JPH0242868B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention comprises (A) a vinyl resin containing a hydrolyzable silyl group at the terminal or side chain, (B) a tin compound, and
(C) A composition comprising one or a mixture of two or more amines having a silicon group bonded to at least one hydrolyzable group in one molecule, which is useful as a coating or paint. The present inventors discovered that a vinyl resin containing a silyl group having a hydrolyzable group at the terminal or side chain is
In addition to the excellent characteristics of vinyl resins such as high gloss, weather resistance, and discoloration resistance, it also has improved adhesion to inorganic materials due to its hydrolyzable silyl group, and is resistant to room-temperature crosslinking due to moisture, especially atmospheric moisture. discovered that it formed a dense network structure and became a resin with excellent solvent resistance, water resistance, heat resistance, high hardness, and weather resistance, and filed a patent application earlier (Japanese Patent Application Laid-Open No. 1989-1999).
36395). The present inventors further investigated silyl group-containing vinyl resins and found various advantages by mixing them with the above (A), (B) and (C), leading to the present invention. The advantage of the composition of the present invention comprising a silyl group-containing vinyl resin (A), a tin compound (B), and an amine (C) is that it improves the physical properties of the coating film, such as solvent resistance, adhesion to organic substances in particular, and weather resistance. It is. Compositions made using general acrylic resins that do not have hydrolyzable silyl groups are used as quick-drying lacquers, but while they have excellent weather resistance, they have poor solvent resistance, adhesion, etc. However, by adding a hydrolyzable silyl group-containing vinyl resin, a coating film with improved solvent resistance, adhesion, and weather resistance can be obtained. The silyl group-containing vinyl resin used in the present invention has at least one, preferably two or more, silyl groups having a hydrolyzable group in one molecule, and most of the silyl groups are

