JP2001164173A - Coated article for building material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coated article for building materials which yields an excellent weather resistance, water resistance and stain-proofing property at the coated surface. SOLUTION: The coated article for building materials is prepared by applying a coating which employs an aqueous dispersion of a fluorine copolymer containing (a) a fluoroolefin-based polymer unit, (b) a propylene-based polymer unit, (c) an ethylene-based polymer unit and/or (d) a butylene-based polymer unit, etc., as the coating base.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a coated article for building material.

[0002]

2. Description of the Related Art Conventionally, cement products for building materials, outer wall materials,
Civil engineering materials such as architectural glass and guardrails are used after being exposed to the external environment.
Coating has been performed to impart antifouling properties to dust and exhaust gas and to make rain streaks less noticeable. Above all, vinylidene fluoride resin, for example, is widely used as a baking type paint because it has good weather resistance, heat resistance, and chemical resistance and dissolves in a solvent at a high temperature. As this vinylidene fluoride resin, a vinylidene fluoride homopolymer or a copolymer of vinylidene fluoride and a fluoroolefin (tetrafluoroethylene, hexafluoropropylene, chlorotrifluoroethylene, etc.) has been proposed. Further, a copolymer of a fluoroolefin and cyclohexyl vinyl ether and various other monomers is soluble in an organic solvent at room temperature, has a transparent and high gloss when used as a paint, and has a high weather resistance. It is known to provide a coating film having excellent properties such as water repellency, oil repellency, stain resistance, and non-adhesion (for example,
No. 4083), and its use is increasing in the field of weather-resistant paints for interiors and exteriors of buildings and the like.

On the other hand, in recent years, from the viewpoints of environmental protection such as air pollution and safety to human bodies, the use of problematic organic solvents has been increasingly regulated, and social demands for water-based paints and powder paints which do not use organic solvents. Is growing. Aqueous dispersion of fluororesin has been studied. For vinylidene fluoride resin, a method of emulsion-polymerizing acrylic monomer in the presence of vinylidene fluoride resin particles (Japanese Patent Laid-Open No.
No. 8884, Japanese Patent Application Laid-Open No. 4-325509) have been proposed.

Aqueous dispersion of copolymers of fluoroolefins with cyclohexyl vinyl ether and other various monomers has been studied, and it has been reported that the copolymers can be produced by emulsion polymerization (JP-A-57-34107). JP-A-61-231044). Further, there has been proposed an aqueous dispersion in which a fluorinated copolymer having a polymerized unit based on a macromonomer having a hydrophilic portion as an essential component is dispersed in water (JP-A-2-225550). It is reported that this aqueous dispersion has excellent film-forming properties and good mechanical strength of a coating film, and can be produced without using an emulsifier or a hydrophilic organic solvent.

However, the stability of the aqueous dispersion of the vinylidene fluoride resin is not always good, and the transparency of the coating film is poor due to the crystallinity of the resin. When the crystallinity is lowered for improvement, there is a problem that the glass transition temperature of the coating film is too low and the stain resistance is deteriorated. These problems are alleviated by seed polymerization of acrylic monomers, but are not sufficient. There was also a problem in film forming properties. Further, the cost of the vinylidene fluoride-based resin increases because it is composed of only a fluoroolefin. Regarding copolymers of fluoroolefins with cyclohexyl vinyl ether and other various monomers, the transparency and film forming properties of the coating film are good and sufficiently practical, but since a liquid monomer is used, a slight However, further improvement has been desired in that tack is generated in the coating film.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a coated article for building material having improved weather resistance, water resistance and stain resistance of a coating surface. The purpose is to provide.

[0007]

Means for Solving the Problems The present invention has been made to solve the above problems, and according to the present invention, the following inventions are provided.

(1) (a) a polymerized unit based on a fluoroolefin, (b) a polymerized unit based on propylene, (c)
A building material characterized by being coated with a paint containing, as a paint base, an aqueous dispersion in which a fluorine-based copolymer containing a polymerized unit based on ethylene and / or (d) a polymerized unit based on butylene is dispersed in water. For painted articles.

(2) (a) a polymerized unit based on fluoroolefin, (b) a polymerized unit based on propylene, (c)
A fluorine-based copolymer containing a polymerization unit based on ethylene and / or a polymerization unit based on (d) butylene and a polymerization unit based on at least one selected from (e) vinyl ester, vinyl ether, isopropenyl ether and allyl ether is A coating material for a building material, wherein a paint containing an aqueous dispersion dispersed in water as a paint base is applied.

(3) (a) a polymerized unit based on a fluoroolefin, (b) a polymerized unit based on propylene, (c)
In the presence of 100 parts by mass of particles of a fluorocopolymer containing polymerized units based on ethylene and / or polymerized units based on (d) butylene, (f) linear, branched and / or Or (meth) acrylate having an alkyl group having a cyclic structure, (g) (meth) acrylate having a hydrophilic polyether chain, (h) other copolymerizable radically polymerizable monomer. A coated article for a building material, wherein a paint containing a composite aqueous dispersion of a fluorocopolymer as a paint base obtained by copolymerizing 5 to 100 parts by mass of a monomer mixture is applied. .

(4) (a) a polymerized unit based on fluoroolefin, (b) a polymerized unit based on propylene, (c)
Of a fluorine-based copolymer comprising a polymerized unit based on ethylene and / or (d) a polymerized unit based on butylene, and (e) a polymerized unit based on at least one selected from vinyl esters, vinyl ethers, isopropenyl ethers and allyl ethers (F) in the presence of 100 parts by weight of particles
A (meth) acrylate having an alkyl group having a linear, branched and / or cyclic structure having 2 to 8 carbon atoms;
(G) obtained by copolymerizing 5 to 100 parts by mass of a monomer mixture comprising a (meth) acrylate having a hydrophilic polyether chain and (h) another copolymerizable radically polymerizable monomer. A coated article for building material, wherein a coating containing a composite aqueous dispersion of a fluorine-based copolymer as a coating base is applied.

Hereinafter, in the present specification, the above (1) to
The fluorine-based copolymer in (4) is referred to as “the fluorine-based copolymer used in the present invention”, and the aqueous dispersion of the fluorine-based copolymer in (1) to (4) is referred to as “the aqueous dispersion in the present invention”. Called.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, preferred embodiments of the present invention will be described in detail. In the present invention, (a) a polymerized unit based on fluoroolefin, (b) a polymerized unit based on propylene as essential components, and (c) a polymerized unit based on ethylene, as a paint base for coating a building material article. And / or (d) an aqueous dispersion of a fluorinated copolymer comprising polymerized units based on butylene. This is one form of the aqueous dispersion in the present invention.

Here, the fluorine-based copolymer used in the present invention is preferably constituted by a composition ratio of polymerized units based on the following monomers (hereinafter, indicated by the monomer names).
That is, (a) 20-80 mol% of fluoroolefin, (b) 2-70 mol% of propylene, (c) ethylene (5)-(70) mol%, (d) butylene (5)-(70) mol% ,

This composition ratio is more preferably (a) 35 to 65 mol% of a fluoroolefin, (b) 4 to 55 mol% of propylene, (c) ethylene (8) to (60) mol%, and (d) butylene. (8) to (60) mol%,

Most preferably, (a) 40 to 60 mol% of fluoroolefin, (b) 6 to 35 mol% of propylene (c) ethylene (10) to (35) mol%, (d) butylene (10) to ( 35) mol%.

Here, the composition ratio of the polymerization units (c) ethylene and (d) butylene is shown in parentheses (5),
(8), (10) and the like have the following meanings. That is, as specified in the claims,
At least one of (c) and (d) is always included, and the other may not be included at all, but (5), (8),
(10) and the like indicate the content of the contained component (c) or (d) alone. (C) and (d)
(5), (8), (1)
0) indicates the total content of both components.

If the proportion of the fluoroolefin polymerized unit (a) is too small, the fluoropolymer used in the present invention is inferior in weather resistance. If the proportion is too large, the compatibility with the (meth) acrylate decreases. Not preferred. The above range is selected in consideration of these.

On the other hand, if the proportion of the polymerized unit (b) is too small, the fluorocopolymer becomes rubbery and the hardness of the coating film becomes insufficient. If it is too large, the melting point becomes too high. Run out. Thus, the above range is selected.

As described above, the polymer units (c) and (d) may be used simultaneously, or only one of them may be used, but at least one of them is always used. If the proportion of (c) and / or (d) is too small, the melting point will be too high, and the crystallization of the coating film will be large and the transparency will be reduced. Conversely, if the amount is too large, the fluorocopolymer becomes rubbery and the hardness is insufficient. The above range is selected as preferable in consideration of these.

