JP3446567B2 - Silicone resin-containing emulsion composition, article having cured coating of the composition, and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicone resin-containing emulsion composition which gives a cured film having excellent film-forming properties and excellent properties such as scratch resistance, weather resistance and chemical resistance. The present invention relates to a metal, plastic, ceramic, wooden building material, structure and other articles and a method for manufacturing the same.

[0002]

2. Description of the Related Art In recent years,
From the viewpoint of environmental pollution and ensuring a safe working environment, it is required to change the dispersion medium from an organic solvent to an aqueous system in the field of paints or coating agents.

Based on this requirement, emulsion-based paints obtained by emulsion-polymerizing radical-polymerizable vinyl monomers, typified by acrylic resins, are widely used as basic materials for coating agents because of their excellent film-forming properties and chemical resistance. Has been done. However, coating agents of this type have the disadvantage of essentially lacking in water resistance and weather resistance.

On the other hand, a silicone resin (resin) obtained by hydrolyzing and condensing a silane compound has a high hardness and is capable of forming a film excellent in weather resistance, water resistance, heat resistance and water repellency. It is attracting attention as a coating agent.
On the other hand, it has the disadvantages of poor film-forming properties, alkali resistance, flexibility of the film, and poor storage stability due to silanol groups rich in condensation activity. Also, the silicone resin is
Since it is generally used in the form of being dissolved in an organic solvent, there are problems of fire and explosion, toxicity to human body, environmental pollution, etc., and development of an emulsion type is required.

Therefore, for the purpose of improving these drawbacks,
Various attempts have been made as described below, but they are still insufficient. (A) A method of emulsifying an alkoxysilane compound or a partial hydrolysis / condensation product thereof with various surfactants to prepare an aqueous emulsion (JP-A-58-213046, JP-A-62-197369, JP-A-62-197369, JP-A-62-197369). 3-115485
No. 3, JP-A-3-200793). A system in which an emulsion obtained by emulsion-polymerizing a polymerizable vinyl monomer is mixed with this emulsion is also known (JP-A-6-344).
665 publication). (B) A method in which a solventless solid silicone resin is forcibly mechanically pulverized and dispersed together with a chain-like silicone compound into an aqueous emulsion (JP-A-7-247434). (C) A method of emulsion-polymerizing a vinyl monomer capable of radical polymerization in the presence of a water-soluble polymer obtained by hydrolyzing an alkoxysilane in water without using a surfactant (JP-A-8-60098). (D) An aqueous emulsion containing a solid silicone resin is obtained by hydrolyzing and condensing an alkoxysilane mixture containing a vinyl-polymerizable alkoxysilane, and a radical-polymerizable vinyl monomer is further added to perform emulsion polymerization to obtain a graft copolymer. Method for obtaining polymer fine particle (solid) emulsion (JP-A-5-209149, JP-A-7-
196750). (E) A method of adding an alkoxysilane to an emulsion obtained by emulsion-polymerizing a radical-polymerizable vinyl monomer, hydrolyzing and condensing it, and introducing a silicone resin into emulsion particles (JP-A-3-45628 and JP-A-8-3409).
Issue). (F) A method of emulsion-polymerizing a vinyl-polymerizable functional group-containing alkoxysilane together with a radical-polymerizable vinyl monomer to prepare an emulsion (JP-A-61-9463 and JP-A-8-27347).

However, in the case of (a), since the active alkoxy group is easily hydrolyzed with time, an alcohol which is an organic solvent is by-produced in the system, and a relatively low polymerization raw material is polymerized. There is. As a result, the by-product alcohol makes the emulsion unstable and changes the degree of polymerization, so that the performance is not constant. If a large amount of a surfactant is used to compensate for these drawbacks, the coating properties such as the hardness and the water resistance of the coating are significantly deteriorated, which is not suitable. Further, since the silicone resin is used alone, it has drawbacks derived from the silicone resin, and the characteristics of the coating are not sufficiently satisfied.

In the case of (b), the solid silicone resin granules having a softening point are forcibly emulsified with a chain organopolysiloxane having OH groups at both ends with the aid of a surfactant. is there. Although this method has the advantage of not containing an organic solvent, since the silicone solid resin has a high polarity, it is difficult to dissolve in a low-polarity liquid organopolysiloxane, and the solid resin must be dispersed using a sand grinder. Therefore, it is difficult to reduce the particle size, and the stability of the emulsion formed is not good. Further, since it is a solid resin, the content of silanol groups is relatively low at 0.1 to 5% by weight, high temperature curing at 200 to 300 ° C. is required, and the workability is inferior to that of the organic solvent solution type. Furthermore, since a chain-like organopolysiloxane is used in combination, the cured coating film is rich in water repellency, but the hardness is low, so the scratch resistance is poor and the durability cannot be said to be sufficient.

In the case of (c), a water-soluble resin containing no surfactant is first prepared by simply hydrolyzing the alkoxysilane in water, and then the surfactant is added to emulsify the radically polymerizable vinyl monomer. Polymerization is the manufacturing method in this case. However, this method also has a drawback that alcohol is also by-produced due to hydrolysis in water. This water-soluble silicone resin is partly incorporated in the emulsion particles, but since it is highly water-soluble, a considerable part remains in water. The active silanol groups contained in the molecules present in water gradually condense and tend to precipitate as a gel. As a result, the emulsion tends to be unstable, and the mutual solubility between the silicone resin component and the vinyl polymerizable component is essentially poor, and it is difficult to obtain uniformity of each component in the cured coating, resulting in deterioration of coating properties. However, it is not completely satisfactory.

In the case of (d), after the alkoxysilane is hydrolyzed in water, an emulsion of a corresponding solid silicone resin is prepared, and the emulsion is polymerized by using the vinyl polymerizable group contained in the silicone resin as a starting point. The acrylic chain is grafted. Also in this method, since the step of hydrolyzing the alkoxysilane is included, alcohol, which is an organic solvent, is included in the system. Therefore, the stability of the emulsion is insufficient. This method aims at solid fine particles capable of imparting lubricity and water repellency, and a silicone resin that plays a role in this function is located at the center of the core, which contributes to prevention of particle aggregation in water and improvement of dispersibility. It is a method for preparing such composite particles grafted with an acrylic chain. Therefore, both components are present in a non-uniform state, and it is better that the silicone resin is sufficiently crosslinked in the particles, and rather, it is preferable that the silicone resin is inactive without the presence of silanol groups. Does not form.

In the case of (e), since the alkoxysilane is post-added to the emulsion, alcohol is produced as a by-product, and it is difficult to be completely taken into the emulsion particles, which is a drawback similar to the other cases. However, the stability of the emulsion and the properties of the cured film are not at a satisfactory level. Also, since the post-addition method is adopted, there is a high possibility that a large amount of silicone resin will be present on the outer shell side,
Therefore, both components in the particles and in the cured coating become non-uniform, and the complementary relationship between the properties of both resins is insufficient.

In the case of (f), a vinyl-polymerizable functional group-containing alkoxysilane is emulsion-polymerized together with a radical-polymerizable vinyl monomer to suppress hydrolysis of the alkoxy group.
Since it is preserved, the alcohol by-products and changes in properties with time are much smaller and better than in other cases. However, it is difficult to include a large amount of silicone resin component in the coating film, and therefore properties such as weather resistance cannot be improved, which is not at a satisfactory level when considering exterior applications.

As described above, each of the conventionally known methods does not contain (i) a low-boiling organic solvent having a high flammability such as alcohol, and (ii) the emulsion has good stability.
ii) Excellent low temperature curability, (iv) Scratch resistance, weather resistance,
Silicone resin-containing emulsions having good properties such as chemical resistance and giving a uniform cured film have not been obtained.

Therefore, an object of the present invention is to provide the above (i) to
It is an object of the present invention to provide a silicone resin-containing emulsion composition having the characteristics (iv), an article on which a cured film of the composition is formed, and a method for producing the same.

[0014]

Means for Solving the Problems and Modes for Carrying Out the Invention As a result of intensive studies for achieving the above-mentioned object, the present inventor has shown that a silanol group-terminated silicone represented by the following average composition formula (1) is preferable. By emulsion-polymerizing a mixed solution containing a resin and a radically polymerizable vinyl monomer as a main component, a solvent having a boiling point of less than 100 ° C. such as alcohol or ketone and an aromatic organic solvent such as benzene, toluene, xylene are substantially contained. Without containing a condensation type silicone resin and a vinyl polymer resin in the same particle of the emulsion,
It has been found that an emulsion having excellent storage stability and good film characteristics can be obtained. Further, by adding a specific curing catalyst, that is, a compound containing a group IA and / or IIA metal element, to this emulsion as a curing catalyst, the curability at low temperature is improved and excellent curability is obtained even at room temperature. Based on this finding, the present invention has been completed.

That is, the present invention provides [A] (1) the following average composition formula (1) R ¹ _m R ² _n Si (OH) _p (OX) _q O _{(4-mnpq) / 2} (1) (formula) In the formula, R ¹ represents an unsubstituted monovalent hydrocarbon group, R ² represents a substituted monovalent hydrocarbon group, and OX represents a hydrolyzable group, m, n, p and q are 0.5 ≦ m ≦ 1.8, 0 ≦ n ≦ 1.0, 0 <p ≦ 1.5, 0 ≦ q ≦ 0.5, 0.5 ≦ m + n ≦ 1.8, and 0 <p + q ≦ 1.5.) 100 parts by weight of a water-insoluble silanol group-containing silicone resin, (2) a radical-polymerizable vinyl monomer, an emulsion polymer of a solution containing 10 to 1000 parts by weight as a main component, and [B] Group IA and / or Group IIA Provided is a silicone resin-containing emulsion composition comprising a compound containing a metal element. Also provided are an article on which a cured coating of this composition is formed, and a method for producing the above article, in which a coating of the above composition is formed on a substrate and the coating is cured at room temperature.

The emulsion composition of the present invention has the following advantages which cannot be obtained by the conventionally known methods. (I) Since both resins form an interpenetrating network structure (IPN) in the emulsion particles, the shortcomings of both resins are complemented, and excellent film-forming properties such as scratch resistance, weather resistance, chemical resistance, etc. A uniform cured film having good characteristics can be obtained. (Ii) In the emulsion particles, the polymers are entangled with each other in a solvent-free state, so that the degree of freedom of the silanol group having a high condensation activity is limited. As a result, condensation of silanol groups is suppressed even in a system having a high silanol group content, and good storage stability can be obtained. Further, since the water-insoluble silicone resin is used, the silicone resin is completely incorporated into the particles, and thus the stability is maintained at a good level. (Iii) On the contrary, as a result of the silanol groups being confined in the particles, their high curing activity is preserved, and a specific curing catalyst, that is, a compound containing a Group IA and / or Group IIA metal element is added. As a result, it exhibits excellent curability even at room temperature or low temperature. (Iv) Since it does not substantially contain a solvent, a good film can be obtained during drying and curing, and since no harmful solvent is volatilized, a good working environment is secured. Further, since it does not contain an alcohol component that promotes the destruction of the emulsion, the stability of the emulsion is maintained in a good state.

From the above, the silicone resin-containing emulsion composition of the present invention is suitable for exterior coatings for structures, building materials and the like, and is also suitable for fields where acrylic emulsions or acrylic silicone resins have been conventionally applied.

The present invention will be described in more detail below.
First, the silanol group-containing silicone resin that constitutes the present invention will be described. This silicone resin is represented by the following average composition formula (1). R ¹ _m R ² _n Si (OH) _p (OX) _q O _{(4-mnpq) / 2} (1)

Here, R ¹ represents an unsubstituted monovalent hydrocarbon group, preferably having 1 to 10 carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-
Alkyl groups such as butyl group, hexyl group, cyclohexyl group, octyl group, decyl group, vinyl group, allyl group, 5
Specific examples thereof include an alkenyl group such as a -hexenyl group and a 9-decenyl group, and an aryl group such as a phenyl group. Among these, a methyl group, a propyl group, a hexyl group, and a phenyl group are preferable. Especially when weather resistance is required, a methyl group is preferable, when a water repellent agent is required, a long-chain alkyl group is preferably used, and when imparting flexibility to a coating, a phenyl group is applied. Good to do.
In this case, it is particularly preferable that the content of methyl groups in all the organic substituents (R ¹ + R ² ) is at least 80 mol%.

R ² represents a substituted monovalent hydrocarbon group. This substituted monovalent hydrocarbon group is the above-mentioned unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms in which some or all of the hydrogen atoms have been substituted with a substituent, and as the substituent, (i) fluorine,
A halogen atom such as chlorine, (ii) a glycidyloxy group,
Epoxy functional groups such as epoxycyclohexyl group, (i
ii) (meth) acrylic functional groups such as methacrylic group and acrylic group, (iv) amino group, aminoethylamino group,
Amino functional groups such as phenylamino group and dibutylamino group, (v) mercapto group, sulfur-containing functional group such as tetrasulfide group, (vi) alkyl ether functional group such as (polyoxyalkylene) alkyl ether group, (vi)
It is possible to apply i) an anionic group such as a carboxyl group and a sulfonyl group, and (viii) a quaternary ammonium salt structure-containing group. Specific examples of the substituted monovalent hydrocarbon group include trifluoropropyl group, perfluorobutylethyl group, perfluorooctylethyl group, 3-
Chloropropyl group, 2- (chloromethylphenyl) ethyl group, 3-glycidyloxypropyl group, 2- (3,4-
Epoxycyclohexyl) ethyl group, 5,6-epoxyhexyl group, 9,10-epoxydecyl group, 3- (meth) acryloxypropyl group, (meth) acryloxymethyl group, 11- (meth) acryloxyundecyl group Three
-Aminopropyl group, N- (2-aminoethyl) aminopropyl group, 3- (N-phenylamino) propyl group,
Examples include 3-dibutylaminopropyl group, 3-mercaptopropyl group, 2- (4-mercaptomethylphenyl) ethyl group, polyoxyethyleneoxypropyl group, 3-hydroxycarbonylpropyl group, 3-tributylammoniumpropyl group. it can. To improve the adhesion to the substrate, epoxy, amino, mercapto functional groups, etc. are preferably applied. In the case of aiming at close blocking with a vinyl polymer, it is preferable to use a (meth) acrylic functional group capable of radical copolymerization or a mercapto functional group having a function as a chain transfer agent. Further, when attempting to crosslink the vinyl polymer with a bond other than a siloxane bond, a functional group capable of reacting with an organic functional group contained in the vinyl polymer may be introduced, for example, an epoxy group (hydroxy group, amino group, etc.). Group, a carboxy group, etc.), an amino group (a reaction with an epoxy group, an acid anhydride group, etc.) and the like.

The OX group represents a hydrolyzable group, and X represents a monovalent hydrocarbon group having 1 to 6 carbon atoms such as an alkyl group, an alkenyl group and an aryl group. Specific examples of the hydrolyzable group OX include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, sec-butoxy group, t.
Examples thereof include butoxy group, isopropenoxy group and phenoxy group. From the viewpoint of hydrolysis / condensation reactivity and stability in emulsion, it is preferable to use a methoxy group, an ethoxy group or an isopropoxy group.

M, n, p and q are each 0.5 ≦ m ≦ 1.
8, 0 ≦ n ≦ 1.0, 0 <p ≦ 1.5, 0 ≦ q ≦ 0.
5, a number satisfying the ranges of 0.5 ≦ m + n ≦ 1.8 and 0 <p + q ≦ 1.5. When m is less than 0.5, the content of R ¹ is low, the coating becomes too hard, and cracks are easily generated in the cured coating, which is not preferable. When m exceeds 1.8, the number of chain units increases, and as a result, the cured coating becomes rubbery and scratch resistance is insufficient, which is not preferable. More preferably, m satisfies the range of 0.6 or more and 1.5 or less. When n exceeds 1.0, the content of bulky R ² increases, which makes it difficult to maintain hardness and reduces weather resistance, which is not preferable. If not required to grant the function of the aforementioned R ^2, the R ² may not be contained. Further, the set optimum range of m + n is the same as the reason why m is explained. The silanol group is an essential component, but if p representing the content of the silanol group exceeds 1.5, the silicone resin becomes unstable, which is not preferable. To ensure good storage stability and high curability at the same time, p
Is more preferably in the range of 0.05 to 0.8, and even more preferably in the range of 0.2 to 0.7. A crosslinkable hydrolyzable group OX may be present in addition to the silanol group, but its abundance q must be 0.5 or less. If it exceeds this range, it is easily hydrolyzed in water, and alcohol as an organic solvent is by-produced in the system,
Not preferable. Further, (p + q), which represents the total number of crosslinkable substituents, needs to satisfy the range of 0 <p + q ≦ 1.5, and when 0 is not cured, when it exceeds 1.5, the molecule becomes It is not preferable because it becomes small and the water solubility becomes excellent.

The silicone resin applicable to the present invention must satisfy the above conditions, at the same time contain a silanol group, and must not dissolve alone in water. Dissolution in water is not preferable because it is not completely incorporated into the particles during emulsion polymerization. Therefore, if the above conditions are satisfied, the silicone resin may be produced by any method, but simply hydrolyzing the hydrolyzable silane compound in water is not sufficient. A specific manufacturing method will be described below.

As a raw material for production, the kind of the hydrolyzable group is chloro or alkoxy, and one, two, three or four hydrolyzable groups are contained, and an organic substituent satisfying the above condition is satisfied. Any silane compound can be used as long as it has a silane compound. Specifically, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldichlorosilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, 5-hexenyltrimethoxysilane, 3-glycidoxypropyltrisilane. Methoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth ) Acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 4-vinylphenyltrimethoxysilane, 3- (4-vinylphenyl) Nyl) propyltrimethoxysilane, 4-vinylphenylmethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3 -(2-aminoethyl)
In addition to so-called silane coupling agents such as aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldiethoxysilane, tetrachloro Silane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, methyltriisopropenoxysilane,
Dimethyldichlorosilane, dimethyldimethoxysilane,
Dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, dimethyldiisopropenoxysilane, trimethylchlorosilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropenoxysilane, ethyltrichlorosilane, ethyltrimethoxysilane, Propyltrichlorosilane, butyltrichlorosilane, butyltrimethoxysilane, hexyltrichlorosilane, hexyltrimethoxysilane, decyltrichlorosilane, decyltrimethoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, cyclohexyltrichlorosilane, cyclohexyltrimethoxysilane, propyl Methyldichlorosilane, propylmethyldimethoxysilane, hexylmethyldichlorsila , Hexyl methyl dimethoxy silane, phenyl methyl dichlorosilane, phenyl methyl dimethoxy silane, diphenyl dichlorosilane, diphenyl dimethoxysilane, dimethyl phenyl chlorosilane,
And silane compounds that can be used as the partial hydrolyzate thereof. It is more preferable to use methoxysilane or ethoxysilane in terms of operability and easiness of distilling off by-products. The usable organosilicon compound is not limited to this. One or a mixture of two or more of these silane compounds may be used.

There are the following two methods for hydrolyzing the hydrolyzable silane compound to obtain the silicone resin usable in the present invention. The first method is toluene,
Aromatic hydrocarbons such as xylene, hexane, hydrocarbons such as octane, methyl ethyl ketone, ketone compounds such as methyl isobutyl ketone, ethyl acetate, ester compounds such as isobutyl acetate, methanol, ethanol, isopropanol, butanol, isobutanol,
This is a method of hydrolysis in an organic solvent selected from alcohols such as t-butanol. In the case of this method, from the completed silicone resin that does not dissolve in water by itself,
It is necessary to remove harmful organic solvents under normal pressure or reduced pressure.
You may simply remove the organic solvent and solidify it as a viscous liquid, or add the high-boiling radically polymerizable vinyl monomer used in the next step, and collect the low-boiling organic solvent in the coexistence of it. It may be removed and taken out as a solution containing no organic solvent. The second method is a method of hydrolyzing a hydrolyzable silane compound other than chlorosilane in water. In order to remove the organic solvent and at the same time to grow the silicone resin to a level at which it does not dissolve in water, it is hydrolyzed and then heated under normal pressure or reduced pressure to distill the organic solvent together with water. By doing so, a silicone resin containing no organic solvent, insoluble in water, dispersed in water or separated / precipitated from water and containing a large amount of silanol groups can be obtained. After separating this silicone resin from water,
A radical-polymerizable vinyl monomer may be added to form a solution thereof, or a radical-polymerizable vinyl monomer may be added to an aqueous solution containing a silicone resin and separated as a vinyl monomer solution containing a silicone resin.

A hydrolysis catalyst may be used in carrying out the hydrolysis. As the hydrolysis catalyst, a conventionally known catalyst can be used, and it is preferable to use a catalyst whose aqueous solution exhibits acidity of pH 2 to 7. Particularly preferred are acidic hydrogen halides, carboxylic acids, sulfonic acids, acidic or weakly acidic inorganic salts, solid acids such as ion exchange resins, and the like. Examples include hydrogen fluoride, hydrochloric acid, nitric acid, sulfuric acid, acetic acid,
Examples thereof include organic carboxylic acids represented by maleic acid, methyl sulfonic acid, and cation exchange resins having a sulfonic acid group or a carboxylic acid group on the surface. The amount of the hydrolysis catalyst is 0.001 to 1 mol of the hydrolyzable group on the silicon atom.
It is preferably within the range of 10 mol%.

Next, the radical polymerizable vinyl monomer as the second component will be described. As the radically polymerizable vinyl monomer, the following conventionally known ones can be applied as long as they are radically polymerizable. (A) Alkyl (meth) acrylate having 1 to 18 carbon atoms in the alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, octyl, 2-ethylhexyl, lauryl, stearyl or cyclohexyl ester of acrylic acid or methacrylic acid Ester, (b) carboxyl group such as acrylic acid, methacrylic acid, maleic anhydride or vinyl monomer containing anhydride thereof, (c) hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate Containing vinyl monomer, (d) (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth)
Amide group-containing vinyl monomers such as acrylamide, N-butoxymethyl (meth) acrylamide and diacetone (meth) acrylamide, amino group-containing vinyl monomers such as (e) dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate,
(F) Alkoxy group-containing vinyl monomers such as methoxyethyl (meth) acrylate and butoxyethyl (meth) acrylate, (g) glycidyl (meth) acrylate, glycidyl group-containing vinyl monomers such as glycidyl allyl ether, (h) vinyl acetate, Vinyl ester monomers such as vinyl propionate, (i) styrene,
Aromatic vinyl monomers such as vinyltoluene and α-methylstyrene, vinyl cyanide monomers such as (j) (meth) acrylonitrile, vinyl halide monomers such as (k) vinyl chloride and vinyl bromide, (l) divinylbenzene, A vinyl monomer containing two or more radically polymerizable unsaturated groups in one molecule such as allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and trimethylolpropane tri (meth) acrylate. (M) a (poly) oxyethylene chain-containing vinyl monomer such as (poly) oxyethylene mono (meth) acrylate having 1 to 100 ethylene oxide groups, and (n) a (meth) acryloxypropyl group at one end. Dimethyl polysiloxane contained, at one end Having a styryl group or α- -methylstyryl one end to the radical polymerizable functional groups such as dimethyl polysiloxane containing group, siloxane units 1
~ 200 diorganopolysiloxanes, (o) vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, 5-hexenyltrimethoxysilane, 3- (meth) acryloxypropyltrimethoxy Silane, 3-
(Meth) acryloxypropyltriethoxysilane, 3
-(Meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 4-vinylphenyltrimethoxysilane, 3
Silane compounds containing radically polymerizable functional groups such as-(4-vinylphenyl) propyltrimethoxysilane and 4-vinylphenylmethyltrimethoxysilane can be exemplified as specific examples, and one of these can be used alone. Alternatively, two or more kinds can be used in combination.

Of these, the radically polymerizable vinyl monomer has an alkyl group having 1 to 18 carbon atoms (meth).
The content of the alkyl acrylate ester is preferably 1 to 100 mol%. If the content is less than 1 mol%, properties such as chemical resistance may not be obtained. It is more preferable to satisfy the range of 30 to 99 mol%. When imparting properties such as solvent resistance or chemical resistance to the cured film, it is preferable to copolymerize a radically polymerizable vinyl monomer having a crosslinkable functional group, and especially to form a siloxane bond by a condensation reaction. A silane compound containing a radically polymerizable functional group represented by (o), and a glycidyl (meth) acrylate classified as (g) having an epoxy functional group capable of crosslinking by a ring-opening reaction of a carboxylic acid / epoxy group, A glycidyl group-containing vinyl monomer such as glycidyl allyl ether is suitable, and since the resin used for the other in the present system is a silanol group-containing silicone resin, a silane compound is more suitable. In this case, a vinyl-polymerizable functional group-containing hydrolyzable silane represented by the following general formula (2) is used as the silane compound.

[0029]

[Chemical 1] In the formula, R ³ is a hydrogen atom or a methyl group, and R ⁴ is a carbon number of 1 to 1.
0 oxygen atom, a divalent organic group such as an alkylene group, an arylene group or an alkylenearylene group which may have an intervening —COO— group, r represents 0, 1 or 2, and R ¹ and X are the same as those described above. Indicates the same meaning.

The following may be mentioned as specific examples of R ⁴ .

[0031]

[Chemical 2]

The content of the above-mentioned vinyl-polymerizable functional group-containing hydrolyzable silane is preferably 0.01 to 10 mol%, particularly preferably 0.1 to 5 mol% based on the whole radical-polymerizable vinyl monomer. If it is too small, the solvent resistance and chemical resistance will not be sufficiently expressed, and if it is too large, it may be unsuitable because the film may be highly crosslinked and cracks may be generated in the coating.

When it is desired to impart lubricity to the surface, it is preferable to copolymerize a diorganopolysiloxane containing a radically polymerizable functional group at one end, as exemplified in (n).

The radical-polymerizable vinyl monomer is added to 1 part by weight of 100 parts by weight of the first component silicone resin.
It is used in the range of 0 to 1000 parts by weight. If it is less than 10 parts by weight, the film-forming property and chemical resistance may be insufficient,
If it exceeds 1000 parts by weight, weather resistance and water resistance may be insufficient. More preferably, the radical-polymerizable vinyl monomer is used in the range of 30 to 500 parts by weight.

