JPS63150344A - Aqueous composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention is directed to the formation of an organic-inorganic composite film comprising a vinyl polymer having a specific structure and an inorganic sol whose particle surface is easily charged to glass. It is an aqueous composition that has excellent film-forming properties and forms a film with good adhesion, water resistance, chemical resistance, heat resistance, and durability on various substrates, and can be used as an antistatic treatment agent for the surface of substances, and as a protective coating. The present invention relates to an organic-inorganic composite aqueous composition useful as a hard coating agent, hard coating agent, or adhesive.

PRIOR ART AND PROBLEMS TO BE SOLVED BY THE INVENTION In recent years, sols of various metal hydroxides or oxides (hereinafter referred to as gold J) have been developed.
12 compound sol. ) has bottomed out.

Taking advantage of the functions and performance of each sol, attempts have been made to apply it alone or in combination with other components to various coating agents and adhesives. Among various types of sols, for example, titanium oxide-based sols, where the surface of the sol particles is easily charged to the glass, have good adhesion to various substrates and form a film with a large antistatic effect. Although it has advantages, it has the disadvantage that the film is not flexible and does not have sufficient water resistance or chemical resistance. It is known that organic polymer compounds are used in combination as a means to improve the flexibility of films obtained from such metal oxide-based sols. Because it has no or only weak affinity with metal oxide sols, films obtained from compositions consisting of such organic polymer compounds and metal oxide sols have poor flexibility. Even if it has been improved, it still has drawbacks such as poor water resistance and chemical resistance.

The purpose of the present invention is to improve the affinity between the organic polymer compound and the metal oxide sol, thereby forming a tough film in which the organic polymer compound and the metal oxide sol are firmly connected to each other. The objective is to develop a new composition that can exhibit the characteristics of both organic and inorganic components.

The present inventors have developed an aqueous composition comprising an aqueous dispersion of a vinyl polymer having a hydrolyzable silyl group in the molecule and a sol of a specific metal hydroxide or oxide whose particle surface tends to be positively charged. However, the present invention was developed based on the discovery that it forms a film that is tough and has excellent water resistance and chemical resistance, and also has excellent layering properties on various substrates and antistatic properties.

That is, in the present invention, the general formula % (R'liH or CH, A is a divalent organic group, R2 is an alkyl group having 1 to 18 carbon atoms, and X is a halogen atom.

It represents a hydrolyzable group selected from an alkoxy group and an acetyl group, and an integer from a11 to a13. ) Aqueous dispersion (I) of a vinyl polymer having at least one structural unit represented by (hereinafter referred to as aqueous dispersion (1)) and element symbols Mg, Cm, Ba, Sr, At%
T's v*Mn, F@l % Co, N
i, Ga, Zr, Nb, In
%Sn.

A sol (...) of a hydroxide or oxide of one or more metals selected from Ce, Ta, and W (hereinafter referred to as sol (If))
It is written as ).

Aqueous dispersion/It which is the first component of the aqueous composition of the present invention
The vinyl polymer having at least one structural unit represented by the above general formula contained in (1) on average can be produced by at least two methods. The first method consists of an organosilicon monomer having in its molecule at least one polymerizable unsaturated group and at least one hydrolyzable group directly bonded to a silicon atom, and other polymerizable monomers ( In the second method, a silane compound C) having a hydrolyzable group directly bonded to a silicon atom is copolymerized with a polymerizable monomer having a group capable of reacting with the silane compound (C). ) and other polymerizable monomers (copolymers).

Examples of the organosilicon monomer used in the first method for producing the vinyl polymer of the present invention include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriptoxysilane, and vinyltris(β-methoxyethoxy). Silane, allyltriethoxysilane, trimethoxysilylglopylarylamine, r-(meth)acryloxyprobyltrimethodisilane, γ-(meth)acryloxyglobiltriethoxysilane, r-(meth)acryloxyglobil Methyldimethoxysilane.

γ-(meth)acryloxyglobil methyldiethoxysilane, γ-(meth)acryloxyglobil tris(β-
methoxyethoxy)silane, N-B-(N-vinylbenzylamino)ethyl-r-aminoglobiltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, 2-styrylethyltrimethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino)globiltrimethoxysilane, (meth)acryloxyethyldimethyl (3-trimethoxysilylglobil)
Examples include ammonium chloride, vinyl diacetoxysilane, vinyl trichlorosilane, etc., and one type or a mixture of two or more types selected from these groups can be used.