In the present invention, examples of the fluoroolefin include trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, trifluoropropylene, tetrafluoropropylene, pentafluoropropylene, hexafluoropropylene, tetrafluorobutylene, pentafluorobutylene and the like. A fluoroolefin having about 2 to 4 carbon atoms containing a fluorine atom is preferable, and a perfluoroolefin is particularly preferable. Most preferably,
It is tetrafluoroethylene. Note that other halogen atoms such as a chlorine atom may be contained together with the fluorine atom.

In the present invention, butylene is
1-butylene, 2-butylene and isobutylene can be used, and isobutylene is most preferred in terms of availability. Further, a mixture thereof may be used.

When the monomer constituting the polymerized unit of the fluorocopolymer used in the present invention is composed of only a gaseous monomer at normal temperature and normal pressure, the remaining monomer after the polymerization is completed Has the characteristic that it can be easily removed just by purging,
Therefore, there is an advantage that coloring or stickiness of the coating film due to the residual monomer does not occur.

The melting point of the fluorine-based copolymer used in the present invention is preferably from 40 to 150 ° C., more preferably from 60 to 120 ° C. If the melting point is too low, the hardness of the coating film will be insufficient. If the melting point is too high, sufficient fluidity will not be obtained at the time of heating and coating will impair the appearance of the coating film. In addition,
In the case of the vinylidene fluoride resin, the hardness of the coating film is insufficient even within the above melting point range, and the transparency is lowered due to the high crystallinity.

In the present invention, the melting point is determined by using a scanning differential calorimeter (DSC) to determine an exothermic peak when the sample is heated at a rate of 10 ° C./min, and using the temperature at that time as the melting point. When the distribution of the melting point peak is wide, the peak top is defined as the melting point. The glass transition temperature of the fluorinated copolymer in the present invention is preferably from -20C to + 80C. More preferably, it is 0 to 70 ° C. If the glass transition temperature is too low, the hardness of the coating film becomes insufficient,
On the other hand, if it is too high, sufficient fluidity cannot be obtained at the time of heating coating, which impairs the appearance of the coating film. On the other hand, in the case of vinylidene fluoride resin, the glass transition temperature is low, and the hardness of the coating film is insufficient.

The content of fluorine atoms in the fluorine-based copolymer used in the present invention is preferably in the range of 20 to 65% by mass, more preferably 30 to 60% by mass. If the content of the fluorine atom is too small, the weather resistance is reduced, and if it is too large, the adhesion of the coating film to the substrate is undesirably reduced.

In the fluorine-based copolymer used in the present invention, (e) a vinyl ester, vinyl ether, isopropenyl ether or allyl ether may be used in addition to the polymerized units based on the monomers (a) to (d). It may be a copolymer containing a polymerized unit based on at least one selected monomer. When polymerized units based on this monomer are contained, not only the pigment dispersibility and the adhesion to the base material are improved, but also the affinity with the acrylic monomer is improved and the transparency of the coating film is improved. It has the feature that weather resistance is improved.

If the amount of the polymerized units based on at least one monomer selected from the above (e) vinyl ester, vinyl ether, isopropenyl ether and allyl ether is too large, the coating film is tacky. On the other hand, if the amount is too small, the effect of improving pigment dispersibility, adhesion to a substrate, affinity with an acrylic monomer, and the like is not sufficiently exhibited.

Therefore, the content of the polymerization unit based on the component (e) is preferably about 5 to 20 mol%.

Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl caprylate, vinyl stearate and the like. Examples of the vinyl ether include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether. Examples of the isopropenyl ether include methyl isopropenyl ether, ethyl isopropenyl ether, propyl isopropenyl ether, butyl isopropenyl ether, and cyclohexyl isopropenyl ether.
Examples of the allyl ether include ethyl allyl ether, propyl allyl ether, butyl allyl ether, and isobutyl allyl ether.

The polymerization unit based on the monomer (e) may contain a reactive group selected from a hydroxyl group, a carboxylic acid group, an epoxy group and a hydrolyzable silyl group. The polymerized unit based on the monomer containing the reactive group contains 2 of the polymerized units based on the monomer (e).
It can be contained in an amount of 0 mol% or more, preferably 25% mol% or more.

Even if the fluorocopolymer has such a reactive group, the stability of the dispersion is not impaired. When the fluorine-based copolymer has a reactive group, when the aqueous dispersion is used as a paint base, by using a curing agent in combination, the resin is crosslinked and extremely excellent in water resistance and solvent resistance. There is an advantage that a coating film having properties can be formed. In this sense, a reactive group can also be considered to correspond to a curable site.

The polymerization unit having a hydroxyl group can be obtained by a method of copolymerizing such a hydroxyl group-containing monomer,
Alternatively, it can be introduced by a method in which a polymer undergoes a polymer reaction to form a polymerization unit containing a hydroxyl group.

Here, the hydroxyl group-containing monomers include hydroxyalkyl vinyl ethers such as hydroxybutyl vinyl ether [HBVE]; hydroxyalkyl allyl ethers such as hydroxyethyl allyl ether; acrylics such as hydroxyethyl acrylate and hydroxyethyl methacrylate. Examples thereof include hydroxyalkyl esters of acid or methacrylic acid.

As a method for causing a polymer to react with a polymer to form a polymer unit having a hydroxyl group,
Examples include a method of copolymerizing a hydrolyzable vinyl ester after polymerization, and then hydrolyzing to form a hydroxyl group.

On the other hand, the carboxylic acid group-containing polymerized unit is formed by copolymerizing a carboxylic acid group-containing monomer, and forming a carboxylic acid group by reacting a polymer having a hydroxyl group with a dibasic acid anhydride. It can be introduced by methods.

Here, examples of the carboxylic acid group-containing monomer include the following. (1) CH ₂ = CHOR ¹ OCOR ² COOM (2) CH ₂ = CHCH ₂ OR ³ OCOR ⁴ COOM (wherein, R ¹ and R ³ are divalent hydrocarbon groups having 2 to 15 carbon atoms, R ² , R ⁴ represents a saturated or unsaturated linear or cyclic divalent hydrocarbon group, and M represents a hydrogen atom, a hydrocarbon group, a group containing an alkali metal or a nitrogen atom.)

The polymerization unit containing an epoxy group can be introduced by copolymerizing a monomer containing an epoxy group. Examples of the epoxy group-containing monomer include epoxy group-containing alkyl vinyl ethers such as glycidyl vinyl ether; epoxy group-containing alkyl allyl ethers such as glycidyl allyl ether; epoxy group-containing alkyl acrylates such as glycidyl acrylate and glycidyl methacrylate or methacrylates. And the like.

The polymerizable unit containing a hydrolyzable silyl group can be introduced by copolymerizing a monomer containing a hydrolyzable silyl group. Examples of the monomer containing a hydrolyzable silyl group include trimethoxyvinylsilane and triethoxyvinylsilane.

The aqueous dispersion in the present invention is a dispersion in which a fluorocopolymer is dispersed in water. The aqueous dispersion in the present invention is sufficiently excellent in dispersion stability without using an emulsifier usually used in an aqueous fluorocopolymer dispersion, but does not exclude the use of an emulsifier. As the emulsifier, a nonionic emulsifier or an anionic emulsifier can be used alone or in combination. Examples of the nonionic emulsifier include alkylphenol ethylene oxide adducts, higher alcohol ethylene oxide adducts, ethylene oxide and propylene oxide block copolymers, and the like. As anionic emulsifiers, alkyl benzene sulfonate, alkyl naphthalene sulfonate,
Examples thereof include higher fatty acid salts, alkyl sulfate salts, alkyl ether sulfate salts, and phosphoric ester salts.

The above-mentioned emulsifier is usually added and used at the time of polymerization, but the same kind of emulsifier and / or different kinds of emulsifier may be added to the aqueous dispersion after polymerization.

The emulsifiers to be added to the aqueous dispersion after polymerization include, in addition to the above emulsifiers, alkali metal salts of dialkylsulfosuccinic acids such as sodium dioctylsulfosuccinate and sodium dinonylsulfosuccinate, and ethylene glycol And a combination with an alkylene glycol such as propylene glycol. The addition of these alkali metal salts of dialkylsulfosuccinic acid and alkylene glycol improves the mechanical and thermal stability of the aqueous dispersion.

In the present invention, the initiation of the emulsion polymerization is carried out by adding a polymerization initiator in the same manner as in the usual initiation of the emulsion polymerization. As the polymerization initiator, a usual radical initiator can be used, and particularly, a water-soluble initiator is preferably employed, and specifically, a persulfate such as ammonium persulfate, hydrogen peroxide or hydrogen peroxide or hydrogen peroxide is used. Sodium, a redox initiator composed of a combination with a reducing agent such as sodium thiosulfate, and an inorganic initiator in which a small amount of iron, ferrous salt, silver sulfate, etc. coexist, or disuccinic peroxide, diglutar Examples thereof include dibasic acid peroxides such as acid peroxide, azobisisobutylamidine hydrochloride, and organic initiators such as azobisisobutyronitrile.

The amount of the polymerization initiator to be used can be appropriately changed depending on the kind thereof, emulsion polymerization conditions and the like, but is usually 0.005 per 100 parts by mass of the monomer to be emulsion-polymerized.
About 0.5 part by mass is preferred. Further, these polymerization initiators may be added all at once, or may be added in portions as needed.

For the purpose of adjusting the pH of the emulsion,
Adjusters may be used. As a pH adjuster, sodium carbonate, potassium carbonate, sodium hydrogen orthophosphate,
Examples thereof include inorganic bases such as sodium thiosulfate and sodium tetraborate, and organic bases such as triethylamine, triethanolamine, dimethylethanolamine, and diethylethanolamine.

The amount of the pH adjuster is usually about 0.05 to 2 parts by weight, preferably about 0.1 to 2 parts by weight, per 100 parts by weight of the emulsion polymerization medium. The higher the pH, the higher the polymerization rate tends to be.

The emulsion polymerization initiation temperature is appropriately selected depending on the type of the polymerization initiator.
00 ° C, particularly about 10 to 90 ° C, is preferably employed.
The polymerization temperature is about 20 to 120 ° C. The reaction pressure can be appropriately selected, but is usually 0.1 to 10MPa.
a, especially about 0.2 to 5 MPa.

In this polymerization method, additives such as a monomer, water, an emulsifier, a polymerization initiator and the like may be charged into a reactor as they are, and polymerization may be carried out. For the purpose of improving the stability and various physical properties such as the gloss of the coating film, pre-emulsification using a stirrer such as a homogenizer before adding a polymerization initiator, and then adding the initiator and then polymerizing. Good. In addition, the monomer may be charged to the reactor all at once, a method of continuously charging the entire amount of the monomer, a method of dividing the total amount of the monomer and charging, a single amount. Various methods can be adopted according to the purpose, such as a method of charging a part of the body and reacting first, and then dividing or continuously charging the rest. In the case of divisional addition, the monomer composition may be different.

The fluorine-based copolymer used in the present invention is obtained by further adding a monomer having the same combination and composition as the particles in the presence of particles of the fluorine-based copolymer which has been polymerized in advance. Emulsion polymerization may be performed. Pre-existing copolymer particles in water make it easier to absorb gaseous monomers and improve the polymerization rate. In this case, the stability of the dispersion liquid can be further improved by performing emulsion polymerization after diluting the particles of the fluorine-based copolymer that has been polymerized in advance.

In this case, the monomer mixture 1 was added to 100 parts by mass of the fluorocopolymer particles previously charged during the polymerization.
It is desirable to carry out the polymerization at a ratio of from 00 to 10,000 parts by mass. If the proportion of the particles of the fluorine-based copolymer to be charged in advance is too low, the effect of improving the polymerization rate is small, and if it is too large, the yield of the aqueous dispersion obtained by one polymerization operation is reduced, which is not economical.

In order to further improve the gas absorption of gaseous monomers, alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol and t-butanol; alkylenes such as ethylene glycol and propylene glycol; A hydrophilic organic compound such as a glycol may be added during polymerization. The amount of addition in this case is preferably 0.1 to 10% by mass, more preferably 1 to 5% by mass, based on the water of the aqueous dispersion.
It is.

If the addition amount is smaller than this, the gas absorbing effect is small, and if it is too large, flammability may occur, which is not preferable.

Next, the aqueous dispersion in the present invention is prepared by dispersing the above-mentioned fluorocopolymer in an aqueous dispersion.
(F) a (meth) acrylate having an alkyl group having a linear, branched and / or cyclic structure having 2 to 8 carbon atoms, (g) having a hydrophilic polyether chain (meth)
Acrylic ester, (h) a monomer mixture comprising a copolymerizable radical polymerizable monomer (hereinafter referred to as (meth)
It is referred to as an acrylate monomer mixture. ) May be emulsion polymerized.

The emulsion polymerization of the (meth) acrylate-based monomer mixture in the aqueous dispersion in which the particles of the fluorine-based copolymer are dispersed is performed by the above-described dispersion of the fluorine-based copolymer. This is to be referred to as a post-reaction on particles or so-called seed polymerization using the particles as seed particles. In the course of emulsion polymerization, a dispersed fluorine-based copolymer of a (meth) acrylate-based monomer mixture As a result of some interaction such as intrusion and swelling into the polymer, the final aqueous dispersion of the fluorine-based copolymer is more fluorine-based than that prepared by mixing both dispersions individually and then mixing. It is expected that a copolymer of the copolymer and the (meth) acrylate monomer mixture can be obtained in which the copolymer is more uniformly dispersed.

As described above, by subjecting the (meth) acrylic acid ester-based monomer mixture to seed polymerization, the mechanical stability and the stability of the fluorine-based copolymer used in the present invention can be maintained while maintaining the properties such as weather resistance. Chemical stability, film forming property, pigment dispersibility, and workability can be further improved.

The (f) (meth) acrylate having an alkyl group having a straight, branched and / or cyclic structure having 2 to 8 carbon atoms includes, for example, ethyl (meth) acrylate, Isopropyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isoamyl (meth) acrylate, isohexyl (meth) acrylate, 2- (meth) acrylate
Examples thereof include ethylhexyl and cyclohexyl (meth) acrylate. (Meth) acrylic acid esters having an alkyl group having a branched and / or cyclic structure having 2 to 8 carbon atoms are preferred. Among them, particularly those having 4 to 6 carbon atoms
(Meth) acrylic acid esters having an alkyl group of (i) are preferable, and t-butyl methacrylate is most preferably used because the coating film has the highest transparency.

(F) the above (meth) acrylate monomer mixture of the above (meth) acrylate having an alkyl group having a linear, branched and / or cyclic structure having 2 to 8 carbon atoms The ratio in the inside is preferably 50 to 99% by mass, particularly preferably 70 to 95% by mass. 5
If the amount is less than 0% by mass, the transparency of the coating film decreases, and the minimum film formation temperature (MFT) decreases. If it exceeds 99% by mass, the stability of the aqueous dispersion is impaired.

Next, as the (g) (meth) acrylic acid ester having a hydrophilic polyether chain, an ester having a polyoxyethylene chain, a polyoxypropylene chain, or a combination thereof having a polyether chain is preferable. Examples of the (meth) acrylate having such a polyether chain include the following general formulas (1) to (4)
The compound represented by these is mentioned.

[0059] ^{_{(1) CH 2 = CR 5}} COOR 6 in _{(CH 2 CH 2 O) m} X ( wherein, R ⁵ is, .R ⁶ represents a hydrogen atom, or a methyl group,
It represents a chain or cyclic alkylene group having 0 to 8 carbon atoms.
m shows the integer of 2-40. X represents a hydrogen atom, a methyl group, a SO ₃ Na group, or a SO ₃ NH ₄ group. )

[0060] ^{_{(2) CH 2 = CR 5}} COOR 6 (CH 2 CH (CH 3) O) n X ( wherein, R ⁵ is, .R ⁶ represents a hydrogen atom, or a methyl group,
It represents a chain or cyclic alkylene group having 0 to 8 carbon atoms.
n shows the integer of 2-40. X represents a hydrogen atom, a methyl group, a SO ₃ Na group, or a SO ₃ NH ₄ group. )

(3) CH ₂ = CR ⁵ COOR ⁶ (CH ₂ CH ₂ O) _p (CH ₂ CH (CH ₃ ) O) _q X (wherein, R ⁵ represents a hydrogen atom or a methyl group. R ⁶ is
It represents a chain or cyclic alkylene group having 0 to 8 carbon atoms.
p represents an integer of 1 to 40, and q represents an integer of 1 to 40.
X represents a hydrogen atom, a methyl group, a SO ₃ Na group, or a SO ₃ NH ₄ group. )

(4) CH ₂ = CR ⁵ COOR ⁶ (CH ₂ CH (CH ₃ ) O) _q (CH ₂ CH ₂ O) _p X (wherein, R ⁵ represents a hydrogen atom or a methyl group. R ⁶ is
It represents a chain or cyclic alkylene group having 0 to 8 carbon atoms.
q represents an integer of 1 to 40, and p represents an integer of 1 to 40.
X represents a hydrogen atom, a methyl group, a SO ₃ Na group, or a SO ₃ NH ₄ group. )

Among them, (1) the (meth) acrylic acid ester having a polyoxyethylene chain is particularly preferable because the aqueous dispersion has good stability. As a (meth) acrylate having such a polyether chain,
For example, trade name MA series (manufactured by Nippon Emulsifier Co., Ltd.), trade name Antox MS-60 (manufactured by Nippon Emulsifier Co., Ltd.), trade name: NK Ester M series (manufactured by Shin-Nakamura Chemical Co., Ltd.), trade name: Blemmer PE series (manufactured by Nippon Yushi Co., Ltd.) ), Eleminor RS-30 (manufactured by Sanyo Chemical Industries, Ltd.) and the like can be used.

