JP2002363485A - Curing composition for floor paint, method for forming coating film for floor, and floor coated with the composition or by method for forming the coating film for floor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve problems that, when an acrylic silicone paint is used as a floor paint, it has low initial curing properties and slowly hibits solvent resistance and chemical resistance as it is cured by moisture, and sometimes these cause troubles in workability and, when the floor is repaired, adhesiveness to an epoxy paint and a urethane paint which are old paints or self-recoating adhesivenss to acrylic silicone under a high temperature and moisture condition in a new painting is sometimes insufficient, thus, limitations for painting are the problems. SOLUTION: The curing composition for floor paints comprises a copolymer (A) component having a main chain essentially comprising a vinyl polymer and both of at least one silicon group bonded to a hydrolysable group and an amino group in the molecule and a curing catalyst component. The method for forming coating films for floors is to use this composition. The floor is made by the method. The problems are solved by the aforesaid items.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to, for example, concrete
, Wood, and plastic flooring materials, and a floor coating curable composition that can be suitably used for application to floors coated with an epoxy, urethane, or acrylic primer, and the composition. The present invention relates to a method for forming a coating film for floors using the same and a method for applying the composition or a method for forming a coating film for floors.

[0002]

2. Description of the Related Art Conventionally, epoxy-based, urethane-based, polyester-based, and acrylic-based paints have been widely used as paints for floor materials such as concrete and wood, and they have a design property, solvent resistance, Provides chemical resistance and aesthetic appearance. However, in recent years, there has been a case where a floor paint is partially applied to a portion exposed to sunlight, and a demand for improvement in weather resistance has come to be issued. In this case, among the above-mentioned paints, the urethane paint has a relatively good balance between solvent resistance and chemical resistance, but has a problem with weather resistance. Acrylic silicone paint and fluororesin paint are available as paints with excellent weather resistance.
The latter is expensive and has a cost problem. JP-A-2000-256612 discloses (A) a polymer in which the hydrolyzable silyl group in the resin solid content shows a specific value in terms of SiO ₂ , (B) a curing agent or a curing catalyst, (C) a pigment,
(D) containing a solvent, the water vapor permeability of the formed coating film,
And by directly applying the coating composition adjusted so that the pigment volume concentration is in a specific range on the surface to be coated, it is possible to impart functions such as improved design and dust resistance, non-slip properties, chemical resistance, A patent application has been filed as a coating method that shortens the construction period.

[0003]

Acrylic silicone paint is most suitable as a paint having a good balance between cost and weather resistance. However, when an acrylic silicone paint is used as a floor paint for a floor, there is a problem in that the initial curing property is low and solvent resistance and chemical resistance are slowly developed because of moisture curing. In addition, when applying a new paint to repair the floor coating, for example, when an epoxy paint or urethane paint is used as the old paint, when acrylic silicone paint is used as a new paint, the old paint There was a problem in adhesion to In addition, even at the time of new coating, there is a case where the self-recoat adhesion is insufficient under high-temperature and high-humidity conditions, and there is a case where there is a restriction in construction.

[0004]

Means for Solving the Problems The present invention relates to the following compositions and painted objects. Copolymer having a main chain substantially composed of a vinyl polymer, having at least one hydrolyzable silicon group bonded to a carbon atom represented by the general formula (1) in the molecule, and having an amino group ( A floor coating curable composition comprising the component (A) and the curing catalyst (B). General formula (1): (In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R ² represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a C 6 to 10 aryl group, and a carbon number. Represents a monovalent group selected from the group consisting of 7 to 10 aralkyl groups.
^{When a} plurality of ¹ or R ² are present, they may be the same or different. a represents an integer of 0 to 2. (Claim 1) The curable composition for floor coatings according to claim 1, which is a compound having an amide group in the copolymer (A) component. (Claim 2) The curing catalyst (B) component is a tin compound.
The floor coating composition according to any one of the preceding claims. (Claim 3) The floor coating curing composition according to any one of claims 1 to 2, wherein the curing catalyst (B) component is a mixture of an acid compound and an amine compound or a reaction product thereof. (Claim 4) in the composition (D) formula as component (2) a silane of the compound described general formula ^{(2): (R 3 O} ) 4-a -Si-R 4 a (2) ( in the formula, R ³ is an alkyl group having 1 to 10 carbon atoms, 6 carbon atoms;
R ⁴ is a monovalent hydrocarbon group selected from an aryl group having 10 to 10 and an aralkyl group having 7 to 12 carbon atoms;
A monovalent hydrocarbon group selected from an alkyl group having 0, an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 12 carbon atoms, a represents 0 or 1) and / or a silicon compound represented by the formula: The floor coating curable composition according to any one of claims 1 to 4, comprising a hydrolysis condensate. (Claim 5) The floor according to any one of claims 1 to 5, comprising a silane compound (C) different from the compound (D), having a group selected from a vinyl group, a mercapto group, an amino group, and an epoxy group. Paint curable composition. (Claim 6) A curable composition for floor coatings, wherein the silane compound (C) according to claim 6 contains an amino group. (7) The curable composition for floor coatings according to any one of (1) to (6), wherein the copolymer (A) component is synthesized in an organic solvent having an aromatic content of 50% by weight or less. Composition. (Claim 8) The composition according to any one of claims 1 to 8, wherein the component (A) contains 2 to 90 parts by weight of an alkyl (meth) acrylate having 4 or more carbon atoms as a copolymerizable monomer. Item 10. The floor coating curable composition according to item 7. (Claim 9) A coating film formed using the curable composition for floor coating according to any one of claims 1 to 9 has a water vapor permeability of 40 g / m.
² · 24h or more, the method of forming the floor coating film being not more than 200g / m ² · 24h. (Claim 10) The curable composition for floor coating according to any one of Claims 1 to 9, which is directly applied to an object to be coated.
The method for forming a floor coating film according to the above. (11) A method for forming a coating film for floors, comprising applying the curable composition for floor coatings according to any one of (1) to (9) on a coating film applied to an object to be coated. . (Claim 12) The floor coating according to any one of claims 1 to 9, wherein the curable composition for floor coating according to any one of claims 1 to 9 is applied on a coating film applied to a substrate. A method for forming a coating film. (Claim 1
3) A method for forming a floor coating film, wherein the coating film applied to the object according to claim 12 is an epoxy-based or acrylic-based coating. (14) A floor obtained by applying the composition according to any one of (1) to (9) or forming a coating film for floor according to any one of (10) to (14). (Claim 15)