Other polymerizable monomers (B) used in the copolymerization with organosilicon monomer (2) in the present invention include acrylic acid, memethacrylic acid, crotonic acid, itaconic acid, maleic acid,
Unsaturated calgon'rR such as malic acid, maleic acid monoethyl ester, etc.; unsaturated sulfonic acids such as styrene sulfonic acid, sulf-ethyl methacrylate, vinyl sulfonic acid, 2-acrylamido-2-methylpro/4-sulfonic acid; Methyl (meth)acrylate,
(Meth)acrylic acid alkyl esters such as ethyl, propyl, butyl, octyl, lauryl, stearyl ester, etc.; Unsaturated alcohols such as allyl alcohol, croton alcohol, etc.; ethylene glycol, diethylene glycol, furopylene gellicol, 1,3-butylene Vinyl etherified polyhydric alcohols such as glycol, neopentyl glycol, glycerin, -27 taerythritol, etc.; monoester compounds of polyhydric alcohols and (meth)acrylic acid or crotonic acid; unsaturated compounds such as glycidyl (meth)acrylate, etc. Glycidyl ester: Unsaturated glycidyl ether such as (meth)allyl glycidyl ether; ethylene glycol dimethacrylate, polyethylene glycolmic (meth)
Acrylate, 1,6-hexane gelicoldi(meth)
Acrylate, trimethylol noronoya nitori (meth)
Polyunsaturated compounds such as acrylate, allyl acrylate, butadiene, isoprene, chloroglene, dicyclopentadiene, divinylbenzene, diallyl phthalate, etc.; Acrylamide rust conductors such as methylolated (meth)acrylamide, methylolated diacetone acrylamide, etc. ; Unsaturated amine compounds such as aminoethyl (meth)acrylate, trimethylaminoethyl (meth)acrylamide, etc.; Aromatic vinyl compounds such as styrene, vinyltoluene, etc.; Decadenide vinyl such as vinyl fluoride, vinyl chloride, etc. ; Vinylidene rhodanides such as vinylidene chloride; Unsaturated cyanide compounds such as (meth)acrylonitrile, crotonitrile, etc.; Olefinic hydrocarbons such as ethylene, propylene, etc.; Monovalent cardenes such as acetic acid, f-ropionic acid, etc. Vinyl ester compounds of acids; unsaturated amide compounds such as (meth)acrylamide; and the like, and one type or a mixture of two or more types selected from these groups can be used. - As the silane compound (C) used in the present invention, the above-mentioned organosilicon monomer (4) can be used as it is, and for example, aminomethyltriethoxysilane.

Aminoalkylalkoxysilanes such as N-β-aminoethylaminomethyltrimethoxysilane, r-aminopropyltrimethoxysila/, N-(trimethoxysilylpropyl)ethylenediamine, N-(dimethoxymethylsilylpropyl)ethylenediamine; γ- Glycid 9xypropyltrimethoxysilane, γ-glycidoxyglopylmethylnomethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-
Epoxyalkylalkoxysilane such as (3,4-ethyloxycyclohexyl)ethylmethyldimethoxysilane: r-mercagutoglobiltrimethoxysilane, γ
- Mercagtoalkylalkoxysilanes such as mercagutoglobil methyldimethoxysilane; methyl silicate, ethyl silicate.

Tetraalkoxysilanes such as globyl silicate, butyl silicate etc.; Alkyltrialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, methyltrimethoxyethoxysilane, ethyltrimethoxysilane etc.; dimethyldimethoxysilane, dimethyljethoxysilane Dialkyldialkoxysilanes such as; γ-chloropropyltrimethoxysilane;
Halogenated alkyl alkoxysilanes such as 3,3.3-trichloropropyltrimethoxysilane; 1 Alkylacyloxysilanes such as methyltriacetoxysilane, dimethyldiacetoxysilane; hydrosilane compounds such as trimethoxysilane, triethoxysilane, etc.; can be mentioned.

One kind or a mixture of two or more kinds selected from these groups can be used.

The polymerizable monomer (c) having a group capable of reacting with the silane compound (C) used in the second method for producing the vinyl polymer in the present invention has a polymerizable unsaturated group in the molecule,
It has a functional group that can react with at least one silane compound (C), and can be used as a functional group. Examples of the polymerizable monomer (B) include unsaturated carboxylic acids, unsaturated sulfonic acids, and unsaturated alcohols among those exemplified as the polymerizable monomer (B).

Examples include vinyl etherified polyhydric alcohols, monoester compounds of polyhydric alcohols and (meth)acrylic acid or crotonic acid, unsaturated glycidyl esters, unsaturated glycidyl ethers, polyunsaturated compounds, acrylamide derivatives, and unsaturated amine compounds. can be used, and one or more of these can be used.

In the present invention, other polymerizable monomers (8 is the polymerizable monomer (B) other than the polymerizable monomer (6)) used in the copolymerization with the polymerizable monomer (6).

The method for constructing the aqueous dispersion (1) used in the present invention will be explained below. In the first method for producing a vinyl polymer, the organosilicon monomer (4) and the polymerizable monomer (B) are subjected to known methods such as emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization. It can be polymerized by the following method. Among these methods, the polymerization product is directly converted into an aqueous dispersion (1).
Emulsion polymerization is most advantageous in that it can be used as In other polymerization methods, the aqueous dispersion (1) must be obtained through a step of emulsifying the vinyl polymer in water and, if necessary, a step of removing the solvent. In the second method, the polymerizable monomer (1) and the polymerizable monomer (3) are polymerized in the same manner as described above to obtain a copolymer, and the copolymer and the silane compound are combined. (C) to form an aqueous dispersion (1), or the reaction product of the polymerizable monomer ① and the silane compound (C) and the polymerizable monomer odor are polymerized in the same manner as above. Then, an aqueous dispersion (1) of vinyl polymer can be obtained. The reaction conditions for reacting the silane compound C) are not particularly limited, and the reaction may be carried out with stirring at room temperature to 100°C. The aqueous dispersion (1) has the role of improving the film-forming properties of the aqueous composition of the present invention, forming a dense continuous film, and imparting flexibility and elasticity to the film. The vinyl polymer contained in the aqueous dispersion (I) must have on average at least one structural unit represented by the general formula % in its molecule. The amounts of the silicon monomer polymerizable monomer (D) and the silane compound (C) must be determined in consideration of the molecular weight of the vinyl polymer. In the present invention, the molecular weight of the vinyl polymer is 2000 to 1
When producing a vinyl polymer by the first method, the organosilicon monomer (4) is preferably used in an amount of 0.1 to 501i out of all the monomers. It is preferable to do so.

When producing a vinyl polymer by the second method, polymerizable monomer (6) is used in an amount of 0.1 to 50% by weight of all monomers, and the resulting copolymer 1 Preferably, the silane compound C) is used in an amount of 0.1 to 1003 parts by weight based on parts by weight of 'oO. The silyl group having a hydrolyzable group introduced into the side chain of the vinyl polymer acts as an interaction point between the vinyl polymer and the sol (II),
It forms a composite of the two and then works to improve adhesion to various substrates.

If the number of structural units of the above general formula is less than one in one molecule, these effects will not be sufficiently exhibited.

Sol (II), which is the second component of the aqueous composition of the present invention, has elemental symbols Mg, Ca, BalSr%At%Ti,
V.

Mn, F@% 00%Ni, Ca, Zr, Nb
, In%Sn.

Single particle particles made by dispersing fine particles of one or more metal hydroxides or oxides selected from C@, 'f&, and W in water and/or an organic solvent. The diameter is lQQmμ or less. The fine particles contained in the sol (If) may be a hydroxide or oxide of a single metal, or a composite hydroxide or oxide of two or more metals. Furthermore, the fine particles may be either primary particles or secondary particles that are aggregates thereof. Such a sol (II
) can be easily manufactured using a known method. The sol (1) used in the present invention has a strong ionic bond (weak covalent bond) compared to, for example, silica sol, and the particle surface tends to be positively charged. It has good adhesion to the base material and has an excellent antistatic effect. Furthermore, sol (V) also has the role of improving the hardness and heat resistance of the film.

There is no limit to the usage ratio of the aqueous dispersion (1) and sol (If), but in order to fully demonstrate the effects and roles of the aqueous dispersion (1) and sol (II) as described above, (1) / (■)
= 5/95 to 9515 (solid content ratio) is preferable, more preferable! L< is (1) 101) - 1o/9
o to 80/20 <solid content ratio).

Effects of the Invention The aqueous composition of the present invention is an aqueous dispersion (1
) and a specific metal oxide or hydroxide sol (Ql) as components, and the vinyl polymer and the fine particles contained in the sol (...) form a complex due to chemical bonds or strong affinity. It has good film-forming properties and forms a dense continuous film, and the film adheres well to difficult-to-adhere substrates such as polyethylene terephthalate, and has water resistance, chemical resistance, and antistatic properties. It has excellent flexibility and heat resistance, and its flexibility can be changed freely by adjusting the monomer composition of the vinyl polymer and changing the ratio of the aqueous dispersion (1) to the fine particles contained in the sol (II). It can be done.

Therefore, the aqueous composition of the present invention includes plastic molded products,
It can be effectively used as an adhesive for films, textile products, paper, wood, metal, etc., an adhesion improver (base treatment agent), an antistatic treatment agent, a protective coating agent, etc.

EXAMPLES The present invention will be explained in detail with reference to Examples, but the scope of the present invention is not limited to these Examples. Sho 1
In the examples, unless otherwise specified, "regret" means parts by weight and "1 part" means parts by weight, respectively.

Reference Example 1 (Aqueous dispersion (1)) 200 parts of water and 2,2'-azobis(2-amidino Add 0.5 part of glopane dihydrochloride and heat to 75°C while slowly blowing nitrogen gas, then add 5 parts of vinyltrimethoxysilane and methyl methacrylate prepared in advance through a dropping funnel. 100 parts of a monomer mixture consisting of 36 parts of ethyl acrylate and 59 parts of ethyl acrylate;
Emulsifier aqueous solution 57 in which 1 part of 8 (manufactured by Sanyo Kasei ■) and 6 parts of Nonipol 200 (manufactured by Sanyo Kasei ■) were added to 50 parts of water.
157 parts of a monomer pre-emulsion obtained from 1 part was added dropwise over 2 hours.

Thereafter, the temperature was maintained at t-75°C, and the mixture was further stirred for 1.5 hours for emulsion polymerization to obtain an aqueous dispersion (1) of a vinyl polymer with a nonvolatile content of 30.1%.

Reference Example 2 (Aqueous Dispersion (2)) As a monomer mixture, 10 parts of glycidyl methacrylate,
43 parts of methyl methacrylate and 4 parts of butyl acrylate
Emulsion polymerization was carried out in the same manner as in Reference Example 1 except that 7 parts were used for a total of 100 parts. The obtained emulsified dispersion was subsequently heated to 75°C, and 11 g of γ-aminoglobiltriethoxysilane was added thereto.
A mixture of 7 parts and 40 parts of water was added and stirring was continued for 2 hours to obtain an aqueous dispersion of vinyl polymer with a non-volatile content of 29.7 parts (2
) was obtained.

Comparative Reference Example 1 (Comparative Dispersion (1)) The polymer side was prepared in the same manner as in Reference Example 1, except that 14 parts of methyl methacrylate and 86 parts of ethyl acrylate, a total of 100 parts, were used as the monomer mixture. p with a hydrolyzable silyl group in the chain
A comparative dispersion liquid (3) was obtained.

Examples 1 to 6 and Comparative Examples 1 to 4 Various sols shown in Table 1 were added to the aqueous dispersions (1) to (2) and the comparative dispersion (1), and the aqueous compositions were prepared by stirring at room temperature. Prepared. The obtained aqueous m-cloth, the aqueous dispersion (1) containing no sol, and the titanium hydrate sol containing no aqueous dispersion were applied to a ester film and various tests were conducted. The test method is described below, and the test results are shown in Table 1.

Test method (1) Coating and drying: Coating was performed using a percoater to give a non-volatile content of 8 to 109/m'' and drying at 150°C for 2 minutes.

■Adhesion (streak test): Use a cutter knife to cut 110 x 10 goblets on the coated surface of the film at 1 gourd intervals, stick a cellophane chip on it, and peel it off. The degree of peeling was scored on a 10-point scale.

10 points Excellent → 1 point Poor ■ Water Resistance The state of whitening of the film after being immersed in tap water for one week at room temperature is evaluated from O (no whitening) to × (whitening).
Furthermore, a gopan eye test was conducted.

■Flexibility: Fold the film in half with the coated side facing outward.
Then, the presence or absence of peeling at the broken line portion was determined.

○ No peeling
It was measured under the conditions of 04RH and 500VO.

The smaller the resistance value, the better the antistatic property.

Claims (1)

[Claims] 1. General formula ▲ mathematical formula, chemical formula, table, etc. in the molecule ▼ (R^1 is H or CH_3, A is a divalent organic group, R^2
is an alkyl group having 1 to 18 carbon atoms, X is a halogen atom,
a hydrolyzable group selected from an alkoxy group and an acetyl group; a represents an integer of 1 to 3; ) Aqueous dispersion of a vinyl polymer having at least one structural unit represented by (I) and element symbols Mg, Ca, B
a, Sr, Al, Ti, V, Mn, Fe, Co, Ni,
An aqueous composition comprising a sol (II) of a hydroxide or oxide of one or more metals selected from Ga, Zr, Nb, In, Sn, Ce, Ta, and W.