The preferred ratio of (g) the (meth) acrylate having a lipophilic polyether chain in the (meth) acrylate-based monomer mixture is 1 to 50% by mass. Yes, 2 to 20% is more preferable. If it is less than 1%, the stability of the aqueous dispersion is impaired, and if it is more than 50%, the water resistance of the coating film is undesirably reduced.

The (meth) acrylate monomer mixture contains (h) other copolymerizable radically polymerizable monomers together with the above (f) and (g) monomers. May be.

The (h) other copolymerizable radically polymerizable monomers include (meth) acrylic acid, maleic acid, crotonic acid and other carboxyl group-containing monomers; (meth) acrylamide, N-methyl ( Amide compounds such as (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide; hydroxyl-containing monomers such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate;
Epoxy group-containing monomers such as glycidyl (meth) acrylate; γ-trimethoxysilane (meth) acrylate,
Radical polymerizable monomers having at least one functional group, such as a hydrolyzable silyl group-containing monomer such as γ-triethoxysilane (meth) acrylate.

The mass ratio of the (h) other copolymerizable radical polymerizable monomer in the (meth) acrylate monomer mixture is from 0 to 30%. When the proportion is more than 30%, the transparency of the coating film is impaired.

The amount of the ((meth) acrylic acid ester monomer mixture) used is 5 to 100 parts by mass, preferably 10 to 80 parts by mass, and more preferably 20 to 100 parts by mass, per 100 parts by mass of the fluorocopolymer. 50 parts by mass.
When the above-mentioned so-called seed polymerization is adopted, 5 to 100 parts of the reaction vessel are added in the presence of 100 parts by mass of the fluorocopolymer.
A part by weight of the (meth) acrylate monomer mixture is charged and emulsion polymerization is performed.

The emulsion polymerization conditions for the above (meth) acrylate monomer mixture can be employed according to the emulsion polymerization conditions for the above-mentioned fluorine-based copolymer except for the polymerization pressure.

The melting point of the composite particles of the fluorine-based copolymer and the copolymer obtained from the above (meth) acrylate monomer mixture (hereinafter also referred to as the composited melting point). Is preferably from 40 to 150 ° C, more preferably from 60 to 140 ° C. If the melting point is too low, the hardness of the coating film will be insufficient, and if the melting point is too high, sufficient fluidity will not be obtained at the time of heating and the appearance of the coating film will be impaired.

Further, the glass transition temperature (hereinafter, referred to as the following) of the composite particles of the fluorine-based copolymer and the copolymer obtained from the above (meth) acrylate-based monomer mixture.
Also referred to as the composited glass transition temperature. ) Is-
It is preferably in the range of 20 to + 80 ° C, more preferably 0 to 70 ° C. If the glass transition temperature is too low, tackiness occurs in the coating film. If the glass transition temperature is too high, the flexibility of the coating film is impaired.

The aqueous dispersion of the present invention can be used as an aqueous paint as it is as a paint base.
If necessary, colorants, plasticizers, UV absorbers, leveling agents, defoamers, pigment dispersants, film forming aids, thickeners, cissing inhibitors, skin burrs, hardeners, etc. The additives to be added may be mixed. Further, a metallic pigment such as an aluminum paste may be used. Examples of the coloring agent include dyes, organic pigments, and inorganic pigments.
As the plasticizer, conventionally known plasticizers, for example, a low molecular weight plasticizer such as dioctyl phthalate, a vinyl polymer plasticizer,
High-molecular-weight plasticizers such as polyester-based plasticizers and the like are included. Dipropylene glycol-
Polyhydric alcohol monoalkyl ethers such as n-butyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, and organic acid esters are used. As the curing agent, for example, a blocked isocyanate such as hexamethylene diisocyanate trimer, and a melamine resin such as methylated melamine and methylolated melamine are used.

Further, a pH adjuster may be added to improve the stability of the aqueous dispersion and to protect the surface of a base material such as a base material for a building material on which the aqueous dispersion is coated. Examples of such a pH adjuster include inorganic salts such as sodium carbonate, potassium carbonate, sodium O-hydrogen phosphate, sodium thiosulfate, and sodium tetraborate, and organic salts such as triethylamine and triethanolamine, and ammonia.

The aqueous dispersion according to the present invention, when used as a paint base to form a coating, has an adhesive property to inorganic and organic substrates to be coated, weather resistance, chemical resistance, In order to further improve the flexibility in addition to the film forming property, an inorganic silicon compound and / or an organic silicon compound can be compounded with the compound.

Examples of such inorganic silicon compounds include water-soluble silicates such as water glass, and water-dispersible colloidal silica.

Examples of the water-soluble silicate include those represented by the formula (I): T ₂ O · KSiO ₂ (I) (wherein T is an alkali metal or —N (CH ₂ CH ₂ OH) ₄ , —N
H (CH ₂ OH) ₄ , —N (CH ₂ CH ₂ OH) ₃ , or —C (NH ₂ ) NH ₂ , and K is 0.5 to 5. )). The water-soluble silicate may or may not have water of crystallization.

More specifically, examples of the aqueous solution of the water-soluble silicate represented by the formula (I) include an alkali metal silicate comprising an alkali metal belonging to Group IA of the periodic table and silicic acid; Aqueous solutions such as tertiary ammonium silicate composed of tertiary ammonium and silicic acid, quaternary ammonium silicate composed of quaternary ammonium and silicic acid, and guanidine silicate composed of guanidine and silicic acid are exemplified. . Alkali metal silicates include sodium silicate, potassium silicate, lithium silicate, cesium silicate, and the like. Tertiary ammonium silicates include triethanolamine silicate and quaternary ammonium silicates Is tetramethanol ammonium silicate,
Examples include tetraethanol ammonium silicate.

A modified water-soluble silicate obtained by reacting one or more of fluorides such as calcium, magnesium, zinc and zirconium with these water-soluble silicates; Used alone or in combination with a metal belonging to Group 2A of the periodic table or a modified water-soluble silicate obtained by reacting one or more of oxides or hydroxides such as zinc, zirconium, vanadium and cesium Can also.

Among the water-soluble silicates, lithium silicate,
Alkali metal silicates such as sodium silicate are preferably used. Particularly in lithium silicate, SiO 2
₂ / Li ₂ O molar ratio of from 3.0 to 25.0, further 3.0
~ 4.8 are preferably used. If the molar ratio is less than 3.0, the water resistance of the resulting coating film may decrease, and if it is greater than 25.0, workability and storage stability during preparation of the coating composition may decrease. There is not preferred. In sodium silicate, SiO ₂ / Na ₂
The molar ratio of O is preferably in the range of 1.5 to 4.0, and more preferably in the range of 3.0 to 4.0. The molar ratio is 1.5
If it is smaller than the above, the water resistance of the resulting coating film may be reduced. If it is larger than 4.0, the workability and the storage stability at the time of preparation of the coating composition may be undesirably reduced.
Further, lithium silicate is preferred from the viewpoint of the transparency of the coating film.

The colloidal silica is produced, for example, by removing sodium from water glass (ion exchange method, acid decomposition method, peptization method), and has a primary particle diameter of 4 to 1
Those having a thickness of 50 nm, preferably 5 to 50 nm, are usually commercially available as aqueous dispersions, and can be used as they are in the present invention.

