JP2000264971A - Composite particle, its dispersion, production of dispersion and coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain composite particles contained in a dispersion having the lowest membrane-forming temperature at a specific temperature or lower, capable of forming a coated membrane excellent in weather resistance, especially in soil resistance by making exist a polymer on the surface of polymer particles. SOLUTION: The composite particles are obtained by making exist at least either one of a polymer of an organic silicon compound or a polymer of an organic metal compound on the surfaces or in the vicinity of the surfaces of polymer particles [preferably polymer particles having 1-29 deg.C glass transition temperature, e.g. (meth)acrylic polymer particles], and having <=90 deg.C lowest membrane-forming temperature. Further, it is preferable that the above existing polymer is chemically bonded to the polymer particles, and also, the amount of the existing polymer based on the polymer particles is 0.5-100 pts.wt. based on 100 pts.wt. polymer particles. The composite particles can be prepared as a dispersion by dispersing them in a poor solvent. A coated membrane formed from the dispersion is excellent in weather resistance and soil resistance.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to composite particles capable of forming a coating film having excellent weather resistance, particularly excellent antifouling properties, a dispersion containing the composite particles, a method for producing the dispersion, and a method for producing the same. The present invention relates to a coating material containing composite particles.

[0002]

2. Description of the Related Art In recent years, from the viewpoints of environmental protection and health and safety, there has been a strong demand for non-polluting coating materials.
The switching from conventional solvent-type coating materials to water-based coating materials, especially water-based dispersions, is being promoted, and their applications are expanding, and accordingly, the performance requirements for coating-based water-based dispersions are becoming increasingly sophisticated. . Conventionally, among the polymer components used in coating materials, (meth) acrylic polymers have excellent transparency and film-forming properties, and therefore have been widely used in coating materials as aqueous dispersions. Polysiloxanes have excellent weather resistance, water repellency, and adhesion to inorganic substrates, and are used in a wide range of fields including coating materials as disclosed in, for example, Japanese Patent Publication No. 52-39691. In order to achieve a synergistic effect of the excellent performance of the (meth) acrylic polymer and the polysiloxane, for example, JP-A-3-45628 and JP-A-4-261454 disclose a coating material obtained by compounding both polymer components. It has been proposed to be used for such purposes.

[0003] However, these composites of (meth) acrylic polymer and polysiloxane have satisfactory anti-fouling properties such as rain streaks when exposed outdoors, even if they have good weather resistance. There was nothing I could do. In addition, Japanese Patent Laid-Open No. 4-2
No. 14747 discloses a polymer latex containing an organopolysiloxane obtained by copolymerizing a carbonyl group-containing monomer and another monomer in the presence of a hydrolyzable silane, and a polyfunctional hydrazine. A self-crosslinking polymer latex composition comprising a derivative has been proposed, and this composition is said to form a coating film having good weather resistance and antifouling properties.
However, it was also difficult for this composition to maintain the weather resistance and antifouling property of the coating film and the property of preventing UV deterioration of the substrate for a long period of time. As described above, when used as a coating material, it has been extremely difficult for a water-based dispersion to exhibit the ability to simultaneously maintain the weather resistance and antifouling properties of the coating film over a long period of time.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide composite particles contained in a dispersion capable of forming a coating film having excellent weather resistance, particularly excellent antifouling properties. Another object of the present invention is to provide a dispersion capable of forming a coating film having excellent weather resistance, particularly excellent antifouling properties, and maintaining these excellent properties for a long period of time. Another object of the present invention is to provide a method for producing the dispersion. Still another object of the present invention is to provide a coating material containing the composite particles.

[0005]

According to the present invention, the following composite particles, a dispersion, a method for producing the dispersion, and a coating material are provided to achieve the above object of the present invention. (1) [I] (a) at least one of a polymer of an organosilicon compound and a polymer of an organometallic compound is present on and / or near the surface of the polymer particles; And [II] composite particles having a minimum film-forming temperature of 90 ° C or lower. (2) (a) The glass transition temperature of the polymer particles is 3 to 27 ° C.
The composite particles according to the above (1), wherein (3) The composite particles according to (1) or (2), wherein the polymer (b) is chemically bonded to the polymer particles (a). (4) A dispersion comprising the composite particles according to any one of (1) to (3) and a poor solvent for the composite particles. (5) The method for producing a dispersion according to (4) above,
(A) a polymer particle having a functional group capable of forming a linking group by reacting with a group represented by OR ² in the following general formula (1) bonded to the surface and / or near the surface; and (B) a poor solvent. (C) polycondensation of a compound represented by the following general formula (1) in a dispersion containing:

[0006]

Embedded image R ¹ nM (OR ² ) z−n (1)

(In the general formula (1), R ¹ represents a hydrogen atom or an organic group having 1 to 8 carbon atoms (excluding a group represented by OR ² ), and R ² represents a C 1 to C 6 organic group. Represents an alkyl group, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms; M represents Si or a trivalent or higher metal atom; n is an integer of 0 or more; Valence,
z-n is an integer of 2 or more, and if R ¹ is present a plurality, each R ¹ may be the same or different, R ²
The same is true for (6) (C) Before the polycondensation of the compound represented by the general formula (1), (A) a functional group bonded to the polymer particles and (D) a compound represented by the following general formula (2) The method for producing a dispersion according to the above (5), wherein the compound is reacted.

[0008]

Embedded image R ¹ xR ³ yM (OR ² ) z-xy (2)

(In the above general formula (2), R¹, R^Two,and
M has the same meaning as in formula (1),^ThreeIs (A) heavy
Reacts with functional groups attached to coalesced particles to form linking groups
Groups (however, OR^TwoExcluding the group represented by)
x is an integer of 0 or more; y is an integer of 1 or more;
Is a valence of M, and z-xy is an integer of 1 or more.
And then R¹When there are a plurality of¹Are the same or
May be different and R ^TwoAnd R^ThreeThe same is true for )
(7) The composite particles according to any one of the above (1) to (3)
Coating material characterized by containing.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The composite particles of the present invention, as described above,
(B) A polymer (b) a polymer of an organosilicon compound and a polymer of an organometallic compound (hereinafter, both) at and / or near the surface of a polymer particle (hereinafter, also simply referred to as “(a) polymer particle”). In addition, at least one polymer of "(b) polymer") is present, and [II] the minimum film-forming temperature of the composite particles is 90 ° C or lower.

FIG. 1 schematically shows a state in which (b) the polymer is present on the surface of the polymer particles and / or in the vicinity of the surface. (A) shows a state in which (B) the polymer 3 existing on the surface of the polymer particles 2 and (B) the polymer 4 existing near the surface coexist. In the present invention,
The fact that the polymer (b) exists in the vicinity of the surface of the polymer particles (a) means, for example, a state in which the polymer (b) is not completely buried inside the polymer particles (a). (B) The polymer is preferably chemically bonded to the surface of the polymer particle and / or in the vicinity of the surface via a linking group, and particularly preferably covalently bonded. The amount of the polymer (b) present on the surface and / or near the surface of the polymer particles (a) is determined by the amount of the polymer particles (a)
The amount is preferably 0.5 to 100 parts by weight, more preferably 1 to 60 parts by weight, particularly preferably 2 to 4 parts by weight with respect to parts by weight.
0 parts by weight. (B) When the amount of the polymer is in the above range, the resulting coating film has excellent weather resistance, particularly excellent antifouling properties. In the composite particles of the present invention, the polymer (b) may be present inside the polymer particles (a).

The average particle diameter of the composite particles of the present invention is preferably 5 μm or less, more preferably 5 μm or less, as measured in a state of being dispersed in the dispersion, from the viewpoint of the stability of the dispersion containing the composite particles. 2 μm or less, more preferably 1 μm
m, particularly preferably 0.03 to 0.5 μm.
The method for measuring the average particle diameter is described in Examples.

In the coating film formed from the dispersion in which the composite particles having such a structure are dispersed, (b) the polymer of the organosilicon compound and / or the polymer of the organometallic compound occupies the entire coating film. The proportion is at least on the surface of the coating film in a high concentration, weather resistance and stain resistance,
Especially excellent in antifouling properties.

The composite particles of the present invention have a minimum film forming temperature of 90.
° C or lower, preferably 80 ° C or lower. Here, the minimum film forming temperature is the lowest temperature at which a coating film can be formed by evaporation of a solvent when a dispersion containing composite particles is applied on a substrate. The specific measurement method is TF
Protzman, J. Appl. Polymer Sci., Vol. 4, 81 (1960).

(A) The polymer particles include polybutadiene latex, styrene-butadiene copolymer latex, (meth) acrylic polymer dispersion, (meth) acrylate-styrene copolymer dispersion obtained by emulsion polymerization, Examples thereof include a polyurethane polymer dispersion, a polyester polymer dispersion, a fluorine-containing copolymer dispersion, and polymer particles present in various known emulsions. Of these, (meth) acrylic polymer particles are preferable as the polymer particles (a) because of their excellent weather resistance and antifouling properties.

Further, the glass transition temperature (T
g) is preferably in the range of 1 to 29 ° C. because it is excellent in balance between film formation, flexibility and stain resistance.
More preferably, it is in the range of -27 ° C. Here, the glass transition temperature is defined as a value calculated as the weight average value of the glass transition temperature of the homopolymer composed of only the structural units constituting the polymer particles (a). Specifically, it is obtained by the following formula and converted to ° C.

[0017]

1 / Tg = Σ Wi / Tgi

Here, Tg: (a) glass transition temperature of polymer particles (indicated in absolute temperature) Tgi: glass transition temperature of homopolymer composed only of structural unit (i) (indicated in absolute temperature) Wi: (a) Weight fraction of structural unit (i) in polymer particles

In the case where the polymer (b) is present in the polymer particles (a), the glass transition temperature is calculated as follows:
Performed as if no polymer was present.

The (b) polymer constituting the composite particle of the present invention is mainly composed of a structural unit represented by-(MO)-, and can have a one-dimensional structure, a two-dimensional structure, or a three-dimensional structure. . Here, M is Si or a trivalent or higher metal atom, and is preferably Si, Ti, or Al.

The compositions of the above-mentioned (a) polymer particles and (b) polymer can be better understood by referring to a method for producing a dispersion containing the composite particles of the present invention described later. .

The coating film obtained from the dispersion of the present invention in which the composite particles of the present invention described above are dispersed in a poor solvent for the composite particles, particularly, (a) the polymer particles are (meth) acrylic polymer particles In the case of, it is excellent in weather resistance and antifouling property, particularly excellent in antifouling property. (A) The dispersion of the composite particles composed of (meth) acrylic polymer particles, which is preferable as the polymer particles, is mainly adopted as an example, and the dispersion of the present invention and the production method thereof will be described below. The poor solvent for the composite particles used in the dispersion of the present invention is a poor solvent for the (meth) acrylic polymer particles constituting the composite particles, and specifically includes water, alcohols, and polyethylene glycol monoalkyl. Examples thereof include ethers, aliphatic hydrocarbons such as n-hexane, and a mixed solvent thereof. Above all, use of water is preferred from the viewpoint of ease of production of the dispersion and working environment when the dispersion is used as a coating material. The ratio of the composite particles and the poor solvent is expressed by a weight ratio (composite particles / poor solvent),
5/95 to 70/30 is preferred, and more preferably 20/70 to 30/30.
/ 80 to 60/40. When the weight ratio is within the above range, when the dispersion of the present invention is applied to, for example, a coating material, the balance between the composite particle concentration and the viscosity of the dispersion is improved, and the coating having a desired thickness is obtained with good workability. A film can be formed.

