JPH1171527A - Curable polymer aqueous dispersion, its production and coating material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject dispersion that can give cured products excellent in resistance to water or solvents and in mechanical strength even when reducing the use amount of an emulsion or without using an emulsion by formulating specific polymer particles and a specific compound to the dispersion. SOLUTION: This dispersion comprises (A) polymer particles of condensate of (i) a polymer containing carboxyl groups, when necessary, hydrolyzable silyl groups and/or silanol groups and groups reactive with a basic nitrogen atom-containing group, (ii) an ethylenic polymer bearing a basic nitrogen atom- containing group (for example, a tertiary amino group and (iii) a polysiloxane of a condensate of an alkoxysilane of the formula: (<1> )a -Si-(X<1> )4-a (R<1> is H, a 1-20C organic group; X<1> is a monovalent group such as a halogen or amino; (a) is 0-3) and (B) a polyfunctional epoxy compound preferably bearing an epoxy group, a hydrolyzable silyl group and/or silanol group in one molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an aqueous dispersion of a curable polymer. More specifically, a specific polymer particles dispersed in an aqueous medium, characterized by being constituted as a polyfunctional epoxy compound as an essential component, the water resistance of the emulsion film, solvent resistance, Paint, which gives a crosslinked film with significantly improved mechanical strength, etc.
The present invention relates to a curable polymer aqueous dispersion useful for a primer treatment agent, an adhesive, a paper and fiber processing agent, a film coating agent, and the like.

[0002] In particular, the aqueous curable polymer dispersion of the present invention is useful for use as a paint or a finish coating agent.

[0003]

2. Description of the Related Art Aqueous polymer dispersions obtained by polymerizing various ethylenically unsaturated monomers are used as emulsion binders in a wide range of applications such as paints, adhesives, paper, and textile processing. These polymer emulsions are usually produced by adding an ethylenically unsaturated monomer and a radical-forming catalyst to emulsion polymerization in the presence of a surfactant (emulsifier).

Conventionally, various methods have been studied for improving the durability of such a polymer emulsion film or cured product, such as water resistance, solvent resistance, and mechanical strength. A so-called thermosetting type polymer is used to form a crosslinked structure by adding a crosslinker to a polymer emulsion and reacting with a reactive group of the polymer. Specifically, a technique of using an amino group as a reactive group and using an epoxy-based cross-linking agent as a curing agent is known, and can improve various properties such as water resistance and solvent resistance. .

On the other hand, when a polymer emulsion having curability is used as a binder for a water-based paint or a finish-coating agent, the polymer is cross-linked due to a heterogeneous dispersion of polymer particles in water. In some cases, a dense film was not obtained, resulting in poor durability, and a balance between hardness and flexibility was sometimes poor.

Further, crosslinkable water-based paints and finish coating agents having curability have tended to be inferior in weather resistance and stain resistance in the past, and more excellent performances have been desired.

[0007]

That is, in the above-mentioned method of curing a polymer emulsion containing an amino group with an epoxy-based cross-linking agent, various physical properties such as water resistance and solvent resistance can be certainly improved. In order to stably obtain a polymer emulsion containing an amino group, a large amount of an emulsifier must be used. As a result, even after the film is formed, a large amount of the emulsifier remains in the polymer film, so that sufficient water resistance is obtained. , Solvent resistance is not obtained, and
There was a problem of reducing the mechanical strength.

[0008] The problem to be solved by the present invention is to reduce the amount of emulsifier used, or to use it without using it at all.
Water resistance, solvent resistance, to provide a curable polymer aqueous dispersion that gives a cured product excellent in mechanical strength, furthermore, the curable polymer aqueous dispersion of the present invention as an aqueous paint or finish coating agent By using the same, it is possible to solve the drawbacks of the conventional water-based paint, and to provide a paint having excellent properties such as weather resistance, stain resistance and flex resistance, and a finish coating agent.

[0009]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that specific polymer particles dispersed in an aqueous medium and
A curable polymer aqueous dispersion composed of a polyfunctional epoxy compound has been found to be able to solve the above problems,
The present invention has been completed.

