JP3300075B2 - Resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel and useful resin composition. More specifically, the present invention relates to a specific fluorine-containing vinyl copolymer (A), a specific curing agent (B),
The organic solvent (C) is contained as an essential component, has extremely low chargeability, and has a very small surface contact angle with water. Therefore, even when used outdoors for a long period of time, it is extremely low. The present invention relates to a resin composition that is not easily contaminated.

[0002] That is, the present invention relates to the present invention
Or a specific fluorine-containing vinyl copolymer having a group forming a salt structure in the side chain, and also having a curing reactive site, and further having a structural unit of polyoxyalkylene, if necessary. The present invention relates to a resin composition containing coalesced (A) as a base resin component and useful as a paint, film, adhesive or sealing agent.

[0003]

2. Description of the Related Art Hitherto, compositions containing a fluorine-containing vinyl copolymer as a base resin component are well known, and such compositions are easily cured or dried at room temperature. Providing a cured product having excellent weather resistance is also well known, and has been put to practical use mainly in coating applications.

[0004] However, the dried coating film obtained in this way has a high chargeability.
In particular, when used outdoors, so-called contaminants such as soot and dust in the air tend to adhere to the surface of the object to be coated, and as a result, the object to be coated is significantly contaminated, and as a result,
It has a serious problem of causing a deterioration in aesthetic appearance.

[0005] By the way, not only the composition containing a fluorine-containing vinyl copolymer as a base resin component, but also generally, the chargeability of the resin composition itself or a coating film or a film obtained from the resin composition is lowered. As a method, a method of simply adding and mixing various compounds such as polyoxyethylene alkylamines, glycerin fatty acid esters, quaternary ammonium salts or alkyl phosphates has been taken. However, the fact is that the durability of the effect is not sufficient, and in addition, there is a so-called adverse effect such as a decrease in mechanical properties of the resin composition itself, and there is no effective decisive factor.

In addition, the contamination of the coating film due to the above-mentioned outdoor exposure has a close relationship with the charging property, and also has a close relationship with the water contact angle of the coating film, in other words, the easiness of wetting with water. It has been experimentally confirmed by the present inventors that a coating film having a smaller water contact angle is less likely to be contaminated.

[0007]

The problem to be solved by the present invention is that the chargeability is extremely small,
An object of the present invention is to provide a highly practical resin composition that has a very small surface contact angle with water, and is therefore extremely resistant to contamination even when used outdoors for a long period of time.

[0008]

An object of the present invention is to provide a compound having a salt-forming group (salt structure-forming group) at the terminal and / or side chain of a molecule, and also having a curing reactive site. And
Further, if necessary, a resin comprising a specific base resin component called a fluorine-containing vinyl copolymer having a structural unit of a polyoxyalkylene chain, a curing agent capable of reacting with the curing reactive site, and an organic solvent Solved by the composition.

[Structure] That is, the present invention basically relates to a fluorine-containing compound having a group forming a salt structure at the terminal and / or side chain of the molecule and also having a curing reactive site. It comprises a vinyl copolymer (A), a curing agent (B) capable of reacting with the above-mentioned curing reactive site, and an organic solvent (C) as essential components. Another object of the present invention is to provide a highly practical resin composition which has a very small water contact angle on the surface and is therefore extremely resistant to contamination even when used outdoors for a long period of time.

Specifically, the above-mentioned fluorine-containing vinyl copolymer (A) has a specific fluoroolefin structural unit or a specific group containing a polyoxyalkylene chain (the same structural unit). Is intended to provide various resin compositions such as those having at the terminal and / or side chain of the molecule,

In addition, a group that forms a salt structure at the terminal and / or side chain of the molecule (salt structure forming group) is
Various resin compositions will be provided, such as carboxylate, phosphate, sulfonate and / or quaternary ammonium salts, or each being a specific monovalent organic group as described below. Further, it is an object of the present invention to provide various resin compositions in which the above-mentioned curing agent (C) is a polyisocyanate compound, a blocked polyisocyanate compound or aminoplast, respectively.

Hereinafter, the present invention will be described in detail. The above-mentioned curing reactive site refers to a reactive polar group (functional group) or a self-curing functional group that participates in the reaction with the curing agent component. Among them, if only the former is specifically exemplified as the curing agent-reactive functional group,
It is a hydroxyl group, a carboxyl group, an epoxy group, an isocyanate group, an amino group, an acid amide group, an unsaturated double bond, or the like. A hydrolyzable silyl group, an N-methylolacrylamide group, an alkyl etherified N-methylolacrylamide group, or an unsaturated double bond.