[Formula] (X is a hydrolyzable group, R ₁ and R ₂ are hydrogen or an alkyl group, aryl group, or aralkyl group having 1 to 10 carbon atoms, and n is an integer of 1, 2, or 3) It will be done. The production of the silyl group-containing vinyl resin of the present invention includes:
Although various methods are possible, the industrial methods include a hydrosilylation reaction using a vinyl resin having a carbon-carbon double bond and hydrosilane, and a method based on copolymerization of a vinyl compound and a silyl compound having a polymerizable double bond. This is an effective method. The details will be explained below. The silyl group-containing vinyl resin of the present invention is easily produced by reacting a hydrosilane compound with a vinyl resin having a carbon-carbon double bond in the presence of a group transition metal catalyst. The hydrosilane compound used in the present invention has the following general formula. (In the formula, R ₁ is an alkyl group having 1 to 10 carbon atoms,
A monovalent hydrocarbon group selected from aryl groups and aralkyl groups, X is a group selected from halogen, alkoxy, acyloxy, aminoxy, phenoxy, thioalkoxy, and amino groups, n is 1 to 3
is an integer up to . ) Specific examples of hydrosilane compounds included in this general formula include methyldichlorosilane,
Halogenated silanes such as trichlorosilane, phenyldichlorosilane; Alkoxysilanes such as methyldiethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, trimethoxysilane, triethoxysilane; methyldiacetoxysilane, phenyldichlorosilane; Examples include acyloxysilanes such as acetoxysilane and triacetoxysilane; various silanes such as methyldiaminoxysilane, triaminoxysilane, methyldiaminosilane, and triaminosilane. The amount of the hydrosilane compound used is based on the carbon-carbon double bond contained in the vinyl resin.
Although any amount can be used, it is preferable to use 0.5 to 2 moles. Although this does not preclude the use of a larger amount of silane, it will simply be recovered as unreacted hydrosilane. Furthermore, in the present invention, halogenated silanes, which are inexpensive basic raw materials and have high reactivity, can be easily used as the hydrosilane compound. The silyl group-containing vinyl resin obtained using halogenated silanes is
When exposed to air, it hardens rapidly at room temperature while generating hydrogen chloride, but it can only be used in limited applications due to problems with the irritating odor and corrosion caused by hydrogen chloride. It is desirable to convert it to other hydrolyzable functional groups. The vinyl resin used in the method is not particularly limited, except for vinyl compounds containing hydroxyl groups, and includes methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate,
Esters of acrylic acid and methacrylic acid such as 2-ethylhexyl acrylate and 2-ethylhexyl methacrylate; carboxylic acids of acrylic acid, methacrylic acid, itaconic acid, fumaric acid; and acid anhydrides such as maleic anhydride; glycidyl acrylate, Epoxy compounds such as glycidyl methacrylate; diethylaminoethyl acrylate, diethylaminoethyl methacrylate,
Amino compounds such as aminoethyl vinyl ether; amide compounds such as acrylamide, methacrylamide, itaconic acid amide, α-ethylacrylamide, crotonamide, fumaric acid diamide, maleic acid diamide, N-butoxymethyl acrylamide, N-butoxymethyl methacrylamide; acrylonitrile, styrene,
A resin whose main component is a copolymer selected from α-methylstyrene, vinyl chloride, vinyl acetate, vinyl propionate, etc. is suitable. When producing these vinyl compounds alone or as a copolymer, by radically copolymerizing a portion of allyl acrylate, allyl methacrylate, diallyl phthalate, etc., a carbon-carbon double layer for hydrosilylation reaction is created in the vinyl resin. It is possible to introduce bonds. The amount of monomer necessary for this purpose can be arbitrarily determined depending on the number of silyl groups in the target resin. Furthermore, n
The molecular weight can be adjusted by adding a chain transfer agent such as -dodecylmercaptan or t-dodecylmercaptan. When polymerizing these vinyl compounds, a solvent may or may not be used, but when used, it is preferable to use a non-reactive solvent such as ethers, hydrocarbons, and acetic esters. In the present invention, a transition metal complex catalyst is required in the step of reacting a hydrosilane compound with a carbon-carbon double bond. As the transition metal complex catalyst, group transition metal complex compounds selected from platinum/rhodium, cobalt/palladium, and nickel are effectively used. This hydrosilylation reaction is achieved at any temperature between 50 and 150 °C,
The reaction time is about 1 to 10 hours. Another method of the invention is based on the formula

[Formula] (In the formula, R ₁ is an alkyl group having 1 to 10 carbon atoms,
A monovalent hydrocarbon group selected from an aryl group and an aralxy group, R ₂ is an organic residue having a polymerizable double bond, and X is a group selected from a halogen, alkoxy, acyloxy, aminoxy, phenoxy, thioalkoxy, and amino group. , n is 1, 2, 3
is an integer. ) It is produced by radical polymerization of the silane compound shown in the following and various vinyl compounds. The silane compounds used in the present invention include:
for example,