The colloidal silica may be used in any of an aqueous dispersion on the acidic side and the basic side.
As the acidic colloidal silica, for example, non-stabilized silica commercially available under the trade name Snowtex-O or Snowtex-OL (manufactured by Nissan Chemical Industries, Ltd.) (pH
2-4) can be used. On the other hand, as the colloidal silica on the basic side, there is silica (pH 8.4 to 10) stabilized by adding a trace amount of an alkali metal ion, an aluminum ion, an ammonium ion or an amine. C,
Snowtex N (all manufactured by Nissan Chemical Industries, Ltd.), trade name Ludox HS-40, HS-30, LS, SM-3
0, TM, AS, AM (all manufactured by DuPont, USA),
Examples thereof include those commercially available under the trade name Nalcoque (manufactured by Nalco Chemical Co., USA) and under the trade name Mittens (manufactured by Monsanto Chemical Co., USA). Note that p
When H is 6 to 8, not only the stability of the colloidal silica is poor, but also the stability of the coating when formed into a coating is reduced, and there is a tendency for aggregation and gelation.

On the other hand, examples of the organosilicon compound include, for example, a compound represented by the general formula (II): R ⁷ _a Si (OR ⁸ ) _4-a (II) (wherein R ⁷ represents a non-hydrolyzable group or a hydrogen atom. , R ⁸
Represents an alkyl group, an aryl group, an alkenyl group or a hydrogen atom, and a is 0, 1 or 2. )).

In the general formula (II), a non-hydrolyzable group
R ⁷ is, for example, an alkyl group such as methyl, ethyl and propyl; an aryl group such as phenyl, tolyl and mesityl; an alkenyl group such as vinyl and allyl;
haloalkyl groups such as γ-chloropropyl group; aminoalkyl groups such as γ-aminopropyl group and γ- (2-aminoethyl) aminopropyl group; γ-glycidoxypropyl group; β- (3,4-epoxycyclohexyl) A) an epoxyalkyl group such as an ethyl group; a methacryloyloxyalkyl group such as a γ-mercaptoalkyl group and a γ-methacryloyloxypropyl group; a hydroxyalkyl group such as a γ-hydroxypropyl group.

Among these substituents R ⁷ , preferred in the present invention are alkyl groups having 8 or less carbon atoms, more preferably alkyl groups having 4 or less carbon atoms, since the reactivity decreases when the substituent has many carbon atoms. A phenyl group which is one of a group and an aminoalkyl group, an epoxyalkyl group, a methacryloyloxyalkyl group, a hydroxyalkyl group and an aryl group to which a substituent is added, and an alkenyl group having 2 to 3 carbon atoms.

The alkyl group, aryl group and alkenyl group represented by R ⁸ are the same as those described above with respect to R ⁷ , but particularly preferred are those having a carbon atom in terms of a decrease in reactivity when the substituent has a large number of carbon atoms. It is an alkyl group of the number 4 or less.

Specific examples of the organosilicon compound represented by the general formula (II) include, for example, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane,
Methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-chloropropyltrimethoxysilane,
γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) aminopropyltrimethoxysilane, γ-
Glycidoxypropyltrimethoxysilane, β- (3,
4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-
Methacryloyloxypropyltrimethoxysilane, γ
-Hydroxypropyltrimethoxysilane and the like, but from the viewpoint of reactivity, film formability, flexibility, etc., methyltrimethoxysilane, phenyltrimethoxysilane, γ-
Methacryloyloxypropyltrimethoxysilane and the like are preferred.

In the present invention, the ratio of the fluorine-based copolymer to the inorganic silicon compound and / or the organic silicon compound in the aqueous dispersion is based on 100 parts by weight of the fluorine-based copolymer.
Inorganic silicon compound and / or organic silicon compound 0.1 to
It is 100 parts by mass, more preferably in the range of 1 to 50 parts by mass. When the inorganic silicon compound and the organic silicon compound are used in combination, this mass part is the total amount of both. If the ratio of the inorganic silicon compound or the like is less than 0.1, the non-staining adhesion of the surface of the obtained coating film may be insufficient,
If it exceeds 100, defects such as cracks are likely to occur in the coating film due to lack of flexibility at the time of forming the coating film or over time.

Further, in the present invention, by supporting the fine particle titanium oxide on the surface of the coating film, the dirt of the organic matter adhered to the surface of the coating film by the reducing power caused by being excited by light having a wavelength having a certain energy. Disassembly to prevent dirt,
It is also possible to use a stain-resistant paint by a so-called semiconductor photocatalytic reaction.

It is preferable to use a titanium oxide having an anatase type crystal structure as the fine particle titanium oxide. The particle size is preferably from 1 to 100 nm. If it is smaller than 1 nm, it is difficult to disperse it well in the coating material.
If it is larger than 0 nm, the light transmittance of the coating film is undesirably reduced. In addition, in order to prevent the fine particle titanium oxide from coming into contact with the paint component and decomposing the paint component, the fine particle titanium oxide may be supported on silica particles by a known technique, or may be included in the silica particles.

The coating composition based on the aqueous dispersion of the present invention (hereinafter referred to as the coating composition of the present invention)
For example, by coating on the surface of a building material base material, it is possible to obtain a coating material for a building material having excellent weather resistance, antifouling property, inconspicuous rain streak, chemical resistance, transparency of a coating film, and low tack. .

Examples of such base materials for building materials include ceramic base materials such as thermosetting cement and asbestos slate, and base materials made of synthetic resin, artificial marble, glass, concrete, wood, metal materials and the like.

As the ceramic substrate, a substrate composed of portland cement, alumina cement, cement containing anhydrous gypsum or gypsum as a main component, a glass fiber reinforced slate plate or the like is preferably used. As the synthetic resin substrate, a substrate composed of an acrylic resin, a polycarbonate resin, a vinyl chloride resin, a polyester resin, a heat-resistant engineering plastic, various thermosetting resins, or the like is preferably used. As the artificial marble base material, those mainly containing unsaturated polyester and those mainly containing acrylic resin are preferably used. As a glass substrate,
Float glass, template glass, heat-absorbing glass, heat-reflecting glass, double-layer glass, tempered glass, laminated glass, crystallized glass, foamed glass, and the like are preferably used. High-strength concrete,
A substrate made of glass fiber reinforced concrete (GRC), carbon fiber reinforced concrete, lightweight cellular foamed concrete (ALC), or the like is preferably used. As the metal material base, a base made of iron, aluminum, magnesium, titanium or the like is preferably used. Furthermore, in order to prevent metal corrosion and improve adhesion, the surface of the metal material is subjected to chemical conversion treatment with phosphate, sulfuric acid, chromic acid, etc.
Surface roughening treatment such as shot blasting and sand blasting may be performed.

Further, it is also possible to apply one or more layers of a paint using an aqueous dispersion of a (meth) acrylic resin on a base material in advance and form a paint film of the paint of the present invention on the paint film. Good. By pre-coating the coating film made of the (meth) acrylic resin, the coating film of the present invention has improved adhesiveness, reduces coating film defects such as peeling of the coating film and blisters, and increases durability. be able to. Examples of the paint using the aqueous dispersion of the (meth) acrylic resin include an aqueous dispersion of a copolymer of methyl methacrylate / butyl methacrylate, and a bisphenol A type epoxy resin added to the copolymer. Those obtained by coating the mixed aqueous dispersion are preferably used.

The method of applying the paint of the present invention or the paint using the aqueous dispersion of the (meth) acrylic resin to a base material for building materials includes air spray, cold spray,
Spray coating such as hot spray, airless spray, aerosol spray; rolling coating such as roller coater and tumbling; flow coating such as flow coater and shower coat; coating using electric properties such as electrodeposition coating; dipping, brush coating, Spatula coating and the like can be mentioned, and it is arbitrarily selected according to the physical properties of the paint, the type of the base material, the thickness of the coating film, the coating work environment, the use environment of the building material, and the like.

[0095]

EXAMPLES The present invention will be specifically described below with reference to synthesis examples and examples, but the present invention is not limited to these examples and the like. The number of parts in the following examples indicates parts by mass unless otherwise specified.

(Synthesis Example 1) Ion-exchanged water 1100 was placed in an autoclave with a stainless steel stirrer having an internal volume of 2.5 L.
g, a fluorine-based anionic emulsifier (FC-143: manufactured by Sumitomo 3M) 4.75 g, a nonionic emulsifier (N-111)
0; manufactured by Nippon Emulsifier) 2.2 parts and t-butanol 4
6.6 g was charged, and air was removed by repeating deaeration with a vacuum pump and pressurization with nitrogen gas. Next, 72 g of tetrafluoroethylene, 1.1 g of propylene, and 1.4 g of ethylene were introduced into the autoclave.

When the temperature in the autoclave reached 70 ° C., the pressure showed 1.34 MPa. Thereafter, 2 cc of a 25% aqueous solution of ammonium persulfate was added to start the reaction. While maintaining the pressure by pressurizing with the decrease in pressure,
861.5 g of a mixed gas of 50 mol% of tetrafluoroethylene, 25 mol% of propylene and 25 mol% of ethylene was continuously added to continue the reaction.

During the reaction, ammonium persulfate 2
30 cc of a 5% aqueous solution was continuously added. Eight hours later, the supply of the mixed gas was stopped, and the autoclave was cooled with water to reach room temperature. Then, unreacted monomers were purged, and the autoclave was opened to obtain an aqueous dispersion having a solid concentration of 43.1%.

A part of the obtained aqueous dispersion was settled by a centrifugal separator, and the polymer was filtered through a glass filter.
After removing water for 5 hours under a reduced pressure of 32 Pa, the mixture was pulverized with an impact hammer mill to obtain a powder of a fluorine-based copolymer. As a result of composition analysis of the copolymer by ¹³ C-NMR, it was found that the polymerization unit based on tetrafluoroethylene was 52 mol%, the polymerization unit based on propylene was 28 mol%, and the polymerization unit based on ethylene was 20 mol%. The melting point is 9
6.2 ° C. Table 1 shows the results.

(Synthesis Example 2) Ion-exchanged water 1010 was added to an autoclave with a stainless steel stirrer having an internal volume of 2.5 L.
Part, 4-hydroxybutyl vinyl ether (HBVE)
5.5 parts of potassium carbonate (K ₂ CO ₃₎ 2.2 parts of a nonionic emulsifier (N-1110; manufactured by Nippon Emulsifier Co., Ltd.) 2.2
Parts, anionic emulsifier (sodium lauryl sulfate)
One part, 46.6 g of t-butanol was charged, and air was removed by repeating deaeration with a vacuum pump and pressurization with nitrogen gas. Next, 94 g of tetrafluoroethylene, 1.0 g of propylene, 2.8 g of ethylene, and 4.9 of isobutylene were used.
Was introduced into the autoclave.

When the temperature in the autoclave reached 70 ° C., the pressure showed 1.54 MPa. Thereafter, 2 cc of a 25% aqueous solution of ammonium persulfate was added to start the reaction. While maintaining the pressure as the pressure decreases, 53 mol% of tetrafluoroethylene, 8.2 mol% of propylene,
684 g of a mixed gas of 19 mol% of ethylene and 18 mol% of isobutylene was supplied from a cylinder and simultaneously 20 g of HBVE liquid.
Was continuously added from a glass ampoule to continue the reaction.

During the reaction, ammonium persulfate 2
30 cc of a 5% aqueous solution was continuously added. After 10 hours, the supply of the mixed gas was stopped, and the autoclave was cooled with water to reach room temperature. After that, unreacted monomers were purged, and the autoclave was opened to obtain an aqueous dispersion having a concentration of 39.5%. The result of composition analysis of this copolymer by ¹³ C-NMR was as follows: 53 mol% of polymerized units based on tetrafluoroethylene, 8.2 mol% of polymerized units based on propylene, 19 mol% based on ethylene, and 19 mol% based on isobutylene. Polymerized unit 18
Mol%, 1.8 mol% of polymerized units based on HBVE. The melting point was 118 ° C. Table 1 shows the results.

(Synthesis Example 3) A 200-mL glass flask equipped with a thermometer, a stirrer, a reflux condenser, and a cooler was prepared.
Synthesis Example 1 except that a monomer having a composition shown in Example 3 of Table 1 was used.
70 g of an aqueous dispersion having a solid content concentration of 32.0% by mass obtained in the same manner as described above was charged (the amount of the fluorine-based copolymer in the dispersion was 24 g), and the mixture was heated to 80 ° C. .
When the temperature reached 80 ° C., 1.2 g of methyl methacrylate, 9.4 g of t-butyl methacrylate, and Blemmer PE200
(Trade name: 0.6 g of (meth) acrylic acid ester having a polyether chain manufactured by NOF Corporation), 0.04 g of nonionic emulsifier (N-1110; manufactured by Nippon Emulsifier Co.), anionic emulsifier (sodium lauryl sulfate) 0.02 g to 1
An aqueous dispersion emulsified as a mass% aqueous solution was added dropwise over 1 hour. After dispersing with stirring for 18 hours,
Heat until warm. When the temperature reached 60 ° C., 1 mL of a 0.5% by mass aqueous solution of ammonium persulfate was added to start the reaction. After a reaction time of 4.5 hours, the mass ratio of the fluorine-based copolymer to the t-butyl methacrylate-based copolymer was 2: 1.
Thus, an aqueous dispersion having a solid concentration of 40.8% by mass was obtained. Table 1 shows the results.

(Synthesis Example 4) A 500-mL glass flask equipped with a thermometer, a stirrer, a reflux condenser, and a condenser was charged with:
Synthesis Example 3 except that a monomer having the composition shown in Example 4 of Table 1 was used.
202.8 g of an aqueous dispersion having a solids concentration of 34.5% and 25.7 g of deoxygenated water obtained in the same manner as described above were prepared (the fluorine-based copolymer in the dispersion was 70.0 g). Under a nitrogen atmosphere, 20.0 g of t-butyl methacrylate, 8.0 g of isobutyl methacrylate, Antox MS-60
A mixture of 2.0 g of (trade name: (meth) acrylate having a polyether chain manufactured by Nippon Emulsifier Co.)
It was added dropwise over a period of minutes. After stirring and dispersing for 18 hours,
Heated to 60 ° C. When the temperature reached 60 ° C., 0.8 mL of a 0.5% by mass aqueous solution of ammonium persulfate was added to start the reaction. After a reaction time of 4.5 hours, an aqueous dispersion having a weight ratio of the fluorine-based copolymer to the t-butyl methacrylate-based copolymer of 7: 3 and a solid concentration of 45.7% by mass was obtained. Table 1 shows the results.

(Synthesis Examples 5 to 10) The monomer composition used in the emulsion polymerization was changed as shown in Tables 1 and 2, and the other conditions were the same as those described in Synthesis Examples 1 to 4. A dispersion was obtained. The results are shown in Tables 1 and 2. In Tables 1 and 2, Synthesis Examples 1 to 10 are referred to as Examples 1 to 10. In addition, the chemical stability and mechanical stability of the aqueous dispersion of Synthesis Example 10 are significantly poorer than those of Synthesis Examples 1 to 9.

[0106]

[Table 1]

[0107]

[Table 2]

The abbreviations in Tables 1 and 2 are as follows. _{EOVE-1: CH 2 = CHOC} 4 H 8 -O- (CH 2 CH 2 O) n H ( average molecular weight _{520) EOVE-2: CH 2} = CHOCH 2 -cycloC 6 H 10 -CH 2 O- (CH 2 CH ₂ O)
_n H (average molecular weight 830) HBVE: 4-hydroxybutyl vinyl ether

The melting point was measured by a scanning differential calorimeter (DSC).
)), The exothermic peak was determined by raising the temperature of the sample at 10 ° C./min, and the temperature at that time was determined as the melting point. When the melting point peak distribution was broad, the peak top was taken as the melting point. Further, the glass transition temperature was defined as a point where two tangents intersect at a portion where a rapid change in the temperature gradient occurs in the same temperature rise curve of the DSC.

The chemical stability is 1 gram per 25 g of aqueous dispersion.
After adding 25 g of 0 mass% calcium chloride aqueous solution and stirring for 1 hour, the mixture was filtered through a 200-mesh wire gauze, and the dry mass ratio of aggregates remaining on the wire gauze was calculated. Pass 500 ppm or less.

The mechanical stability was as follows: 50 g of the aqueous dispersion was stirred with a homogenizer (trade name: Biomixer: manufactured by Nippon Seiki Seisakusho) at 5,000 rpm for 5 minutes, filtered through a 200-mesh wire gauze, and left on the wire gauze. The percentage of the dry mass of the aggregate was calculated. Pass 500 ppm or less.

Further, in a, b, c, d, e and other compositions, for example, the composition of tetrafluoroethylene is "9
The term “0/52” means that “90” in the molecule is 90 mol% in the feed monomer, and “52” in the denominator is the polymerization based on tetrafluoroethylene in the copolymer. Indicates that the unit is 52 mol%.

(Examples 1 and 2) 71 parts of an aqueous dispersion of the fluorocopolymer obtained as described above (Synthesis Examples 1 and 2), 5.4 parts of a film-forming auxiliary, and 0.3 parts of a thickener , 0.8 part of dispersant, 0.6 part of defoamer, 0.8 part of ultraviolet absorber, 1 ion-exchanged water
Using 0.3 parts, a clear paint was blended. The film-forming aid was butyl carbitol acetate, and the thickener was B
ERMODOLPUR2150 (manufactured by Akzo), dispersant: Noscosperse 44-C (manufactured by San Nopco), defoamer: FS Antifoam 90 (manufactured by Dow Corning)
It is.

