JPH11130962A - Silicone-resin-containing emulsion composition, article with cured film formed therefrom, and production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silicone-resin-contg. emulsion compsn. which does not contain a low-boiling or arom. org. solvent, has good emulsion stability and film-forming properties, and gives a uniform cured film excellent in room-temp. to low-temp. curability, scratch resistance, weatherability, and chemical resistance. SOLUTION: This compsn. contains an emulsion polymn. product [A] of a soln. contg., as the main ingredients, 100 pts.wt. water-insoluble silanol-group- contg. silicone resin of the formula: R<1> m R<2> n Si(OH)p (OX)q O(4-m-n-p-q)/2 (wherein R<1> is a nonsubstd. monovalent hydrocarbon group; R<2> is a substd. monovalent hydrocarbon group; OX is a hydrolyzable group; 0.5<=m<=1.8; 0<=n<=1.0 provided 0.5<=m+n<=1.8; 0<p<=1.5; and 0<=q<=0.5 provided 0<p+q<=1.5) and 10-1,000 pts.wt. free-radical-polymerizable vinyl monomer and a compd. [B] contg. a metal element of the group IA and/or a metal element of the group IIA.

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, and the formation of this cured film. TECHNICAL FIELD The present invention relates to articles such as metal, plastic, ceramic, wooden building materials, structures, and the like, and a method of manufacturing the same.

[0002]

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

Based on this requirement, emulsion paints obtained by emulsion polymerization of radically polymerizable vinyl monomers represented by acrylic resin have been widely used as basic materials for coating agents because of their excellent film-forming properties and chemical resistance. Have been. However, this type of coating agent has the disadvantage of essentially lacking water resistance and weather resistance.

On the other hand, a silicone resin (resin) obtained by hydrolyzing and condensing a silane compound has the ability to form a film having high hardness and excellent weather resistance, water resistance, heat resistance and water repellency. It is attracting attention as a coating agent.
On the other hand, there are drawbacks in that the film formability, alkali resistance, film flexibility are poor, and the storage stability is poor due to the silanol group having a high condensation activity. In addition, silicone resin
Generally, since it is used in a form dissolved in an organic solvent, there are problems of danger of fire and explosion, toxicity to human body, environmental pollution, and the like, and development of emulsion type is required.

Therefore, in order to improve these disadvantages,
Various attempts have been made as described below, but are still insufficient. (A) A method of emulsifying an alkoxysilane compound or a partial hydrolyzate / condensate thereof using various surfactants to form an aqueous emulsion (JP-A-58-213046; JP-A-62-197369; 3-115485
No. JP-A-3-200793). A system is also known in which this emulsion is further mixed with an emulsion obtained by emulsion polymerization of a polymerizable vinyl monomer (JP-A-6-344).
665). (B) A method in which a solvent-free 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 in which a radically polymerizable vinyl monomer is emulsion-polymerized 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, followed by 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 in which alkoxysilane is added to an emulsion obtained by emulsion polymerization of a radical polymerizable vinyl monomer, and the mixture is hydrolyzed and condensed to introduce a silicone resin into emulsion particles (JP-A-3-45628, JP-A-8-3409).
No.). (F) A method in which an emulsion is prepared by emulsion polymerization of a vinyl polymerizable functional group-containing alkoxysilane together with a radical polymerizable vinyl monomer (JP-A-61-9463, JP-A-8-27347).

However, in the case of (a), since the active alkoxy group is easily hydrolyzed with the lapse of time, alcohol as an organic solvent is produced as a by-product in the system, and relatively low polymerization raw materials are polymerized. There is. As a result, the by-product alcohol makes the emulsion unstable and the degree of polymerization changes, so that the performance is not constant. It is not appropriate to use a large amount of a surfactant in order to make up for these drawbacks, since the coating properties such as hardness and water resistance of the coating are greatly reduced. In addition, since the silicone resin is used alone, it has disadvantages derived from the silicone resin, and the properties of the coating film are not sufficiently satisfied.

[0007] In the case of (b), a method of forcibly emulsifying particles of a solid silicone resin having a softening point together with a chain organopolysiloxane having OH groups at both ends with the aid of a surfactant is used. is there. Although this method has the advantage of not containing an organic solvent, it is difficult to dissolve in a low-polarity liquid organopolysiloxane due to the high polarity of the silicone solid resin, and the solid resin must be dispersed using a sand grinder. Therefore, it is difficult to reduce the particle size, and there is a disadvantage that the stability of the formed emulsion is not good. Further, since the resin is a solid resin, the content of silanol groups is relatively low at 0.1 to 5% by weight, and high-temperature curing at 200 to 300 ° C. is required, and workability is inferior to that of an organic solvent solution type. Furthermore, since a chain organopolysiloxane is used in combination, the cured film is rich in water repellency, but the hardness is low, so that the scratch resistance is inferior and the durability is not sufficient.

In the case of (c), a surfactant-free water-soluble resin is first prepared by simply hydrolyzing an alkoxysilane in water, and then a surfactant is added to emulsify the radically polymerizable vinyl monomer. Polymerization is the production method in this case. However, this method also has a disadvantage that alcohol is by-produced due to hydrolysis in water. This water-soluble silicone resin is partially incorporated into the emulsion particles, but because of its high water solubility, a considerable portion remains in water. Active silanol groups contained in molecules existing in water are gradually condensed and easily precipitated 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 film, so that the film properties are deteriorated. It is not satisfactory.

In the case of (d), after the alkoxysilane is hydrolyzed in water, an emulsion of the corresponding solid silicone resin is prepared, and the emulsion polymerization is carried out starting from the vinyl polymerizable group contained in the silicone resin. Acrylic chains are grafted. Since this method also includes a step of hydrolyzing alkoxysilane, the system contains an alcohol as an organic solvent in the system. Therefore, the stability of the emulsion is insufficient. This method aims at solid particles capable of imparting lubricity and water repellency, and the silicone resin responsible for this function is located at the center of the nucleus, contributing to preventing aggregation of particles in water and improving dispersibility. This is a method for preparing such composite particles having an acrylic chain grafted thereon. Therefore, it is preferable that both components are present in a non-uniform state, and that the silicone resin should be sufficiently crosslinked in the particles, and should be inactive because no silanol groups are present. Is not formed.

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

In the case of (f), the alkoxysilane having a vinyl polymerizable functional group is emulsion-polymerized together with a radical polymerizable vinyl monomer, and the hydrolysis of the alkoxy group is suppressed.
As it is preserved, the by-products and the aging of the properties of the alcohol over time, as in other cases, are fairly small and good. However, it is difficult to incorporate a large amount of a silicone resin component into the coating film, so that properties such as weather resistance cannot be improved, and this is not a satisfactory level for exterior use.

As described above, each of the conventionally known methods does not contain (i) a highly flammable low-boiling organic solvent such as an alcohol, and (ii) the emulsion has good stability.
ii) excellent low-temperature curability, (iv) scratch resistance, weather resistance,
No silicone resin-containing emulsion having good properties such as chemical resistance and giving a uniform cured film has been obtained.

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

[0014]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted intensive studies in order to achieve the above object, and as a result, it has been found that a silicone having a silanol group end represented by the following average composition formula (1) is preferable. Emulsion polymerization of a mixed solution containing a resin and a radically polymerizable vinyl monomer as main components substantially contains 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 and xylene. Without containing the condensation type silicone resin and vinyl polymer resin in the same particles of the emulsion,
It has been found that an emulsion having excellent storage stability and giving good film properties can be obtained. Further, by adding a specific curing catalyst, that is, a compound containing a Group IA and / or IIA metal element, as a curing catalyst to the emulsion, the curability at low temperatures is improved and excellent curability at room temperature is provided. This has led to the achievement of the present invention.

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) In the formula, R ¹ represents an unsubstituted monovalent hydrocarbon group, R ² represents a substituted monovalent hydrocarbon group, OX represents a hydrolyzable group, and 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) an emulsion polymer of a solution containing 10 to 1000 parts by weight of a radical polymerizable vinyl monomer as a main component, and [B] a Group IA and / or IIA metal Provided is a silicone resin-containing emulsion composition comprising a compound containing an element. The present invention also provides an article having a cured film of the composition formed thereon, and a method for producing the article, wherein a film of the composition is formed on a substrate and the film is cured at room temperature.

The emulsion composition of the present invention has the following advantages which could not be obtained by a conventionally known method. (I) Since both resins form an interpenetrating network structure (IPN) in the emulsion particles, the deficiencies of both resins are complemented, and excellent film-forming properties, scratch resistance, weather resistance, chemical resistance, etc. Good properties and uniform cured film can be obtained. (Ii) In the emulsion particles, the polymers are entangled with each other in a solventless state, so that the degree of freedom of the silanol group having a high condensation activity is limited. As a result, even in a system having a high silanol group content, condensation of silanol groups is suppressed, and good storage stability is obtained. In addition, since a water-insoluble silicone resin is used, the silicone resin is completely incorporated into the particles, so that the stability is maintained at a good level. (Iii) Conversely, as a result of the silanol groups being constrained in the particles, their high curing activity is preserved, and a specific curing catalyst, that is, a compound containing a Group IA and / or IIA metal element is added. Thereby, excellent curability is exhibited even at room temperature to low temperature. (Iv) Since a solvent is not substantially contained, a good film is obtained at the time of drying and curing, and a harmful solvent is not volatilized, so that a good working environment is secured. Further, since the emulsion does not contain an alcohol component that promotes the destruction of the emulsion, the stability of the emulsion is maintained in a favorable state.

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

Hereinafter, the present invention will be described in more detail.
First, the silanol group-containing silicone resin constituting the present invention will be described. The present 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 one having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-group.
Alkyl group such as butyl group, hexyl group, cyclohexyl group, octyl group, decyl group, vinyl group, allyl group, 5
Specific examples include alkenyl groups such as -hexenyl group and 9-decenyl group, and aryl groups such as phenyl group. Among these, a methyl group, a propyl group, a hexyl group, and a phenyl group are preferred. In particular, a methyl group is preferable when weather resistance is required, a long-chain alkyl group is preferably used when a water repellent is required, and a phenyl group is used when a film is provided with flexibility. Good to do.
In this case, it is particularly preferable that the content of the methyl group in all the organic substituents (R ¹ + R ² ) is at least 80 mol%.

R ² represents a substituted monovalent hydrocarbon group. The substituted monovalent hydrocarbon group is obtained by substituting a part or all of the hydrogen atoms of the above unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms with a substituent. Examples of the substituent include (i) fluorine,
A halogen atom such as chlorine, (ii) a glycidyloxy group,
An epoxy functional group such as an epoxycyclohexyl group, (i
ii) a (meth) acryl functional group such as a methacryl group or an acrylic group, (iv) an amino group, an aminoethylamino group,
Amino functional groups such as phenylamino group and dibutylamino group; (v) sulfur-containing functional groups such as mercapto group and tetrasulfide group; (vi) alkyl ether functional groups such as (polyoxyalkylene) alkyl ether group;
i) Anionic groups such as a carboxyl group and a sulfonyl group, and (viii) a group containing a quaternary ammonium salt structure are applicable. Specific examples of the substituted monovalent hydrocarbon group include a trifluoropropyl group, a perfluorobutylethyl group, a perfluorooctylethyl group,
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 , 3
-Aminopropyl group, N- (2-aminoethyl) aminopropyl group, 3- (N-phenylamino) propyl group,
Examples include a 3-dibutylaminopropyl group, a 3-mercaptopropyl group, a 2- (4-mercaptomethylphenyl) ethyl group, a polyoxyethyleneoxypropyl group, a 3-hydroxycarbonylpropyl group, and a 3-tributylammoniumpropyl group. it can. In order to improve the adhesion to the substrate, it is preferable to apply an epoxy, amino, mercapto functional group or the like. In order to achieve a tight block with a vinyl polymer, it is preferable to use a (meth) acryl functional group capable of radical copolymerization or a mercapto functional group having a function as a chain transfer agent. When cross-linking is attempted with a bond other than the siloxane bond with the vinyl polymer, 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) 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 a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a sec-butoxy group, and t.
-Butoxy, isopropenoxy, phenoxy and the like. It is preferable to use a methoxy group, an ethoxy group, or an isopropoxy group in view of hydrolysis / condensation reactivity and stability in an emulsion.

Each of m, n, p, and q is 0.5 ≦ m ≦ 1.
8, 0 ≦ n ≦ 1.0, 0 <p ≦ 1.5, 0 ≦ q ≦ 0.
5, a number that satisfies the range of 0.5 ≦ m + n ≦ 1.8 and 0 <p + q ≦ 1.5. If 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. If m exceeds 1.8, the number of chain units increases, and as a result, the cured film becomes rubbery and the abrasion resistance becomes insufficient, which is not preferable. More preferably, m should satisfy the range of 0.6 or more and 1.5 or less. If n exceeds 1.0, the content of bulky R ² is increased, so that it is difficult to maintain the hardness and the weather resistance is undesirably reduced. If it is not necessary to provide the function by R ² described above, this R ² may not be contained. The set optimum range of m + n is also the same as the reason for explaining m. The silanol group is an essential component. However, 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 0.05 to 0.8, and still more preferably 0.2 to 0.7. A crosslinkable hydrolyzable group OX may be present other than the silanol group, but the amount 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 preferred. Further, (p + q) representing the total number of the crosslinkable substituents must satisfy the range of 0 <p + q ≦ 1.5. It is not preferable because the water content becomes small and the water solubility becomes excellent.

The silicone resin applicable to the present invention must satisfy the above conditions, and at the same time, contain a silanol group, and must not be dissolved alone in water. When dissolved in water, it is not preferable because it is not completely incorporated into the particles during emulsion polymerization. Therefore, as long as 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 the production, the type of hydrolyzable group is chloro or alkoxy, and an organic substituent containing 1, 2, 3 or 4 hydrolyzable groups and satisfying the above conditions is used. Any silane compound can be used. Specifically, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldichlorosilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, 5-hexenyltrimethoxysilane, 3-glycidoxypropyltrisilane Methoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meta ) Acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 4-vinylphenyltrimethoxysilane, 3- (4-vinylf 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, tetrachlorosilane 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, hexylmethyldichlorosila , Hexyl methyl dimethoxy silane, phenyl methyl dichlorosilane, phenyl methyl dimethoxy silane, diphenyl dichlorosilane, diphenyl dimethoxysilane, dimethyl phenyl chlorosilane,
And a partial hydrolyzate thereof can be used as a usable silane compound. It is more preferable to use methoxysilane or ethoxysilane from the viewpoint of operability and easy removal of 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 obtaining the silicone resin usable in the present invention by hydrolyzing the hydrolyzable silane compound. The first is toluene,
Aromatic hydrocarbons such as xylene, hexane, hydrocarbons such as octane, ketone compounds such as methyl ethyl ketone and methyl isobutyl ketone, ester compounds such as ethyl acetate and isobutyl acetate, methanol, ethanol, isopropanol, butanol, isobutanol,
This is a method of hydrolyzing in an organic solvent selected from alcohols such as t-butanol. In the case of this method, from a silicone resin that is not dissolved in water by itself,
It is necessary to remove harmful organic solvents under normal pressure or reduced pressure.
The organic solvent may be simply removed and solidified as a viscous liquid, or a high-boiling radical polymerizable vinyl monomer used in the next step is added, and the low-boiling organic solvent is co-precipitated. And may be 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 grow the silicone resin to a level that 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 a large amount of silanol groups, containing no organic solvent, insoluble in water, dispersed in water or separated and precipitated from water, can be obtained. After separating this silicone resin from water,
A radically polymerizable vinyl monomer may be added and used as a solution thereof, or a radically polymerizable vinyl monomer may be added to an aqueous solution containing a silicone resin and separated as a silicone resin-containing vinyl monomer solution.

In carrying out the hydrolysis, a hydrolysis catalyst may be used. 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, and solid acids such as ion exchange resins. Examples include hydrogen fluoride, hydrochloric acid, nitric acid, sulfuric acid, acetic acid,
Examples thereof include an organic carboxylic acid represented by maleic acid, methyl sulfonic acid, and a cation exchange resin 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 per mol of the hydrolyzable group on the silicon atom.
Preferably it is in the range of 10 mol%.

Next, the radical polymerizable vinyl monomer as the second component will be described. As the radically polymerizable vinyl monomer, conventionally known ones shown below can be applied as long as radical polymerization is possible. (A) C1-C18 alkyl (meth) acrylate of an 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; (e) amino group-containing vinyl monomers such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate;
(F) alkoxy group-containing vinyl monomers such as methoxyethyl (meth) acrylate and butoxyethyl (meth) acrylate; (g) glycidyl group-containing vinyl monomers such as glycidyl (meth) acrylate and glycidyl allyl ether; (h) vinyl acetate; Vinyl ester monomers such as vinyl propionate, (i) styrene,
Aromatic vinyl monomers such as vinyltoluene and α-methylstyrene, (j) vinyl cyanide monomers such as (meth) acrylonitrile, (k) halogenated vinyl monomers such as vinyl chloride and vinyl bromide, (l) divinylbenzene, Vinyl monomers 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. Containing dimethylpolysiloxane 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
Specific examples include silane compounds having a radically polymerizable functional group such as-(4-vinylphenyl) propyltrimethoxysilane and 4-vinylphenylmethyltrimethoxysilane. One of these compounds may be used alone. Alternatively, two or more kinds can be used in combination.

Among them, a radical polymerizable vinyl monomer having an alkyl group having 1 to 18 carbon atoms (meth)
It is preferable that the content of the alkyl acrylate is 1 to 100 mol%. If the content is less than 1 mol%, characteristics such as chemical resistance may not be obtained. More preferably, it satisfies 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 particularly to form a siloxane bond by a condensation reaction. A silane compound containing a radical polymerizable functional group shown in (o), and a glycidyl (meth) acrylate classified into (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 in the present system, the resin used for the other is a silicone resin containing a silanol group, and thus a silane compound is more suitable. In this case, as the silane compound, a vinyl polymerizable functional group-containing hydrolyzable silane represented by the following general formula (2) is used.

[0029]

Embedded image In the formula, R ³ is a hydrogen atom or a methyl group, and R ⁴ is a group having 1 to 1 carbon atoms.
0 oxygen atoms, -COO- interposed may be an alkylene group or the like group, an arylene group, a divalent organic group such as alkylene arylene group, r represents 0, 1 or 2, R ^1, X is as above Indicates the same meaning.

Specific examples of R ⁴ include the following.

[0031]

Embedded image

The content of the vinyl polymerizable functional group-containing hydrolyzable silane is preferably from 0.01 to 10 mol%, more preferably from 0.1 to 5 mol%, of the whole radically polymerizable vinyl monomer. If the amount is too small, the expression of solvent resistance and chemical resistance becomes insufficient, and if the amount is too large, crosslinking may be excessively high and cracks may occur in the coating, which may be inappropriate.

