JP2002097417A - Organosiloxane-containing water-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water-based resin composition which is utilized in water based coating materials, is excellent in storage stability, and can give reduced stains when coating films prepared from the composition are exposed outdoors. SOLUTION: The organosiloxane-containing water-based resin composition comprises a water-based resin and an organosiloxane having an organic group including an alkyl group, an aryl group and carboxyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-based resin coating composition for use as an exterior coating for automobiles and buildings.

[0002]

2. Description of the Related Art In recent years, in the field of coating, conversion from a solvent-based paint using an organic solvent to a water-based paint using water as a solvent has been actively studied from the viewpoint of environmental protection. However, compared with the solvent-based paint, the water-based paint is inferior in its coating film properties, for example, weather resistance and stain resistance,
There are many cases where adoption is forgotten, and improvement in performance is desired. For the purpose of solving the above-mentioned problem that water-based paint has,
Many proposals have been made to introduce organosiloxanes into water-based paints. For example, JP-A-4-175343,
JP-A-4-57868 and the like provide an acrylic silicone emulsion which gives a coating film having excellent weather resistance by complexing an organic polymer particle with an organosiloxane. However, a coating film using the emulsion obtained by this method has not been able to solve the drawbacks of the conventional water-based paint, that is, poor stain resistance.

[0003] In addition, WO94 / 06870,
JP-A-00-44836 discloses a method in which a specific organosilicate and / or a condensate or a modified product thereof and a synthetic resin emulsion are used. Since the surface of the coating film obtained by these methods can be made hydrophilic,
Although it has improved stain resistance compared to conventional water-based paints, it is a so-called two-pack paint in which a synthetic resin emulsion is mixed with a specific organosilicate and / or a condensate or a modified product thereof before painting. , Not only has the disadvantage of compounding work at the painting site,
Since the pot life is as short as several hours at most, it is extremely inconvenient for actual use.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a water-based resin composition which can be used for a one-pack water-based paint having excellent stain resistance.

[0005]

Means for Solving the Problems The present inventors have studied diligently and found that an aqueous resin composition containing an aqueous resin and an organosiloxane having a specific composition can be used for a one-pack type aqueous paint having excellent stain resistance. And found the present invention. That is, an organosiloxane-containing aqueous resin composition comprising an aqueous resin and an organosiloxane represented by the following average composition formula (1).

[0006] ^{_{H p R 1 q R 2 r}} R 3 s Q t SiO (4-pqrst) / 2 (1) ( In the formula, R ¹ is a linear or branched C 1 to 3
It represents one or more hydrocarbon groups selected from alkyl groups up to 0 and cycloalkyl groups having 5 to 20 carbon atoms. R ² is selected from an unsubstituted or aryl group having 6 to 20 carbon atoms and substituted by at least one substituent selected from the group consisting of an alkoxy group having 1 to 20 carbon atoms and a halogen atom. Represents one or more hydrocarbon groups. R
³ is a fluoroalkyl group having 1 to 30 carbon atoms, or a vinyl group, an epoxy group, a keto group, a formyl group, a hydrazine group, a hydroxyl group, a thiol group, an isocyanate group, an isothiocyanate group, an amino group, an imino group, and a cyclic carbonate group. , An ester group, a phosphino group, a polyoxyalkylene group, a sulfonic acid group and / or a salt thereof, phosphoric acid and / or a salt thereof.
Represents one or more organic groups containing one group. Q represents a group consisting of one or more organic groups containing at least one selected from the group consisting of a carboxyl group and / or a salt thereof. 0 ≦
p <4, 0 <q <4, 0 <r <4, 0 ≦ s <4, 0 <t
<4, (p + q + r + s + t) <4. )

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
Examples of the aqueous resin used in the present invention include a water-soluble resin and an emulsion (latex) having a number average particle size of 30 to 800 nm, preferably 50 to 400 nm. Examples of the water-soluble resin include polyvinyl alcohol, polyacrylamide, a water-soluble acrylic polymer, a water-soluble urethane polymer, and a water-soluble fluororesin.

The above-mentioned emulsions include, for example, acrylic resin emulsions, acrylic silicone resin emulsions, urethane resin emulsions, fluorine resin emulsions, styrene-butadiene resin emulsions, acrylonitrile-butadiene resin emulsions, styrene-isoprene resin emulsions, and vinyl chloride resin emulsions. , An ethylene / vinyl acetate resin emulsion, an ethylene / vinyl chloride resin emulsion, and a natural rubber emulsion. Among them, as the aqueous resin used in the present invention, an acrylic resin emulsion and an acrylic silicone resin emulsion are preferable from the viewpoints of durability, chemical resistance, high degree of freedom in resin design, and the like. As the acrylic resin-based emulsion, those obtained by radical copolymerization of an acrylic monomer and another monomer copolymerizable with the acrylic monomer can be used.

The acrylic monomer is not particularly limited, but includes, for example, methyl (meth) acrylate (indicating either methyl acrylate or methyl methacrylate; the same applies hereinafter), and ethyl (meth).
Acrylate, n-butyl (meth) acrylate, i-
Alkyl group-containing (meth) acrylic monomers such as butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl (meth) acrylate; 2
Hydroxyl-containing (meth) acrylic monomers such as -hydroxyethyl (meth) acrylate; ethylenically unsaturated carboxylic acids such as (meth) acrylic acid; dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate Amino group-containing (meth) acrylic monomers; amide-containing (meth) acrylic monomers such as (meth) acrylamide and ethyl (meth) acrylamide; nitrile group-containing (meth) acrylic monomers such as acrylonitrile An epoxy group-containing (meth) acrylic monomer such as glycidyl (meth) acrylate;

Other monomers copolymerizable with the acrylic monomer include aromatic hydrocarbon vinyl monomers such as styrene, methylstyrene, chlorostyrene and vinyltoluene; maleic acid, itaconic acid, croton Acid, fumaric acid,
Citruconic acid, etc. | ethylenically unsaturated carboxylic acids; sulfonic acid-containing vinyl monomers such as styrene sulfonic acid and vinyl sulfonic acid; acid anhydrides such as maleic anhydride and itaconic anhydride; vinyl chloride, vinylidene chloride , Chloroprene and other chlorine-containing monomers; hydroxyethyl vinyl ether, hydroxypropyl vinyl ether and other hydroxyl-containing alkyl vinyl ethers; ethylene glycol monoallyl ether, propylene glycol monoallyl ether, diethylene glycol monoallyl ether and other alkylene glycol monoallyl ethers; ethylene and propylene And α-olefins such as isobutylene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl pivalate; methyl vinyl ether and ethyl vinyl ether Vinyl ethers such as ether, butyl vinyl ether and cyclohexyl vinyl ether; and allyl ethers such as ethyl allyl ether and butyl allyl ether.

The acrylic resin emulsion is obtained, for example, by an emulsion polymerization method. There is no particular limitation on the method of emulsion polymerization, and the monomer, chain transfer agent, surfactant, radical polymerization initiator, and other additives used as necessary in an aqueous medium by a conventionally known method. An emulsion can be produced by polymerizing a monomer in a dispersion system containing the agent component as a basic composition component.

As the acrylic silicone resin emulsion, for example, those shown in the following 1) and 2) can be used. 1) An acrylic silicone resin emulsion obtained by emulsion polymerization of a silicon-containing acrylic monomer and a monomer used in the above-described acrylic resin emulsion. 2) When emulsion-polymerizing a monomer used in the above-mentioned acrylic resin emulsion in the presence or absence of a silicon-containing acrylic monomer, during or after emulsion polymerization, alkoxysilane and / or Acrylic silicone resin emulsion modified with silicone using organoalkoxysilane. Here, the silicon-containing acrylic monomer is not particularly limited.
(Meth) acryloxypropyltrimethoxysilane, γ
-(Meth) acryloxypropyltriethoxysilane,
Hydrolyzable silyl group-containing vinyl monomers such as γ- (meth) acryloxypropylmethyldimethoxysilane and γ- (meth) acryloxypropylmethyldiethoxysilane can be exemplified.

Specific examples of the above alkoxysilane and / or organoalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane and the like. Tetraalkoxysilanes;
Methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n- Butyltrimethoxysilane, n-butyltriethoxysilane, n-
Pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane,
Cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,
2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3
-Isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, 2-
Trialkoxysilanes such as (3,4-epoxycyclohexyl) ethyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyl Diethoxysilane, di-i-propyldimethoxysilane, di-i-
Propyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n-hexyldimethoxysilane, di-n −
Hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n
Dialkoxysilanes such as -octyldimethoxysilane, di-n-octyldiethoxysilane, di-n-cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane and diphenyldiethoxysilane; trimethylmethoxysilane;
Monoalkoxysilanes such as trimethylethoxysilane can be exemplified. These alkoxysilanes and / or organoalkoxysilanes may be used alone or
A mixture of more than one species can be used.

The organosiloxane used in the composition of the present invention is represented by the following general formula (1). ^{_{H p R 1 q R 2 r}} R 3 s Q t SiO (4-pqrst) / 2 (1) wherein p, q, r, s, t is, 0 ≦ p <4,0 <q <4,
0 <r <4, 0 ≦ s <4, 0 <t <4, (p + q + r +
s + t) <4. By using the organosiloxane of the formula (1) in combination with the above-mentioned water-based resin, it is possible to prevent stain resistance which cannot be achieved by the water-based resin alone, and particularly to prevent urban-type rain streak stains which have recently been desired to be improved. Become. Regarding rain streaks, as shown in "Coating Technology, August 1997, p. 65", etc.,
In particular, it is known that improvement can be achieved by reducing the water contact angle on the surface. Organosiloxane is generally water-repellent, and when added to an aqueous resin, increases the contact angle of water. As a special case, the aforementioned WO 94/06870,
In the method disclosed in Japanese Patent Application Laid-Open No. 2000-44836, alkyl silicate is mainly used, and Si
-OR is converted into Si-OH by using an acid or the like as a catalyst in some cases to make the surface hydrophilic. However, since mainly Si-OR which is unstable in the presence of water is used, a polymerization reaction occurs during storage as a coating solution, so that the pot life is extremely short.

The organosiloxane of the present invention achieves both the hydrophilicity of the coating surface and the stability of the coating by using mainly alkyl, aryl and carboxyl groups at the silicone chain and terminal. is there. R ¹ represents a linear or branched alkyl group having 1 to 30 carbon atoms and a hydrocarbon group composed of one or more kinds selected from cycloalkyl groups having 5 to 20 carbon atoms. Among them, preferred are those having 1 to 1 carbon atoms.
One or more hydrocarbon groups selected from 0 alkyl groups, and among them, a methyl group is particularly preferable in terms of price, heat resistance, and weather resistance.

R ² is an aryl having 6 to 20 carbon atoms which is unsubstituted or substituted with at least one substituent selected from the group consisting of an alkoxy group having 1 to 20 carbon atoms and a halogen atom. 1 selected from the group
Represents a species or a hydrocarbon group composed of two or more species. Surprisingly, when an organosiloxane composed mainly of R ¹ and Q is used without R ² , the effect of making the surface of the coating film hydrophilic is small, and the presence of R ² significantly increases the surface. Was found to exhibit a hydrophilic effect. Among them, a phenyl group is preferably used in view of weather resistance, heat resistance, and compatibility with an aqueous resin. There is no particular limitation on the range in which the aryl group is used, but if it is used in a large amount, the organosiloxane may be solidified and hinder the use. For example, usually, 0 <(r / (p + q + r + s + t)) ≦
0.8, preferably 0.01 ≦ (r / (p + q + r + s)
+ T)) ≦ 0.5 is used.

Q represents a group consisting of one or more organic groups containing at least one selected from the group consisting of a carboxyl group and / or a salt thereof. When Q has one carboxyl group and / or its salt, it may be a so-called monobasic acid or a polybasic acid having two or more. For example, the following equations (2), (3), and (4) can be exemplified. —CH ₂ CH ₂ CH ₂ COOB (2)

[0018]

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[0019]

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In the formula, R ⁴ represents a substituted or unsubstituted divalent organic group; R ⁵ represents the same or different substituted or unsubstituted monovalent organic group; and R ⁶ represents a substituted or unsubstituted monovalent organic group. Shows a trivalent organic group. B represents a hydrogen atom or a base forming a counter ion with a carboxyl group, for example, an alkali metal, an alkaline earth metal, a transition metal atom such as Al or Fe, ammonium, or a substitution represented by the following formula (5). Ammonium and the like can be exemplified. HNR ⁷ R ⁸ R ⁹ (5) (R ⁷ , R ⁸ and R ⁹ are each independently a hydrogen atom or a straight or branched carbon number which is unsubstituted or substituted with a hydroxyl group. Represents an alkyl group of 1 to 20)

The organic group containing at least one selected from the group consisting of a carboxyl group and / or a salt thereof not only imparts dispersibility of the organosiloxane to water, but also forms a coating film coated in combination with an aqueous resin. It is presumed to have contributed to the surface hydrophilicity. The content in the organosiloxane of the formula (1) is not particularly limited, and is used in the range of 0 <(t / (p + q + r + s + t)) <1.0, preferably 0.01 ≦ (t / (p + q +
r + s + t)) ≦ 0.8, more preferably 0.02 ≦
(T / (p + q + r + s + t)) ≦ 0.5, particularly preferably 0.03 ≦ (t / (p + q + r + s + t)) ≦ 0.
3 is used.

The hydrogen group (H) is not essential, but may be introduced for the purpose of, for example, causing a crosslinking reaction with a vinyl group in the presence of a catalyst such as platinum to improve the physical properties of the film. However,
In an aqueous solvent, hydrolysis and high molecular weight may progress and become unstable, so that 0 ≦ (p / p + q + r + s +
t)) <0.3 is preferably applied.

R ³ represents a fluoroalkyl group having 1 to 30 carbon atoms, a vinyl group, an epoxy group, a keto group, a formyl group, a hydrazine group, a hydroxyl group, a thiol group, an isocyanate group, an isothiocyanate group, an amino group, an imino group. , Cyclic carbonate group, ester group, phosphino group,
It represents one or more organic groups containing at least one group selected from the group consisting of polyoxyalkylene groups, sulfonic acid groups and / or salts thereof, phosphoric acid and / or salts thereof. These can be appropriately introduced when it is necessary to improve the performance of the coating film depending on the use. For example, improvement of weather resistance and dispersibility,
The purpose is to improve the physical properties of the film by crosslinking. Therefore,
R ³ is not indispensable, and may be introduced as long as it does not impair the purpose of the present invention, and 0 ≦ (s / (p + q +
r + s + t)) <1.0, but usually 0 ≦
(S / (p + q + r + s + t)) ≦ 0.2, more preferably 0 ≦ (s / (p + q + r + s + t)) ≦ 0.
Used in the range of 1.

The organosiloxane represented by the formula (1)
Can be manufactured by any method.
For example, H, R¹, R^Two, R^Three, Q-containing alkoxysilane, c
Hydrogenates and condenses logenated silanes and hydroxyl silanes
, H, R¹, R^Two, R ^Three, Silicone with Q
A method of polymerizing an oligomer using a catalyst such as an acid;
R having a vinyl group in an organosiloxane having H
¹, R^Two, R^Three, Q precursor using a catalyst such as platinum
Examples of the method for idrosilylation are illustrated.
Combine to synthesize the desired organosiloxane.

The method utilizing hydrosilylation is a method which can be suitably used particularly when introducing various groups such as R ³ and Q. For example, after reacting with allylsuccinic anhydride and methylphenylhydrogensilicone using a platinum catalyst, it can be converted into methylphenylsilicone having a corresponding dicarboxylic acid group by hydrolyzing with triethylamine as a catalyst. Others butenoic acid (anhydride), maleic acid (anhydride), itaconic acid (anhydride) dodecenylsuccinic acid (anhydride), 5-norbornene-2,3-dicarboxylic acid (anhydride) 3,4,5,6- Tetrahydrophthalic acid (anhydride)
Various carboxyl groups can be introduced by a hydrosilylation reaction using such a method. In addition, a method utilizing hydrosilylation is an effective method, for example, a fluoroalkyl group can be introduced by using perfluoroalkyl allyl ether and an epoxy group can be introduced by using allyl glycidyl ether, and can be carried out by a known method.

Although the appropriate composition of the organosiloxane used in the composition of the present invention differs depending on the aqueous resin used together, the surface energy is preferably higher than that of the aqueous resin, and more preferably 2 dyne / cm or more. . When the surface energy is smaller than the above, the improvement of the stain resistance of the coating film is poor as compared with the case of using only the aqueous resin. Here, the surface energy can be measured, for example, by the following method. That is, a substrate having a coating of each of the above-mentioned organosiloxane and water-based resin was prepared, and deionized water or the like was added dropwise to the substrate.
The contact angle θ at 0 ° C. was measured, and the following Cell and Ne were measured.
The respective surface energies can be obtained from the ummann empirical formula.

[0027]

(Equation 1)

[In the formula, the vertical axis represents the surface energy (dyn / cm) of the film obtained by measuring the contact angle of deionized water or the like, and the vertical axis represents the surface energy of water or the like divided by 72.8 d in the case of deionized water.
yn / cm (20 ° C.)}. ]

There is no particular limitation on the molecular weight of the organosiloxane used in the present invention. However, if the molecular weight is too small, there is a concern of bleeding out from the coating film. Conversely, if the molecular weight is too large, handling when combined with an aqueous resin is considered. Is usually difficult to obtain, the number average molecular weight is 10
In the range of 00 to 500,000, more preferably 2000 to
Use in the range of 100,000.

The ratio of the amount of the aqueous resin to the amount of the organosiloxane used in the composition of the present invention is not particularly limited, and may be appropriately set according to the purpose. Usually, the weight ratio of the aqueous resin to the organosiloxane is 99%. 0.9 / 0.1 to 0.1 / 9
It is used in the range of 9.9, more preferably 99/1 to 5/95. In producing the organosiloxane-containing aqueous resin composition of the present invention, the method of introducing the organosiloxane represented by the formula (1) may be any method. For example, a method of mixing a separately produced aqueous resin with the organosiloxane represented by the formula (1), a method of producing the aqueous resin in the presence of the organosiloxane represented by the formula (1), and the like can be exemplified. .

The organosiloxane represented by the formula (1) used in the present invention has a carboxyl group and / or a salt thereof and can be self-emulsified in water depending on the composition. Forcible emulsification using an agent, a protective colloid or the like may be used. Examples of the surfactant and the protective colloid include organosiloxane modified with a hydrophilic group represented by the same average composition formula as the above-mentioned average composition formula (1), fatty acid soap, rosin acid soap, and alkyl sulfonate. , Alkyl succinate,
Anionic surfactants such as dialkylaryl sulfonate, alkyl sulfosuccinate, polyoxyethylene alkyl sulfate, polyoxyethylene alkylaryl sulfate, polyoxyethylene alkylaryl sulfate, polyoxyethylene alkyl ether, polyoxyethylene Nonionic surfactants such as alkyl aryl ethers, polyoxyethylene sorbitan fatty acid esters, oxyethylene oxypropylene block copolymers, and known reaction products of ethylene oxide and phosphoric acids;
A cationic surfactant containing a quaternary ammonium salt or the like,
(Partially saponified) Polymer dispersion stabilizers such as polyvinyl alcohol and the like, and combinations thereof.

In the organosiloxane-containing aqueous resin composition of the present invention, crosslinking may be introduced for the purpose of improving the physical properties of the film, for example, improving water resistance and film strength, or improving the bleed-out of the organosiloxane. Included in the range. For the crosslinking, a known aqueous crosslinking method can be used. For example, melamine, (blocked) isocyanates,
A method by thermal crosslinking of epoxy, oxazoline, hydrazide or the like, a UV or electron beam crosslinking technique, or the like may be used. Further, a method of utilizing metal crosslinking using a polyvalent metal complex by utilizing an anionic group contained in the aqueous resin or a carboxyl group contained in the organosiloxane represented by the average composition formula (1) used in the present invention is also available. This is the preferred method. The polyvalent metal mentioned here is a metal having two or more valences, for example, calcium, magnesium, zinc, barium, aluminum,
Examples include zirconium, cadmium, nickel, iron, strontium, bismuth, beryllium, cobalt, lead, copper, and antimony. Among them, zinc and zirconium are particularly preferred. Usually, the above metal complex is used in the form of an aqueous solution, and for example, those described in JP-A-62-250078 are used. In introducing the crosslinking, any method may be used. For example, a method of introducing a crosslinking group into an aqueous resin or an organosiloxane, or a method of adding a separate crosslinking agent such as melamine or (block) isocyanate. Are used.

The organosiloxane-containing aqueous resin composition of the present invention may contain, if necessary, components usually added to paints and the like, such as pigments, fillers, dispersants, light stabilizers, ultraviolet absorbers, and antioxidants. , Wetting agents, thickeners, rheology control agents, defoamers, plasticizers, film-forming aids, rust inhibitors,
Dyes, preservatives and the like can be selected and combined depending on the purpose.

The organosiloxane-containing aqueous resin composition of the present invention is useful as a top coat for architectural finishing coating materials or paints. In particular, as compared with the conventional water-based paints, it is possible to provide features such as improvement in stain resistance due to the surface hydrophilicity effect. The surface hydrophilicity can be typically represented by the contact angle of water, and the setting varies depending on the purpose, but the above-mentioned features can be exhibited by preferably setting the contact angle of water to 70 ° or less. . The setting of the water contact angle depends on the composition and structure of the aqueous resin and the organosiloxane used, but can be carried out by a method such as determining the weight ratio of the aqueous resin and the organosiloxane. The weight ratio is not particularly limited. As the architectural finish coating material or paint, the base material is, for example, an inorganic building material or a building structure such as concrete, cement mortar, slate plate, calcical plate, gypsum board, extruded plate, foamable concrete, woven fabric, nonwoven fabric Or building materials based on metal or the like,
In addition, various base materials such as steel structures, household appliances having a metal base, automobiles, home appliances having a plastic base, and automobile parts may be mentioned, and paints applied to various bases including these bases either directly or through an undercoat paint. Or, it is a top coat of an architectural finish, and more specifically, as a top coat for a multi-layer finish paint containing a sealerless filler, the finish paint is a thin finish paint, a thick finish paint, a stone finish. Materials, elastic finishing materials, etc., and synthetic resin emulsion paints such as gloss paint or flat paint, wood paints, tile paints, plastic paints, and metal paints such as automotive paints, automotive repair paints, and household electrical appliances. No.

[0035]

Examples are shown below. The methods for measuring various physical properties used in the examples are as follows. [1] Number average particle size Wet particle size analyzer (Microtrack manufactured by Nikkiso Co., Ltd.)
UPA-9230).

[2] Molecular weight Using gel permeation chromatography,
It was determined from a calibration curve of dimethyl silicone standard. (Equipment used) ・ Apparatus: Tosoh Corporation HLC-8020 LC-3A ・ Column: Tosoh Corporation TSKgel G-1000 HXL TSKgel G-2000 HXL TSKgel G-4000 HXL ・ Data processing: Shimadzu Corporation CR- 4A ・ Carrier: chloroform

[3] Contact Angle of Member The contact angle of the member was measured using a contact angle meter (C Kyowa Interface Science Co., Ltd.)
AX150), the contact angle was measured one minute after dropping deionized water or the like in a 20 ° C. environment.

[4] Surface energy A glass plate is coated with a liquid containing an aqueous resin and an organosiloxane, dried at room temperature for 1 day, dried at 20 ° C. for 20 hours to form a film, and contacted by the method of [3]. Measure the angle and Sel
1 and Newmann's empirical formula (formula 1).

[5] Formulation of paint formulation and outdoor exposure test Formulations of the respective Examples and Comparative Examples were used as paint according to the following formulation formula. Pigment dispersion (the following components are dispersed in a colloid mill.) Water 82.5 parts Dispersant: Poise 530 (product name, manufactured by Kao Corporation) 7.5 parts 5% aqueous solution of sodium tripolyphosphate 7.5 Part Thickener: 3% aqueous solution of Daicel HEC SP-600 (product name, manufactured by Daicel Chemical Industries, Ltd.) 25.0 parts Antifoaming agent: SN Deformer 777 (product name, manufactured by San Nopco Co., Ltd.) 2.5 Part: rutile-type titanium oxide: Taipaque R-930 (product name, manufactured by Ishihara Sangyo Co., Ltd.) 375.0 parts let down component (implement the following formulation in addition to the above pigment dispersion) Formulation of each example and comparative example (In terms of solid content) 460.0 parts Ethylene glycol monobutyl ether 45.0 parts Ethylene glycol mono 2-ethylhexyl ether 90.0 parts Water 30.0 parts Antifoam SN Defoamer 777 (product name, manufactured by San Nopco Co., Ltd.) 1.0 part

Outdoor exposure test: The composition of each of the Examples and Comparative Examples was applied as a paint on a 10 × 20 cm alumite plate with a wire coater so as to have a dry film thickness of 100 g / m 2, and was heated at room temperature. A test specimen was obtained by drying for 4 weeks. This specimen was fixed outdoors (Yokomitsu, Kawasaki-ku, Kawasaki-shi) so that the coating surface was perpendicular to the ground and oriented in the north direction, and the rainwater was adjusted to flow from the alumite eaves to the coating surface during rainfall. did. One month and six months after the start of exposure, the determination was made according to the following criteria. Judgment criteria ：: No rain streaks were observed. ：: The whole is dirty, but no rain streak is seen. Δ: The whole is dirty, and a slight rain streak is observed. X: Rain streaks are remarkably observed.

[0041]

Synthesis Example 1 Methylphenyl hydrogen silicone having a number average molecular weight of 5000 (p = 0.30, q =
1.60, r = 0.10, s = 0, t = 0) 100 parts,
100 parts of dioxane and 0.11 part of a 5% solution of chloroplatinic acid in isopropanol are placed in a reactor having a reflux condenser, a thermometer and a stirrer, heated to 80 ° C., and dried with 5-norbornene-2,3-dicarboxylic anhydride. 100 parts of a 30% dioxane solution of the product was added dropwise over 30 minutes, followed by stirring for 1 hour to obtain an acid anhydride group-containing polyorganosiloxane solution. To 10 parts of the acid anhydride group-containing polyorganosiloxane solution, 1 part of triethylamine and 0.5 part of water were added, and the mixture was stirred at room temperature for 30 minutes (organosiloxane solution (a)).
When the IR spectrum of this solution was measured, no absorption by an acid anhydride group was observed, and absorption by a carboxylic acid was observed at 1714 cm ^-1 . The surface energy of this organosiloxane was 63 dyne / cm.

[0042]

Synthesis Example 2 Methyl hydrogen silicone having a number average molecular weight of 5000 (p = 0.30, q = 1.70,
r = 0, s = 0, t = 0) 100 parts, dioxane 100
Parts, 0.11 part of a 5% solution of chloroplatinic acid in isopropanol was placed in a reactor having a reflux condenser, a thermometer, and a stirrer, heated to 80 ° C., and treated with 5-norbornene-2,3-dicarboxylic anhydride. 100 parts of a 30% dioxane solution is added to 30 parts.
Then, the mixture was stirred for 1 hour to obtain an acid anhydride group-containing polyorganosiloxane solution. To 10 parts of this acid anhydride group-containing polyorganosiloxane solution, 1 part of triethylamine and 0.5 part of water were added, followed by stirring at room temperature for 30 minutes (organosiloxane solution (b)). IR of this solution
When the spectrum was measured, no absorption by an acid anhydride group was observed, and absorption by a carboxylic acid was observed at 1714 cm ^-1 . The surface energy of this organosiloxane is 2
It was 1 dyne / cm.

[0043]

Synthesis Example 3 Methylphenyl hydrogen silicone having a number average molecular weight of 5000 (p = 0.30, q =
1.60, r = 0.10, s = 0, t = 0) 100 parts,
100 parts of dioxane and 0.11 part of a 5% solution of chloroplatinic acid in isopropanol are placed in a reactor having a reflux condenser, a thermometer and a stirrer, heated to 80 ° C., and 80 parts of a 30% solution of allylsuccinic anhydride in dioxane is obtained. Was added dropwise over 30 minutes, followed by stirring for 1 hour to obtain an acid anhydride group-containing polyorganosiloxane solution. For 10 parts of the acid anhydride group-containing polyorganosiloxane solution, 1 part of triethylamine,
0.5 parts of water was added, and the mixture was stirred at room temperature for 30 minutes. Further, 10 parts of a 50% dioxane solution of allyl glycidyl ether was added and reacted at 50 ° C. for 1 hour (organosiloxane solution (c)). When the IR spectrum of this solution was measured, no absorption of an acid anhydride group was observed, and 1714 cm
^{At -1} , absorption by a carboxylic acid and absorption of an epoxy group were observed. The surface energy of this organosiloxane was 65 dyne / cm.

[0044]

Synthesis Example 4 Methylphenyl hydrogen silicone having a number average molecular weight of 5000 (p = 0.30, q =
1.40, r = 0.10, s = 0, t = 0) 100 parts,
100 parts of dioxane and 0.11 part of a 5% solution of chloroplatinic acid in isopropanol are placed in a reactor having a reflux condenser, a thermometer and a stirrer, heated to 80 ° C., and dried with 5-norbornene-2,3-dicarboxylic anhydride. 100 parts of a 30% dioxane solution of the product was added dropwise over 30 minutes, followed by stirring for 1 hour to obtain an acid anhydride group-containing polyorganosiloxane solution. To 10 parts of the acid anhydride group-containing polyorganosiloxane solution, 1 part of triethylamine and 0.5 part of water were added, and the mixture was stirred at room temperature for 30 minutes (organosiloxane solution (d)).
When the IR spectrum of this solution was measured, no absorption by an acid anhydride group was observed, and absorption by a carboxylic acid was observed at 1714 cm ^-1 . The surface energy of this organosiloxane was 69 dyne / cm.

[0045]

Synthesis Example 5 Preparation of acrylic latex (1). In a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, 514 parts by weight of ion-exchanged water and 25% of a surfactant (trade name: Adecaria Soap SE-1025N, manufactured by Asahi Denka Kogyo KK) 7.2 parts by weight of an aqueous solution was added, the temperature in the reaction vessel was raised to 80 ° C., and 13.5 parts by weight of a 2% aqueous solution of ammonium persulfate was added and stirred for 5 minutes. Next, 62.6 parts by weight of methyl methacrylate, 108.4 parts by weight of butyl acrylate, 9 parts by weight of methacrylic acid, 120.2 parts by weight of ion-exchanged water, and Adecaria Soap SE-
A mixture of 5.76 parts by weight of a 25% aqueous solution of 1025N, 10.8 parts by weight of a 25% aqueous solution of polyoxyethylene nonylphenyl ether (trade name: Emulgen 950, manufactured by Kao Corporation), and 9 parts by weight of a 2% aqueous solution of ammonium persulfate Was allowed to flow into the reaction vessel from the dropping tank over 1 hour. During the inflow, the temperature in the reaction vessel was kept at 80 ° C. After the inflow ends,
The temperature in the reaction vessel was kept at 80 ° C. for 0.75 hours.
Next, 280.1 parts by weight of methyl methacrylate, 430.9 parts by weight of butyl acrylate, 9.0 parts by weight of methacrylic acid,
384 parts by weight of ion-exchanged water, Adecaria Soap SE-1
A mixed solution of 23.0 parts by weight of a 25% aqueous solution of 025N and 36.0 parts by weight of a 2% aqueous solution of ammonium persulfate was allowed to flow into the reaction vessel from the dropping tank over 2.5 hours. After the inflow was completed, the temperature in the reaction vessel was set at 80 ° C. and maintained for 1.5 hours. Subsequently, the mixture was cooled to room temperature, the pH was adjusted to 8 by adding a 25% aqueous ammonia solution, and the mixture was filtered through a 100-mesh wire net to obtain an acrylic latex (1) having a solid content of 46% and an average particle size of 1020 °. . The surface energy of this acrylic latex was 37 dyne / cm.

[0046]

Synthesis Example 6 Preparation of acrylic latex (2). In a reactor having a reflux condenser, a dropping tank, a thermometer and a stirrer, 514 parts by weight of ion-exchanged water and 25% of a surfactant (trade name: Adecaria Soap SE-1025N, manufactured by Asahi Denka Kogyo KK) 7.2 parts by weight of an aqueous solution was added, the temperature in the reaction vessel was raised to 80 ° C., and 13.5 parts by weight of a 2% aqueous solution of ammonium persulfate was added and stirred for 5 minutes. Next, 51.8 parts by weight of methyl methacrylate, 108.4 parts by weight of butyl acrylate, 10.8 parts by weight of diacetone acrylamide, 9 parts by weight of methacrylic acid, 120.2 parts by weight of ion-exchanged water, Adecaria Soap SE-1025
5.76 parts by weight of an N25% aqueous solution, polyoxyethylene nonyl phenyl ether (trade name: Emulgen 950,
A mixture of 10.8 parts by weight of a 25% aqueous solution of Kao Corporation and 9 parts by weight of a 2% aqueous solution of ammonium persulfate was allowed to flow into the reaction vessel from the dropping tank over 1 hour. During the inflow, the temperature in the reaction vessel was kept at 80 ° C. After the inflow was completed, the temperature in the reaction vessel was set at 80 ° C. and maintained for 0.75 hours. Next, 236.9 parts by weight of methyl methacrylate, 43 butyl acrylate
0.9 parts by weight, 43.2 parts by weight of diacetone acrylamide, 9.0 parts by weight of methacrylic acid, 384 ion-exchanged water
Parts by weight, 23.0 parts by weight of 25% aqueous solution of Adecaria Soap SE-1025N, 2% aqueous solution of ammonium persulfate 3
6.0 parts by weight of the mixed solution was dropped into the reaction vessel by 2.5 drops from the dropping tank.
Allowed to flow over time. After the inflow was completed, the temperature in the reaction vessel was set at 80 ° C. and maintained for 1.5 hours. Subsequently, the mixture was cooled to room temperature, and a 25% aqueous ammonia solution was added to adjust the pH to 8
Then, the mixture was filtered through a 100-mesh wire gauze to obtain an acrylic latex (2) having a carbonyl group having a solid content of 46% and an average particle size of 1020 °. The surface energy of this acrylic latex was 35 dyne / cm.

[0047]

Synthesis Example 7 Methylphenylhydrogen silicone having a number average molecular weight of 5000 (p = 0.20, q =
1.40, r = 0.40, s = 0, t = 0) 100 parts,
300 parts of dioxane and 15 parts of 5-norbornene-2,3-dicarboxylic anhydride are put into a reactor equipped with a reflux condenser, a thermometer and a stirrer, heated to 90 ° C., and heated to 90 ° C. to prepare dichlorodicyclopentadienyl platinum. 5.0 parts of a .25% dioxane solution was added, and the mixture was reacted with stirring for 4 hours. Thereafter, 34 parts of allylacetone was added dropwise over 10 minutes, and the mixture was further stirred for 3 hours to obtain an acid anhydride group- and keto group-containing polyorganosiloxane solution. To the obtained polyorganosiloxane solution, 18.5 parts of triethylamine and 5 parts of water were added, and the mixture was stirred at room temperature for 30 minutes. Thereafter, 150 parts of water was further added. And an aqueous organosiloxane solution (e) containing a keto group. When the IR spectrum of this solution was measured, no absorption of an acid anhydride group was observed, and 1714c
Absorption by carboxylic acid was observed at m ^-1 . The surface energy of this organosiloxane was 67 dyne / cm.

[0048]

Synthesis Example 8 Methylphenylhydrogen silicone having a number average molecular weight of 5000 (p = 0.20, q =
1.40, r = 0.40, s = 0, t = 0) 100 parts,
300 parts of dioxane and 10 parts of 5-norbornene-2,3-dicarboxylic anhydride are placed in a reactor having a reflux condenser, a thermometer, and a stirrer, heated to 90 ° C., and mixed with 0% of dichlorodicyclopentadienyl platinum. 5.0 parts of a .25% dioxane solution was added, and the mixture was reacted with stirring for 4 hours. Thereafter, 32 parts of hexene was added dropwise over 10 minutes, and the mixture was further stirred for 3 hours to obtain an acid anhydride group-containing polyorganosiloxane solution. To the obtained polyorganosiloxane solution, 12.3 parts of triethylamine and 5 parts of water were added, and the mixture was stirred at room temperature for 30 minutes. Thereafter, 150 parts of water was further added. And an aqueous organosiloxane solution (f) containing a keto group. When the IR spectrum of this solution was measured, no absorption by an acid anhydride group was observed, and absorption by a carboxylic acid was observed at 1714 cm ^-1 . The surface energy of this organosiloxane was 62 dyne / cm.

[0049]

Example 1 Acrylic latex (1) 50 of Synthesis Example 5
g to the organosiloxane solution obtained in Synthesis Example 1 (a)
6. A water dispersion having a solid content of 15 wt% prepared by adding water.
4 g was added over about 10 minutes under stirring at room temperature to obtain an organosiloxane-containing aqueous resin composition. The composition was left to stand at room temperature for one week and then coated again. However, there was almost no change in the viscosity of the liquid, and no problem was found in the film formability.
This composition was coated on a glass plate with a bar coater so as to have a thickness of 100 μm, and dried at room temperature for 2 days to obtain a glass plate having a transparent and smooth coating film. When the contact angle of water of this coating film was measured, 67
Degree. Further, after the organosiloxane-containing aqueous resin composition was formed into a paint in accordance with the above-mentioned coating composition, an outdoor exposure test was conducted. As a result, it was １ in one month and ○ in six months.

[0050]

Comparative Example 1 According to (Synthesis Example 1) of JP-A No. 12-44836, an alkoxysilane-modified condensate was synthesized by the following method. 100 parts of an ethylsilicate condensate having an average molecular weight of 750, which is a condensate of tetraalkoxysilane, and polyethylene glycol 200 having an average molecular weight of 200
After mixing 106.7 parts (manufactured by Wako Pure Chemical Industries, Ltd.) and further adding 0.02 parts of dibutyltin dilaurate as a catalyst,
The ethanol removal reaction was performed at 75 ° C. for 8 hours to obtain an alkoxysilane-modified condensate (silica residual ratio 20.9%).
5.3 parts of this alkoxysilane-modified condensate were used in place of 6.5 g of an aqueous dispersion having a solid content of 15 wt%, prepared by adding water to the organosiloxane solution (a) obtained in Synthesis Example 1. A composition with the acrylic latex of Synthesis Example (5) was prepared in the same manner as in Example 1. When this composition was allowed to stand at room temperature, the viscosity increased rapidly after about 2 hours, and coating became impossible after 4 hours.

[0051]

Comparative Example 2 Acrylic latex (1) 50 of Synthesis Example 5
g to the organosiloxane solution obtained in Synthesis Example 2 (b)
6. A water dispersion having a solid content of 15 wt% prepared by adding water.
4 g was added over about 10 minutes under stirring at room temperature to obtain an organosiloxane-containing aqueous resin composition. The composition was left to stand at room temperature for one week and then coated again. However, there was almost no change in the viscosity of the liquid, and no problem was found in the film formability.
This composition was coated on a glass plate with a bar coater so as to have a thickness of 100 μm, and dried at room temperature for 2 days to obtain a glass plate having a transparent and smooth coating film. When the contact angle of water of this coating film was measured, 93
Degree. Further, after the organosiloxane-containing aqueous resin composition was formed into a paint in accordance with the above-mentioned coating composition, an outdoor exposure test was conducted. As a result, ○ was obtained in one month, and × in six months.

[0052]

Comparative Example 3 The acrylic latex (1) of Synthetic Example 5 was left at room temperature for one month and then coated again, but there was almost no change in the viscosity of the liquid, and no problem was found in the film formability. The acrylic latex (1) was applied on a glass plate with a bar coater so as to have a thickness of 100 μm, and dried at room temperature for 2 days to obtain a glass plate having a transparent and smooth coating film. The contact angle of water of this coating film was measured and found to be 82 degrees. Further, after preparing this acrylic latex (1) as a paint in accordance with the above-mentioned paint formulation, an outdoor exposure test was conducted. As a result, ○ was obtained in one month, and × in six months.

[0053]

Example 2 Acrylic latex (2) 50 of Synthesis Example 6
After adding 0.55 parts of adipic acid dihydrazide to g, 6.5 g of an aqueous dispersion having a solid content of 15 wt% prepared by adding water to the organosiloxane solution (a) obtained in Synthesis Example 1,
The mixture was added at room temperature under stirring over about 10 minutes to obtain an organosiloxane-containing aqueous resin composition. The composition was left to stand at room temperature for one week and then coated again. However, there was almost no change in the viscosity of the liquid, and no problem was found in the film formability. This composition was coated on a glass plate with a bar coater so as to have a thickness of 100 μm, and dried at room temperature for 2 days to obtain a glass plate having a transparent and smooth coating film.
The contact angle of water of this coating film was measured to be 68 degrees. Further, after the organosiloxane-containing aqueous resin composition was formed into a paint in accordance with the above-mentioned coating composition, an outdoor exposure test was conducted. As a result, it was １ in one month and ○ in six months.

[0054]

Comparative Example 4 Acrylic latex (2) 50 of Synthesis Example 6
0.55 parts of adipic dihydrazide was added to g, to obtain an aqueous resin composition. The composition was left to stand at room temperature for one week and then coated again. However, there was almost no change in the viscosity of the liquid, and no problem was found in the film formability. Put this composition on a glass plate for 10
Apply with a bar coater to a thickness of 0 micron,
By drying at room temperature for 2 days, a glass plate having a transparent and smooth coating film was obtained. The contact angle of water of this coating film was measured and found to be 81 degrees. Further, after the organosiloxane-containing aqueous resin composition was formed into a paint in accordance with the above-mentioned coating composition, an outdoor exposure test was conducted. As a result, ○ was obtained in one month, and × in six months.

[0055]

Example 3 Acrylic latex (1) 50 of Synthesis Example 5
g to the organosiloxane solution obtained in Synthesis Example 3 (c)
6. A water dispersion having a solid content of 15 wt% prepared by adding water.
4 g was added over about 10 minutes under stirring at room temperature to obtain an organosiloxane-containing aqueous resin composition. The composition was left to stand at room temperature for one week and then coated again. However, there was almost no change in the viscosity of the liquid, and no problem was found in the film formability.
This composition was coated on a glass plate with a bar coater so as to have a thickness of 100 μm, and dried at room temperature for 2 days to obtain a glass plate having a transparent and smooth coating film. When the water contact angle of this coating film was measured, 70
Degree. Further, after the organosiloxane-containing aqueous resin composition was formed into a paint in accordance with the above-mentioned coating composition, an outdoor exposure test was conducted. As a result, it was １ in one month and ○ in six months.

[0056]

Example 4 Acrylic latex (1) 50 of Synthesis Example 5
g to the organosiloxane solution obtained in Synthesis Example 4 (d)
6. A water dispersion having a solid content of 15 wt% prepared by adding water.
4 g was added over about 10 minutes under stirring at room temperature to obtain an organosiloxane-containing aqueous resin composition. The composition was left to stand at room temperature for one week and then coated again. However, there was almost no change in the viscosity of the liquid, and no problem was found in the film formability.
This composition was coated on a glass plate with a bar coater so as to have a thickness of 100 μm, and dried at room temperature for 2 days to obtain a glass plate having a transparent and smooth coating film. When the water contact angle of this coating film was measured,
Degree. Further, after the organosiloxane-containing aqueous resin composition was formed into a paint in accordance with the above-mentioned coating composition, an outdoor exposure test was conducted. As a result, it was １ in one month and ○ in six months.

[0057]

Example 5 Acrylic latex (2) 50 of Synthesis Example 6
After adding 7.5 g of butyl cellosolve, 3.1 g of the aqueous organosiloxane solution (e) obtained in Synthesis Example 7 and 3.5 g of acetone to the resulting solution, the international patent publication number WO96-0 was added.
12 g of a 23% aqueous solution of polysemicarbazide obtained according to the method of Example 5 of No. 1252 was added to obtain an organosiloxane-containing aqueous resin composition. The composition was left to stand at room temperature for one week and then coated again. However, there was almost no change in the viscosity of the liquid, and no problem was found in the film formability. This composition was coated on a glass plate with a bar coater so as to have a thickness of 100 μm, and dried at room temperature for 2 days to obtain a glass plate having a transparent and smooth coating film. The contact angle of water of this coating film was measured and found to be 64 degrees. Further, after the organosiloxane-containing aqueous resin composition was formed into a paint in accordance with the above-mentioned coating composition, an outdoor exposure test was conducted. As a result, ◎ in 1 month, ○ in 6 months
Met.

[0058]

Example 6 A solution 5 obtained by adding 10 g of triethylamine and 2.3 g of a 20% aqueous solution of zinc ammonium carbonate to 100 g of the aqueous solution of organosiloxane (f) obtained in Synthesis Example 8
g of silicone-modified acrylic latex G-620
A surfactant (Emulgen 950, manufactured by Kao Corporation, 25% aqueous solution) (0.8 g) was added to 50 g obtained by adding 30 phr of butyl cellosolve (produced by Asahi Kasei Corporation) to obtain an organosiloxane-containing aqueous resin composition. The composition was left to stand at room temperature for one week and then coated again. However, there was almost no change in the viscosity of the liquid, and no problem was found in the film formability. This composition was coated on a glass plate with a bar coater so as to have a thickness of 100 μm, and dried at room temperature for 2 days to obtain a glass plate having a transparent and smooth coating film. The contact angle of water of this coating film was measured to be 61 degrees. Further, after the organosiloxane-containing aqueous resin composition was formed into a paint in accordance with the above-mentioned coating composition, an outdoor exposure test was conducted. As a result, in one month,
It was good even for 6 months.

[0059]

EFFECT OF THE INVENTION The organosiloxane-containing aqueous resin composition of the present invention is used for an aqueous paint and has excellent storage stability.
In addition, when a coating film composed of the composition is exposed outdoors, rain streak contamination can be reduced, and in particular, dirt immediately after coating film formation can be prevented, and reduction of rain streak contamination can be maintained for a long time. it can.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 133/00 C09D 133/00 175/04 175/04 183/04 183/04 183/07 183/07 201 / 04 201/04 F-term (reference) 4J002 AC01W BB05W BB06W BC05W BD03W BD12W BG01W BG02W BG04W BG05W BG06W BG07W BG10W BG13W CD19W CK02W CP03X FD310 GH01 HA07 4J0CA02 CA02 CA02 CA02 CA02 CA02 CA02 CA02 CA02 FB02 LA03 LA08 LB01 4J038 CA011 CA041 CA071 CB051 CC041 CD021 CD091 CE021 CG001 CG161 CG171 DG001 DL042 DL082 DL092 DL121 DL122 GA01 GA03 GA06 GA07 GA08 GA09 GA12 GA13 GA14 MA08 MA10 MA14 NA05 PC02 PC07 PC10

Claims (7)

[Claims] 1. An organosiloxane-containing aqueous resin composition comprising an aqueous resin and an organosiloxane represented by the following average composition formula (1). ^{_{H p R 1 q R 2 r}} R 3 s Q t SiO (4-pqrst) / 2 (1) ( In the formula, R ¹ is a linear or branched C 1 to 3
It represents one or more hydrocarbon groups selected from alkyl groups up to 0 and cycloalkyl groups having 5 to 20 carbon atoms. R ² is selected from an unsubstituted or aryl group having 6 to 20 carbon atoms and substituted by at least one substituent selected from the group consisting of an alkoxy group having 1 to 20 carbon atoms and a halogen atom. Represents one or more hydrocarbon groups. R
³ is a fluoroalkyl group having 1 to 30 carbon atoms, or a vinyl group, an epoxy group, a keto group, a formyl group, a hydrazine group, a hydroxyl group, a thiol group, an isocyanate group, an isothiocyanate group, an amino group, an imino group, and a cyclic carbonate group. , An ester group, a phosphino group, a polyoxyalkylene group, a sulfonic acid group and / or a salt thereof, phosphoric acid and / or a salt thereof.
Represents one or more organic groups containing one group. Q represents a group consisting of one or more organic groups containing at least one selected from the group consisting of a carboxyl group and / or a salt thereof. 0 ≦
p <4, 0 <q <4, 0 <r <4, 0 ≦ s <4, 0 <t
<4, (p + q + r + s + t) <4. ) 2. The p, q, r, s, and t of the organosiloxane represented by the average composition formula (1) is 0 <(r / (p + q + r + s + t)) ≦ 0.8 0.01 ≦ (t / ( The organosiloxane-containing aqueous resin composition according to claim 1, wherein the number satisfies the range of (p + q + r + s + t)) ≦ 0.8. 3. The organosiloxane-containing aqueous resin composition according to claim 1, wherein the surface energy of the organosiloxane represented by the average composition formula (1) is larger than that of the aqueous resin. 4. The aqueous resin is an acrylic resin emulsion,
The organosiloxane-containing aqueous resin composition according to any one of claims 1 to 3, wherein the organosiloxane-containing aqueous resin composition is one or more kinds selected from an acrylic silicone resin emulsion, a urethane resin emulsion, and a fluororesin emulsion. 5. A coated article coated with a paint containing the organosiloxane-containing aqueous resin composition according to claim 1, wherein the coated surface has a water contact angle of 70 ° or less. 6. A paint for a building exterior top coat, comprising the organosiloxane-containing aqueous resin composition according to claim 1. Description: 7. An automotive topcoat paint containing the organosiloxane-containing aqueous resin composition according to claim 1. Description: