JPH0873802A - Curable resin composition for coating compound - Google Patents

Abstract

PURPOSE: To obtain the subject composition capable of forming a coating film having low-temperature curing properties and excellent finished appearance. CONSTITUTION: This curable resin composition for coating compound comprises (a) a hydroxyl group-containing fluororesin, (b) a polyepoxide, (c) a silicon condensate as a dimer to a polymer of 100 monomers of a silicon monomer of the general formula Si(OR1 )4 (R1 is hydrogen atom or a 1-3C alkyl group) and (d) a tin chelate compound. This curable resin composition for coating compound comprises (a) the hydroxyl group-containing fluororesin, (b) the polyepoxide, (e) a modified silicon condensate which is the silicon condensate of as dimer to a polymer of 100 monomers of a silicon monomer of the general formula Si(OR1 )4 (R1 is hydrogen atom or a 1-3C alkyl group) and in which R1 in the silicon condensate is substituted with a 1-24C monofunctional hydrocarbon group (which contain an ether bond and/or an ester bond) and (f) a metal chelate compound.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel curable resin composition for paints.

[0002]

2. Description of the Related Art Conventionally, as a weatherproof coating composition, a coating composition having a hydroxyl group-containing fluororesin as a base resin and a block polyisocyanate compound or an amino resin as a crosslinking agent is generally used. . However, when a block polyisocyanate compound is used as a cross-linking agent, low-temperature curability, performance such as stain resistance is inferior, and when an amino resin is used as a cross-linking agent, low-temperature curability, stain resistance, acid resistance, etc. It has the drawback of being inferior in sex.

In addition to the above-mentioned coating composition, a curable resin composition prepared by blending a metal chelate compound with a mixture of a hydroxyl group-containing resin, polyepoxide and an organosilane compound is disclosed in JP-A-2-73825. ing. As the metal chelate compound, the publication specifically describes an aluminum chelate compound, a zirconium chelate compound, and a titanium chelate compound.

However, the composition using the above-mentioned metal chelate compound has a drawback that the cured product turns yellow, and in addition to these drawbacks, the composition using the aluminum chelate compound has a storage stability of the composition. However, the low temperature curability is inferior in those using zirconium chelate compound or titanium chelate compound. Further, in the composition of the above publication, a resin containing fluorine as a hydroxyl group-containing resin has poor compatibility with an organosilane compound, resulting in reduced transparency of the cured product or uneven curing. Therefore, there is a drawback that physical (workability) and chemical performance are deteriorated.

[0005]

Means for Solving the Problems As a result of intensive studies conducted by the present inventors to solve the above problems, a coating material containing a hydroxyl group-containing fluororesin, a polyepoxide, a silicon condensate and a tin chelate compound. Curable resin composition for
Further, it was found that a curable resin composition for coating material containing a hydroxyl group-containing fluororesin, a polyepoxide, a modified silicon condensate and a metal chelate compound solves all the above problems, and has completed the present invention. .

That is, the present invention provides the following components (a) hydroxyl group-containing fluororesin, (b) polyepoxide,
(C) a silicon condensate of 2 to 100 mer of a silicon monomer represented by the general formula Si (OR ₁ ) ₄ (wherein R ₁ represents a hydrogen atom or a C _1-3 alkyl group), and (D) A curable resin composition for coatings, which contains a tin chelate compound (hereinafter, this is referred to as "first invention"), and

The following components (a) hydroxyl group-containing fluororesin, (b) polyepoxide,
(E) A silicon condensate of a silicon monomer represented by the general formula Si (OR ₁ ) ₄ (wherein R ₁ represents a hydrogen atom or a C _1-3 alkyl group), which is a 2-100 mer. And a part of R ₁ in the silicon condensate is substituted with a C _1-24 monovalent hydrocarbon group (which may contain an ether bond and / or an ester bond). And (f) a metal chelate compound, which are related to a curable resin composition for coatings (hereinafter referred to as "second invention").

First, the hydroxyl group-containing fluororesin (a) and polyepoxide (b) used in the first and second inventions will be described.