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The curable resin composition for floor coatings of the present invention comprises a copolymer having a silyl group bonded to a hydrolyzable group as a base resin having curability at room temperature in the presence of moisture. (A) A component is contained.

The main component of the copolymer (A) is a copolymer of an acrylic monomer and an amino group-containing monomer, and if necessary, an amide group-containing monomer and other monomers. (Hereinafter, also referred to as a main chain substantially consisting of an acrylic copolymer chain), the coating film formed from the curable resin composition for floors of the present invention to be obtained. It is preferable because weather resistance, chemical resistance and the like become excellent.

[0007] The phrase that the main chain of the copolymer (A) component substantially consists of an acrylic copolymer chain means that 50% by weight or more of the units constituting the main chain of the copolymer (A) component. It is preferable that 70% by weight or more is formed from an acrylic monomer unit.

Further, the copolymer (A) component contains a reactive silyl group having a hydrolyzable group bonded to a carbon atom, so that the coating film has water resistance, alkali resistance,
Excellent acid resistance and the like. In the copolymer (A) component, the number of silicon groups bonded to the hydrolyzable group is 2 or more, preferably 3 or more per molecule of the copolymer (A) component.
It is preferable that the number is equal to or more than that the coating film formed from the composition of the present invention has excellent durability such as weather resistance and solvent resistance.

The copolymer (A) component is described in, for example,
It can be produced by a hydrosilylation method or a solution polymerization method using a monomer containing a reactive silyl group described in JP-A-4-36395, JP-A-57-55954, etc. In view of the above, it is particularly preferable to use a monomer containing a reactive silyl group and to produce the monomer by a solution polymerization method using a radical polymerization initiator.

Examples of the hydrolyzable group of the hydrolyzable silicon group include a halogen and an alkoxy group, and among them, an alkoxy group is useful because of easy control of the reaction.

The copolymer (A) component has a number average molecular weight of 1
3,000 or more, 30,000 or less, 3000 or more, 2500
0 or less is preferable. Further, the coating film formed using the composition of the present invention has excellent physical properties such as durability and the like.
It is preferably from 00 to 20,000.

The copolymer (A) component may be used alone or in combination of two or more.

The copolymer (A) component is, for example, a polymerizable 2
A monomer (a) containing a reactive silyl group bonded to a heavy bond and a carbon atom, an amino group-containing monomer (b), and optionally a amide group-containing monomer (c); It can be produced by polymerizing a (meth) acrylic acid monomer (d) and another vinyl monomer (e). Specific examples of the monomer (a) include, for example,

[0014]

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[0015]

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[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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And a (meth) acrylate having a reactive silyl group bonded to a carbon atom at a terminal through a urethane bond or a siloxane bond. Among them, the compound represented by the general formula (4) is preferable from the viewpoint of excellent copolymerizability and polymerization stability, and excellent curability and storage stability of the obtained composition.

The content of the silyl group-containing monomer (a) in the monomer composition of the copolymer (A) is preferably 1 to 90% by weight. The durability of the coating film formed using the composition of the present invention is excellent, and from the viewpoint of increasing the strength, 3% by weight or more,
It is preferably 90% by weight or less, more preferably 5% by weight or more and 70% by weight or less, particularly preferably 10% by weight or more and 50% by weight or less.