Next, the above coating material was applied by air spray at a rate of 50 to 100 g / m ^{2 on} the surface of a SUS304 plate whose surface had been subjected to a chemical conversion treatment with chromic acid, and dried in a hot air drying oven at 100 ° C. for 100 seconds. To obtain a painted stainless steel plate.

Example 3 71 parts of the aqueous dispersion of the fluorocopolymer obtained as described above (Synthesis Example 3), 5.4 parts of a film-forming auxiliary, 0.3 part of a thickener, and 0 part of a dispersant 0.8 parts, defoamer 0.6 parts, ultraviolet absorber 0.8 parts, ion-exchanged water 10.
Clear coating was performed using 3 parts. The film forming aid was butyl carbitol acetate, and the thickener was BER
MODOL PUR2150 (manufactured by Akzo), dispersant: Noscosperse 44-C (manufactured by San Nopco), antifoaming agent: FS Antifoam 90 (manufactured by Dow Corning)
It is.

Next, the above coating material was applied by airless spray at a rate of 50 to 100 g / m ² to the surface of a cement-based exterior building material “Honban: Kesera” (manufactured by Asahi Glass Co., Ltd.).
The coated exterior building material was obtained by drying in a hot air drying oven at 100 ° C. for 100 seconds.

(Example 4) Methyl methacrylate / methac
50% aqueous solution of 40/60 (%) copolymer of butyl acrylate
In 60 parts of the dispersion, 5.4 parts of a film-forming auxiliary, 0.3 part of a thickener,
Using 0.8 parts of a dispersant and 0.6 parts of an antifoaming agent,
A krill resin paint was formulated. This acrylic resin paint
Airless spray on GRC plate 200-220g / m ^Two 
And dried in a hot air drying oven at 100 ° C for 100 seconds.
After drying, an acrylic resin undercoating film was formed.

Next, 71 parts of an aqueous dispersion of the fluorine-based copolymer of Synthesis Example 4, lithium silicate (SiO ₂ / Li ₂ O molar ratio 4.5, trade name: lithium silicate 45, manufactured by Nissan Chemical Industries, Ltd.) 3.5), 5.4 parts of a film-forming auxiliary, and 0.1 part of a thickener.
Using 3 parts, 0.8 part of a dispersant, 0.6 part of an antifoaming agent, 0.8 part of an ultraviolet absorber, and 10.3 parts of ion-exchanged water, a clear paint for overcoating was blended. The film forming aid was butyl carbitol acetate, and the thickener was BERMODOL.
PUR2150 (manufactured by Akzo), dispersant is Noscosperse 44-C (manufactured by San Nopco), and defoaming agent is FS Antifoam 90 (manufactured by Dow Corning).

This fluorine-based overcoat is applied on the undercoat at a rate of 50 to 100 g / m ² ,
Was dried in a hot-air drying furnace for 100 seconds to form a coated GRC plate.

Example 5 To 60 parts of a 50% aqueous dispersion of a 40/60 (%) copolymer of methyl methacrylate / butyl methacrylate was added 5.4 parts of a film-forming aid and 0.3 part of a thickener 0.3. Department,
Acrylic resin paint for undercoat was compounded using 0.8 parts of a dispersant and 0.6 parts of an antifoaming agent. This acrylic resin paint is applied to a polycarbonate resin plate by air spraying for 200 to 22
0 g / m ^{2 at} a rate of 1 g in a hot air drying oven at 100 ° C.
After drying for 00 seconds, an acrylic resin undercoat film was formed.

Next, 71 parts of an aqueous dispersion of the fluorine-based copolymer of Synthesis Example 5, 3.5 parts of colloidal silica (trade name: Snowtex C-20, manufactured by Nissan Chemical Industries, Ltd.), and film-forming aid 5 0.4 parts, thickener 0.3 parts, dispersant 0.8 parts, defoamer 0.6 parts, ultraviolet absorber 0.8 parts, ion-exchanged water 10.
Using 3 parts, a clear paint for overcoating was blended. In addition,
Butyl carbitol acetate as a film-forming aid, B as a thickener
ERMODOL PUR2150 (manufactured by Akzo), dispersant Noscosperse 44-C (manufactured by San Nopco), and defoaming agent FS Antifoam 90 (manufactured by Dow Corning).

This fluorine-based overcoat is applied on the undercoat at a rate of 50 to 100 g / m ² ,
The coating was dried in a hot air drying oven for 100 seconds to form a coated polycarbonate resin plate.

Example 6 A 60% aqueous dispersion of a 50/50 (%) mixture of a 40/60 (%) copolymer of methyl methacrylate / butyl methacrylate and a 50/50 (%) mixture of a bisphenol A type epoxy resin was prepared. An acrylic resin paint for undercoating was blended using 5.4 parts of a film assistant, 0.3 parts of a thickener, 0.8 parts of a dispersant, and 0.6 parts of an antifoaming agent. This acrylic resin paint is applied to an artificial marble plate mainly composed of polymethyl methacrylate resin at a rate of 200 to 220 g / m ² by air spray, and dried for 100 seconds in a hot air drying furnace at 100 ° C., and the acrylic resin undercoat film is applied. Was formed.

Next, 71 parts of the aqueous dispersion of the fluorine-based copolymer of Synthesis Example 6 were mixed with ethyl silicate (ethyl silicate 4
0: manufactured by Colcoat Co., Ltd.) 7 parts, film forming aid 5.4 parts, thickener 0.3 parts, dispersant 0.8 parts, defoamer 0.6 parts, ultraviolet absorber 0.8 parts, ion Clear paint was formulated using 10.3 parts of exchanged water. The film forming aid was butyl carbitol acetate, and the thickener was BERMODOL PUR.
2150 (Akzo), Noscosperse 4 dispersant
4-C (manufactured by San Nopco) and an antifoaming agent are FS Antifoam 90 (manufactured by Dow Corning).

This fluorine-based overcoat is applied on the undercoat at a rate of 50 to 100 g / m ² ,
Was dried in a hot air drying oven for 100 seconds to form a painted artificial marble plate.

Example 7 A film was formed on 60 parts of a 50% aqueous dispersion of a 40/60 (%) copolymer of methyl methacrylate / butyl methacrylate and a 50/50 (%) mixture of a bisphenol A type epoxy resin. Acrylic resin paint for undercoat was compounded using 5.4 parts of an auxiliary agent, 0.3 parts of a thickener, 0.8 parts of a dispersant, and 0.6 parts of an antifoaming agent. This acrylic resin paint is applied to a float glass plate by air spraying for 200 to 2
The composition was applied at a rate of 20 g / m ² and dried in a hot air drying oven at 100 ° C. for 100 seconds to form an acrylic resin undercoat.

Next, 71 parts of the aqueous dispersion of the fluorine-based copolymer of Synthesis Example 7, 0.8 parts of anatase-type titanium oxide powder having an average particle diameter of 50 μm, 5.4 parts of a film-forming aid, and 0 parts of a thickener 0 .3
Parts, a dispersant 0.8 parts, an antifoaming agent 0.6 parts, an ultraviolet absorber 0.8 parts, and ion-exchanged water 10.3 parts, and stirred and mixed using a ball mill to form a clear paint. .

The film forming aid was butyl carbitol acetate, and the thickener was BERMODOL PUR2150.
(Manufactured by Akzo), dispersant Noscosperse 44-C
(Manufactured by San Nopco), antifoaming agent is FS Antifoam 9
0 (manufactured by Dow Corning).

This fluorine-based overcoat is applied on the undercoat at a rate of 50 to 100 g / m ² ,
And dried in a hot air drying furnace for 100 seconds to form a coated glass plate.

Example 8 A film was formed on 60 parts of a 50% aqueous dispersion of a 40/60 (%) copolymer of methyl methacrylate / butyl methacrylate and a 50/50 (%) mixture of a bisphenol A type epoxy resin. Acrylic resin paint for undercoat was compounded using 5.4 parts of an auxiliary agent, 0.3 parts of a thickener, 0.8 parts of a dispersant, and 0.6 parts of an antifoaming agent. This acrylic resin paint is air-sprayed on wooden plywood at 200-220 g /
m ² and dried in a hot air drying oven at 100 ° C. for 100 seconds to form an acrylic resin undercoat.