That is, the present invention provides an aqueous dispersion of a curable polymer exhibiting at least curability, a polymer having a carboxyl group (A), an ethylenic polymer having a basic nitrogen atom-containing group (B) and The present invention relates to a curable polymer aqueous dispersion containing polymer particles [X] composed of a polysiloxane (C) and a polyfunctional epoxy compound [Y], and is preferably a polysiloxane (C). But,
The following general formula (1)

[0011]

(R ¹ ) _a —Si— (X ¹ ) _4-a (1) (wherein, R ¹ is a hydrogen atom or an organic group having 1 to 20 carbon atoms, X ¹ is a halogen atom, an alkoxy group, A monovalent group selected from an acyloxy group, a hydroxy group, an aminoxy group, a phenoxy group, a thioalkoxy group or an amino group, a
Is an integer of 0, ¹ to 3, R ¹ and X ¹ bonded to a Si atom
When each is two or more, they may be the same or different groups), and are preferably ethylenic polymer having a basic nitrogen atom-containing group. The basic nitrogen atom-containing group of the compound (B) is a tertiary amino group, and preferably, the polyfunctional epoxy compound [Y] contains an epoxy group, a hydrolyzable silyl group and / or a silanol in one molecule. The present invention relates to an aqueous dispersion of a curable polymer which is a compound having a group.

Preferably, the polymer (A) having a carboxyl group is a polymer having a hydrolyzable silyl group and / or a silanol group, and more preferably, the polymer (A) having a carboxyl group is a basic polymer. It is a polymer having a group reactive with a nitrogen atom-containing group, more preferably the group reactive with a basic nitrogen atom is an epoxy group, and the acid value of the polymer (A) having a carboxyl group Is 10 to 200, and the weight average molecular weight is 100,
000 or more and gel fraction (acetone-insoluble content) is 9
A curable polymer aqueous dispersion in which the ethylenic polymer (B) having a basic nitrogen atom-containing group of 5% by weight or less is a polymer having a hydrolyzable silyl group and / or a silanol group. .

More preferably, the weight ratio of the polymer (A) having a carboxyl group and the ethylenic polymer (B) having a group containing a basic nitrogen atom is expressed by a solid fraction (A):
(B) = 1: 1 to 1:20, preferably wherein the polysiloxane (C) is a polymer (A) having a carboxyl group
And the total amount of the ethylenic polymer having a basic nitrogen atom-containing group (B) and [(A) +
(B)]: (C) = 100: 0.5 to 1: 1.

The present invention also relates to a curable polymer aqueous dispersion in which the polymer particles [X] have an acid value of 3 to 50, and preferably the pH of the curable polymer aqueous dispersion is 7 to 12.

In an aqueous medium containing a polymer (A) having a carboxyl group and a polysiloxane (C),
Polymer particles obtained by polymerizing monomers having an ethylenically unsaturated monomer having a basic nitrogen atom-containing group as an essential component [X]
A method for producing an aqueous dispersion of a curable polymer, which comprises adding a polyfunctional epoxy compound [Y], and then a polymer (A) having a carboxyl group, The present invention relates to a method for producing a curable polymer aqueous dispersion obtained by polymerizing monomers containing a carboxyl group-containing ethylenically unsaturated monomer as an essential component in an aqueous medium.

Further, the present invention relates to a paint containing the aqueous dispersion of the curable polymer.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Polymer particles [X] in the present invention
Is composed of at least three polymers: a polymer having a carboxyl group (A), an ethylenic polymer having a basic nitrogen atom-containing group (B), and a polysiloxane (C).

In the aqueous dispersion, the carboxyl group of the polymer (A) having a carboxyl group is used for stably dispersing the polymer particles [X] in an aqueous medium.

The carboxyl group in the polymer (A) having a carboxyl group is used as a cross-linkable reactive group with the polyfunctional epoxy compound [Y], or with the polyfunctional epoxy compound [Y] and ethylene. It is used as a functional group that promotes a reaction with a basic nitrogen atom-containing group in the reactive polymer (B).

The content of the carboxyl group in the polymer (A) having a carboxyl group is not particularly limited, but the acid value is 1 in view of the balance between dispersibility and water resistance.
It is preferably from 0 to 200. If the acid value is less than 10, the polymer particles [X] cannot be stably dispersed in the aqueous medium.

