JPH0368894B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing aminosilane-modified resins. The novel aminosilane modified resin according to the present invention is
It is useful as a base resin for paints, adhesives, sealants, potting agents, etc., and when blended with other resins, it is useful as a crosslinking agent or adhesion imparting agent. Methods for introducing hydrolyzable silyl groups into various organic polymers include (1) a method in which an allyl-containing polymer and a hydrosilane compound are subjected to a hydrosilylation reaction in the presence of a platinum catalyst, (2) a method in which a hydrolyzable silyl group-containing monomer is Both)
(3) A method of reacting an epoxide-containing polymer with an aminosilane, and (4) a method of condensation reaction of a hydroxyl group-containing polymer and a silane compound containing a hydrolyzable group. However, with methods (1) and (2), it is difficult to obtain a cured product with good adhesion to organic substances, with method (3), the cured product has poor flexibility, and with method (4), the cured product has poor adhesion to organic substances. Because of the poor chemical resistance and hydrolysis resistance of the hydrolyzable silyl group-containing resin, it has not been possible to obtain a cured product of a hydrolyzable silyl group-containing resin with a good balance of solvent resistance, adhesion to organic substances, and flexibility. As a result of intensive research aimed at improving the above-mentioned physical properties, the present inventors found that a compound containing a (meth)acryloyl group (methacryloyl group, or acryloyl group) and an aminosilane compound were mixed under substantially anhydrous conditions with Michael It has been found that the compound obtained by addition is effective in improving the above physical properties. In other words, the novel aminosilane-modified resin of the present invention, either alone or by blending with various resins, has good adhesion to organic substances, solvent resistance, and the selection of a compound containing a (meth)acryloyl group. It was discovered that the material has good flexibility, leading to the present invention. That is, the present invention provides a compound (A) having a number average molecular weight of 100 to 100,000 and containing at least one acryloyl group or methacryloyl group in one molecule,
It is shown by the following formula (In the formula _,
~10 alkyl group, aryl group, or aralkyl group, and _R2 represents a divalent alkyl group, aryl group, or aralkyl group having 1 to 10 carbon atoms. n is 1~
An integer of 3, m represents an integer of 1 to 10. ) The aminosilane compound (B) is substantially used in a ratio of 0.2 equivalent or more of the primary amino group contained in the above compound (B) to 1 equivalent of the (meth)acryloyl group contained in the above compound (A). This article describes a novel method for producing aminosilane-modified resins, which is characterized by carrying out the reaction under anhydrous conditions. Typical examples of the (meth)acryloyl group-containing compound (A) used in the present invention are methyl (meth)acrylate, butyl (meth)acrylate, and γ-
Monofunctional (meth)acrylates such as (meth)acryloxypropyltrimethoxysilane; polyfunctional (meth)acrylates such as ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate; ethylene glycol, propylene glycol, glycerin , polyester (meth)acrylate () obtained by co-condensation of a polyfunctional alcohol such as trimethylolpropane with a polyfunctional dibasic acid such as phthalic acid or trimethic acid, and (meth)acrylic acid (for example, Toagosei Chemical Industry Co., Ltd.) Made by Aronx N6100, M6200,
M6400X, M6420X, M-6300, M-7100, M-
8030, M-8100, etc.); ε-caprolactone 2
- Polyester (meth)acrylate () obtained by ring-opening polymerization using an organic titanate catalyst in the presence of a hydroxyl group-containing (meth)acrylate such as hydroxyethyl (meth)acrylate (for example, Plaxel FM manufactured by Daicel Chemical Industries, Ltd.) 1,
FM-4, FM-8, FA-1, FA-4, FA-8
); polyfunctional alcohols such as ethylene glycol, trimethylolpropane, polyester polyols, polyether polyols, and tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, hexamethylene diisocyanate,
isophorone diisocyanate, A polyurethane (meth)acrylate obtained by adding a hydroxyl group-containing (meth)acrylate such as 2-hydroxy (meth)acrylate to an isocyanate group-containing polyurethane resin obtained by polyaddition of a polyfunctional isocyanate such as Aronx M-1100, M-1200 manufactured by Kogyo Co., Ltd. and Viscoat 813, 823 manufactured by Osaka Organic Chemical Industry Co., Ltd.); Silanol group-containing polysiloxane and hydrolyzable silyl groups such as γ-(meth)acryloxypropyltrimethoxysilane Silicone (meth)acrylate obtained by condensation of containing (meth)acrylate; Epoxy (meth)acrylate obtained by condensing epoxy resin such as Epicote 828 (manufactured by Ciel) with (meth)acrylic acid or hydroxyl group-containing (meth)acrylate
Acrylate; polyether (meth)acrylate obtained by condensation of polyethylene glycol, polypropylene glycol, and (meth)acrylic acid; hydroxyl group of polyester (meth)acrylate () tolylene diisocyanate, diphenylmethane 4,4'-diisocyanate, hexa methylene diisocyanate, isophorone diisocyanate, Examples include polyester urethane (meth)acrylates obtained by reacting polyfunctional isocyanates such as. Moreover, the compound (B) used in the present invention is γ-
Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxysilane,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si
(OMe) ₃ ,
H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si
Examples include aminosilane compounds such as (OEt) ₃ . To obtain the desired aminosilane-modified resin from the (meth)acryloyl group-containing compound (A) and the aminosilane compound (B), (A) and (B) are mixed under substantially anhydrous conditions at room temperature to 200°C. All you have to do is mix and react at a certain temperature. The present invention is characterized in that an aminosilane-modified resin is obtained by an addition reaction between the (meth)acryloyl group of compound (A) and the amino group of compound (B).
When it is desired to selectively react only the primary amine, it is preferable to add compound (A) to compound (B). Further, in order to suppress radical polymerization of the (meth)acryloyl group of compound (A) during the reaction, it is preferable to add a polymerization inhibitor such as hydroquinone, benzoquinone, phenothiazine, or methoquinone before the reaction. As the polymerization inhibitor, methoquinone is preferred from the viewpoint of coloring properties. Although this reaction proceeds without a catalyst, catalysts that promote the addition reaction, such as dimethyl bunzylamine,
Tertiary amines such as 2,4,6-tris(dimethylaminoethyl)phenol, quaternary ammonium salts such as benzyltrimethylammonium hydroxide, and alkalis such as sodium methoxide can also be used. In addition, the ratio of reaction components (A) and (B) in this reaction is 1 (meth)acryloyl group contained in compound (A)
The primary amino group contained in compound (B) is
0.2 to 20 equivalents, preferably 0.8 to 10 equivalents. When this equivalent ratio is less than 0.2, the effects of the present invention, such as the effect of improving adhesion to organic substances, are small.
Moreover, even if the amount exceeds 20 equivalents, there will be no problem in terms of synthesis or the properties of the obtained resin, but it will be disadvantageous from a cost perspective. Although it is not necessary to use a solvent in carrying out this reaction, a solvent may be used if it is easier to carry out the reaction depending on the properties of the reaction components.
Such solvents include toluene, xylene, butyl acetate, and the like. To carry out this reaction, it is necessary to remove water in the reaction system in advance, and in this sense, if an aromatic solvent such as toluene is used, water can be removed in advance by azeotropic distillation. is possible. The aminosilane-modified resin obtained in this way has a hydrolyzable silyl group, and can be used as a base resin for paints, adhesives, sealants, potting agents, etc., or can be blended with other resins to act as a crosslinking agent or to impart adhesion. It is useful as a drug. In curing the novel aminosilane-modified resin of the present invention, curing catalysts can be used, including alkyl titanates; acidic compounds such as phosphoric acid, p-toluenesulfonic acid, and acidic phosphoric acid ester; ethylenediamine, tetraethylene; Amines such as pentamine; organic tin compounds such as dibutyltin dilaurate and dibutyltin malate; basic compounds such as sodium hydroxide and sodium methylate, and the like are used. The amount of these curing catalysts used is based on the aminosilane modified resin.
It is used in an amount of 0.005 to 10 parts by weight, preferably 0.1 to 8 parts by weight. The present invention will be specifically explained below using examples.
The numbers in the examples are by weight. Example 1 62 parts (1 mole) of ethylene glycol and 202 g of hexamethylene diisocyanate were placed in a reactor equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a cooling tube.
(1.2 mol), 40 parts of butyl acetate were charged, stirred and reacted at 120°C for 6 hours under a nitrogen atmosphere, then the temperature was lowered to 80°C, and 1 part of methoquinone, 40 parts of 2-hydroxyethyl acrylate, and 100 parts of butyl acetate were added. plus 80
The mixture was reacted at ℃ for 2 hours to obtain an acryloyl group-containing polyurethane resin. Next, after lowering the temperature to 30°C, 45 parts of γ-aminopropyltriethoxysilane and 93 parts of butyl acetate were added.
The mixture was reacted at 30°C for 2 hours, and then at 60°C for 2 hours to obtain an aminosilane-modified resin solution (solid content concentration: 60%). In the infrared absorption spectrum of the obtained resin, absorption at 1630 and 1410 cm ^-1 due to acryloyl groups completely disappeared, and the number average molecular weight by GPC method was 1900. Example 2 Hydroxyethyl acrylate was placed in a reactor equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a cooling tube.
40 parts (0.4 mol), ε-caprolactone 228 parts (2
mol), 0.05 part of tetrabutyl titanate, and 1 part of methoquinone were reacted at 120°C in a nitrogen atmosphere for 12 hours to form hydroxyethyl acrylate and ε-
A polycaprolactone containing acryloyl at one end and having a molar ratio of caprolactone of 1:5 was obtained. Furthermore, 33.6 parts (0.2 mol) of hexamethylene diisocyanate and 100 parts of xylene were added and reacted at 80°C for 2 hours to obtain polycaprolactone containing acroyl at both ends. N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane after cooling to 20°C.
Add 88.4 parts (0.4 mol) and 160 parts of xylene and heat at 30°C.
After reacting for 2 hours at 60° C., an aminosilane modified resin solution (solid content concentration 60%) was obtained. In the infrared absorption spectrum of the obtained resin, the absorption of acryloyl groups at 1630 cm -1 and 1410 cm ^-1 completely disappeared, and the number average molecular weight by GPC method was 2000. Example 3 340 parts of Aronix M6200 (bifunctional oligoester acrylate manufactured by Toagosei Chemical; acryloyl group equivalent: 340), 373 parts of xylene, and γ-aminopropyl were placed in a reactor equipped with a stirring device, a thermometer, a nitrogen introduction tube, and a cooling tube. Prepared 220 parts of triethoxysilane,
The reaction was carried out at 30°C for 2 hours in a nitrogen atmosphere and then at 60°C for 2 hours to obtain an aminosilane modified resin solution (solid content concentration 60%). In the obtained resin, the infrared absorption of acryloyl groups of 1630 cm -1 and 1410 cm ^-1 completely disappeared, and the number average molecular weight by GPC method was 2000. 0.5 part of dibutyltin dilaurate was added to 100 parts of the aminosilane-modified resin solution obtained in Examples 1 to 3, diluted with xylene to a coating viscosity, and then mixed with Amirak (amino alkyd resin paint manufactured by Kansai Paint).
Physical properties after 7 days at room temperature after spray painting on a painted polished mild steel plate (Amilac white was painted on a degreased polished mild steel plate and baked at 130℃ for 30 minutes) and on a polyethylene sheet to a film thickness of 60 μm. I took measurements. 【table】

Claims (1)

[Scope of Claims] 1 (A) A compound having a number average molecular weight of 100 to 100,000 and containing at least one acryloyl group or methacryloyl group in one molecule, and (B) the following formula: (In the formula, X is a hydrolyzable group selected from the group consisting of halogen, alkoxy, acyloxy, ketoximate, amino, acid amide, aminooxy, mercapto, and alkenyloxy groups, and R ₁ is an alkyl group having 1 to 10 carbon atoms. , represents an aryl group or an aralkyl group, and R ₂ represents a divalent alkyl group having 1 to 10 carbon atoms, an aryl group, or an aralkyl group. n represents an integer of 1 to 3, and m represents an integer of 1 to 10. ) in a proportion of 0.2 or more equivalents of the primary amino group contained in the above (B) compound per 1 equivalent of the acryloyl group or methacryloyl group contained in the above (A) compound. A method for producing a novel aminosilane-modified resin characterized by reacting it under anhydrous conditions. 2. The method for producing an aminosilane-modified resin according to claim 1, wherein the main chain of the compound (A) is mainly polyester. 3. The method for producing an aminosilane-modified resin according to claim 1, wherein the main chain of the compound (A) is mainly polyurethane. 4. The method for producing an aminosilane-modified resin according to claim 1, wherein the main chain of the compound (A) is mainly silicone. 5. The method for producing an aminosilane-modified resin according to claim 1, wherein the compound (B) is γ-aminopropyltrimethoxysilane. 6. The method for producing an aminosilane-modified resin according to claim 1, wherein the compound (B) is γ-aminopropyltriethoxysilane. 7. The method for producing an aminosilane-modified resin according to claim 1, wherein the compound (B) is N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane.