JPH01135872A - Cold-setting composition - Google Patents

Abstract

PURPOSE:To obtain the present composition for extended-type top-coating material, having remarkably improved stain-resistance without lowering the elongation and weather-resistance of the coating film, by compounding a specific amount of a specific silane compound, etc., to a vinyl copolymer containing hydrolyzable silyl group. CONSTITUTION:(A) 100pts.wt. of a silyl group-containing vinyl polymer having main chain composed essentially of a vinyl polymer chain and >=1 Si atom bonded to a hydrolyzable group at the terminal or side chain per one molecule is compounded with (B) 0.1-100pts.wt., preferably 0.5-20pts.wt. of a silane compound expressed by formula I-formula III (R<1> is 1-10C univalent alkyl, aralkyl, etc.; X is halogen, hydroxy, etc.; R<2> is 3-200C univalent alkyl, preferably 10-20C trimethoxysilane) and (C) 0-20pts.wt., preferably 0.01-10pts.wt. of a curing catalyst (e.g., dibutyltin dilaurate).

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a room temperature curable resin composition with improved stain resistance. More specifically, the present invention relates to a resin composite acid product for an elongated top coat material that uses a vinyl copolymer having a hydrolyzable silyl group and has improved stain resistance.

(Problems with conventional technology) Hydrolyzable silyl group-containing vinyl resin forms a dense network structure due to moisture in the air at room temperature, resulting in high gloss, weather resistance, discoloration resistance, and adhesion to inorganic substrates. It is known to be an excellent resin.

On the other hand, in the field of paints, there is active development of elongated top coat paints that follow cracks in concrete and other substrates and provide waterproofness and aesthetic appeal. However, in order to ensure the elongation of the paint film, it was necessary to use a flexible resin composition, and as a result, it was not always satisfactory in terms of stain resistance against exhaust gas, dung, etc. .

(Means for Solving the Problems) As a result of intensive studies in response to the strong demands of the market, the present inventors have found that the following silane compound is added to a hydrolyzable silyl group-containing vinyl copolymer. It was discovered that the stain resistance could be significantly improved without reducing the elongation and weather resistance of the coating film, leading to the present invention.

That is, the present invention provides: (4) a silyl group-containing vinyl polymer whose main chain is substantially composed of a vinyl polymer chain and which has at least one silicon atom in each molecule bonded to a hydrolyzable group at the terminal or side chain; Polymer 100 parts by weight (B) Formula % Formula % () (In the formula, R1 is a hydrocarbon group selected from a monovalent alkyl group having 1 to 10 carbon atoms, an aralkyl group, and an aryl group, and X is a halogen, hydroxy, A group selected from alkoxy, acyloxy, aminoxy, phenoxy, thioalkoxy, amino, ketoximate, and alkenyloxy groups, R2 represents a monovalent alkyl group having 3 to 200 carbon atoms, and n is 0 to
Indicates an integer of 2. ) 0.1 to 100 parts by weight of a silane compound represented by
C) A room temperature curable resin composition containing 0 to 20 parts by weight of a curing catalyst.

(5) The silyl group-containing vinyl polymer is obtained by copolymerizing a vinyl monomer and a hydrolyzable silyl group-containing monomer, and contains some urethane bonds, urea bonds, or siloxane bonds in the main chain or side chain. But that's fine. On this occasion,
The vinyl monomer used is not particularly limited, and includes methyl (meth)acrylate, ethyl (meth)acrylate,
Butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, trifluoroethyl (meth)acrylate, pentafluoropropyl (meth)acrylate, polycarbonate Acid (maleic acid, fumaric acid, itaconic acid, etc.) with 1 to 20 carbon atoms
esters of unsaturated carboxylic acids such as diesters or half esters with linear or branched alcohols; aromatic hydrocarbons such as styrene, α-methylstyrene, chlorostyrene, styrene sulfonic acid, 4-hydroxystyrene, vinyltoluene, etc. Vinyl compounds; vinyl esters and allyl compounds such as vinyl acetate, vinyl propionate, and diallyl phthalate; vinyl compounds containing nitrile groups such as (meth)crylonitrile; vinyl compounds containing epoxy groups such as glycidyl (meth)acrylate; dimethylaminoethyl ( Vinyl compounds containing amino groups such as meth)acrylate, diethylaminoethyl (meth)acrylate, vinylpyridine, and aminoethyl vinyl ether; (meth)acrylamide, itaconic acid diamide, α-ethyl (meth)acrylamide, crotonamide, maleic acid diamide, fumar Vinyl compounds containing amide groups such as acid diamide, N-vinylpyrrolidone, N-butoxymethyl (meth)acrylamide, N,N-dimethylacrylamide, N-methylacrylamide, acryloylmorpholine; 2-hydroxyethyl (meth)acrylate, 2- Hydroxypyl (meth)acrylate, 2-hydroxyethyl vinyl ether,
N-methylol(meth)crylamide, Aronix 57
00 (Toagosei ■), Placel FA-1, P
laccel FA-4, laccel FM-1,
Hydroxyl group-containing vinyl compounds such as Placcel FM-4 (manufactured by Daicel Chemical ■); (meth)acrylic acid, maleic acid, fumaric acid, itaconic acid and their salts (alkali metal salts, ammonium salts, amine salts, etc.), maleic anhydride Unsaturated carboxylic acids such as acids, acid anhydrides, or salts thereof; other vinyl compounds such as vinyl methyl ether, vinylidene chloride, chloroprene, propylene, butadiene, isoprene, maleimide, N-vinylimidazole, vinyl sulfonic acid, etc. can be mentioned.

Specifically, hydrolyzable silyl group-containing monomers include CH2=CHBi(OOHa)B, CCH2=CH81
cI, (J-I3 CH2=CHOOO(CFIs+)3Si(OCHa)
2, CH2=OHOOO(CH2)351(OCHa)
a, EI3 CH2=CHCOO(OR2)a 8 iC12,0)
+2=cHOOo(CH2)3Si01B, (EH
8 0H2=O(OHa)000(CH2)3Si(OCH
a) 2.0H2=C(CHa)000(CI(2)3S
i(OCHa)3, H3 0H2=0(CHa)Coo(CH2)38i 012
, CH2=C(CJ(a)C00(Of(2)381
C1a, 0 0? Ha II ll 0H2=C(CH3)000(CH2)38i(002
H5)3, fI3 CHz=C(CHa)COO(CH2)B8i (OC
21-I5)2, etc.

Regarding the production method of copolymers of these hydrolyzable silyl group-containing monomers and vinyl monomers, for example,
86395, 57-36109, 58-15781
0 etc. may be used. Particularly preferred is solution polymerization using an azo radical initiator such as azobisisobutyronitrile. In addition, n-dodecyl mercaptan, t-dodecyl mercaptan, n-
Butyl mercaptan, γ-mercaptopropyltrimethoxysilane, r-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane,
γ-Mercaptopropylmethyljethoxysilane, (C
HaO)8Si-8-8-8i-(OCHa)
3, (CH30)3S 1-8B S 1(OCHa
) 3 etc. can be used to adjust the molecular weight. In particular, if a chain transfer agent having a hydrolyzable silyl group in the molecule, such as r-mercaptopropyltrimethoxysilane, is used, the hydrolyzable silyl group can be introduced at the end of the silyl group-containing vinyl polymer.

Polymerization solvents include hydrocarbons (toluene, xylene, n-hexane, cyclohexane, etc.), acetic acid esters (ethyl acetate, butyl acetate, etc.), alcohols (methanol, ethanol, isopropanol, n-butanol, etc.), and ether. The solvent is not particularly limited as long as it is a non-reactive solvent such as ethyl cellosolve, butyl cellosolve, cellosolve acetate, etc., ketones (methyl ethyl ketone, ethyl acetoacetate, acetylacetone, diacetone alcohol, methyl isobutyl ketone, acetone, etc.).

The silane compound as the component ω) is represented by the formula (1), (If) or a surface, and the alkyl group represented by R2 in the formula has 3 to 200 carbon atoms, preferably 6 to 200 carbon atoms, and more preferably.

Preferably, it is 10 to 20, and can be synthesized by the following method.

■ A hydrocarbon compound having a molecular weight of 42 to 3,000 and having an allyl group at one end is prepared by the following formula (wherein R1 is a hydrocarbon group selected from a monovalent alkyl group having 1 to 10 carbon atoms, an aralkyl group, and an aryl group). , X is a group selected from halogen, hydroxy, alkoxy, acyloxy, aminoxy, phenoxy, thioalkoxy, amino, ketoximate, alkenyloxy group, n is 0
A method for obtaining a silane compound (1) by hydrosilylation with a hydrosilane compound represented by (representing an integer of ~2).

(2) A method in which an allyl group is introduced at one end of an alcohol having a hydroxyl group at one end and a molecular weight of 42 to 3,000 by Williamson's ether synthesis method, and then hydrosilylated with the above hydrosilane to obtain the silane compound (1).

(2) A method of obtaining a silane compound (2) by capping an alcohol having a molecular weight of 42 to 3,000 with an isocyanatosilane having a hydroxyl group at one end.

etc.

The hydrosilylation reaction between an allyl group and a hydrosilane compound is carried out at a temperature of 50 to 150°C using a group II transition metal complex compound selected from platinum, rhodium, cobalt, palladium, and nickel as a catalyst, and the reaction time is 1. ~
It progresses quantitatively in 4 hours.

The reaction between hydroxyl groups and isocyanatosilanes can be carried out with or without a catalyst, but if you want the addition reaction to proceed quickly, use organic tin compounds such as dibutyltin dilaurate or tin octylate, dimethylbenzylamine, or triethylamine. Tertiary amine compounds such as the following can be used.

The reaction temperature is 50 to 150°C, and the reaction is monitored by the absorption of NCO in the infrared absorption spectrum at 2270 cm1.

Examples of hydrocarbon compounds having an allyl group at one end include 1-propene, 1-pentene, 1-octene, 1-decene, 1-tetradecene, 1-hexadecene,
Examples include 1-octadecene.

Alcohols having a hydroxyl group at one end include 1-propanol, 1-pentanol, 1-octatool, 1
-decanol, 1-tetradecanonyl, 1-hexadecanol, 1-octadecanol and the like.

Specific examples of hydrosilane compounds include trichlorosilane, methyldichlorosilane, dimethylchlorosilane,
Halogenated silanes such as phenyldichlorosilane; alkoxysilanes such as trimethoxysilane, triethoxysilane, methyldimethoxysilane, methyljethoxysilane, phenyldimethoxysilane; triacetoxysilane, methyldiacetoxysilane, phenyl Acyloxysilanes such as diacetoxysilane include dimethylethylmethyloxime silane; triaminoxysilane, methyldiaminoxysilane, methyldiaminosilane, and the like.

Specific examples of the isocyanatosilane include γ-isocyanate, propyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, and the like.

(Specifically, as the curing catalyst of component 0, organic tin compounds such as dibutyltin dilaurate, dibutyltin simalate, dioctyltin dilaurate, dioctyltin simalate, tin octylate; phosphoric acid, monomethyl phosphate, monoethyl phosphate, monobutyl Phosphate, monooctyl phosphate, monodecyl phosphate, dimethyl phosphate, diethyl phosphate,
Phosphoric acid or phosphoric acid ester such as dibutyl phosphate, dioctyl phosphate, didecyl phosphate; propylene oxide, butylene oxide, cyclohexene oxide, glycidyl methacrylate, glycidol, allyl glycidyl ether, γ-glycidoxypropyltrimethoxysilane, r-glyside Xyprobyltriethoxysilane, γ-glycidoxypropylmethyldimecardura E (manufactured by Yuka Shell), Epicote 8
28 (manufactured by Yuka Shell), Epicor) 1001 (manufactured by Yuka Shell), addition reaction products of epoxy compounds and phosphoric acid and/or monoacidic phosphoric acid esters; alkyl titanates; organoaluminum; maleic acid para Acidic compounds such as toluenesulfonic acid; hexylamine, di-2-ethylhexylamine, N,N-dimethyldodecylamine,
Examples include amines such as dodecylamine; alkaline compounds such as sodium hydroxide and potassium hydroxide.

Although curing can proceed without addition of these curing catalysts (C), when it is desired to proceed with curing quickly, they can be used alone or in combination.

The mixing ratio of the above-mentioned hydrolyzable silyl group-containing vinyl resin, the silane compound (B), and the curing catalyst (O) is (A):(B):(C)=100:0.
1-100:0-20, preferably (A:■):(C)
= 1 o o: 0.5-20: 0.01-10. If component B is less than 0.1 part by weight, no improvement in stain resistance is observed, and if it exceeds 100 parts by weight, the compatibility decreases and the coating film may be rough, which is not preferable.

A dehydrating agent may or may not be used in the composition of the present invention, but if long-term stability is to be ensured, or
It is preferable to use a dehydrating agent in order to ensure stability under conditions where the composition is divided into containers and used repeatedly. As a dehydrating agent, specifically, methyl orthoformate, ethyl orthoformate, methyl orthoacetate, ethyl orthoacetate, methyltrimethoxysilane, γ-
There are hydrolyzable ester compounds such as methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, methyl silicate, and ethyl silicate. These hydrosieving ester compounds may be added in advance to the reaction system before the polymerization reaction of the silyl group-containing vinyl copolymer (A), added to the reaction system during polymerization, or added after the polymerization. Good too.

The composition of the present invention may contain additives such as various pigments, ultraviolet absorbers, anti-settling agents, leveling agents, etc. depending on the purpose; cellulose such as nitrocellulose, cellulose acetate butyrate; alkyd resins, acrylic resins, vinyl chloride, etc. Resins such as chlorinated polypropylene, chlorinated rubber, and polyvinyl butyral can be added.

(Example) Next, examples of the present invention will be described.

Synthesis Example 1 (Synthesis A-1 of silyl group-containing vinyl polymer) Xylene 87077 was charged into a reactor equipped with a stirring device, a thermometer, a nitrogen introduction tube, a dropping funnel, and a cooling tube, and 110
Heat to ℃. Butyl acrylate 511F1 Methyl methacrylate 4881. A solution containing 10 g of γ-methacryloxypropyltrimethoxysilane 3511N-methylolacrylamide and 5 y of azobisisobutyronitrile was continuously added to the reactor for 3 hours. After completing the monomer addition, separately prepared azobisisobutyronitrile I
A solution of 11 toluene 200J7 was added for another 1 hour, and after another 1 hour, polymerization was carried out to obtain a silyl group-containing vinyl resin (A
-1) was obtained.

The nonvolatile content concentration of the obtained silyl group-containing vinyl resin solution was 61%. The number average molecular weight determined by GPC method was 28,000.

Synthesis Example 2 (Synthesis A-2 of silyl group-containing vinyl polymer) 37 (l) of xylene was charged into a reactor equipped with a stirring device, a thermometer, a nitrogen introduction pipe, a dropping funnel, and a cooling pipe, and the temperature was heated to 110°C.
Heat to. Butyl acrylate 485, F, methyl methacrylate 389Ii1 γ-methacryloxypropyltrimethoxysilane 11711 A solution containing N-methylolacrylamide 9I and azobisisobutyronitrile 3I was continuously added to the reactor for 3 hours. After adding the monomer, add azobisisobutyronitrile 0, which was prepared separately.
．． 5,91) A solution of toluene 200.9 was added for another 1 hour, and polymerization was carried out for another 1 hour to obtain a silyl group-containing vinyl resin (A-2).

The nonvolatile content concentration of the obtained silyl group-containing vinyl resin solution was 60%. The number average molecular weight determined by the GPO method was 26,000.

Synthesis Example 3 (Synthesis of silane compound B-1) In a pressure container,
2,521 l of 1-octadecene was charged, and a 10% isopropanol solution of 142 I of trichlorosilane and 0.5,9 of chloroplatinic acid were added under a nitrogen atmosphere, and the mixture was reacted at 90°C for 4 hours. After the reaction, an infrared absorption spectrum was measured, and it was found that the infrared absorption of the allyl group at 1640 cm had disappeared. Thereafter, unreacted trichlorosilane was distilled off at 100° C. under reduced pressure (5 Torr). Furthermore, 192I methanol was added, and the generated hydrogen chloride gas was removed under reduced pressure.
Furthermore, 100 I of methyl orthoformate was added and the transesterification proceeded at 60°C for 2 hours, after which the volatiles were distilled off under reduced pressure (5 Torr).

Synthesis Example 4 (Synthesis of silane compound B-2) 1 in a pressure container
- Undecene was charged at 1541, and a 10π isopropanol solution of 142 I trichlorosilane and 0.5,9 chloroplatinic acid was added under a nitrogen atmosphere, and the mixture was reacted at 90° C. for 4 hours. After the reaction, an infrared absorption spectrum was measured, and it was found that the infrared absorption of the allyl group at 1640 cm had disappeared. Thereafter, unreacted trichlorosilane was distilled off at 100° C. under reduced pressure (5 Torr). Furthermore, 192Ii methanol was added, and the generated hydrogen chloride gas was removed under reduced pressure.
Furthermore, 100 I of methyl orthoformate was added, and the transesterification was carried out at 60° for 2 hours, after which volatile substances were distilled off under reduced pressure (5 Torr).

Synthesis Example 5 (Synthesis of silane compound B-3) In a pressure container,
1-Undecene was charged with 154I, and 1211 of methyldichlorosilane and 0.5.9 of a 10% isopropanol solution of chloroplatinic acid were added under a nitrogen atmosphere, and the mixture was heated at 90°C for 4 hours.
Allowed time to react. After the reaction, an infrared absorption spectrum was measured, and it was found that the infrared absorption of the allyl group at 1640 cm −1 had disappeared. Thereafter, unreacted methyldichlorosilane was distilled off at 100° C. under reduced pressure (5 Torr). 12 more
8 g of methanol was added, the generated hydrogen chloride gas was removed under reduced pressure, and 100 I of methyl orthoformate was added.
After proceeding with transesterification for 2 hours at
) to remove volatiles.

(Preparation of white enamel) Titanium oxide (manufactured by Gohara Sangyo, OR-90) 26. F.

17.9 g of xylene was added and dispersion was performed for 1 hour using a paint shaker to obtain white enamel.

Examples 1-6, Comparative Examples 1-2 Silyl group-containing vinyl resin (A) obtained in Synthesis Example 1.2
white enamel paint, silane compound (J3) obtained in Synthesis Examples 3 to 5, curing catalyst of commercially available organotin compound TN801 (manufactured by Sakai Chemical Co., Ltd., dioctyltin malate) (with O as the first
The compositions shown in the table (parts by weight) were blended and further diluted with xylene to a coating viscosity to form a paint.

The white enamel paints of Examples and Comparative Examples were spray-painted onto a degreased aluminum plate by a conventional method, and then left at room temperature for one day to conduct a stain resistance test.

To test stain resistance, pour a 2π water slurry solution of carbon for paint onto the paint film, leave it at room temperature overnight, press it with adhesive tape to remove Yuto carbon, and check the degree of carbon stains on the paint film. Evaluation was made using a gray scale for contamination (based on JIS-LO805).

For elongation, a film was prepared to have a dry film thickness of 30 μm, cured and dried at room temperature for 7 days, and the resulting coating film was measured at room temperature at a tensile speed of 200 mm/min.

As can be seen from Table 1, the stain resistance of paints made from the compositions of the present invention is greatly improved.

Claims (2)

[Claims] (1) (A) A silyl group-containing vinyl polymer whose main chain consists essentially of a vinyl polymer chain and which has at least one silicon atom in each molecule bonded to a hydrolyzable group at the terminal or side chain. 100 parts by weight (B) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) (In the formula , R^1 is a monovalent alkyl group having 1 to 10 carbon atoms,
A hydrocarbon group selected from an aralkyl group and an aryl group; represents a monovalent alkyl group, and n represents an integer of 0 to 2. ) A room temperature curable composition containing 0.1 to 100 parts by weight of a silane compound represented by the following formula and 0 to 20 parts by weight of a curing catalyst (C). (2) R^2 of the silane compound (B) has 10 to 20 carbon atoms
The composition according to claim 1, which is trimethoxysilane.