On the other hand, when the acid value exceeds 200, the number of carboxyl groups imparting hydrophilicity to the polymer particles [X] increases, and the water resistance of the film decreases.

The polymer particles [X] are particles stabilized by dispersion with the polymer (A) having a carboxyl group as described above, and the acid value of the whole polymer particles [X] is as follows:
The acid value is preferably in the range of 3 to 50 in view of the dispersion stability of the particles and the water resistance of the obtained film.

Here, the acid value means a numerical value indicating the amount of the carboxyl group contained in the polymer (A) having a carboxyl group or the polymer particles [X], and the polymer (A) having a carboxyl group. Alternatively, it is the number of mg of potassium hydroxide required to neutralize the free carboxyl group contained in 1 g of the polymer particles [X], and the measurement is carried out under the conditions shown in Examples described later.

The polymer (A) having a carboxyl group is
In addition to the carboxyl group, if the polymer further contains a hydrolyzable silyl group and / or silanol group, the polymer (A) having a carboxyl group and the polysiloxane (C) described later
Is preferred because the reactive group improves the mechanical strength and solvent resistance of the resulting emulsion film.

Here, the hydrolyzable silyl group or silanol group is represented by the following general formula (2)

[0026]

Embedded image

(Wherein, R ² is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an aryl group and an aralkyl group, X ² is a halogen atom, a hydroxy group, an alkoxy group, A group selected from an acyloxy group, an aminooxy group, a phenoxy group, a thioalkoxy group and an amino group, and b represents 0, 1 or 2), an alkoxy group, a substituted alkoxy group, a phenoxy group, a halogen atom , Isopropenyloxy group, acyloxy group, iminooxy group or the like bonded silicon atom, which is easily hydrolyzed to form a silanol group. Specific examples include an alkoxysilyl group, a phenoxysilyl group, a halosilyl group, an isopropenyloxysilyl group, an acyloxysilyl group, and an iminooxysilyl group.

The content of the hydrolyzable silyl group or silanol group in the polymer (A) having a carboxyl group is as follows:
Although not subject to any particular limitation, the amount is preferably 0.02 to 0.5 mmol per 1 g of the polymer (A). When the amount of the hydrolyzable silyl group or silanol group in 1 g of the polymer (A) is less than 0.02 mmol, the reactivity with the polysiloxane (C) is poor. 1 g of the polymer (A)
If the content exceeds 0.5 mmol, the dispersion stability of the polymer particles [X], the film formability of the obtained film, and the like will decrease.

The polymer (A) having a carboxyl group has, in addition to the carboxyl group, a group reactive with a basic nitrogen atom-containing group in the ethylenic polymer (B) described later. Is preferred. The polymer (A) having a carboxyl group and the basic nitrogen atom-containing group are linked by the reactive group, and the amount of the non-crosslinked polymer remaining in the cured product when cured with the polyfunctional epoxy compound [Y] is reduced. As a result, various properties such as water resistance, in particular, solvent resistance are improved.

The group reactive with such a basic nitrogen atom-containing group is not particularly limited, and specific examples thereof include an epoxy group, an isocyanate group, a blocked isocyanate group, and an acetoacetyl group. Among them, when the reactive group is an epoxy group, it is preferable because the solvent resistance of the obtained cured product is remarkably improved.

The group having reactivity with the basic nitrogen atom-containing group in the polymer (A) having a carboxyl group and the basic nitrogen atom-containing group in the ethylenic polymer (B) are curable polymer. It may react during the production of the combined aqueous dispersion to form crosslinks in the polymer particles [X]. However, from the viewpoint of various physical properties such as film forming properties, water resistance, solvent resistance, and mechanical strength, curing is performed. It is preferable that the polymer particles remain uncrosslinked in the previous polymer particles and are crosslinked to form a film by reacting a reactive functional group at the time of forming the film or after the film is formed, because various physical properties are remarkably improved.

The molecular weight of the polymer (A) having a carboxyl group is not particularly limited, but if the polymer (A) remains in the film as a strong hydrophilic low molecular weight component, the water resistance of the film becomes poor. For worsening, the molecular weight of the polymer (A) is preferably a high molecular weight.
The weight average molecular weight is preferably 100,000 or more.

Here, the weight average molecular weight is determined by dissolving a polymer constituting the polymer (A) having a carboxyl group in a solvent (tetrahydrofuran) and measuring the resulting solution by gel permeation chromatography (GPC method). The weight average molecular weight in terms of polystyrene is referred to, and the measurement is carried out under the conditions described in Examples described later.

In order to increase the molecular weight, for example, the polymer (A) having a carboxyl group may be cross-linked three-dimensionally, but the gel represented by the acetone-insoluble portion of the polymer (A) having a carboxyl group may be used. Preferably, the fraction is 95% by weight or less.

When the gel fraction of the polymer (A) having a carboxyl group is 95% by weight or less, the stability at the time of producing the ethylenic polymer (B) described later is improved.
The resulting film also has good film forming properties.

Further, a polymer (A) having a carboxyl group
Is physically or chemically complexed with a polysiloxane (C) described later (a state in which polymer chains penetrate each other or a state in which polymer chains are chemically bonded), For the above reasons, the composite preferably has a gel fraction of 95% by weight or less in the entire composite.

The gel fraction of the polymer (A) having a carboxyl group in the present invention is an index indicating the extent to which the polymer constituting the polymer (A) having a carboxyl group is involved in cross-linking. This is represented by measuring the solvent-insoluble content (% by weight) of the above polymer.

Specifically, a polymer film is formed from the polymer (A) having a carboxyl group or an aqueous dispersion containing the polymer (A) having a carboxyl group, and the polymer film is immersed in acetone for cross-linking. The gel fraction is calculated by eluting the unrelated polymer and measuring the remaining acetone-insoluble matter. A specific measurement method includes a method performed under the conditions described in Examples described later.

Further, a polymer (A) having a carboxyl group
Even in the case where the polysiloxane (C) is complexed with the polysiloxane (C), the gel fraction can be measured under the conditions described in Examples described later.

Depending on the application field in which the aqueous dispersion of the curable polymer is used, the film-forming property of the film is often required in use, and in this case, a carboxyl group containing a carboxyl group constituting the A phase is used. The glass transition temperature (Tg) of the polymer (A) having the above is preferably in the range of −60 to 30 ° C.

The polymer (A) having a carboxyl group is
Although not specified, for example, acrylic polymer,
Addition polymers of ethylenically unsaturated monomers such as butadiene-based polymers (hereinafter abbreviated as “ethylenic polymers”), urethane polymers including urea and polymers having urethane bonds, polyester polymers, etc. And mixtures of these various polymers, for example, mixtures of acrylic polymers / urethane polymers, and grafted (blocked) products of various polymers, for example, grafted acrylic polymers onto unsaturated polyester polymers. Objects can also be used.

In particular, when the polymer (A) having a carboxyl group is designed in consideration of the adjustment of the acid value and molecular weight and the introduction of a reactive group capable of crosslinking with a basic nitrogen atom-containing group as described above, Ethylene polymers are preferred because they are easy to design and can be easily manufactured by the method described below.

Next, the ethylenic polymer (B) in the present invention has a basic nitrogen atom-containing group as a crosslinkable reactive group with the polyfunctional epoxy compound [Y]. Examples of the basic nitrogen atom-containing group include, for example, N, N-
Examples thereof include a dialkylamino group, a piperidine group, a piperazine group, an imidazole group, a pyrrolidine group, a pyridinyl group, a morpholine group, an aziridinyl group, an N-monoalkylamino group, an amino group, a phenylamino group, and a benzylamino group.

Among these functional groups, particularly, the basic nitrogen atom-containing group in the ethylenic polymer (B) is an N, N-dialkylamino group, a piperidine group, a piperazine group, an imidazole group, a pyrrolidine group, a pyridinyl group, Morpholine group,
When it is a tertiary amino group such as an aziridinyl group, the reactivity with the polyfunctional epoxy compound [Y] is high, and the crosslink density of the cured product obtained even when cured under mild heat treatment conditions is increased. It is preferable because various physical properties such as water resistance, solvent resistance, and mechanical strength can be remarkably improved.

