JP2010043222A - Silicone-acrylic based resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silicone-acrylic-based resin composition having improved stain resistance. <P>SOLUTION: The silicone-acrylic-based resin composition, including 0.1-30 wt.% of the following component (A) and 70-99.9 wt.% of the (co)polymer of the following component (B), wherein the total amount of the component (A) and the component (B) of the (co)polymer is 100 wt.%, is used. Component (A): an alkoxysilane condensate containing an alkylene oxide group. Component (B): a monomer including a (meth)acrylic monomer or a monomer mixture including the (meth)acrylic monomer and a copolymerizable monomer therewith. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a silicon-acrylic resin composition used for paints and the like.

  In recent years, there has been a strong demand for pollution-free paints for environmental protection and safety and health, and conventional solvent-based paints are being made water-based. The same applies to silicon-acrylic paints, and since they are excellent in weather resistance, water repellency, and stain resistance following fluororesin paints, they are widely used, and there is a strong demand for making these paints water-based.

  However, when it becomes aqueous, the alkoxysilyl group contained in the resin is hydrolyzed to produce a silanol group, but the produced silanol group condenses with time, increasing the viscosity of the paint or gelling. There's a problem.

  In order to solve these problems, Patent Document 1 discloses a silicon-acrylic resin composition comprising an aqueous emulsion using an alkoxysilane compound not containing a polymerizable double bond such as methyltrimethoxysilane. .

  The alkoxysilane compound not containing a polymerizable double bond has a property of hydrolyzing in the presence of water to form a Si—O—Si bond. When this alkoxysilane compound is contained in the synthetic resin emulsion, alkoxysilyl groups are incorporated into the synthetic resin particles, and contact with water is reduced, making hydrolysis less likely. Therefore, such an alkoxysilane-containing emulsion has improved stability when used as a paint.

JP 07-268301 A

  By the way, recently, from the viewpoint of maintaining aesthetics, an improvement in stain resistance is also required for a coating film obtained from the silicon-acrylic resin composition disclosed in Patent Document 1.

  Accordingly, an object of the present invention is to obtain a silicon-acrylic resin composition having improved contamination resistance.

The present invention comprises 0.1 to 30% by weight of the following component (A) and 70 to 99.9% by weight of the (co) polymer of the component (B) (provided that the components (A) and (B) ( The total amount of the (co) polymer is 100% by weight.), And the (B) component is (co) polymerized in the presence of the following (A) component: The component (B) contains 70 to 99.9% by weight with respect to the component (A) 0.1 to 30% by weight (provided that the total amount of the component (A) and the component (B) is 100% by weight. And a silicon-acrylic resin composition.
(A) Component: Alkylene oxide group-containing alkoxysilane condensate.
Component (B): a monomer composed of a (meth) acrylic monomer, or a monomer mixture composed of a (meth) acrylic monomer and a monomer copolymerizable therewith.

  Since the resin composition for paints of this invention uses an alkylene oxide group-containing alkoxysilane condensate as the component (A), the weather resistance can be maintained, the stain resistance can be improved, and the low pollution property can be expressed. it can.

  The silicon-acrylic resin composition according to the present invention has an alkylene oxide group-containing alkoxysilane condensate (hereinafter referred to as “component (A)”) as a siloxane compound, and a (meth) acrylic monomer. The resin composition which has the polymer or copolymer (henceforth "(co) polymer") which polymerized the monomer containing the body or its mixture (henceforth "(B) component"). Or a resin composition obtained by (co) polymerizing the component (B) in the presence of the component (A).

[(A) component]
The alkylene oxide group-containing alkoxysilane condensate as the component (A) is a condensate obtained by hydrolyzing and condensing a siloxane compound having an alkylene oxide group with water or the like, and contributes to an improvement in stain resistance. It is an ingredient. Examples of the component (A) include polyethylene oxide group-containing alkoxysilanes having a molecular weight of 500 to 3000, and specific examples include “Dynasilane 4144” (trade name) manufactured by Degussa Co., Ltd.

[Component (B)]
The monomer containing the (B) component (meth) acrylic monomer or a mixture thereof is a monomer composed of a (meth) acrylic monomer, or a (meth) acrylic monomer, This refers to a monomer mixture composed of this and a copolymerizable monomer (hereinafter simply referred to as “co-monomer”), and a polymer obtained by emulsion polymerization is emulsion stability. This contributes to improvement of weather resistance and weather resistance. In the present invention, the expression “(meth) acryl” means “acryl or methacryl”.

  Examples of the (meth) acrylic monomer include alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, (meth) acrylic acid, (meth) acrylonitrile, (meth) acrylamide monomer, and the like. can give.

  Specific examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, (meth). T-butyl acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, Examples include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like.

  Furthermore, specific examples of the alkoxyalkyl (meth) acrylate include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, and the like.

  Examples of the (meth) acrylamide monomer include (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, and Nn-propoxy. Examples thereof include methyl (meth) acrylamide, Nn-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide, N-alkoxymethyl (meth) acrylamide, dimethyl (meth) acrylamide and the like.

  These (meth) acrylic monomers may be used alone, or two or more of them may be used in combination according to the purpose and purpose. Among these, when one or a plurality of monomers selected from cyclohexyl (meth) acrylate, hydroxyethyl (meth) acrylate, and t-butyl (meth) acrylate or a mixture thereof is used, the weather resistance is improved. More preferable in terms.

  Next, the copolymerizable monomer is a monomer copolymerizable with the (meth) acrylic monomer, and is an unsaturated carboxylic acid such as maleic acid, itaconic acid, crotonic acid, fumaric acid, citraconic acid or the like. Examples thereof include styrene monomers such as acid, styrene, α-methylstyrene, and chlorostyrene, vinyl esters such as vinyl acetate, vinyl propionate, and vinyl versatate. These monomers may be used alone or in combination of two or more. Furthermore, as a crosslinkable monomer, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycidyl (meth) acrylate, triallyl cyanurate , Triallyl isocyanate, divinylbenzene, and the like can also be used.

  The content ratio of the comonomer in the component (B) is preferably comonomer / (meth) acrylic monomer = 0/100 to 50/50 (weight ratio), It is preferable to set it as 0.1 / 99.9-30 / 70. When the content ratio of the comonomer is more than 50% by weight, there may be a problem that the weather resistance is deteriorated or the film forming property is deteriorated.

  As the copolymer monomer, a monomer having an alkoxy group is preferably used. The content ratio of the comonomer in the monomer mixture as the component (B) is preferably 0.1% by weight or more, and more preferably 0.5% by weight or more. If it is less than 0.1% by weight, the water resistance and waterproofness tend to be inferior. On the other hand, the upper limit of the content ratio is preferably 5% by weight, and preferably 1% by weight. If it is more than 5% by weight, the stability of the emulsion may be deteriorated and gelation may occur, and the flexibility of the resulting polymer may be deteriorated, resulting in inferior film-forming properties.

[Production of silicon-acrylic resin composition]
Next, a method for producing a silicon-acrylic resin composition using the components (A) and (B) will be described.

  As a method for producing the silicon-acrylic resin composition according to the present invention, the (B) component is (co) polymerized and then mixed with the component (A) (hereinafter referred to as “first production method”). And the method of (co) polymerizing the component (B) in the presence of the component (A) (hereinafter referred to as “second production method”).

  In both the first production method and the second production method, the (co) polymerization reaction of the component (B) is performed. As this (co) polymerization reaction, (B) component (meth) acrylic monomer or a monomer mixture of (meth) acrylic monomer and copolymerization monomer is used as a reaction vessel. A batch polymerization method in which emulsion polymerization is performed, a monomer dropping polymerization method in which the component (B) is dropped into water containing an emulsifier and emulsion polymerization is performed, and the component (B) is emulsified with an emulsifier, and this is dropped. There are various methods such as an emulsion monomer dropping polymerization method. These methods may be any method as long as the polymerization of substantially the same composition proceeds from the beginning to the end of the emulsion polymerization, but from the viewpoint of ensuring the stability of the emulsion at the time of production, the monomer dropping polymerization method, the emulsion monomer dropping A polymerization method is preferred.

  In the first production method, the component (A) is mixed after the emulsion polymerization of the component (B). In the second production method, the component (A) is mixed before or during the emulsion polymerization of the component (B). The In the second production method, when the batch polymerization method is used, the component (A) is charged into a reaction vessel. Moreover, in the monomer dropping polymerization method and the emulsion monomer dropping polymerization method, the component (A) may be charged into a reaction vessel, charged into a dropping solution, or charged into both.

  Examples of the emulsifier include non-polymerizable surfactants and polymerizable surfactants. Examples of the non-polymerizable surfactant include anionic, cationic and nonionic surfactants. Specifically, anionic surfactants include sodium dodecylbenzenesulfonate, sodium dialkylsulfosuccinate, sodium lauryl sulfate, sodium polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl ether ammonium sulfate, polyoxyethylene alkyl phenyl ether. Examples thereof include ammonium sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl phenyl ether phosphate, and the like.

  Examples of the cationic surfactant include lauryl trimethyl ammonium chloride and trimethyl octadecyl ammonium chloride. Furthermore, nonionic surfactants include amphoteric surfactants such as lauryl betaine and lauryl dimethylamine oxide; polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene oxypropylene block polymer, polyethylene glycol fatty acid ester, And polyoxyethylene sorbitan fatty acid ester.

  Examples of the polymerizable surfactant include anionic polymerizable surfactants and nonionic polymerizable surfactants. Specific examples of the anionic polymerizable surfactant include sodium propenyl-2-ethylhexylbenzenesulfosuccinate, sulfate of polyoxyethylene (meth) acrylate, polyoxyethylene alkylpropenyl ether sulfate ammonium salt, (meth) acrylic. Examples thereof include a phosphoric acid ester of an acid polyoxyethylene ester and a polyoxyethylene alkylaryl sulfate salt structure and a polymerizable property such as an isopropenyl group and an aryl group.

  Specific examples of the nonionic polymerizable surfactant include polyoxyethylene alkylbenzene ether (meth) acrylic acid ester, polyoxyethylene alkyl ether (meth) acrylic acid ester, and polyoxyethylene alkyl aryl ether structure. And nonionic polymerizable surfactants such as those having polymerizability such as isopropenyl group and aryl group.

  These non-polymerizable surfactants and polymerizable surfactants that are emulsifiers may be used alone or in combination of two or more.

  Among these, polymerizable surfactants such as anionic polymerizable surfactants and nonionic polymerizable surfactants can improve the stability of the emulsion during production and the weather resistance of the coating film comprising the resulting composition. Can be further improved, which is preferable.

  Although the usage-amount of the said emulsifier is not specifically limited, 0.5-5 weight% is preferable with respect to the usage-amount of (B) component, and 1-3 weight% is more preferable. When there is too much usage-amount of the said emulsifier, there exists a tendency for the water resistance of a coating film to fall. On the other hand, when there is too little usage-amount of the said emulsifier, a resin particle will become large easily. Since the particle diameter of the resin is greatly influenced by the type of emulsifier, the amount of the resin used needs to be appropriately selected within the above range depending on the emulsifier used.

  In the emulsion polymerization of the component (B), a polymerization initiator is generally used. Specific examples of such a polymerization initiator include persulfates, azo polymerization initiators, hydroperoxides, peroxides, and the like. And oxides.

  Specific examples of the azo polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), and 2,2′-azobis-2. -Methylbutyronitrile, 1,1'-azobis-1-cyclohexanecarbonitrile, dimethyl-2,2'-azobisisobutyrate, 4,4'-azobis-4-cyanovaleric acid, 2,2 ' -Azobis- (2-amidinopropane) dihydrochloride, 2,2-azobis (2,4-dimethyl-4-methoxyvaleronitrile) and the like.

  Furthermore, specific examples of the hydroperoxides include hydrogen peroxide and t-butyl hydroperoxide, and specific examples of the peroxide include benzoyl peroxide and lauroyl peroxide.

  Specific examples of the persulfate include persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate. These hydroperoxides, peroxides, and persulfates are often used as redox polymerization initiators in combination with reducing agents such as sodium hyposulfite, sodium hydrogensulfate, tartaric acid, and L-ascorbic acid. . Among these initiators, an azo polymerization initiator is preferably used from the viewpoint of water resistance.

  The amount of the polymerization initiator used, the reaction temperature of the emulsion polymerization, and the reaction time may be determined by appropriately adjusting the reaction so that the reaction proceeds moderately and the desired (co) polymer emulsion is obtained. For example, the amount of the polymerization initiator used is usually 0.05 to 2 parts by weight, preferably 0.1 to 1 part by weight per 100 parts by weight of component (B). Moreover, the reaction temperature of emulsion polymerization is usually 50 to 100 ° C, preferably 60 to 90 ° C. The reaction time is usually 1 to 16 hours and preferably 2 to 10 hours.

  In the silicon-acrylic resin composition of the present invention, at this time, the mixing ratio (weight ratio of the (co) polymer of the component (A) and the component (B), provided that the component (A) and the component (B) or The total amount with the (co) polymer is 100% by weight.) As (A) / (B), 0.1 / 99.9 or more is required, and 1/99 or more is preferable. If it is less than 0.1 / 99.9, the weather resistance and water resistance tend to be insufficient. On the other hand, the upper limit needs 30/70, and 25/75 or less is good. If it is more than 30/70, the stability of the emulsion may be lowered to cause gelation, or the flexibility of the resulting polymer may be insufficient, and the film forming property may be deteriorated.

  The solid content concentration of the silicone-acrylic resin composition of the emulsion thus obtained is 30 to 75 from the viewpoint of workability such as ease of coating, maintenance of the coating thickness, and coating properties. % By weight is preferred, and 35 to 65% by weight is more preferred. The viscosity is preferably from 50 to 30,000 mPa · s, more preferably from 100 to 20,000 mPa · s, from the viewpoint of ease of coating and workability such as paint applicability. Furthermore, the average particle diameter is preferably 0.05 to 0.5 μm, more preferably composed of fine particles of about 0.08 to 0.3 μm, and in this case, the film forming ability is excellent.

Most of the alkoxysilyl groups (-SiOCH ₃ etc.) of the component (A) in the silicon-acrylic resin composition in the present invention are contained in a stable state inside the emulsion particles, and the silyl groups are not in the paint state. It is difficult to condense and therefore the paint is kept stable.

  Colloidal silica may be added to the silicon-acrylic resin composition in the present invention. Furthermore, the silicon-acrylic resin composition according to the present invention may further contain a pigment to form a silicon-acrylic paint. These silicon-acrylic resin compositions and silicon-acrylic paints are excellent in weather resistance, stain resistance and the like, and are more preferable.

  Examples of the pigment include titanium oxide, calcium carbonate, barium carbonate, kaolin, carbon black, bengara, and phthalocyanine blue.

  When the colloidal silica is contained, the content of the colloidal silica is preferably 0.4 parts by weight or more and preferably 5 parts by weight or more per 100 parts by weight (in terms of solid content) of the silicon-acrylic resin composition. If the amount is less than 0.4 parts by weight, the contact angle of the resulting coating film with water is not sufficiently small, and the effect of improving the stain resistance tends to be poor. On the other hand, the upper limit of the content is preferably 40 parts by weight, and preferably 20 parts by weight. When the amount is more than 40 parts by weight, the dispersion stability of silica tends to be insufficient, or the gloss of the coating film tends to decrease.

  In addition, when the pigment is contained, the content of the pigment is 30 wt. Per 100 parts by weight (in terms of solid content) of the total amount of the component (A) and the component (B) in the silicon-acrylic resin composition. Part or more is good, and 65 parts by weight or more is preferable. When the amount is less than 30 parts by weight, the concealability tends to be insufficient. On the other hand, the upper limit of the content is preferably 250 parts by weight, and preferably 105 parts by weight. When the amount is more than 250 parts by weight, the elongation of the paint tends to be insufficient or the gloss of the coating film tends to be lowered.

  The silicon-acrylic resin composition and silicon-acrylic paint obtained by the above method can be used as a resin composition or paint for paint as it is or by adjusting the concentration. For example, a film-forming auxiliary, a viscosity adjusting agent, water and the like can be added to obtain a resin composition for paint.

  These silicon-acrylic resin compositions and silicon-acrylic paints may be used as colored paints by adding a plasticizer, a thickener, etc. within a range that does not impair the purpose. In addition, depending on the purpose of use, flame retardants such as halogen-containing phosphate esters, halogen-containing organic sulfur phosphorus compounds, aluminum hydroxide, antimony trioxide, and antimony pentoxide; UV absorption of benzophenone, benzotriazole, and salicylic acid Agents; hindered amine light stabilizers; antifoaming agents, antiseptic and antifungal agents, pH adjusting agents, film-forming aids, wetting agents, antifreezing agents, aqueous paints, and the like can be added.

  The silicon-acrylic resin composition and the silicon-acrylic paint according to the present invention have good stability, are difficult to thicken and gel, and can exhibit excellent weather resistance and stain resistance. For example, it is used for coating interior materials, exterior wall materials, automobiles, large structures, steel equipment, home appliances, woodwork products and the like of buildings.

  Hereinafter, although the composition of this invention is demonstrated still in detail based on an Example etc., this invention does not receive a restriction | limiting at all by these. First, it describes about the measuring method and raw material of each physical property which were obtained. In this example (including the table), the physical properties of the composition containing no pigment are referred to as “film properties”, and the physical properties of the composition containing the pigment are referred to as “film properties”.

<Measurement method for physical properties, etc.>
[Non-volatile content]
This was carried out according to the method specified in JIS K 6833.
[viscosity]
In accordance with the method specified in JIS K 6833, measurement was performed at 25 ° C. and 12 rpm using a BM viscometer.
[PH]
This was carried out according to the method specified in JIS K 6833.

[Measurement of minimum film-forming temperature (MFT)]
The composition was applied to a thermal gradient test apparatus (manufactured by Niji Shoji Co., Ltd.) using a 0.2 mm applicator, and MFT was measured according to JIS K6828-2.

[Particle size]
Using a particle size measuring instrument (manufactured by Otsuka Electronics Co., Ltd .: ELS-8000), the sample was diluted with ionic water and measured so that the scattering intensity was 8000-12000.

[Manufacture of test film]
CS-12, which will be described later, was blended in the emulsion so that the minimum film-forming temperature (MFT) was 0 ° C., and was applied so that the dry film thickness was about 1 mm. Cured for a day to produce a test film.

[Water absorption rate]
The obtained test film is cut into 3 cm × 3 cm and immersed in water at 23 ° C. for 7 days, then the test film is taken out, water droplets on the surface are wiped off, and the weight is immediately measured. And a water absorption is computed by the following formula.
Water absorption (%) = 100 × (film weight after immersion−film weight before immersion) / film weight before immersion

[Elution rate]
The test film is cut into 3 cm × 3 cm and immersed in water at 23 ° C. for 7 days. Then, the test film is taken out, water droplets on the surface are wiped off, dried for 3 hours with a dryer at 105 ° C., and the weight is measured. And the elution rate is calculated by the following formula.
Elution rate (%) = 100 × (film weight before immersion−film weight after drying) / film weight before immersion

[Contact angle]
CS-12 was blended in the emulsion so that the MFT was 0 ° C., and a glass plate was applied so that the dry film thickness was about 0.1 mm, followed by curing at 23 ° C. and 50% RH for 14 days.
The glass plate after curing was immersed in ion exchange water for 1 day, and then dried under conditions of 23 ° C. and 50% RH. And the contact angle with respect to water was measured using Kyowa Interface Science Co., Ltd. product: Drop Master 500.

[Glossiness]
The composition or paint was applied on a glass plate using an applicator so that the dry coating thickness was 0.15 mm, and dried and cured at 23 ° C. and 50% RH for 7 days to form a coating film.
The glossiness (%) of the 60 ° specular surface of the obtained coating film was measured using a gloss meter (manufactured by Nippon Denshoku Industries Co., Ltd., model VG-1) according to the method specified in JIS K 5400.

[Strength (room temperature, low temperature)]
According to JIS A6909 7.29 elongation test, the said test film | membrane measured the film | membrane strong elongation at the time of 23 degreeC and -10 degreeC.

[Rain pollution]
Applying water-based epoxy sealer to a slate plate and drying it, CS-12 and pigment paste are blended into the emulsion so that the MFT is 0 ° C., a white paint is produced, and the dry coating film is 0.25 mm. It was applied by coating twice so that After curing for 14 days under conditions of 23 ° C. and 50% RH, the specimen was exposed outdoors, and the degree of rain streak was visually evaluated according to the following criteria.
○: No rain-stained dirt △: Rain-stained dirt is low ×: Rain-stained dirt is severe

<Raw materials>
[Monomer]
-Methyl methacrylate: manufactured by Mitsubishi Rayon Co., Ltd., hereinafter abbreviated as "MMA".
・ 2-ethylhexyl acrylate: manufactured by Mitsubishi Chemical Corporation, hereinafter abbreviated as “2EHA”.
Acrylic acid: manufactured by Mitsubishi Chemical Corporation, hereinafter abbreviated as “AA”.
-2-Hydroxyethyl methacrylate: Mitsubishi Rayon Co., Ltd., hereinafter abbreviated as “HEMA”.

[emulsifier]
Anionic reactive emulsifier: ADEKA Corporation: SR-10, hereinafter abbreviated as “SR-10”.
Anionic emulsifier: Sanyo Kasei Co., Ltd .: ES-70, hereinafter abbreviated as “ES-70”.

[Polymerization initiator]
・ 4,4′-azobis-4-cyanovaleric acid: manufactured by Otsuka Chemical Co., Ltd., hereinafter referred to as “ACVA”.
・ 2,2-Azobisisobutyronitrile: manufactured by Otsuka Chemical Co., Ltd., hereinafter referred to as “AIBN”.
Ammonium peroxide: manufactured by ADEKA Corporation, hereinafter referred to as “APS”.

[Silicon compounds]
<Alkylene oxide group-containing alkoxysilane condensate>
• Dynasilane: Degussa Co., Ltd .: Dynasilane 4144, hereinafter referred to as “Dynasilane 4144”.
<Alkoxysilane condensate containing no alkylene oxide group>
KC-89S: Shin-Etsu Chemical Co., Ltd .: KC-89S, hereinafter referred to as “KC-89S”.
SZ-6030: Toray Dow Corning Silicone Co., Ltd .: SZ-6030, hereinafter referred to as “SZ-6030”.

[Others]
Film-forming aid: Texanol isobutyrate (2,2,4-trimethyl-1,3-pentanediol monoisobutyrate) (manufactured by Chisso Corporation: Texanol CS-12, hereinafter "CS-12" Called.)
White pigment: Titanium paste (Dainippon Ink & Chemicals, Inc .: SD-7021, hereinafter referred to as “titanium paste”)

[Examples 1 to 5, Comparative Example 1]
AA and a silicon compound in the amounts shown in Table 1 are blended (in Examples 1 and 3 to 5, AA and Dynasilane 4144 are blended. In Example 2, AA, Dynasilane 4144, SZ-6030, and In Comparative Example 1, AA and KC-89S are blended.) The mixture is preliminarily hydrolyzed and condensed at 23 ° C. for 24 hours to obtain a mixture of AA and an alkoxysilane condensate. Thereafter, the remaining monomers listed in Table 1 were mixed to prepare a preliminary emulsion.
Next, in a reaction vessel equipped with a stirrer, a temperature controller, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen gas introduction tube, the amounts of emulsifier and deionized water listed in Table 1 were charged, and the nitrogen gas was charged. While being introduced, the temperature was raised to 65 ° C., and the preliminary emulsion and the polymerization initiator were dropped using a dropping funnel over 3 hours, respectively, and polymerization and condensation were carried out at 65 to 70 ° C. After completion of dropping, the mixture was aged at 70 to 75 ° C. for 2.5 hours and then cooled to obtain a composition.

To 100 parts by weight (solid content) of the obtained emulsion composition, 22 parts by weight of CS-12 was added to prepare a coating composition, and 53 parts by weight of titanium paste was further added to the coating composition. A coating composition was prepared.
The above physical properties and the like were measured using the obtained coating composition and coating composition. The results are shown in Table 1.

Claims (7)

0.1 to 30% by weight of the following component (A) and 70 to 99.9% by weight of the (co) polymer of the component (B) (provided that the (co) polymer of the components (A) and (B) And a total amount of 100% by weight).
(A) Component: Alkylene oxide group-containing alkoxysilane condensate.
Component (B): a monomer composed of a (meth) acrylic monomer, or a monomer mixture composed of a (meth) acrylic monomer and a monomer copolymerizable therewith. Obtained by (co) polymerizing the component (B) in the presence of the following component (A),
The component (B) contains 70 to 99.9% by weight with respect to the component (A) 0.1 to 30% by weight (provided that the total amount of the component (A) and the component (B) is 100% by weight) %), A silicon-acrylic resin composition.
(A) Component: Alkylene oxide group-containing alkoxysilane condensate.
Component (B): a monomer composed of a (meth) acrylic monomer, or a monomer mixture composed of a (meth) acrylic monomer and a monomer copolymerizable therewith.   The monomer copolymerizable with the (meth) acrylic monomer in the component (B) is a monomer having an alkoxy group, and the content ratio in the monomer mixture is 0.1 to 5 3. The silicon-acrylic resin composition according to claim 1, wherein the content is% by weight.   2. The (meth) acrylic monomer is at least one monomer selected from cyclohexyl (meth) acrylate, hydroxyethyl (meth) acrylate, and t-butyl (meth) acrylate. 4. The silicon-acrylic resin composition as described in any one of 1 to 3.   An azo polymerization initiator is used as a polymerization initiator used for the (co) polymer of the component (B) or a polymerization initiator used for the (co) polymerization of the component (B). 5. The silicon-acrylic resin composition as described in any one of 4 above.   Colloidal silica content containing 0.4 to 40 parts by weight (in terms of solid content) of colloidal silica per 100 parts by weight (in terms of solid content) of the silicon-acrylic resin composition according to any one of claims 1 to 5. Silicon-acrylic resin composition.   A silicon-acrylic paint comprising a pigment in the silicon-acrylic resin composition according to claim 1.