[0013] If only typical examples of the curing agent (C) used in combination with the curable site are given as examples, the curing reactive site may be a hydroxyl group, a carboxyl group, an amino group or In the case of a group having a so-called active hydrogen atom, such as an acid amide group,
Isocyanate-based curing agents, aminoplast-based curing agents, polyepoxy compounds or acid anhydrides,
When the curing reactive site is an epoxy group or the like, it is a polyamine or a polybasic acid. In the case of an isocyanate group, it is various polyhydroxy compounds such as a glycol.

Further, when the curing reactive site is a so-called self-curing functional group (self-reactive group) such as a hydrolyzable silyl group, the curing accelerator is used as a curing accelerator. A catalyst for hydrolysis or condensation,
For example, various acidic compounds such as sulfuric acid, hydrochloric acid or phosphoric acid, various amine compounds such as monomethylamine or triethylamine, di-n-butyltin dilaurate, di-n-butyltin diacetate or di-
Various organic tin compounds, such as n-butyltin dioctate, can be used.

Furthermore, as the above-mentioned group having a salt structure (salt structure-forming group), only typical ones are exemplified, and a carboxylic acid group, a phosphoric acid group, a sulfonic acid group and / or a quaternary group can be used. Such as ammonium salts,
Above all, it is a monovalent organic group represented by the following general formula (II).

The above-mentioned fluorine-containing vinyl copolymer (A),
That is, to prepare a fluorine-containing vinyl copolymer having a salt structure-forming group, in addition, also having a curing reactive site, and further, if necessary, also having a structural unit of a polyoxyalkylene chain, Of course, known and commonly used methods can be applied, but, inter alia, a salt structure-forming group-containing monomer, a curing reactive site-containing monomer, and a fluorine-containing monomer, if necessary. , The polyoxyalkylene chain structural unit-containing monomers, and, if necessary, further using other vinyl monomers, these monomers in an organic solvent, Copolymerization is recommended because it is the simplest method.

[0017] used in this case, first, if Todomere to illustrate only typical as a salt structure-forming group-containing monomer, such as carboxyethyl vinyl ether, inside
Metal salts of unsaturated carboxylic acids containing an ether group or the like; metal salts or ammonium salts of various unsaturated phosphoric monomers such as vinylphosphinic acid and acid phosphoxyethyl (meth) acrylate;

Metal salts or ammonium salts of various sulfonic acid group-containing vinyl monomers such as p-styrenesulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid; polyoxyalkylene-mono-sulfonic acid-mono Metal salts or ammonium salts of various vinyl monomers containing a sulfonic acid group containing a polyoxyalkylene chain, such as (meth) acrylate, polyoxyalkylene-alkenyl (alkyl) phenol mono-sulfonate;

Alternatively, vinylpyridine, N, N-dimethylaminostyrene, N, N-dialkylaminoalkyl (meth) acrylate, N- (N ′, N′-dialkylaminoalkyl) acrylamide, N- (N ′, N ′) −
Dialkylaminoalkyl) methacrylamide,
Various nitrogen-containing vinyl monomers such as benzyl chloride, methyl bromide or dibutyl sulfate. Various monomers obtained by quaternization with various commonly used quaternizing agents. In addition, as the monomer having a salt structure-forming group, CHR ₁
ＣＲCR ₂ COOH (wherein R ₁ and R ₂ are hydrogen atoms or methyl
Represents a hydroxyl group. ) Salts of unsaturated monocarboxylic acids represented by
And salts of unsaturated dicarboxylic acids are not included.

In particular, the following general formula is one of the most effective examples of the present invention.

Embedded image Wherein R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and each represents a hydrogen atom or a halogen atom, an alkyl group, a cycloalkyl group,
An aryl group or an aralkyl group or a —SO ₃ M-containing group (where M represents one atom ion or an atomic group selected from the group consisting of metal ions or ammonium salts), and R
_At least one of R ₁ , R ₂ , R ₃ or R ₄ is
—SO ₃ M; and R ₅ , R ₆ , R ₇ ,
R ₈ , R ₉ and R ₁₀ each represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, which may be the same or different, Further, m is an integer of zero or 1, and n is a natural number of 1 or more. And a monomer having a salt structure-forming group of a monovalent organic group represented by the following formula in the main part.

Here, the monomers having a salt structure-forming group represented by the above general formula (II) as a main part thereof include:
In the general formula,-(CH2) n-
A monomer having a structure substituted with a vinyl group or an alkenyl group having 3 to 18 carbon atoms is particularly desirable.