【formula】

[Formula] CH ₂ = CHSi(OCH ₃ ) ₃ , CH ₂ = CHSiCl ₃ , etc. These silane compounds are synthesized by various methods, but for example, acetylene, allyl acrylate, allyl methacrylate, diallyl phthalate and methyldimethoxysilane, methyldichlorosilane, trimethoxysilane, trichlorosilane are synthesized under a group transition metal catalyst. It can be produced by reaction. As the vinyl compound used in the present invention, it is possible to use the compounds used in the synthesis of vinyl resin in the above method, but in addition to those described in the method, 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate, methacrylate, 2-hydroxypropyl acrylate, 2
-Hydroxypropyl methacrylate, 2-hydroxy vinyl ether, N-methylol acrylamide, Aronix 5700 (manufactured by Toagosei Co., Ltd.)
Vinyl compounds containing hydroxyl groups such as hydroxyl groups are also possible. Synthesis of these copolymers of vinyl compounds and silane compounds is carried out by a normal solution polymerization method, and in order to obtain a vinyl compound, a silane compound, a radical initiator, and a silyl group-containing copolymer with an appropriate molecular weight. If necessary, a chain transfer agent such as n-dodecylmercaptan or t-dodecylmercaptan is added and the reaction is carried out at 50 to 150°C. A solvent may or may not be used, but when used, it is preferable to use a non-reactive solvent such as ethers, hydrocarbons, and ethyl acetate. In the silyl group-containing vinyl resin thus obtained, the hydrolyzable group can be converted into another hydrolyzable group by a known method. In this way, a silyl group-containing vinyl resin whose main chain consists essentially of a vinyl polymer and which has at least one silicon group bonded to a hydrolyzable group at the terminal or side chain in one molecule is obtained. available. The tin compound used in the present invention is not particularly limited, and tin compounds commonly used as curing catalysts for hydrolyzable silyl group-containing compounds can be used. For example, (n-C ₄ H ₉ ) ₂ Sn (OCOC ₁₁ H ₂₃ -n) ₂ , (n-C ₄ H ₉ ) ₂ Sn (OCOCH=CHCOOCH ₃ ) ₂ , (n-C ₄ H ₉ ) ₂ Sn (OCOCH=CHCOOC ₄ H ₉ −
n) ₂ , (n- _{C3H17 ) 2Sn ( OCOC11H23} -n) ₂ , (n- _{C3H17 ) 2Sn} (OCOCH= _CHCOOCH3 ) ₂ , (n- _{C3H17 ) 2} Sn(OCOCH=CHCOOC ₄ H ₉ −
n) ₂ , (n-C ₃ H ₁₇ ) ₂ Sn (OCOCH=CHCOOC ₃ H ₁₇ −
carboxylic acid type organic tin compounds such as iso) ₂ , Sn(OCOC ₈ H ₁₇ -n) ₂ , (n-C ₄ H ₉ ) ₂ Sn(SCH ₂ COO), (n-C ₄ H ₉ ) ₂ Sn (SCH ₂ COOC ₃ H ₁₇ -iso) ₂ , (n-C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COO), (n-C ₈ H ₁₇ ) ₂ Sn (SCH ₂ CH ₂ COO), (n-C ₈ H ₁₇ ) ₂ Sn
(SCH ₂ COOCH ₂ CH ₂ OCOH ₂ S), (n-C ₈ H ₁₇ ) ₂ Sn
(SCH ₂ COOCH ₂ CH ₂ CH ₂ CH ₂ COOH ₂ S), (n-C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ -iso) ₂ , (n-C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOC ₁₂ H ₂₅ −n) ₂ , mercaptide-type organotin compounds such as

【formula】

【formula】

Sulfide-type organotin compounds such as [Formula], organotin oxides such as (n-C ₄ H ₉ ) ₂ SnO, (n-C ₈ H ₁₇ ) ₂ SnO, and (n-C ₄ H ₉ )SnO, ₍ n− _C8H17 )SnO
reaction products of organic tin oxides such as ethyl silicate, ethyl silicate 40, dimethyl maleate, diethyl maleate, dioctyl maleate, dimethyl phthalate, diethyl phthalate, dioctyl phthalate, etc.;
etc. are included. The amine used in the present invention is one having a silicon group bonded to at least one hydrolyzable group in one molecule, and there are no particular limitations beyond that. These include, for example, NH ₂ (CH ₂ ) ₃ Si
(OC ₂ H ₅ ) ₃ , NH(CH ₂ ) ₂ NH(CH ₂ ) ₃ Si
Silane coupling agent containing an amino group such as (OCH ₃ ) ₃ ;

Reaction products with silane coupling agents containing epoxy groups such as [Formula]; silane coupling agents containing amino groups mentioned above and ethylene oxide, butylene oxide, epichlorohydrin, epoxidized soybean oil, and other shells.
Reaction products with compounds containing epoxy groups such as Epicote 828 and Epicote 1001 manufactured by Co., Ltd.; silane coupling agents containing the above epoxy groups and ethylamine, diethylamine, triethylamine, ethylenediamine, hexanediamine, diethylenetriamine, triethylenetetramine, Reaction products with aliphatic amines such as tetraethylenepentamine, aromatic amines such as aniline and diphenylamine, alicyclic amines such as cyclopentylamine and cyclohexylamine, and amines such as ethanolamine; Silane coupling agent containing ethyl silicate, ethyl silicate 40, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ
- methacryloxypropyltrimethoxysilane and a silane coupling agent containing the above-mentioned epoxy group, a silane coupling agent containing the above-mentioned amino group, etc., and a compound containing a hydrolyzable silyl group with water and, if necessary, acidic or This includes reactants obtained by adding an alkaline catalyst and performing partial hydrolysis. Furthermore, by mixing a compound containing an epoxy group with these amines, it is possible to further improve the adhesion to organic substances. Although the proportion of the composition in the present invention is not particularly limited, the main chain is substantially made of a vinyl polymer and the silyl compound has at least one silicon group in one molecule bonded to a hydrolyzable group at the terminal or side chain. 0.01 to 10 parts by weight of the tin compound (B), preferably 0.1 to 8 parts by weight, per 100 parts by weight of the group-containing vinyl resin (A), silicon bonded to at least one hydrolyzable group in one molecule. The amine (C) having a group is blended in an amount of 0.01 to 20 parts by weight, preferably 0.1 to 15 parts by weight. In addition to the above component (A), a tin compound is added as a curing catalyst.
By blending and using (B) and a specific amine (C), it is possible to obtain a coating film with excellent adhesion to a substrate or base material when applied to an organic material and cured. On the other hand, coating films obtained using a curing catalyst in which a silane coupling agent alone that does not contain an amino group or an amine alone that does not contain a hydrolyzable silyl group are added to a tin compound do not contain the curing catalyst of the present invention. The adhesion to organic substances is inferior to that when using The silyl group-containing vinyl resin composition of the present invention is
Since it can be cured at room temperature or low temperature, it is useful as a paint, coating agent, or adhesive. In particular, the present invention has excellent adhesion to organic materials, so it can be applied not only to paints, coatings, and adhesives on inorganic surfaces, but also to organic surfaces (wood, paper, plastic, top coatings on organic paints, etc.) As a result, the range of uses can be expanded dramatically. Furthermore, it is also possible to improve physical properties such as surface hardness by adding a compound such as ethyl silicate which can be co-condensed with the silyl group-containing vinyl resin of the present invention. It can also be blended with various resins currently used as paints and coating agents, such as lacquer paints, acrylic lacquer paints, thermosetting acrylic paints, alkyd paints, melamine paints, epoxy paints, etc. They can be mixed and used in appropriate proportions, and can improve the physical properties of currently used paints and coating agents, such as adhesion and weather resistance. The silyl group-containing vinyl resin composition of the present invention is
It is possible to incorporate various fillers, pigments, etc. Various fillers and pigments can be used, such as various silicas, calcium carbonate, magnesium carbonate, titanium oxide, iron oxide, and glass fiber. In this way, it is useful not only for the above-mentioned uses, but also as a coating composition for aircraft, buildings, automobiles, glass, etc., a sealing composition, and a surface treatment agent for various inorganic materials. Next, the present invention will be specifically explained using examples. Synthesis Example 1 In 90 g of xylene solvent heated to 90°C, 30 g of styrene, 16 g of allyl methacrylate, 20 g of methyl methacrylate, 19 g of n-butyl methacrylate, 14 g of butyl acrylate, 4 g of maleic anhydride, n-
