JP6666827B2 - Silicone resin-containing emulsion composition and cured film-forming substrate - Google Patents

Description

  The present invention relates to a silicone resin-containing emulsion composition, particularly to a silicone resin-containing emulsion composition that is cured by a condensation reaction of a hydrolyzable group and / or a silanol group, and a cured film-forming substrate.

  In recent years, from the viewpoint of environmental protection and ensuring a safe working environment, in the field of paints and coating agents, there has been a demand for changing the dispersion medium from an organic solvent system to an aqueous system. Based on this requirement, an emulsion paint obtained by emulsion polymerization of a vinyl polymerizable monomer represented by an acrylic resin is widely used as a basic material of a coating agent because of its excellent film-forming property and chemical resistance. However, this type of coating has inherent disadvantages such as poor weatherability, water resistance, and heat resistance.

  On the other hand, silicone resins obtained by hydrolyzing and polymerizing silane compounds are attracting attention as coating agents because of their ability to form films with high hardness and excellent weather resistance, water resistance, heat resistance, and water repellency. . However, all of the currently established emulsion formulations for silicone resins have drawbacks.

  For example, an aqueous solution obtained by hydrolyzing an alkoxysilane compound in water can maintain stability only under limited conditions such as a low concentration of about several percent or a narrow pH range, and a large amount of alcohol is by-produced. There is a problem that the system becomes unstable when mixed with other emulsions.

  In addition, a method of emulsifying a polymer of a silicone resin to obtain an emulsion requires that the polymer be in a liquid state. However, since the liquid polymer has a low molecular weight, harmful substances such as organotin are required to obtain a cured film after drying. There is a problem that a metal catalyst and a high-temperature and long-time drying process are required.

  On the other hand, in order to use a solid silicone resin in an aqueous formulation, a silicone resin solution produced in an organic solvent such as toluene or xylene is emulsified as it is, or a solution replaced with another organic solvent is emulsified. Although it is necessary to emulsify (Patent Documents 1 and 2), this method contains a large amount of an organic solvent in spite of being a water-based formulation, and completely satisfies the above-mentioned environmental protection and securement of a safe working environment. Could not.

  Further, the coating made of the above-mentioned solid silicone resin has advantages such as high hardness, but is inferior in flexibility and has problems such as cracks due to expansion and contraction of the base material. As a solution to this problem, a method in which an acrylic resin or the like is used in combination with a silicone resin has been proposed (Patent Documents 3 and 4). However, in practice, the compatibility of both polymers is insufficient upon drying and curing. There is a problem that separation and uniform coating cannot be obtained. Also, a method has been proposed in which an emulsion is prepared by emulsion polymerization of a vinyl polymerizable functional group-containing alkoxysilane together with a radical polymerizable vinyl monomer (Patent Documents 5 and 6). It is difficult to contain a large amount, and there is a problem that characteristics such as weather resistance cannot be improved.

  It is known that an aqueous silicone emulsion obtained by polymerizing a polydiorganosiloxane having a terminal hydroxyl group in the presence of colloidal silica gives a silicone rubber coating softer than a silicone resin (Patent Document 7). ), There is a problem that heat resistance is inferior because polydiorganosiloxane is used as a main material, and when used as a coating agent, a film having sufficient hardness cannot be obtained, and inferior abrasion resistance also becomes a problem. ing.

JP 2008-138059 A Patent No. 4775543 Patent No. 3319353 Patent No. 3336922 JP-A-61-009463 JP-A-8-27347 Patent No. 1735572

  SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has reduced environmental problems as compared with conventional silicone resin emulsions, has good stability, and has a high hardness coating film to be obtained. And a cured film-forming substrate.

（式中、Ｒ^１は前述の通りであり、Ｒ^２は水素原子又はメチル基、Ｒ^３は二価の有機基、ｒは０，１又は２を示し、Ｘ^１は上記Ｘと同様又は水素を示す。）、
前記オルガノシリコーンレジンエマルジョン（Ｉ）は、前記（Ｂ）成分のノニオン系乳化剤以外の乳化剤を含まないものであり、かつ、加水分解性基ＯＸの加水分解による副生物であるアルコール以外の有機溶剤を含まないものであることを特徴とするシリコーン樹脂含有エマルジョン組成物を提供する。 In order to solve the above-mentioned problems, according to the present invention, an organosilicone resin emulsion (I) containing the following components (A) to (C) and an emulsion (II) containing a polymer of the following component (D) are provided. A mixed solution,
(A) an organosilicone resin having a viscosity of 100,000 mm ² / s or less at 25 ° C. represented by the following average composition formula (1): 100 parts by mass,
_{^{R 1 m Si (OX) p}} (OH) q O (4-m-p-q) / 2 ··· (1)
(Wherein, R ¹ is an unsubstituted monovalent hydrocarbon group, OX is a hydrolyzable group, and X represents a monovalent hydrocarbon group. M, p, and q are 0.5 ≦ m ≦ 1.8, It is a number that satisfies 0.05 ≦ p ≦ 1.0, 0 ≦ q ≦ 0.5, and 0.05 ≦ p + q ≦ 1.5.)
(B) Nonionic emulsifier: 1 to 50 parts by mass,
(C) water: 25 to 2,000 parts by mass,
(D) a copolymer of a vinyl polymerizable functional group-containing hydrolyzable silane represented by the following general formula (2) and a radical polymerizable vinyl monomer other than the vinyl polymerizable functional group-containing hydrolyzable silane, A polymer having a vinyl polymerizable functional group-containing hydrolyzable silane unit represented by the following general formula (2) in an amount of 0.01 to 10 mol% based on all monomer units in the copolymer: Component (A) 100 10 to 1,000 parts by mass with respect to parts by mass,

(Wherein, R ¹ is as described above, R ² is a hydrogen atom or a methyl group, R ³ is a divalent organic group, r is 0, 1 or 2, and X ¹ is the same as X described above or hydrogen. .),
The organosilicone resin emulsion (I) does not contain an emulsifier other than the nonionic emulsifier of the component (B), and contains an organic solvent other than alcohol which is a by-product of the hydrolysis of the hydrolyzable group OX. The present invention provides a silicone resin-containing emulsion composition characterized in that the emulsion composition does not contain the same.

  Such a silicone resin-containing emulsion composition of the present invention has reduced environmental problems compared to conventional silicone resin emulsions, has good stability, and has a high hardness coating film. Things.

  In this case, it is preferable that the dispersion medium of the emulsion (II) is water.

  Such a silicone resin-containing emulsion composition is preferred because it further reduces environmental problems.

  Further, in this case, in the component (D), the radical polymerizable vinyl monomer other than the vinyl polymerizable functional group-containing hydrolyzable silane represented by the general formula (2) has an alkyl group having 1 to 18 carbon atoms ( Preference is given to alkyl (meth) acrylates.

  Such a radical polymerizable vinyl monomer is preferable because the film obtained from the silicone resin-containing emulsion composition has excellent chemical resistance and flexibility.

  In addition, the present invention provides a cured film-formed substrate on which a cured film of the silicone resin-containing emulsion composition is formed.

  As described above, the cured film of the silicone resin-containing emulsion composition of the present invention has high hardness, is highly flexible, has good adhesion, weather resistance, and heat resistance, and has excellent water repellency. It can be formed on a suitable substrate.

  The organosilicone resin emulsion (I) according to the present invention is a stable emulsion of a silicone resin which forms a high-hardness film with good weather resistance, water resistance and heat resistance. The organosilicone resin emulsion (I) The present invention is a mixed solution of a specific vinyl polymerizable functional group-containing hydrolyzable silane and an emulsion (II) containing a polymer obtained by copolymerizing another radical polymerizable vinyl monomer with 0.01 to 10% by mole of the present invention. The silicone resin-containing emulsion composition has reduced environmental problems compared to conventional silicone resin emulsions, has good stability, and has excellent weatherability, water resistance, heat resistance, and flexibility after room temperature or heat curing, A high hardness coating can be obtained.

The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that the organosilicone resin having a viscosity of 100,000 mm ² / s or less at 25 ° C. represented by the following average composition formula (1) of the component (A): And an emulsion of an organosilicone resin (I) containing no organic solvent other than alcohol by-produced by hydrolysis of the hydrolyzable group OX, and a radical polymerizable polymer having a hydrolyzable group and / or silanol group in the molecule. The mixed solution of the emulsion (II) containing a vinyl polymer as a main component has reduced environmental problems and good stability as compared with the conventional silicone resin emulsion, and has excellent weather resistance, water resistance and heat resistance of the obtained coating. And provided a coating having high hardness and completed the present invention. Hereinafter, the silicone resin-containing emulsion composition and the cured film-forming substrate of the present invention will be described in detail.

（式中、Ｒ^１は前述の通りであり、Ｒ^２は水素原子又はメチル基、Ｒ^３は二価の有機基、ｒは０，１又は２を示し、Ｘ^１は上記Ｘと同様又は水素を示す。）、
前記オルガノシリコーンレジンエマルジョン（I）は、前記（Ｂ）成分のノニオン系乳化剤以外の乳化剤を含まないものであり、かつ、加水分解性基ＯＸの加水分解による副生物であるアルコール以外の有機溶剤を含まないものであることを特徴とするシリコーン樹脂含有エマルジョン組成物である。 That is, the present invention is a mixed solution of an organosilicone resin emulsion (I) containing the following components (A) to (C) and an emulsion (II) containing a polymer of the following component (D):
(A) an organosilicone resin having a viscosity of 100,000 mm ² / s or less at 25 ° C. represented by the following average composition formula (1): 100 parts by mass,
_{^{R 1 m Si (OX) p}} (OH) q O (4-m-p-q) / 2 ··· (1)
(Wherein, R ¹ is an unsubstituted monovalent hydrocarbon group, OX is a hydrolyzable group, and X represents a monovalent hydrocarbon group. M, p, and q are 0.5 ≦ m ≦ 1.8, It is a number that satisfies 0.05 ≦ p ≦ 1.0, 0 ≦ q ≦ 0.5, and 0.05 ≦ p + q ≦ 1.5.)
(B) Nonionic emulsifier: 1 to 50 parts by mass,
(C) water: 25 to 2,000 parts by mass,
(D) a copolymer of a vinyl polymerizable functional group-containing hydrolyzable silane represented by the following general formula (2) and a radical polymerizable vinyl monomer other than the vinyl polymerizable functional group-containing hydrolyzable silane, A polymer having a vinyl polymerizable functional group-containing hydrolyzable silane unit represented by the following general formula (2) in an amount of 0.01 to 10 mol% based on all monomer units in the copolymer: Component (A) 100 10 to 1,000 parts by mass with respect to parts by mass,

(Wherein, R ¹ is as described above, R ² is a hydrogen atom or a methyl group, R ³ is a divalent organic group, r is 0, 1 or 2, and X ¹ is the same as X described above or hydrogen. .),
The organosilicone resin emulsion (I) does not contain an emulsifier other than the nonionic emulsifier of the component (B), and contains an organic solvent other than alcohol which is a by-product of the hydrolysis of the hydrolyzable group OX. It is a silicone resin-containing emulsion composition characterized in that it does not contain the same.

Organosilicon resin emulsion (I)
The organosilicone resin emulsion (I) in the present invention contains the following components (A) to (C), does not contain an emulsifier other than the nonionic emulsifier of the following component (B), and has a hydrolyzable group. It does not contain any organic solvent other than alcohol which is a by-product of the hydrolysis of OX.

  In the present invention, “containing no organic solvent other than alcohol which is a by-product of hydrolysis of the hydrolyzable group OX” means that the organosilicone resin emulsion (I) is a by-product of the hydrolysis of the hydrolyzable group OX. Not containing at all an organic solvent other than alcohol which is, of course, substantially not containing an organic solvent other than alcohol which is a by-product by hydrolysis of the hydrolyzable group OX, that is, intentionally included There is no matter, and there is no influence on the stability, and a small amount (residue or impurity) of the hydrolyzable group OX to the extent that there is no environmental problem may include organic solvents other than alcohol which is a by-product of hydrolysis of the hydrolyzable group OX. It is a thing.

<(A) An organosilicone resin represented by the following average composition formula (1)>
The (A) organosilicone resin having a hydrolyzable group, which constitutes the present invention, will be described. The organosilicone resin is represented by the following average composition formula (1).
^{_{R 1 m Si (OX) p}} (OH) q O (4-m-p-q) / 2 ··· (1)
(Wherein, R ¹ is an unsubstituted monovalent hydrocarbon group, OX is a hydrolyzable group, and X represents a monovalent hydrocarbon group. M, p, and q are 0.5 ≦ m ≦ 1.8, It is a number that satisfies 0.05 ≦ p ≦ 1.0, 0 ≦ q ≦ 0.5, and 0.05 ≦ p + q ≦ 1.5.)

R ¹ represents an unsubstituted monovalent hydrocarbon group and preferably has 1 to 10 carbon atoms, and is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a hexyl group, a cyclohexyl group, or octyl. Specific examples include an alkyl group such as a group and a decyl group, and an alkenyl group such as a vinyl group, an allyl group, a 5-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 preferred. In particular, a methyl group is preferable when weather resistance is required, a long-chain alkyl group is preferable when water repellency is required, and a phenyl group is preferably used when imparting flexibility to a film. Further, R ¹ may be used alone or in combination of a plurality of groups. In the case of using together, the content of the methyl group of R ¹ is preferably at least 80 mol% or more.

  The OX group represents a hydrolyzable group, and X represents a monovalent hydrocarbon group such as an alkyl group having 1 to 6 carbon atoms, 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, an n-butoxy group, a sec-butoxy group, a t-butoxy group, an isopropenoxy group, and a phenoxy group. . It is preferable to use a methoxy group or an ethoxy group in view of hydrolysis / condensation reactivity, stability in an emulsion, and easy availability of raw materials.

  m, p, and q are numbers satisfying the ranges of 0.5 ≦ m ≦ 1.8, 0.05 ≦ p ≦ 1.0, 0 ≦ q ≦ 0.5, and 0.05 ≦ p + q ≦ 1.5, respectively. Represent.

m is low the content of R ¹ is less than 0.5, the film becomes too hard, cracks are likely to occur in the cured coating. When m exceeds 1.8, the number of chain units increases, and as a result, the cured film becomes rubbery and the abrasion resistance is insufficient. Preferably, the number satisfies the range of 0.6 ≦ m ≦ 1.5.

  The hydrolyzable group OX involved in the cross-linking reaction is an essential component. However, when p representing the content of the OX group exceeds 1.0, a large amount of alcohol by-produced when hydrolyzed in the emulsion is generated. The emulsion becomes unstable. In order to ensure good storage stability and high curability at the same time, the range of p is 0.05 ≦ p ≦ 1.0, preferably 0.2 ≦ p ≦ 0.8.

  Further, a silanol group may be present in addition to the OX group, but the amount q of the silanol group must be 0.5 or less. If it exceeds this range, a condensation reaction occurs in the emulsion to easily increase the molecular weight, and the stability of the emulsion is impaired. Also, (p + q) representing the total number of hydrolyzable groups and silanol groups must satisfy the range of 0.05 ≦ p + q ≦ 1.5. When the film is dried and cured, a film having sufficient strength cannot be obtained.

(A) The viscosity at 25 ° C. of the organosilicone resin must be 100,000 mm ² / s or less. If it exceeds 100,000 mm ² / s, stirring and mixing during the production of the emulsion becomes difficult, and an emulsion having a small particle size and high stability cannot be obtained. In addition, a high-viscosity organosilicone resin having a hydrolyzable group and / or a silanol group and having a viscosity exceeding 100,000 mm ² / s easily causes solidification or gelation when a condensation reaction occurs during storage. Handling becomes difficult.

  The (A) organosilicone resin in the present invention may be produced by any method as long as the above conditions are satisfied. However, simply hydrolyzing a hydrolyzable silane compound in water can remove alcohols by-produced. It cannot be removed and is unsuitable as the method for producing the organosilicone resin (A) in the present invention. A specific manufacturing method will be described below.

  As a raw material for producing the organosilicone resin of the component (A), the type of the hydrolyzable group is chloro or alkoxy, and one, two, three or four hydrolyzable groups are contained. Any silane compound having an organic substituent satisfying the conditions can be used. Specifically, tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, methyltriisopropeno Xysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiisopropoxysilane, dimethyldibutoxysilane, dimethyldiisopropenoxysilane, trimethylchlorosilane, trimethylmethoxysilane, trimethylethoxysilane, trimethylisopropenoxysilane, ethyltrichloro Silane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrichlorosilane, propyltrimethoxysilane, propyltriet Sisilane, butyltrichlorosilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrichlorosilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrichlorosilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrichlorosilane, phenyltrisilane Methoxysilane, phenyltriethoxysilane, cyclohexyltrichlorosilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, propylmethyldichlorosilane, propylmethyldimethoxysilane, propylmethyldiethoxysilane, hexylmethyldichlorosilane, hexylmethyldimethoxysilane, Hexylmethyldiethoxysilane, phenylmethyldichlorosilane, phenylmethyldimethoate Sisilane, phenylmethyldiethoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, dimethylphenylchlorosilane, dimethylphenylmethoxysilane, dimethylphenylethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane , Vinylmethyldichlorosilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, 5-hexenyltrichlorosilane, 5-hexenyltrimethoxysilane, 5-hexenyltriethoxysilane, and partial hydrolyzates thereof can be used. Examples of the silane compound include, but are not limited to, organosilicon compounds that can be used. It is more preferable to use methoxysilane or ethoxysilane from the viewpoints of operability, easy removal of by-products, and availability of raw materials. One or a mixture of two or more of these silane compounds may be used.

  An example of a method for obtaining the organosilicone resin (A) in the present invention by hydrolyzing the hydrolyzable silane compound will be described below. That 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, This is a method of hydrolyzing in an organic solvent selected from alcohols such as isobutanol and t-butanol. In the case of this method, it is necessary to remove the organic solvent from the resulting organosilicone resin solution under normal pressure or reduced pressure. The organic solvent residue after the removal step is preferably 1,000 ppm or less.

  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, organic carboxylic acids represented by maleic acid, methyl sulfonic acid, and cation exchange resins having sulfonic acid or carboxylic acid groups on the surface. The amount of the hydrolysis catalyst is preferably in the range of 0.001 to 10 mol% based on 1 mol of the hydrolyzable group on the silicon atom.

<(B) Nonionic emulsifier>
Next, the nonionic emulsifier as the component (B) will be described. The nonionic emulsifier (B) is not particularly limited as long as the organosilicone resin (A) can be emulsified and dispersed in water. Examples thereof include polyoxyethylene alkyl ether, polyoxyethylene propylene alkyl ether, and polyoxyethylene alkyl. Examples thereof include phenyl ether and polyoxyethylene fatty acid ester. From the viewpoint of retention of hydrolyzable groups and / or silanol groups in the emulsion and stability of the emulsion, particularly, polyoxyethylene alkyl ether, polyoxyethylene propylene Alkyl ethers are preferred.

  Specific examples of these include polyoxyethylene octyl ether, polyoxyethylene nonyl ether, polyoxyethylene decyl ether, polyoxyethylene propylene decyl ether, polyoxyethylene lauryl ether, polyoxyethylene propylene lauryl ether, polyoxyethylene tridecyl Ether, polyoxyethylene propylene tridecyl ether, polyoxyethylene myristyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and the like. These nonionic emulsifiers can be used alone or in combination of two or more.

  The organosilicone resin emulsion (I) in the present invention does not contain any emulsifier other than the nonionic emulsifier of the component (B). Anionic surfactants such as alkyl sulfates, alkyl benzene sulfonates, alkyl sulfosuccinates, alkyl phosphates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, quaternary ammonium salts, alkyl When a cationic surfactant such as an amine acetate or an amphoteric surfactant such as an alkyl betaine or an alkyl imidazoline is used, a part of a hydrolyzable group and / or a silanol group is consumed in an emulsion by causing a condensation reaction. It cannot be used because it impairs the film-forming properties during later drying and curing.

  The amount of the component (B) added must be 1 to 50 parts by mass with respect to 100 parts by mass of the component (A). When the amount is less than 1 part by mass, it is difficult to emulsify, and when the amount is more than 50 parts by mass, there is a concern that the hardness, water resistance, heat resistance, water repellency, transparency, and adhesion to the substrate of the coating may be reduced. Preferably it is 2 to 30 parts by mass, more preferably 3 to 20 parts by mass.

<(C) water>
The organosilicone resin emulsion (I) in the present invention contains water as the component (C). The organosilicone resin emulsion (I) can be prepared by mixing with the components (A) and (B) described above and emulsifying and dispersing according to a conventional method. In this case, the content of the water of the component (C) is 25 to 2,000 parts by mass, particularly preferably 50 to 1,000 parts by mass, per 100 parts by mass of the component (A).

  Furthermore, the average particle diameter of the obtained emulsion is preferably 50 to 1,000 nm, particularly preferably 100 to 800 nm. In the present invention, the average particle size can be measured by a submicron particle size distribution analyzer (Coulter N4Plus) manufactured by Beckman Coulter, Inc.

  The organosilicone resin emulsion (I) may contain the following optional components in addition to the components (A) to (C). However, the organosilicone resin emulsion (I) does not contain an organic solvent other than alcohol which is a by-product of hydrolysis of the hydrolyzable group OX.

  The “alcohol as a by-product of the hydrolysis of the hydrolyzable group OX” in the present invention is an alcohol (s) represented by XOH (X is as described above), and “the alcohol of the hydrolyzable group OX”. "Organic solvents other than alcohol which is a by-product of decomposition" include ketone compounds, ester compounds, ether compounds, and alcohol compounds other than alcohols represented by XOH, which are generally used as organic solvents. Can be

  In order to improve the stability of the emulsion, it is preferable to adjust the inside of the system to pH 3 to 9. In this case, a combination of an acid and a basic compound serving as a buffer for adjusting the pH, such as acetic acid and sodium acetate, disodium hydrogen phosphate and citric acid, may be added. It is preferable that the pH range is from pH 3 to pH 9 because there is no fear that condensation of silanol groups easily proceeds or the stability of the emulsion itself is impaired. More preferably, the pH is adjusted to 4 to 8. In addition, preservatives, thickeners and the like may be added as optional components.

Emulsion (II)
The emulsion (II) in the present invention contains a polymer of the following component (D).

（式中、Ｒ^１は前述の通りであり、Ｒ^２は水素原子又はメチル基、Ｒ^３は二価の有機基、ｒは０，１又は２を示し、Ｘ^１は上記Ｘと同様又は水素を示す。） <(D) polymer>
The component (D) is a copolymer of a vinyl polymerizable functional group-containing hydrolyzable silane represented by the following general formula (2) and a radical polymerizable vinyl monomer other than the vinyl polymerizable functional group-containing hydrolyzable silane. And a polymer having a vinyl polymerizable functional group-containing hydrolyzable silane unit represented by the following general formula (2) in an amount of 0.01 to 10 mol% based on all monomer units in the copolymer.

(Wherein, R ¹ is as described above, R ² is a hydrogen atom or a methyl group, R ³ is a divalent organic group, r is 0, 1 or 2, and X ¹ is the same as X described above or hydrogen. Is shown.)

The polymer of the component (D) has ^one molecule OX capable of undergoing a condensation reaction with a hydrolyzable group and / or a silanol group contained in the organosilicone resin of the component (A) in the organosilicone resin emulsion (I). It is necessary to include it in. In order to introduce this functional group, a vinyl polymerizable functional group-containing hydrolyzable silane represented by the general formula (2) is used as a copolymer monomer.

In the above general formula (2), R ¹ is as described above, R ² is a hydrogen atom or a methyl group, R ³ is an alkylene having 1 to 10 carbon atoms which may intervene an oxygen atom, a —COO— group, or the like. A divalent organic group such as a group, an arylene group or an alkylene arylene group, r represents 0, 1 or 2, and X ¹ is the same as X described above or represents hydrogen.

Specific examples of R ³ may be mentioned as follows.

  Examples of the vinyl polymerizable functional group-containing hydrolyzable silane represented by the above general formula (2) include vinyl trimethoxy silane, vinyl triethoxy silane, vinyl methyl dimethoxy silane, vinyl methyl diethoxy silane, 5-hexenyl tri Methoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxy Examples thereof include silane, 4-vinylphenyltrimethoxysilane, 3- (4-vinylphenyl) propyltrimethoxysilane, and 3- (4-vinylphenyl) propylmethyldimethoxysilane.

  The content of the vinyl polymerizable functional group-containing hydrolyzable silane represented by the above general formula (2) is 0.01 to 0.01 with respect to all monomer units constituting the polymer (copolymer) of the component (D). It is 10 mol%, and particularly preferably 0.1 to 5 mol%. If it is less than 0.01 mol%, the reaction rate with the silicone resin will be reduced, and a uniform coating will not be obtained, and properties such as solvent resistance, chemical resistance, weather resistance, and heat resistance will be insufficient. If it is more than 10 mol%, the crosslinking is excessively high, and cracks may occur in the coating, which is not suitable.

  The radical polymerizable vinyl monomer other than the vinyl polymerizable functional group-containing hydrolyzable silane represented by the general formula (2) is not particularly limited as long as it is capable of radical polymerization. Can be applied. (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 Vinyl monomer containing, (d) (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, amide group-containing vinyl monomer such as diacetone (meth) acrylamide, (e) dimethylaminoethyl Amino group-containing vinyl monomers such as 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 ester monomers such as vinyl acetate and vinyl propionate; (i) aromatic vinyl monomers such as styrene, vinyl toluene and α-methylstyrene; Vinyl cyanide monomers such as (meth) acrylonitrile; (k) vinyl halide monomers such as vinyl chloride and vinyl bromide; (l) divinylbenzene, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol A vinyl monomer containing two or more radically polymerizable unsaturated groups in one molecule such as recall di (meth) acrylate and trimethylolpropane tri (meth) acrylate; and (m) an ethylene oxide group having 1 to 100 ( (Poly) oxyethylene chain-containing vinyl monomer such as poly) oxyethylene mono (meth) acrylate, (n) dimethylpolysiloxane containing (meth) acryloxypropyl group at one end, styryl group or α-methyl at one end Specific examples include diorganopolysiloxanes having a radically polymerizable functional group at one terminal such as dimethylpolysiloxane containing a styryl group and having 1 to 200 siloxane units. They can be used alone or in combination of two or more.

  Among these, the radical polymerizable vinyl monomer other than the vinyl polymerizable functional group-containing hydrolyzable silane represented by the above general formula (2) includes carbon radicals having 1 carbon atom from the viewpoint of chemical resistance and flexibility of the coating. It is preferably an alkyl (meth) acrylate having from 18 to 18 alkyl groups.

  The copolymer is used in an amount of 10 to 1,000 parts by mass based on 100 parts by mass of the component (A). If the amount is less than 10 parts by mass, the film-forming property and the chemical resistance may be insufficient, and if it exceeds 1,000 parts, the weather resistance and the water resistance may be insufficient. More preferably, the copolymer is used in the range of 30 to 500 parts by mass.

  The polymer of the component (D) is used after being prepared as an emulsion (II) and then mixed with an organosilicone resin emulsion (I) containing the components (A) to (C). As a preparation method, a vinyl copolymerizable functional group-containing hydrolyzable silane represented by the above general formula (2) is radically copolymerized with 0.01 to 10 mol% of another radically polymerizable vinyl monomer to obtain a polymer. Even when emulsification is performed later, the vinyl polymerizable functional group-containing hydrolyzable silane represented by the general formula (2) and other radically polymerizable vinyl monomers are first emulsified, and a polymer is formed by radical polymerization in emulsified particles. Alternatively, a polymer emulsion may be prepared. However, since the polymer is usually solidified after the polymerization, the latter method of emulsifying the monomer first and polymerizing in the emulsified particles is more preferable.

  Examples of the radical polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, aqueous hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxymaleic acid, succinic peroxide, and 2,2′-azobis-. Water-soluble types such as [2-N-benzylamidino] propane hydrochloride, benzoyl peroxide, cumene hydroperoxide, dibutyl peroxide, diisopropyl peroxy dicarbonate, cumyl peroxy neodecanoate, cumyl peroxy octoate, An oil-soluble type such as azoisobutyronitrile, or a redox system using a reducing agent such as sodium acid sulfite, Rongalit, or ascorbic acid together can be used. The amount of the polymerization initiator used is 0.1 to 10% by mass based on the total amount of the vinyl polymerizable functional group-containing hydrolyzable silane represented by the general formula (2) and other radical polymerizable vinyl monomers. It may be used, and preferably 0.5 to 5% by mass.

  The dispersion medium of the emulsion (II) is preferably water. By using water as a dispersion medium, the finally obtained silicone resin-containing emulsion composition has further reduced environmental problems.

  An organosilicone resin emulsion (I) containing (A) to (C) and an emulsion (II) containing a polymer of component (D) are used as a mixed solution by mixing the respective emulsions before use. . After mixing, it can be crosslinked and cured at room temperature by a condensation reaction of a hydrolyzable group and / or a silanol group. However, in order to accelerate the curing rate or obtain excellent film properties, the organosilicone resin emulsion (I) When mixing with the emulsion (II), a silanol condensation catalyst may be added as necessary.

  As the curing catalyst for the condensation, conventionally known ones can be used. For example, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, sodium formate, n-hexylamine, tributylamine, diazabicyclo Basic compounds such as undecene, tetraisopropyl titanate, tetrabutyl titanate, aluminum triisobutoxide, aluminum triisopropoxide, aluminum acetylacetonate, aluminum perchlorate, aluminum chloride, cobalt octylate, cobalt acetylacetonate, Zinc octylate, zinc acetylacetonate, iron octylate, iron acetylacetonate, tin acetylacetonate, dibutyltin dioctylate, dibutyltin dilaurate, dibutyltin Metal-containing compounds such as oxides; p-toluenesulfonic acid; acidic compounds such as trichloroacetic acid; and fluorine-containing compounds such as potassium fluoride, sodium fluoride, tetramethylammonium fluoride, and sodium hexafluorosilicate. Can be These condensation catalysts are preferably used in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the organosilicone resin of the component (A).

  The silicone resin-containing emulsion composition of the present invention thus obtained has a reduced environmental problem, good stability, and a high hardness of the obtained film as compared with conventional silicone resin emulsions. It becomes a containing emulsion composition.

  The silicone resin-containing emulsion composition of the present invention is applied to a transparent or opaque substrate surface such as a metal, ceramic inorganic material, glass, wood, paper product, and plastic, and cured at room temperature or by heating to form a cured film. (Protective film) can be formed. This cured film is high in hardness, rich in flexibility, good in adhesiveness and weather resistance, and can also impart water repellency, so that it can be used as a surface treatment agent for exterior building materials such as metals, ceramics, and wood. It is suitable as a coating material such as a coating agent, a protective coating agent for a metal surface such as a pre-coated metal, a charge controlling coating agent for an electrophotographic carrier, or an adhesive.

  When the base material is metal, it can be used for surface protection of iron and stainless steel building construction materials and aluminum sash building materials, etc., or base treatment such as anti-corrosion treatment coating, 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 magnetic or heat-sensitive recording film, a packaging film, a surface protective coating such as vinyl cloth, or a binder for imparting functions.

  When the substrate is a wood or paper product, it can be applied to a surface protection coating of plywood, a surface protection for thermal recording, a water resistance imparting coating to be applied to a printing surface, and the like. Further, since it has water repellency, it can be applied as a surface protective film of synthetic leather or the like. It can also be applied as a water-soluble binder for water-resistant printing inks.

  When the base material is an inorganic material, for mortar, concrete, or cement exterior wall material or ceramic panel, ALC board, sizing board, gypsum board, brick, glass, ceramic, artificial marble, etc. Can be applied as a 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 substrates can be obtained.

  As a method for applying the silicone resin-containing emulsion composition of the present invention to a substrate, various conventionally known coating methods such as a dipping method, a spray method, a roll coating method, and a brush coating method can be used. The amount of the silicone resin-containing emulsion composition to be applied is not particularly limited, but is usually preferably such that the thickness of the coating after drying is from 0.1 to 1,000 μm, particularly from 1 to 100 μm.

  Hereinafter, the present invention will be specifically described with reference to Production Examples, Examples, and Comparative Examples, but the present invention is not limited to the following Examples. In addition, in the following examples, a part shows a mass part and% shows a mass%.

[Production Example 1]
An organosilicone resin represented by an average composition formula: [(CH ₃ ) _1.0 (C ₆ H ₅ ) _0.5 Si (OCH ₃ ) _0.7 (OH) _0.1 O _0.9 ] (at 25 ° C.) Viscosity: 100 mm ² / s) 50 parts by mass, and 2.5 parts by mass of “Neugen XL-40” (trade name: manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene decyl ether, HLB = 10.5) as a nonionic emulsifier 3.5 parts by mass of “Neugen XL-400D” (trade name: manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyalkylene decyl ether, 65% aqueous solution of HLB = 18.4) and 44.0 parts by mass of deionized water were homogenized. The mixture was emulsified and dispersed using a disper and had a nonvolatile content of 52% at 105 ° C./3 hours and an average particle size (using a submicron particle size distribution analyzer Coulter N4Plus manufactured by Beckman Coulter, Inc.). Measurement) to obtain a 250nm white organosilicone resin emulsion (A-1). After storing A-1 at 40 ° C. for 1 month, water was removed at 105 ° C., and the non-volatile components obtained remained oily. In addition, GPC measurement of this non-volatile content was performed, and as a result of comparison with the raw material organosilicone resin, it was confirmed that they were almost the same.

[Production Example 2]
Average composition formula: 50 parts by mass of an organosilicone resin (viscosity at 25 ° C .: 30 mm ² / s) represented by [(CH ₃ ) _1.0 Si (OCH ₃ ) _0.2 O _1.4 ], a nonionic emulsifier 3.5 parts by mass of "Neugen XL-40", 4.9 parts by mass of "Neugen XL-400D" and 41.6 parts by mass of deionized water were emulsified and dispersed using a homodisper, and the mixture was heated at 105C for 3 hours. A white organosilicone resin emulsion (A-2) having a nonvolatile content of 43% and an average particle diameter of 210 nm (measured using a submicron particle size distribution analyzer Coulter N4Plus manufactured by Beckman Coulter, Inc.) was obtained. After storing A-2 at 40 ° C. for one month, water was removed at 105 ° C., and the non-volatile components obtained remained oily. In addition, GPC measurement of this non-volatile content was performed, and as a result of comparison with the raw material organosilicone resin, it was confirmed that they were almost the same.

[Production Example 3]
An organosilicone resin represented by an average composition formula: [(CH ₃ ) _1.0 (C ₆ H ₅ ) _0.5 Si (OCH ₃ ) _0.7 (OH) _0.1 O _0.9 ] (at 25 ° C.) Viscosity: 100 mm ² / s) 50 parts by mass, 2.5 parts by mass of “Neugen XL-40” as a nonionic emulsifier, 3.5 parts by mass of “Neugen XL-400D”, “Newcol 291M” (anionic emulsifier) Brand name: 0.5% by mass of sodium alkylsulfosuccinate (manufactured by Japan Emulsifier Co., Ltd.) and 0.5 parts by mass of deionized water are emulsified and dispersed using a homodisper, and the nonvolatile content at 105 ° C./3 hours is obtained. Is 52% and the average particle size (measured using a submicron particle size distribution analyzer Coulter N4Plus manufactured by Beckman Coulter, Inc.) is 260 nm. It was obtained John (A-3). After storing A-3 at 40 ° C. for one month, the non-volatile components obtained by removing water at 105 ° C. formed a sticky film, and a part of the film was insoluble in toluene. GPC measurement of this non-volatile content was carried out, and as a result of comparison with the raw material organosilicone resin, the non-volatile content of A-3 had a high molecular weight and a peak shape different from that of the raw material.

[Production Example 4]
A polymerization vessel equipped with a stirrer, a condenser, a thermometer and a nitrogen gas inlet was charged with 540 parts by mass of deionized water, 0.47 parts by mass of sodium carbonate as a pH buffer and 4.70 parts by mass of boric acid, and stirred. After the temperature was raised to 60 ° C., the atmosphere was replaced with nitrogen. To this were added 1.75 parts by mass of Rongalite, 0.12 parts by mass of a 1% aqueous solution of disodium ethylenediaminetetraacetate, and 0.04 parts by mass of a 1% aqueous solution of ferrous sulfate, and 336 parts by mass of methyl methacrylate (3 parts by mass). 1.36 mol), 140 parts by mass (1.09 mol) of butyl acrylate, 33 parts by mass (0.13 mol) of γ-methacryloxypropyltrimethoxysilane, t-butyl hydroperoxide (69% pure). 1 part by mass, 14.0 parts by mass of a reactive surfactant Aqualon KH-10 (trade name: polyoxyethylene (10) -1- (allyloxymethyl) alkyl ether ammonium sulfate manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Aqualon KH -5 (trade name: manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene (5) -1- (allyloxymethyl) alkyl ether sulfate) (Monium) A mixed solution consisting of 7.0 parts by mass 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 complete the polymerization. Was. The nonvolatile content of the obtained emulsion (B-1) at 105 ° C./3 hours was 49.1% and pH 7.1.

[Production Example 5]
A polymerization vessel equipped with a stirrer, a condenser, a thermometer and a nitrogen gas inlet was charged with 540 parts by mass of deionized water, 0.47 parts by mass of sodium carbonate as a pH buffer and 4.70 parts by mass of boric acid, and stirred. After the temperature was raised to 60 ° C., the atmosphere was replaced with nitrogen. To this were added 1.75 parts by mass of Rongalite, 0.12 parts by mass of a 1% aqueous solution of disodium ethylenediaminetetraacetate, and 0.04 parts by mass of a 1% aqueous solution of ferrous sulfate, and 336 parts by mass of methyl methacrylate (3 parts by mass). .36 mol), 140 parts by mass (1.09 mol) of butyl acrylate, 2.1 parts by mass of t-butyl hydroperoxide (69% pure content), Aqualon KH-10 (trade name: reactive surfactant) 14.0 parts by mass of polyoxyethylene (10) -1- (allyloxymethyl) alkyl ether ammonium sulfate), Aqualon KH-5 (trade name: manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene (5 ) -1- (Allyloxymethyl) alkyl ether ammonium sulfate) A mixed solution consisting of 7.0 parts by mass was maintained at a temperature of 60 ° C. in the polymerization vessel. While over 2.5 hours added uniformly to complete the polymerization by 2 hours at further 60 ° C.. The nonvolatile content of the obtained emulsion (B-2) at 105 ° C./3 hours was 47.9% and pH 7.2.

(Examples 1 to 5, Comparative Examples 1 to 6)
The silicone resin emulsion prepared in Production Examples 1 to 3 and the emulsion of (meth) acrylic polymer (copolymer) prepared in Production Examples 4 to 5, and sodium acetate as a curing catalyst were mixed in the composition shown in Table 1. This was a silicone resin-containing emulsion composition (Examples 1 to 5, Comparative Examples 1 to 6). Thereafter, the composition was applied to a polished steel sheet having a clean surface using a wire bar so that the film thickness after curing was 15 μm, and the composition was cured under the conditions shown in Table 1, and the appearance of the coating surface was visually observed. Then, the curability was confirmed by a tackiness by touch with a finger, and the film hardness was confirmed by a pencil hardness according to JIS K-5400. Table 1 shows the results. Comparative Examples 1 and 2 used the emulsion (A-3) that was not the organosilicone resin emulsion (I) of the present invention, and Comparative Examples 3 and 4 were emulsions that were not the emulsion (II) of the present invention. In Comparative Examples 5 and 6, the amount of the silicone resin in the silicone resin emulsion and the amount of the copolymer in the (meth) acrylic emulsion were 100 parts by mass: 10 to 1000 parts by mass. Is not.

[Evaluation method]
(Appearance / visual observation) ：: Uniform, ム ラ: Slight unevenness, X: Non-uniform (tack feeling / touch) ：: None, △: Slightly tacky, X: Sticky (pencil hardness) According to JIS K-5400

  According to Table 1, since the silicone resin-containing emulsion compositions of Examples 1 to 5 were superior in stability to the silicone resin-containing emulsion compositions of Comparative Examples 1 to 6, a uniform coating was formed. And a coating without stickiness was obtained. In addition, the silicone resin-containing emulsion compositions of Examples 1 to 5 provided higher hardness coatings than the silicone resin-containing emulsion compositions of Comparative Examples 1 to 6.

  Note that the present invention is not limited to the above embodiment. The above embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and has the same effect. It is included in the technical range.

Claims (4)

A mixed solution of an organosilicone resin emulsion (I) containing the following components (A) to (C) and an emulsion (II) containing a polymer of the following component (D),
(A) an organosilicone resin having a viscosity of 100,000 mm ² / s or less at 25 ° C. represented by the following average composition formula (1): 100 parts by mass,
_{^{R 1 m Si (OX) p}} (OH) q O (4-m-p-q) / 2 ··· (1)
(Wherein, R ¹ is an unsubstituted monovalent hydrocarbon group, OX is a hydrolyzable group, and X represents a monovalent hydrocarbon group. M, p, and q are 0.5 ≦ m ≦ 1.8, It is a number that satisfies 0.05 ≦ p ≦ 1.0, 0 ≦ q ≦ 0.5, and 0.05 ≦ p + q ≦ 1.5.)
(B) Nonionic emulsifier: 1 to 50 parts by mass,
(C) water: 25 to 2,000 parts by mass,
(D) a copolymer of a vinyl polymerizable functional group-containing hydrolyzable silane represented by the following general formula (2) and a radical polymerizable vinyl monomer other than the vinyl polymerizable functional group-containing hydrolyzable silane, A polymer having a vinyl polymerizable functional group-containing hydrolyzable silane unit represented by the following general formula (2) in an amount of 0.01 to 10 mol% based on all monomer units in the copolymer: Component (A) 100 10 to 1,000 parts by mass with respect to parts by mass,

(Wherein, R ¹ is as described above, R ² is a hydrogen atom or a methyl group, R ³ is a divalent organic group, r is 0, 1 or 2, and X ¹ is the same as X described above or hydrogen. .),
The organosilicone resin emulsion (I) does not contain an emulsifier other than the nonionic emulsifier of the component (B), and contains an organic solvent other than alcohol which is a by-product of the hydrolysis of the hydrolyzable group OX. A silicone resin-containing emulsion composition characterized in that the emulsion composition does not contain an optical semiconductor .   The emulsion composition according to claim 1, wherein the emulsion (II) is water as a dispersion medium.   In the component (D), the radical polymerizable vinyl monomer other than the vinyl polymerizable functional group-containing hydrolyzable silane represented by the general formula (2) is a (meth) acrylic acid having an alkyl group having 1 to 18 carbon atoms. The silicone resin-containing emulsion composition according to claim 1 or 2, which is an alkyl ester. A cured film-formed substrate having a cured film of the silicone resin-containing emulsion composition according to any one of claims 1 to 3 formed on a surface of the substrate.