The emulsion composition of the present invention comprises an emulsion polymer of a silicone resin and a radical-polymerizable vinyl monomer. The emulsion composition of the present invention is a highly flammable organic compound having a boiling point of less than 100 ° C. Non-dispersible in solvents, aromatic organic solvents that are harmful to the human body, and water (water-insoluble)
It does not contain the organic solvent of. In this case, the organic solvent is not particularly limited, but methanol, ethanol,
Alcohols such as propanol, isopropanol and t-butanol, aromatics such as toluene and xylene,
Acetone, ketones such as methyl ethyl ketone, esters such as ethyl acetate, butyl acetate, isobutyl acetate,
Specific examples include diethyl ether, ethers such as tetrahydrofuran, acetonitrile, etc., but these solvents cause environmental pollution, are harmful to the human body, impair the stability of emulsion, and apply It is preferable that these solvents are essentially not contained, because they hinder the formation of a uniform film afterwards. However, as described above, in the composite emulsion of (silicone resin + acrylic resin), it was impossible to form a substantially solvent-free emulsion by the method known so far. The cause is that the silicone resin containing a silanol group rich in reaction activity at the molecular end,
Although it is soluble in water in low molecular weight products, it is unstable and changes significantly over time if no organic solvent is present. Conversely, it becomes considerably stable in high molecular weight products, but it becomes insoluble in water and there is no organic solvent. It tends to be solidified and it becomes difficult to emulsify. Therefore, as described above, the examples of using the organic solvent together or using the alkoxysilane compound or its partial hydrolyzate as the raw material have been described so far. In the present invention, prior to carrying out emulsion polymerization, from a solution of a silicone resin that has been polycondensed to a level that is insoluble in water by itself, an organic compound such as an alcohol by-produced when the hydrolyzable silane compound is hydrolyzed. By removing the solvent as much as possible and then subjecting it to a solution of a radically polymerizable vinyl monomer that has been subjected to emulsion polymerization, an emulsion containing substantially no organic solvent can be obtained. Therefore, the emulsion of the present invention may contain a small amount of non-removable organic solvent, but in order to avoid the above problems, the amount of organic solvent is Is preferably 0 to 5% by weight, more preferably 0 to 2% by weight.

The emulsion composition of the present invention contains the above-mentioned water-insoluble silanol group-containing silicone resin and a radically polymerizable vinyl monomer as main components, and the amount of the organic solvent is substantially the above organic solvent. It can be produced by emulsion polymerization of a solution not containing.

In this case, a surfactant is used in the emulsion polymerization. As the surfactant, various conventionally known nonionic, cationic and anionic surfactants and radically polymerizable functional groups are used. Reactive emulsifiers contained can be applied. Specifically, nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene carboxylic acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, alkyl trimethyl ammonium chloride, alkyl benzyl. Cationic surfactants such as ammonium chloride, anionic surfactants such as alkyl or alkylallyl sulphates, alkyl or alkylallyl sulfonates and dialkyl sulfosuccinates, amphoteric ion type interfaces such as amino acid type and betaine type Activator, JP-A-8-2734
No. 7, the sulfonate in the molecule,
Various reactive surfactants including radical-polymerizable (meth) acrylates containing hydrophilic groups such as polyoxyethylene chains and quaternary ammonium salts, and derivatives such as styrene and maleic acid ester compounds can be shown. Examples of such a surfactant are as follows.

[0038]

[Chemical 3]

[0039]

[Chemical 4]

[0040]

[Chemical 5]

These surfactants may be used alone or in combination of 2.
You may use it in combination of 2 or more types. The surfactant is 0. 0 with respect to the total amount of the first component and the second component (active ingredient).
It is preferable to use 5 to 15% by weight, particularly 1 to 10%
It is recommended to use the weight%.

A radical polymerization initiator is used in the emulsion polymerization, and examples of the radical polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, hydrogen peroxide solution, t-butyl hydroperoxide, t-butyl peroxymaleic acid, succinic acid peroxide, 2,2 '
Water-soluble type such as azobis- [2-N-benzylamidino] propane hydrochloride, benzoyl peroxide, cumene hydroperoxide, dibutyl peroxide, diisopropyl peroxydicarbonate, cumyl peroxy neodecanoate, cumyl peroxy An oil-soluble type such as octoate or azoisobutyronitrile, a redox system in which a reducing agent such as acidic sodium sulfite, rongalite or ascorbic acid is used in combination can be used. The polymerization initiator may be used in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on the radically polymerizable vinyl monomer.

Next, the method for producing the emulsion of the present invention will be described in more detail. Suitable methods are roughly classified into the following two methods.

In the first method, in the first step, the organic solvent containing a silanol group alone is distilled off from the water-insoluble silicone resin solution, so that only the active ingredient is substantially contained, and the organic solvent is removed in the second step. The removed silicone resin is added to and dissolved in a radically polymerizable vinyl monomer compound to form a solution, and a surfactant is used in the third step to emulsify the silicone resin-containing vinyl monomer solution prepared in the second step. It is a method of polymerizing into an emulsion. In the step of distilling off the solvent, the highly active silanol group is preserved, so it is preferable to remove it at the lowest possible temperature. Therefore, this method is suitable when a silicone resin having a relatively small silanol group content and excellent stability is used because the organic solvent is once separated. If necessary, a so-called solvent replacement method may be employed in which the organic solvent is distilled off in the presence of a radically polymerizable vinyl monomer having a relatively high boiling point, and the radically polymerizable vinyl monomer is used instead of the solvent. As a method of emulsion polymerization, after emulsifying all at once,
Various conventionally known methods such as a batch charging method for polymerizing, a monomer adding method for polymerizing while continuously adding a solution containing a radical-polymerizable vinyl monomer or an emulsion thereof can be applied. Further, a seed polymerization method in which a part of the emulsion is preliminarily polymerized and then the rest of the emulsion is added for polymerization, and a core / shell polymerization method in which the monomer composition of the core and the shell are changed can be applied.

The emulsion of the radical-polymerizable vinyl monomer-containing solution is preferably prepared by adding the radical-polymerizable vinyl monomer-containing solution to an aqueous surfactant solution and emulsifying it using a homomixer or a high-pressure homogenizer. Emulsion polymerization is completed at a temperature of 10 to 90 ° C., preferably 30 to 80 ° C., usually for 3 to 8 hours.

In the second method, the hydrolyzable silane compound is hydrolyzed in water in the first step, and further subjected to condensation polymerization to obtain a reaction containing a silicone resin of the above formula (1) containing a silanol group at the molecular end. A mixture is obtained, and an organic solvent such as an alcohol by-produced by hydrolysis in the second step and other hydrolysis by-products are distilled off to obtain only the silanol group-containing silicone resin component of the formula (1) and water. In the third step, a radical-polymerizable vinyl monomer compound is added, and a silicone resin existing in a dispersed or insoluble state in an aqueous system is dissolved in the vinyl monomer compound to obtain a radical-polymerizable vinyl containing a silicone resin. Separated from the aqueous layer as a monomer solution, and using a surfactant in the fourth step, the radical-polymerizable silicone resin-containing polymer prepared in the third step Nirumonoma solution is a method of emulsion polymerization. In this method, since there is no state in which the silicone resin alone exists during the process, it is possible to suppress the condensation of the silanol groups having high reaction activity. Therefore, this method is suitable for water-insoluble silicone resins, which are rich in silanol groups. In addition, the silicone resin hydrolyzed and condensed in water gives a film with higher hardness and flexibility and is excellent in curability as compared with a silicone resin of the same composition prepared in an organic solvent. Therefore, this is the preferred method.

The emulsion composition of the present invention comprises the above (A) silanol group-containing emulsion (emulsion polymer).
In addition, (B) a compound containing a Group IA and / or Group IIA metal element is added as a curing catalyst.
Specifically, hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide and barium hydroxide, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, Sodium hydrogen carbonate, potassium hydrogen carbonate, lithium chloride, sodium chloride, potassium chloride, cesium chloride, magnesium chloride, calcium chloride, barium chloride, potassium fluoride, sodium fluoride, sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, sulfuric acid Inorganic salts such as sodium hydrogen, potassium hydrogen sulfate, sodium hexafluorosilicate, lithium formate, sodium formate, potassium formate, cesium formate, lithium acetate, sodium acetate, potassium acetate, cesium acetate, magnesium acetate, acetic acid Calcium, barium acetate, sodium oxalate, organic acid salts such as potassium oxalate, sodium methylate, potassium methylate, alkoxides such as sodium ethylate, IA Group and / or IIA of the water glass, sodium ions such as sodium silicate
Aqueous colloidal silica containing a group metal element is applicable, and one or more of these may be used in combination. Note that these curing catalysts are preferably water-soluble.

The addition amount of the compound containing the group IA and / or group IIA metal element is (A) the silicone resin (a) in the silanol group-containing emulsion (emulsion polymer).
And the total amount of radically polymerizable monomer (b) (a + b)
The amount is preferably 0.001 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, based on 100 parts by weight. If it is less than 0.001 part by weight, the effect as a curing catalyst is not sufficiently exhibited, and if it exceeds 20 parts by weight, the weather resistance, water resistance and coating film appearance may be deteriorated.

The pH of the emulsion composition after the addition of the compound containing the Group IA and / or Group IIA metal element is preferably in the range of 8 to 12. When the pH of the emulsion composition is out of this range, the stability of the emulsion composition may be deteriorated, and the curability may be deteriorated or the appearance of the coating film may be poor due to microgel.

The compound containing a Group IA and / or Group IIA metal element is preferably an inorganic salt in terms of operability and availability. Furthermore, because of its strong ability as a curing catalyst, the group IA and / or group IIA metal elements are
It is preferable to use a compound which is an element selected from i, Na, K and Cs. Furthermore, since the pH of the emulsion composition is preferably in the range of 8 to 12,
Sodium hydroxide, potassium hydroxide, sodium carbonate,
Basic compounds such as potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate, and water glass are more preferable.

In the present invention, a compound containing a group IA and / or IIA metal element having a high catalytic activity is added to a silicone resin-containing emulsion (emulsion polymer) containing a silanol group having a high condensation activity as the component (A). By adding, the coating film can be cured at 5 to 200 ° C., particularly 10 to 150 ° C., but it is also possible to perform room temperature curing or low temperature curing at 5 to 40 ° C., particularly 10 to 30 ° C. By coating the emulsion composition on a substrate and drying or curing at room temperature or low temperature, it is easy to form a coating film having excellent coating properties on the substrate.

Although the emulsion composition of the present invention can be cross-linked and cured at room temperature as described above, other silanol condensation catalyst is used if necessary in order to accelerate the curing rate or obtain excellent coating properties. It may be added at any time. Conventionally known curing catalysts for condensation can be used. For example, basic compounds such as n-hexylamine, tributylamine, diazabicycloundecene, tetraisopropyl titanate, tetrabutyl titanate, aluminum triisobutoxide, and aluminum. Triisopropoxide, aluminum acetylacetonate, aluminum perchlorate, aluminum chloride, cobalt octylate, cobalt acetylacetonate, zinc octylate, zinc acetylacetonate, iron acetylacetonate, tin acetylacetonate, dibutyltin dioctylate, dibutyl Metal-containing compounds such as tin dilaurate and dibutyltin oxide, acidic compounds such as p-toluenesulfonic acid and trichloroacetic acid, tetramethylammoniumfluora Such as fluorine-containing compounds such as de the like. These condensation catalysts can be used in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the silicone resin.

When the composition of the present invention is used as a paint, if an extender pigment consisting mainly of inorganic particles, a coloring pigment or an anticorrosive pigment is added, further abrasion resistance, weather resistance, heat resistance, chemical resistance and high resistance can be obtained. It is preferable because various functions such as refractive index and antistatic property are improved. As the pigment, cerium oxide, tin oxide, zirconium oxide, antimony oxide,
Rare earth oxides, titanium oxide, composite sols of these oxides, aluminum, clay, silica / silica powder, diatomaceous earth,
Talc, mica, kaolin, barite, aluminum hydroxide, zinc hydroxide, aluminum oxide, aluminum silicate, aluminum phosphate, organic solvent dispersion type silica sol such as water or alcohol, alumina sol, titania sol, zirconia sol and the like constitution or anticorrosion pigment, And those whose surface is treated with a silane coupling agent, carbon black, graphite, ceramic black,
Colored pigments such as zinc oxide, iron oxide, cadmium red, chromium oxide, cobalt green, gine green, cobalt blue, phthalocyanine blue, navy blue, cadmium yellow, titanium yellow and silver, and surface treatment of these with a silane coupling agent. Examples thereof include azo, azo lake, phthalocyanine, quinacridone and isoindolinone organic pigments. The amount of these pigments added is preferably 900 parts by weight or less based on 100 parts by weight of the solid content of the emulsion. More preferably, the amount is 500 parts by weight or less. If it is too large, it is not preferable because it lacks film-forming properties and it is difficult to form a uniform film.

Furthermore, a water-soluble or water-dispersible organic resin can be added to the composition of the present invention. The purpose of using an organic resin is to provide a cured film with flexibility, flexibility, adhesiveness,
The point is to impart chemical resistance and the like. Examples of such organic resin include polyvinyl alcohol, water-soluble polyester resin, water-soluble or water-dispersible epoxy resin, water-soluble or water-dispersible acrylic resin, water-soluble or water-dispersible silicone-acrylic resin, urethane resin and the like. be able to. The amount of these organic resins added is preferably 50 parts by weight or less based on 100 parts by weight of the solid content of the emulsion. It is more preferable to add 30 parts by weight or less. When the organic resin component is too much, heat resistance, weather resistance and the like are deteriorated, which is not preferable.

In addition, for the purpose of imparting excellent coating performance, a leveling agent may be added, or various conventionally known ultraviolet absorbers, hindered amine light stabilizers, and good solution stability may be added to obtain excellent weather resistance. A storage stabilizer and the like can be used for the purpose of obtaining the property.

The boiling point is 100 for the purpose of improving the film-forming property.
A film-forming auxiliary having a temperature of not less than 0 ° C can be added. This film forming aid remains in the film even after most of the water is vaporized, and by imparting fluidity to the film until it is completely cured, it repairs the rough film during vaporization, and in particular, makes the film uniform. It is to be given. Particularly, it is effective when the formed acrylic polymer has a high glass transition point. Also,
In order to obtain a good film, it is necessary that the non-reactive film forming auxiliary agent finally disappears from the cured film, and it does not contain a hydroxyl group that may be bonded to a silicon atom by a transesterification reaction. It is preferable. Therefore, the film formation auxiliary is 100 ° C. or higher, preferably 100 to 250 ° C.,
In particular, an organic solvent having a boiling point of 100 to 200 ° C. is preferable. If the boiling point is too high, it may easily remain in the coating. Specifically, alcohols such as 1-butanol, isobutyl alcohol, 2-pentanol, 3-pentanol, isopentyl alcohol, methyl lactate, ethyl lactate, and 3-methyl-3-methoxybutanol, 1,2
-Propanediol, 1,3-butanediol, 1,4
-Butanediol, 2,3-butanediol, 1,5-
Pentanediol, 2-methyl-2,4-pentanediol, glycerin, polyols such as trimethylolpropane, 2-butoxyethanol, 2-phenoxyethanol, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, diethylene glycol monobutyl ether. Ethylene glycol derivatives such as acetate, 1-
Methoxy-2-propanol, 1-ethoxy-2-propanol, 1-methoxy-2-methylethyl acetate, 1-ethoxy-2-methylethyl acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol mono Ethyl ether, propylene glycol derivatives such as dipropylene glycol monomethyl ether acetate, butylene glycol derivatives such as 3-methoxybutyl acetate, ketones such as cyclohexanone, butyl acetate, isobutyl acetate, γ-butyrolactone, propylene carbonate, dibutyl phthalate. And the like. In particular, alkylene glycol derivatives such as 2-ethoxyethyl acetate, 2-butoxyethyl acetate, diethylene glycol monobutyl ether acetate, 1-ethoxy-2-methylethyl acetate and dipropylene glycol monomethyl ether acetate have leveling properties. Is preferred. These organic solvents are inferior in water solubility to low boiling point alcohols such as methanol and ethanol, so that they do not impair the stability of the emulsion and contribute only to formation of a uniform film. Further, even if the boiling point is 100 ° C. or more, such as toluene or xylene, those that do not uniformly disperse in water do not exert the effect, and may adversely affect. Aromatic compounds are also undesirable because they are harmful to the human body. This film-forming aid may be added to the vinyl monomer solution before emulsion polymerization, or may be added to the emulsion after emulsion polymerization, without changing its action. The addition amount is preferably 20 parts by weight or less based on 100 parts by weight of the total amount of the silanol group-containing silicone resin and the radically polymerizable vinyl monomer. If it is added in an amount of more than 20 parts by weight, the amount of the film-forming aid remaining in the film after the completion of curing increases, and the properties of the film become insufficient, which is not preferable.

The emulsion composition of the present invention is applied to the surface to be protected of a transparent or opaque substrate such as metal, ceramic, glass, wood product, paper product, plastic, etc. By forming a cured coating film of the emulsion composition, it is possible to impart properties such as scratch resistance, weather resistance and chemical resistance.

In this case, the coating thickness is appropriately selected, but is usually 0.01 to 100 μm, particularly 0.05 to 80.
μm. As a coating method, a dipping method, a spray method, a roll coating method, a brush coating method or the like can be adopted, and the curing condition is usually room temperature to 200 ° C. and 1 minute to 200 hours.

That is, since the silicone resin-containing emulsion composition according to the present invention contains a large amount of silicone resin, the cured film has a high hardness, is highly flexible, has good adhesiveness and weather resistance, and is further repellent. Since it can also be water-based, it is suitable for surface treatments for exterior building materials, paints such as top coat agents, water repellents, and adhesives. When the base material is metal, it can be used for surface treatment of steel or stainless steel structural materials for construction or aluminum sash construction materials, or for surface treatment such as anticorrosion coating, electrocoating for automobiles or electric appliances, or electrophotographic carrier. It can be suitably used for the surface protective coating of the magnetic powder used. When the substrate is plastic, it can be suitably used as a plastic plate, a magnetic or thermosensitive recording film, a packaging film, a surface protective coating for vinyl cloth, or a function-imparting binder. When the base material is wood or paper, plywood surface protection coating,
It can be applied to surface treatment of heat-sensitive recording paper, coating for imparting water resistance to the printed surface, and the like. Further, since it also has water repellency, it can be applied as a surface protective coating of synthetic leather or the like. Further, it can be applied as a water-soluble binder for water-resistant printing ink. When the base material is an inorganic material, mortar, concrete, or cement exterior wall material or ceramic panel (ALC plate, sizing board,
Gypsum board), bricks, glass, ceramics, artificial marble, and other surface protective coatings, and can be applied as surface treatment paints. It can also be used as a base polymer of an adhesive, and by adding another organic resin or a silane coupling agent, an adhesive effective for adhesion between different kinds of substrates can be obtained.

[0060]

The silicone resin-containing emulsion composition of the present invention does not substantially contain a low boiling point or aromatic organic solvent, has good emulsion stability, good film-forming property, and room temperature to low temperature. Excellent in curability, scratch resistance, weather resistance,
It has excellent properties such as chemical resistance and gives a uniform cured film.

[0061]

EXAMPLES The present invention will be specifically described below with reference to Preparation Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following examples,% means% by weight and part means part by weight.

Preparation Example 1 A 2 liter flask was charged with 408 g (3.0 mol) of methyltrimethoxysilane, and 786 g of water was added at 0 ° C. under a nitrogen atmosphere and mixed well. Here, under ice cooling, a 0.05N hydrochloric acid aqueous solution 216
g was added dropwise over 40 minutes to cause a hydrolysis reaction.
After completion of dropping, stir at 10 ° C or lower for 1 hour and further at room temperature for 2 hours.
The hydrolysis reaction was completed by stirring for a period of time.

Then, the produced methanol and water are mixed with 70
The mixture was distilled off under reduced pressure at 60 ° C. and 60 Torr and continued until no methanol was detected in the distillate. Early 88
Methanol is no longer detected when concentrated to%,
At the same time, the liquid began to turn cloudy. When this solution was allowed to stand for one day and night, it was separated into two layers and the silicone resin was precipitated.

A part of this solution was sampled and the precipitated silicone resin was dissolved with methyl isobutyl ketone and separated from water. After dehydration, the silanol groups were quantified by reacting with methyl Grignard, and the silanol group content was 8.2% (relative to silicone resin). As a result of GPC measurement, the number average molecular weight of this silicone resin was 1.8 × 10 ³ . As a result of infrared absorption spectrum analysis, it was confirmed that the obtained silicone resin can be represented by the following average composition formula, since no methoxy group remains. Therefore, no organic solvent is by-produced from this silicone resin. (CH ₃ ) _1.0 Si (OH) _0.34 O _1.33

Next, to the above solution, methyl methacrylate (M
MA) (300 g, 3 mol) was added to dissolve the precipitated silicone resin, and the silicone resin-containing MMA solution was isolated from the aqueous layer. 505 g of an MMA solution having a nonvolatile content of 40.2% (105 ° C. × 3 hours) was obtained.