Among them, only typical examples of the monomers are exemplified by sodium mono-methylsulfosuccinate-mono-vinyl ester and ammonium mono-ethylsulfosuccinate-mono-vinyl. Esters, potassium mono-propylsulfosuccinate-mono-propenylvinyl ester, ammonium mono-octylsulfosuccinate-mono-butenyl ester or sodium mono-octylsulfosuccinate-mono-propenyl ester;

Alternatively, sodium mono-2-ethylhexylsulfosuccinate-mono-propenyl ester, sodium mono-stearylsulfosuccinate-mono-propenyl ester, sodium di-n-butylsulfosuccinate-mono-vinyl ester, 1- Calcium chloro-2-propylsulfosuccinate-mono-propenyl vinyl ester, sodium 1,1-dibromosulfosuccinate di-vinyl ester or (3-methoxy-
Various sulfosuccinic unsaturated compounds, such as sodium 2-hydroxy-propyl) sulfosuccinate-mono-vinyl ester.

The amount of the salt structure-forming group-containing monomer to be used is suitably in the range of 1 to 50% by weight based on all the monomers. When the amount is less than 1% by weight, the effects of the present invention cannot be sufficiently exhibited. On the other hand, when the amount is more than 50% by weight, the weather resistance of a cured product is remarkably reduced. In any case, it is not preferable.

Next, if only a typical example of the monomer containing a curing reactive site is exemplified, when the curing reactive site is a hydroxyl group, 2-hydroxyethyl vinyl ether or 3-hydroxyethyl is used. Various hydroxyl group-containing vinyl ethers such as propyl vinyl ether; 2-hydroxy various vinyl ethers as described above
When the addition reaction product of a coupler Rorakuton; 2-hydroxyethyl (meth) allyl ether, 3 over such as hydroxypropyl (meth) allyl ether, various hydroxyl group-containing allyl ethers; such various allyl ethers of these on supra and kind, addition reaction products of caproyl lactone;

2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3
-Hydroxy propyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate such as, various hydroxyl group-containing (meth) acrylate; and these upper supra various hydroxyl group-containing (meth) acrylates, addition reaction between Ca caprolactone Products, etc.

When the curing reactive site is a carboxyl group, (meth) acrylic acid, crotonic acid, maleic acid,
Various carboxyl group-containing monomers such as fumaric acid;
Of which, like itaconic acid, maleic acid, fumaric acid,
Various polyvalent carboxyl group-containing monomers and one having 1 carbon atom
Monoesters (half esters) with monoalkyl alcohols represented by the following formulas (18) to (18) are particularly typical examples,

When the curing reactive site is an epoxy group, glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, (meth) allyl glycidyl ether and the like are particularly typical. When the curing reactive site is an isocyanate group, isocyanate ethyl (meth) acrylate, isocyanate ethyl vinyl ether and the like are particularly typical examples,

When the curing reactive site is an acid amide group or an amino group, various amino groups such as N, N-dimethylaminoethyl (meth) acrylamide or N, N-diethylaminoethyl (meth) acrylamide Containing amide-based monomers; or N, N-dimethylaminoethyl (meth) acrylamide or N, N
Various N, N-dialkylaminoalkyl (meth) such as -diethylaminoethyl (meth) acrylamide
Acrylates and the like are particularly typical.

When the curing reactive site is a hydrolyzable silyl group, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, allyltrimethoxysilane, trimethoxysilylethylvinylether, triethoxysilyl Ethyl vinyl ether, trimethoxysilylpropyl vinyl ether, γ-
Various hydrolyzable silyl group-containing monomers such as (meth) acryloyloxypropyltrimethoxysilane, (meth) acryloyloxypropyltriethoxysilane or (meth) acryloyloxypropylmethyldimethoxysilane; or N-methylolacrylamide Alternatively, various self-curable functional group-containing monomers such as alkyl ethers thereof are particularly representative.

Further, as one method for introducing an unsaturated double bond as one of the curing reactive sites, for example, the hydroxyl group of the fluorine-containing vinyl copolymer containing a hydroxyl group may be replaced with a compound such as maleic anhydride. A method in which various unsaturated acid anhydrides are subjected to a ring-opening addition reaction, or a method in which various isocyanate group-containing vinyl monomers such as isocyanate ethyl (meth) acrylate are subjected to an addition reaction to the hydroxyl groups. There are methods.

The fluorine-containing vinyl copolymer (A) into which the unsaturated double bond has been introduced by such a method utilizes so-called active energy rays such as ultraviolet rays and light, radical generators and heat. Self-curing reaction itself, or at that time, various polyfunctional unsaturated compounds such as ethylene glycol-diacrylate, trimethylolpropane-triacrylate,
It can be used as a reactive diluent component or a curing agent component.

The amount of the curing reactive site-containing monomer used is suitably in the range of 1 to 40% by weight based on all the monomers. When the amount is less than 1% by weight, the mechanical strength of the cured product becomes inferior. On the other hand, when it exceeds 40% by weight, the weather resistance of the cured product becomes inferior. Absent.

Further, the fluorine-containing monomer, which is an indispensable component of the fluorine-containing vinyl copolymer (A), is a compound containing a fluorine atom in the molecule and having a polymerizable unsaturated diamine. A compound that also has a heavy bond, and preferably refers to the following general formula when polymerized

Embedded image Wherein W, X, Y and Z in the formula each represent a hydrogen atom, a halogen atom, an alkyl group or a halogenated alkyl group, which may be the same or different; At least one of X, Y or Z is a fluorine atom. ] Can be introduced into the main chain.

Of those, only typical ones are exemplified, and vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene,
Various fluorine-containing α-olefins, such as chlorotrifluoroethylene, bromotrifluoroethylene, pentafluoropropylene or hexafluoropropylene;

Or various perfluoroalkyl-perfluorovinyl ethers such as trifluoromethyltrifluorovinylether, pentafluoroethyltrifluorovinylether or heptafluoropropyltrifluorovinylether; and various (per) fluoroalkylvinylethers (However,
The carbon number of this alkyl group is in the range of 1 to 18. ), But

In particular, from the viewpoint of weather resistance, the fluoroolefin structural unit represented by the above general formula (I) is introduced into the molecule of the fluorine-containing vinyl copolymer (A) by copolymerization. From vinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene , chlorotrifluoroethylene and hexafluoro
It is desirable to use at least one fluorine-containing vinyl monomer selected from the group consisting of propylene .

The amount of the fluorine-containing vinyl monomer to be used is suitably in the range of 20 to 70% by weight based on all monomers. When the amount is less than 20% by weight, the weather resistance of the coating film obtained is inevitably deteriorated. On the other hand, when the amount exceeds 70% by weight, the fluorine-containing vinyl copolymer is inevitably dissolved in solvents. In any case, it is not preferable because the property is lowered. Of course, these above-mentioned fluorine-containing vinyl monomers may be used alone or in combination of two or more.

Next, the vinyl monomers containing a polyoxyalkylene chain structural unit are represented by the following general formula:

Embedded image Wherein R ₁₂ and R ₁₃ are the same or different and each represents a hydrogen atom or an alkoxy group having 1 to 4 carbon atoms, and R ₁₄ represents a hydroxyl group or a carbon number Represents an alkoxy group of 1 to 4, p is an integer of 2 to 4, and q is 1 to 2
It is assumed to be an integer of 00. The compounds having a monovalent organic group represented by the following formulas are particularly typical, but polyethylene glycol-mono- (meth) acrylate, Polypropylene glycol-mono- (meth) acrylate, polytetraethylene glycol-mono-
(Meth) acrylate, polyoxyethylene nonylphenol-mono- (meth) acrylate or polyoxyethylene nonyl allylphenol.

Further, in addition to the various monomers as listed above, other copolymerizable vinyl monomers used as required, needless to say, include those listed above. , Respectively, a salt structure-forming group-containing monomer, a curing reactive site-containing monomer, a fluorine-containing monomer, and, if necessary, a polyoxyalkylene chain structural unit-containing monomer. As long as they have copolymerizability, they can be used without any trouble. However, if only typical ones are exemplified, methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate can be used. Various acrylates;

Various methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate and benzyl methacrylate; ethylene, propylene, butene-1
Various halogenated olefins except fluoroolefins such as vinyl chloride and vinylidene chloride; various α-olefins such as styrene, α-methylstyrene, p-tert-butylstyrene, and vinyltoluene; Various aromatic vinyl compounds;

Vinyl-2,2-dimethylpropanoate, vinyl-2,2-dimethylbutanoate, vinyl-
2,2-dimethylpentanoate, vinyl-2,2-dimethylhexanoate, vinyl-2-ethyl-2-methylbutanoate, vinyl-2-ethyl-2-methylpentanoate or vinyl-3- Chloro-2,2-dimethylpropanoate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate,
Various aliphatic carboxylic acid vinyl esters such as vinyl caprylate, vinyl caprate, vinyl laurate or vinyl stearate, branched aliphatic vinyl carboxylate having 10 carbon atoms or branched aliphatic vinyl carboxylate having 11 carbon atoms Or vinyl benzoate or p
-Various carboxylic acid vinyl esters having a cyclic structure, such as -tert-butyl vinyl benzoate;

Methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-
Various (substituted) alkyl or aralkyl vinyl ethers such as pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, 2-ethylhexyl vinyl ether, chloromethyl vinyl ether, chloroethyl vinyl ether, benzyl vinyl ether or phenethyl ethyl vinyl ether;

Or cyclopentyl vinyl ether,
Various cycloalkyl vinyl ethers such as cyclohexyl vinyl ether or methylhexyl vinyl ether.

In order to prepare the fluorine-containing vinyl copolymer (A) from the various monomers listed above, any known and commonly used polymerization method can be applied. Is the most convenient.

As the solvents used at this time, any solvents can be used as long as they can dissolve the fluorine-containing vinyl copolymer (A). Various hydrocarbons such as toluene, xylene, cyclohexane, n-hexane, and octane; methanol, ethanol, isopropanol, n-butanol, isobutanol, sec-butanol, and ethylene glycol monomethyl ether are only examples. Various alcohols, such as;

Various esters such as methyl acetate, ethyl acetate, n-butyl acetate and amyl acetate; or acetone, methyl ethyl ketone, methyl isobutyl ketone,
Various ketones such as cyclohexanone,
These may be used alone or in combination of two or more.
Of course.

Polymerization may be carried out by a conventional method using such solvents and various known and commonly used radical polymerization initiators such as azo-based or peroxide-based ones. Depending on the molecular weight regulators, lauryl mercaptan, octyl mercaptan, dodecyl mercaptan, 2-mercaptoethanol, octyl thioglycolate, 3-mercaptopropionic acid or α-
Various chain transfer agents, such as methylstyrene dimer, can also be used.

The curing agent (B), which can react with the curing reactive site in the fluorine-containing vinyl copolymer (A) thus obtained, comprises a curing agent according to the type of the curing reactive site.
It is important to select and use it in order to achieve a sufficient effect.

As described above, when a polyisocyanate compound is used as the curing agent (C), various aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; xylylene diisocyanate, isophorone diisocyanate And various organic diisocyanates such as various aromatic diisocyanates such as tolylene diisocyanate and 4,4′-diphenylmethane diisocyanate;

Further, addition reaction products of these organic diisocyanates with polyhydric alcohols, low molecular weight polyester resins (polyester polyols) or water; or various organic diisocyanates listed above Polymers (including isocyanurate-type polyisocyanate compounds), isocyanates,
Biuret body and the like.

Examples of particularly typical commercial products of such polyisocyanate compounds include "Varnock D-
750, D-800, DN-950, DN-970, D
N-980, DN-981 or 15-455 "[product of Dainippon Ink and Chemicals, Inc.];
L, N, HL or LL "(manufactured by Bayer AG, Germany);" Takenate D-102, D-202, D-1
10N or D-123N "[product of Takeda Pharmaceutical Co., Ltd.];" Coronate L, HL, EH or 203 "
[Products of Nippon Polyurethane Industry Co., Ltd.]; or “Duranate 24A-90EX” [Products of Asahi Kasei Corporation]
And so on.

The term "blocked polyisocyanate compound" refers to a compound which can be obtained by blocking various organic diisocyanates listed above with known and commonly used blocking agents. Among them, only representative commercial products are exemplified, and "Barnock D-550" or "Barnock B"
7-887-60 or B9-282 "[product of Dainippon Ink and Chemicals, Inc.];" Takenate D-815-
N] [Products of Takeda Pharmaceutical Co., Ltd.];
DDITOL) VXL-80] [Hoechst Synthesis Co., Ltd.
Product]; "Coronate 2507" [product of Nippon Polyurethane Industry Co., Ltd.] and the like.

Furthermore, if only typical examples of the above-mentioned aminoplasts are given as examples, various amino group-containing compounds such as melamine, urea, acetoguanamine, benzoguanamine, steroganamin or spiroguanamine, and formaldehyde , A condensate obtained by reacting various aldehyde compounds such as paraformaldehyde, acetaldehyde or glyoxal by a conventional method, or a product obtained by etherifying each of these condensates with a monoalcohol. However, it goes without saying that any of those usually used for paints can be used.

Among them, it is desirable to use mono-alcohols of C _{1 to} C ₄ which are partially or completely etherified, and only those aminoplasts which are particularly typical are used. By way of example only, hexamethyletherified methylolmelamine, hexabutyletherified methylolmelamine, methylbutyl mixed etherified methylolmelamine, methyletherified methylolmelamine, butyletherified methylolmelamine or isobutyletherified methylolmelamine;
Or condensates thereof and the like.

