JP2734006B2 - Curable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a curable composition exhibiting room temperature curability in one liquid.

[Conventional technology]

Conventionally, an acrylic synthetic resin containing a hydrolyzable silyl group has been provided as a synthetic resin exhibiting room temperature curability. When such an acrylic synthetic resin is applied to form a coating film, hydrolyzable silyl groups contained by moisture in the atmosphere are hydrolyzed to silanol groups, and silane bonds are generated by the silanol groups. And cures at room temperature.

[Problems to be solved by the invention]

However, the conventional acrylic synthetic resin containing a hydrolyzable silyl group has a problem that the curing speed is extremely slow. For example, the addition of a curing agent having a silyl group such as dibutyltin dilaurate increases the curing speed, but the addition of such a curing agent makes the solution of the acrylic synthetic resin unstable and easily causes gelation. It is difficult to become one liquid.

[Means for solving the problem]

The present invention provides, as a means for solving the above conventional problems, a curable polymer comprising a polymer having a polymerizable carbon-carbon double bond and having a hydrolyzable silyl group, and a transition metal salt of a fatty acid. It provides a composition.

The method for producing a polymer having a polymerizable carbon-carbon double bond and having a hydrolyzable silyl group (hereinafter, simply referred to as a polymer) according to the present invention includes a polymerizable carbon-carbon double bond. (Hereinafter referred to as vinyl monomer A)
) And a vinyl monomer having a hydrolyzable silyl group (hereinafter referred to as vinyl monomer B), and the polymer further comprises the vinyl monomer A Further, another vinyl monomer copolymerizable with the vinyl monomer B (hereinafter, referred to as a vinyl monomer C) may be copolymerized.

[Vinyl monomer A]

The vinyl monomer A is a vinyl monomer having a polymerizable carbon-carbon double bond, for example, polymerization of oleic acid, linoleic acid, linoleic acid, soybean oil fatty acid, safflower oil fatty acid, dehydrated castor oil fatty acid and the like. A higher fatty acid having a possible carbon-carbon double bond, a vinyl monomer having a functional group capable of reacting with the fatty acid, for example, a hydroxyl group, a glycidyl group, etc., for example, β-hydroxyethyl methacrylate, β
-Obtained by reacting hydroxyethyl acrylate, glycidyl methacrylate, glycidyl acrylate, glycidyl allyl ether, allyl alcohol, etc., and further acrylic acid, methacrylic acid, itaconic acid,
It can also be obtained by esterifying an α-β unsaturated fatty acid such as crotonic acid, citraconic acid, and atropic acid with an alcohol having a polymerizable carbon-carbon double bond.

[Vinyl monomer B]

The vinyl monomer B is a vinyl monomer having a hydrolyzable silyl group, and the hydrolyzable silyl group has the following structure.

Wherein R is an alkyl group having 1 to 10 carbon atoms, an aryl group, a divalent hydrocarbon group, X is for example -OCH _3, alkoxyl groups such as -OC ₂ H ₅ selected from aralkyl groups, -Cl, -Br And a hydrolyzable group such as halogen.

Specific examples of the vinyl monomer having a hydrolyzable silyl group include γ-methacryloxypropyltrimethoxysilane and N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane. -Hydrochloride, vinyltriacetoxysilane, vinyltrimethoxysilane and the like.

[Vinyl monomer C]

The vinyl monomer C is copolymerizable with the vinyl monomer A and the vinyl monomer B. Examples of the vinyl monomer C include methyl acrylate, ethyl acrylate, n-butyl acrylate, iso- Butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate,
Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, 2
-Ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, iso-butyl vinyl ether, n-butyl vinyl ether, styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, vinyl chloride,
Vinyl monomers such as vinylidene chloride, vinyl fluoride, vinylidene fluoride, ethylene, propylene, isoprene, chloroprene, butadiene, and functional groups such as carboxyl group, hydroxyl group, methylol group, amino group, acid amide and glycidyl group It is also possible to use a vinyl monomer having Among the vinyl monomers having such a functional group, those having a carboxyl group include acrylic acid, methacrylic acid, and itaconic acid, and those having a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, and β-hydroxyethyl methacrylate. Hydroxypropyl acrylate, β-hydroxypropyl methacrylate, allyl alcohol, etc. having a methylol group include N-methylol acrylamide, N-methylol methacrylamide, etc., and those having an amino group include dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate. Acrylamide, methacrylamide and the like having an acid amide group, and glycidyl acrylate, glycidyl methacrylate, and glycidyl as those having a glycidyl group. Allyl ether and the like. The above examples do not limit the invention.

