JPH0739525B2 - Curable composition - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel curable composition having improved properties. More specifically, the main chain is substantially composed of a vinyl polymer, has at least one silicon group bonded to a hydrolyzable group in one molecule, and further has a long carbon number of 10 or more as a copolymerization component. Containing a (meth) acrylic acid ester (methacrylic acid ester or acrylic acid ester) having a chain alkyl group,
The present invention relates to a curable composition containing a silyl group-containing vinyl resin having a molecular weight of 500 to 100,000 and a matting agent.

[0002]

BACKGROUND OF THE INVENTION The inventors of the present invention have found that a vinyl resin containing a silyl group having a hydrolyzable group at a terminal or a side chain is a characteristic of the vinyl resin and has high gloss and weather resistance. As well as excellent characteristics such as resistance and discoloration resistance,
Hydrolyzable silyl group improves adhesion to inorganic substances, and water, especially in the air, forms a dense network structure by room temperature crosslinking with water, and has excellent solvent resistance, water resistance, heat resistance, high hardness, and weather resistance. The inventors have found that it can be used as a resin, and have previously filed a patent application (Japanese Patent Laid-Open No. 54-86395).

[0003]

[Means for Solving the Problems] The present inventors have further studied silyl group-containing vinyl resins, and have added silyl group-containing vinyl resins with long-chain alkyl groups having 10 or more carbon atoms as a copolymerization component. It was found that the physical properties are greatly improved by copolymerizing the (meth) acrylic acid ester that it has.

That is, one of the improvements in physical properties brought about by copolymerizing a (meth) acrylic acid ester having a long-chain alkyl group is improvement in abrasion resistance.

The silyl group-containing vinyl resin previously applied for a patent forms a dense network structure by being crosslinked and cured by heating at room temperature, low temperature or high temperature for a short time in the presence or absence of a catalyst. Therefore, it is superior in abrasion resistance and scratch resistance compared to other commercially available resins, but it is necessary to add a matting agent to the resin obtained by copolymerizing (meth) acrylic acid ester having a long chain alkyl group. In addition to the matte effect of the painted surface, the improvement of adhesion, wear resistance,
It has been found that the scratch resistance is dramatically improved.

The silyl group-containing vinyl resin according to the invention previously filed for a patent contains a hydrolyzable silyl group, and as shown in the formulation of a silane coupling agent which is usually used, has an adhesiveness to an inorganic substance. Although excellent, the adhesion to organic substances was insufficient. However, it has been found that the addition of a matting agent to a resin obtained by copolymerizing a (meth) acrylic acid ester having a long-chain alkyl group further improves the adhesion to inorganic substances and the adhesion to organic substances. For this reason, it has been greatly improved not only for coatings, coatings and adhesion on the surface of inorganic materials, but also for application to the surface of organic materials (wood, paper, plastics, top coating on organic paints, etc.).

The silyl group-containing vinyl resin of the present invention can be produced by various methods, which will be described below.
Industrially, a method of (A) a hydrosilylation reaction between a vinyl-based resin having a carbon-carbon double bond and hydrosilane, and (B) a copolymerization of a vinyl-based compound and a silyl compound having a polymerizable double bond are used. This is an effective method. The details will be described below.

(A) The silyl group-containing vinyl resin in the present invention comprises a hydrosilane compound and a vinyl resin having a carbon-carbon double bond containing a (meth) acrylic acid ester as a copolymerization component and a Group VIII transition metal. It is easily produced by reacting under the catalyst of.

The hydrosilane compound used in the present invention has the following general formula.

[0010]

[Chemical 1] (In the formula, R ¹ is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group, and an aralkyl group;
X is halogen, alkoxy, acyloxy, aminoxy,
A group selected from phenoxy, thioalkoxy, and amino groups, and n is an integer from 1 to 3. ).

Specific examples of the hydrosilane compound included in this general formula include halogenated silanes such as methyldichlorosilane, trichlorosilane and phenyldichlorosilane; methyldiethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, Alkoxysilanes such as trimethoxysilane and triethoxysilane; Acyloxysilanes such as methyldiacetoxysilane, phenyldiacetoxysilane and triacetoxysilane;
Examples include various silanes such as methyldiaminoxysilane, triaminoxysilane, methyldiaminosilane, and triaminosilane. The amount of the hydrosilane compound used can be an arbitrary amount with respect to the carbon-carbon double bond contained in the vinyl resin, but it is preferably 0.5 to 2 times the molar amount. It does not prevent the use of a higher amount of silane, but is only recovered as unreacted hydrosilane.

In the present invention, a transition metal complex catalyst is required at the stage of reacting the hydrosilane compound with the carbon-carbon double bond. As the transition metal complex catalyst, platinum,
A Group VIII transition metal complex compound selected from rhodium, cobalt, palladium and nickel is effectively used. This hydrosilylation reaction is achieved at any temperature of 50 to 130 ° C., and the reaction time is about 1 to 10 hours.

Further, in the present invention, a highly reactive halogenated silane can be easily used as a hydrosilane compound with an inexpensive basic raw material. A silyl group-containing vinyl resin obtained by using halogenated silanes cures rapidly at room temperature while generating hydrogen chloride when exposed to air, but is limited due to the problem of irritating odor and corrosion due to hydrogen chloride. Further, it is desirable to further convert the halogen functional group into another hydrolyzable functional group since it can be practically used only for the above-mentioned purpose.
As the hydrolyzable functional group, an alkoxy group, an acyloxy group, an aminoxy group, a phenoxy group, a thioalkoxy group,
An amino group etc. are mentioned.

As a method of converting the halogen functional group into these hydrolyzable functional groups, methanol, ethanol, 2-methoxyethanol, sec-butanol, t
Specific examples of the method include reacting alcohols and phenols such as ert-butanol and phenol, alkali metal salts of alcohols and phenols, alkyl orthoformates such as methyl orthoformate and ethyl orthoformate with a halogen functional group. To be

As a method of converting to an acyloxy group,
Carboxylic acids such as acetic acid, propionic acid, benzoic acid,
Specific examples include a method of reacting an alkali metal salt of a carboxylic acid with a halogen functional group.

As a method of converting to an aminoxy group,
Reacting hydroxylamines such as N, N-dimethylhydroxylamine, N, N-diethylhydroxylamine, N, N-methylphenylhydroxylamine and N-hydroxypyrrolidine, alkali metal salts of hydroxylamines and the like with halogen functional groups. The method is specifically mentioned.

As a method of converting to an amino group, N,
Specific examples include a method of reacting an alkali metal salt of primary and secondary amines such as N-dimethylamine, N, N-methylphenylamine and pyrrolidine with a halogen functional group. .

As a method of converting to a thioalkoxy group, a method of reacting a thioalcohol such as ethyl mercaptan or thiophenol and thiophenols, an alkali metal salt of thioalcohol and thiophenols with a halogen functional group is specifically mentioned. Can be mentioned.

Regarding the silyl group introduced into the vinyl resin by the hydrosilylation reaction, it is necessary not only to convert it to another hydrolyzable substituent in the case of a halogen functional group but also to form another alkoxy group or an acyloxy group. It can be converted into a hydrolyzable functional group such as an amino group or an aminoxy group according to the above.

The temperature at which the hydrolyzable functional group on the silyl group directly introduced by the hydrosilylation reaction is converted to another hydrolyzable functional group is preferably 50 to 150 ° C. Further, these exchange reactions can be accomplished with or without a solvent, but when used, an inert solvent such as ethers, hydrocarbons and acetic acid esters is suitable.

The vinyl resin used in the present invention is not particularly limited except that it contains a (meth) acrylic acid ester having a long-chain alkyl group having 10 or more carbon atoms as an essential component, and methyl acrylate, Acrylic acid such as methyl methacrylate, butyl acrylate, butyl methacrylate, methacrylic acid ester; acrylamide, methacrylamide, N-methylol acrylamide, N-
Monomers containing amide groups such as methylol methacrylamide, epoxy groups such as glycidyl acrylate and glycidyl methacrylate, amino groups such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate, aminoethyl vinyl ether; other acrylonitrile, iminol methacrylate, styrene, α A resin whose main component is a copolymer selected from methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene and the like is suitable.

During the production of a homopolymer or a copolymer of these vinyl compounds, a part of allyl acrylate, allyl methacrylate, diallyl phthalate or the like is radically copolymerized to obtain a carbon-carbon for hydrosilylation reaction in the vinyl resin. It is possible to introduce a carbon double bond. The amount of the monomer used for this purpose can be arbitrarily determined according to the number of silyl groups in the intended resin, but usually the molecular weight per silyl group is 300 to 4,000. Good to set. Furthermore, the molecular weight is 500 to 100,
To obtain a vinyl resin containing about 000 silyl groups, α
A chain transfer agent such as -dodecyl mercaptan or t-dodecyl mercaptan may be added if necessary. A solvent may or may not be used in the polymerization of these vinyl compounds, but when used, ethers, hydrocarbons,
The use of non-reactive solvents such as acetates is preferred.

The (meth) acrylic acid ester having a long-chain alkyl group having 10 or more carbon atoms used in the present invention is not particularly limited and is selected from solubility, polymerizability, appearance of coating film, required performance and the like. It is possible, but usually 10 to 30 carbon atoms
A (meth) acrylic acid ester having a long-chain alkyl group of is preferable. Specific examples include the following.

As the methacrylic acid ester, lauryl methacrylate: CH ₂ ═C (CH ₃ ) COOC ₁₂ H
₂₅ , tridecyl methacrylate: CH ₂ = C (CH ₃ ).
COOC ₁₃ H ₂₇ , cetyl methacrylate: CH ₂ ═C
(CH ₃ ) COOC ₁₆ H ₃₂ , stearyl methacrylate: CH ₂ ═C (CH ₃ ) COOC ₁₈ H ₃₇ , CH ₂
= C (CH ₃ ) COOC ₂₂ H ₄₅ , and a mixture of two or more alkyl groups can also be used. For example, a methacrylic acid alkyl ester (Mitsubishi Rayon Co., Ltd.) which is a mixture of alkyl groups having 12 and 13 carbon atoms. Made Acryester S
L), methacrylic acid alkyl esters and the like, which are available as a mixture having an alkyl group having 9 to 11 carbon atoms.

Similarly, as the acrylic ester, tridecyl acrylate: (CH ₂ ═CHCOOC ₁₃ H
₂₇ ), stearyl acrylate: (CH ₂ = CHCOO
C ₁₈ H ₃₇ ), a mixture of alkyl acrylates having an alkyl group having 12 and 13 carbon atoms, and the like.

The content of the (meth) acrylic acid ester having a long chain alkyl group is 1 in the silyl group-containing vinyl resin.
Within the range of from 95 to 95% by weight, it can be selected according to the intended use and the required physical properties, and preferably from 5 to 50% by weight.

(B) Another method of the present invention is

[Chemical 2] (In the formula, R ¹ is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group, and an aralkyl group;
R ² is an organic residue having a polymerizable double bond, X is a group selected from halogen, alkoxy, acyloxy, aminoxy, phenoxy, thioalkoxy and amino groups, and n is an integer of 1, 2, 3. ), Various vinyl compounds, and a (meth) acrylic acid ester having a long-chain alkyl group are radically polymerized.

The silane compound used in the present invention is, for example,

[Chemical 3]

[Chemical 4] Etc.

These silane compounds can be synthesized by various methods. For example, acetylene, allyl acrylate, allyl methacrylate, diallyl phthalate and methyldimethoxysilane, methyldichlorosilane are combined with VII.
It can be produced by reacting under the catalyst of a Group I transition metal.

The amount of the silane compound is usually set so that the molecular weight per silyl group is 300 to 4,000.

As the vinyl compound used in the present invention, it is possible to use the compound used at the time of synthesizing the vinyl resin in the above Method A, but 2-hydroxyethyl acrylate other than those described in Method A is used. , 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-
A vinyl compound containing a hydroxyl group such as hydroxy vinyl ether is also possible.

The synthesis of the copolymer of the vinyl compound and the silane compound is carried out by a usual solution polymerization method. Vinyl compounds, silane compounds, radical initiators,
N-dodecyl mercaptan, if necessary, to obtain a silyl group-containing copolymer having a molecular weight of 500 to 100,000,
Add a chain transfer agent such as t-dodecyl mercaptan and add 50
React at ~ 150 ° C. The solvent may or may not be used, but when used, ethers, hydrocarbons,
The use of non-reactive solvents such as acetates is preferred. In the silyl group-containing vinyl resin thus obtained, the hydrolyzable group can be converted by the same method as the method A.

The silyl group-containing vinyl resin of the present invention, when exposed to the atmosphere, forms a network structure at room temperature and hardens. Since the curing rate in this case changes depending on the atmospheric temperature, the relative humidity and the type of the hydrolyzable group, it is necessary to fully consider the type of the hydrolyzable group in use.

In curing the silyl group-containing vinyl resin in the present invention, a curing agent may or may not be used depending on the curing conditions, but in order to satisfy physical properties such as room temperature curing, high hardness and workability. It is practical to use a curing catalyst.

The present invention is not limited by the curing catalyst used, but examples of the curing catalyst include organotin compounds, acidic phosphoric acid esters, reaction products of acidic phosphoric acid esters and amines, saturated or unsaturated compounds. Examples include saturated polycarboxylic acids or acid anhydrides thereof and organic titanate compounds. Usually, the addition amount of these curing catalysts is preferably 20% by weight or less based on the resin.

The type of matting agent used in the present invention is not particularly limited, and commonly used matting agents can be used. Specific examples include silica type matting agents and polyethylene wax type matting agents. Matting agents, polycarbonate type delustering agents, polypropylene wax type delustering agents and the like can be mentioned. The matting agent is 0.1 parts by weight based on 100 parts by weight of the silyl group-containing vinyl resin solid matter.
It is used in an amount of 5 to 20 parts by weight.

Since the composition of the present invention can be cured at room temperature or low temperature, it is useful as a paint or coating agent.

In addition, it is also possible to improve the physical properties such as surface hardness by adding a compound capable of co-condensing with the silyl group-containing vinyl resin of the present invention such as ethyl silicate. In addition, it is possible to blend with various resins currently used as paints and coating agents, and the adhesion of these paints and coating agents currently used,
Physical properties such as weather resistance can be improved.

Various fillers, contents and the like can be mixed in the silyl group-containing vinyl resin in the present invention. As the filler and the content, various silicas, calcium carbonate, magnesium carbonate, titanium oxide, iron oxide, glass transition and the like can be used. Thus, it is useful not only for the above-mentioned applications, but also as a coating composition for aircraft, buildings, automobiles, glass, etc., a sealing composition and a surface treatment agent for various inorganic and organic substances.

[0040]

EXAMPLES The present invention will now be specifically described with reference to examples.

Synthesis Example 1 30 g of styrene was added to 90 g of xylene heated to 90 ° C.
g, γ-methacryloxypropyltrimethoxysilane 2
6 g, methyl methacrylate 52 g, butyl acrylate 2
A solution of 2 g of azobisisobutyronitrile in 7 g, 4 g of acrylamide and 0.7 g of n-dodecyl mercaptan was added dropwise and reacted for 10 hours to give a molecular weight of 15,000.
A silyl group-containing vinyl resin was obtained.

Synthesis Example 2 In 90 g of xylene heated to 90 ° C., 26 g of stearyl methacrylate and 17 g of styrene, 26 g of γ-methacryloxypropyltrimethoxysilane, 39 g of methyl methacrylate, 27 g of butyl acrylate, 4 g of acrylamide, n- A solution of 2 g of azobisisobutyronitrile in 0.7 g of dodecyl mercaptan was added dropwise, and
The reaction was carried out for a time to obtain a silyl group-containing vinyl resin having a molecular weight of 15,000.

Synthesis Examples 3 to 7 Various silyl group-containing vinyl resins shown in Table 1 were synthesized in the same manner as in Synthesis Examples 1 and 2. The polymerization temperature was 90 ° C. and the polymerization time was 10 hours.

Synthetic Examples 8 to 13 Various silyl group-containing vinyl resins shown in Table 2 were synthesized using various long-chain alkyl methacrylates in the same manner as in Synthetic Examples 1 and 2.

[0045]

[Table 1]

[Table 2]

The silyl group-containing vinyl resins of Comparative Examples 1 to 20 and Examples 1 to 11 and Synthesis Examples 1 to 13 were prepared as shown in Table 3.
A curing catalyst and a matting agent shown in 4 were added, diluted with xylene to an appropriate coating viscosity, and then spray coated on a commercially available polyester printed plywood polished with # 800 to prepare a test piece. The drying conditions were room temperature for 1 day (scratch resistance) or 7 days (friction resistance, adhesion).

[Abrasion resistance test (abrasion resistance)] A canvas was fixed to the contact portion of an eraser abrasion tester, and 1 kg /
The degree of wear of the coated surface after 1,000 times of test with a load of cm ² .
It was evaluated by the degree of scratches (○: almost no change,
(Triangle | delta): Slightly scratched or worn, X: Severe, severely worn).

[Abrasion resistance test (scratch resistance)] After rubbing lightly with a commercially available business card, judgment was made based on how much scratches were produced (○: almost no scratches, ×: severe scratches) ).

[Adhesiveness Test] The glutinous cellotape peeling test ((100/100) was 1
0 points and (0/100) are 0 points. ) Evaluated.

[0050]

[Table 3]

[Table 4]

[0051]

As shown in Tables 3 and 4, the curable composition of the present invention contains long-chain alkyl methacrylate as a copolymerization component, and is used in the coating film formed by the composition. Adhesion, abrasion resistance, and scratch resistance are all significantly improved. In particular, the abrasion resistance and the scratch resistance are remarkably improved.

Claims (3)

[Claims] 1. The main chain consists essentially of a vinyl polymer,
One (meth) acrylic acid ester having at least one silicon group bonded to a hydrolyzable group in one molecule and further having a long-chain alkyl group having 10 or more carbon atoms as a copolymerization component
~ 95 wt%, molecular weight 500 ~ 100,00
Curable composition which mix | blends 0.5-20 weight part of matting agents with respect to 100 weight part of vinyl type resin solid content of 0 of silyl group. 2. The curable composition according to claim 1, wherein the copolymerization component is a (meth) acrylic acid ester having a long-chain alkyl group having 10 to 30 carbon atoms. 3. A (meth) acrylic acid ester having a long-chain alkyl group having 10 to 30 carbon atoms is used as a copolymerization component.
The curable composition according to claim 1, which comprises -50% by weight.