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

The radical polymerizable vinyl monomer is added to 100 parts by weight of the silicone resin as the first component.
Used in the range of 0 to 1000 parts by weight. If it is less than 10 parts by weight, the film-forming properties 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 a 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 radically polymerizable vinyl monomer. The emulsion composition of the present invention has a substantially flammable organic compound having a boiling point of less than 100 ° C. Non-dispersible (non-water-soluble) in solvents, aromatic organic solvents harmful to the human body, and water
Containing no organic solvent. 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, and isobutyl acetate;
Specific examples include ethers such as diethyl ether and tetrahydrofuran, and acetonitrile.However, these solvents cause environmental pollution, are harmful to the human body, impair the stability of the emulsion, It is preferable that these solvents are not essentially contained because they hinder formation of a uniform film afterwards. However, as described above, in a composite emulsion of (silicone resin + acrylic resin), it has been impossible to form an emulsion substantially containing no solvent by the methods known hitherto. The cause is that the silicone resin containing silanol group rich in reaction activity at the molecular terminal,
Low molecular weight compounds are soluble in water, but are unstable and significantly change with time in the absence of organic solvents.On the other hand, high molecular weight compounds are quite stable, but become insoluble in water and do not contain organic solvents. This is because it tends to be solidified, which makes it difficult to emulsify. For this reason, as described above, an organic solvent is used in combination, or an alkoxysilane compound or a partial hydrolyzate thereof is used as a raw material. In the present invention, before the emulsion polymerization is carried out, from the solution of the silicone resin alone polycondensed to a level insoluble in water, an organic compound containing alcohol and the like by-produced when the hydrolyzable silane compound is hydrolyzed. By removing the solvent as much as possible and further subjecting it to a radical polymerizable vinyl monomer solution for emulsion polymerization, an emulsion containing substantially no organic solvent can be obtained. Therefore, the emulsion of the present invention may contain a trace amount of an organic solvent that cannot be removed, but the amount of the organic solvent is determined by the first component and the second component in order to avoid the above problems. Is preferably 0 to 5% by weight, more preferably 0 to 2% by weight, based on the total of

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 substantially contains the organic solvent in the above amount. Can be produced by emulsion polymerization of a solution containing no.

In this case, a surfactant is used in the emulsion polymerization. Examples of the surfactant include various known nonionic, cationic and anionic surfactants, and functional groups capable of radical polymerization. Containing reactive emulsifiers are applicable. Specifically, nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl 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 alkyl allyl sulfate, alkyl or alkyl allyl sulfonate, dialkyl sulfosuccinate, amphoteric surfactants such as amino acid type and betaine type Activator, JP-A-8-2732
No. 7, a sulfonate in the molecule,
Various reactive surfactants including derivatives such as polyoxyethylene chains, radically polymerizable (meth) acrylates containing hydrophilic groups such as quaternary ammonium salts, styrene, and maleic ester compounds can be used. Examples of such surfactants are as follows.

[0038]

Embedded image

[0039]

Embedded image

[0040]

Embedded image

These surfactants may be used alone or in combination.
More than one species may be used in combination. The surfactant is added in an amount of 0.1 to the total amount of the first component and the second component (active ingredient).
It is preferable to use 5 to 15% by weight, especially 1 to 10% by weight.
It is good to use% by weight.

A radical polymerization initiator is used in the above emulsion polymerization. Examples of the radical polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, aqueous hydrogen peroxide, t-butyl hydroperoxide, and the like. t-butylperoxymaleic acid, succinic peroxide, 2,2 ′
Water-soluble types such as -azobis- [2-N-benzylamidino] propane hydrochloride, benzoyl peroxide, cumene hydroperoxide, dibutyl peroxide, diisopropylperoxydicarbonate, cumylperoxy neodecanoate, cumylperoxy An oil-soluble type such as octoate and azoisobutyronitrile, and a redox system using a reducing agent such as sodium acid sulfite, Rongalit, and ascorbic acid together can be used. The amount of the polymerization initiator used may be 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on the radical polymerizable vinyl monomer.

Next, the method for producing the emulsion of the present invention will be described more specifically. The preferred methods are roughly classified into the following two methods.

In the first method, the organic solvent is distilled off from the solely water-insoluble silicone resin solution containing a silanol group in the first step to make the active ingredient substantially only, 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 the silicone resin-containing vinyl monomer solution prepared in the second step is emulsified by using a surfactant in the third step. This is a method of polymerizing into an emulsion. In the step of distilling off the solvent, the highly active silanol groups are preserved, so it is preferable to remove them at as low a temperature as possible. Therefore, this method is suitable when a silicone resin having a relatively low silanol group content and excellent stability is used because the organic solvent is once separated. If necessary, a so-called solvent substitution method may be employed in which the organic solvent is distilled off in the presence of a relatively high-boiling radical polymerizable vinyl monomer, and the radical polymerizable vinyl monomer is used instead of the solvent. As a method of emulsion polymerization, after emulsifying all at once,
Conventionally known various methods such as a batch charging method for polymerization and a monomer addition method for polymerizing while continuously adding a radical polymerizable vinyl monomer-containing solution or an emulsion thereof can be applied. Further, a seed polymerization method in which a part of the emulsion is polymerized in advance and then the remaining emulsion is added, and a core / shell polymerization method in which the monomer composition of the core and the shell is 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 using a homomixer or a high-pressure homogenizer. Emulsion polymerization is completed at a temperature of 10 to 90C, preferably 30 to 80C, usually for 3 to 8 hours.

In the second method, the hydrolyzable silane compound is hydrolyzed in water in the first step, further subjected to condensation polymerization, and the reaction comprising the silicone resin having a silanol group at the molecular terminal and having the above formula (1). A mixture is obtained, and in the second step, an organic solvent such as alcohol by-produced by hydrolysis from the reaction mixture and other hydrolysis by-products are distilled off, and only the silanol group-containing silicone resin component of the formula (1) and water are removed. A vinyl monomer compound capable of being radically polymerized in the third step is added thereto, and the silicone resin present in a water-based dispersed or insoluble state is dissolved in the vinyl monomer compound, and the radical polymerizable vinyl containing the silicone resin is dissolved. Separated from the aqueous layer as a monomer solution, and further using a surfactant in the fourth step, the silicone resin-containing radical polymerizable compound 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 in the middle of the process, it is possible to suppress condensation of silanol groups having a high reaction activity. Therefore, this method is suitable for a silicone resin rich in silanol groups but insoluble in water. In addition, the silicone resin hydrolyzed and condensed in water has a higher hardness, gives a highly flexible film, and is excellent in curability as compared with a silicone resin having the same composition prepared in an organic solvent. Therefore, this is a preferable method.

The emulsion composition of the present invention comprises the above-mentioned (A) a silanol group-containing emulsion (emulsion polymer).
And (B) a compound containing a Group IA and / or IIA metal element as a curing catalyst.
Specifically, hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, 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 hydrogen, potassium hydrogen sulfate and 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 can be used in combination. Incidentally, these curing catalysts are preferably water-soluble.

The amount of the compound containing a Group IA and / or IIA metal element may be as follows: (A) the silicone resin (a) in the silanol group-containing emulsion (emulsion polymer);
And the total amount of the radical polymerizable monomer (b) (a + b)
It is preferably in the range of 0.001 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, per 100 parts by weight. If the amount 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, weather resistance, water resistance, and appearance of a coating film may be deteriorated.

It is preferable that the pH of the emulsion composition after the addition of the compound containing a Group IA and / or IIA metal element is 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 is deteriorated, and the curability may be lowered or the appearance of the coating film may be poor due to microgel.

The compound containing a Group IA and / or IIA metal element is preferably an inorganic salt from the viewpoint of operability and availability. Further, because of its strong ability as a curing catalyst, Group IA and / or IIA metal elements are
It is preferable to use a compound that 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 preferred.

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

The emulsion composition of the present invention can be crosslinked and cured at room temperature as described above. However, in order to accelerate the curing rate or obtain excellent film properties, another silanol condensation catalyst may be used as necessary. It may be added sometimes. 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, 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; tetramethylammonium fluora 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, a coloring pigment or an anticorrosive pigment mainly composed of inorganic particles is blended, the abrasion resistance, weather resistance, heat resistance, chemical resistance, and the like can be further improved. It is preferable because various functions such as refractive index and antistatic property are improved. The pigments include 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,
Constitutional or anticorrosive pigments such as talc, mica, kaolin, barite, aluminum hydroxide, zinc hydroxide, aluminum oxide, aluminum silicate, aluminum phosphate, water or alcohol-dispersed silica sol, alumina sol, titania sol, zirconia sol; And those surfaces treated with a silane coupling agent, carbon black, graphite, ceramic black,
Color 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, silver, etc., and surface treatment of these surfaces with silane coupling agents And azo-based, azo lake-based, phthalocyanine-based, quinacridone-based and isoindolinone-based 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 present emulsion. More preferably, the amount is 500 parts by weight or less. If the amount is too large, the film-forming properties are lacking and a uniform film is hardly formed, which is not preferable.

Further, the composition of the present invention may contain a water-soluble or water-dispersible organic resin. The purpose of using an organic resin is to provide a cured film with flexibility, flexibility, adhesion,
The point is to provide chemical resistance and the like. Examples of such an organic resin include polyvinyl alcohol, a water-soluble polyester resin, a water-soluble or water-dispersible epoxy resin, a water-soluble or water-dispersible acrylic resin, a water-soluble or water-dispersible silicone-acryl resin, a urethane resin, and the like. be able to. The addition amount of these organic resins is preferably 50 parts by weight or less based on 100 parts by weight of the solid content of the present emulsion. More preferably, the content is 30 parts by weight or less. If the amount of the organic resin component is too large, heat resistance, weather resistance and the like are undesirably reduced.

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

Further, in order to improve the film forming property, a boiling point of 100
A film forming auxiliary agent having a temperature of not lower than ° C can be added. This film forming aid remains in the film even after most of the water has vaporized, and by imparting fluidity to the film until it is completely cured, repairs the rough film during vaporization, and in particular, improves the uniformity of the film. Is to be granted. This is particularly effective when the acrylic polymer formed has a high glass transition point. Also,
In order to obtain a good film, the non-reactive film forming aid must eventually disappear from the cured film, and does not contain hydroxyl groups that may be bonded to silicon atoms by transesterification. Is preferred. Therefore, the film forming aid is 100 ° C. or higher, preferably 100 to 250 ° C.,
Particularly, 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;
-Propanediol, 1,3-butanediol, 1,4
-Butanediol, 2,3-butanediol, 1,5-
Polyols such as pentanediol, 2-methyl-2,4-pentanediol, glycerin and 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 Propylene glycol derivatives such as ethyl ether and 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 a leveling property. Is preferred. These organic solvents are inferior in water solubility as compared with low boiling alcohols such as methanol and ethanol, so that they do not impair the stability of the emulsion and contribute only to the formation of a uniform film. Further, even if the boiling point is 100 ° C. or higher, such as toluene and xylene, which do not disperse uniformly in water, do not exhibit the effect and may adversely affect the water. Aromatic compounds are also harmful to the human body and are not preferred. This film forming aid may be added to the vinyl monomer solution before the emulsion polymerization or added to the emulsion after the emulsion polymerization, and the action does not change. 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 radical polymerizable vinyl monomer. If it is added in excess of 20 parts by weight, the amount of the film-forming aid remaining in the film even after the completion of curing becomes large, and the properties of the film become insufficient, which is not preferable.

The emulsion composition of the present invention is applied to a surface to be protected of a transparent or opaque substrate such as metal, ceramic, glass, wood product, paper product, plastic, etc., and is cured to form the above-mentioned article. A cured film of the emulsion composition is formed, whereby properties such as scratch resistance, weather resistance, and chemical resistance can be imparted.

In this case, the thickness of the coating is appropriately selected, but is usually 0.01 to 100 μm, particularly 0.05 to 80 μm.
μm. In addition, as a coating method, an immersion method, a spray method, a roll coating method, a brush coating method, or the like can be adopted, and the curing conditions are usually room temperature to 200 ° C. for 1 minute to 200 hours.

That is, since the silicone resin-containing emulsion composition according to the present invention contains a large amount of a silicone resin, the cured film has high hardness, high flexibility, good adhesion and weather resistance, and furthermore repellency. Since it can be imparted with water, it is suitable for coating materials such as a base treatment agent for exterior building materials and a top coat agent, a water repellent or an adhesive. When the base material is metal, it can be used for surface protection or anti-corrosion treatment of iron, stainless steel construction materials and aluminum sash construction materials, etc., electrodeposition coating coating for automobiles or electric appliances, or carrier for electrophotography. It can be suitably used for the surface protection coating of the magnetic powder used. When the substrate is plastic, it can be suitably used as a plastic plate, a film for magnetic or thermal recording, a film for packaging, a surface protective coating such as vinyl cloth, or a binder for imparting functions. If the substrate is wood or paper related, plywood surface protective coating,
It can be applied to surface treatment of thermal recording paper, coating for imparting water resistance to the printed surface, and the like. In addition, since it has water repellency, it can be applied as a surface protective film of synthetic leather or the like. Furthermore, it can be applied as a water-soluble binder for a water-resistant printing ink. When the base material is an inorganic material, a mortar, concrete, or cement exterior wall material or ceramic panel (ALC board, sizing board,
Gypsum board), brick, glass, porcelain, artificial marble, etc. can be applied as a surface protective coating and a surface treatment paint. 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 bonding between different kinds of base materials can be obtained.

[0060]

EFFECTS OF THE INVENTION 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, has good film forming properties, and has a room temperature to low temperature. Excellent 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 described in detail with reference to Preparation Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following examples,% indicates% by weight, and part indicates parts by weight.

[Preparation Example 1] 408 g (3.0 mol) of methyltrimethoxysilane was charged into a 2 liter flask, and 786 g of water was added at 0 ° C. under a nitrogen atmosphere and mixed well. Here, under ice cooling, 0.05N hydrochloric acid aqueous solution 216
g was added dropwise over 40 minutes to cause a hydrolysis reaction.
After completion of the dropwise addition, the mixture was stirred at 10 ° C or lower for 1 hour, and further stirred at room temperature for 2 hours.
The mixture was stirred for an hour to complete the hydrolysis reaction.

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

A part of the solution was sampled, and the precipitated silicone resin was dissolved using methyl isobutyl ketone and separated from water. After the dehydration treatment, methyl Grignard was reacted to quantify silanol groups. As a result, the content of silanol groups was 8.2% (vs. 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 recognized that the obtained silicone resin could be represented by the following average composition formula since no methoxy group remained. Therefore, no organic solvent is produced as a by-product from this silicone resin. (CH ₃ ) _1.0 Si (OH) _0.34 O _1.33

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

Next, deionized water was added to 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, and the temperature was raised to 60 ° C. while stirring, followed by purging with nitrogen. To this, 1.75 parts of Rongalite,
1% aqueous solution of disodium ethylenediaminetetraacetate
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% pure) , A 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 / trade name) A mixed solution consisting of 7.0 parts was 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 concentration of the obtained emulsion was 50.1%, and the pH was adjusted to 7.0 by adding aqueous ammonia as needed.
Adjusted to zero.

Example 1 To 1400 parts of the silicone resin-containing emulsion obtained in Preparation Example 1, 70 parts of a 10% by weight aqueous solution of sodium hydrogencarbonate was added, 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, 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, and emulsion compositions were obtained.

[Examples 5 to 9, Comparative Examples 2 and 3] Preparation Example 1
In the same manner as described above, emulsion polymerization is carried out with the composition shown in Tables 1 to 4, after preparing a silicone resin-containing emulsion, and by adding a curing catalyst with the composition shown in Tables 1 to 4, each emulsion composition is obtained. Obtained.

The cured films of the silicone resin-containing emulsion compositions prepared in Examples 1 to 9 and Comparative Examples 1 to 3 were evaluated in the following procedure. The formulations shown in Tables 1 to 4 were applied to a polished steel sheet having a clean surface and a cured film thickness of 20 μm.
And cured under the conditions shown in Tables 1-4.

Regarding the cured film, JIS K-5400
Measurement of the pencil hardness of the cured film according to the above, cross-cut adhesion test using cellophane tape, 3% NaOH aqueous solution or 5% sulfuric acid aqueous solution is dropped on the film, and the change of the film after observation at room temperature for 1 day is observed. Chemical properties, solvent resistance to observe the change of the film after rubbing the film with absorbent cotton containing xylene 30 times, and weather resistance of the film after 3000 hours irradiation using Sunshine Long Life Weser Meter did.

The adhesion was expressed as 100/100 when the film was completely adhered. The chemical resistance, solvent resistance and weather resistance were evaluated as good when there was no deterioration or coloration of the film, and poor adhesion. And those that were lightly yellowed were evaluated as Δ, and those that were peeled or yellowed were evaluated as x. Table 1 shows the results.
Are shown in FIGS.

Further, the storage stability of the emulsion itself is 4
The determination was made based on layer separation after storage at 0 ° C. for 30 days, the presence or absence of a gel, 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

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Masaaki Yamaya 1-10 Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Technology Laboratory

Claims (8)

[Claims] [A] (1) The following average composition formula (1): R ¹ _m R ² _n Si (OH) _p (OX) _q O _{(4-mnpq) / 2} (1) (wherein R ¹ Represents an unsubstituted monovalent hydrocarbon group, R ² represents a substituted monovalent hydrocarbon group, OX represents a hydrolyzable group, and m, n, p, and q represent 0.5 ≦ m ≦ 1.8 and 0 ≦ n ≦ 1. 0.0, 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 silanol group-containing silicone resin, (2) an emulsion polymer of a solution containing 10 to 1000 parts by weight of a radical polymerizable vinyl monomer as a main component, and [B] a group IA and / or IIA metal element. A silicone resin-containing emulsion composition comprising a compound. 2. The compound (B) containing a compound containing a Group IA and / or IIA metal element as the component (B) has a content of (1),
(2) 0.001 to 100 parts by weight of the total amount of the components
The composition according to claim 1, wherein the composition has a pH of 8 to 12 by weight. 3. The composition according to claim 1, wherein the compound containing component (B), a metal element belonging to Group IA and / or IIA, is an inorganic salt. 4. The compound [B] containing a Group IA and / or IIA metal element, which contains at least one element selected from the group consisting of Li, Na, K and Cs. Or the composition according to 3. 5. The composition according to claim 4, wherein the compound containing the component IA and / or IIA metal element of component (B) is sodium carbonate, potassium carbonate, sodium hydrogen carbonate or potassium hydrogen carbonate. 6. An article formed by forming a cured film of the composition according to claim 1. Description: 7. The method for producing an article according to claim 6, wherein a film of the composition according to any one of claims 1 to 5 is formed on a substrate, and the film is cured at room temperature. . 8. The method according to claim 7, wherein the substrate is metal, ceramic, glass, wood, paper or plastic.