JP2508664B2 - Curable resin composition for paint - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial application field) The present invention relates to a novel and useful curable resin composition. More specifically, the present invention is a polymer of fluoroolefin monomers excluding vinylidene fluoride, a specific fluoroolefin polymer and a hydrolyzable silyl group-containing acrylic polymer as essential components. The present invention relates to a resin composition having a moisture-curing property, which comprises containing.

(Prior Art) Conventionally, as a high weather resistance coating resin that is soluble in a solvent and forms a continuous coating film at room temperature, a non-crosslinking type resin such as tetrafluoroethylene-vinylidene fluoride copolymer, hexa Fluoropropylene-vinylidene fluoride copolymer, tetrafluoroethylene-vinylidene fluoride-
Hexafluoropropylene copolymer, vinylidene fluoride homopolymer, chlorotrifluoroethylene homopolymer,
Known are chlorotrifluoroethylene-cycloalkyl vinyl ether-alkyl vinyl ether copolymers, and cross-linked type vinylidene fluoride copolymers containing a hydroxyl group, hydrolyzable silyl group, etc. and hexafluoropropylene copolymers. Has been.

However, the coating film obtained from such a non-crosslinking type resin has insufficient solvent resistance and adhesion to the substrate, and the coating film obtained from the crosslinking type resin has insufficient adhesion to the substrate. , There was a limit in its use.

(Problems to be Solved by the Invention) As a result of intensive studies made by the present inventors in view of the above-mentioned drawbacks of the prior art, as a result, a fluoroolefin polymer is blended with an acrylic polymer containing a hydrolyzable silyl group. As a result, it was found that a curable resin composition having excellent adhesion to various substrates and solvent resistance was obtained, and the present invention was completed.

[Structure of Invention]

(Means for Solving the Problems) The present invention will be summarized. The present invention provides a fluoroolefin-based polymer (A) obtained by polymerizing at least one fluoroolefin monomer excluding vinylidene fluoride. ) And a hydrolyzable silyl group-containing acrylic polymer (B) as essential components and, if necessary, also a curing agent (C), or the curing agent (C). ) And a curing catalyst and / or a catalyst (D) for hydrolyzing or condensing the above-mentioned hydrolyzable silyl group.
In addition, the former (A) component / the latter (B) of the above-mentioned fluoroolefin polymer (A) and the above-mentioned hydrolyzable silyl group-containing acrylic polymer (B) The present invention aims to provide a novel and useful curable resin composition, which comprises a component by weight ratio within the range of 10/90 to 90/10.

 Hereinafter, the configuration of the present invention will be described in detail.

The fluoroolefin polymer (A) used in the present invention means a fluoroolefin monomer other than vinylidene fluoride, that is, vinyl fluoride, trifluoroethylene, tetrafluoroethylene, bromotrifluoroethylene, chloro. Trifluoroethylene, pentafluoropropylene, hexafluoropropylene and (per) fluoroalkyl trifluorovinyl ether [where the carbon number of the (per) fluoroalkyl group is 1 to
Assume that it is 18. ] A fluoroolefin monomer selected from the group consisting of the following is particularly representative, and a polymer obtained by polymerizing at least one of such fluoroolefin monomers is referred to. It is appropriate that the amount of the class used be 5 to 100% by weight, preferably 10 to 100% by weight, based on the total monomers.

In the present invention, other copolymerizable monomers can be used when preparing the target fluoroolefin polymer (A) component from the above fluoroolefin monomers.

As such a copolymerizable monomer, vinyl acetate,
Vinyl propionate, vinyl butyrate, vinyl pivalate,
Vinyl ester of linear or branched aliphatic carboxylic acid such as vinyl caproate, vinyl caprate, vinyl caprylate, vinyl versatate, vinyl laurate or vinyl stearate; cycloaliphatic ring such as cyclohexanecarboxylic acid vinyl ester Formula carboxylic acid vinyl ester; aromatic carboxylic acid vinyl ester such as benzoic acid vinyl ester, pt-butyl benzoic acid vinyl ester or salicylic acid vinyl ester; hydroxyalkyl vinyl ether such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether or hydroxybutyl vinyl ether; Methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether,
Linear or branched aliphatic or cycloaliphatic vinyl ethers such as n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether or cyclohexyl vinyl ether; monofunctional epoxy groups such as glycidyl vinyl ether and glycidyl (meth) acrylate Polymers; acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, monoethyl maleate, monobutyl maleate, monobutyl fumarate, monobutyl itaconic acid,
Monomers containing a carboxyl group such as monovinyl adipate and monovinyl sebacate; basic such as dimethylaminoethyl vinyl ether, dimethylaminopropyl vinyl ether, N-dimethylaminopropyl (meth) acrylamide and dimethylaminoethyl (meth) acrylate Nitrogen-containing vinyl monomers; ethylene,
Α such as propylene, butene-1 or hexene-1
-Olefins; halogenated olefins other than the above-mentioned fluoroolefin monomers such as vinyl chloride or vinylidene chloride; aromatic vinyl monomers such as styrene, α-methylstyrene or vinyltoluene; methyl (meth) acrylate, Ethyl (meth) acrylate,
Butyl (meth) acrylate, cyclohexyl (meth)
Acrylate, (meth) acrylic acid esters such as β-hydroxyethyl (meth) acrylate or phosphoric acid ester of β-hydroxyethyl (meth) acrylate; and further (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth ) Monomers such as acrylamide or N-butoxymethyl (meth) acrylamide; a monomer containing a hydrolyzable silyl group such as vinyltrimethoxysilane, vinyltriethoxysilane or γ- (meth) acryloyloxypropyltrimethoxysilane. There is a class.

Polymerization by batch operation, semi-continuous operation or continuous operation using known techniques such as bulk polymerization, solution polymerization and emulsion polymerization using a radical polymerization initiator in the presence of the monomers described above. Just do it.

Examples of such a radical polymerization initiator include diacyl peroxides such as acetyl peroxide or benzoyl peroxide; ketone peroxides such as methyl ethyl ketone peroxide or cyclohexanone peroxide; hydrogen peroxide, t-butyl hydroperoxide or cumene hydro Hydroperoxides such as peroxides; Dialkyl peroxides such as di-t-butyl peroxide or dicumyl peroxide; Alkyl peroxyesters such as t-butyl peroxyacetate or t-butyl peroxypivalate; Azo-based initiators such as azobisisobutyronitrile or azobisisovaleronitrile; or persulfates such as ammonium persulfate or potassium persulfate And the like are used, the reducing agent of sodium bisulfite or such inorganic sodium metabisulfite, or such organic reducing agent cobalt naphthenate or dimethylaniline may also be used if necessary.

Solvents used in the polymerization reaction include hydrocarbons such as toluene, xylene, cyclohexane, n-hexane or octane; esters such as methyl acetate, ethyl acetate or butyl acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone or methyl amyl. Ketones such as ketones; amides such as dimethylformamide or dimethylacetamide;
An alcoholic solvent such as methanol, ethanol, i-propanol, n-butanol, i-butanol, sec-butanol or ethylene glycol monoalkyl ether or a mixture thereof is used.

Further, in this polymerization, various chain transfer agents such as lauryl mercaptan, octyl mercaptan, 2-mercaptoethanol or α-methylstyrene dimer can also be used as a molecular weight regulator.

The reaction temperature at the time of the polymerization reaction is preferably in the range of −20 ° C. to 130 ° C., and the pressure at the beginning of the reaction is 1
A range of from about 100 kg / cm ^{2 to about} 100 kg / cm ² , preferably a range of from 5 kg / cm ^{2 to} 60 kg / cm ² is suitable.

The number average molecular weight (▲ ▼) of the fluoroolefin polymer thus obtained is from 1,000 to 300,000, preferably from the viewpoint of film-forming property and solvent solubility of the polymer.
It is 5,000 to 200,000.

Next, the hydrolyzable silyl group-containing acrylic polymer (B) component used in the present invention will be described.

The acrylic polymer (B) component having such a hydrolyzable silyl group means a compound represented by the general formula (X) _3-a (R ₁ ) _a Si (in the formula, R ₁ is a hydrogen atom or has 1 carbon atom
To 10 alkyl groups, aryl groups, aralkyl groups, X is a halogen atom, an alkoxy group, an acyloxy group, an iminoxy group, a phenoxy group, a mercapto group, an amino group, an alkenyloxy group, an alkoxyalkoxy group, and a is 0 or 1.
Represents an integer of 2) and contains a repeating unit derived from an acrylic acid ester or a methacrylic acid ester (hereinafter collectively referred to as an acrylic monomer) as an essential component. Refers to coalescence.

Specific examples of acrylic monomers include methyl (meth)
Acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate,
There are 2-ethylhexyl (meth) acrylate, cyclohexyl methacrylate, benzyl (meth) acrylate, and the like, and alkyl (meth) acrylate having an alkyl group having 1 to 4 carbon atoms is preferable.

In the present invention, when the above-mentioned acrylic monomer is (co) polymerized to prepare the polymer (B) component, another copolymerizable ethylenically unsaturated monomer can be used.

As such a copolymerizable ethylenically unsaturated monomer, the one used when synthesizing the above-mentioned fluoroolefin polymer (A) component can be used. For example, monomers having no reactive functional group such as vinyl ethers, vinyl esters, aromatic vinyl monomers and the like, and reactive functional groups such as phosphoric acid group, hydroxyl group, carboxyl group, amino group or epoxy group. Monomers such as vinyl ethers, vinyl esters, and (meth) acrylic esters having are used.

The method for producing the acryl-based polymer (B) containing a hydrolyzable silyl group of the present invention is not particularly limited, but it can be produced by a known method generally classified into the following four.

: Hydrosilane, that is, (X) _3-a (R ₁ ) _a SiH (wherein R ₁ , X
And a are the same as above) and an acrylic polymer having a carbon-carbon double bond in the side chain and / or the terminal thereof are subjected to a hydrosilylation reaction in the presence of a Group VIII transition metal catalyst.

Vinyl represented by: (X) _3-a (R ₁ ) _a SiR ₂ (wherein R ₁ , X and a are the same as defined above, and R ₂ represents an organic group having a polymerizable double bond) A monomer and an acrylic monomer are copolymerized.

Acrylic monomers in the presence of a chain transfer agent containing a hydrolyzable silyl group represented by (X) _3-a (R ₁ ) _a Si (wherein R ₁ , X and a are the same as above) Is (co) polymerized.

: In combination with the above, that is, in the presence of a hydrolyzable silyl group-containing chain transfer agent, the formula (X) _3-a (R ₁ ) _a SiR ₂ (wherein
R ₁ , X and a are the same as described above, and R ₂ represents an organic group having a polymerizable double bond) and an acrylic monomer are copolymerized.

Of these, the method or is preferred from the viewpoint of simplicity and curability.

The vinyl monomer containing a hydrolyzable silyl group used in the above-mentioned method is represented by the formula (X) _3-a (R ₁ ) _a SiR
₂ (in the formula, R ₁ , X and a are the same as above, R ₂ represents an organic group having a polymerizable double bond), a halosilyl group, an alkoxyryl group, an acyloxysilyl group, an iminoxysilyl group. , Phenoxysilyl group, mercaptosilyl group, aminosilyl group, alkenyloxysilyl group,
It refers to a monomer containing a functional group that is easily hydrolyzed, such as an alkoxyalkoxysilyl group.

Specific examples of such a monomer include γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, γ- (meth) acryloyloxypropyltriisopropenyloxysilane, γ- (Meth) acryloyloxypropyltriiminooxysilane, γ- (meth) acryloyloxypropyltriacetoxysilane, β-
(Meth) acryloyloxyethyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinylmethyldiethoxysilane, vinyldiethylmethoxysilane, Vinyltris (β-methoxyethoxysilane), vinyltriisopropenyloxysilane, vinyltris (dimethyliminooxy) silane, vinyltris (methylethyliminooxy) silane, vinyltrichlorosilane, vinyltriphenoxysilane, allyltrimethoxysilane, trimethoxysilyl Ethyl vinyl ether, triethoxysilylethyl vinyl ether, methyldimethoxysilylethyl vinyl ether, trimethoxysilane Le propyl vinyl ether, triethoxysilylpropyl vinyl ether, and the like.

Next, the chain transfer agent containing a hydrolyzable silyl group used in the above or the above method is originally used for controlling the molecular weight of the copolymer. It is used for the purpose of introducing a hydrolyzable silyl group to the molecular chain end of the polymer, and is preferably used in combination with a monomer containing the silyl group, that is, in the method.

Specific examples of such a hydrolyzable silyl group-containing chain transfer agent include γ-mercaptopropyltrimethoxysilane,
γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane or γ-mercaptopropyltriisopropenyloxysilane. These hydrolyzable silyl group-containing monomers and hydrolyzable silyl group-containing chain transfer agents are used to introduce a hydrolyzable silyl group per 1000 g of resin solid content from the viewpoint of curability and stability of the obtained polymer. It is preferably used in an amount such that the amount is in the range of 0.1 to 3 mol.

The acrylic polymer (B) component containing a hydrolyzable silyl group of the present invention is obtained by using a radical polymerization initiator in the presence of the above-mentioned monomers and, if necessary, the chain transfer agent. , Batch polymerization, solution (pressurization) polymerization, or other known technique is used to carry out the polymerization by a batch, semi-continuous or continuous operation. In that case, it is needless to say that the polymerization initiator, the solvent, and the general chain transfer agent can be the same as those used for synthesizing the fluoroolefin polymer (A) component.

Regarding the solvent, it is preferable to use a solvent containing an alcohol solvent from the viewpoint of improving the storage stability of the obtained copolymer.

Further, in such a solvent, for the purpose of removing a trace amount of water existing in the reaction system, trialkyl orthoformate such as trimethyl orthoformate, triethyl orthoformate and tributyl orthoformate; trimethyl orthoacetate, triethyl orthoacetate or Trialkyl orthoacetates such as tributyl orthoacetate; orthoborate trialkyls such as trimethyl orthoborate, triethyl orthoborate or tributyl orthoborate; tetramethylsilicate, tetraethylsilicate, tetrabutylsilicate, tetra (2-
A tetra (substituted) alkyl silicate simple substance such as methoxyethyl) silicate or tetra (2-chloroethyl) silicate; a substance having the same effect as the above tetra (substituted) alkylsilicates such as tetraphenylsilicate or tetrabenzyl silicate (hereinafter, the same effective substance) Or a dimer of tetraethyl silicate,
Trimer, tetramer or hexamer, or "ethyl silicate 40" (a product of Colcoat Co., Ltd., a tetramer of tetraethyl silicate, a mixture of pentamer and hexamer), each tetra (substituted) alkyl silicate alone, or the silicate One or a mixture of two or more kinds of hydrolyzable ester compounds such as condensates of the same simple substance; trialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane and ethyltrimethoxysilane or partial hydrolysis thereof. When the decomposition condensate, or the polymerization solvent and the monomer to be copolymerized do not contain active hydrogen having reactivity with an isocyanate group, benzenesulfonyl isocyanate, p-toluenesulfonyl isocyanate, phenylisocyanate is used. , P- chlorophenyl isocyanate, 2,4-toluene diisocyanate, m- xylylene diisocyanate or hexamethylene diisocyanate, preferably benzenesulfonyl isocyanate,
Monoisocyanates such as p-toluenesulfonyl isocyanate, phenyl isocyanate or p-chlorophenyl isocyanate may be added to the solvent before the polymerization and to the resin solution after the polymerization.

The amount of the stabilizer used for removing a trace amount of water existing in the above reaction system is usually 0.5 to 75 parts by weight with respect to 100 parts by weight of the hydrolyzable silyl group-containing acrylic polymer (B) component. %, Preferably 2 to 60% by weight.

The number average molecular weight (▲ ▼) of the acrylic polymer (B) component thus obtained is 1,000 to 300,000, preferably 3,000 from the viewpoint of film-forming property and solvent solubility of the polymer.
~ 100,000.

The ratio of the above-mentioned fluoroolefin polymer (A) component and hydrolyzable silyl group-containing acrylic polymer (B) component used in the present invention is, that is, the former (A) component. The ratio by weight of the latter component (B) is preferably in the range of 30/70 to 70/30, but normally, even if it is in the range of 20/80 to 80/20, There is no hindrance, and in particular, the fluoroolefin polymer, such as weather resistance, does not deteriorate the properties originally possessed by the fluoroolefin polymer. From the viewpoint of improvement, the range of 30/70 to 70/30 as described above is more preferable, and the range of about 35 / about 65 to about 65 / about 35 is more suitable.

In the present invention, when the component (A) or the component (B) contains a reactive functional group such as a hydroxyl group, an epoxy group, an amino group, a carboxyl group, a phosphoric acid group and an amide group, it may be added as necessary. By adding a curing agent (C) capable of reacting with these functional groups or a curing catalyst accelerating the reaction between the functional group and the curing agent (C) to further increase the cross-linking density of the coating film. It is possible to improve the sex.

Typical examples of such curing agent (C) component include aminoplast, polyisocyanate compound, blocked polyisocyanate compound, polybasic acid, polybasic acid anhydride, polyamine compound, polyepoxy compound, and epoxy group in one molecule. There are a compound having a hydrolyzable silyl group, a compound having an amino group and a hydrolyzable silyl group in one molecule, and the like.

First of all, as typical examples of aminoplast, amino group-containing compound components such as melamine, urea, acetoguanamine, benzoguanamine and spiroguanamine, and aldehyde compounds such as formaldehyde, paraformaldehyde, acetaldehyde or glyoxal are known and commonly used. Examples of the condensate obtained by reacting by the method described above, or those obtained by etherifying each of these condensates with alcohol, but any one commonly used for coating materials should be used. You can

Among them, those partially or completely etherified with C _{1 to} C ₄ alcohols are preferable, and specific examples of such aminoplasts include hexamethyletherified methylolmelamine, hexabutyletherified methylolmelamine, and methylbutyl mixture. Etherified methylol melamine, methyl etherified methylol melamine,
Examples thereof include butyl etherified methylol melamine, isobutyl etherified methylol melamine, and condensation products thereof.

In particular, it is preferable to use methyl etherified methylol melamine from the viewpoint of compatibility with the fluoroolefin polymer (A) component.

On the other hand, as a typical example of the polyisocyanate compound,
Aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; Cyclic aliphatic diisocyanates such as xylene diisocyanate and isophorone diisocyanate; or Organic diisocyanates such as tolylene diisocyanate and aromatic diisocyanates such as 4,4'-diphenylmethane diisocyanate Or, addition products of these organic diisocyanates with polyhydric alcohols, low molecular weight polyester resins, water, and the like, and further the above-mentioned polymers of organic diisocyanates with each other, isocyanate biuret, and the like can be mentioned. Typical examples of commercially available compounds are "Bernock D-750, -800, DN-950, -970, -980, -981 or 15-455" [Dainippon Ink Industry Co., Ltd. products],
"Desmodur L, N, HL or LL" (product of Bayer AG, West Germany), "Takenate D-102, -202, -11
0N or −123N ”(Takeda Pharmaceutical Co., Ltd. product),“ Coronate L, HL, EH or 203 ”(Nippon Polyurethane Industry Co., Ltd. product) or“ Duranate 24A to 90EX ”
(A product of Asahi Kasei Corporation).

Further, as a representative example of the blocked polyisocyanate compound, a compound obtained by blocking various polyisocyanate compounds such as those listed above with a known and commonly used blocking agent is designated, and a typical commercially available block polyisocyanate compound is mentioned. An example of the product is "Barnock D
-550 "[Product of Dainippon Ink and Chemicals, Inc.]," Takenate B815-N "[Product of Takeda Pharmaceutical Co., Ltd.]," ADDITOL VXL-80 "[Hoechst Synthesis Co., Ltd.]
Product] or "Coronate 2507" [product of Nippon Polyurethane Industry Co., Ltd.]. Of these (block) polyisocyanate compounds, from the viewpoint of compatibility with the fluoroolefin polymer (A), “coronate” is particularly preferable.
It is preferable to use a compound having an isocyanurate ring in the molecule, such as "2507 or EH" or "Burnock D-980 or -981".

Typical examples of the above-mentioned polybasic acid are acrylic resin or polyester resin having two or more carboxyl groups in one molecule, pyromellitic acid, trimellitic acid, or the like.

Typical polybasic acid anhydrides are acrylic resins having two or more acid anhydride groups in one molecule, trimellitic anhydride, pyromellitic dianhydride, and the like.

Typical examples of polyamine compounds include diethylenetriamine, triethylenetetramine, polyamidoamine, and acrylic polymers having two or more amino groups in one molecule.

Typical examples of the polyepoxy compound include polyglycidyl ethers of polyhydric alcohols such as ethylene glycol, glycerin, pentaerythritol, and sorbitol, and acrylic resins having two or more epoxy groups in one molecule.

Typical examples of the compound having both an epoxy group and a hydrolyzable silyl group in one molecule are γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylisopropenyloxysilane and γ-glycidoxypropyltris. Examples thereof include silane coupling agents having an epoxy group such as (dimethyliminooxy) silane.

Then, as typical examples of the compound having both an amino group and a hydrolyzable silyl group in one molecule, γ-aminopropyltrimethoxysilane, γ-dimethylaminopropyltrimethoxysilane, γ- (2-aminoethyl) amino. Examples include silane coupling agents containing an amino group such as propyltrimethoxysilane.

The amount of the above-mentioned curing agent (C) component used is (A),
(B) The total amount of both components may be 0 to 60 parts by weight based on 100 parts by weight.

In the present invention, when a polyisocyanate compound, a blocked isocyanate compound or aminoplast is used as the curing agent (C) component, the curing agent (C)
A curing catalyst can be blended to promote the reaction between the component and the reactive group in the component (A) or the component (B).

Typical examples of the curing catalyst component include dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, triethylamine and dimethylaminoethanol when a (block) polyisocyanate compound is used as the curing agent (C) component. In addition, when aminoplast is used as the curing agent (C) component, paratoluenesulfonic acid, phosphoric acid or a mono- or dialkyl ester of phosphoric acid, or "NACURE 15
5, 2500X, X-49-110, 5225 or 3525 "(manufactured by King, USA) and the like, such as dinonylnaphthalenedisulfonic acid, dodecylbenzenesulfonic acid, or organic amine block compounds thereof.

In the present invention, the catalyst (D) for hydrolysis-condensation reaction which accelerates the hydrolysis-condensation reaction of the hydrolyzable silyl group in the component (B) can be used, if necessary.

When a group that promotes the hydrolysis-condensation reaction of a hydrolyzable silyl group such as an amino group, a phosphoric acid group or a sulfonic acid group is present in the component (A) or the component (B), it is particularly hydrolyzable. The curing reaction proceeds without adding the silyl group hydrolysis-condensation catalyst (D) to form a cured coating having excellent solvent resistance. However, when the above groups are not present in the component (A) or the component (B), hydrolysis-
It is necessary to use the condensation catalyst (D) component.

Representative examples of the catalyst (D) for hydrolysis-condensation of a hydrolyzable silyl group include butylamine, dibutylamine, hexylamine, t-butylamine, ethylenediamine, triethylamine, isophoronediamine, imidazole, lithium hydroxide, water Basic compounds such as sodium oxide, potassium hydroxide, sodium methylate; tetrapropyl titanate, tetrabutyl titanate, tin octylate, lead octylate, cobalt octylate, zinc octylate, calcium octylate, lead naphthenate, naphthenic acid Metal-containing compounds such as cobalt, dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin malate; p-toluenesulfonic acid, trichloroacetic acid, phosphoric acid, monoalkyl phosphoric acid, dialkyl phosphoric acid, β-hydrid Examples thereof include acidic compounds such as a phosphoric acid ester of roxyethyl (meth) acrylate, monoalkylphosphorous acid, and dialkylphosphorous acid, and in particular, dibutyltin diacetate, dibutyltin dioctate,
Tin compounds such as dibutyltin dilaurate and dibutyltin malate are preferred. The amount of this catalyst used is usually 0 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the hydrolyzable silyl group-containing acrylic polymer (B).

Further, in the curable resin composition of the present invention, known organic or inorganic pigments, metal powders of aluminum, copper, brass, gold, silver, nickel and the like, ultraviolet absorbers, antioxidants, etc., as required. Various additives and the like can be added.

In order to obtain the curable resin composition of the present invention, the above-mentioned respective components and additives are mixed and dispersed or dissolved in an organic solvent by a known method, for example, a glass bead mill, a dispersion mixer such as a homodisper. Just do it. The non-volatile content is usually in the range of 10 to 80% by weight, preferably 20 to 60% by weight.

When the curable resin composition of the present invention is used as a coating composition, it is applied by a known and commonly used method such as spray coating, brush coating, and roll coater, and is left at room temperature for about 1 to 7 days for moisture curing, or Alternatively, a cured coating film can be formed by baking at a temperature of 60 to 250 ° C for 5 seconds to 40 minutes.

The curable resin composition of the present invention is a paint for home appliances, or an exterior paint such as a building, roof tile or pre-coated metal (PCM), or various automobile paints such as an automobile enamel paint, a metallic base paint or a clear paint. Further, it can be used as a surface protective film for glass or ceramic products, a film, a sealing agent, an adhesive and the like.

(Examples) Next, the present invention will be described more specifically by reference examples, examples and comparative examples. The present invention is not limited to these examples. In the following, all parts and percentages are by weight unless otherwise specified.

Reference Example 1 [Preparation Example of Fluoroolefin Polymer (A)] 330 g of methyl isobutyl ketone, 4.2 g of tert-butyl peroxypivalate and 84 g of hydroxybutyl vinyl ether were placed in a stainless pressure tube having an internal volume of 1000 ml. Beoba 9 were charged 126g and 84g of cyclohexanecarboxylic acid vinyl (Netherlands branched vinyl esters of aliphatic carboxylic acids manufactured by shell C _9), cooled to -70 ° C. in a dry ice / methanol bath by blowing nitrogen gas The air in the pressure resistant tube was replaced.

Liquefied and collected 126 g of hexafluoropropylene
Was charged and sealed.

Then, the pressure resistant tube was placed in a rotary constant temperature water tank heated to 60 ° C., reacted for 16 hours and then opened to obtain a copolymer solution. This product has a nonvolatile content of 53% and a number average molecular weight of 9,
000. Hereinafter, this polymer solution is abbreviated as A-1.

Reference Example 2 [Preparation Example of Fluoroolefin Polymer (A)] A polymer solution (A-2) was prepared in the same manner as in Reference Example 1 except that the types and amounts of the monomers used were changed as follows. Got

Chlorotrifluoroeletin 126 g Hydroxybutyl vinyl ether 42 g Ethyl vinyl ether 42 g Beovar 9 210 g This product had a nonvolatile content of 53% and a number average quantity of 17,000.

Reference Example 3 [Preparation Example of Hydrolyzable Silyl Group-Containing Acrylic Polymer (B)] 400 parts of toluene and 400 parts of n-butanol were placed in a reactor equipped with a stirrer, a thermometer, a nitrogen introducing tube and a reflux cooling tube.
The temperature was raised to 105 ° C. in a nitrogen atmosphere. Then, at the same temperature, 700 parts of methyl methacrylate, 120 parts of n-butyl methacrylate, and 110 parts of n-butyl acrylate.
Parts, γ-methacryloyloxypropyltrimethoxysilane 70 parts, toluene 200 parts, azobisisobutyronitrile 6 parts, t-butylperoxyoctate 10 parts and t-butylperoxybenzoate 5 parts. Dropped over time. Thereafter, the temperature is raised to 110 ° C and
The mixture was kept for 5 hours to obtain a solution of a vinyl polymer having a nonvolatile content of 50% and a number average molecular weight of 9,000 and containing a trimethoxysilyl group. Hereinafter, this is abbreviated as B-1.

Reference Examples 4 to 6 [Preparation Example of Hydrolyzable Silyl Group-Containing Acrylic Polymer (B)] Reference Example 3 except that the types and amounts of the monomers used were changed as shown in Table 1. Similarly, acrylic polymers (B-2) to (B-4) containing a hydrolyzable silyl group.
I got

Examples 1 and 2 A curable resin prepared by mixing the fluoroolefin polymer (A) component, the hydrolyzable silyl group-containing acrylic polymer (B) component, the curing agent (C) and the like in the proportions shown in Table 2. A composition was obtained.