〔polymerization〕

In order to produce the polymer of the present invention, a comonomer composed of vinyl monomer A and vinyl monomer B and, if desired, vinyl monomer C is converted into toluene, xylol, ethyl acetate, n-butyl acetate, Methanol, ethanol, isopropanol, n-butanol, acetone, methyl ethyl ketone,
Methyl isobutyl ketone, ethyl cellosolve, n-butyl cellosolve, methylene chloride, trichloroethane, trichloroethylene, 2,4-dichloroethylene, n
-By polymerization in an organic solvent such as hexane, cyclohexane or mineral spirit using an oil-soluble polymerization initiator such as benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide or azobisisobutyronitrile.

In the above comonomer, the vinyl monomer A is usually 50 to
About 99% by weight is mixed, and the vinyl monomer B is usually mixed at about 1 to 50% by weight. The polymerization initiator is usually added in an amount of about 0.1 to 2% by weight based on the comonomer, and the comonomer is usually added in an amount of 30 to 60% by weight based on the organic solvent.
Degree.

For polymerization, usually a stirrer, thermometer, condenser,
And a reactor equipped with a heating means, wherein the comonomer is heated and stirred in the organic solvent in the presence of the polymerization initiator. The heating temperature at this time is usually about 50 to 100 ° C.

Thus, the polymer of the present invention is obtained. To prepare the curable composition of the present invention, a transition metal salt of a fatty acid is added to the polymer of the present invention. As the transition metal salt of the fatty acid used in the present invention, lauric acid, myristic acid, palmitic acid, stearic acid, desirably higher fatty acids having 12 or more carbon atoms such as titanium, zircon, chromium,
It is a salt of a transition metal such as molybdenum and cobalt.

In the curable composition of the present invention, the transition metal salt of the fatty acid is usually added in an amount of about 0.05 to 0.1% by weight based on the polymer.

[Action]

The curable composition of the present invention comprises a polymer having a polymerizable carbon-carbon double bond and a hydrolyzable silyl group, and a transition metal salt of a fatty acid, and is usually provided as an organic solvent solution. However, the solution is stable for a long period of time and does not cause gelation or separation of the polymer. When the curable composition of the present invention is applied to a desired surface to be coated and dried to form a coating film, first, a polymerizable double bond contained in a polymer of the composition is a catalyst of a transition metal salt of a fatty acid. By the action, the polymer is polymerized at ordinary temperature to form a network, and then the hydrolyzable silyl groups are hydrolyzed by moisture in the atmosphere to form silanol groups, and the silanol groups react with each other to form a silane bond to form a network.

〔The invention's effect〕

Therefore, the curable composition of the present invention is extremely stable and can withstand long-term storage even when a transition metal salt of a fatty acid is mixed, but a polymerizable double bond forms a transition metal salt of the fatty acid when a coating film is formed. It rapidly cures at room temperature due to the catalytic action, and quickly becomes a coating film with high solvent resistance and heat resistance and high mechanical strength. Further, the secondary curing by hydrolysis of silyl groups causes the solvent resistance and heat resistance of the coating film. Properties and mechanical strength are further improved.

〔Example〕

Example 1 (Synthesis of a vinyl monomer A ₁₎ stirrer, hydroquinone thermometer, a condenser, and the reactor was subjected to the heating means, 280 parts by weight of dehydrated castor oil fatty acid, 142 parts by weight of glycidyl methacrylate, as a polymerization inhibitor 0.4 parts by weight and 1 part by weight of tetrabutylammonium chloride as an esterification catalyst were charged, reacted at 80 ° C. for 3 hours in a nitrogen atmosphere, and cooled after confirming that the acid value was 1 or less. Thus obtaining a vinyl monomer A _1.

Example 2 (Synthesis of a vinyl monomer A ₂₎ in Example 1 and the same reactor, 381 parts by weight of soybean oil fatty acid glycidyl ester, 86 parts by weight of methacrylic acid, 0.4 part by weight of hydroquinone monomethyl ether as a polymerization inhibitor, an ester 1 part by weight of tetramethylammonium chloride was charged as an oxidation catalyst, reacted at 80 ° C. for 6 hours in a nitrogen atmosphere, and cooled after confirming that the acid value was 0.3 or less. Thus obtaining a vinyl monomer A _2.

Example 3 (Production of polymer solution (1)) 100 parts by weight of xylol and 100 parts by weight of toluene were charged into the same reactor as in Example 1, heated to 100 ° C and stirred, and the following mixture was continuously added dropwise over 3 hours. did.

Vinyl monomer A ₁ 30 parts by weight Styrene 20 methyl methacrylate 30 n-butyl acrylate 30 γ-methacryloxypropyl methoxysilane 10 azobisisobutyronitrile 1 additional 2 hours after continuous addition of the mixture Polymerization was carried out by heating and stirring at 100 ° C., followed by cooling. The obtained polymer solution (1) had a solid content of 50% by weight and a viscosity X (Gardner Holtz).

Example 4 (Production of polymer solution (2)) 100 parts by weight of toluene and 100 parts by weight of butyl acetate were charged into the same reactor as in Example 1, heated to 115 ° C and stirred, and the following mixture was continuously added dropwise over 3 hours. did.

Vinyl monomer A ₂ 50 parts by weight Styrene 20 n-butyl acrylate 20 γ-methacryloxypropylmethoxysilane 10 benzoyl peroxide 2 After the mixture is continuously dropped, the mixture is further heated and stirred at 120 ° C. for 2 hours. The polymerization was carried out and then cooled. The obtained polymer solution (2) had a solid content of 50% by weight and a viscosity S (Gardner Holtz).

Example 5 (Production of polymer solution (3)) 100 parts by weight of toluene and 100 parts by weight of butyl acetate were charged into the same reactor as in Example 1, heated to 90 ° C and stirred, and the following mixture was continuously dropped over 2 hours. did.

Dicyclopentenyl acrylate 30 parts by weight Styrene 30 methyl methacrylate 12 n-butyl acrylate 20 vinyltrimethoxysilane 8 azobisisobutyronitrile 1 加熱 After the mixture is continuously dropped, the mixture is heated and stirred at 105 ° C for 3 hours. Then, polymerization was carried out and then cooled. The obtained polymer solution (3) had a solid content of 50% by weight and a viscosity of Z (Gardner Holtz).

Comparative Example 1 (Production of Polymer Solution (4)) 100 parts by weight of toluene and 100 parts by weight of xylol were charged into the same reactor as in Example 1, heated to 100 ° C. and stirred, and the following mixture was continuously dropped over 2 hours. .

Styrene 40 parts by weight Methyl methacrylate 20 n-butyl acrylate 30 γ-methacryloxypropyl methoxysilane 10 azobisisobutyronitrile 1 〃 After the mixture is continuously dropped, the mixture is heated and stirred at 105 ° C. for further 3 hours for polymerization. And then cooled. The obtained polymer solution (4) had a solid content of 50% by weight and a viscosity U (Gardner Holtz).

Comparative Example 2 (Production of Polymer Solution (5)) 100 parts by weight of toluene and 100 parts by weight of xylol were charged into the same reactor as in Example 1, heated and stirred at 100 ° C., and the following mixture was continuously dropped over 2 hours. .

Vinyl monomer A ₁ 30 parts by weight Styrene 20 メ チ ル methyl methacrylate 20 ｎn-butyl acrylate 30 ア ゾ azobisisobutyronitrile 1 〃 After the mixture is continuously dropped, the mixture is heated and stirred at 105 ° C. for further 3 hours to carry out polymerization. And then cooled. The obtained polymer solution (5) had a solid content of 50% by weight and a viscosity S (Gardner Holtz).

(Evaluation of coating film) Examples 3 to 5 20 parts by weight of titanium oxide with respect to 100 parts by weight of polymer solutions (1) to (5) produced in Comparative Examples 1 and 2;
An undercoat paint was prepared using a paint shaker at a ratio of 50 parts by weight of calcium carbonate and 30 parts by weight of talc.

Separately adjust the clear lacquer with each polymer solution,
A top coat was prepared. For both the undercoat and the topcoat, Examples 3, 4, and 5 Comparative Example 2 contains 0.25% by weight of cobalt octenoate (8% xylol solution) and 0.25% by weight of zircon octenoate (8% xylol solution based on the polymer solution). ) Was added.

After a lapse of one week at 25 ° C. after the coating, a coating film test was performed. Table 1 shows the results.

According to Table 1, the curable composition of the present invention, Example 3,
The coating film consisting of the undercoat paint and the top coat paint obtained from the polymer solution of 4,5 has excellent results in any of adhesion, solvent resistance, water resistance, moisture resistance, and salt spray resistance. In the case of Comparative Example 1 consisting of a polymer solution having only a hydrolyzable silyl group, the crosslinking was slow, so that the solvent resistance was particularly poor, and a comparison was made of a polymer having only a polymerizable carbon-carbon double bond. In the case of Example 2, the crosslinking is quick and the solvent resistance is good, but since it has no silane bond, the adhesion,
Poor water resistance and salt spray resistance.

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Yoshihiro Sokita 8-3 Ninocho, Mizuho-ku, Nagoya-shi, Aichi Pref. Inside the laboratory of Natco Paint Co., Ltd. (72) Inventor Hironori Hata 8 Ninocho, Mizuho-ku, Nagoya-shi, Aichi No. 3 Inside the laboratory of Natco Paint Co., Ltd.

Claims (1)

(57) [Claims] 1. A curable composition comprising a polymer having a polymerizable carbon-carbon double bond and having a hydrolyzable silyl group, and a transition metal salt of a fatty acid.