JP2003055459A - Composite particle, dispersion thereof, method for producing dispersion, and coating material - Google Patents

Abstract

(57) Abstract: A composite particle capable of forming a coating film having excellent initial antifouling property, a dispersion containing the composite particle, a method for producing the dispersion, and a coating material containing the composite particle. To provide. A composite particle is a dispersion containing a polymer particle having a functional group capable of forming a linking group by reacting with OR ² of the formula (1) bonded to the surface thereof, and a poor solvent. And equation (1)
Is obtained by polycondensation of a compound containing at least one compound represented by the formula (1), and a polymer of a nitrogen atom-containing organic silicon compound is present on the surface of the polymer particles. R ¹ nM (OR ² ) zn (1) (R ¹ is an organic group having 1 to 8 carbon atoms including a nitrogen atom (however,
OR ² except a group represented by), R ² is an alkyl group, an acyl group or an aryl group having 6 to 10 carbon atoms having 1 to 6 carbon atoms,
M is 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, and zn is an integer of 2 or more. )

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art In recent years, from the viewpoint of environmental protection and health and safety, there has been a strong demand for pollution-free coating materials.
The conventional solvent-based coating materials are being switched to water-based coating materials, especially water-based dispersions, and their applications are expanding, and the performance requirements for water-based dispersions for coatings are also becoming more sophisticated. .

Among the polymer components conventionally used in coating materials, (meth) acrylic polymers have excellent transparency and film-forming properties, and are therefore widely used as coating materials in water. In addition, polysiloxane has excellent weather resistance, water repellency, and adhesion to an inorganic substrate, and is used in a wide range of fields including coating materials as disclosed in, for example, Japanese Patent Publication No. 52-39691. With the aim of achieving a synergistic effect of the excellent performance of these (meth) acrylic polymers and polysiloxanes, for example, JP-A-3-
In Japanese Patent No. 45628 and Japanese Unexamined Patent Publication No. 4-261454, it is proposed that both polymer components are combined and used as a coating material or the like.

However, even if the composite of these (meth) acrylic polymer and polysiloxane has good weather resistance, it has satisfactory antifouling properties such as rain streaks when exposed to the outdoors. There was nothing I could do. In addition, Japanese Patent Laid-Open No. 4-2
Japanese Patent No. 14747 discloses a polymer latex containing an organopolysiloxane obtained by copolymerizing a carbonyl group-containing monomer with 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 it is said that this composition forms a coating film having good weather resistance and antifouling property.
However, it was also difficult for this composition to maintain the weather resistance and antifouling property of the coating film and the UV deterioration preventing property for the substrate for a long period of time.

More importantly, since the coating film at the initial stage of coating is relatively hydrophobic and does not get wet with water, the self-cleaning effect of rainwater and the like is small, and the rain line antifouling property immediately after completion can be satisfied. There was no. As described above, when it is used as a coating material, it is extremely difficult for the water-based dispersion to exhibit the weather resistance and antifouling property of the coating film at the same time and capable of maintaining the initial coating for a long period of time.

[0006]

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 and especially excellent initial antifouling property. Another object of the present invention is to provide a dispersion capable of forming a coating film having excellent weather resistance, particularly excellent initial antifouling property, and maintaining these excellent properties from the initial stage for a long period of time.

Another object of the present invention is to provide a method for producing the above dispersion. Still another object of the present invention is to provide a coating material containing the above composite particles.

[0008]

According to the present invention, the following composite particles, a dispersion, a method for producing a dispersion, and a coating material are provided to achieve the above object of the present invention. (1) (A) Polymer particles having a functional group capable of reacting with a group represented by OR ² of the following general formula (1) to form a linking group on the surface and / or in the vicinity of the surface, and (B) ) In a dispersion containing a poor solvent, (C) the following general formula (1) R ¹ nM (OR ² ) zn (1) (in the above general formula (1), R ¹ represents a nitrogen atom). Contains 1 carbon
~ 8 represents an organic group, R ² represents 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, M is Si or a metal atom having 3 or more valences the stands, n is an integer of 0 or more, z is the valence of M, z-n is an integer of 2 or more, and if R ¹ is present a plurality, each R ¹ is the same or different Alternatively, a plurality of R ^{2 s} may be the same or different. Obtained by polycondensing a compound containing at least one compound represented by the formula (1), and (b) a polymer of a nitrogen atom-containing organosilicon compound and nitrogen on the surface and / or in the vicinity of the surface of the polymer particle. At least one of the polymers of the atom-containing organometallic compound is present, and composite particles are provided.

(2) (C) Before polycondensing the compound represented by the above general formula (1), the functional group bonded to the polymer particles (A) and the following general formula (2) are represented. reacting a that compound (D), characterized in that it is obtained by the composite particles according to (1); in ^{R 3 xR 4 yM (OR 2} ) zxy ... (2) ( the general formula (2), R ² , And M are represented by the general formula (1)
R ³ is a hydrogen atom or has 1 to 1 carbon atoms.
8 represents an organic group (excluding the group represented by OR ² ), and R ⁴ is a group capable of reacting with the functional group bonded to the polymer particle (A) to form a linking group (provided OR ² is excluded), x is an integer of 0 or more, y is an integer of 1 or more, z is a valence of M, and z-xy is an integer of 1 or more. , And when plural R ² are present, each R ² may be the same or different, and R ³ and R ⁴ are also the same. (3) (a) The glass transition temperature of the polymer particles is 0 to 40.
The composite particle according to (1) or (2), which is in the range of ° C.

(4) The above (b) polymer is the above (a)
Characterized by being chemically bonded to polymer particles (1)
The composite particles according to any one of (3) to (3). (5) The (A) polymer particles are multiphase polymer particles composed of a polymer phase (a) of the core part (A ′) and a polymer phase (b) of the shell part, and Polymer particles in which a functional group capable of reacting with the group represented by OR ² of the formula (1) to form a linking group is bonded to the surface and / or the vicinity of the surface of the polymer phase (b), A) Polymer particles are (a ')
(I) 2 to 70% by weight of the polymer phase (a) in the core part and 98 to 30% by weight of the polymer phase (b) in the shell part (here,
The total of (a) and (b) is 100% by weight), and (ii) the polymer phase of the shell part of the (a ') polymer particles (b). (B) a polymer exists on the surface and / or in the vicinity of the surface, and (iii) the polymer phase (a) of the core part and the polymer phase (b) of the shell part.
Satisfies the following condition (1) or (2): Condition (1): a monomer unit constituting the polymer phase of the core part; Condition (2) that the monomer unit constituting the polymer phase of the shell portion is different from the monomer unit constituting the polymer phase of the core portion and the monomer unit constituting the polymer phase of the shell portion When and are the same, the amount ratio of the monomer units in the core part and the shell part must be different.

(6) The composite according to (5), wherein the (b) polymer is chemically bonded to the polymer phase (b) of the shell part of the (a ') polymer particle. particle. (7) A dispersion comprising the composite particle according to any one of (1) to (6) and a poor solvent for the composite particle. (8) A method for producing the dispersion according to (7), wherein
(A) Polymer particles having a functional group capable of reacting with the group represented by OR ² of the general formula (1) to form a linking group on the surface and / or in the vicinity of the surface, and (B) a poor solvent. In a dispersion liquid containing (C) a compound containing at least one compound represented by the following general formula (1) is polycondensed; R ¹ nM (OR ² ) zn (1) (In the general formula (1), R ¹ is a nitrogen atom-containing carbon atom 1
8 organic groups represent (excluding the group represented by OR ^2), R ² is an alkyl group having 1 to 6 carbon atoms, an acyl group or an aryl group having 6 to 10 carbon atoms having 1 to 6 carbon atoms Represent, 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, z−n is an integer of 2 or more, and R ¹ is present in plural numbers. , Each R ¹ may be the same or different, and a plurality of R ² may be the same or different. ).

(9) (C) Before the polycondensation of the compound represented by the general formula (1), the functional group bonded to the polymer particles (A) and the general formula (2) are represented. The method for producing a dispersion according to (8), wherein the compound (D) is reacted; R ³ xR ⁴ yM (OR ² ) zxy (2) (in the general formula (2), R ² , And M are represented by the general formula (1)
R ³ is a hydrogen atom or has 1 to 1 carbon atoms.
8 represents an organic group (excluding the group represented by OR ² ), and R ⁴ is a group capable of reacting with the functional group bonded to the polymer particle (A) to form a linking group (provided OR ² is excluded), x is an integer of 0 or more, y is an integer of 1 or more, z is a valence of M, and z-xy is an integer of 1 or more. , And when plural R ² are present, each R ² may be the same or different, and R ³ and R ⁴ are also the same. (10) The polymer particle (A) is a multiphase polymer particle composed of a polymer phase (a) of a core portion (A ′) and a polymer phase (b) of a shell portion, It is a polymer particle in which a functional group capable of reacting with the group represented by OR ² of the general formula (1) to form a linking group is bonded to the surface and / or the vicinity of the surface of the polymer phase (b). The method for producing a dispersion according to (8) or (9), which is characterized in that.