Hydroxyl group-containing fluororesin (a): The hydroxyl group-containing fluororesin (a) used in the present invention is a base resin component containing a hydroxyl group as an essential functional group. The hydroxyl group of the hydroxyl group-containing fluororesin (a) has a hydroxyl value of about 20 to 30.
A range of 0, preferably about 20 to 200 is suitable. When the hydroxyl value is less than about 20, the low temperature curing property of the coating film and the durability of the coating film are deteriorated. On the other hand, when it exceeds about 300, many unreacted hydroxyl groups remain in the coating film, so that the coating film has poor water resistance. It is not preferable because it decreases.

The hydroxyl group-containing fluororesin (a) has a number average molecular weight of about 3,000 to 200,000, preferably 5,000 to 80,000. When the number average molecular weight is less than about 3,000, the durability of the coating film is reduced, while when it exceeds about 200,000, the polyepoxide (b) component, the silicon condensate (c) or the modified silicon condensate (e) component is used. It is not preferable because the compatibility with and decreases the performance of the coating film, and the amount of the diluent solvent increases and the solid content of the coating decreases.

Further, the hydroxyl group-containing fluororesin (a) may contain a carboxyl group, and the content thereof is preferably about 50 or less, preferably 30 or less as an acid value. If the acid value exceeds about 50, the coating film performance such as curability and water resistance of the coating film deteriorates, which is not preferable. As the hydroxyl group-containing fluororesin, a radical polymer (a-1) containing a fluoroolefin as a monomer component and a monomer containing a perfluoroalkyl group or a perfluoroalkenyl group and an acryloyl group as a monomer component are used. The radical polymer (a-2) is preferable.

Radical Polymer (a-1) The radical polymer (a-1) comprises a fluoroolefin, a hydroxyl group-containing radically polymerizable unsaturated monomer and, if necessary, other radically polymerizable unsaturated monomer. Is a polymer obtained by radical polymerization reaction of. Examples of fluoroolefins include vinyl fluoride, vinylidene fluoride, ethylene trifluoride chloride and tetrafluoroethylene chloride. Among these, trifluoroethylene chloride and tetrafluoroethylene chloride are particularly preferable.

Examples of the hydroxyl group-containing radically polymerizable unsaturated monomer include hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxypentyl vinyl ether, ethylene glycol monoallyl ether, diethylene glycol monoallyl vinyl ether, triethylene glycol monoallyl ether. Etc.

Other radically polymerizable unsaturated monomers include, for example, ethylene, propylene, 1-butylene, 2
Α-olefins such as butylene and isobutylene, vinyl ethers such as ethyl vinyl ether, isobutyl vinyl ether, butyl vinyl ether and cyclohexyl vinyl ether, vinyl acetate, vinyl lactate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl piperate, caprylic acid. Aliphatic vinyl esters such as vinyl, isopropenyl acetate, fatty acid isopropenyl esters such as isopropenyl propionate, the above hydroxyl group-containing radically polymerizable unsaturated monomer and carboxylic acid anhydride (for example, maleic anhydride, itaconic anhydride, anhydrous Radical-polymerizable unsaturated carboxylic acid obtained by reaction with succinic acid, phthalic anhydride, 1,2-cyclohexanedicarboxylic acid anhydride, and the like.

The mixing ratio of each of the above monomers is
Based on the total weight of the monomer components as 100, the fluoroolefin is 20 to 80% by weight, preferably 30 to 70% by weight, the hydroxyl group-containing radically polymerizable unsaturated monomer is 3 to 80% by weight,
It is preferably in the range of 5 to 50% by weight, and other radically polymerizable unsaturated monomers in the range of 0 to 77% by weight, preferably 10 to 65% by weight.

The radical polymerization reaction of the above-mentioned monomer is carried out at a temperature of about -20 in the presence of a polymerization initiator in an organic solvent which dissolves the monomer and is inactive with the unsaturated group or hydroxyl group of the monomer. ~ 1
50 ° C, preferably about 5 to 95 ° C, pressure about 0 to 30 kg / c
m ² · G, preferably about 0-10 kg / cm ² · G. Examples of the above-mentioned organic solvent include aromatic hydrocarbons such as toluene and xylene, ketones such as acetone, methyl ethyl ketone and cyclohexanone, alcohols such as methanol, ethanol, propanol and butanol, cellosolve, dimethyl carbitol and tetrahydrofuran. Examples thereof include ethers, acetic acid esters such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate. Examples of the polymerization initiator include peroxides such as di-1-propylperoxycarbonate, tert-butylperoxybutyrate, and benzoyl peroxide, azobis-is.
Examples thereof include azo compounds such as o-butyronitrile and azobisvaleronitrile.

Radical Polymer (a-2) The radical polymer (a-2) is a perfluoroalkyl group- or perfluoroalkenyl group-containing acrylic monomer,
It is a polymer obtained by radically polymerizing a hydroxyl group-containing acrylic monomer and, if necessary, other vinyl monomers. Examples of the perfluoroalkyl group- or perfluoroalkenyl group-containing acrylic monomer include perfluorobutylethyl methacrylate, perfluorooctylethyl methacrylate, perfluoroisononylethyl methacrylate, perfluorodecylethyl methacrylate, perfluorononenyloxybenzyl. Oxyethyl methacrylate and the like are preferable.

Examples of the hydroxyl group-containing acrylic monomer include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, (poly) ethylene glycol mono (meth) acrylate, ( Examples thereof include poly) propylene glycol mono (meth) acrylate and adducts of these with caprolactone (eg, ε-caprolactone).

Other vinyl monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth).
C _1-24 alkyl (meth) acrylates or cycloalkyl (meth) acrylates such as acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth ) Acid group-containing vinyl monomers such as acrylic acid and maleic acid, aromatic vinyl monomers such as styrene and vinyltoluene, nitrile monomers such as (meth) acrylonitrile, (meth) acrylamide, N-methylol (meth) acrylamide, etc. Amide monomers and the like.

The above radical polymerization reaction of the monomer is carried out at a temperature of about 40 to 40 in the presence of a polymerization initiator in an organic solvent which dissolves the monomer and is inactive with the unsaturated groups and hydroxyl groups of the monomer. 25
It is carried out at 0 ° C., preferably about 50 to 180 ° C. for about 1 to 24 hours. Examples of the organic solvent and the polymerization initiator include the same ones as described above.

The polyepoxide (b) has an average of about 2 or more epoxy groups in one molecule, preferably about 2-1.
Those having an average molecular weight of 100 and an average molecular weight in the range of about 130 to 100,000 are preferable. When the number of the epoxy groups is less than about 2 on average in one molecule, low temperature curability is deteriorated, which is not preferable.

As the polyepoxide (b), for example,
Polymers of epoxy group-containing ethylenically unsaturated monomers and, if necessary, other vinyl monomers; bis (3,4-
Epoxy cyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4 -Epoxycyclohexenecarboxylic acid ethylene glycol diester, 3,
Alicyclic epoxy compounds such as 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate; (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether,
Examples thereof include aliphatic epoxy compounds such as epoxidized polybutadiene and triglycidyl isocyanurate.

The above-mentioned polymer of the epoxy group-containing ethylenically unsaturated monomer and, if necessary, other vinyl-based monomer is particularly preferably an average molecular weight of about 8,000 to 100,00.
A range of 0 is preferred. In the above-mentioned polymer, as the epoxy group-containing ethylenically unsaturated monomer, for example, glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, allyl glycidyl ether,
3,4-epoxycyclohexylmethyl (meth) acrylate and the like are preferable.

Examples of the other vinyl-based monomer copolymerized with the epoxy group-containing ethylenically unsaturated monomer as required include, for example, the above-mentioned C _1-24 alkyl (meth) acrylate or cycloalkyl (meth). ) Acrylates, perfluoroalkyl group- or perfluoroalkenyl group-containing ethylenically unsaturated monomers, aromatic vinyl monomers, nitrile monomers, amide monomers, hydroxyl group-containing acrylic monomers and the like.

Curable resin composition for paint of the first invention: First
The curable resin composition for coating composition of the invention comprises (a) a hydroxyl group-containing fluororesin, (b) a polyepoxide, and (c) a general formula Si.
(OR ₁ ) ₄ (In the formula, R ₁ represents a hydrogen atom or a C _1-3 alkyl group.) A silicon condensate of 2 to 100 mer of a silicon monomer, and (d) a tin chelate compound. Is included.

In the silicon condensate (c), the C _1-3 alkyl group represented by the general formula is methyl, ethyl or n.
-Propyl, iso-propyl and the like can be mentioned. Among the silicon condensates (c), those having an average of about 2 to 10 mer and about 3 to 6 mer are particularly preferable from the viewpoints of curability, finished appearance and coating film performance. Specific examples of the silicon monomer represented by the general formula include tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, and dimethoxydiethoxysilane.

As the silicon condensate, for example, "Colcoat ES40""trade name, manufactured by Colcoat Co., Ltd., hereinafter, similarly, a mixture of tetraethyl silicate 1 to 10 mer, average about 4 mer", "Colcoat MS51""Tetra 1 to 10-mer mixture of methyl silicate, about tetramer "and the like. These Colconian silicon condensates are generally

[0028]

Embedded image

It is considered to have the structure of The tin chelate compound (c) is a compound in which an organic chelating agent is chelated to part or all of divalent or tetravalent tin atoms. As the organic chelating agent, conventionally known organic chelating agents can be used. The organic chelating agent is at least one selected from oxygen atom, sulfur atom and nitrogen atom.
Compounds containing atoms of the species are included. Among the above,
Compounds containing an oxygen atom, and further compounds capable of forming keto-enol tautomers are suitable.

Examples of the compound capable of forming the keto-enol tautomer include β-diketones (acetylacetone etc.), acetoacetic acid esters (methyl acetoacetate etc.),
Malonates (ethyl malonate, etc.), and aldehydes having a hydroxyl group at the β-position (salicylaldehyde, etc.),
Examples thereof include esters having a hydroxyl group at the β-position (such as methyl salicylate). Among these, it is particularly preferable to use acetoacetic acid esters and β-diketones.

The tin chelate compound (c) is prepared, for example, by mixing an organic chelating agent in a ratio of about 1 to 10 with respect to 1 mol of a divalent or tetravalent tin compound, and heating the mixture if necessary. can do. As the tin compound described above, for example, organic acid salts, alkoxides, hydroxides, halides, sulfides, and combinations thereof can be used.

Examples of the organic acid salts and alkoxides of the above tin compounds include, for example, the following general formula (I) Sn (OR ₂ ) ₂ (I)

And the general formula (II) (R ₃ ) _n Sn (OR ₂ ) _4n (II)

(In each formula, R ₂ is the same or different and represents a monovalent hydrocarbon group having 1 to 24 carbon atoms or a —OCR ₃ group, and R ₃ is the same or different and is 1 to 1 carbon atoms. A valent hydrocarbon group, and n represents 0 or an integer of 1 to 2).

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by the above general formulas (I) and (II) include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group. It may be any type of group and combinations of these groups.

The aliphatic hydrocarbon group may be linear or branched and may contain an unsaturated bond, for example, methyl, ethyl, n-propyl, iso-propyl,
n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, tert-pentyl, neo-pentyl, n-hexyl, n-heptyl, n-octyl, n-
Nonyl, n-decyl, dodecyl, tridecyl, tetradecyl and the like can be mentioned. Examples of the alicyclic hydrocarbon group include cyclohexyl.

Examples of the aromatic hydrocarbon group include phenyl, methylphenyl, dimethylphenyl, toluyl, xylyl and the like. Further, examples of the group in which the aliphatic hydrocarbon group and the aromatic hydrocarbon group are combined include benzyl, phenethyl and the like. Among these hydrocarbon groups, an alkyl group having 1 to 24 carbon atoms and a phenyl group are preferable.

Among the above tin compounds, the organic acid salt of the general formula (II) in which R ₂ is —OCR ₃ is excellent in storage stability and low temperature curability. Further, in the general formula (II), it is preferable that R ₃ is an alkyl group having 1 to 24 carbon atoms or a phenyl group. Further, in the above-mentioned general formula (II), particularly, those in which n is 0 or 1 are excellent in storage stability, low temperature curability and the like. Specific examples of the tin compounds represented by the above general formulas (I) and (II) include the following.

Examples of the organic acid salt of the tin compound of the general formula (I) include tin diacetate, tin dibutyrate, tin dihexylate and tin dioctate. Examples of alkoxides of tin compounds include tin dimethoxy, tin diethoxy, tin dipropoxy, tin dibutoxy, and the like.

As the tin compound of the general formula (II), examples of organic acid salts include tin tetraacetate, tin tetraoctate, butyltin triacetate, butyltin tributyrate, butyltin trihexylate, butyltin trioctate, butyltin trioctate. Laurate, butyltin trimethyl malate, octyltin triacetate, octyltin tributyrate, octyltin trihexylate, octyltin trioctate, octyltin trilaurate, octyltin trimethylmalate,
Phenyltin tributyrate, phenyltin trilaurate, dibutyltin diacetate, dibutyltin dibutyrate, dibutyltin dihexylate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin diethylmalate, dioctyltin diacetate, dioctyltin dibutyrate, dioctyltin Dihexylate, dioctyl tin dioctate, dioctyl tin dilaurate, dioctyl tin diethyl malate and the like can be mentioned. Examples of alkoxides of tin compounds include butyltin trimethoxy, butyltin tributoxy, octyltin trimethoxy, phenyltin trimethoxy, dibutyltin dimethoxy, dioctyltin dimethoxy, dioctyltin dibutoxy, and the like.

Among the above, tin tetraacetate, tin tetraoctate, butyltin triacetate, butyltin tributyrate, butyltin trioctate and the like are particularly preferable. Examples of halides of tin compounds include stannous chloride compounds and stannous chloride compounds.

Examples of sulfides of tin compounds include those represented by the general formula (III) Sn (SR ₄ ) ₂ (III)

And the general formula (IV) (R ₃ ) _n Sn (SR ₄ ) _4-n (IV)

(In each formula, R ₄ is the same or different and is a monovalent hydrocarbon group having 1 to 24 carbon atoms or --C _m H _2m COOR.
₃ , m is an integer of 1 to 4. R ₃ and n
Indicates the same meaning as described above. ) Is included. The monovalent hydrocarbon group having 1 to 24 carbon atoms represented by R ₄ includes the same ones as described above.

Examples of the sulfide of the tin compound represented by the general formula (III) include Sn (SCH ₂ COOC _{8
H 17) 2, Sn (SC} 4 H 9) 2 and the like. Examples of the sulfide of the tin compound represented by the general formula (IV) include C ₄ H ₉ Sn (SCH ₂ COOC ₈ H ₁₇ ) ₃ , (C _{4
H 9) 2 Sn (SCH 2} COOC 8 H 17) 2, C 8 H 17 Sn
_{(SCH 2 COOC 8 H 17)} 3, (C 8 H 17) 2 Sn (SC
_{H 2 COOC 8 H 17) 2} , C 4 H 9 Sn (SC 4 H 9) 3,
_{(C 4 H 9) 2 Sn} (SC 4 H 9) 2 and the like.

As the tin chelate compound (c), an organic chelating agent chelated to divalent tin, for example, a compound represented by the formula:

[0047]

Embedded image

And a tetravalent tin chelated with an organic chelating agent, for example:

[0049]

[Chemical 3]

Examples include those represented by: In the above formula, A is the same or different and represents R ₃ , OR ₂ or SR ₄ ,

[0051]

[Chemical 4]

Indicates a chelate ring structure formed by an organic chelating agent. R ₃ , OR ₂ and SR ₄ have the same meanings as described above.

Specific examples of the tin chelate compound (c) include, for example, monobutylbis (ethylacetoacetate) tin acetate, monobutylbis (acetylacetonato) tin octoate, monobutylbis (ethylacetoacetate) tin laurate and bis (propylacetoacetate) tin diacetate. Acetate, bis (propylacetoacetate) tin dilaurate, bis (acetylacetonato) tin diacetate, bis (acetylacetonato) tin dioctate, bis (acetylacetonato) tin dilaurate, bis (ethylacetoacetate) tin dioctate, bis (ethylacetoacetate) Acetate) tin didiacetate, bis (ethyl acetoacetate) tin dilaurate, bis (propyl acetoacetate) tin dioctate, etc.

In the present invention, the hydroxyl group-containing fluororesin (a), polyepoxide (b), silicon condensate (c) and tin chelate compound (d) are preferably blended in the following proportions.

Hydroxyl group-containing fluororesin (a): about 5-94
%, Preferably in the range of 15-75% by weight,
If it is less than about 5% by weight, the finished appearance and performance of the coating film deteriorates, while if it exceeds about 94% by weight, the performance of the coating film deteriorates, which is not preferable.

Polyepoxide (b): about 5 to 94% by weight, preferably about 10 to 75% by weight, and if it is out of this range, the curability is lowered, which is not preferable.

Silicon condensate (c): about 0.1 to 50% by weight, preferably about 1 to 30% by weight, and if it is out of this range, the curability is deteriorated, which is not preferable.

Tin chelate compound (d): about 0.001
-20% by weight, preferably 0.01-10% by weight. When it is less than about 0.001% by weight, curability decreases, while when it exceeds about 20% by weight, the finish appearance and water resistance of the coating film are reduced. It is not preferable because it deteriorates the property.

Curable resin composition for coating composition of the second invention: Second
The curable resin composition for coating composition of the invention comprises (a) a hydroxyl group-containing fluororesin, (b) a polyepoxide, and (e) a general formula Si.
(OR ₁ ) ₄ (in the formula, R ₁ represents a hydrogen atom or a C _1-3 alkyl group), which is a silicon condensate of 2 to 100 mer of a silicon monomer, A modified silicon condensate in which a part of R _{1 in} the compound is substituted with a C _4-24 monovalent hydrocarbon group (which may contain an ether bond and / or an ester bond), and (f) It contains a metal chelate compound. In the modified silicon condensate (e),
The C _4-24 monovalent hydrocarbon group has the above-mentioned carbon number of 1 to
Among the monovalent hydrocarbon groups of ₂₄ , those of C _4-24 can be mentioned.

The C _4-24 monovalent hydrocarbon group containing an ether bond is, for example, the following general formula (V):

[0061]

[Chemical 5]

(In the formula, p represents an integer of 2 or 3, s represents an integer of 1 or 2, and R ₅ represents a C _1-8 alkyl group, provided that C _p and R ₅ are carbon atoms. The total number is 4 to 2
There are four. ), And the following general formula (VI)

[0063]

[Chemical 6]

(In the formula, p has the same meaning as described above.)
The following are listed. Examples of the C _4-24 monovalent hydrocarbon group containing an ether bond include:

[0065]

[Chemical 7]

And the like. C containing an ester bond
Examples of the monovalent hydrocarbon group of _4-24 include, for example, the following general formula (VII)

[0067]

Embedded image

(In the formula, R ₆ represents a C _1-8 alkyl group, an aryl group or an aralkyl group, and p has the same meaning as described above.). In the general formula (VII), examples of the alkyl group include methyl, ethyl, n-butyl, iso-butyl, pentyl, hexyl,
Examples thereof include octyl and cyclohexyl, examples of the aryl group include phenyl, toluyl, xylyl and the like, and examples of the aralkyl group include a benzyl group and the like.

Examples of the C _4-24 monovalent hydrocarbon group containing an ester bond include, for example,

[0070]

[Chemical 9]

And the like. Further, the C _4-24 monovalent hydrocarbon group containing an ether bond and an ester bond is, for example,

[0072]

[Chemical 10]

(In the formula, t represents an integer of 2 to 10, and p and R ₆ have the same meanings as described above.) And the like.
Examples of the C _4-24 monovalent hydrocarbon group containing an ether bond and an ester bond include:

[0074]

[Chemical 11]

And the like. As the modified silicon condensate (e), for example, a silicon condensate (c) and a C _4-24 alcohol (which may contain an ether bond or an ester bond) are dealcoholized to give R _{1 of the} silicon condensate. Part of C
It can be produced by substituting a monovalent hydrocarbon group of _4-24 .

Preferred examples of the metal chelate compound (f) include tin chelate compounds, aluminum chelate compounds, zirconium chelate compounds and titanium chelate compounds. Examples of the tin chelate compound include those mentioned above.

Examples of the aluminum chelate compound include organic aluminum (eg, aluminum iso-
Propylate, aluminum n-butyrate, aluminum sec-butyrate, aluminum tert-butyrate, etc.) and the above organic chelating agent can be used. Specifically, for example, tris (ethylacetoacetate) aluminum, tris (n-propylacetoacetate) aluminum, tris (iso-propylacetoacetate) aluminum, tris (n-butylacetoacetate) aluminum, tris (acetylacetonato). ) Aluminum, tris (propionylacetonato) aluminum and the like.

As the zirconium cholate compound, for example, organic zirconium (eg, tetramethyl zirconate, tetra iso-propyl zirconate, tetra n
-Butyl zirconate, tetra iso-butyl zirconate, tetra tert-butyl zirconate, etc.) and the above organic chelating agent can be used. Specifically, for example, tetrakis (ethylacetoacetate) zirconium, tetrakis (n-propylacetoacetate) zirconium, tetrakis (iso-propylacetoacetate) zirconium, tetrakis (n-butylacetoacetate) zirconium, tetrakis (acetylacetonato). ) Zirconium, tetrakis (propionylacetonato) zirconium and the like can be mentioned.

Examples of titanium chelate compounds include organic titanium (eg, tetramethyl titanate, tetra iso-propyl titanate, tetra n-butyl titanate, tetra iso-butyl titanate, tetra
(tert-butyl titanate, etc.) and the organic chelating agent can be used. Specifically, for example,
Tetrakis (ethylacetoacetate) titanium, tetrakis (n-propylacetoacetate) titanium, tetrakis (iso-propylacetoacetate) titanium, tetrakis (n-butylacetoacetate)
Examples include titanium, tetrakis (acetylacetonato) titanium, tetrakis (propionylacetonato) titanium, and the like.

In the present invention, hydroxyl group-containing fluororesin (a), polyepoxide (b), modified silicon condensate (e)
It is preferable that the metal chelate compound (f) and the metal chelate compound (f) are blended in the following ratios.

Hydroxyl group-containing fluororesin (a): about 5-94
%, Preferably in the range of 15-75% by weight,
If it is less than about 5% by weight, the finished appearance and performance of the coating film deteriorates, while if it exceeds about 94% by weight, the performance of the coating film deteriorates, which is not preferable.

Polyepoxide (b): about 5 to 94% by weight, preferably about 10 to 75% by weight, and if it is out of this range, the curability is lowered, which is not preferable.

Modified silicon condensate (e): about 0.1 to 50% by weight, preferably about 1 to 30% by weight, and if it is out of this range, the curability is deteriorated, which is not preferable.

Metal chelate compound (f): about 0.001
-20% by weight, preferably 0.01-10% by weight. When it is less than about 0.001% by weight, curability decreases, while when it exceeds about 20% by weight, the finish appearance and water resistance of the coating film are reduced. It is not preferable because it deteriorates the property.

The curable resin compositions (I) and (II) for paints of the present invention are preferably used as an organic solvent solution in which the above-mentioned components are dissolved or dispersed in an organic solvent.
Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as acetone, ketyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, propyl acetate and butyl acetate, ethylene glycol monobutyl ether and the like. Alcohol-based.
The organic solvent has a solid content of the resin composition of usually about 1
It is preferable to mix them in the range of 0 to 90% by weight.

The curable resin compositions (I) and (II) for paints of the present invention contain, in addition to the above-mentioned components, a colorant, a filler, an ultraviolet stabilizer, an ultraviolet absorber, a fluidity adjusting agent, if necessary. Agents and other additives can be added. The curable resin composition for coating material of the present invention can be cured by heating after being applied to a substrate.

The base material is not particularly limited, and is a conventionally known base material, specifically, treated or untreated metal, plastic, paper, fiber, a plate-like material coated with these materials, Examples include molds. As a method for applying to the base material, for example, a usual coating means such as spray coating, brush coating, roller coating, and dip coating can be used. The dry film thickness is about 1 to 100 μm, preferably about 10
It is preferable to apply the coating so as to be in the range of 60 μm.

The heating is usually carried out at a temperature of about 60 ° C. or higher, preferably about 60 to 300 ° C.
Also, the heating time varies greatly depending on the temperature,
The range is about 10 seconds at about 250 ° C. and about 3 hours at about 60 ° C.

[0089]

The curable resin composition for coating composition of the present invention does not react at all at room temperature (about 20 ° C.), but the reaction rapidly occurs when a temperature of about 60 ° C. is applied, so that the composition is stable in storage. Exhibits excellent effects and excellent low temperature curability. Further, since it has the above-mentioned resin composition, the finished appearance of the coating film, the acid resistance, the outdoor bacillus (stain resistance) and the like are excellent.

[0090]

EXAMPLES The present invention will be described in more detail below with reference to examples.

Production Example of Silicon Resin “Colcoat ES40” 530 g (trade name, manufactured by Colcoat, average tetramer of tetraethyl silicate, the same meaning below) Benzyl alcohol 470 g Tris (acetylacetonato) aluminum 200 g of ethanol was removed from 1 g of the mixture at 160 ° C. for 6 hours to obtain a silicone resin. This product has 6 out of 12 ethoxy groups on average in one molecule.

[0092]

[Chemical 12]

Has been replaced by.

Production Example of Silicon Resin “Colcoat ES40” 740 g 3-Methyl 3-methoxybutanol 700 g Tris (acetylacetonato) aluminum 0.05 g A mixture of 270 g was removed for 3 hours at 160 ° C. to obtain a silicon resin. It was This product has 6 out of 12 ethoxy groups on average in one molecule.

[0095]

[Chemical 13]

Has been replaced by.

Examples 1 to 14 and Comparative Examples 1 to 3 Various components shown in Table 1 were blended (solid content), and then diluted with xylene so that the resin solid content was 50% by weight. 14 and the coating compositions of Comparative Examples 1 to 3 were obtained.

[0098]

[Table 1]

In Table 1, * 1 to * 5 have the following meanings. * 1: Brand name, manufactured by Asahi Glass Co., Ltd., copolymer of fluoroolefin and vinyl ether, hydroxyl value 52, acid value 0
Things. * 2: Product name, manufactured by Asahi Glass Co., Ltd., copolymer of fluoroolefin and vinyl ether, hydroxyl value 47, acid value 5
Things. * 3: 3,4-epoxycyclohexylmethyl-3,4
-Epoxy cyclohexane carboxylate * 4: Uban 20SE-60, trade name, manufactured by Mitsui Toatsu Co., Ltd., butylated melamine resin. * 5: Campeflon No. 160, product name, Kansai Paint Co., Ltd., fluorine-blocked polyisocyanate-curable organic solvent-based paint

The obtained coating composition was applied to the material so that the dry film thickness would be 40 μm, and the coating composition was dried at 120 to 160 ° C. for 30 minutes.
The coating was obtained by heating for a minute. The following coating film performance test was conducted on this coating film.

Gloss: A white coated plate was used as a material. 6
The 0 ° specular reflectance (%) was measured. Gel fraction: A glass plate was used as the material. The coating film was peeled off from the glass plate and extracted with acetone in a Soxhlet extractor at reflux temperature for 6 hours, and the remainder of the coating film was expressed in% by weight. Acid resistance: Migaki mild steel plate was used as the material. 0.4 cc of 40 wt% sulfuric acid water was added dropwise, and after drying at 75 ° C. for 15 minutes, the depth (μm) of the added sulfuric acid water trace (etching) was measured. Outdoor baculo: A white paint board was used as the material. The gloss retention and color difference were determined by the methods described below.

The gloss retention was determined by (60 ° specular reflectance after outdoor baculo / 60 ° specular reflectance before outdoor baculo) × 100. As for the color difference, ΔE ^* ab was determined based on the color difference between the coating film before and after outdoor bacground based on JIS Z8730.

The appearance of the coating film was examined for abnormalities in the coating film state (glossiness, tingling, cracks, peeling, and opaque "smudge"). The results are summarized in Table 2.

[0104]

[Table 2]

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Claims (3)

[Claims] 1. The following component (a) hydroxyl group-containing fluororesin, (b) polyepoxide, (c) general formula Si (OR ₁ ) ₄ (wherein R ₁ represents a hydrogen atom or a C _1-3 alkyl group). A curable resin composition for a coating material, which comprises a 2 to 100-mer silicon condensate of a silicon monomer represented by the formula (4) and (d) a tin chelate compound. 2. The following components (a) hydroxyl group-containing fluororesin, (b) polyepoxide, (e) general formula Si (OR ₁ ) ₄ (wherein R ₁ represents a hydrogen atom or a C _1-3 alkyl group). .) A silicon condensate of 2 to 100 mer of a silicon monomer, wherein a part of R ₁ in the silicon condensate is a C _1-24 monovalent hydrocarbon group (this is A curable resin composition for coating material, which comprises a modified silicon condensate substituted with an ether bond and / or an ester bond) and (f) a metal chelate compound. 3. The curable resin composition for coating composition according to claim 2, wherein the metal chelate compound (f) is at least one metal chelate compound selected from an aluminum chelate compound and a tin chelate compound.