A solution of 2 g of azobisisobutyronitrile dissolved in 2 g of dodecyl mercaptan was added dropwise and reacted for 10 hours to obtain a vinyl polymer containing allylic unsaturated groups with a molecular weight of 8,000. In the infrared absorption spectrum of this product, absorption due to carbon-carbon double bond at 1648 cm ^-1 and absorption of acid anhydride at 1780 cm ^-1 were observed.
40 g of solvent is removed from the resulting polymer solution under reduced pressure. A solution of 1.5 g of methyldimethoxysilane and 0.0005 g of chloroplatinic acid dissolved in isopropanol was added to 16 g of the obtained vinyl copolymer solution containing an allylic unsaturated group, and the mixture was reacted at 90° C. for 6 hours under sealed conditions. In the infrared absorption spectrum of this product, the absorption at 1648 cm ^-1 disappeared, and a silyl group-containing vinyl polymer was obtained. Synthesis Example 2 Styrene was added to 70g of xylene heated to 90℃.
30g, γ-methacryloxypropyltrimethoxysilane 22g, methyl methacrylate 22g, n-butyl methacrylate 15g, butyl acrylate 18g, n
A solution of 2 g of azobisisobutyronitrile dissolved in 1 g of -dodecyl mercaptan was added dropwise and reacted for 10 hours to obtain a silyl group-containing vinyl resin with a molecular weight of 12,000. Synthesis Example 3 Styrene was added to 70g of xylene heated to 90℃.
30 g, 22 g of γ-methacryloxypropyltrimethoxysilane, 52 g of methyl methacrylate, 15 g of n-butyl methacrylate, 18 g of butyl acrylate, 4 g of acrylamide, 10 g of n-butanol, 1 g of n-dodecylmercaptan, and 2 g of azobisisobutyronitrile. was added dropwise and reacted for 10 hours to obtain a silyl group-containing vinyl resin with a molecular weight of 12,000. Synthesis Example 4 Styrene was added to 70g of xylene heated to 90℃.
30 g, γ-methacryloxypropyltrimethoxysilane 22 g, methyl methacrylate 22 g, n-butyl methacrylate 13 g, butyl acrylate 18 g, acrylamide 4 g, maleic anhydride 2 g, n-butanol 10 g, n-dodecyl mercaptan 4 g, and azobis A solution containing 2 g of isobutyronitrile was added dropwise, and the mixture was reacted for 10 hours to obtain a silyl group-containing vinyl resin with a molecular weight of 6,000. Examples 1 to 5, Comparative Examples 1 to 5 To the resin solutions obtained in Synthesis Examples 1 to 4 above, 3 parts of a tin compound and an amine were added to 100 parts of resin,
Dilute it with xylene to a coating viscosity (15 seconds in a food cup test) and apply it to the organic coating shown in Table 1.
Similarly, the heat treatment shown in Table 1 was performed, and the adhesion was measured one day later. As a comparative example, resins obtained in Synthesis Examples 1 to 4 were prepared in which a tin compound was added but no amine was added, and the results were compared to Comparative Examples 1 to 5.
It is also shown in Table-1.

【table】

【table】

Claims (1)

[Scope of Claims] 1 (A) A silyl group-containing polymer whose main chain is substantially composed of a vinyl polymer and which has at least one silicon group per molecule bonded to a hydrolyzable group at the terminal or side chain. A vinyl resin, (B) a tin compound, and (C) an amine having a silicon group bonded to at least one hydrolyzable group in one molecule, or a mixture of two or more of the above (A), ( A coating composition containing B) and (C) as active ingredients. 2. The composition according to claim 1, wherein the amine (C) is a silane coupling agent containing an amino group. 3. The composition according to claim 1, wherein the amine (C) is a reaction product of a silane coupling agent containing an amino group and a silane coupling agent containing an epoxy group. 4. The composition according to claim 1, wherein the amine (C) is a reaction product of a silane coupling agent containing an amino group and a compound containing an epoxy group. 5. The composition according to claim 1, wherein the amine (C) is a reaction product of an epoxy group-containing silane and an amine. 6. The composition according to claim 1, wherein the amine (C) is a partial hydrolyzate of a silane coupling agent containing an amino group and a compound containing a hydrolyzable silyl group.