Next, 7 parts of deionized water was placed in a polymerization vessel equipped with a stirrer, a condenser, a thermometer and a nitrogen gas inlet.
30 parts, 0.47 parts of sodium carbonate as a pH buffer and 4.70 parts of boric acid were charged, the temperature was raised to 60 ° C. with stirring, and then the atmosphere was replaced with nitrogen. 1.75 parts of Rongalit,
1% aqueous solution of disodium ethylenediaminetetraacetate
At the same time as adding 12 parts, 0.04 part of a 1% aqueous solution of ferrous sulfate, 560 parts of a silicone resin-containing MMA solution, 140 parts of butyl acrylate, 2.1 parts of t-butyl hydroperoxide (69% of pure content). , Reactive surfactant Aqualon RN-20 (Daiichi Kogyo Seiyaku Co., Ltd./trade name) 1
4.0 parts, Aqualon HS-10 (Daiichi Kogyo Seiyaku Co., Ltd.)
(Manufactured / commercial name) 7.0 parts of a mixed solution is uniformly added over 2.5 hours while maintaining the temperature in the polymerization vessel at 60 ° C, and further reacted at 60 ° C for 2 hours to carry out polymerization. Completed. The solid content concentration of the obtained emulsion was 50.1%, and ammonia water was added to adjust the pH to 7.
Adjusted to 0.

Example 1 To 1400 parts of the silicone resin-containing emulsion obtained in Preparation Example 1 was added 70 parts of a 10% by weight aqueous solution of sodium hydrogen carbonate, and the mixture was stirred and mixed at room temperature for 10 minutes to obtain the desired emulsion. A composition (pH 8.4) was obtained.

[Examples 2 to 4 and Comparative Example 1] In the same manner as in Example 1, a curing catalyst was added in the composition shown in Tables 1 to 4 to obtain each emulsion composition.

[Examples 5 to 7, Comparative Examples 2 and 3] In the same manner as in Preparation Example 1, emulsion polymerization was carried out with the compounding compositions shown in Tables 1 to 4 to prepare silicone resin-containing emulsions, and then Tables 1 to 1 were prepared. Each emulsion composition was obtained by adding a curing catalyst in the composition shown in FIG.

The cured coatings of the silicone resin-containing emulsion compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 3 were evaluated by the following procedure. The formulations shown in Tables 1 to 4 were applied to a polished steel plate with a clean surface, and the film thickness after curing was 20 μm.
And was cured under the conditions shown in Tables 1 to 4.

Regarding the cured film, JIS K-5400
Measure the pencil hardness of the cured coating according to the standard, cross-cut adhesion test using cellophane tape, drop 3% NaOH aqueous solution or 5% sulfuric acid aqueous solution on the coating, and observe the change of the coating after standing at room temperature × 1 day Chemical resistance, solvent resistance to observe the change of the film after rubbing the film 30 times with absorbent cotton containing xylene, and weather resistance of the film after irradiation for 3000 hours using a sunshine long life weather meter did.

Regarding the adhesion, 100/100 is the one that is completely adhered, and the chemical resistance, the solvent resistance and the weather resistance are ◯ when there is no deterioration of the properties of the coating and coloring, and the adhesion is poor. Also, light yellowing was judged as Δ, and peeling or yellowing was judged as x. The results are shown in Table 1.
~ 4.

Further, the storage stability of the emulsion itself is 4
It was judged by the layer separation after storage at 0 ° C. for 30 days, the presence or absence of a gel-like substance, and the like. The results are shown in Tables 1 to 4.

[0074]

[Table 1]

[0075]

[Table 2]

[0076]

[Table 3]

[0077]

[Table 4] KBM-503: 3-methacryloxypropyltrimethoxysilane KBM-502: 3-methacryloxypropylmethyldimethoxysilane

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Masaaki Yamatani Masaaki Yamatani, Hitomi, Matsuida-cho, Usui-gun, Gunma 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (56) Reference JP 61-9463 A JP, A) JP 4-261454 (JP, A) JP 6-344665 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 83/00-83/16 C08F 2/00-2/60 C09D 183/00-183/16

Claims (9)

(57) [Claims] 1. [A] (1) The following average composition formula (1) R ¹ _m R ² _n Si (OH) _p (OX) _q O _{(4-mnpq) / 2}
(1) (In the formula, R ¹ represents an unsubstituted monovalent hydrocarbon group, R ² represents a substituted monovalent hydrocarbon group, and OX represents a hydrolyzable group. M, n, p,
q is 0.5 ≦ m ≦ 1.8, 0 ≦ n ≦ 1.0, 0 <p ≦
1.5, 0 ≦ q ≦ 0.5, 0.5 ≦ m + n ≦ 1.8, 0
It is a number that satisfies <p + q ≦ 1.5. ] Water-insoluble silanol group-containing silicone resin represented by 100 parts by weight, (2) Radical-polymerizable vinyl monomer Emulsion polymer of a solution containing 10 to 1000 parts by weight as a main component, and [B] Group IA and / Alternatively, a silicone resin-containing emulsion composition comprising a compound containing a Group IIA metal element. 2. The content of the compound containing a Group IA and / or Group IIA metal element of the component [B] is (1) above.
(2) 0.001 to 100 parts by weight of the total amount of components
The composition according to claim 1, which is 20 parts by weight and has a pH of 8 to 12. 3. The composition according to claim 1, wherein the compound containing a Group IA and / or Group IIA metal element of the component (B) is an inorganic salt. 4. The compound containing a Group IA and / or Group IIA metal element of the component [B] contains at least one element selected from Li, Na, K and Cs. Or the composition according to 3. 5. The composition according to claim 4, wherein the compound containing the Group IA and / or Group IIA metal element of the component (B) is sodium carbonate, potassium carbonate, sodium hydrogen carbonate or potassium hydrogen carbonate. 6. The following general formula (2): (In the formula, R ³ is a hydrogen atom or a methyl group, R ⁴ is a carbon atom of 1 to
A divalent organic group such as an alkylene group, an arylene group or an alkylenearylene group which may have an oxygen atom, a —COO— group or the like, r represents 0, 1 or 2, and R ¹ and X are as described above. Indicates the same meaning. The composition according to any one of claims 1 to 5, wherein the vinyl-polymerizable functional group-containing hydrolyzable silane represented by (4) is contained in an amount of 0.01 to 10 mol% of the whole radical-polymerizable vinyl monomer of the component (A). . 7. An article formed with a cured coating of the composition according to claim 1. 8. A method for producing an article according to claim 6, wherein a film of the composition according to any one of claims 1 to 6 is formed on a substrate and then the film is cured at room temperature. . 9. The method according to claim 8, wherein the substrate is metal, ceramic, glass, wood, paper or plastic.