As the amino group-containing monomer (b), N, N-
Dimethylaminoethyl (meth) acrylate, N, N-
Diethylaminoethyl (meth) acrylate, N, N-
Dimethylaminopropyl (meth) acrylate, N, N
-Diethylaminopropyl (meth) acrylate, t-
Butylaminoethyl (meth) acrylate, t-butylaminopropyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate, 3-diethylaminopropyl (meth) acrylate, N- [2- (meth)
Acryloyloxyethyl] piperidine, N- [2-
(Meth) acryloyloxyethyl] pyrrolidine, N-
[2- (meth) acryloyloxyethyl] morpholine and the like. Among them, tertiary amino group-containing monomers are preferable, and from the viewpoint of imparting polymerizability and adhesion, N, N
-Dimethylaminoethyl (meth) acrylate, N, N
-Diethylaminoethyl (meth) acrylate is preferred.

The total amount of the monomer (b) may be appropriately adjusted according to the type and the amount of the monomer (a) to be used. ,
10% by weight or less, further 0.2% by weight or more, 5% by weight
The content is particularly preferably 0.4% by weight or more and 3% by weight or less. The monomers (b) can be used alone or in combination of two or more.

As the amide group-containing monomer (c), (meth) acrylamide, α-ethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N,
N-dimethylacrylamide, N, N-diethylacrylamide, N, N-dimethylaminopropylacrylamide, N-methyl (meth) acrylamide (meth) acryloylmorpholine and the like can be mentioned.

Among them, N, N-dimethylacrylamide,
N, N-diethylacrylamide and N, N-dimethylaminopropylacrylamide are preferred.

The total amount of the monomer (c) used may be appropriately adjusted according to the type and the amount of the monomer (a) used, but is usually 0.1% by weight of the total amount of the polymerization components used. It is preferably at least 10 wt%, more preferably at least 0.2 wt% and at most 5 wt%, particularly preferably at least 0.3 wt% and at most 3 wt%.

The monomers (c) can be used alone or in combination of two or more. Specific examples of the component (d) include, for example, i-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate Octyl (meth) acrylate, nonyl (meth) acrylate, decanyl (meth)
Acrylate, undecanyl (meth) acrylate, laurylmethyl (meth) acrylate, palmitoyl (meth) acrylate, stearyl (meth) acrylate,
Burenma -SLMA (meth) mixture of C ₁₂ -C ₁₈ alkyl esters of acrylic acid; manufactured by NOF Corporation), and the like cyclohexyl methacrylate is. 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, because solubility in a solvent containing an aliphatic compound is improved.
G, decanyl (meth) acrylate, undecanyl (meth) acrylate, lauryl methyl (meth) acrylate
, Palmitoyl (meth) acrylate, stearyl (meth) acrylate and Blemma-SLMA are preferred. In particular, lauryl methyl (meth) acrylate, palmitoyl (meth) acrylate, stearyl (meth) acrylate, and Bremma-SLMA are more preferable. The amount to be used is preferably 2% by weight or more and 90% by weight or less based on the total amount of the polymerization components used. From the viewpoint of solubility in a solvent during polymerization and dilution and stability of polymerization, the content is preferably 5% by weight or more and 60% by weight or less. In particular,
The content is more preferably from 10% by weight to 50% by weight.

Other vinyl monomers (e) include, for example, styrene, α-methylstyrene, methyl (meth)
Acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, benzyl (meth)
Acrylate, cyclohexyl (meth) acrylate,
Trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, (meth) acrylonitrile, glycidyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxystyrene, HE-10, H
E-20, HP-1, HP-20 (all of them are terminal hydroxyl group-containing acrylate oligomers manufactured by Nippon Shokubai Chemical Industry Co., Ltd.), FM-1 and FM- of the Placel series.
4, FA-1, FA-4 (all manufactured by Daicel Chemical Industries, Ltd.), Aronix M-5700, compounds such as macromonomers AS-6, AN-6, AA-6, AB-6, AK-6 (These are manufactured by Toa Gosei Chemical Industry Co., Ltd.), (Meta)
Examples include (meth) acrylic compounds containing a phosphate ester group, such as condensation products of hydroxyalkyl esters of acrylic acid and phosphoric acid or phosphoric acid esters, and (meth) acrylates containing urethane bonds or siloxane bonds. Among these, the point that the obtained copolymer (A) component has excellent compatibility with the silicon compound represented by the following general formula (1) and / or its partially hydrolyzed condensate (D) component: Therefore, it is preferable to contain n-butyl methacrylate.

In the present invention, for the purpose of further improving the weather resistance of a coating film formed from the obtained composition of the present invention, for example, a segment formed by a urethane bond or a siloxane bond in a main chain is formed of a vinyl-based segment. Copolymer 5
It may be introduced in the production of the copolymer (A) component within a range not exceeding 0% by weight.

These may be used alone or in combination of two or more. The copolymer (A) component may contain a group such as a carboxyl group or an amino group. In this case, the curability and adhesion are improved, but the carboxyl group bonded to the polymer chain is improved. In the case of an amino group or an amino group, the activity is weak, and it is difficult to obtain a cured product having good characteristics even when the composition is used for curing instead of a curing catalyst.

The solvent used in the solution polymerization method is preferably a weak solvent. The amount of the weak solvent used is preferably at least 30% by weight, more preferably at least 50% by weight, particularly preferably at least 70% by weight in the total polymerization solvent.

Examples of the weak solvent include a third type organic solvent according to the Industrial Safety and Health Act and a solvent corresponding to the third type organic solvent, and preferably a solvent containing an aliphatic hydrocarbon. Specifically, a non-aqueous solvent having an aromatic content of 50% by weight or less is exemplified, and examples thereof include a case of 40% by weight or less and 30% by weight or less. The amount of the monomer ((d) + (e)) may be appropriately adjusted according to the type and amount of the monomer used. % By weight, more preferably 15% by weight or more and 90% by weight or less, particularly preferably 46% by weight or more and 80% by weight or less.

In the solution polymerization, if necessary, for example, n-dodecyl mercaptan, t-dodecyl mercaptan, n-butyl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, (CH ₃ O) ₃ Si-S-S-S-S
i (OCH ₃ ) ₃ , (CH ₃ O) ₃ Si—S ₈ —Si (OC
The molecular weight of the resulting copolymer (A) component may be adjusted by using a chain transfer agent such as H ₃ ) ₃ alone or in combination of two or more kinds. In particular, when a chain transfer agent having an alkoxysilyl group in a molecule such as γ-mercaptopropyltrimethoxysilane is used, a reactive silyl group can be introduced into the terminal of the copolymer (A) component. It is preferred. The amount of the chain transfer agent to be used is preferably 0.05% by weight or more and 10% by weight or less, particularly preferably 0.1% or more and 10% by weight or less based on the total amount of the used polymerization components.

The curing catalyst (B) comprises an organometallic catalyst system,
Acid-based or acid / amine-based catalysts can be used. Examples of the organic metal catalyst include an organic tin compound, an organic titanium compound, an organic titanium compound, an organic zirconium compound, an organic iron compound, and the like. An organic tin compound, an acid or an acid / amine-based catalyst is preferable, and an acid or acid / amine-based curing catalyst is particularly preferable in terms of a good balance between curability and pot life. Specific examples of the organotin compound include dioctyltin bis (2-
Ethylhexyl maleate), a reaction product of dioctyl tin oxide and ethyl silicate, a reaction product of dibutyl tin oxide and ethyl silicate, dibutyl tin dilaurate, dibutyl tin bis (ethyl maleate), dibutyl tin bis (butyl maleate) ), Dibutyltin bis (2-ethylhexyl maleate), dibutyltin bis (lauryl maleate), dibutyltin bis (palmitoyl maleate), dibutyltin bis (stearyl maleate), dibutyltin bis (oleyl maleate) ). These are preferably blended in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the copolymer (A) component. Further, the amount is preferably from 0.2 to 10 parts by weight, more preferably from 0.5 to 5 parts by weight.
Particularly preferred is not more than parts by weight.

The use of an acid catalyst as the curing catalyst component (B) is preferred from the viewpoint of the solvent resistance of the coating film. Examples of the acid-based catalyst include an organic phosphate ester-based catalyst, a sulfonic acid-based catalyst, a system in which phosphoric acid is mixed with an organic amine, a system in which sulfonic acid and an organic amine are mixed, and a system in which an organic carboxylic acid is mixed with an organic amine. A system in which an organic amine is blended with an organic carboxylic acid is preferable from the viewpoint of achieving a balance between curability and pot life.

Specific examples of the organic phosphoric ester type include:
There are phosphoric acids or phosphate esters such as phosphoric acid, monomethyl phosphate, monoethyl phosphate, monobutyl phosphate, monooctyl phosphate, monodecyl phosphate, dimethyl phosphate, diethyl phosphate, didodecyl phosphate. In the sulfonic acid system, dodecylbenzenesulfonic acid is typical. Specific examples of organic carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, hexanoic acid, octylic acid, 2-ethylhexanoic acid, decanoic acid, dodecanoic acid, stearic acid, oleic acid, linoleic acid, and palmitic acid. Is typical.

Among them, acetic acid, propionic acid, hexanoic acid,
Octylic acid and 2-ethylhexanoic acid are preferred, and hexanoic acid, octylic acid and 2-ethylhexanoic acid are more preferred.

When an acid compound and an organic amine compound are used in combination, the cured state can be adjusted by using a silane coupling agent described later. However, considering the effect on aminosilane, which is a silane coupling agent,
It is desirable that the amine is added in an excess of acid / amine equivalent. Specific examples of the organic amine compound here include triethylamine, dodecylamine, diisopropanolamine, dimethyldodecylamine, and morpholine.

Of these, dodecylamine and dimethyldodecylamine are preferred, and dimethyldodecylamine is more preferred.

As the silane coupling agent (C), a silane coupling agent containing a group selected from a vinyl group, a mercapto group, an amino group and an epoxy group and different from the compound (D) can be used. , Vinyl silane,
Mercaptosilane, epoxysilane and aminosilane can be exemplified and are preferable.

These silane coupling agents can be used alone or in combination for the purpose of obtaining the effect of imparting adhesion. As these silane coupling agents, epoxy silane and amino silane are preferable, and amino silane is particularly preferable. Specific examples of epoxysilane include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and the like. Specific examples of aminosilane include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β
-(Aminoethyl) -γ-aminopropyltriethoxysilane. Further, a reaction product of the aminosilane and an epoxysilane or an epoxy compound can also be used. That is, specific examples thereof include a reaction product of bisphenol A type bifunctional epoxy compound (Epicoat 828; manufactured by Yuka Shell Epoxy Co., Ltd.) and γ-aminopropyltriethoxysilane in a ratio of 1: 2 (molar ratio), N-β- (aminoethyl)
And a 1: 2.2 (molar ratio) reaction product of γ-aminopropyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane.

The compounding amount of the silane coupling agent (C) is 0 to 100 parts by weight of the copolymer (A).
It is at least 20 parts by weight, preferably at least 0.1 part by weight and at most 10 parts by weight, more preferably at least 0.3 part by weight and at most 5 parts by weight.

The compound (D) is used together with the above-mentioned copolymer (A) to improve the stain resistance of the coating film formed from the composition and to improve the adhesion between the coating film and the object to be coated. following general formula ^{(2) (R 3 O)} 4-a -Si-R 4 a (2) ( wherein, R ³ is an alkyl group having 1 to 10 carbon atoms is a component for, to 6 carbon atoms
R ⁴ is a monovalent hydrocarbon group selected from an aryl group having 10 to 10 and an aralkyl group having 7 to 12 carbon atoms;
A monovalent hydrocarbon group selected from an alkyl group having 0, an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 12 carbon atoms, a represents 0 or 1) and / or a silicon compound represented by the formula: By using it as the hydrolyzed condensate (D) component, the stain resistance of the obtained coating film is improved.

When the compound (D) is used, at least 3 parts by weight and 100 parts by weight of the copolymer (A)
It is preferably not more than 3 parts by weight, more preferably not less than 3 parts by weight and not more than 70 parts by weight, more preferably not less than 5 parts by weight and not more than 50 parts by weight.

Specific examples of the compound (D) include, for example, tetramethyl silicate, tetraethyl silicate, tetra n-propyl silicate, tetra-i-propyl silicate, tetra-n-butyl silicate, tetra-i
A tetraalkyl silicate such as butyl silicate;
Methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, octadecyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, methyltri-s
-Silane coupling agents such as octyloxysilane, methyltriphenoxysilane, methyltriisopropoxysilane, and methyltributoxysilane.

Among them, preferred are tetramethyl silicate, tetraethyl silicate, a partially hydrolyzed cocondensate of tetramethoxysilane and tetraethoxysilane, tetra-n-propyl silicate and tetra-i-propyl silicate. More preferred are tetramethyl silicate, tetraethyl silicate and a partially hydrolyzed cocondensate of tetramethoxysilane and tetraethoxysilane. Further, as the partially hydrolyzed condensate of the silicon compound, for example, by adding water to the tetraalkyl silicate or trialkoxysilane, triaryloxysilane, or the like in a usual manner and partially hydrolyzing and condensing the compound, or Examples thereof include those which are hydrolyzed in the presence of an acidic substance and water in the above-mentioned tetraalkyl silicate or alcohol-based solvent.

As specific examples, for example, MSI51,
ESI40, ESI48, HAS-1, HAS-10
(The above are manufactured by Colcoat Co., Ltd.), MS51, MS56
(Mitsubishi Chemical Co., Ltd.) and the like, and tetraalkyl silicate partial hydrolysis condensates, for example, AFP-1 (Shin-Etsu Chemical Co., Ltd.) and the like trialkoxysilane partial hydrolysis condensates and the like.

The curable resin composition for a top coating composition of the present invention comprises a resin (A) component + a curing catalyst (B) component + a silicon compound and / or a partially hydrolyzed condensate (D) component thereof, for example, using a stirrer or the like. The resin (A) component and the silicon compound and / or the partial hydrolysis condensate (D) component can be further obtained by adding a dehydrating agent to the mixture. By blending, the storage stability of the composition can be improved over a long period of time.

Specific examples of the dehydrating agent include, for example, methyl orthoformate, ethyl orthoformate, methyl orthoacetate, ethyl orthoacetate, trimethyl orthopropionate, triethyl orthopropionate, trimethyl orthoisopropionate, triethyl orthoisopropionate. Hydrolysable ester compounds such as trimethyl orthobutyrate, triethyl orthobutyrate, trimethyl orthoisobutyrate, and triethyl orthoisobutyrate; or dimethoxymethane, 1,1-dimethoxyethane, 1,1-dimethoxypropane, 1,1-dimethoxybutane; Or ethyl silicate (tetramethoxysilane), methyl silicate
(Tetramethoxysilane), methyltrimethoxysilane and the like. In this, from the point of dehydration effect,
Methyl orthoacetate is preferred. These may be used alone or in combination of two or more. The dehydrating agent comprises (A)
It is used in an amount of 100 parts by weight or less, preferably 50 parts by weight or less, more preferably 30 parts by weight or less based on 100 parts by weight of the components. Further, the resin (A) component may be added to the component before polymerization, may be added during the polymerization of the resin (A) component, or may be mixed with the obtained resin (A) component and other components. It may be added at any time, and there is no particular limitation. In addition, the curable resin composition for floor coatings of the present invention includes, for example, titanium oxide, ultramarine, navy blue, zinc white, red iron oxide, graphite, lead white, carbon black, transparent iron oxide, and aluminum powder commonly used in coatings. Pigments such as inorganic pigments, organic pigments such as azo pigments, triphenylmethane pigments, quinoline pigments, anthraquinone pigments, and phthalocyanine pigments;
Additives such as diluents, ultraviolet absorbers, light stabilizers, anti-sagging agents, leveling agents; cellulose such as nitrocellulose, cellulose acetate butyrate; epoxy resins, melamine resins, vinyl chloride resins, fluororesins, chlorinated polypropylene , A resin such as chlorinated rubber, polyvinyl butyral, and polysiloxane may be appropriately added.

The curable resin composition for floor coatings of the present invention comprises:
For example, it is applied to the object to be coated by a usual method such as dipping, spraying, brushing, application using a spray, etc., and it can be formed into a coating film by curing normally at room temperature or by baking at 30 ° C. or more. .

The curable resin composition for floor coatings of the present invention comprises:
For example, it is suitably used as a paint for floors of buildings such as ceramics, cement, ceramic moldings and the like, and for repair and repair.

Next, the curable resin composition for floor coatings of the present invention will be described in more detail with reference to Examples, but the present invention is not limited to only these Examples. Synthesis Example of Copolymer (A) Solvent (1) was charged into a reactor equipped with a stirrer, thermometer, cooling refluxer, nitrogen gas inlet tube and dropping funnel, and 110 ° C. while introducing nitrogen gas. The monomer shown in Table 1 was placed in a dropping funnel while maintaining the temperature at 110 ° C.
It was dropped at a constant speed over time.

Further, the solvent (2) was dropped into the reaction vessel at a constant speed over 1 hour. Then, after continuously stirring at 110 ° C. for 3 hours, the mixture was cooled to room temperature. Finally, the solvent (3) was added and stirred to obtain copolymers (A-1 to A-8).

The solvents (1), (2), (3) and the vinyl monomer composition are listed in Table 1.

The solid content concentration and the number average molecular weight of the obtained thermosetting resin composition at room temperature were measured by gel permeation chromatography (GPC).

[0057]

[Table 1]

A process of white enamel using a room temperature curable resin
In 100 parts by weight of the obtained copolymer (A-1 to A-8),
Titanium oxide (CR-95, Ishihara Sangyo Co., Ltd.) as a pigment
66.7 parts by weight), dispersed in a paint conditioner using a glass bead for 2 hours, and adjusted to a solid content of 60% as shown in Table 2 to obtain a white enamel (AT-1).
AT-8) was obtained. (In Table 2, NV represents the solid content concentration in the enamel. PWC represents the weight ratio of the pigment to the entire solid content in the enamel.)

[0059]

[Table 2]

The obtained white enamel (AT-1 to AT-
8) The curing agent (B) component was blended as shown in Table 3, and thinner was added thereto, followed by stirring with a stirrer for 5 minutes to obtain paints (AR-1 to AR-11). The composition was applied to a slate plate by air spray and cured at 23 ° C. for 1 day to obtain a coating film. (ES used for compound (D) in Table 3)
(I48 is made by Colcoat)

[0061]

[Table 3]

The surface state, pigment dispersion stability, solvent resistance, adhesion, and viscosity increase after storage at 50 ° C. of the obtained coating film were evaluated according to the following methods. Table 4 shows detailed curing agent (B) components of the components in the overcoat paint .

[0063]

[Table 4]

Method of preparing base material for evaluation For use as a floor on a slate plate (epoxy paint, Archfloor EH SK Kaken), (urethane paint,
Kifuro-UT Eske Kaken) (acrylic paint,
Teravere-AE Nippon Paint)
0.25 to 0.3 kg / m ^{2 was} applied, dried at room temperature for 3 to 4 hours, and then dried at 80 ° C. for 24 hours to obtain a substrate for evaluation. In addition, about the physical property, it evaluated using the base material shown below. Substrate A: Akifurol-EH [no polishing] Substrate B: Akifurol-UT [no polishing] Substrate C: Teraval-AE [no polishing] (a) Gloss measurement of coating film 3 ~ 4 at room temperature after coating with Ekifuro-EH
After drying for 24 hours under an atmosphere of 80 ° C., the coating shown in Table 3 (AR-1 to AR-11, urethane) was applied, cured at 23 ° C. for 7 days, and then a gloss meter GM268 (Minolta Co., Ltd.) )). Urethane used was Archifru-UT. (B) Pigment dispersion stability The aluminum base material (A-5052P) was degreased, and the top coat paint (mixed paint of white enamel / primary color) shown in Table 3 was applied by air-spray for 1 hour and 2 hours. Every three hours, half of the substrate was run down and the substrate was set upright. After drying at room temperature for 1 hour and curing for 24 hours in an atmosphere of 23 ° C. × 55% RH, a change in hue between the first layer and the second layer (flow coating) was determined by ΔE. Urethane used was Archifru-UT. (C) Storage stability test at 50 ° C After the white enamel was prepared, the viscosity increase after storage at 50 ° C for one month was determined. Urethane used was Archifru-UT. (D) Solvent resistance Xylene rubbing test After coating the floor plate with an Archfloor EH, 3-4 at room temperature
After drying for 24 hours under an atmosphere of 80 ° C. for 24 hours, the coating shown in Table 3 (AR-1 to AR-11, urethane) was applied, cured at 23 ° C. for one day, and then dipped in gauze. ,
The surface of the coating film was rubbed 50 times and the state of the coating film was observed. Urethane used was Archifru-UT. (Evaluation Criteria) 膨: No swelling or scratch marks were observed, and the surface condition was good. Δ: Scratches are observed. X: Swelling is observed and undercoat paint is observed. (C) Self-recoat adhesion test One day after coating (AR-1 to AR-11, urethane (Archfloor-UT)) shown in Table 3 on a slate plate (35 ° C., humidity 85% RH) After curing for 2 days, 7 days, and 14 days, the top coat paints (AR-1 to AR-11) were applied again.
After curing under the conditions of days (35 ° C., humidity 85% RH), the adhesion was evaluated by measuring the grid adhesion in accordance with JIS K 5400. (D) Adhesion test Primary adhesion evaluation Akifuro-EH, Akifuro-U on the plate
H, after coating with Teravere-AE, drying at room temperature for 3 to 4 hours, and drying at 80 ° C. for 24 hours, the results are shown in Table 3 (AR-1 to AR-11, urethane (Akifurol-UT) )) After painting, room temperature (23 ° C, humidity 55% RH)
The adhesion after curing for one day was evaluated by measuring the grid adhesion in accordance with JIS K 5400. (Cutter guide: used at intervals of 2 mm.) Evaluation of secondary adhesion Adhesion after immersion in warm water at 50 ° C. for 7 days was measured according to JIS K5.
Evaluation was made by measuring the grid adhesion according to the standard 400. (Cutter guide: used at intervals of 2 mm.) (Evaluation results) 10: Each cut is thin and smooth on both sides, and there is no peeling at every intersection of the cut and the square. 8: There is slight peeling at the intersection of the cuts, no peeling at a glance, and the area of the defective portion is within 5% of the area of the entire square. 6: Peeling was found on both sides of the cut and at the intersection, and the area of the defective portion was 5 to 15% of the total square area. 4: The width of the peeling due to the cut is wide, and the area of the defective portion is 15 to 35% of the total square area. 2: The width of peeling due to cuts is wider than 4 points, and the area of the defective portion is 35 to 65% of the total square area. 0: The peeling area is 65% or more of the total square area. (E) Accelerated weathering test The aluminum base material (A-5052P) was degreased, and an epoxy paint was applied as a primer, and the room temperature (23 ° C., humidity 5)
After curing at 5% RH for 1 day, the results are shown in Table 3 (AR-1 to A-A).
R-11, urethane (Akifloor-UT))
Painted with a spray, cured at room temperature (23 ° C., humidity 55% RH) for 14 days, and then sunshine weather meter 3000
Evaluation was made based on the 60 ° gloss retention after the Hr test. (F) Stain resistance (ΔL value) SK # 1000 Primer (manufactured by SK Kaken Co., Ltd.) is applied on an aluminum plate (A5052P), and one day later, each top coat is applied, and it is outdoors in Settsu City, Osaka. After three months of vertical exposure to rain streaks, the color of the coating film surface was measured using CR-300 (manufactured by Minolta), and the difference (Δ) was obtained from the obtained L value (lightness).
L value). Table 5 shows the results. Urethane used was Archifru-UT. (G) Lifting resistance test The first layer was applied on the peeling sheet, and the second layer was applied every time, and the lit property of the first layer was evaluated. The same test was also performed on a mortar plate. The test results are shown in (Table 8). Urethane paint for floor is Akifloor-U
T was used. (Evaluation results) ：: No lifting.

Δ: Lifting 50% ×: Lifting 100% (H) Water vapor permeability test A method described in JIS K5400 using a coating film cured at 20 ° C. × 50% for 7, 14, 30, and 90 days. The measurement was performed according to. The test results are shown in (Table 9). (I) Abrasion resistance test Apply two layers of various top coatings on a mortar plate and apply at 20 ° C x
After curing at 50% for 28 days, the abrasion resistance was evaluated using a taper abrasion tester. The test results are shown in (Table 10).
The urethane paint used was Archfloor-UT. (V) Line tape resistance A variety of top coats are applied to an epoxy base coat on a concrete substrate, and after 1 day and 7 days, a line tape and vinyl tape are applied, and at 20 ° C. × 50%. After curing for 28 days, each tape was peeled off, and the peelability when peeled off was evaluated. The test results are shown in (Table 11). Urethanes shown in Tables 5 to 11,
Urethane paint and urethane paint for floors are Akifloor-UT
Is shown. Table 6 shows the thickening rate, dispersion stability, gloss value evaluation of the cured coating film, solvent resistance, and accelerated weather resistance test results of the resin.

Table 7 shows the results of the adhesion test.

As shown in Table 7, the adhesion was greatly improved by copolymerizing the amino group, and the old coating film (base material A: epoxy, base material B: urethane, base material C: acrylic) was obtained. Sufficient adhesion is exhibited without polishing. In addition, the self-recoat adhesiveness of acrylic silicon under high-temperature and high-humidity conditions, which has been a problem in the case of new coating, exhibits sufficient adhesion.

As shown in Table 8, by copolymerizing the amino group, the adhesion to the mortar plate was improved, and as a result, the lifting during self-recoating was improved.

As shown in Table 9, compared with the conventional urethane paint, the water vapor permeability is higher, and when applied for floors, it is possible to improve the problems such as swelling of the coating film due to moisture of the base material.

As shown in Table 10, the coating system in which the amino group was copolymerized was improved in the abrasion resistance of the coating film as compared with the urethane coating material. It is anticipated that the decrease in will be kept small.

As shown in Table 11, by copolymerizing the amino group, the line tape resistance was improved and the peeling of the coating film during the repair of the coating film was reduced.

The adhesion to inorganics, which has been a problem of epoxy and urethane paints, which are conventional paints for floors, can be sufficiently exhibited.

[0073]

[Table 5]

[0074]

[Table 6]

[0075]

[Table 7]

[0076]

[Table 8]

[0077]

[Table 9]

[0078]

[Table 10]

[0079]

[Table 11]

[0080]

According to the present invention, a composition containing a resin obtained by polymerizing a composition containing a specific monomer at a specific ratio is used as a floor coating, and the composition is used. The method of forming a coating film for flooring, or the composition or the coating method of forming a coating film, provides a composition having excellent effects such as excellent adhesion, solvent resistance, pigment dispersion stability, and water vapor permeability. Forming method and floor.

Claims (15)

[Claims] The main chain is substantially composed of a vinyl polymer, has at least one hydrolyzable silicon group bonded to a carbon atom represented by the general formula (1) in the molecule, and has an amino group. A floor coating curable composition comprising a copolymer (A) component and a curing catalyst (B) component. General formula (1): (In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R ² represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a C 6 to 10 aryl group, and a carbon number. Represents a monovalent group selected from the group consisting of 7 to 10 aralkyl groups.
^{When a} plurality of ¹ or R ² are present, they may be the same or different. a represents an integer of 0 to 2. ) 2. The floor coating curable composition according to claim 1, which is a compound having an amide group in the copolymer (A) component. 3. The floor coating curing composition according to claim 1, wherein the curing catalyst (B) component is a tin compound. 4. The curing catalyst (B) is a mixture of an acid compound and an amine compound or a reaction product thereof.
The coating composition for floor coatings according to any one of claims 1 to 3. 5. The composition of the formula (2) as component (D)
Silane compound formula described ^{(2): (R 3 O} ) 4-a -Si-R 4 a (2) ( wherein, R ³ is an alkyl group having 1 to 10 carbon atoms, 6 carbon atoms
R ⁴ is a monovalent hydrocarbon group selected from an aryl group having 10 to 10 and an aralkyl group having 7 to 12 carbon atoms;
A monovalent hydrocarbon group selected from an alkyl group having 0, an aryl group having 6 to 10 carbon atoms and an aralkyl group having 7 to 12 carbon atoms, a represents 0 or 1) and / or a silicon compound represented by the formula: The floor coating curable composition according to any one of claims 1 to 4, comprising a hydrolysis condensate. 6. The floor according to claim 1, comprising a silane compound (C) having a group selected from a vinyl group, a mercapto group, an amino group and an epoxy group, which is different from the compound (D). Paint curable composition. 7. A floor coating curable composition, wherein the silane compound (C) according to claim 6 contains an amino group. 8. The copolymer (A) having an aromatic content of 5%.
The floor coating curable composition according to any one of claims 1 to 7, which is synthesized in an organic solvent of 0% by weight or less. 9. The component (A) according to any one of claims 1 to 8, wherein the copolymerizable monomer contains an alkyl (meth) acrylate having 4 or more carbon atoms in an amount of 2 to 90 parts by weight. Item 2. The floor coating curable composition according to item 1. 10. A coating film formed using the curable composition for floor coating according to any one of claims 1 to 9, having a water vapor permeability of 40 g / m ² · 24 h or more and 200 g / m ² · 24 h. A method for forming a coating film for floors, which is as follows. 11. A method for forming a floor coating film according to claim 10, wherein the floor coating curable composition according to any one of claims 1 to 9 is directly applied to an object to be coated. 12. A method for forming a coating film for floors, comprising applying the curable composition for floor coatings according to any one of claims 1 to 9 onto a coating film applied to an object to be coated. . 13. The floor coating according to claim 10, wherein the curable composition for floor coating according to any one of claims 1 to 9 is applied on a coating film applied to an object to be coated. A method for forming a coating film. 14. A method for forming a coating film for floors, wherein the coating film applied to the object according to claim 12 or 13 is epoxy or acrylic. 15. A floor obtained by applying the composition according to any one of claims 1 to 9 or forming a coating film for floors according to any one of claims 10 to 14.