Next, 71 parts of an aqueous dispersion of the fluorocopolymer of Synthesis Example 8, 0.8 parts of anatase type titanium oxide powder having an average particle diameter of 50 μm, 5.4 parts of a film-forming aid, and 0 parts of a thickener .3
Parts, a dispersant 0.8 parts, an antifoaming agent 0.6 parts, an ultraviolet absorber 0.8 parts, and ion-exchanged water 10.3 parts, and stirred and mixed using a ball mill to form a clear paint. . The film forming aid was butyl carbitol acetate, the thickener was BERMODOL PUR2150 (manufactured by Akzo), the dispersant was Noscosperse 44-C (manufactured by San Nopco), and the defoaming agent was FS Antifoam 90 ( Dow Corning).

This fluorine-based overcoat is applied on the undercoat at a rate of 50 to 100 g / m ² ,
Was dried in a hot air drying furnace for 100 seconds to form a coated plywood.

Example 9 A film was formed on 60 parts of a 50% aqueous dispersion of a 40/60 (%) copolymer of methyl methacrylate / butyl methacrylate and a 50/50 (%) mixture of a bisphenol A type epoxy resin. An acrylic resin paint for undercoating was blended using 5.4 parts of an auxiliary agent, 0.3 parts of a thickener, 0.8 parts of a dispersant, and 0.6 parts of an antifoaming agent. This acrylic resin paint is applied to a SUS304 plate by air spraying for 200 to 2
The composition was applied at a rate of 20 g / m ² and dried in a hot air drying oven at 100 ° C. for 100 seconds to form an undercoat acrylic resin film.

Next, 71 parts of the aqueous dispersion of the fluorocopolymer of Synthesis Example 9, 5.4 parts of a film-forming auxiliary, 0.3 part of a thickener, 0.8 part of a dispersant, and 0 parts of an antifoaming agent .6 parts, UV absorber 0.8
Parts and 10.3 parts of ion-exchanged water, and a clear paint was blended.

The film forming aid was butyl carbitol acetate, and the thickener was BERMODOL PUR215.
0 (manufactured by Akzo), dispersant Noscosperse 44-C
(Manufactured by San Nopco), antifoaming agent is FS Antifoam 9
0 (manufactured by Dow Corning).

This fluorine-based overcoat is applied on the undercoat at a rate of 50 to 100 g / m ² ,
Was dried in a hot air drying furnace for 100 seconds to form a coated stainless steel plate.

Comparative Example 1 71 parts of an aqueous dispersion of the fluorine-based copolymer of Synthesis Example 10, 5.4 parts of a film-forming auxiliary, and 0.1 part of a thickener were added.
3 parts, a dispersant 0.8 parts, a defoaming agent 0.6 parts, and a deionized water 10.3 parts were blended with a clear paint.

The film-forming aid was butyl carbitol acetate, and the thickener was BERMODOL PUR215.
0 (manufactured by Akzo), dispersant Noscosperse 44-C
(Manufactured by San Nopco), antifoaming agent is FS Antifoam 9
0 (manufactured by Dow Corning).

Next, the above paint was applied at a rate of 200 to 220 g / m ² by air spray on the surface of a SUS304 plate whose surface was subjected to a chemical conversion treatment with chromic acid, and dried in a hot air drying oven at 100 ° C. for 100 seconds. To form a painted stainless steel plate.

The coated articles obtained in Examples 1 to 9 and Comparative Example 1 were tested for film forming properties, weather resistance, water resistance, transparency of coating films, and stain resistance according to the following criteria. .

Evaluation of film-forming properties: た indicates that a coating film could easily be formed on a substrate, and X indicates that it could not be formed. Weather resistance evaluation: A sample whose gloss significantly decreased after 3000 hours of a QUV test using a fluorescent ultraviolet weather tester manufactured by Q Panel Co. was evaluated as x, and a sample whose gloss retention of 60 ° or more was 60% or more was evaluated as ○.

Evaluation of water resistance: After immersion in hot water at 60 ° C. for one week, the coating was evaluated for blistering or peeling. X was given for peeling, etc., and o was given for none. Evaluation of Transparency of Coating Film: When the coating film appeared opaque visually, it was evaluated as x, and when it was transparent, it was evaluated as ○.

Evaluation of stain resistance: Exposure was carried out outdoors at 45 ° on the south side for one year, and those having a color difference ΔL of 5 or less after the preservation plate and the water spray were rated as ○, and those exceeding 5 were rated as x. The results are shown in Table 3.

[0144]

[Table 3]

[0145]

According to the present invention, the weather resistance, water resistance,
It is intended to provide a coating material for building materials having excellent stain resistance and the like, and is extremely useful.

Further, since the coated article for building materials of the present invention basically uses a paint based on a stable aqueous dispersion without using an organic solvent, a volatile organic solvent is generated at the time of coating. There is no risk of fire or harm to the human body.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 2E110 AA12 AA26 AA65 BB04 4J002 BB041 BB141 BB171 BD121 BD151 BD161 BN031 DJ006 DJ016 EX036 EX066 EX076 EX086 GH01 HA07 4J038 CD091 CD121 CD131 CP031 DL022 DL032 GA01 GA03 GA06 HA07 GA07 JC32 KA10 KA20 LA06 MA08 MA10 NA03 NA04 NA05 PA07 PB05 PC02 PC03 PC04 PC06 PC08

Claims (8)

[Claims] 1. A fluorine-containing copolymer comprising (a) a polymerized unit based on a fluoroolefin, (b) a polymerized unit based on propylene, (c) a polymerized unit based on ethylene and / or (d) a polymerized unit based on butylene. A coating material for a building material, characterized in that a coating material containing an aqueous dispersion liquid dispersed in water as a coating base is applied. 2. (a) polymerized units based on fluoroolefin, (b) polymerized units based on propylene, (c) polymerized units based on ethylene and / or (d) polymerized units based on butylene, and (e) vinyl ester A paint containing, as a paint base, an aqueous dispersion in which a fluorine-based copolymer containing a polymerized unit based on at least one selected from vinyl ether, isopropenyl ether and allyl ether is dispersed in water. Painted articles for building materials. 3. A fluorine-containing copolymer comprising (a) a polymerized unit based on a fluoroolefin, (b) a polymerized unit based on propylene, (c) a polymerized unit based on ethylene and / or (d) a polymerized unit based on butylene. (F) a (meth) acrylic ester having an alkyl group having a linear, branched and / or cyclic structure having 2 to 8 carbon atoms in the presence of 100 parts by mass of particles of (Meth) acrylic acid ester having an ether chain, (h) a monomer mixture 5 of other copolymerizable radically polymerizable monomers
A coated article for a building material, wherein a paint containing, as a paint base, an aqueous dispersion of a complexed fluorocopolymer obtained by copolymerizing 100 parts by mass is applied. 4. Polymerized units based on (a) fluoroolefins, (b) polymerized units based on propylene, (c) polymerized units based on ethylene and / or (d) polymerized units based on butylene, and (e) vinyl esters In the presence of 100 parts by mass of a particle of a fluorine-based copolymer containing a polymerized unit based on at least one selected from vinyl ether, isopropenyl ether and allyl ether, (f) a linear, branched C 2-8 chain (Meth) acrylic acid ester having an alkyl group having a cyclic and / or cyclic structure,
(G) obtained by copolymerizing 5 to 100 parts by mass of a monomer mixture comprising a (meth) acrylate having a hydrophilic polyether chain and (h) another copolymerizable radically polymerizable monomer. A coated article for building material, wherein a coating containing a composite aqueous dispersion of a fluorine-based copolymer as a coating base is applied. 5. An undercoat film formed by coating at least one coating film of a paint using an aqueous dispersion of a (meth) acrylic resin, and a paint containing the aqueous dispersion as a paint base on the paint film. The coated article for a building material according to any one of claims 1 to 4, wherein a coating is applied. 6. A coating composition in which 0.1 to 100 parts by mass of a solid content of an inorganic silicon compound and / or an organosilicon compound is applied to 100 parts by mass of a solid content of the aqueous dispersion. Item 6. A coated article for building material according to any one of Items 1 to 4. 7. A coating composition in which 0.1 to 100 parts by mass of a solid content of fine particle titanium oxide is mixed with 100 parts by mass of a solid content of the aqueous dispersion.
The coated article for building materials according to any one of the above. 8. The base material of the building material coated article is selected from the group consisting of a ceramic base material, a synthetic resin base material, an artificial marble base material, a glass base material, a concrete base material, a wood base material, and a metal material base material. It is at least one selected substrate.
8. The coated article for building materials according to any one of 7.