Further, those which can be used as the curing agent (C) include polyepoxy compounds, acid anhydrides, polyamines, polybasic acids, polyhydroxy compounds and the like. And epoxy resins such as bisphenol A diglycidyl ether; various common resins such as glycerin polyglycidyl ether, sorbitol polyglycidyl ether, and polyoxyethylene diglycidyl ether. Polyepoxy compounds; various acid anhydrides such as maleic anhydride, phthalic anhydride, trimellitic anhydride, tetrachlorophthalic anhydride, hexahydrophthalic anhydride, and pyromellitic anhydride;

Or various polyamines such as hexamethylenediamine, isophoronediamine, dicyandiamide; succinic acid, adipic acid, sebacic acid, dodecanediacid (dodecanedicarboxylic acid), phthalic acid, isophthalic acid,
Various polybasic acids such as terephthalic acid; various polyhydroxy compounds such as ethylene glycol, propylene glycol, 1,4-butanediol (1,4-butylene glycol), 1,6-hexanediol, and sorbitol; is there.

Next, the organic solvent (C) will be described. When the resin composition of the present invention is put to practical use in the form of a film, such as a paint or a film, aromatic hydrocarbons, aliphatic hydrocarbons or esters, particularly from the viewpoint of film-forming properties. It is desirable to use such as. The significance of using such organic solvents as an essential component of the resin composition of the present invention is that the resin composition is always kept in a uniform state, and that it can be easily put to practical use. ,
This is because the desired various performances can be sufficiently exhibited.

As the organic solvent (C), it is needless to say that any of those used in the polymerization reaction can be used. Of those, particularly representative ones are exemplified. Various hydrocarbons such as toluene, xylene, cyclohexane, n-hexane and octane; and various esters such as ethyl acetate, n-butyl acetate and amyl acetate.

The mixing ratio of the fluorine-containing vinyl copolymer (A), the curing agent (B) and the organic solvent (C) in the resin composition of the present invention is as follows. A) The curing agent (B) is added in an amount of 0. 0 to 100 parts by weight.
It is in the range of 001 to 200 parts by weight. The organic solvent (C) is blended at a ratio of 10 to 2,000 parts by weight based on 100 parts by weight of the solid content of the fluorinated vinyl copolymer (A).

Further, the above (A) to (C)
In preparing a coating material by using the essential components of the present invention, known and commonly used curing accelerators can also be used, but only particularly typical curing accelerators are exemplified. If so, tetraisopropyl titanate,
Tetra-n-butyl titanate, tin octylate, lead octylate, cobalt octylate, zinc octylate, calcium octylate,

Zinc naphthenate, cobalt naphthenate, di-n-butyltin diacetate, di-n-butyltin dioctoate (di-n-butyltin dioctate), di-n-
Various metal-containing compounds such as butyltin dilaurate or di-n-butyltin maleate; or such as p-toluenesulfonic acid, trichloroacetic acid, phosphoric acid, monoalkylphosphoric acid, dialkylphosphoric acid, monoalkylphosphorous acid or dialkylphosphorous acid And various acidic compounds.
The amount of the curing accelerator is 0.01 to 10 parts by weight based on 100 parts by weight of the fluorine-containing vinyl copolymer (A).

The resin composition of the present invention may further contain, if necessary, an organic or inorganic pigment, a flow regulator, a color separation inhibitor, an ultraviolet absorber or an antioxidant. Various known additives such as nitrocellulose, cellulose acetate butyrate, and various cellulose derivatives; or ketone resin, petroleum resin, acrylic copolymer resin, oil-free alkyd resin, alkyd resin, Various resins such as epoxy resin, chlorinated polyethylene, chlorinated polypropylene or chlorinated rubber can be added. Above all, acrylic resins are suitable in terms of compatibility.

The resin composition of the present invention thus obtained is
Paints for automotive top coating, automotive repair, woodworking, construction, building exterior, building materials, glass or various plastics materials or products, or various metal materials or products such as aluminum and stainless chrome plating It can also be widely used for molding materials, various films or sheets, sealing agents, and adhesives.

[0065]

EXAMPLES Next, the present invention will be described more specifically with reference examples, examples and comparative examples. In the following, all parts and percentages are by weight unless otherwise specified. .

Reference Example 1 [Preparation Example of Fluorine-Containing Vinyl Copolymer (A)] In a stainless steel autoclave having an inner volume of 5,000 ml, 1,000 parts of xylene and 10 parts of bis (1,2,2) were added. 2,6,6-pentamethylpiperidinyl) sebacate, tert-butyl peroxypivalate and 200 parts of cyclohexyl vinyl ether, 100 parts
Parts of ethyl vinyl ether, 100 parts of cyclohexanecarboxylic acid, 100 parts of 4-hydroxybutyl vinyl ether and 5 parts of potassium vinylphosphonate were charged, and nitrogen gas was blown in to replace the air in the autoclave.

Further, after 495 parts of liquefied and collected hexafluoropropylene were charged and sealed, the autoclave was kept at 60 ° C., and reacted for 15 hours. Average molecular weight is 1
7,000 solutions of the target copolymer were obtained. Hereinafter, this is abbreviated as polymer (A-1).

Reference Examples 2 to 6 Each of the polymers (A) was prepared in the same manner as in Reference Example 1 except that the types and amounts of the monomers to be used were changed as shown in Table 1. -2), a solution of five types of fluorine-containing vinyl copolymers, a polymer (A-3), a polymer (A-4), a polymer (A-5) and a polymer (A ') were obtained. However, only the polymer (A ′) is a copolymer solution for control.

[0069]

[Table 1]

<< Footnotes to Table 1 >> Abbreviation of “HFP” ……………… Hexafluoropropylene “CTFE” …………… Abbreviation of chlorotrifluoroethylene

"VPK": abbreviation for potassium vinylphosphonate "p-SSONa": abbreviation for sodium parastyrene sulfonate "QASDM": dimethylaminoethyl methacrylate "S-1" in the form of quaternized with methyl bromide Sulfosuccinic unsaturated compound having the following structure

[0072]

Embedded image "S-2" Sulfosuccinic unsaturated compound having the following structure

[0073]

Embedded image "PE-350""BlemmerPE-35"
0 "[polyethylene glycol monomethacrylate manufactured by NOF Corporation] vinyl monomer containing a polyoxyalkylene chain structural unit

"HBVE" ... hydroxybutyl vinyl ether "AGE" allyl glycidyl ether "VTES" vinyl triethoxysilane

"CHVE" ...... Cyclohexyl vinyl ether "EVE" ...... Ethyl vinyl ether "CHCAV" ...... Vinyl cyclohexanecarboxylate "VV9" ... … “Beoba 9” (Shell, Netherlands, a vinyl ester of a branched fatty acid with 9 carbon atoms)

"TBPV": abbreviation for tert-butyl peroxypivalate

[0077]

[Table 2]

<< Footnote to Table 1 >> This is a value indicating the hydroxyl value of the copolymer solution, and the unit is KOH mg / g. This is a value indicating the epoxy equivalent of the copolymer solution, and the unit is g / mol.

[0079]

[Table 3]

[0080]

[Table 4]

Examples 1 to 7 and Comparative Examples Each of the copolymer solutions obtained in each of the reference examples, “Taipek CR-95” (a titanium oxide white pigment manufactured by Ishihara Sangyo Co., Ltd.), and xylene / N-butyl acetate = 50 /
And a mixed solvent of 50 (volume ratio) in a ratio as shown in Table 2 and mixed with a batch SG mill.
Various coatings were obtained by dispersing the particles until the particle size became 5 μm (μm) or less to form a coating, and further blending a curing agent component as shown in the same table.

Next, each paint was treated with toluene / xylene / “Solvesso 100” / n-butyl acetate =
The spray viscosity was adjusted with a mixed solvent of 40/20/10/30 (volume ratio) and spray-coated on an aluminum plate having a thickness of 0.8 mm so that the film thickness became 30 to 40 μm. .

Thereafter, each coated plate was dried at room temperature for 7 days and subjected to various performance evaluation tests. Among them, only in Examples 5 and 6, after painting, allowed to dry at room temperature for 10 minutes,
Thereafter, baking was performed in an oven at 170 ° C. for 20 minutes and subjected to various performance evaluation tests. The results of these various coating film performances are summarized in Table 2.

[0084]

[Table 5]

<< Footnotes in Table 2 >>"CR-95" ... "Taipe CR-9"
Abbreviation of "5" Abbreviation of the above-mentioned xylene / n-butyl acetate = 50/50 (volume ratio)

"DN-950": Abbreviation of "Barnock DN-950" [isocyanate prepolymer manufactured by Dainippon Ink and Chemicals, Inc.] "D-550" ... "Barnock D-55
0 "(block polyisocyanate compound manufactured by Dojo)
Abbreviation for

"N-153": Abbreviation of "Lacamide N-153-IM-65" (a polyamide resin manufactured by the same company) "L-117": "Super Becca" Min
L-117-60 "(butyl etherified melamine resin manufactured by the same company)" DBTDL ": abbreviation for dibutyltin dilaurate

"Contact angle" represents the contact angle of water with respect to each coating film. The smaller the value, the more easily it is wetted by water.

"Contamination" ... 1 liter of water
And one for the test specified in JIS Z-8901.
The test piece was immersed in 5 g of suspended dust consisting of 5 g of two types of mixed dust [product of the Japan Powder Industry Technology Association] for 10 minutes, pulled up, and then washed with a shower for 2 minutes. As one cycle, this was performed for two cycles. Thereafter, the test piece was dried, and the color difference (ΔE) from the untested test piece was measured. The value was used as data. The larger this value is, the more remarkable the degree of dirt is.

"Accelerated weathering resistance" ... 3,0 measured by Sunshine Weatherometer manufactured by Suga Test Instruments Co., Ltd.
Evaluation was made based on the gloss retention (%) after the lapse of 00 hours.

[0091]

[Table 6]

From these results, it can be seen that the resin composition of the present invention has a very high practicality which gives a cured product excellent in stain resistance and weather resistance.

[0093]

As described above, in the resin composition of the present invention, the cured product has extremely low chargeability,
Since the water contact angle is small, it has excellent contamination and weather resistance,
Particularly, when it is used as a paint, it can be useful and highly practical. In addition, there is an effect of having a useful use as an adhesive, a film, a sheet sealing agent and the like.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-5-32725 (JP, A) JP-A-5-25420 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 27/12-27/20

Claims (9)

(57) [Claims] 1. A fluorine-containing vinyl copolymer (A) having a group forming a salt structure at a terminal and / or a side chain of a molecule and also having a curing reactive site, and the curing reaction curing agent capable of reacting with sex site (B), and an organic solvent (C), it is one which contains as an essential ingredient, the salt structure
Is a carboxylate [provided that CHR ₁ =
CR ₂ COOH (wherein R ₁ and R ₂ are hydrogen atoms or methyl
Represents a group. A) a salt of an unsaturated monocarboxylic acid represented by
Excludes salts of unsaturated dicarboxylic acids. ], Phosphate, sulfo
Selected from the group consisting of phosphates and quaternary ammonium salts
A resin composition, characterized in that it is at least one of the following. 2. A salt structure at a terminal and / or a side chain of a molecule.
And a curing reactive site.
-Containing vinyl copolymer (A) having the above-mentioned curing reaction
A curing agent (B) capable of reacting with an acidic moiety and an organic solvent (C)
Is contained as an essential component, wherein the salt structure
The group forming is represented by the following general formula ◎ Wherein R ₁ , R ₂ , R ₃ and R ₄ are each
Hydrogen atoms, which may be the same or different,
Or a halogen atom, an alkyl group, a cycloalkyl group,
Aryl group or aralkyl group, or -SO ₃ M-containing group
(However, M is from metal ion and ammonium salt
One atomic ion or atomic group selected from the group consisting of
Shall be represented. ) And R ₁ ,
At least one of R ₂ , R ₃ and R ₄ is -SO ₃
M, and R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and
And R ₁₀ are each the same or different
Good, hydrogen atom or alkyl having 1 to 20 carbon atoms
Group, cycloalkyl group, aryl group , or aralkyl
And m is an integer of 0 or 1.
And n is a natural number of 1 or more.
You. ] The resin composition which is a monovalent organic group shown by these. 3. A salt structure at the terminal and / or side chain of the molecule.
And a curing reactive site.
-Containing vinyl copolymer (A) having the above-mentioned curing reaction
A curing agent (B) capable of reacting with an acidic moiety and an organic solvent (C)
Is a resin composition containing as an essential component, a salt
The group forming the structure is represented by the following general formula ◎ Wherein R ₁₁ is an alkyl having 1 to 20 carbon atoms.
Group, cycloalkyl group, aryl group or aralkyl
And M represents a metal ion and
One atomic ion selected from the group consisting of ammonium salts
Or an atomic group, and m is zero or
Is an integer of 1, and n is a natural number of 1 or more.
Shall be. ] The resin composition which is a monovalent organic group shown by these. 4. The above-mentioned fluorine-containing vinyl copolymer (A)
Has the following general formula : Wherein W, X, Y and Z in the formula are
Hydrogen atom, halogen, which may be one or different
Represents an atom, an alkyl group or a halogenated alkyl group
And at least one of W, X, Y and Z
One is a fluorine atom. Those having a fluoroolefin structural unit represented by, the resin composition according to any one of claims 1 to 3. 5. The above-mentioned fluorine-containing vinyl copolymer (A)
Has polyoxyalkylene at the terminal and / or side chain of the molecule.
5. The method according to claim 1, wherein said compound has a chain-containing group.
The resin composition according to any one of the above. Wherein said the curing reactive site is a hydroxyl group, according to claim 1 to the resin composition according to any one of the 5. 7. The method according to claim 1, wherein the curing agent (B) is a polyisocyanate.
The resin composition according to any one of claims 1 to 6 , which is a salt compound . Wherein said the curing agent (B) is a blocked polyisocyanate compound, any of claims 1 to 6
The resin composition according to any one of the above. 9. The method according to claim 1, wherein the curing agent (B) is aminoplast.
Der Ru, claims 1 to resin composition according to any one of 6.