Next, this resin composition was applied to an aluminum plate (A-5052P) degreased with toluene using a doctor blade so that the dry film thickness would be 50 μm, and then cured under the conditions shown in Table 2 to form a coating film. Got About the obtained coating film No. 2
The adhesion and solvent resistance were evaluated by the method described in the footnote outside the table. The results are shown in Table 2.

Comparative Examples 1 and 2 except that the component (B) was not used and the mixing ratio and the curing conditions as described in Table 2 were followed,
It was made into a paint and formed into a film in the same manner as in Examples 1 to 4, and this was used as a comparative control sample. The coating performance of this product is also shown in Table 2.

As is clear from Table 2, the curable resin composition of the present invention has excellent adhesiveness to the substrate and is also excellent in solvent resistance.

1) Coronate EH: a polyisocyanate having an isocyanate ring, manufactured by Nippon Polyurethane Industry Co., Ltd. Isocyanate group content = 21.3%, solid content = 100%.

2) Put a cut line on the coating film with a safety razor blade, make 100 Gobang stitches at 1 mm intervals, peel off that portion with cellophane tape, and then attach it to an aluminum plate The number of gobang eyes is shown. The larger this value, the better the adhesion.

3) After rubbing the coating film 50 times with a rubbing tester (load = 1 kg) using xylene as a solvent, the appearance of this coating film was visually judged.

[Criteria]

◎ No abnormality ○ Slightly decreased gloss △ Remarkably decreased gloss × Complete disappearance of coating film [Effect of the invention] The curable resin composition of the present invention is excellent in solvent resistance and adhesion and is a fluoroolefin. It has an advantage that excellent properties such as weather resistance originally possessed by the system polymer are retained.
Therefore, the curable resin composition of the present invention is used as a paint for household appliances, buildings, exterior paints such as roof tiles or PCM, or for automobiles, especially as an enamel paint, metallic base paint or clear paint for automobiles, and further for glass. It can be applied as a surface protective film for ceramic products, a film, a sealing agent, an adhesive, etc., but is by no means limited to the above-mentioned application range.

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Claims (3)

(57) [Claims] 1. A fluoroolefin polymer (A) obtained by polymerizing at least one fluoroolefin monomer excluding vinylidene fluoride, and a hydrolyzable silyl group-containing acrylic polymer (B). And a curing agent (C), if necessary, or a curing agent (C).
And a curing catalyst and / or a catalyst (D) for hydrolyzing or condensing the hydrolyzable silyl group described above, and further, the fluoroolefin polymer (A) and the hydrolyzate described above. Component (A) / Latter (B) with degradable silyl group-containing acrylic polymer (B)
A curable resin composition for coatings, characterized in that the ratio by weight of the components is in the range of 20/80 to 80/20. 2. The fluoroolefin polymer (A) is vinyl fluoride, trifluoroethylene, tetrafluoroethylene, bromofluoroethylene, chlorofluoroethylene, pentafluoropropylene, hexafluoropropylene and (per) fluoroalkyl. Trifluorovinyl ether (provided that the (per) fluoroalkyl group has 1 to 18 carbon atoms. ] The curable resin composition for coating materials according to claim 1, which is obtained by polymerizing at least one fluoroolefin monomer obtained from the group consisting of: 3. The above-mentioned hydrolyzable silyl group-containing acrylic polymer (B) has the general formula (X) _3-a (R ₁ ) _a Si [wherein R ₁ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an aryl group or an aralkyl group, X is a halogen atom, an alkoxy group, an acyloxy group, an iminoxy group, a phenoxy group, a mercapto group, an aminoalkenyloxy group or It represents an alkoxyalkoxy group, and a is an integer of 0, 1 or 2. ] The curable resin for a coating composition according to claim 1, which has a hydrolyzable silyl group represented by: and also has a repeating unit derived from an acrylic acid ester or a methacrylic acid ester. Composition.