When the polymer particles (a) of the composite particles are composed of particles other than the (meth) acrylic polymer particles, a poor solvent is selected according to the type of the polymer, and the same viewpoint as described above is applied. The weight ratio of the composite particles to the poor solvent can be selected from the following formula, but the preferred poor solvent is water, and the weight ratio of the composite particles to the poor solvent is in the above range.

Next, the method for producing the dispersion of the present invention will be described. The dispersion of the present invention has (A) a functional group capable of forming a linking group by reacting with the group represented by OR ² in the general formula (1) (hereinafter, also simply referred to as “linking group-forming functional group”). (C) Polycondensation of the compound represented by the general formula (1) in a dispersion containing polymer particles bonded to the surface and / or near the surface and (B) a poor solvent. Can be manufactured. Further, in the above method,
Before the polycondensation of the alkoxide compound (C), the polymer particles (A) and (D) the compound represented by the general formula (2) are allowed to react with each other in advance to obtain a preferable result.

The dispersion used for producing the dispersion of the present invention may be prepared by forming the polymer particles (A) by emulsion polymerization in an aqueous medium, or by adding the polymer obtained by solution polymerization to (B). ) It can be prepared by dispersing in a poor solvent. As the linking group-forming functional group bonded to the surface and / or near the surface of the polymer particle (A), the group represented by OR ² in the general formula (1) or the R 2 in the general formula (2) There is no particular limitation as long as it can form a linking group by reacting with the group represented by ³ , specifically, a carboxyl group, an acid anhydride group, a hydroxyl group,
Epoxy group, amino group, amide group, silanol group, hydrazide group, carbonyl group, acetyl group, and the like,
Among them, carboxyl group, amino group, silanol group,
This is preferable because the above reaction proceeds favorably. The monomer amount of the linking group-forming functional group is in the range of 0.1 to 30% by weight, particularly 0.5 to 20% by weight on the surface and / or near the surface of the polymer particles (A). Preferably it is present in a concentration.

When the (A) polymer particles are composed of a (meth) acrylic polymer, (A) a monomer used in the polymerization for preparing a dispersion containing the polymer particles is (meth)
It is preferable to use the alkyl ester of acrylic acid and the monomer having the linking group-forming functional group in combination and copolymerize them. The alkyl of the (meth) acrylic acid alkyl ester monomer may be substituted, and the alkyl preferably has 1 to 20 carbon atoms, including the substituent. As the monomer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate , Sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n-amyl (meth) acrylate, i-amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, n
-Octyl (meth) acrylate, n-nonyl (meth)
Acrylate, i-nonyl (meth) acrylate, p-
t-butylcyclohexyl (meth) acrylate, n-
Examples thereof include alkyl (meth) acrylates such as decyl (meth) acrylate and n-dodecyl (meth) acrylate, cycloalkyl (meth) acrylates, and benzyl (meth) acrylate. These (meth) acrylates can be used alone or in combination of two or more.

Examples of the monomer having a linking group-forming functional group include the following. (I) Carboxyl group: α, β-ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid, itaconic acid, fumaric acid, maleic acid, crotonic acid; α, β such as itaconic acid, fumaric acid, maleic acid, etc. Monoalkyl esters or monoamides of ethylenically unsaturated dicarboxylic acids (II) acid anhydride groups: acid anhydrides of α, β-ethylenically unsaturated dicarboxylic acids such as itaconic acid, fumaric acid and maleic acid (III ) Hydroxyl group: hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-
Hydroxyalkyl (meth) acrylates such as hydroxypropyl (meth) acrylate and 3-hydroxypropyl (meth) acrylate; and other N-methylol (meth) acrylamide (IV) amino group: 2-aminoethyl (meth) acrylate, 2 -Dimethylaminoethyl (meth) acrylate,
Aminoalkyl (meth) acrylates such as 2-aminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate, and 2-butylaminoethyl (meth) acrylate (V) Epoxy group: glycidyl (meth) acrylate,
Allyl glycidyl ether, etc.

The copolymerization ratio of the alkyl (meth) acrylate and the monomer having a functional group forming a linking group is such that the weight ratio of the former to the latter (the former / the latter) is 70/30 to 99.9.
/0.1, particularly preferably 80/20 to 99.5 / 0.5.

The (meth) acrylic polymer may be copolymerized with other monomers other than the above-mentioned monomers as long as the object of the present invention is not impaired. Other monomers that can constitute the (meth) acrylic polymer include, for example, 1,3
-Aliphatic conjugated dienes such as butadiene, isoprene and chloroprene; aromatic vinyl compounds such as styrene, α-methylstyrene and vinyltoluene; vinyl carboxylate esters such as vinyl acetate, vinyl propionate and vinyl benzoate; ) Vinyl cyanide compounds such as acrylonitrile; polymerizable UV-absorbing monomers such as p- (meth) acryloxyphenyl salicylate, 2-hydroxy-4- (meth) acryloxybenzobenzophenone; 2- (2′-hydroxy -5 '-(meth) acryloxyethylphenyl) benzotriazole, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4-
(Meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloyloxy-
1,2,2,6,6-pentamethylpiperidine, 4-
(Meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl -4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethyl Piperidine, 4-crotonoyloxy-2,2,6
6-tetramethylpiperidine, 4-crotonoylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-
Polymerizable radical-scavenging monomers such as tetramethylpiperidine can be mentioned. These other monomers can be used alone or in combination of two or more. Further, it is preferable to use the above-mentioned polymerizable UV-absorbing monomer and / or the above-mentioned polymerizable radical-scavenging monomer, and the preferable use amount is 0.1 to 10% by weight based on all the monomers.

The dispersion in which the particles of the (meth) acrylic polymer are dispersed in a poor solvent may be prepared, for example, by a method in which the above-mentioned monomer is copolymerized in an aqueous solvent by an emulsion polymerization method, And then emulsified in a poor solvent (hereinafter, simply referred to as “emulsification method”). The emulsion polymerization is carried out using a radical polymerization initiator and in a soap-free system or in the presence of an emulsifier. Examples of the radical polymerization initiator include an oxidizing agent composed of organic hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, and paramenthane hydroperoxide, a sugar-containing iron pyrophosphate formulation, a sulfoxylate formulation, and the like. A redox initiator comprising a combination with a reducing agent such as a sugar iron pyrophosphate / sulfoxylate mixed formulation; persulfates such as potassium persulfate and ammonium persulfate; azobisisobutyronitrile, dimethyl-2,2'- Azo compounds such as azobisisobutyrate and 2-carbamoylazaisobutyronitrile; organic peroxides such as benzoyl peroxide, lauroyl peroxide, and t-butylperoxy-2-ethylhexanoate; Can,
Preferred are the above-described redox initiators and persulfates.
The amount of the radical polymerization initiator to be used is generally 0.05 to 5 parts by weight, preferably about 0.1 to 2 parts by weight, per 100 parts by weight of all the monomer components used.

Examples of the emulsifier include an anionic emulsifier, a nonionic emulsifier, a cationic emulsifier, an amphoteric emulsifier and the like. In particular, a radical polymerizable ethylenically unsaturated bond is contained in the molecule. Are preferred. Examples of the anionic emulsifier include an alkali metal salt of a higher alcohol sulfate, an alkali metal salt of an alkylbenzene sulfonic acid, an alkali metal salt of a dialkyl succinate sulfonic acid, an alkali metal salt of an alkyl diphenyl ether disulfonic acid, and polyoxyethylene alkyl ( Or alkylphenyl) ether sulfate, etc., and trade name of Latemul S-1
80A (manufactured by Kao Corporation), Eleminor JS-2 (manufactured by Sanyo Kasei Co., Ltd.), Aqualon HS-10 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adecaria Soap SE-10N (Asahi Denka Kogyo Co., Ltd.) And reactive emulsifiers such as Antox MS-60 (Nippon Emulsifier Co., Ltd.). Examples of the nonionic emulsifier include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and the like, and trade names such as Aqualon RS-20 (Daiichi Kogyo Seiyaku Co., Ltd.) and Adecaria Soap NE-20
(Made by Asahi Denka Kogyo KK) and the like. Examples of the cationic surfactant include alkylpyridinyl chloride and alkylammonium chloride. As the amphoteric emulsifier, lauryl betaine is suitable. The amount of the emulsifier used is usually 5 parts by weight or less per 100 parts by weight of all the monomer components used.

The emulsion polymerization is desirably carried out using a soap-free system or a reactive emulsifier so as not to impair the weather resistance of the resulting coating film. In the emulsion polymerization, a radical transfer initiator, an emulsifier and, if necessary, a chain transfer agent, an electrolyte, a pH adjuster, and the like are used in combination to form a total monomer component 1
Usually, 100 to 500 parts by weight of water, a radical polymerization initiator and an emulsifier are used in an amount within the above range per 100 parts by weight, and the polymerization temperature is 5 to 100 ° C, preferably 50 to 90 ° C.
C. and a polymerization time of 0.1 to 10 hours. As a polymerization method at that time, a batch method, a method of dividing or continuously adding a monomer, a method of dividing or continuously adding a pre-emulsion of a monomer, or a method of combining these methods stepwise Although it is possible to employ the like, especially when using a low water-soluble monomer, using a high-pressure homogenizer or an ultrasonic disperser,
It is preferable to prepare a pre-emulsion by forcibly emulsifying water and an emulsifier, and then polymerize by a batch polymerization method, a divided or continuous addition method, or the like. Further, the polymerization conversion rate at that time is preferably 99.5% by weight or more.

In the solution polymerization in the emulsification method, one or more monomers having a hydrophilic functional group such as a carboxyl group or an amino group may be used in combination in consideration of emulsification in a poor solvent, particularly an aqueous solvent. preferable. In this solution polymerization,
Examples of the organic solvent in which the organic solvent and the radical polymerization initiator are used include esters such as methyl acetate and ethyl acetate; aromatic hydrocarbons such as benzene, toluene and xylene; ketones such as acetone, cyclohexanone and methyl ethyl ketone. Alcohols such as methanol, ethanol and isopropanol; ethers such as 1,4-dioxane and diethylene glycol monomethyl ether; Examples of the radical polymerization initiator used for the solution polymerization include, for example, the various radical initiators exemplified for the emulsion polymerization, and preferred are azo compounds and organic peroxides. The amount of the radical polymerization initiator used in the solution polymerization is usually 0.1 to 20 per 100 parts by weight of all the monomer components used.
Parts by weight, preferably about 0.5 to 10 parts by weight. At the time of solution polymerization, in addition to an organic solvent and a radical polymerization initiator, a chain transfer agent or the like may be used in combination, if necessary, and the solvent is usually 10 to 1000 per 100 parts by weight of all monomer components.
Using the parts by weight and the radical polymerization initiator in an amount within the above range, the polymerization temperature is 5 to 100C, preferably 50 to 90C,
The polymerization is performed under the conditions of a polymerization time of 0.1 to 10 hours.

To the polymer solution obtained by the solution polymerization, a poor solvent, preferably water, and if necessary, a neutralizer, an emulsifier, etc. are added, and the mixture is stirred under heating or non-heating to emulsify the solution. Alternatively, the polymer solution is added dropwise to water to which a neutralizing agent, an emulsifier, or the like is added as required, and the solution is stirred under heating or non-heating to emulsify the solution. A dispersion of particles of the acrylic polymer can be obtained. The organic solvent used in the solution polymerization is desirably reduced or removed from the dispersion by heating, steam distillation or the like after emulsification.

Further, a dispersion liquid of the particles of the (meth) acrylic polymer is obtained by using a part of the above-mentioned monomers and using the emulsion polymerization method or the polymer emulsion obtained by the emulsification method as a seed to prepare the remaining monomer. It can also be prepared by emulsion polymerization of the monomer. Monomers used in that case,
A radical polymerization initiator, an emulsifier added as needed,
The components such as the chain transfer agent and the polymerization conditions are the same as in the case of the emulsion polymerization method.

The dispersion thus prepared contains (A) 10 to 60% by weight, particularly 20 to 50% by weight, of polymer particles.
Is preferably contained at a concentration of Also, (A)
The average particle size of the polymer particles is from 0.01 to 1 μm, especially from 0.1 to 1 μm.
It is preferably from 0.3 to 0.5 μm. This average particle size is the average particle size of the particles in the dispersion. The method for measuring the average particle size is described in Examples.

The dispersion of the present invention is obtained by dispersing the polymer particles (A) thus prepared in a dispersion (B) in a poor solvent, and (C) the dispersion of the following general formula (1) ) Can be produced by polycondensation of the compound represented by Hereinafter, the compound represented by the general formula (1) will be abbreviated simply as “(C) alkoxide compound” as a representative of the alkoxide compound which is a typical compound included therein.

[0038]

Embedded image R ¹ nM (OR ² ) z−n (1)

In the above general formula (1), R¹Is a hydrogen atom
Or an organic group having 1 to 8 carbon atoms (however, OR^TwoGroup represented by
Excluding). R^TwoIs an alkyl group having 1 to 6 carbon atoms,
An acyl group having 1 to 6 carbon atoms or an ant having 6 to 10 carbon atoms
Represents a hydroxyl group. M represents Si or a trivalent or higher metal atom.
You. n is an integer of 0 or more; z is the valence of M;
z-n is an integer of 2 or more. And R¹Exists multiple times
If each R¹May be the same or different; ^Two
The same applies to.

In the above method, before the polycondensation of the alkoxide compound (C), the polymer particles (A) and (D) a compound represented by the following general formula (2), which are described below again, When reacted, (A) the linking group-forming functional group bonded to the polymer particles and R ³ of the general formula (2) are bonded to form a linking group, and (A) the polymer Since the group represented by M (OR ² ) is chemically bonded to the surface and / or the vicinity of the surface of the coalesced particles, the polymer formed in the polymerization process of the (C) alkoxide compound (1) efficiently (a) the polymer particles And is preferred. Hereinafter, the compound represented by the general formula (2) is also represented by an alkoxide compound which is a typical compound included therein.
It is simply referred to as “(D) alkoxide compound”.

[0041]

Embedded image R ¹ xR ³ yM (OR ² ) z-xy (2)

In the above general formula (2): R¹, R^Two, And M
Has the same meaning as in formula (1). R^ThreeIs (A) polymerization
Reacts with the linking group-forming functional group bound to the body particles to link
A group capable of forming a group (however, OR^TwoExcluding the group shown by)
Represents x is an integer of 0 or more; y is an integer of 1 or more
Where z is the valence of M and zxy is one or more integers.
Is a number. And R¹When there are a plurality of¹Is the same
May be one or different; ^TwoAnd R^ThreeIs the same as
You.

In the general formulas (1) and (2), M is preferably Si, Ti, Al or the like, and more preferably Si. In the general formulas (1) and (2), examples of the organic group having 1 to 8 carbon atoms for R ¹ include a methyl group, an ethyl group, an n-propyl group, and an i-type group.
-Propyl group, n-butyl group, i-butyl group, sec-
Alkyl groups such as butyl group, t-butyl group, n-hexyl group, n-octyl group, γ-chloropropyl group, γ-bromopropyl group, 3,3,3-trifluoropropyl group, γ-glycid Xypropyl group, γ- (meth) acryloxypropyl group, γ-mercaptopropyl group, γ-
Examples include an aminopropyl group, a vinyl group, a phenyl group, and a 3,4-epoxycyclohexylethyl group. In general formulas (1) and (2), examples of the alkyl group or acyl group of R ² having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, i-propyl, and n-butyl. Group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group,
Examples include an acetyl group, a propionyl group, and a butyryl group. Examples of the aryl group having 6 to 10 carbon atoms of R ² include a phenyl group, a tolyl group, a xylyl group, and a benzyl group.

The group represented by R ³ in the general formula (2) can react more easily with (a) a linking group-forming functional group chemically bonded to the polymer particles than the group represented by OR ^2. Those are preferred, and specific examples include a glycidyl group and an amino group.

Specific examples of the alkoxide compound (C) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, and methyltrimethoxysilane. , Methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, n-butyltrimethoxysilane , I-butyltrimethoxysilane, γ
-Chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane Γ-glycidoxypropyldimethoxyalkylsilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyldiethoxyalkylsilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-
Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxy Cyclohexylethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane and the like;

Organic titanium compounds such as tetramethoxytitanium, tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, methyltrimethoxytitanium and methyltriethoxytitanium; and organic aluminum compounds such as triethoxyaluminum and tripropoxyaluminum. Can be. Of these, dimethyldimethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, i-
Butyltrimethoxysilane and phenyltriethoxysilane are preferred. These (C) alkside compounds are represented by 1
Species can be used alone or in combination of two or more.

Specific examples of the alkoxide compound (D) include a compound overlapping with the alkoxide compound (C). In addition, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyl Trimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3
-Hydroxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane Γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylalkyldimethoxysilane, γ-glycidoxypropylalkyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3-ureidopropyltrimeth Shishiran, 3-c can be mentioned laid propyl triethoxysilane. Among them, γ-glycidoxypropyltrimethoxysilane,
γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyldimethoxymethylsilane, and γ-glycidoxypropyldiethoxymethylsilane are preferred.
These (D) alkside compounds can be used alone or in combination of two or more.

The dispersion of the present invention in which the composite particles are dispersed can be obtained by polymerizing the alkoxide compound (C) in the dispersion in which the polymer particles (A) are dispersed as described above. Preferably, for the reasons already described, good results can be obtained by pre-reacting the (D) alkoxide compound with the (A) polymer particles and then polycondensing the (C) alkoxide compound. In any case, the (D) alkoxide compound may be present when the (C) alkoxide compound is polycondensed. When the alkoxide compound (C) is subjected to polycondensation, the compound in which zn is 1 in the general formula (1) is added to a small amount of the alkoxide compound (C), preferably to 1 mole of the alkoxide compound (C). , 1
/ 2 mol or less. Excessive addition is preferably avoided because the progress of polycondensation stops and the molecular weight does not become high.

The reaction between the (D) alkoxide compound and the (A) polymer particles is carried out at pH 2 to 1 in which the (A) polymer particles are dispersed.
To the dispersion adjusted to 0, the alkoxide compound (D) is preferably added in an amount of 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polymer particles (A). It can be carried out by stirring at a temperature of 20 to 90 ° C, preferably 40 to 80 ° C for 0.1 to 6 hours.

In the polycondensation of the alkoxide compound (C), the pH of the dispersion is adjusted to preferably 4 to 10, more preferably 5 to 10.
To 9.5, more preferably 6 to 9, and adding the (C) alkoxide compound, at a temperature of 30 ° C. or more, preferably 50 to 90 ° C., more preferably 60 to 80 ° C.,
It can be performed by stirring for 0.1 to 10 hours. (C) The alkoxide compound is preferably added in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the polymer particles (A).
0 parts by weight, more preferably 1 to 60 parts by weight.
When the amount of the alkoxide compound (C) is within the above range, a sufficient amount of the polymer of the (C) alkoxide compound is chemically bonded to the surface and / or the vicinity of the surface of the polymer particles (A). From the resulting dispersion, a coating film having excellent weather resistance and antifouling properties can be obtained.

Since the polycondensation proceeds by hydrolysis of the group represented by OR ² in the general formula (1) and subsequent dehydration condensation, water must be present in the polycondensation system. Therefore, when the poor solvent used in the dispersion is other than water, water is added so that water is present in the polycondensation system in an amount of 1% by weight or more, preferably 10% by weight or more, depending on the type of the solvent. It is necessary to.

In order to improve weather resistance, a light stabilizer can be added to the dispersion of the present invention. Such light stabilizers are not particularly limited. For example, organic light stabilizers such as organic nickel-based and hindered amine-based light stabilizers conventionally used in paints, synthetic rubbers, synthetic resins, synthetic fibers, and the like can be used. Although bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (1,2,2,6,6-pentamethyl-) are preferably used.
4-piperidyl) sebacate, 4-benzoyloxy-
2,2,6,6-tetramethylpiperidine, tetraxy (2,2,6,6-tetramethyl-4-piperidyl)-
Hindered amine light stabilizers such as 1,2,3,4-butanetetracarboxylate. The amount of the light stabilizer is per 100 parts by weight of the dispersion (solid content) of the present invention.
Usually, it is 10 parts by weight or less, preferably 5 parts by weight or less, and may be added after being dissolved in a monomer and / or a solvent, or may be added by dispersing in water in advance. In this case, when the compounding amount of the light stabilizer exceeds 10 parts by weight, the coating film tends to be discolored and the storage stability of the dispersion tends to decrease.

In order to improve the weather resistance, (A)
A polymer of the alkoxy compound as the component (C) may be present inside the polymer particles. In order for the polymer of the alkoxy compound to be present inside the polymer particles (A), the alkoxy compound is reacted with the polymer particles (A) 100 (A) before reacting the polymer particles (A) with the alkoxy compound (D). Not more than 50 parts by weight per part by weight, added to the dispersion of the polymer particles (A) to be absorbed into the polymer particles (A), and the absorbed alkoxy compound is added in the subsequent polycondensation step of the (C) alkoxy compound. It can be carried out by polycondensation.

When water is used as a poor solvent in the dispersion of the present invention, methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl may be used to improve film-forming properties and wettability. Alcohols such as alcohol, n-amyl alcohol, n-hexyl alcohol; cellosolves such as methyl cellosolve, ethyl cellosolve, n-propyl cellosolve, i-propyl cellosolve, n-butyl cellosolve, n-hexyl cellosolve; methyl carbitol, ethyl Organic solvents such as carbitols such as carbitol; cellosolve acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; and phosphates such as tri-n-butoxymethyl phosphate can be blended in the dispersion. The compounding amount of the organic solvent is usually 20% by weight or less, preferably 10% by weight or less, more preferably 5% by weight or less of the total aqueous dispersion.

As the ultraviolet absorbing component, for example, p
Methacryloxyphenyl salicylate, 2-hydroxy-4-methacryloxybenzophenone, 2- (2 ′
-Hydroxy-5'-methacryloxyethylphenyl) benzotriazole and the like. Further, as additives other than the above, water-soluble or water-dispersible resins generally used as aqueous resins, for example, polyester resins, epoxy resins, acrylic resins, carboxylated aromatic vinyl resins such as styrene-maleic acid resins And urethane resins, as well as defoamers, thickeners, stabilizers against heat, leveling agents, lubricants, antistatic agents, dyes, pigments, fungicides, and the like.

[0056]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Here, parts and% are based on weight.

Example 1 A 2-liter separable flask equipped with a stirrer, a thermometer, a heater, a monomer addition pump, and a nitrogen gas introducing device was charged with 70 parts of ion-exchanged water and Adekaly, a reactive emulsifier. 0.2 parts of soap SE-10N and 0.3 parts of potassium persulfate were charged, the gas phase was replaced with nitrogen gas for 15 minutes, and the temperature was raised to 80 ° C. In a separate container, use ion-exchanged water 3
0 parts, the reactive emulsifier 1.0 part, n-butyl acrylate 15 parts, 2-ethylhexyl acrylate 15 parts,
25 parts of methyl methacrylate, 40 parts of cyclohexyl acrylate, 2-hydroxyethyl methacrylate 2
And 3 parts of acrylic acid were mixed and stirred, and then an ultrasonic homogenizer (RUS-60 manufactured by Nippon Seiki Seisaku-sho, Ltd.)
In 0), the monomer was finely dispersed to prepare a pre-emulsion. Next, this pre-emulsion was continuously dropped into the separable flask over 3 hours. During the dropwise addition, nitrogen gas was introduced to maintain the internal temperature at 80 ° C. After completion of the dropwise addition, the mixture was aged at 85 to 95 ° C. for another 2 hours to complete the polymerization reaction.
7, to obtain an aqueous copolymer dispersion A.

After that, γ-
Glycidoxypropyldimethoxymethylsilane 1 part, γ
-2 parts of glycidoxypropyltriethoxysilane were added and stirred vigorously for about 1 hour. Next, after 6 parts of methyltriethoxysilane and 2 parts of tetraethoxysilane were added, the temperature was raised to 70 ° C., and stirring was continued for 3 hours to carry out polycondensation. Thereafter, the mixture was cooled and filtered through a wire mesh of 120 mesh (JIS) to obtain an aqueous coating dispersion comprising composite particles of a (meth) acrylic polymer and polysiloxane. The solid content concentration of this dispersion was 45.1%, and the average particle size of the composite particles (measured with a Coulter Nanosizer, the same applies hereinafter) was 130 nm.

Example 2 After preparing the aqueous copolymer dispersion A of Example 1, 5 parts of methyltriethoxysilane and 2 parts of tetraethoxysilane were further added, and the mixture was vigorously stirred for about 30 minutes and absorbed. Thereafter, the temperature of the reaction vessel was raised to 70 ° C., and the reaction was carried out for 3 hours to obtain an aqueous copolymer dispersion B. Except that the aqueous copolymer dispersion B was used in place of the aqueous copolymer dispersion A of Example 1, and the components (D) and (C) shown in Table 1 were used,
A dispersion for aqueous coating was obtained in the same manner as in Example 1.

Example 3 In Example 1, 0.5 parts of 2- (2'-hydroxy-5'-methacryloxyethylphenyl) benzotriazole (RUVA), 4-methacryloyloxy-
2,2,6,6-tetramethylpiperidine (HALS)
After adding 0.5 part to prepare a copolymer dispersion A, 10 parts of methyltriethoxysilane, the component (D) shown in Table 1,
A water-based coating dispersion was obtained in the same manner as in Example 2, except that the components (C) and (C) were added.

Example 4 A copolymer dispersion was prepared in the same manner as in Example 1 except that the proportions of the components used were changed as shown in Table 1. A dispersion was obtained.

Comparative Example 1 An aqueous coating dispersion was obtained in the same manner as in Example 1 except that the amounts of the components used for preparing the aqueous copolymer dispersion were changed as shown in Table 2. Was.

Comparative Example 2 An aqueous coating dispersion was obtained in the same manner as in Example 3 except that no alkoxysilane was used.

Comparative Example 3 An aqueous coating dispersion was obtained in the same manner as in Example 1, except that methyltriethoxysilane and tetraethoxysilane were not used.

Comparative Example 4 To a mixed solution of 20 parts by weight of ethanol and 15 parts by weight of 12% aqueous ammonia, 6 parts by weight of methyltriethoxysilane and 2 parts by weight of tetraethoxysilane were added and reacted at 60 ° C. for 4 hours (polycondensation). Thereafter, the mixture was further purged with nitrogen at the same temperature for 4 hours to obtain dispersion particles. The dispersion particles obtained above were mixed with the aqueous copolymer dispersion A prepared in Example 1 to obtain a dispersion for aqueous coating.

Using the aqueous coating dispersions obtained in Examples 1 to 4 and Comparative Examples 1 to 4, paints were prepared according to the following formulation. <Mill base> CR97 (pigment, manufactured by Ishihara Sangyo Co., Ltd.) 20 parts SN Twisted Sunto 5027 (dispersant, Fujitsu Yoshitsusho) 0.5 part Na hexametaphosphate (dispersant) 1 part Ethylene glycol (antifreeze) 0.29 Part SN113 (antifoaming agent, manufactured by San Nopco) 0.05 part water 5.96 parts <let down> 27.80 parts of the above-mentioned mill base 78.49 parts of a dispersion for aqueous coating SN612, 20% aqueous solution (thickener, manufactured by San Nopco) 0.25 parts B1016 (antifoaming agent, manufactured by Asahi Denka Co., Ltd.) 0.05 parts SN113 (antifoaming agent, manufactured by San Nopco) 0.05 parts CS-12 (film forming aid, manufactured by Chisso Corporation) 3.69 parts

An iron plate (JIS-314) obtained by degreased each paint obtained by the above-mentioned composition with xylene and an alkaline detergent.
1, SPEC board, 0.8 × 70 × 1500 mm) using an airless spray gun, the coating thickness after drying is about 50
After coating to a thickness of μm, it was dried at 60 ° C. for 30 minutes. (1) Evaluation of film forming property The obtained coating film was visually observed for the presence or absence of cracks, and the film forming property was evaluated in the following five steps. 5: None 4: Very small 3: Slightly recognized 2: Partially recognized 1: Fully recognized

(2) Evaluation of carbon contamination The carbon dispersion was applied to the coated plate prepared above, dried at room temperature for 30 minutes, washed with water, and the contamination level and color difference ΔL were measured. Was done. 5: Color difference ΔL10 or less 4: Color difference ΔL10 or more and 20 or less 3: Color difference ΔL20 or more and 30 or less 2: Color difference ΔL30 or more and 40 or less 1: Color difference ΔL40 or more

(3) Rain Streak Test After the above-prepared mounting plate was exposed outdoors at 90 ° north side in Yokkaichi City for 3 months, the contamination level and the color difference ΔL were measured, and the following five-step evaluation was performed. . 5: Color difference ΔL5 or less 4: Color difference ΔL5 or more and 10 or less 3: Color difference ΔL10 or more and 15 or less 2: Color difference ΔL15 or more and 20 or less 1: Color difference ΔL20 or more

(4) Accelerated weathering test The coated plate prepared above was tested for sunshine weather meter (WEL-SUN HC, manufactured by Suga Test Instruments Co., Ltd.).
), The gloss retention after exposure at 63 ° C. for 2,000 hours was measured, and the following five-level evaluation was performed from the measurement results. The gloss was measured by measuring a 60-degree specular gloss based on JIS K5400. 5: Gloss retention of 80% or more 4: Gloss retention of 70% to less than 80% 3: Gloss retention of 60% to less than 70% 2: Gloss retention of 50% to less than 60% 1: Gloss retention of less than 50% Tables 3 and 4 show the test results of Table 3 together with the properties of the aqueous dispersion.
It was shown to.

[0071]

[Table 1]

[0072]

[Table 2]

(Description of Tables 1 and 2) nBA: n-butyl acrylate 2EHA: 2-ethylhexyl acrylate MMA: methyl acrylate CHMA: cyclohexyl acrylate HEMA: 2-hydroxyethyl acrylate AA: acrylic acid RUVA: 2- (2 ′) -Hydroxy-5'-methacryloxyethylphenyl) benzotriazole HALS: 4-methacryloyloxy-2,2,6,6
-Tetramethylpiperidine MTES: Methyltriethoxysilane TEOS: Tetratriethoxysilane GPTMS: γ-glycidoxypropyltrimethoxysilane GPDMMS: γ-glycidoxypropyldimethoxymethylsilane

[0074]

[Table 3]

[0075]

[Table 4]

The following is clear from the results shown in Tables 3 and 4. The dispersions of Examples 1 to 4 contain the composite particles of the present invention, and coatings prepared from these dispersions give coating films having excellent film-forming properties, excellent weather resistance and antifouling properties. On the other hand, a coating material prepared from a dispersion containing composite particles having a minimum film-forming temperature exceeding 90 ° C. is extremely poor in film-forming properties (Comparative Example 1). A coating film formed from a coating material prepared from a dispersion in which the acrylate polymer particles were not treated with the alkoxide compound and in which no polymer of the alkoxide compound was present was inferior in antifouling property and weather resistance (Comparative Example 2). . A coating film formed from a paint prepared from a dispersion in which the polymer of the alkoxide compound is not present, though treated with the alkoxide compound, is slightly inferior in antifouling property, inferior in weather resistance and film forming property (Comparative Example 3). ). Also,
A coating formed from a coating simply prepared from a dispersion containing an acrylate polymer and a polysiloxane has poor weather resistance (Comparative Example 4).

[0077]

As described above, a coating film is formed from the dispersion containing the composite particles of the present invention with good film-forming properties, and the formed coating film has excellent weather resistance and antifouling properties, particularly excellent antifouling properties. Good properties last for a long time. Therefore, a coating material having the above-mentioned excellent properties can be obtained from the coating material of the present invention prepared using the dispersion of the present invention. Therefore, the dispersion of the present invention containing the composite particles of the present invention is particularly suitable for use in enamel paint and clear paint, and can be used for plastic films, plastic molded articles, paper, fiber, wood, metal, glass, concrete, It is useful as a coating material for a wide range of materials such as ceramics, slate, marble, ceramics, gypsum, leather, etc., for interior and exterior of buildings, for building materials, for steel structures, for concrete structures, for precast materials, and for automobile interior and exterior. It can be applied to a wide range of fields, such as wear, aluminum coating, sealant, and floor polish.

[Brief description of the drawings]

FIG. 1 is a schematic view schematically showing a composite particle of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Composite particle 2 Polymer particle 3,4 Polymer

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C09D 7/12 C09D 7/12 Z 183/10 183/10 185/00 185/00

Claims (7)

[Claims] 1. (I) (a) the surface of polymer particles and / or
Alternatively, (b) at least one of a polymer of an organosilicon compound and a polymer of an organometallic compound is present near the surface, and [II] the minimum film-forming temperature is 90 ° C. or lower. Characteristic composite particles. (2) The glass transition temperature of the polymer particles is 1
The composite particle according to claim 1, wherein the temperature is in the range of -29 ° C. 3. The composite particles according to claim 1, wherein the polymer (b) is chemically bonded to the polymer particles (a). 4. A dispersion comprising the composite particles according to claim 1 and a poor solvent for the composite particles. 5. The method for producing a dispersion according to claim 4, wherein (A) a functional group capable of forming a linking group by reacting with a group represented by OR ² in the following general formula (1) is provided on the surface. And / or (C) polycondensing a compound represented by the following general formula (1) in a dispersion containing polymer particles bonded in the vicinity of the surface and (B) a poor solvent. A method for producing a dispersion. Embedded image R ¹ nM (OR ² ) z−n (1) (In the above general formula (1), R ¹ is a hydrogen atom or a carbon atom.
To 8 organic groups (excluding the group represented by OR ² ), wherein R ² is an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms Represents
M represents Si or a metal atom having a valence of 3 or more, n is an integer of 0 or more, z is a valence of M, zn is an integer of 2 or more, and a plurality of R ¹ are present. If each R ¹
May be the same or different, and the same applies to R ² . ) (C) a compound represented by the above general formula (1)
Before the polycondensation of the product, (A) is bonded to the polymer particles.
A functional group and (D) a compound represented by the following general formula (2)
6. The method according to claim 5, wherein
Construction method. Embedded image R¹xR^ThreeyM (OR^Two) Zxy (2) (in the above general formula (2), R¹, R^Two, And M are general formulas
Has the same meaning as in the case of (1),^ThreeIs to (A) polymer particles
Group capable of forming a linking group by reacting with a binding functional group
(However, OR^TwoEx), and x is 0 or more
Is an integer above, y is an integer of 1 or more, and z is an element of M
A valence, zxy is an integer of 1 or more, and
R¹When there are a plurality of¹Are the same or different
May be, R ^TwoAnd R^ThreeThe same is true for ) 7. A coating material containing the composite particles according to claim 1. Description: