JPS63314279A - Coating composition - Google Patents

Abstract

PURPOSE:To prepare a coating compsn. having excellent solvent resistance, adhesion, weather resistance, etc., by incorporating a vinyl resin having a particular silyl group, a thin compd. and an amine having a silicon group bonded to a hydrolyzable group as active ingredients. CONSTITUTION:A silyl group-contg. vinyl resin having a principal chain composed of a vinyl polymer and having at least one, per molecule, silicon group bonded to a hydrolyzable group at the terminal or side groups thereof is produced e.g., by reacting a hydrosilane compd. (e.g., methyldichlorosilane) with a vinyl resin in the presence of a catalyst. The produced resin, a tin compd. (e.g., one of formula I or formula II) and at least one amine having at least one, per molecule, silicon group bonded to a hydrolyzable group (e.g., an amino group-contg. silane coupling agent of formula III) are incorporated as active ingredients, thereby obtaining the desired coating compsn.

Description

Detailed Description of the Invention The present invention provides (4) a vinyl resin containing a hydrolyzable silyl group at the terminal or side chain, (B) a tin compound, and (C1
The present invention relates to a composition comprising one or a mixture of two or more amines having a silicon group bonded to at least one hydrolyzable group in the molecule, and which is useful as a coating or paint.

The present inventors have discovered that a vinyl resin containing a silyl group with a hydrolyzable group at the terminal or side chain has excellent characteristics such as high gloss, weather resistance, and discoloration resistance, which are characteristics of vinyl resins. The hydrolyzable silyl group improves adhesion to inorganic substances, and water, especially atmospheric water, forms a dense network structure through room-temperature crosslinking, resulting in improved solvent resistance, water resistance,
It was discovered that the resin had excellent heat resistance, high hardness, and weather resistance, and a patent application was filed for it (Japanese Patent Application Laid-Open No. 54-86895).
.

The present inventors further investigated silyl group-containing vinyl resins and found various advantages by mixing them with the above (4), CB) and (C), leading to the present invention.

The advantage of the composition of the present invention comprising the silyl group-containing vinyl resin (4), the tin compound CB), and the 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. be.

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 and
Although there is a problem with poor adhesion, 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 silyl group having a hydrolyzable group in one molecule,
Preferably, it has two or more silyl groups, and most of the silyl groups are Xn-
8i (EH (X is a hydrolyzable group, R1 and R2 are hydrogen or an alkyl group having 1 to 10 carbon atoms, an aryl group, or an aralkyl group, and n is an integer of 1.2.8).

The silyl group-containing vinyl resin of the present invention can be produced by various methods, including (1) a hydrosilylation reaction between a vinyl resin having a carbon-carbon double bond and hydrosilane;
and (2) a method based on copolymerization of a vinyl compound and a silyl compound having a polymerizable double bond is an industrially effective method. The details will be explained below.

(2) The silyl group-containing vinyl resin of the present invention can be easily produced by reacting a hydrosilane compound with a vinyl resin having a carbon-carbon double bond under the catalyst of a Group V (2) transition metal. The hydrosilane compound used in the present invention has the following general formula.

(R1) 8-n
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 hydrosilane compounds included in this general formula include methyldichlorosilane, trichlorosilane,
Halogenated silanes such as phenyldichlorosilane; alkoxysilanes such as methyljethoxysilane, methyldimethoxysilane, phenyldimethoxysilane, trimethoxysilane, triethoxysilane; methyldiacetoxysilane, phenyldiacetoxysilane, triacetoxysilane Acyloxysilanes such as: various silanes such as methyldiaminoxysilane, doriaminoxysilane, methyldiaminoxysilane, and triaminosilane.

The amount of the hydrosilane compound to be used can be any arbitrary amount, but it is preferably used in an amount of 0.5 to 2 times the mole of carbon-carbon double bonds contained in the vinyl resin. Although this does not preclude the use of a larger amount of silane, unreacted hydrosilane will simply be recovered.

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. Silyl group-containing vinyl resins obtained using halogenated silanes harden quickly at room temperature while generating hydrogen chloride when exposed to air, but are limited due to problems with irritating odor and corrosion caused by hydrogen chloride. It is desirable to further subsequently convert the halogen functional group to another hydrolyzable functional group, since it can only be used practically in applications where the halogen functional group is used.

■The vinyl resin used in the method is not particularly limited, except for vinyl compounds containing hydroxyl groups, such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, and butyl methacrylate. , 2-ethylhexyl acrylate, methacrylic acid 2
- Esters of acrylic acid and methacrylic acid such as ethylhexyl; carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid; and acid anhydrides such as maleic anhydride; epoxy compounds such as glycidyl acrylate and glycidyl methacrylate; diethylamino Amino compounds such as ethyl acrylate, diethylaminoethyl methacrylate, aminoethyl vinyl ether; acrylamide, methacrylamide, itaconic acid amide, α-ethylacrylamide, crotonamide, fumaric acid diamide, maleic acid diamide, N-butoxymethyl acrylamide, N-butoxymethyl A resin whose main component is an amide compound such as methacrylamide; a copolymer selected from acrylonitrile, styrene, 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, the molecular weight can be controlled by adding a chain transfer agent such as n-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, a V2 group transition metal complex compound selected from platinum, rhodium, cobalt, palladium and nickel is effectively used. This hydrosilylation reaction is achieved at any temperature between 50 and 150°C,
The reaction time is about 1 to 10 hours.

(R1) 8-n ■ Another method of the present invention is the formula (R2) 8i-XH (wherein 1 is a monovalent group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group, and an aralkyl group). a hydrocarbon group, R2 is an organic residue having a polymerizable double bond, X is a group selected from halogen, alkoxy, acyloxy, aminoxy, phenoxy, thioalkoxy, and amino group, n is an integer of 1.2.3 It is produced by radical polymerization of the silane compound shown in (.) and various vinyl compounds.

Examples of the silane compounds used in the present invention include CH2=OH8i(QC!H8)8, CH2=CH81
C1a, H8 CH2=OHOOO(CH2)B8i(C0Ha)2,
CH2=OHCOO(CH2)aSi(C0Ha) 8
, H8 C! H2=OHOOOO(CH2)88i012, CH2
=OHOO(OH2)gS 1C1a,H8 CH2=C(CH3)000(CH2”)B8i(OC
Ha)2.0H2=C! (CHa)C! 00(C!H2
)88i(OCHa)8,? H8 0H2=C(CHa)C00(OH2)B8iC12,
CH2=C(OHs)000(CH2)gsiclg,
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 the catalyst of a group II transition metal. It can be produced by reacting with

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 method (2), 2-hydroxyethyl acrylate, 2-hydroxyethyl acrylate, 2- Hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-
Vinyl compounds containing hydroxyl groups such as hydroxypropyl methacrylate, 2-hydroxy vinyl ether, N-methylol acrylamide, Aronix 5700 (manufactured by Toagosei Co., Ltd.) are also possible.

Synthesis of these copolymers of vinyl compounds and silane compounds is carried out using a normal solution polymerization method.
A silane compound, a radical initiator, and a chain transfer agent such as n-dodecyl mercaptan or t-dodecyl mercaptan are added as necessary to the pass to obtain a silyl group-containing copolymer with an appropriate molecular weight, and the reaction is carried out at 50 to 150°C. . The solvent is
It 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 silyl group-containing vinyl resin thus obtained, the hydrolyzable group can be converted into another hydrolyzable group by a known method.

In this way, the main chain consists essentially of a vinyl polymer,
In addition, a silyl group-containing vinyl resin having at least one silicon group bonded to a hydrolyzable group at the terminal or side chain in one molecule can be used.

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-04H9)28n(OOOOx IH2B-n)
2, (n-C! 4H9) 28 n (OCOCH=
G! HC! 0OOH8) 2, (n-04H9) 28
n (OCOCflIG!HC(1)C4H9-n)
2, (n-caHt7)28n(OOOCttH2a
-n) 2, (nC8H17) 28 n (OOOCE
[CH(X)OCH8) 2, (n 08H17) 28
n((X:01lid■α')QC4H9-n) 2,(
n-OaHx7)28n(OcO(I-OHCOOCa
H17-iso)2.8n(QCα:38H17n)2
, etc., (n-04H9)28n(S(12cOO), (n-0
4Hg) 28n(80H2■0C8H17-iso
)2, (n-C8H17)2Sn(8(m2COO),
(n-08H17)28n(SOH20H2COO),
(n'(38H17) 28 n (8CH2C00C
H2CH20COH28), (n-OsH17) 28
n (5CH2COOCH2CE2CH2CH20CO
H2S ), (n(38Hi7)2Sn(SCH2CO
OCBH17-i so) 2, (n-CgH17)2
8n(SCH2(X)QC!t2H2s-n)2.

(n-CnH2)8n(SCH2COOOsHty-i
So) (n-04H9)8n(SOH2Cα)CgH
(n-04H9)-8n=8, (n-04H9)2SnO1(n-OaHt7)2Sn
Organic tin oxide such as O1, and (n-04H9)8nO1(n-CsHx7)Sn
Contains reaction products of organic tin oxides such as O and ester compounds such as ethyl silicate, ethyl silicate 40, dimethyl maleate, diethyl maleate, dioctyl maleate, dimethyl phthalate, diethyl phthalate, dioctyl phthalate, etc. It will be done.

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, NH2(CH2) 3 S i (
OC2H5) 35NH(CH2) 2NH(CH2)
A silane coupling agent containing an amino group such as 8S i (OCHs) 3; A reaction product of the above silane coupling agent containing an amino group and a silane coupling agent; A silane coupling agent containing the above amino group and ethylene oxide , butylene oxide, epichlorohydrin, epoxidized soybean oil, and other Shell ■ Epicote 828, Epicote 100
Reaction product with a compound containing an epoxy group such as 1; the above silane coupling agent containing an epoxy group and ethylamine, diethylamine, triethylamine, ethylenediamine,
Aliphatic amines such as hexanediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine, aromatic amines such as aniline and diphenylamine, alicyclic amines such as cyclopentylamine and cyclohexylamine, and amines such as ethanolamine. Reactants: the above amino group-containing silane coupling agent and ethyl silicate, ethyl silicate 40, methyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane , and a compound containing a hydrolyzable silyl group, such as the above-mentioned epoxy group-containing silane coupling agent or the above-mentioned amino group-containing silane coupling agent, by adding water and, if necessary, an acidic or alkaline catalyst, to partially hydrolyze. This includes reactants obtained by decomposition, etc. 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. For 100 parts by weight of the group-containing vinyl resin (A), a tin compound (B) and an amine having a silicon group (C)
It is blended in a proportion of 0.01 to 20 parts by weight, preferably 0.1 to 15 parts by weight.

In addition to the above components (8), a tin compound CB is added as a curing catalyst.
) 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 substance 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 useful as a paint, coating agent, or adhesive because it can be cured at room temperature or at a low temperature. In particular, the present invention has excellent adhesion to organic materials, so it can be used for paints, coatings, and adhesives on inorganic surfaces.
It can be applied to organic surfaces (wood, paper, plastic, top coats on organic paints, etc.), and the range of uses can be expanded dramatically.

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 coatings, such as lacquer paints, acrylic lacquer paints, thermosetting acrylic paints, alkyd paints, melamine paints, epoxy paints, etc. They can be mixed and used in suitable proportions, and can improve the physical properties of currently used paints and coatings, such as adhesion and weather resistance.

The silyl group-containing vinyl resin composition of the present invention can contain various fillers, pigments, and the like. Fillers and pigments that can be used include various silicas, calcium carbonate, magnesium carbonate, titanium oxide, iron oxide, and glass fiber. It is also useful as a coating composition for automobiles, glass, etc., a sealing composition, and a surface treatment agent for various inorganic materials.

Next, the present invention will be specifically explained with reference to examples.

Synthesis Example 1 In a 90y xylene solvent heated to 90°C, styrene 30f1 allyl methacrylate 16f1 methyl methacrylate 20y, n-butyl methacrylate 19f1 butyl acrylate 14g, maleic anhydride 4f1 n-dodecyl mercaptan 2y and azobisisobutyl A solution of ronitrile 2y was added dropwise and reacted for 10 hours, and the molecular weight was 8000.
A vinyl polymer containing an allylic unsaturated group was obtained. In the infrared absorption spectrum of this product, absorption due to the carbon-carbon double bond of 1648an-1 and absorption of acid anhydride at 1780an-' were observed. 40 f of solvent is removed from the obtained polymer solution under reduced pressure.

Obtained allylic unsaturated group-containing vinyl copolymer solution 1
6y and 1.5y of methyldimethoxysilane.

A solution of 0.0005 f of chloroplatinic acid dissolved in isopropanol was added and reacted under sealed conditions at 90° C. for 6 hours.

In the infrared absorption spectrum of this product, the absorption of 1648an-' disappeared, and a silyl group-containing vinyl polymer was obtained.

Synthesis Example 2 Styrene a was added to 70F xylene heated to 90℃.
o yl γ-methacryloxypropyltrimethoxysilane 22g, methyl methacrylate 22y1 n-butyl methacrylate 151, butyl acrylate 1gf1 n-dodecylmercaptan 1y, azobisisobutyronitrile 2
A solution containing g was added dropwise and reacted for 10 hours until the molecular weight was 1.
A vinyl resin containing 2,000 silyl groups was obtained.

Synthesis Example 3 In 70f xylene heated to 90°C, 80% styrene was added.
f1γ-methacryloxypropyltrimethoxysilane 2
2 f, methyl methacrylate 52 g, methacrylic acid n-
Butyl 15f1 Butyl acrylate 181, Acrylamide 411 n-Butanol 10f1 A solution of 2 g of azobisin butyronitrile dissolved in 1 g of n-dodecyl mercaptan was added dropwise and reacted for 10 hours until the molecular weight was 12,000.
A silyl group-containing vinyl resin was obtained.

Synthesis Example 4 Styrene 30g was added to 70g of xylene heated to 90°C.
f1 γ-Methacryloxypropyltrimethoxysilane 22f1 Methyl methacrylate 22f1 Methacrylic acid n-
Butyl 18f1 Butyl acrylate 18f1 Acrylamide 4g, Maleic anhydride 2g, n-butanol 10g,
A solution of 2 f azobisisobutyronitrile dissolved in 4 g of n-dodecyl mercaptan was added dropwise and 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 Resin 100 was added to the resin solution obtained in Synthesis Examples 1 to 4 above.
8 parts of a tin compound and amine were added to the mixture, diluted with xylene to a coating viscosity (15 seconds by Ford cup test), applied to the organic coating shown in Table 1, and subjected to the heat treatment shown in Table 1. The adhesion was measured after 1 day. 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 Example 1.
It is also shown in Table 1 as ~5.

(Note) *I DTL: Dibutyltin dilaurate *2
A-1120: NH2CH2 manufactured by Nippon Unicar
CH2■42420H28i (O48)8*8 S
tannONJ-IF: Manufactured by Sankyoki ■ (n-C5Ht
7) 2 an (OCOCH<HCOOR) 2 and (n
08H17)2Sn(SCH2Cα)OBH12-i
so), a mixture (where R: C4 to Cl2) of 7
Reactant reacted at 0°C for 8 hours *58 tann: NZ-20 (n-OsHx7)2Sn=8 manufactured by Sankyoki ■ Reactant reacted for 3 hours *7 5 tann: F-9B manufactured by Sankyoki ■ (n -c4H9)28n(SCH2cH2000R)
2 (However, R: 04~Cl2) *8 A-1120'' Made by Nippon Unicar (Go3 Shirereri U~-to).

Partial hydrolyzate of A-1120 and ethyl silicate *908nSi: Reaction product made by reacting 28nO (n-OsHx7) manufactured by Sankyoki ■ and ethyl silicate 40 at 170°C for 4 hours (=, 7 pieces, t) "1 Manufactured by "°"-1 *10 A-187 A reaction product made by reacting A-187 and ethylenediamine at 70°C for 8 hours.

Claims (6)

[Claims] (1) (A) The main chain consists essentially of a vinyl polymer,
A silyl group-containing vinyl resin having at least one silicon group in one molecule bonded to a hydrolyzable group at the terminal or side chain, (B) a tin compound, and (C) at least one hydrate in one molecule. A coating composition containing as an active ingredient one or a mixture of two or more amines having a silicon group bonded to a decomposable group, and the above (A), (B), and (C). (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.