(11) A coating material containing the composite particle as set forth in any one of (1) to (6).

[0014]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in more detail below. Composite Particles As described above, the composite particles of the present invention include (I) (a) polymer particles (hereinafter, also simply referred to as “(a) polymer particles”) on the surface and / or in the vicinity of the surface. ) At least one of a polymer of a nitrogen atom-containing organosilicon compound and a polymer of a nitrogen atom-containing organometallic compound is present.

FIG. 1A shows one embodiment of the structure of the composite particle of the present invention. In FIG. 1 (A), the composite particle 1 is (a)
It is composed of polymer particles 2, (a) polymer (3) existing on the surface of the polymer particles (2) and (b) polymer 4 existing near the surface. In the present invention, the presence of the (b) polymer in the vicinity of the surface of the (b) polymer particle means, for example, a state in which the (b) polymer is not completely buried inside the (b) polymer particle. .

The polymer (b) is preferably chemically bonded to the surface and / or in the vicinity of the surface of the polymer particle (a) through a linking group, and particularly preferably covalently bonded. In the composite particles of the present invention, the polymer (b) may be present inside the polymer particles (a).

The amount of the polymer (b) present on the surface of the polymer particle (a) and / or in the vicinity of the surface thereof is 0.5 to 100 parts by weight based on 100 parts by weight of the polymer particle (a). Is more preferable, 1 to 60 parts by weight is more preferable, and 2 to 40 parts by weight is particularly preferable. (B) When the amount of the polymer is within the above range, the weather resistance of the resulting coating film,
In particular, the result is excellent in initial antifouling property.

The term "initial antifouling property" as used herein means that the film does not become soiled by a raindrop test in a short period of about one month, and it is achieved by a low contact angle between the coating film and water at the initial production stage. (A) As the polymer particles, a polybutadiene latex obtained by emulsion polymerization, a styrene-butadiene copolymer latex, a (meth) acrylic polymer dispersion,
(Meth) acrylate-styrene copolymer dispersion, polyurethane polymer dispersion, polyester polymer dispersion, fluorine-containing copolymer dispersion, and other known polymer particles present in various emulsions. it can.

Among them, (meth) acrylic polymer particles are preferable as the (a) polymer particles because of their excellent weather resistance and antifouling property. Further, the glass transition temperature (Tg) of the polymer particles is preferably in the range of 0 to 40 ° C. because of excellent balance of film-forming property, flexibility and stain resistance. Is more preferable.

Here, the glass transition temperature is defined as a value calculated as a weight average value of the glass transition temperatures of (a) a homopolymer consisting only of structural units constituting polymer particles. Specifically, it is obtained by the following mathematical formula and converted into ° C. 1 / Tg = Σ Wi / Tgi where: Tg: (a) glass transition temperature of polymer particles (absolute temperature display) Tgi: glass transition temperature of homopolymer consisting of structural unit (i) (absolute temperature display) Wi: (a) Weight fraction of structural unit (i) in polymer particles When the polymer (b) is present in the polymer particles (b), the glass transition temperature can be calculated by ) Assuming no polymer is present.

The (b) polymer constituting the composite particles of the present invention has an organic group containing a nitrogen atom, is mainly composed of a structural unit represented by-(MO)-, and has a one-dimensional structure, It can have a two-dimensional structure or a three-dimensional structure. Here, M is Si or a metal atom having a valence of 3 or more, and is preferably Si, Ti or Al. The composition of the above-mentioned (a) polymer particles and (b) polymer will be better understood by referring to the method for producing a dispersion containing the composite particles of the present invention described later.

The coating film obtained from the dispersion in which the composite particles described above are preferably dispersed in a poor solvent of the composite particles, particularly when the (a) polymer particles are (meth) acrylic polymer particles, Excellent weather resistance and stain resistance, especially stain resistance. Further, the composite particles of the present invention, (a) polymer particles,
(A ′) 2 to 70% by weight of the polymer phase (a) in the core part and 98 to 30% by weight of the polymer phase (b) in the shell part (here,
A multiphase polymer particle (hereinafter, also referred to as “(a ′) multiphase polymer particle”) consisting of (a) and (b) is 100% by weight. At least one of the polymer of the nitrogen atom-containing organosilicon compound and the polymer of the nitrogen atom-containing organometallic compound is present on the surface and / or in the vicinity of the surface of the polymer phase (b) of the shell part of the united particle (a ′). It may be the existing composite particles.

In this case, the polymer phase (a) of the core part and the polymer phase (b) of the shell part satisfy the following condition (1) or (2). Condition (1): a monomer unit constituting the polymer phase (a),
Different from the monomer unit constituting the polymer phase (b). Condition (2): When the monomer units constituting the polymer phase (a) and the monomer units constituting the polymer phase (b) are the same, the polymer phase (a) and the polymer phase ( The amount ratio of the monomer unit is different from that in b).

The above condition (1) or condition (2) is
(A ′) It is a condition showing that the polymer phase (a) of the core part and the polymer phase (b) of the shell part of the multiphase polymer particles are different in composition. For example, the polymer phase (a) of the core part
The monomer components constituting (A, B, C) are the monomer components constituting the polymer phase (b) of the shell part (A, B, C).
In the case of B), (A, B, D) or (A, B, C, D), the condition (1) is satisfied.

Further, for example, the monomer components constituting the polymer phase (a) are (A, B, C), and the monomer components constituting the polymer phase (b) are also (A, B, C). Even if it is the same as C), the condition (2) is satisfied when the amount ratio of at least one of the monomer components A, B, and C is different between the two. FIG. 1 (B) shows one embodiment of the structure of the composite particles of the present invention in which the polymer particles are multiphase polymer particles. Figure 1 (B)
Then, the composite particles 1'include the polymer phase (a) 5 of the core part, the polymer phase (b) 6 of the shell part covering the core part, and the polymer of the shell part of the multiphase polymer particles (a '). The polymer (ii) 3 is present on the surface of the phase (b) 6 and the polymer (ii) 4 is present near the surface of the phase (b) 6.

In the present invention, multiphase polymer particles (a ')
The core part is composed of the polymer phase (a) which constitutes the inside of the composite particle, and the shell part is composed of the polymer phase (b) which constitutes the outside of the composite particle. The shell portion preferably completely covers the core portion, but it does not necessarily have to completely cover the core portion. In the present invention, the presence of (a ′) in the vicinity of the surface of the polymer phase (b) in the shell portion of the multiphase polymer particles means, for example, the polymer (b) 3 in FIG. 1 (B). Further, the polymer is not completely buried inside the polymer phase of the shell part.

The polymer (b) is preferably chemically bonded to the shell part polymer phase surface of the (a ′) multiphase polymer particles and / or in the vicinity of the surface via a linking group, and a covalent bond. Is particularly preferable. In addition, the composite particles of the present invention have a polymer (b) inside the multiphase polymer particles (a ′).
May exist.

The amount of the polymer (b) present on the surface and / or in the vicinity of the surface of the polymer phase (b) in the shell portion of the multiphase polymer particle (a ′) is such that the multiphase polymer particle (a ′) is present. The amount is preferably 0.5 to 100 parts by weight, more preferably 1 to 60 parts by weight, and particularly preferably 2 to 40 parts by weight, relative to 100 parts by weight. When the amount of the polymer (b) is in the above range, the coating film formed from the composite particles of the present invention has excellent weather resistance, particularly excellent initial antifouling property.

As the multiphase polymer particles (a ′), the following can be preferably mentioned. (1) Polymer particles in which the gel content of the polymer phase (a) in the core part and the gel content of the polymer phase (b) in the shell part differ by 5% by weight or more. Here, the gel content of the lower one may be 0% by weight. The gel content is calculated as the insoluble content of an organic solvent such as toluene. (2) The glass transition temperature of the polymer phase (a) of the core part and the glass transition temperature of the polymer phase (b) of the shell part are 2 ° C. or higher,
Polymer particles in which each polymer phase preferably has a composition different by 5 ° C. or more.

The multiphase polymer particles (2 ′) of (2) above will be described below. The glass transition temperature of each polymer phase of the core portion and shell portion of the multiphase polymer particles (a ′) is set according to the performance required for the coating film formed from the composite particles. For example, when importance is attached to the stain resistance and hardness of the coating film, the Tg of the polymer phase (b) in the shell part is preferably 5 ° C. or more, more preferably more than the Tg of the polymer phase (a) in the core part. Is 10 ° C. or higher, and the Tg of the polymer phase (b) in the shell part is preferably 10 to 90 ° C.,
The temperature is more preferably 20 to 80 ° C., and the Tg of the polymer phase (a) of the core part is preferably −50 to 10 ° C., more preferably −45 to 5 ° C.

When importance is attached to the flexibility and adhesion of the coating film, the Tg of the polymer phase (b) in the shell part is preferably 5 ° C. or more than the Tg of the polymer phase (a) in the core part. And more preferably 10 ° C. or more, and the Tg of the polymer phase (b) in the shell part is preferably −50 to 30 ° C., more preferably −40 to 20 ° C., and the polymer phase (a The Tg of) is preferably 10 to 90 ° C, more preferably 20 to 70 ° C.

Here, the Tg of the polymer phase (a) of the core part and the Tg of the polymer phase (b) of the shell part are as described above in (a).
It can be determined in the same manner as Tg of polymer particles. Such multi-phase polymer particles (a ′) in which the glass transition temperatures of the polymer phase of the shell part and the core part are different from each other are obtained according to the desired glass transition temperature of each polymer phase of the shell part and the core part. Polymers that compose (homopolymers or copolymers)
Is selected, and a monomer capable of forming a polymer is polymerized.

As described above, each polymer phase has a composition in which the glass transition temperature of the polymer phase (a) of the core portion and the glass transition temperature of the polymer phase (b) of the shell portion differ by 2 ° C. or more. The polymer particles (a ') have been described. The following description regarding the multiphase polymer particles (a ′) is generally applied to the multiphase polymer particles (a ′).

In the multiphase polymer particles (a ′), the polymer phase (a) in the core portion occupies 2 to 70% by weight, preferably 10 to 60% by weight, and the polymer phase (b) in the shell portion comprises It comprises 98 to 30% by weight, preferably 90 to 40% by weight. here,
The total amount of both is 100% by weight. When the polymer phase (a) of the core part is less than 2% by weight (the polymer phase (b) of the shell part exceeds 98% by weight), the object of the present invention cannot be achieved, while the polymer of the core part is not achieved. Even if the phase (a) exceeds 70% by weight (the polymer phase (b) in the shell portion is less than 30% by weight), the object of the present invention is not achieved, and either case is not preferable.

In order to improve the weather resistance of the coating formed from the composite particles of the present invention, the polymer phase (a) in the core part and the polymer phase (b) in the shell part of the multiphase polymer particles (a ′). )
UV-absorbing monomer and / or
Alternatively, a radical scavenging monomer may be copolymerized. Specific examples of these monomers are preferred polymers constituting the polymer phases (a) and (b) in the method for preparing a dispersion liquid of multiphase polymer particles (a ′) described later (meth). It is exemplified as a monomer that may be further copolymerized with the acrylic ester polymer.

The copolymerization amount of the ultraviolet absorbing monomer and / or the radical scavenging monomer is preferably 0.1 to 30% by weight of the multiphase polymer particles (a ′). The multiphase polymer particles (a ′) described above are obtained, for example, by first forming (co) polymerizing the polymer phase (a) of the core part and then (co) polymerizing the polymer phase (b) of the shell part. It is obtained by forming. As another method, the polymer phase (a) of the core part is used.
The polymer phase (b) of the more hydrophilic shell part is first formed by (co) polymerization, and then the polymer phase (a) of the relatively hydrophobic core part is formed by (co) polymerization. Thus, a method of forming the polymer phase (a) inside the polymer phase (b) can be mentioned.

The coating film obtained from the dispersion in which the above-described composite particles are preferably dispersed in a poor solvent for the composite particles has a polymer, particularly in the core portion and shell portion of the multiphase polymer particles (a ′). When the phase is a (meth) acrylic polymer, a (meth) acrylic silicone polymer, a fluorine-containing polymer, polyurethane, or a urethane / acrylic polymer, the weather resistance and antifouling property are excellent, and especially the antifouling property is excellent. In addition, the diene polymer is excellent in antifouling property and mechanical property.

<Preferable Physical Properties of Composite Particle> On the surface and / or in the vicinity of the surface of the polymer particle (a) of the present invention,
(B) Composite particles in which the polymer exists, and (b) composite particles in which the (b) polymer exists on the surface and / or in the vicinity of the surface of the polymer phase of the shell part of the multiphase polymer particles (b). The average particle size of is preferably 5 μm or less, more preferably 2 μm or less, still more preferably 1 μm or less, as a value measured in a state of being dispersed in the dispersion from the viewpoint of stability of the dispersion containing the composite particles. , Particularly preferably 0.
It is 03 to 0.5 μm. The method for measuring the average particle diameter is shown in the examples described later.

The minimum film-forming temperature of the composite particles of the present invention is preferably 90 ° C. or lower, more 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 the solvent when the dispersion containing the composite particles is applied on the substrate. The specific measurement method is TF Protzman, J. Appl. Polymer Sci., Volume 4, 81 (19
60).

A coating film formed from a dispersion containing composite particles having such a structure and physical properties contains a polymer of a nitrogen atom-containing organosilicon compound and / or a polymer of a nitrogen atom-containing metal compound (b). Even if the proportion of the entire coating film is small, since the polymer (b) is present on the surface of the coating film at a high concentration, it has excellent weather resistance and stain resistance,
Particularly excellent in initial antifouling property.

Dispersion and Manufacturing Method Thereof The dispersion of the present invention contains the composite particles as described above and a poor solvent. (A) A preferred embodiment of a dispersion of composite particles composed of (meth) acrylic polymer particles as polymer particles, or (a) each polymer phase of multiphase polymer particles is a (meth) acrylic polymer. The dispersion of the present invention and the method for producing the same will be described below, mainly using as an example the embodiment of the dispersion in which the composite particles each composed of is dispersed.

<Solvent for Dispersion> The poor solvent for the composite particles preferably used in the dispersion of the present invention is a poor solvent for the polymer constituting the composite particles, for example, a (meth) acrylic polymer, and specifically, Specific examples thereof include water, alcohols, polyethylene glycol monoalkyl ethers, aliphatic hydrocarbons such as n-hexane, and mixed solvents thereof. Of these, water is preferred from the viewpoints of ease of manufacturing the dispersion and the working environment when the dispersion is used as a coating material.

The weight ratio (composite particles / poor solvent) of the composite particles to the poor solvent is preferably 5/95 to 70/30,
It is more preferably 20/80 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 composite particle concentration of the dispersion and the viscosity are well balanced, and the workability is good and the desired thickness is applied. A film can be formed.

When the polymer particles (a) constituting the composite particles are composed of a material other than the (meth) acrylic polymer, the multiphase polymer particles (a ′) constituting the composite particles are (meth). When composed of something other than an acrylic polymer, a poor solvent can be selected according to the type of the polymer, and the weight ratio of the composite particles and the poor solvent can be selected from the same viewpoint as above, The preferred poor solvent is water, and the weight ratio of the composite particles and the poor solvent is in the above range.

<Preparation Method of Dispersion> Next, the preparation method of the dispersion of the present invention will be described. (A) on the surface and / or near the surface of the polymer particles,
(B) A dispersion (hereinafter also referred to as “dispersion (i)”) containing composite particles containing a polymer and a poor solvent is (A).
A functional group capable of reacting with the group represented by OR ² in the general formula (1) to form a linking group (hereinafter, also simply referred to as “linking group-forming functional group”) is bound to the surface and / or the surface vicinity. (C) in a dispersion liquid containing the polymer particles (B) and a poor solvent (B) (hereinafter, also referred to as “dispersion liquid (i)”).
It can be produced by a method of polycondensing the compound represented by the general formula (1).

In the above method, before (C) the polycondensation of the compound represented by the general formula (1), the (A) polymer particles and (D) the general formula (2) are previously represented. The desired result is obtained by reacting with the compound. Here, the above-mentioned (A) polymer particles correspond to the above-mentioned (A) polymer particles. Further, (a ') on the surface and / or in the vicinity of the surface of the polymer phase of the shell part (b) of the multiphase polymer particles,
(B) A dispersion containing composite particles containing a polymer and a poor solvent (hereinafter, also referred to as “dispersion (ii)”) is
(A ′) Multiphase polymer particles in which the functional group forming the linking group of the general formula (1) is bonded to the surface and / or the vicinity of the surface of the polymer phase (b) of the shell part (hereinafter referred to as “(A ') Also referred to as "multiphase polymer particles") and (B) a poor solvent (hereinafter also referred to as "dispersion (ii)"),
(C) It can be produced by a method of polycondensing the compound represented by the general formula (1).

In the above method, before (C) the polycondensation of the compound represented by the general formula (1), the (A ′) multiphase polymer particles and (D) the general formula (2) are previously prepared. A preferable result is obtained by reacting with a compound represented by the formula (1). Here, the (A ′) multiphase polymer particles correspond to the above (A ′) multiphase polymer particles.

<Preparation Method of Dispersion (i)> Dispersion (i) used in producing Dispersion (i) of the present invention.
Can be prepared, for example, by producing the polymer particles (A) by emulsion polymerization in an aqueous medium, or by dispersing the polymer obtained by solution polymerization in the poor solvent (B).

Examples of the functional group forming a linking group bonded to the surface of the polymer particle (A) and / or in the vicinity of the surface include
There is no particular limitation as long as it is capable of reacting with the group represented by OR ² of the general formula (1) or the group represented by R ⁴ of the general formula (2) to form a linking group. Carboxyl group, acid anhydride group, 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, the above reaction Is preferable in that

The amount of the linking group-forming functional group monomer is
(A) on the surface of the polymer particles and / or in the vicinity of the surface,
0.1 to 30% by weight, especially 0.5 to 20% by weight
It is preferable to be present at a concentration in the range of. When the (A) polymer particles are composed of a (meth) acrylic polymer, an alkyl ester of (meth) acrylic acid is used as a monomer used for polymerization when preparing a dispersion liquid containing the (A) polymer particles. It is preferable to copolymerize with the above-mentioned monomer having a functional group forming a linking group.

The alkyl of the (meth) acrylic acid alkyl ester may be substituted, and the carbon number of the alkyl is
It is preferably 1 to 20 including a substituent. Examples of the monomer include 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 may 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 and crotonic acid; α, β such as itaconic acid, fumaric acid and maleic acid -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; Other N-methylol (meth) acrylamide and the like (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,
Regarding the copolymerization ratio of (meth) acrylic acid alkyl ester such as allyl glycidyl ether and the monomer having a linking group-forming functional group, the weight ratio of the former and the latter (the former / the latter) is 70/30 to 99.9 / 0. 0.1, particularly preferably 80/20 to 99.5 / 0.5.

The (meth) acrylic polymer is a range in which a monomer other than the above monomers (hereinafter, simply referred to as "other monomer") does not impair the achievement of the object of the present invention. And may be copolymerized. Examples of other monomers that can form the (meth) acrylic polymer include aliphatic conjugated dienes such as 1,3-butadiene, isoprene, and chloroprene; aromatics such as styrene, α-methylstyrene, and vinyltoluene. Vinyl compounds; carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate;
Vinyl cyanide compounds such as (meth) acrylonitrile; p
-(Meth) acryloxyphenyl salicylate, 2-hydroxy-4- (meth) acrylooxybenzophenone and other polymerizable UV absorbing monomers; 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-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 4-croto Noylamino-2,
Examples thereof include polymerizable radical scavenging monomers such as 2,6,6-tetramethylpiperidine and 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine. These other monomers can be used alone or in combination of two or more.

Of these other monomers, it is preferable to use the above polymerizable UV absorbing monomer and / or the above polymerizable radical scavenging monomer, and the preferable amount thereof is the total amount It is 0.1 to 10% by weight in the body. A dispersion liquid in which particles of a (meth) acrylic polymer are dispersed in a poor solvent is, for example, a method of copolymerizing the monomer by an emulsion polymerization method in an aqueous solvent, or a method of copolymerizing the monomer by a solution polymerization method. Then, it can be prepared by a method of emulsifying in a poor solvent (hereinafter, simply referred to as "emulsification method") or the like.

The emulsion polymerization is carried out using a radical polymerization initiator and in the presence of a soap-free system or an emulsifier. Examples of the radical polymerization initiator include, for example, cumene hydroperoxide, diisopropylbenzene hydroperoxide, an oxidizing agent composed of an organic hydroperoxide such as paramenthane hydroperoxide, and a sugar-containing iron pyrophosphate prescription, a sulfoxylate prescription, and the like. Redox-based initiators in combination with reducing agents such as sugar pyrophosphate / sulfoxylate mixed formulations; 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. Yes, preferably the above redox System initiator, persulfate.

The amount of the radical polymerization initiator used is usually 0.05 to 100 parts by weight based on 100 parts by weight of all the monomer components used.
It is about 5 parts by weight, preferably about 0.1 to 2 parts by weight. Examples of the emulsifiers include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, amphoteric emulsifiers, and the like. In particular, reactive compounds having a radical-polymerizable ethylenically unsaturated bond in the molecule. Emulsifiers are preferred.

Examples of the anionic emulsifiers include alkali metal salts of higher alcohol sulfuric acid esters, alkali metal salts of alkylbenzene sulfonic acids, alkali metal salts of succinic acid dialkyl ester sulfonic acids, alkali metal salts of alkyl diphenyl ether disulfonic acids, and polyoxy. In addition to sulfate ester salts of ethylene alkyl (or alkylphenyl) ether, etc., the brand name is Latemur S-
180A (manufactured by Kao Corporation), Eleminol JS-2 (manufactured by Sanyo Kasei Co., Ltd.), Aqualon HS-10 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Aqualon BC-10 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) ), Adecaria Soap SE-10N (manufactured by Asahi Denka Kogyo KK), Antox MS-60 (Nippon Emulsifier Co., Ltd.) and the like.

Examples of the nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether and the like, as well as trade names of Aqualon RS-20 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and ADEKA REASOAP NE. A reactive emulsifier such as -20 (manufactured by Asahi Denka Kogyo Co., Ltd.) can be used. As a cationic emulsifier,
Examples thereof include alkylpyridinyl chloride and alkylammonium chloride. Lauryl betaine is suitable as the amphoteric emulsifier.

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. Emulsion polymerization is preferably carried out using a soap-free system or a reactive emulsifier, as it does not impair the weather resistance of the resulting coating film. In the emulsion polymerization, in addition to the radical polymerization initiator and the emulsifier, if necessary, a chain transfer agent, an electrolyte, a pH adjusting agent and the like are used in combination, and 100 parts by weight of all the monomer components are added.
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, and the polymerization temperature is 5 to 5.
100 ° C., preferably 50 to 90 ° C., polymerization time 0.1 to
It is carried out under the condition of 10 hours.

As the 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 adding these in stages Although it is possible to adopt a combined method, particularly when a low water-soluble monomer is used, a high pressure homogenizer or an ultrasonic disperser is used to force emulsification of the monomer, water and emulsifier in advance. After preparing the pre-emulsion, it is preferable to carry out polymerization by a batch polymerization method, a method of adding in a divided manner or continuously. The polymerization conversion rate at that time is preferably 99.5% by weight or more.

At the time of 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 organic solvents in which organic solvents, radical polymerization initiators and the like 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.

As the radical polymerization initiator used for solution polymerization, for example, various radical initiators exemplified for the above-mentioned emulsion polymerization and the like can be mentioned, and azo compounds and organic peroxides are preferable. The amount of the radical polymerization initiator used in the solution polymerization is usually 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of all the monomer components used.

In the solution polymerization, in addition to an organic solvent and a radical polymerization initiator, if necessary, a chain transfer agent and the like are used in combination, and usually 10 to 1000 parts by weight of the solvent are added per 100 parts by weight of all the monomer components. Parts and radical polymerization initiator in an amount within the above range, and the polymerization temperature is 5 to 100 ° C., preferably 5
Polymerization is carried out under conditions of 0 to 90 ° C. and polymerization time of 0.1 to 10 hours.

To the polymer solution obtained by the solution polymerization, a poor solvent, preferably water, and a neutralizing agent, an emulsifier, etc., if necessary, are added and stirred with or without heating to emulsify the solution. , Or, if necessary, the polymer solution is added dropwise to water to which a neutralizing agent, an emulsifying agent, etc. have been added, and the mixture is stirred under heating or non-heating to emulsify the solution to obtain the object (meth). A dispersion liquid of acrylic polymer particles can be obtained. The organic solvent used in solution polymerization is preferably reduced or removed from the dispersion by heating, steam distillation or the like after emulsification.

Further, the dispersion liquid of the particles of the (meth) acrylic polymer uses a part of the above-mentioned monomer, and uses the emulsion polymerization method or the polymer emulsion obtained by the emulsification method as a seed, and the remaining monomer It can also be prepared by emulsion polymerization of a monomer. Monomer used at that time,
Radical polymerization initiator or an emulsifier added as necessary,
Components such as a chain transfer agent and polymerization conditions are the same as those in the emulsion polymerization method.

The dispersion liquid (i) thus prepared contains
(A) Polymer particles are 10 to 60% by weight, especially 20 to 5
It is preferably contained at a concentration of 0% by weight. The average particle size of the (A) polymer particles is 0.01 to 1 μm,
It is particularly preferably 0.03 to 0.5 μm. The average particle size is the average particle size of the particles in the dispersion liquid (i). The method for measuring the average particle size is shown in the examples.

<Preparation Method of Dispersion (ii)> Dispersion (ii) used for producing Dispersion (ii) of the present invention.
Can be prepared, for example, by producing the above-mentioned (A ′) multiphase polymer particles by emulsion polymerization in an aqueous medium. When each of the polymer phases (a) and (b) of the core part and the shell part of the (A ') multiphase polymer particles is composed of a (meth) acrylic polymer, it contains (A') multiphase polymer particles. In the polymerization when preparing the dispersion liquid (ii), the above-mentioned (meth)
(Co) polymerization using an alkyl ester of acrylic acid to form the polymer phase (a) of the core part, and then the above-mentioned (meth) acrylic acid as a monomer used for forming the polymer phase (b). It is preferable that the alkyl ester of 1) and the above-mentioned monomer having a functional group forming a linking group are used in combination and copolymerized to form the polymer phase (b) of the shell part. As another method, the polymer phase (b) of the shell part, which is more hydrophilic than the polymer phase (a) of the core part, is first formed by polymerization, and then the weight of the polymer part (a) of the relatively hydrophobic core part is formed. A method of forming the coalescence phase (a) inside the polymer phase (b) by polymerization is mentioned. At this time, the monomer for forming the polymer phase (b) is appropriately selected so as to be more hydrophilic than the polymer phase (a).

The copolymerization ratio of the (meth) acrylic acid alkyl ester for forming the polymer phase (b) of the shell part and the monomer having a functional group forming a linking group is the weight ratio of the former and the latter (the former / Latter) is 70 / 30-99.9 / 0.1,
It is particularly preferably 80/20 to 99.5 / 0.5. The (meth) acrylic polymer of the polymer phase (a) of the core part and the polymer phase (b) of the shell part is within the range in which the other monomer described above does not impair the achievement of the object of the present invention. It may be copolymerized.

The dispersion (ii) in which the multiphase polymer particles (A ') are dispersed in a poor solvent is, for example, the dispersion (i) in which the polymer particles (A) are dispersed in a poor solvent as described above. It can be prepared by a method in which the same monomer as that used in the preparation is copolymerized in an aqueous solvent by an emulsion polymerization method. The emulsion polymerization is performed using a radical polymerization initiator and in the presence of a soap-free system or an emulsifier.

As the radical polymerization initiator, the same ones as mentioned above can be mentioned, and the above-mentioned redox type initiator and persulfate are preferable. The amount of the radical polymerization initiator used is usually 0.05 per 100 parts by weight of all monomers used for forming the polymer phase (a) of the core part and the polymer phase (b) of the shell part. ~ 5 parts by weight, preferably 0.
It is about 1 to 2 parts by weight.

Examples of the emulsifiers include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers and amphoteric emulsifiers. In particular, a radically polymerizable ethylenically unsaturated bond is included in the molecule. Reactive emulsifiers having are preferred. As the anionic emulsifier, nonionic emulsifier and cationic surfactant, the same ones as described above can be mentioned.

The amount of the emulsifier used is usually 100 parts by weight of all the monomer components used for forming the polymer phase (a) of the core part and the polymer phase (b) of the shell part.
It is 5 parts by weight or less. Emulsion polymerization is preferably carried out using a soap-free system or a reactive emulsifier, as it does not impair the weather resistance of the resulting coating film.

In the emulsion polymerization, in addition to a radical polymerization initiator and an emulsifier, a chain transfer agent, an electrolyte, a pH adjusting agent and the like are used in combination, if necessary, and the weight of the polymer phase (a) in the core part and the weight in the shell part is increased. Polymerization is usually performed using 50 to 500 parts by weight of water, a radical polymerization initiator and an emulsifier in an amount within the above range, based on 100 parts by weight of all the monomer components used for forming the combined phase (b). Temperature 5 to 100 ° C, preferably 50 to
It is carried out under the conditions of 90 ° C., polymerization time (polymerization time for forming the polymer phase (a) and the polymer phase (b)) for 0.1 to 10 hours.

As the polymerization method at that time, a batch method or a method of dividing or continuously adding the monomers is used in any polymerization for forming the polymer phase (a) and the polymer phase (b). It is possible to adopt a method of adding a pre-emulsion of monomers in a divided or continuous manner, or a method of combining these methods stepwise, but especially when a monomer having low water solubility is used. Is a high pressure homogenizer or an ultrasonic disperser to prepare a pre-emulsion by forcibly emulsifying the monomer, water and emulsifier in advance,
Polymerization is preferably carried out by a batch polymerization method, a method of dividing or continuously adding, or the like. Further, the polymerization conversion rate at that time is preferably 98% by weight or more.

The dispersion liquid (ii) thus prepared contains
10 to 60% by weight of (A ') multiphase polymer particles, especially 2
It is preferably contained at a concentration of 0 to 50% by weight. The average particle size of the (A ′) multiphase polymer particles is 0.0
It is preferably 1 to 1 μm, and particularly preferably 0.03 to 0.5 μm. The average particle size is the average particle size of the particles in the dispersion liquid (ii). The method for measuring the average particle size is shown in the examples.

<Manufacturing Method of Dispersion> The dispersion of the present invention comprises the polymer particles (A) or (A ′) thus prepared.
It can be produced by polycondensing (C) the compound represented by the following general formula (1) in the dispersion liquid in which the multiphase polymer particles are dispersed in the (B) poor solvent.

The method for producing the dispersion according to the present invention will be described below by using the dispersion liquid in which the polymer particles (A) are dispersed in the poor solvent (B). (A ') multiphase polymer particles Even when the dispersion liquid in which (B) is dispersed in the poor solvent is used, the dispersion can be produced in the same manner. Hereinafter, the compound represented by the general formula (1) will be simply referred to as “(C) alkoxide compound” as a representative of alkoxide compounds that are typical compounds included therein.

R ¹ nM (OR ² ) zn (1) In the general formula (1), R ¹ represents a nitrogen atom-containing organic group having 1 to 8 carbon atoms. R ² is an alkyl group having 1 to 6 carbon atoms, an acyl group having 1 to 6 carbon atoms, or 6 to 10 carbon atoms.
Represents an aryl group.

M represents Si or a metal atom having a valence of 3 or more. n is an integer of 0 or more, z is the valence of M,
z-n is an integer of 2 or more. When a plurality of R ¹ 's are present, each R ¹ may be the same or different, and a plurality of R ^2's may be the same or different.

In the above method, before the polycondensation of the (C) alkoxide compound, the (A) polymer particles and (D) a compound represented by the general formula (2) described below are previously prepared. When reacted, the linking group forming functional group bonded to the polymer particle (A) and R ⁴ of the general formula (2) are bonded to form a linking group, and the linking group is used to form the linking group (A) Since the group represented by M (OR ² ) is chemically bonded to the surface of the coalesced particle and / or in the vicinity of the surface, the polymer produced in the polymerization process of the (C) alkoxide compound (1) is efficiently (a) the polymer particle It is preferable that it is chemically bonded to. In the following, 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”.

R ³ xR ⁴ yM (OR ² ) zxy (2) In the general formula (2): R ² and M have the same meanings as in the general formula (1). R ³ represents a hydrogen atom or an organic group having 1 to 8 carbon atoms (excluding the group represented by OR ² ), R ⁴
Represents a group capable of forming a linking group by reacting with the linking group-forming functional group bonded to the polymer particle (A) (excluding the group represented by OR ² ).

X is an integer of 0 or more, and y is an integer of 1 or more.
Is a number, z is a valence of M, and z-xy is 1 or more.
Is an integer. And R²If there are multiple R²
R may be the same or different and R ³And R^FourAs well
Is. As M in the general formulas (1) and (2)
Are preferably Si, Ti, Al and the like.
Si is particularly preferable.

In the general formula (1), examples of the organic group having a nitrogen atom of R ¹ and having 1 to 8 carbon atoms include 3-aminopropyl group and N- (2-aminoethyl) -3.
-Aminopropyl group, N- (6-aminohexyl) -3
-Aminopropyl group, N- (2-aminoethyl) -3-
Aminoisobutyl group, 3-aminopropyldiisopropyl group, 3-ureidopropyl group, N-phenyl-3-aminopropyl group, N-benzyl-3-aminopropyl group, 3- (m-aminophenoxy) propyl group, m- Examples thereof include aminophenyl group and p-aminophenyl group, and particularly preferably 3-aminopropyl group and N-
(2-aminoethyl) -3-aminopropyl group may be mentioned.

Examples of the alkyl group having 1 to 6 carbon atoms or the acyl group having 1 to 6 carbon atoms of R ^{2 in} the general formulas (1) and (2) include, for example, methyl group, ethyl group, n-propyl group, i- Propyl group, n-butyl group, i-butyl group, s
ec-butyl group, t-butyl group, n-pentyl group, n-
Hexyl group, acetyl group, propionyl group, butyryl group and the like can be mentioned. Examples of the aryl group having 6 to 10 carbon atoms for R ² include phenyl group, tolyl group, xylyl group,
Examples thereof include a benzyl group.

R ³ in the general formula (2) has 1 to 8 carbon atoms.
Examples of the organic group include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-hexyl group, n- Alkyl group such as octyl group, 3-chloropropyl group, 3-bromopropyl group, 3,3,3-trifluoropropyl group, 3-glycidoxypropyl group, 3-
Examples thereof include (meth) acryloxypropyl group, 3-mercaptopropyl group, 3-aminopropyl group, vinyl group, phenyl group and 3,4-epoxycyclohexylethyl group.

The group represented by R ⁴ in the general formula (2) can react more easily than the group represented by OR ² with the functional group forming a linking group chemically bonded to the polymer particle (a). Those that are preferable are, and specific examples thereof include a glycidyl group and an amino group. Specific examples of the (C) alkoxide compound include 3-aminopropyltrimethoxysilane and 3-aminopropyltrimethoxysilane.
Aminopropyltriethoxysilane, N-2- (aminoethyl) 3-aminopropyltrimethoxysilane, N-
2- (aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (6-aminohexyl) -3-aminopropyltrimethoxysilane, N- (6-aminohexyl) -3-aminopropyltriethoxysilane, N-
(2-aminoethyl) -3-aminoisobutyltrimethoxysilane, N- (6-aminohexyl) -3-aminopropyltriethoxysilane, 3-aminopropyldiisopropyltrimethoxysilane, 3-aminopropyldiisopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-benzyl-3-aminopropyltrimethoxysilane Silane, N-benzyl-3-aminopropyltriethoxysilane, 3- (m-aminophenoxy) propyltrimethoxysilane, 3- (m-aminophenoxy) propyltriethoxysilane, m-aminophenyltrimethoxysila , M- aminophenyl triethoxysilane, p- aminophenyl trimethoxysilane,
Examples thereof include nitrogen atom-containing organic silicon compounds such as p-aminophenyltriethoxysilane.

Of these, particularly preferred are 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2- (aminoethyl) 3-aminopropyltrimethoxysilane and N-2- (aminoethyl). 3-aminopropyltriethoxysilane, N-2-
(Aminoethyl) 3-aminopropylmethyldimethoxysilane and N-2- (aminoethyl) 3-aminopropylmethyldiethoxysilane can be mentioned.

These (C) alkoxide compounds have 1
They may be used alone or in combination of two or more. Specific examples of the (D) alkoxide compound include:
(C) Some compounds overlap with the alkoxide compound,
In addition, 3-aminopropyltrimethoxysilane, 3
-Aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 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)
Examples thereof include ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3-ureidopropyltrimethoxysilane, and 3-ureidopropyltriethoxysilane. .

Of these, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyldimethoxymethylsilane, γ-glycidoxypropyldiethoxymethylsilane, 3- (Meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropyltriethoxysilane are preferable.

These (D) alkoxide compounds have 1
They may be used alone or in combination of two or more. The dispersion (i) in which the composite particles of the present invention are dispersed is
Dispersion liquid (i) in which the above-mentioned (A) polymer particles are dispersed
It can be obtained by polymerizing the (C) alkoxide compound. Preferably, for the reasons already mentioned, (D) in advance
Good results are obtained by reacting the alkoxide compound with the (A) polymer particles and then polycondensing the (C) alkoxide compound. In any case, the (D) alkoxide compound may coexist when the (C) alkoxide compound is polycondensed.

When polycondensing the (C) alkoxide compound, a small amount of the (C) alkoxide compound, preferably 1 mol of the (C) alkoxide compound, is added to the compound of the general formula (1) in which zn is 1. However, 1/2 mol or less may be added. Excessive addition should be avoided because the polycondensation does not proceed to a high molecular weight.
The reaction between the (D) alkoxide compound and the (A) polymer particles is carried out by adding (A) polymer particles dispersed in a dispersion liquid adjusted to pH 2 to 10 to (A) polymer particle 100 parts by weight. D) Alkoxide compound is preferably 0.1 to 2
0 parts by weight, more preferably 0.5 to 10 parts by weight,
At a temperature of 20 to 90 ° C, preferably 40 to 80 ° C, 0.
It can be performed by stirring for 1 to 6 hours.

When the dispersion (ii) is produced,
Alternatively, the component (D) may be reacted with the polymer phase (b) by using the component (D) in the amount shown above in the polymerization step for forming the polymer phase (b). The polycondensation of the (C) alkoxide compound is carried out by adjusting the pH of the dispersion liquid to preferably 4 to 1
0, more preferably 5 to 9.5, still more preferably 6 to
Adjust to 9, add (C) alkoxide compound, and
0 ° C or higher, preferably 50 to 90 ° C, more preferably 6
It can be performed by stirring at a temperature of 0 to 80 ° C. for 0.1 to 10 hours.

The addition amount of the (C) alkoxide compound is
The amount is preferably 0.5 to 100 parts by weight, more preferably 1 to 60 parts by weight, based on 100 parts by weight of the polymer particles (A). When the amount of the (C) alkoxide compound added is within the above range, a sufficient amount of the polymer of the (C) alkoxide compound is chemically bonded to the surface of the polymer particle (A) and / or in the vicinity of the surface to obtain Weather resistance, from the dispersion
A coating film excellent in antifouling property can be obtained.

Since polycondensation proceeds by hydrolysis of the group represented by OR ² in the general formula (1) and subsequent dehydration condensation, it is necessary that water be present in the polycondensation system. Therefore, when the poor solvent used in the dispersion liquid is other than water, water is added so that the 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 kind of the solvent. It is necessary to.

A light stabilizer may be added to the dispersion of the present invention in order to improve weather resistance. Such a light stabilizer is not particularly limited, and for example, any of the light stabilizers conventionally used for paints, synthetic rubbers, synthetic resins, synthetic fibers, etc., such as organic nickel type and hindered amine type, can be used. Although bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-) can also be used,
4-piperidyl) sebacate, 4-benzoyloxy-
2,2,6,6-Tetramethylpiperidine, tetraxy (2,2,6,6-tetramethyl-4-piperidyl)-
It is a hindered amine light stabilizer such as 1,2,3,4-butanetetracarboxylate.

The light stabilizer is used in an amount of usually 10 parts by weight or less, preferably 5 parts by weight or less, per 100 parts by weight of the dispersion (solid content) of the present invention. It may be dissolved and added, or may be dispersed in water in advance and added. In this case, if the amount of the light stabilizer added exceeds 10 parts by weight, the coating film tends to be discolored or the storage stability of the dispersion liquid tends to be deteriorated.

In order to improve the weather resistance, (A)
A polymer of the alkoxy compound which is the component (C) may be present inside the polymer particles. In order to allow the polymer of the alkoxy compound to exist inside the polymer particle (A), the polymer compound 100 (A) before the reaction of the alkoxy compound with the polymer particle (A) and the alkoxy compound (D) is performed. 50 parts by weight or less per part by weight is added to the dispersion liquid of the polymer particles (A) to be absorbed inside the polymer particles (A), and the absorbed alkoxy compound is added in the subsequent polycondensation step of the alkoxy compound (C). It can be carried out by polycondensation.

When water is used as the poor solvent in the dispersion of the present invention, methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol and n-butyl are used in order to improve film-forming property and wettability. Alcohols such as alcohol, n-amyl alcohol and n-hexyl alcohol; cellosolves such as methyl cellosolve, ethyl cellosolve, n-propyl cellosolve, i-propyl cellosolve, n-butyl cellosolve and 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; phosphates such as tri-n-butoxymethyl phosphate can be added to the dispersion.

The content of the organic solvent is usually 20% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less based on the total aqueous dispersion. Further, as the ultraviolet absorbing component, for example, p-methacryloxyphenyl salicylate, 2-hydroxy-4-methacryloxybenzophenone, 2- (2'-hydroxy-5'-methacryloxyethylphenyl) benzotriazole, etc. may be blended. it can.

Further, as additives other than the above, water-soluble or water-dispersible resins generally used as water-based resins, for example, carboxylated aroma such as polyester resin, epoxy resin, acrylic resin, styrene-maleic acid resin and the like. In addition to group vinyl resins, urethane resins, etc., defoamers, thickeners, heat stabilizers, leveling agents, lubricants,
Antistatic agents, dyes, pigments, antifungal agents and the like can be used.

The dispersion containing the composite particles of the present invention and the method for producing the same have been described above. Next, a coating material using the dispersion will be described. Coating Material The dispersion of the present invention can be used as it is or as a coating material by adding a pigment, a dispersant, an antifoaming agent, a preservative, a film-forming agent, a crosslinking agent, and the like.

The coating material is applied to the surface of the object to be coated. As for the coating, the thickness of the formed coating film is usually 10 to 10.
It is performed so as to be in the range of 1000 μm. As a method of applying the coating material, various known methods can be used, for example, application with a brush, hopper application,
Bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating,
Examples thereof include roll coating.

Thereafter, by drying at room temperature to 200 ° C., a coating film is formed on the surface of the article to be coated. The formed coating film has excellent weather resistance and antifouling property, particularly antifouling property, and these excellent properties last for a long period of time. Therefore, the coating material of the present invention containing the composite particles of the present invention is extremely suitable for use in enamel paints and clear paints, in particular, for plastic films, plastic molded products, paper,
It is useful as a coating material for a wide range of materials such as fiber, wood, metal, glass, concrete, ceramics, slate, marble, ceramics, gypsum, leather, etc. for interior and exterior of buildings, building materials, steel structures, concrete structures. It can be used in a wide range of fields such as materials, precast materials, interior and exterior of automobiles, aluminum coating, sealants, floor polishes, etc.

[0104]

EXAMPLES Hereinafter, the embodiments of 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.

[0105]

Example 1 A separable flask having a capacity of 2 liters equipped with a stirrer, a thermometer, a heater, a monomer addition pump, and a nitrogen gas introducing device, 70 parts of ion-exchanged water, and ADEKA rear soap which is a reactive emulsifier. SE-10N0.2
And 0.3 part of potassium persulfate were charged, the gas phase part was replaced with nitrogen gas for 15 minutes, and the temperature was raised to 80 ° C.

In a separate container, 30 parts of ion-exchanged water, 1.0 part of the reactive emulsifier, 15 parts of n-butyl acrylate, 2
-Ethylhexyl acrylate 15 parts, methyl methacrylate 25 parts, cyclohexyl acrylate 40 parts, 2
-Hydroxyethyl methacrylate 2 parts, acrylic acid 3
After mixing and stirring the parts, a pre-emulsion was prepared by further finely dispersing the monomers with an ultrasonic homogenizer (RUS-600 manufactured by Nippon Seiki Seisakusho Co., Ltd.).

Next, this pre-emulsion was continuously added dropwise to the separable flask over 3 hours. Nitrogen gas was introduced during the dropping, and the internal temperature was kept at 80 ° C. After completion of the dropping, the mixture was aged at 85 to 95 ° C. for 2 hours to complete the polymerization reaction, then cooled to 25 ° C. and adjusted to pH 7 with aqueous ammonia to obtain an aqueous copolymer dispersion A. Then, 1 part of γ-glycidoxypropyldimethoxymethylsilane and 2 parts of γ-glycidoxypropyltriethoxysilane were added to this separable flask, and the mixture was vigorously stirred for about 1 hour. Next, 6 parts of methyltriethoxysilane,
After adding 3 parts of N-2- (aminoethyl) 3-aminopropylmethyldimethoxysilane, the temperature was raised to 70 ° C. and 3
The stirring was continued for polycondensation. Then cool, 1
The mixture was filtered through a 20-mesh (JIS) wire mesh to obtain an aqueous coating dispersion composed of 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 by Nanosizer manufactured by Coulter, the same applies hereinafter) was 130 nm.

[0108]

[Example 2] <Production of core part> In a separable flask having a capacity of 2 liters, equipped with a stirrer, a thermometer, a heater, a monomer addition pump and a nitrogen gas introducing device, 70 parts of ion-exchanged water and a reactive emulsifier. ADEKA rear soap SE-1
0.4 parts of 0N, 3.3 parts of n-butyl acrylate, 1.7 parts of methyl methacrylate, 0.15 parts of acryl were charged, the gas phase part was replaced with nitrogen gas for 15 minutes, and the temperature was 60 ° C.
After the temperature was raised to 0, 0.1 part of potassium persulfate was charged to 80
After the temperature was raised to ° C, a polymerization reaction was carried out for 0.5 hours.

In a separate container, 13 parts of ion-exchanged water, 1.0 part of the reactive emulsifier, 11 parts of n-butyl acrylate, 6 parts of methyl methacrylate, 0.35 part of acrylic acid and 0.1 part of potassium persulfate are mixed. After stirring, ultrasonic homogenizer (RUS-6 manufactured by Nippon Seiki Co., Ltd.)
(00) to finely disperse the monomers to prepare a pre-emulsion.

Then, this pre-emulsion was continuously added dropwise to the separable flask over 1 hour. Nitrogen gas was introduced during the dropping, and the internal temperature was kept at 80 ° C. After the dropping was completed, the mixture was aged at 80 ° C. for 0.5 hour to form a core portion. <Production of shell part, preparation of dispersion> In a separate container, 32 parts of ion-exchanged water, 1.0 part of the reactive emulsifier, 13 parts of 2-ethylhexyl acrylate, 30 parts of methyl methacrylate.
Part, 30 parts of cyclohexyl methacrylate, 2.5 parts of ethylene glycol dimethacrylate, 1 part of 2-hydroxyethyl methacrylate, 1 part of acrylic acid, and 0.1 part of potassium persulfate were mixed and stirred, and then an ultrasonic homogenizer ( A pre-emulsion was prepared by finely dispersing the monomer with RUS-600 manufactured by Nippon Seiki Seisakusho Co., Ltd.

Next, this pre-emulsion was continuously added dropwise to the separable flask over 3 hours. Nitrogen gas was introduced during the dropping, and the internal temperature was kept at 80 ° C. After completion of the dropping, the mixture was aged at 85 to 95 ° C. for 2 hours to complete the polymerization reaction to form a shell part, then cooled to 25 ° C., adjusted to pH 5 with ammonia water, and 5 parts of methyltriethoxysilane, After adding 2 parts of tetratriethoxysilane with stirring, the mixture was treated at 75 ° C. for 3 hours to obtain an aqueous copolymer dispersion. <Production of Composite Particles and Production of Coating Dispersion> Thereafter, 1 part of γ-glycidoxypropyldimethoxymethylsilane and 2 parts of γ-glycidoxypropyltriethoxysilane were added to the separable flask, and the mixture was stirred for about 1 hour. Vigorously stirred over. Next, 6 parts of methyltriethoxysilane,
After adding 3 parts of N-2- (aminoethyl) 3-aminopropylmethyldimethoxysilane, the temperature was raised to 70 ° C. and stirring was continued for 3 hours to carry out polycondensation. Then cool, 12
It was filtered through a wire mesh of 0 mesh (JIS) to obtain an aqueous coating dispersion composed of composite particles of a (meth) acrylic polymer and polysiloxane. The solid content concentration of this dispersion was 47.1%, and the average particle size of the composite particles (measured by Nanosizer manufactured by Coulter, the same applies hereinafter) was 110 nm.

[0112]

[Example 3] <Production of core part and shell part and preparation of dispersion> Using the monomer composition shown in Table 1, the distribution of the monomer was the same as that of Example 2, and the other was Example 2 Polymerization reaction was performed in the same manner as above to form a core part and a shell part, and an aqueous copolymer dispersion liquid was prepared. <Production of Composite Particles and Production of Coating Dispersion> In the same manner as in Example 1, composite particles were produced and an aqueous coating dispersion was obtained. The solid content concentration of this dispersion was 47.
0%, the average particle size of the composite particles was 115 nm.

[0113]

Comparative Example 1 An aqueous coating dispersion was obtained in the same manner as in Example 1 except that the alkoxysilane was not used.

[0114]

Comparative Example 2 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 1. . (Evaluation of Aqueous Coating Dispersion) The aqueous coating dispersions obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were used to prepare a coating composition having the following composition.

<Mill base> CR97 (pigment, manufactured by Ishihara Sangyo Co., Ltd.) 20 parts SN Daispersant 5027 (dispersant, Fujii Yoshitsusho) 0.5 part Na hexametaphosphate (dispersant) 1 part Ethylene glycol (antifreeze agent) 0.29 parts SN113 (antifoaming agent, manufactured by San Nopco) 0.05 parts Water 5.96 parts <Let Down> The above-mentioned mill base 27.80 parts Dispersion for aqueous coating 78.49 parts SN612, 20% aqueous solution (thickener , San Nopco) 0.25 part B1016 (antifoaming agent, manufactured by Asahi Denka Co., Ltd.) 0.05 part SN113 (antifoaming agent, manufactured by San Nopco) 0.05 part CS-12 (film forming auxiliary, manufactured by Chisso Corporation) 3 .69 parts Each coating material obtained by the above formulation was degreased with xylene and an alkaline cleaning agent (JIS-3141, SPEC
Plate, 0.8 × 70 × 1500 mm) airless spray
A gun was used to apply a coating film having a thickness of about 50 μm after drying, followed by drying at 60 ° C. for 30 minutes. (1) Evaluation of Film Formability The presence or absence of cracks was visually observed in the obtained coating film, and the film formability was evaluated according to the following 5 grades.

5: None 4: Very minutely recognized 3: Slightly recognized 2: Partially recognized 1: Entire surface (2) Evaluation of carbon stainability Carbon dispersion liquid on the coated plate prepared above Was applied, dried at room temperature for 30 minutes, and washed with water to measure the contamination level and the color difference ΔL, and the following 5 grades were evaluated.

5: Color difference ΔL10 or less 4: Color difference ΔL10 over 20 or less 3: Color difference ΔL20 over 30 or less 2: Color difference ΔL30 over 40 or less 1: Color difference ΔL40 over (3) Contact angle The contact angle of the coated plate with water was measured. (4) Rain streak test The coated plate prepared above was exposed outdoors at 90 degrees north of Yokkaichi city for 1 month or 3 months, and then the contamination level and the color difference ΔL were measured, and the following 5 grades were evaluated. .

5: Color difference ΔL5 or less 4: Color difference ΔL5 over 10 or less 3: Color difference ΔL10 over 15 or less 2: Color difference ΔL15 over 20 or less 1: Color difference ΔL20 over (5) Accelerated weather resistance test Above About the coated plate prepared in, sunshine weather meter (Suga Test Instruments Co., Ltd., WEL-SUN HC
Type) was used to measure the gloss retention rate after exposure at 63 ° C. for 2,000 hours, and the following 5 grades were evaluated from the measurement results. The gloss was measured by measuring a specular gloss of 60 degrees based on JIS K5400.

5: Gloss retention rate 80% or more 4: Gloss retention rate 70% or more and less than 80% 3: Gloss retention rate 60% or more and less than 70% 2: Gloss retention rate 50% or more and less than 60% 1: Gloss retention rate 50 The test results of less than% are shown in Table 1 together with the properties of the aqueous dispersion.

[0120]

[Table 1]

[Brief description of drawings]

FIG. 1 is a schematic view schematically showing composite particles according to the present invention.

[Explanation of symbols]

1 ... Composite particles 2 ... Polymer particles 3 ... Polymer 4 ... Polymer 5 ... Polymer phase of core 6 ... Polymer phase of shell part

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J030 CA02 CB03 CB17 CC10 CC16                       CC21 CD11 CE02 CG20                 4J035 BA11 CA061 CA081 CA111                       CA191 CA211 CA261 GA02                       GB01                 4J038 CA021 CA022 CA041 CA042                       CA111 CA112 CC041 CC042                       CD091 CD092 CG141 CG142                       CH031 CH032 CH041 CH042                       CH071 CH072 CH081 CH082                       CP071 CP072 DG031 DG032                       DL051 DL052 DL081 DL082                       DL091 DL121 DL122 GA03                       GA06 GA07 GA09 JC30 KA06                       LA02 MA07 MA08 MA10 MA13                       NA03 NA05

Claims (11)

[Claims] 1. (A) Polymer particles in which a functional group capable of reacting with a group represented by OR ² of the following general formula (1) to form a linking group is bound on the surface and / or in the vicinity of the surface:
In a dispersion containing (B) a poor solvent, (C) the following general formula (1) R ¹ nM (OR ² ) zn (1) (wherein R ¹ is nitrogen. Carbon number including atom 1
~ 8 represents an organic group, R ² represents 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, M is Si or a metal atom having 3 or more valences the stands, n is an integer of 0 or more, z is the valence of M, z-n is an integer of 2 or more, and if R ¹ is present a plurality, each R ¹ is the same or different Alternatively, a plurality of R ^{2 s} may be the same or different. Obtained by polycondensing a compound containing at least one compound represented by the formula (1), and (b) a polymer of a nitrogen atom-containing organosilicon compound and nitrogen on the surface and / or in the vicinity of the surface of the polymer particle. At least one of the polymers of the atom-containing organometallic compound is present, and composite particles are provided. 2. (C) Before polycondensing the compound represented by the above general formula (1), the functional group bonded to the polymer particles (A) and the following general formula (2). A composite particle according to claim 1, which is obtained by reacting a compound (D); R ³ xR ⁴ yM (OR ² ) zxy (2) (in the general formula (2), R ² , And M are general formula (1)
R ³ is a hydrogen atom or has 1 to 1 carbon atoms.
8 represents an organic group (excluding the group represented by OR ² ), and R ⁴ is a group capable of reacting with the functional group bonded to the polymer particle (A) to form a linking group (provided OR ² is excluded), x is an integer of 0 or more, y is an integer of 1 or more, z is a valence of M, and z-xy is an integer of 1 or more. , And when plural R ² are present, each R ² may be the same or different, and R ³ and R ⁴ are also the same. ). 3. The glass transition temperature of (a) polymer particles is 0.
The composite particles according to claim 1 or 2, wherein the composite particles are in the range of -40 ° C. 4. The composite particle according to any one of claims 1 to 3, wherein the (b) polymer is chemically bonded to the (a) polymer particle. 5. The (A) polymer particles are multiphase polymer particles comprising (A ′) a core polymer phase (a) and a shell polymer phase (b). , OR of general formula (1)
² is a polymer particle in which a functional group capable of reacting with the group represented by 2 to form a linking group is bonded to the surface and / or the vicinity of the surface of the polymer phase (b), and the above (a) polymer particle is , (I ') (i) 2 to 70% by weight of the polymer phase (a) in the core part and 98 to 30% by weight of the polymer phase (b) in the shell part (wherein (a) and (b) A total of 100% by weight), and (ii) the polymer phase of the shell part of the polymer particle (b) on the surface and / or in the vicinity of the surface (ii) (B) A polymer is present, and (iii) the polymer phase (a) of the core part and the polymer phase (b) of the shell part satisfy the following condition (1) or (2). The composite particle according to claim 1 or 2, wherein: Condition (1): a monomer unit constituting the polymer phase of the core part and a monomer unit constituting the polymer phase of the shell part. Condition (2) different from the monomer unit; when the monomer unit constituting the polymer phase of the core part and the monomer unit constituting the polymer phase of the shell part are the same, the core part and the shell The ratio of the amount of monomer units differs from that of the parts. 6. The composite particle according to claim 5, wherein the (b) polymer is chemically bonded to the polymer phase (b) of the shell portion of the (a ′) polymer particle. . 7. A dispersion comprising the composite particle according to claim 1 and a poor solvent for the composite particle. 8. The method for producing a dispersion according to claim 7, wherein (A) a functional group capable of reacting with a group represented by OR ² of the following general formula (1) to form a linking group is a surface. And / or a compound containing at least one compound represented by the following general formula (1) in a dispersion containing polymer particles bound to the vicinity of the surface and (B) a poor solvent. R ¹ nM (OR ² ) zn (1) (In the general formula (1), R ¹ is a carbon atom having a nitrogen atom of 1).
8 organic groups represent (excluding the group represented by OR ^2), R ² is an alkyl group having 1 to 6 carbon atoms, an acyl group or an aryl group having 6 to 10 carbon atoms having 1 to 6 carbon atoms Represent, 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, z−n is an integer of 2 or more, and R ¹ is present in plural numbers. , Each R ¹ may be the same or different, and a plurality of R ² may be the same or different. ). 9. (C) Before polycondensing the compound represented by the general formula (1), the functional group bonded to the polymer particles (A) and the following general formula (2). The method for producing a dispersion according to claim 8, wherein the compound (D) is reacted; R ³ xR ⁴ yM (OR ² ) zxy (2) (in the general formula (2), R ² , And M are general formula (1)
R ³ is a hydrogen atom or has 1 to 1 carbon atoms.
8 represents an organic group (excluding the group represented by OR ² ), and R ⁴ is a group capable of reacting with the functional group bonded to the polymer particle (A) to form a linking group (provided OR ² is excluded), x is an integer of 0 or more, y is an integer of 1 or more, z is a valence of M, and z-xy is an integer of 1 or more. , And when plural R ² are present, each R ² may be the same or different, and R ³ and R ⁴ are also the same. ) 10. The (A) polymer particles are multiphase polymer particles comprising (A ′) a core polymer phase (a) and a shell polymer phase (b). , O in the general formula (1)
9. The polymer particles, wherein the functional group capable of reacting with the group represented by R ² to form a linking group is bonded to the surface and / or the vicinity of the surface of the polymer phase (b). Alternatively, the method for producing the dispersion according to Item 9. 11. A coating material comprising the composite particle according to claim 1. Description: