylic acid- (2
-Sulfoethyl) ester sodium, acrylic acid-
(2-sulfoethyl) ester potassium, sodium methacrylate- (2-sulfoethyl) ester, sodium acrylate- (3-sulfopropyl) ester, potassium acrylate- (3-sulfopropyl) ester, methacrylate- (3-sulfoethyl) ester Propyl) ester sodium and the like.

[0025]

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Wherein R ¹ is hydrogen or a methyl group, R ²
Represents an alkyl group or an acyl group having 8 to 24 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, n represents an integer of 0 to 50, m represents an integer of 0 to 20, and M represents an alkali metal or ammonium. )

[0027]

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(Wherein, R ¹ is an alkyl group, alkenyl group or aralkyl group having 6 to 18 carbon atoms, R ² is hydrogen or an alkyl group, alkenyl group or aralkyl group having 6 to 18 carbon atoms, R ³ is hydrogen or A propenyl group, A represents an alkylene group having 2 to 4 carbon atoms, n represents an integer of 1 to 200, and M represents an alkali metal or ammonium.)

[0029]

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(Wherein R ¹ is hydrogen or a methyl group, R ²
Is an alkyl group of 1 to 25, R ³ is an alkyl group of 1 to 25, R ⁴ is an alkyl group or benzyl group of 1 to 25 carbon atoms, R ⁵ is an alkyl group or benzyl group of 1 to 25 carbon atoms, and A is An alkylene group having 2 to 4 carbon atoms, p is an integer of 0 to 2, q is an integer of 0 to 2, n is an integer of 1 or more, m is an integer of 1 or more, and M is an alkali metal or ammonium. )

[0031]

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[0032]

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[0033]

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[0034]

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In each of the formulas (4), (5), (6) and (7), R ¹ is hydrogen or a methyl group, R ² is an alkyl group having 1 to 20 carbon atoms, and R ² is an alkyl group having 1 to 20 carbon atoms. Alkenyl group, cycloalkyl group having 5 to 12 carbon atoms, 5 to 5 carbon atoms
A hydrocarbon group such as an aryl group of 10 or 6 to 19 carbon atoms, such as an aralkyl group, or a group in which a part thereof is substituted with a hydroxyl group, a carboxylic acid group, or the like, or a polyoxyalkylene alkyl ether group (where the alkyl moiety has 2 carbon atoms; And 4, an organic group containing an alkylene oxide compound such as a polyoxyalkylene alkylphenyl ether group (the alkyl portion has 0 to 20 carbon atoms and the alkylene portion has 2 to 4 carbon atoms), and A has 2 to 2 carbon atoms. 4 alkylene groups or substituted alkylene groups, n is an integer of 0 to 200, and M represents an alkali metal, ammonium, an organic amine base or an organic quaternary ammonium base.

[0036]

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Wherein M represents an alkali metal, ammonium, an organic amine base or an organic quaternary ammonium base.

[0038]

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(Wherein, R ¹ is hydrogen or a methyl group, n is an integer of 1 to 20, and M is an alkali metal, ammonium, an organic amine base or an organic quaternary ammonium base.)

[0040]

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(Wherein, R ¹ is hydrogen or a methyl group, n is an integer of 2 or more, A is an alkylene group having 2 to 4 carbon atoms, M is an alkali metal, ammonium, an organic amine base or an organic quaternary ammonium base. These reactive surfactants are present in the emulsion as a copolymer obtained by radical polymerization on the emulsion particles, adsorbed as unreacted substances on the emulsion particles, or are present in the emulsion aqueous phase. Or it is adsorbed to emulsion particles as a copolymer with a water-soluble monomer or a copolymer of monomers, or is present in an emulsion aqueous phase.

By increasing the ratio of the particular states, it is possible to improve the water resistance of the film obtained from the emulsion. The reactive surfactant is
It can be identified by pyrolysis gas chromatogram mass spectrometry (Py-GC-MS) or pyrolysis mass spectrometry (Py-MS) of a film obtained from the emulsion. Alternatively, after separating the aqueous phase component of the emulsion,
It is also possible to identify by fast atom bombardment mass spectrometry (FAB mass spectrum).

The water-based paint for stone preparation of the present invention must contain the semicarbazide derivative composition (B) having an average number of semicarbazide residues of 2.5 or more. It is presumed that when the composition functions as a curing agent, the excellent effects of the present invention are exhibited. Here, the average number of semicarbazide residues in the composition needs to be 2.5 or more. By satisfying this range, a complex crosslinked structure is formed at the time of forming a coating film, and excellent effects such as excellent water resistance are exhibited. Preferably it is 2.5 or more and 20 or less, more preferably 3 or more and 20 or less.

The average number of semicarbazide residues is the number of semicarbazide groups per molecule. The number average molecular weight of the semicarbazide composition in terms of styrene measured by gel permeation chromatography (GPC) is M, and 1 gram of the semicarbazide composition. When the number of moles of the semicarbazide group contained therein is S, it is defined by the number represented by M × S.

For the purpose of improving the water resistance of the coating film obtained from the stone-finished water-based paint, a semicarbazide derivative which is insoluble or hardly soluble in water can be used as the semicarbazide derivative. The semicarbazide derivative composition is obtained by reacting a polyisocyanate compound with a hydrazine compound. For example, in one molecule
It can be obtained by reacting a polyisocyanate compound having an average of 2 or more, preferably 3 or more NCO groups with a hydrazine compound.

Further, the semicarbazide derivative composition (B) is preferably a semicarbazide derivative represented by the following formula (11).

[0047]

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(Wherein R ¹ is a linear or branched alkylene diisocyanate having 2 to 20 carbon atoms, an unsubstituted or alkyl group having 1 to 18 carbon atoms,
A cycloalkylene diisocyanate having 5 to 20 carbon atoms substituted with an alkoxy group having 8 to 8 carbon atoms or an alkylene group having 1 to 6 carbon atoms, which is not substituted or has 1 to 1 carbon atoms
C6-20 arylene diisocyanate substituted with an alkyl group having 8 or an alkoxy group having 1 to 8 carbon atoms, and an unsubstituted or an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms A polyisocyanate residue having no terminal isocyanate group, derived from a trimer to a 20-mer oligomer of at least one diisocyanate selected from the group consisting of aralkylenediisocyanates having 8 to 20 carbon atoms substituted with a group, or R ¹ represents a triisocyanate residue without derived from alkylene diisocyanates having 2 to 20 carbon atoms which is substituted with isocyanatoalkyl group having 1 to 8 carbon atoms, terminal isocyanate groups; R ² is straight A chain or branched alkylene group having 2 to 20 carbon atoms, a cycloalkylene group having 5 to 20 carbon atoms Or unsubstituted or substituted or represents an arylene group having 6 to 10 carbon atoms which is substituted with an alkyl group or an alkoxy group having 1 to 8 carbon atoms having 1 to 18 carbon atoms; each R ³ is independently Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; n is 0 or 1; l and m are each 0 or a positive integer, provided that 2
≦ (l + m) ≦ 20, preferably 3 ≦ (l + m)
≦ 20. In the formula (11), the semicarbazide derivative where l + m = 2 is obtained by reacting a diisocyanate compound having two -NCO groups in one molecule with a hydrazine compound.

In order to obtain a film having higher crosslinking efficiency, toughness and excellent water resistance, the semicarbazide derivative represented by the formula (11) has three or more -NCO groups in one molecule. Desirably, it is obtained by reacting a polyisocyanate compound with a hydrazine compound. Polyisocyanate compounds having 3 to 20 —NCO groups in one molecule and semicarbazide derivatives derived therefrom are described, for example, in WO 96/01252.
No. pamphlet.

Here,-in one molecule of polyisocyanate
When the number of NCO groups does not exceed 20, the number of semicarbazide groups is relatively appropriate, and the semicarbazide derivative composition (B)
Is not so high that it can be handled.
It is also preferable from the viewpoint of compatibility with the polycarbonyl compound. The polyisocyanate compound having 3 to 20 -NCO groups in one molecule is obtained by oligomerizing a diisocyanate compound. For example, a diisocyanate is a buret bond, a urea bond, an isocyanurate bond,
Polyisocyanate compound oligomerized by urethane bond, allophanate bond, uretdione bond, etc.,
Further examples include 1,8-diisocyanato-4-isocyanatomethyloctane and a combination thereof.

Specifically, a polyisocyanate compound having an isocyanurate structure or a burette structure as a basic skeleton is preferable from the viewpoints of hardness, chemical resistance, heat resistance and the like of the coating film. Further, as a film having excellent flexibility of a coating composition obtained from a coating composition with an acrylic emulsion (A) having an ald group or a keto group, those having a urethane structure as a basic skeleton can be exemplified.

In the present invention, the hydrazine compound is converted to a monoaldehyde represented by the following formula (2) in order to prevent the semicarbazide derivative or the polyisocyanate compound as a raw material thereof from being polymerized by chain extension of the hydrazine compound. Alternatively, it can be used by reacting with a monoketone or the like and blocking as a hydrazone group. R ⁴ R ⁵ C ＝ O (12) (wherein, R ⁴ and R ⁵ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, 5 carbon atoms)
To 20 cycloalkyl groups, or unsubstituted or C1 to C18 alkyl groups or C1 to C8
Represents an aryl group having 6 to 10 carbon atoms, which is substituted with an alkoxyl group, and R ⁴ and R ⁵ may form a cyclic structure in some cases. In this case, the resulting semicarbazide derivative has a semicarbazide group blocked as a semicarbazone group,
It is a terminal blocker of the semicarbazide derivative of the above formula (11).

The elimination of the monoaldehyde or monoketone used as a blocking agent from the semicarbazide derivative composition (B) is carried out by hydrolysis and distillation before mixing with the acrylic emulsion (A) having an ald or keto group. Alternatively, the composition may be used as it is as a curing agent to form a water-based paint, applied to the surface of a substrate, and then spontaneously released during the curing process. Therefore, as the blocking agent, a monoketone having a boiling point of 30 to 200 ° C., for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like are preferable.

Further, in order to assist the dispersion stability and solubility of the semicarbazide derivative represented by the formula (11) and / or the semicarbazide derivative comprising the terminal-blocked compound in an aqueous medium, the following formula (13) is used. It can be used by mixing with at least one selected from the hydrophilic group-containing compound and / or the terminal blocker.

[0055]

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(Wherein, R ¹¹ is a linear or branched alkylene diisocyanate having 2 to 20 carbon atoms, an unsubstituted or alkyl group having 1 to 18 carbon atoms,
A cycloalkylene diisocyanate having 5 to 20 carbon atoms substituted with an alkoxy group having 8 to 8 carbon atoms or an alkylene group having 1 to 6 carbon atoms, which is not substituted or has 1 to 1 carbon atoms
C6-20 arylene diisocyanate substituted with an alkyl group having 8 or an alkoxy group having 1 to 8 carbon atoms, and an unsubstituted or an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms A polyisocyanate residue having no terminal isocyanate group, derived from a trimer to a 20-mer oligomer of at least one diisocyanate selected from the group consisting of aralkylenediisocyanates having 8 to 20 carbon atoms substituted with a group, or R ¹¹ represents an alkylene derived from isocyanate, triisocyanate residue free of having a terminal isocyanate group having 2 to 20 carbon atoms which is substituted with isocyanatoalkyl group having 1 to 8 carbon atoms; R ¹² represents a linear A chain or branched alkylene group having 2 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, Group or unsubstituted or substituted with or represents an arylene group having 6 to 10 carbon atoms which is substituted with an alkyl group or an alkoxy group having 1 to 8 carbon atoms having 1 to 18 carbon atoms; each R ¹³ is each independently Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; n is 0 or 1; and p and q are each 0 or a positive integer, r is a positive integer, and 3 ≦ ( (p + q + r) ≦ 20) The compound in which the semicarbazide group of the hydrophilic group-containing compound represented by the formula (13) is blocked as a semicarbazone group has at least one of the terminal groups H ₂ NR ¹³ N— in the formula (13). Exemplary ethynylphenylbiadamantane derivatives R ⁵ R ⁴ C = NR ¹³ in which a blocked end group (formula represented by N-, R ^4, R ⁵ are each independently hydrogen atom, linear or branched carbon atoms An alkyl group having 1 to 20 carbon atoms, a cycloalkyl having 5 to 20 carbon atoms C 6 carbon atoms which are unsubstituted or substituted by an alkyl group having 1 to 18 carbon atoms or an alkoxy group having 1 to 8 carbon atoms
Represents an aryl group of from 10 to 10, and R ⁴ and R ⁵ may optionally form a cyclic structure together. ) It can also be used as a terminal blocker of a hydrophilic group-containing compound.

That is, at least one selected from the semicarbazide derivative represented by the above formula (11) and / or the terminal blocker, and the hydrophilic group-containing compound and / or the terminal blocker represented by the above formula (13) Semicarbazide derivative composition (B) containing at least one selected from the group consisting of:
Can be advantageously used as a curing agent for the acrylic emulsion (A) having an ald group or a keto group.

Then, at least one selected from the semicarbazide derivative represented by the formula (11) and / or the terminal blocker, and the hydrophilic group-containing compound represented by the formula (13) and / or the terminal blocker At least one chosen
In a composition containing
It is desirable to be within the range of / 1/10/90. As a result, a water-based paint having a stable coating film and excellent curing performance can be obtained.

At least one selected from the semicarbazide derivatives represented by the formula (11) of the present invention and a compound represented by the formula (13)
The composition containing at least one selected from the hydrophilic group-containing compounds represented by the formula:
It can be obtained by the method described in No. 01252 pamphlet. In the present invention, it is preferable to use a mixture of the semicarbazide derivative composition (B) and a ketone acid and / or a salt thereof as a curing agent for the acrylic emulsion (A) having an ald group or a keto group. This is because a film having high crosslinking efficiency, toughness, and excellent water resistance can be obtained.

In this case, it is more preferable that the semicarbazide derivative composition (B) is a semicarbazide derivative represented by the formula (11). Further, it is more preferable that the semicarbazide derivative composition (B) is a poorly water-soluble semicarbazide derivative. Here, poor water solubility means that the solubility in 100 g of water at 25 ° C. is 5 g or less.

The semicarbazide derivative composition (B) of the present invention is dispersed in an aqueous medium and dissolved in an aqueous medium so as to be easily mixed with the acrylic emulsion (A) having an ald group or a keto group. Preferably, at least one state selected from the group consisting of: When dispersing or dissolving the semicarbazide derivative composition (B) of the present invention in water, the above-mentioned formula (13) may be optionally used.
Other surfactants other than the hydrophilic group-containing compound represented by may be added. Examples of such surfactants include:
Higher fatty acids, acidic fatty alcohols, alkyl sulfonates, alkyl succinates, polyoxyethylene alkyl sulfates, polyoxyethylene alkyl aryl sulfates,
Anionic surfactants such as salts of alkyl sulfosuccinates and alkenyl succinates, and nonionic surfactants typified by known reaction products of ethylene oxide with long-chain fatty alcohols or phenols and phosphoric acids Nonionic surfactants such as polyoxyethylene alkylaryl ethers, polyoxyethylene sorbitan fatty acid esters, oxyethylene oxypropylene block copolymers, and known reaction products of ethylene oxide and phosphoric acids, and quaternary ammonium salts. Cationic surfactants, polymer dispersion stabilizers such as (partially saponified) polyvinyl alcohol, and the like, and combinations thereof.

In particular, a hydrophilic group-containing compound represented by the formula (13) or an alkenyl succinate is preferred because of its high affinity with the semicarbazide derivative of the formula (11). In the present invention, ketone acids and / or salts thereof include:
Examples include monoketone monocarboxylic acids represented by the formula (14), monoketone dicarboxylic acids represented by the formula (16), and a combination thereof.

[0063]

Embedded image

R ^{1 ′} is a hydrogen atom or a straight-chain or branched C 1-8 unsubstituted or substituted by a hydroxyl group or a C 1-8 alkoxy group.
Represents 30 alkyl groups. R ^{2 ′} is a linear or branched C 1-30 unsubstituted or substituted with a hydroxyl group or a C 1-8 alkoxy group.
Represents an alkylene group. p represents 0 or 1. X is
Each independently represents a hydrogen atom, an alkali metal, ammonium or a substituted ammonium represented by the formula (15).

HNR ^{3 ′} R ^{4 ′} R ^{5 ′} (15) (R ^{3 ′} , R ^{4 ′} and R ^{5 ′} are each independently a hydrogen atom,
Or a linear or branched C1-C20 alkyl group which is not substituted or substituted with a hydroxyl group. Further, R ^{3 ′} and R ^{4 ′,} or R ^{3 ′} , R ^{4 ′} and R ^{5 ′} may jointly form a cyclic structure. )｝

[0066]

Embedded image

R ¹ and R ² are each independently unsubstituted or substituted with a hydroxyl group or an alkoxy group having 1 to 8 carbon atoms, which is linear or branched and has 1 to 30 carbon atoms. Represents an alkylene group. q and r each represent 0 or 1. Y and Z each independently represent a hydrogen atom, an alkali metal, ammonium or a substituted ammonium represented by the formula (15).

HNR ^{3 ′} R ^{4 ′} R ^{5 ′} (15) (R ^{3 ′} , R ^{4 ′} and R ^{5 ′} are each independently a hydrogen atom,
Or a linear or branched C1-C20 alkyl group which is not substituted or substituted with a hydroxyl group. Further, R ^{3 ′} and R ^{4 ′,} or R ^{3 ′} , R ^{4 ′} and R ^{5 ′} may jointly form a cyclic structure. Specific examples of the monoketone carboxylic acids include, for example, pyruvic acid, levulinic acid, acetoacetic acid, ketocapric acid, ketoundecanoic acid, ketostearic acid, ketoheneicosenoic acid, ketoglyconic acid and the like. Specific examples of the monoketone dicarboxylic acid include, for example, ketomalonic acid, acetone dicarboxylic acid, 2-ketoglutaric acid, acetone diacetic acid, acetone dipropionic acid, and the like.

The ketone acid salt can be obtained by neutralizing the above ketone acid with a base. Examples of the base used for the neutralization include hydroxides of alkali metals such as KOH, NaOH, and LiOH, amines represented by the formula (15), and a combination thereof. Specific examples of the amines include, for example, ammonia, diethylamine, dipropylamine, dibutylamine, N-methylethanolamine, diethanolamine, dimethylcyclohexylamine, methyldiethanolamine, dimethylethanolamine, triethanolamine, triethylamine, pyrrolidine, piperidine, Morpholine and the like.

By mixing the semicarbazide derivative composition (B) with the ketone acid, for example, when a monoketone monocarboxylic acid is used as the ketone acid, the following equilibrium reaction occurs, and the hydrophilicity of the obtained semicarbazide derivative composition is improved. It is assumed that it can be controlled.

[0071]

Embedded image

As can be seen from the above equation, the hydrophilicity of the semicarbazide derivative composition of the present invention is controlled by
The H ₂ O concentration greatly affects the mixing ratio of the semicarbazide derivative composition (B) and the ketone acid. That is, H ₂
If the O concentration is small, the above equilibrium equation shifts to the production system, and the amount of ketone acid or its salt introduced into the semicarbazide derivative composition increases, and as a result, the hydrophilicity of the semicarbazide derivative composition increases. Conversely, when the H ₂ O concentration is high, the hydrophilicity of the semicarbazide derivative composition (B) decreases. In the present invention, the H ₂ O concentration can be arbitrarily set for the purpose of controlling hydrophilicity.

In the present invention, the mixing of the semicarbazide derivative composition (B) with the ketone acid and / or its salt can be carried out in any ratio, but the ketone to the semicarbazide residue in the semicarbazide derivative composition (B) can be mixed. The ratio of keto groups in the acid is preferably in the range of 0.001 to 10 in terms of (keto group) / (hydrazine group) equivalent ratio. The mixing of the semicarbazide derivative composition (B) and the ketone acid can be performed in an arbitrary temperature range without a solvent or in a solvent. Specific examples of the solvent include water, t-
Alcohols such as butanol, isopropanol and 2-butoxyethanol; ether solvents such as dioxane, tetrahydrofuran and diethylene glycol dimethyl ether; amide solvents such as dimethylformamide and dimethylacetamide; lactam solvents such as N-methyl-2-pyrrolidone; Sulfoxide solvents such as sulfoxide; ester solvents such as ethyl acetate and cellosolve acetate; aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as n-hexane; and the like, and combinations thereof. .

The water-based paint for stone preparation of the present invention contains an acrylic emulsion (A) having an ald group or a keto group and a semicarbazide derivative composition (B) having an average number of semicarbazide residues of 2.5 or more. The nonvolatile content of the crosslinked aqueous emulsion composition to be formed is preferably from 20 to 70%, more preferably from 30 to 65%.

The water-based paint for stone preparation of the present invention needs to contain the aggregate (C). As the aggregate, transparent aggregate,
Examples include colored aggregates, liquid colored particles disclosed in JP-A-64-16879 or JP-A-8-151541, and colored dispersed particles containing a pigment on a scale. Examples of transparent aggregates include feldspar, silica sand, silica stone, cold water stone, glass beads, and transparent synthetic resin beads. Colored aggregates include marble powder, granite powder, serpentine,
Examples include fluorite, colored silica sand powder, and colored ceramic powder.

The aggregate (C) contains at least 5% by weight, preferably at least 20% by weight of an aggregate having a particle size of 0.05 to 8.0 mm, preferably 0.1 to 5.0 mm. It is desirable that If the aggregate having the particle size of the aggregate (C) which is equal to or larger than the above lower limit is included within the above range, the transparency of the coating film obtained from the aqueous coating material for stone preparation can be obtained, and the particle size can be obtained. If the amount of the aggregate is less than or equal to the upper limit in the range of the amount, the aggregate is less likely to fall off from the coating film and the construction is easy.

It is preferred that the aggregate (C) is a mixture of a transparent aggregate and a colored aggregate. In this case, the weight ratio of the transparent aggregate to the colored aggregate is preferably from 1/99 to 99/1, and more preferably from 5/95 to 95/5. It is preferable that the amount of the aggregate (C) in the aqueous coating material for stone preparation is 5 to 80% by weight. When the amount of the aggregate is 5% by weight or more, a natural stone pattern is obtained in the coating film, and when the amount is 80% by weight or less, the durability of the coating film is excellent.

The aqueous paint for stone preparation of the present invention may contain a pigment. Specific examples include coloring pigments such as carbon black, red iron oxide, and titanium oxide; extender pigments such as calcium carbonate, talc, mica, clay, diatomaceous earth, pearlite, and aluminum hydroxide; portland cement; and zinc oxide. Further, it can be used for the above-mentioned liquid colored particles or colored dispersed particles.

Further, a surfactant can be used in the aqueous coating material for stone preparation of the present invention. Surfactants that can be used include, for example, sodium, potassium, or ammonium salts of hexametaphosphoric acid, sodium, potassium, or ammonium salts of tripolyphosphoric acid, sodium salts of polymers having a carboxylic acid group such as polyacrylic acid, Potassium salt or ammonium salt. In addition, for example, anionic surface activity represented by salts such as higher fatty acids, resin acids, acidic fatty alcohols, sulfates, higher alkyl sulfonic acids, alkyl allyl sulfonates, sulfonated castor oil, sulfosuccinates, and alkenyl succinic acids. Agents or nonionic surfactants represented by known reaction products of ethylene oxide with long-chain fatty alcohols or phenols and phosphoric acids;
A cationic surfactant containing a quaternary ammonium salt or the like,
(Partially saponified) Polymer dispersion stabilizers such as polyvinyl alcohol, methylcellulose, hydroxyethylcellulose and polyvinylpyrrolidone; thickeners such as polyether-based thickeners; plasticizers such as dibutyl phthalate; diethylene glycol monobutyl ether; ethylene glycol Monobutyl ether, 2,2,4-trimethyl-1,3
-Film-forming aids such as butanediol isobutyrate and diisopropyl glutarate, and combinations thereof.

It is preferable to apply a transparent top coat to the coating film using the water-based paint for stone preparation of the present invention, and the coating amount is 0.1 to 0.5 kg / m ^2. preferable. Examples of transparent topcoats include acrylic resin, vinyl acetate / acrylic resin, styrene / acrylic resin, acrylic / urethane resin, polyurethane resin,
A solvent-based or water-based resin mainly containing a fluorine resin, a silicone / acrylic resin, or the like can be given.

When the aqueous paint for stone preparation of the present invention is used, for example, concrete, cement mortar, slate board, flexil board, PC board, ALC
Inorganic base materials such as boards, scalp boards, gypsum boards, extruded boards, concrete blocks, etc., metals, wood, plastics, stones, etc. can be used, but primer, sealer coating, cement filler, or other undercoating is performed in advance. It is preferable to keep it.

The water-based paint for stone preparation of the present invention is
The coating can be performed using a known coating tool such as a paint spray gun such as a ricin gun, a universal gun, or a three-head gun.
The applied film thickness of the water-based paint for stone preparation of the present invention is 0.1 to 10.0 kg / m ² , preferably 0.1 to 10.0 kg / m ² , based on the applied amount.
About 3 to 5.0 kg / m ² is appropriate. The stone-based water-based paint is preferably applied so as to have a smooth surface or a smooth uneven pattern over the entire surface of the resin layer,
If necessary, the paint can be flattened after or before drying using a sander or the like.

[0083]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to Reference Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples. The parts and percentages in the examples are by weight. The measuring methods of various measurements used in the examples are as follows. Molecular weight distribution: It was determined from a calibration curve of a polystyrene standard using gel permeation chromatography.

(Equipment used) · Apparatus: Tosoh Corporation HLC-8020 · Column: Tosoh Corporation TSKgel G-5000 HXL TSKgel G-4000 HXL TSKgel G-2000 HXL · Data processing: Tosoh SC8010 · Carrier: Tetrahydrofuran semicarbazide Method for measuring group content About 0.2 g (W grams) of a sample is dissolved in 10 cc of dimethylacetamide. To this, 5 cc of a solution of 2.5 g of cyclohexyl isocyanate dissolved in 50 cc of dimethylacetamide is added and left at room temperature for 1 hour. Thereafter, 3.2 g of di-n-butylamine was added to 100 parts of toluene.
Add 10 cc of the solution dissolved in cc, and leave for 30 minutes. Thereafter, 70 cc of isopropanol is added, a small amount of bromocresol green is added as an indicator, and the mixture is titrated with 0.1 N hydrochloric acid (factor F) (titration A).
The same operation is performed without adding a sample (titration value B).
The semicarbazide group content (unit is meq)
/ G) is required.

(BA) × 0.1 × F / W Weather Resistance Test A VP sealer (manufactured by Kansai Paint Co., Ltd., sealer) was applied on a flexible plate using a brush so as to be 50 g / m ^2. Then, after drying at room temperature for 2 hours, with respect to the emulsion of each Example or Comparative Example, a 2 mm-thick water-based paint for stone preparation adjusted according to the following finishing material composition was applied, and the emulsion was applied at room temperature for 24 hours. Let dry. On top of this coating, 200 g / g of the transparent topcoat shown in Reference Example 1
m ² was applied with a brush and dried at room temperature for 2 weeks to obtain a test body. Subsequently, a sunshine type weatherometer (WEL-SUN-D, manufactured by Suga Test Instruments Co., Ltd.)
C) was used to carry out an exposure test (rain cycle: 12 minutes / hour, black panel temperature: 60 to 66 ° C.). After 1500 hours of exposure, the state was visually determined according to the following criteria. A similar test piece was prepared except that the top coat was not applied, and the same test was performed.

Criteria 基準: No blisters, shine, cracks are seen at all. Δ: Blistering, gloss, cracking is observed. ×: Blisters, gloss, cracks are remarkably observed. (Mixing of finishing materials) Emulsions of Examples and Comparative Examples 100.0 parts Emulgen 950 (25% aqueous solution) * 1 0.5 parts CS-12 * 2 7.5 parts Water 2.0 parts 3% aqueous solution of Himetroze 90SH30000 Note 3 20.0 parts SN-deformer 113 Note 4 0.3 parts Silica sand 4 10.0 parts Marble powder # 100 100.0 parts Calcium carbonate SS-30 Note 5 210.0 parts (Note) Note 1 Nonionic interface Activator: Kao Corporation * 2 Film-forming aid: Chisso Corporation * 3 Thickener: Shin-Etsu Chemical Co., Ltd. * 4 Defoamer: Sannopco Corporation * 5 Calcium carbonate: Nitto Powder Bond strength test and bond strength test after immersion manufactured by Kako Co., Ltd. Mortar plate (70 mm ×
A VP sealer (manufactured by Kansai Paint Co., Ltd., sealer) was applied to a 70 mm × 20 mm) with a brush so as to be 50 g / m ^2, and dried at room temperature for 2 hours. With respect to the emulsion (2), a water-based paint for finishing stones prepared according to the above-mentioned finishing material composition was applied to a thickness of 2 mm, and dried at room temperature for 24 hours. On top of this coating, 200 g / g of the transparent topcoat shown in Reference Example 1
m ² was applied with a brush and dried at room temperature for 2 weeks to obtain a test body. Using this specimen, JIS-A
The adhesion strength and the adhesion strength after water immersion were measured by the method specified in -6909.

[0087]

[Reference Example 1] [Adjustment of transparent top coat] Stirrer, reflux condenser,
In a reaction vessel equipped with a dropping tank and a thermometer, 8 parts of methacrylic acid, 55 parts of methyl methacrylate,
37 parts of ethylhexyl, 300 parts of water, ammonium sulfosuccinate diester (trade name; Latemul S-180)
A, 20 parts of a 20% aqueous solution of Kao Corporation) is added, the temperature in the reaction vessel is raised to 78 ° C., and 0.5 parts of ammonium persulfate is added and maintained for 1 hour. Thus, the seed particles of the first stage were prepared, and the pH was 1.8 when the hydrogen ion concentration was measured. Next, methacrylic acid 3
Mixture, 219 parts of methyl methacrylate, 178 parts of 2-ethylhexyl acrylate, and 300 parts of water, 20 parts of a 20% aqueous solution of latemul S-180A, and 1.0 part of ammonium persulfate in a reaction vessel. It is allowed to flow over 3 hours from separate dripping tanks. During the inflow, the temperature in the reaction vessel is maintained at 80 ° C. After the inflow is completed, the temperature in the reaction vessel is kept at 85 ° C. and maintained for 6 hours. After cooling to room temperature, the hydrogen ion concentration was measured to be 2.5. After adjusting the pH to 8 by adding a 25% aqueous ammonia solution, the mixture was filtered through a 100-mesh wire net. The dry weight of the filtered agglomerates was very low, 0.01% based on the total monomer. The solid content of the obtained emulsion was 44.4%, and the average particle size was 1220 °. After mixing this emulsion according to the following formulation, a transparent topcoat was obtained.

(Formulation of top coat) 100.0 parts of the above emulsion 15.0 parts of diisopropyl glutarate 10.0 parts of ethylene glycol monobutyl ether 10.0 parts of water

[0089]

Reference Example 2 [Synthesis Example of Acrylic Emulsion (1) Having Aldo Group or Keto Group] Methacrylic acid 8 was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank and a thermometer.
Parts, 3 parts of diacetone acrylamide, 49 parts of methyl methacrylate, 40 parts of butyl acrylate, 300 parts of water, and 20 parts of a 20% aqueous solution of latemul S-180A, and after raising the temperature in the reaction vessel to 78 ° C. And 0.5 parts of ammonium persulfate are added and kept for 1 hour. Thus, the seed particles of the first stage were prepared, and the pH was 1.8 when the hydrogen ion concentration was measured. Next, 4 parts of methacrylic acid,
A mixture of 12 parts of diacetone acrylamide, 169 parts of methyl methacrylate, and 215 parts of butyl acrylate, and water 3
00 parts, 20 parts of a 20% aqueous solution of latemul S-180A,
A mixed solution of 1.0 part of ammonium persulfate is allowed to flow into the reaction vessel from a separate dropping tank over 3 hours. During the inflow, the temperature in the reaction vessel is maintained at 80 ° C. After the inflow is completed, the temperature in the reaction vessel is kept at 85 ° C. and maintained for 6 hours. After cooling to room temperature, the hydrogen ion concentration was measured to be 2.8. After adjusting the pH to 8 by adding a 25% aqueous ammonia solution, the mixture was filtered through a 100-mesh wire net. The dry weight of the filtered agglomerates was very low, 0.01% based on the total monomer. The solid content of the obtained emulsion is 4
4.4% and an average particle diameter of 1100 °.

[0090]

Reference Example 3 [Synthesis Example of Acrylic Emulsion (2) Having Aldo Group or Keto Group] Methacrylic acid 6 was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank and a thermometer.
Parts, acrylic acid 2 parts, diacetone acrylamide 3
, 25 parts of styrene, 21 parts of methyl methacrylate, 43 parts of 2-ethylhexyl acrylate, 300 parts of water, and 20 parts of a 20% aqueous solution of latemul S-180A, and the temperature in the reaction vessel was raised to 78 ° C. , 0.5 part of ammonium persulfate is added and kept for 1 hour. Thus, the seed particles of the first stage were prepared, and the pH was 1.8 when the hydrogen ion concentration was measured. Next, a mixed solution of 12 parts of diacetone acrylamide, 110 parts of styrene, 76 parts of methyl methacrylate, and 202 parts of 2-ethylhexyl acrylate, 300 parts of water, and sodium p-styrenesulfonate (trade name: Spinomer NaSS, Tosoh Corporation) 2)
A mixture of 20 parts of a 0% aqueous solution and 1.0 part of ammonium persulfate is allowed to flow into the reaction vessel from separate dropping tanks over 3 hours. During the inflow, the temperature in the reaction vessel is maintained at 80 ° C. After the inflow is completed, the temperature in the reaction vessel is kept at 85 ° C. and maintained for 6 hours. After cooling to room temperature, the hydrogen ion concentration was measured to be 2.5. After adjusting the pH to 8 by adding a 25% aqueous ammonia solution, the mixture was filtered through a 100-mesh wire net. The dry weight of the filtered agglomerates was very low, 0.01% based on the total monomer. The solid content of the obtained emulsion was 44.5%, and the average particle size was 1,000 °.

[0091]

Reference Example 4 [Synthesis Example of Acrylic Emulsion (3) Having Aldo Group or Keto Group] In a reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank and a thermometer, methacrylic acid 8 was added.
Parts, acrylamide 2 parts, diacetone acrylamide 6
Parts, styrene 35 parts, methyl methacrylate 20 parts, 2-ethylhexyl acrylate 54 parts, water 350 parts, reactive surfactant (trade name: Adecaria Soap SE-1025)
N, 25 parts of a 20% aqueous solution of Asahi Denka Kogyo Co., Ltd.) is added, the temperature in the reaction vessel is raised to 78 ° C., and 0.5 parts of ammonium persulfate is added and maintained for 1 hour. Thus, the seed particles of the first stage were prepared, and the pH was 2.2 when the hydrogen ion concentration was measured. Next, 19 parts of diacetone acrylamide, 100 parts of styrene, 35 parts of methyl methacrylate, 2-ethylhexyl acrylate 221
Part, water 250 parts, a mixture of 15 parts of a 20% aqueous solution of sodium acrylate- (2-sulfoethyl) ester (trade name: ANTOXMS-2N, manufactured by Nippon Emulsifier Co., Ltd.), and 1.0 part of ammonium persulfate The liquid is allowed to flow from the dropping tank over 3 hours. During the inflow, the temperature in the reaction
Keep at ° C. After the inflow is completed, the temperature in the reaction
C. and hold for 6 hours. After cooling to room temperature, the hydrogen ion concentration was measured to be 2.5. After adjusting the pH to 8 by adding a 25% aqueous ammonia solution, the mixture was filtered through a 100-mesh wire net. The dry weight of the filtered agglomerates was very low, 0.01% based on the total monomer. The solid content of the obtained emulsion was 44.5%, and the average particle size was 11%.
It was 20Å.

[0092]

Reference Example 5 Synthesis Example of Polyisocyanate Compound A 222 parts of isophorone diisocyanate, 168 parts of hexamethylene diisocyanate, and 2.4 parts of water as a burette agent were mixed with ethylene glycol methyl ether acetate and trimethyl phosphate at a ratio of 1: 1. The mixture was dissolved in 130 parts (by weight) of a mixed solvent and reacted at a reaction temperature of 160 ° C. for 1.5 hours. The first reaction was performed using a thin-film distillation can to obtain 1.0 mm
The second time is 0.1 mmHg / 2 under the condition of Hg / 160 ° C.
Excess isophorone diisocyanate and hexamethylene diisocyanate and the solvent were distilled off and recovered by a two-stage treatment under the condition of 00 ° C.

The obtained polyisocyanate compound A is
Cobourette-type polyisocyanate of isophorone diisocyanate and hexamethylene diisocyanate, the remaining isophorone diisocyanate is 0.7% by weight,
0.1% by weight of remaining hexamethylene diisocyanate,
The NCO content is 19.6% by weight and the viscosity is 20,000 (±
3000) mPa. s / 40 ° C., number average molecular weight is about 80
0 (± 100) with an average -NCO functionality of about 3.
It was 7.

[0094]

Reference Example 6 [Synthesis Example of Semicarbazide Derivative A] In a reactor having a reflux condenser, a thermometer and a stirrer, 22 parts of tetrahydrofuran and polyisocyanate A (polyisocyanate compound A was prepared by adding 79.6% of ethyl acetate with ethyl acetate) As a solution, N
23 parts of polyoxyethylene methyl ether (trade name; UNIOX (trademark) M1)
000, manufactured by NOF Corporation, with a hydroxyl value of 56.9)
10 parts, dibutyltin dilaurate 0.001 as a catalyst
The reaction was conducted at 60 ° C. for 4 hours. Next, a reflux condenser,
To 147 parts of tetrahydrofuran placed in a reactor having a thermometer and a stirrer, 7.3 parts of hydrazine monohydrate was added at room temperature over 30 minutes while stirring, and the mixture was further stirred for 1 hour. The reaction product obtained above was added to this reaction solution with stirring at 40 ° C. over 1 hour, and then further stirred at 40 ° C. for 4 hours. Thereafter, 182 parts of water was added at 40 ° C. over 30 minutes, and stirring was continued for another 30 minutes. The tetrahydrofuran, ethyl acetate, hydrazine, water and the like in the obtained reaction solution are distilled off under heating and reduced pressure to obtain a solid content of 30%.
% Of an aqueous dispersion of the semicarbazide derivative A was obtained. Further, when all the solvent was removed and the content of the semicarbazide group was measured, it was 2.6 meq / g.

[0095]

Reference Example 7 [Synthesis Example of Semicarbazide Derivative B] 20 parts of hydrazine monohydrate was added at room temperature to 230 parts of isopropyl alcohol in a reactor having a reflux condenser, a thermometer and a stirrer. A solution prepared by dissolving 42 parts of the above polyisocyanate A in 168 parts of tetrahydrofuran was added at 40 ° C. over about 1 hour, and stirring was continued at 40 ° C. for 3 hours. Tetrahydrofuran in the obtained reaction solution,
By distilling hydrazine, water, etc. under heating and reduced pressure,
The semicarbazide derivative was obtained as a white solid. When the semicarbazide group content was measured, it was 4.1 meq / g.

To 27 parts of the semicarbazide derivative were added 2 parts of pyruvic acid and 58 parts of water, and the mixture was stirred at 30 ° C. for 30 minutes. Then, 3.6 parts of a 10% aqueous ammonia solution was added, and the mixture was further stirred at 30 ° C. for 1 hour. To obtain a derivative B comprising a homogeneous and transparent semicarbazide derivative and a ketone acid salt.
Was obtained.

[0097]

Reference Example 8 [Synthesis Example of Semicarbazide Derivative C] 168 parts of hexamethylene diisocyanate, water 1.
5 parts were mixed solvent of ethylene glycol methyl ether acetate and trimethyl phosphate in a ratio of 1: 1 (weight ratio) 13
0 parts, and reacted at a reaction temperature of 160 ° C. for 1 hour. The obtained reaction solution was first used under a condition of 1.0 mmHg / 160 ° C. and a
Excess hexamethylene diisocyanate and the solvent were distilled off and recovered by a two-stage treatment under the condition of mHg / 200 ° C. to obtain a residue. The residue obtained contained 99.9% by weight of polyisocyanate C (buret type polyisocyanate of hexamethylene diisocyanate) and 0.1% by weight of residual hexamethylene diisocyanate. The viscosity of the residue obtained is 1900 (± 20
0) mPa. s / 25 ° C., number average molecular weight is about 600 (±
100) and the average number of -NCO functional groups is about 3.3,-
The NCO group content was 23.3% by weight.

To a reactor having a reflux condenser, a thermometer and a stirrer, 80 parts of hydrazine monohydrate was added to 1,000 parts of isopropyl alcohol at room temperature with stirring for about 30 minutes. Content 2
A solution prepared by dissolving 144 parts of (3.3% by weight) in 576 parts of tetrahydrofuran was added over about 1 hour at 10 ° C., and stirring was further continued at 40 ° C. for 3 hours, and 1000 parts of water was added. Subsequently, isopropyl alcohol, hydrazine, tetrahydrofuran, water and the like in the obtained reaction solution were distilled off under reduced pressure by heating to obtain 168 parts of a semicarbazide derivative C having a biuret structure. When the semicarbazide group content was measured, it was 4.6 meq / g.

[0099]

Example 1 100 parts of an acrylic emulsion (1) having an ald group or a keto group synthesized in Reference Example 2 and a solid content concentration of the semicarbazide derivative A obtained in Reference Example 30 of 30
% Of an aqueous solution was added, and mixed at room temperature for 30 minutes. Then, a finishing material was blended and subjected to each test. Table 1 shows the results.

[0100]

Example 2 100 parts of an acrylic emulsion (1) having an ald group or a keto group synthesized in Reference Example 2 and 4.7 parts of an aqueous solution of the semicarbazide derivative B obtained in Reference Example 7 were added. After minute mixing, a finishing material was blended and subjected to each test. Table 1 shows the results.

[0101]

Example 3 100 parts of an acrylic emulsion (1) having an ald group or a keto group synthesized in Reference Example 2 and a solid concentration of 30 of the semicarbazide derivative C obtained in Reference Example 8
% Of an aqueous solution was added, and mixed at room temperature for 30 minutes. Then, a finishing material was blended and subjected to each test. Table 1 shows the results.

[0102]

Example 4 100 parts of an acrylic emulsion (2) having an ald group or a keto group synthesized in Reference Example 3 and a solid concentration of 30 of the semicarbazide derivative A obtained in Reference Example 6
% Aqueous solution was added and mixed at room temperature for 30 minutes.
Finishing materials were blended and subjected to each test. Table 1 shows the results.

[0103]

Example 5 100 parts of an acrylic emulsion (2) having an ald group or a keto group synthesized in Reference Example 3 and 5.9 parts of an aqueous solution of the semicarbazide derivative B obtained in Reference Example 7 were added. After minute mixing, a finishing material was blended and subjected to each test. Table 1 shows the results.

[0104]

Example 6 100 parts of an acrylic emulsion (2) having an ald group or a keto group synthesized in Reference Example 3 and a solid content concentration of the semicarbazide derivative C obtained in Reference Example 8 of 30
% Aqueous solution was added and mixed at room temperature for 30 minutes, and then a finishing material was blended and subjected to each test. Table 1 shows the results.

[0105]

Example 7 100 parts of an acrylic emulsion (3) having an ald group or a keto group synthesized in Reference Example 4 and a solid concentration of 30 of the semicarbazide derivative A obtained in Reference Example 6
% Aqueous solution was added and mixed at room temperature for 30 minutes.
Finishing materials were blended and subjected to each test. Table 1 shows the results.

[0106]

Example 8 100 parts of an acrylic emulsion (3) having an ald group or a keto group synthesized in Reference Example 4 and 9.8 parts of an aqueous solution of the semicarbazide derivative B obtained in Reference Example 7 were added. After minute mixing, a finishing material was blended and subjected to each test. Table 1 shows the results.

[0107]

Example 9 100 parts of an acrylic emulsion (3) having an ald group or a keto group synthesized in Reference Example 4 and a solid content concentration of the semicarbazide derivative C obtained in Reference Example 30 of 30
% Aqueous solution was added and mixed at room temperature for 30 minutes.
Finishing materials were blended and subjected to each test. Table 1 shows the results.

[0108]

Comparative Example 1 A reaction vessel equipped with a stirrer, a reflux condenser, a dropping tank and a thermometer was charged with 6 parts of methacrylic acid, 2 parts of acrylic acid, 25 parts of styrene, and 24 parts of methyl methacrylate.
Part, 2-ethylhexyl acrylate 43 parts, water 300
, 20 parts of a 20% aqueous solution of sulfosuccinic acid diester ammonium salt (trade name: Latemul S-180A, manufactured by Kao Corporation) was added, and the temperature in the reaction vessel was raised to 78 ° C, and then 0.5 parts of ammonium persulfate was added. Add 1 part and keep for 1 hour. This prepares the first stage seed particles,
When the hydrogen ion concentration was measured, it was pH 1.8.
Next, 110 parts of styrene, 133 methyl methacrylate
Part, a mixture of 157 parts of 2-ethylhexyl acrylate, 300 parts of water, and 2 parts of sodium p-styrenesulfonate (trade name: Spinomer NaSS, manufactured by Tosoh Corporation)
A mixture of 20 parts of a 0% aqueous solution and 1.0 part of ammonium persulfate is allowed to flow into the reaction vessel from separate dropping tanks over 3 hours. During the inflow, the temperature in the reaction vessel is maintained at 80 ° C. After the inflow is completed, the temperature in the reaction vessel is kept at 85 ° C. and maintained for 6 hours. After cooling to room temperature, the hydrogen ion concentration was measured to be 2.5. After adjusting the pH to 8 by adding a 25% aqueous ammonia solution, the mixture was filtered through a 100-mesh wire net. The dry weight of the filtered agglomerates was very low, 0.01% based on the total monomer. The solid content of the obtained emulsion was 44.5%, and the average particle size was 960 °. Finishing materials were blended and subjected to each test. Table 2 shows the results.

[0109]

Comparative Example 2 8 parts of methacrylic acid, 2 parts of acrylamide, 35 parts of styrene, 26 parts of methyl methacrylate, 54 parts of 2-ethylhexyl acrylate were placed in a reaction vessel equipped with a stirrer, reflux condenser, dropping tank and thermometer. , Water 35
0 parts, reactive surfactant (trade name: Adecaria Soap S)
25 parts of a 20% aqueous solution of E-1025N (manufactured by Asahi Denka Kogyo KK) are charged, the temperature in the reaction vessel is raised to 78 ° C., and 0.5 part of ammonium persulfate is added and maintained for 1 hour. Thus, the seed particles of the first stage were prepared, and the pH was 1.8 when the hydrogen ion concentration was measured. Next, 100 parts of styrene, 129 parts of methyl methacrylate,
146 parts of 2-ethylhexyl acrylate, 250 parts of water,
Acrylic acid- (2-sulfoethyl) ester sodium (trade name: ANTOX MS-2N, Japan Emulsifier Co., Ltd.)
15% of a 20% aqueous solution of
The mixed solution with the mixed solution is allowed to flow from the dropping tank over 3 hours. During the inflow, the temperature in the reaction vessel is maintained at 80 ° C. After the inflow is completed, the temperature in the reaction vessel is kept at 85 ° C. and maintained for 6 hours. After cooling to room temperature, the hydrogen ion concentration was measured to be 2.5. After adjusting the pH to 8 by adding a 25% aqueous ammonia solution, the mixture was filtered through a 100-mesh wire net. The dry weight of the filtered agglomerates was very low, 0.01% based on the total monomer. The solid content of the obtained emulsion was 44.2%, and the average particle size was 1100 °. Finishing materials were blended and subjected to each test. Table 2 shows the results.

[0110]

Comparative Example 3 An emulsion was obtained in the same manner as in Comparative Example 2, except that a part of the monomer composition in the second stage of emulsion polymerization of the emulsion was changed to 54 parts of methyl methacrylate and 221 parts of 2-ethylhexyl acrylate. The dry weight of the filtered agglomerates was very low, 0.01% based on the total monomer. The solid content of the obtained emulsion is 4
4.2% and an average particle diameter of 1100 °. Finishing materials were blended and subjected to each test. Table 2 shows the results.

[0111]

Comparative Example 4 100 parts of an acrylic emulsion (3) having an ald group or a keto group synthesized in Reference Example 4 and 6.7 parts of a 5% aqueous solution of adipic dihydrazide were added.
After mixing at room temperature for 30 minutes, a finishing material was blended and subjected to each test. Table 2 shows the results.

[0112]

[Table 1]

[0113]

[Table 2]

[0114]

According to the water-based paint for stone preparation of the present invention, a coating film which does not crack over time and which can maintain a sufficient adhesive strength and has high durability and water resistance can be formed. it can. When the stone-finish aqueous coating composition is exposed outdoors, the coating film is not whitened or brittle due to light, heat, rain, dew condensation, etc., and a coated film capable of maintaining a good finished appearance for a long period of time is obtained.

Claims (3)

[Claims] 1. An acrylic emulsion having an aldo group or a keto group (A) and a semicarbazide derivative composition (B) having an average number of semicarbazide residues of at least 2.5.
And a water-based paint for finishing stones comprising the aggregate (C). 2. The acrylic emulsion (A) having an ald group or a keto group contains at least two kinds of emulsion polymerization type polymers in the same particle, and has at least one ald group or a keto group in a molecule. 0.5% by weight or more of the ethylenically unsaturated carbonyl group-containing monomer (a), 0.1 to 20% by weight of the ethylenically unsaturated carboxylic acid monomer (b), and In the presence of seed particles obtained by supplying a monomer system [1] containing not more than 99.4% by weight of another polymerizable unsaturated monomer (c) and emulsion-polymerizing in an aqueous medium, ethylenic acid is added. The unsaturated carboxylic acid monomer (b) is obtained by supplying a monomer system [2] having a weight ratio of 0 or less than the weight ratio contained in the monomer system [1], and performing emulsion polymerization in an aqueous medium. Claim 1 A water-based paint for finishing stone as described in the above. 3. An ethylenically unsaturated monomer having a sulfonate group as an emulsifier is used as an emulsifier with respect to 100 parts by weight of each of the monomer systems [1] and [2]. Monomer, an ethylenically unsaturated monomer having a sulfate group, or a mixture thereof,
And an ethylenically unsaturated monomer selected from any of the above.
The water-based paint for stone preparation according to claim 2, wherein the water-based paint is used in an amount of from 0.5 to 20 parts by weight.