The content of the basic nitrogen atom-containing group in the ethylenic polymer (B) is not particularly limited, but may be 0.05 to 2.0 per gram of the ethylenic polymer (B).
It is preferably mmol. 0.05 g of a basic nitrogen atom-containing group was added to 1 g of the ethylenic polymer (B).
If it is less than 1, it is not preferable from the viewpoint of curability with the polyfunctional epoxy compound [Y]. If the amount exceeds 2.0 mmol per 1 g of the ethylenic polymer (B), the dispersion stability of the polymer particles [X] and the water resistance of the obtained cured product are not preferred.

The content of the basic nitrogen atom-containing group in the entire polymer particle [X] is determined by the curability with the polyfunctional epoxy compound [Y], the dispersion stability of the polymer particle [X], From the viewpoint of the water resistance of the obtained cured product, polymer particles [X] 1
g is 0.03 to 0.1.
Preferably it is in the range of 7 mmol.

When the ethylenic polymer (B) contains a hydrolyzable silyl group and / or a silanol group in addition to the basic nitrogen atom-containing group, the ethylenic polymer (B) will be referred to as the ethylenic polymer (B) later. Polysiloxane (C) is preferred because it is linked by the reactive group, and the mechanical strength and solvent resistance of the resulting emulsion film are improved.

Here, the hydrolyzable silyl group or silanol group includes a functional group represented by the above general formula (2).

The content of the hydrolyzable silyl group and / or silanol group in the ethylenic polymer (B) is not particularly limited, but may be 0.02 to 1 g per 1 g of the ethylenic polymer (B). Preferably, it is 1.0 mmol. If the amount of the hydrolyzable silyl group or silanol group in 1 g of the polymer (B) is less than 0.02 mmol, the reactivity with the polysiloxane (C) is inferior. Also,
If the amount exceeds 1.0 mmol in 1 g of the ethylenic polymer (B), the hydrolyzable silyl group or silanol group in the polymer (B) may cause the dispersion stability of the polymer particles [X] and the resulting film. , Etc., deteriorates the film forming property and the like.

The molecular weight of the ethylenic polymer (B) is not particularly limited, but the weight average molecular weight of the obtained cured product is preferably from the viewpoint of physical properties such as water resistance, solvent resistance and mechanical strength. It is preferably at least 100,000.

From the viewpoint of various properties such as water resistance of the obtained cured product, the weight ratio of the polymer (A) having a carboxyl group and the ethylenic polymer (B) having a group containing a basic nitrogen atom is as follows: (A): 1: 0.5 to solid fraction ratio of (B)
Preferably it is 1: 100. More specifically,
From the viewpoint of water resistance, (A) :( B) = 1: 1 to 1: 100
Is more preferable.

From the viewpoint of storage stability as an aqueous dispersion of a curable polymer, a polymer having a carboxyl group (A) and an ethylenic polymer having a basic nitrogen atom-containing group (B)
Is 1: 0.5 in the solid fraction ratio of (A) :( B).
１ ： 1: 20 is preferred. By setting the ratio of the solid content of the polymer (B) to 1 part by weight of the polymer (A) to 20 parts by weight or less, the storage stability as a curable polymer aqueous dispersion is remarkably improved. Various physical properties of the cured product,
From the balance of the storage stability as the curable polymer aqueous dispersion, the solid fraction ratio of (A) :( B) is 1: 1 to 1: 2.
Most preferably, it is in the range of 0.

Next, the polysiloxane (C) in the present invention, when present in the polymer particles [X], increases the resistance to, for example, ultraviolet rays, oxygen, water, or various solvents to improve the durability. It is used to improve weather resistance and stain resistance when used as a paint or a finishing coating agent.

The polysiloxane (C) is not particularly limited. However, the polysiloxane (C) is used as the aqueous dispersion of the curable polymer in the present invention because it is easily obtained by the durability of the resulting film and the production method described later. Is preferably a condensate of a silane compound represented by the following general formula (1).

[0055]

(R ¹ ) _a —Si— (X ¹ ) _4-a (1) (wherein, R ¹ is a hydrogen atom or an organic group having 1 to 20 carbon atoms, X ¹ is a halogen atom, an alkoxy group, A monovalent group selected from an acyloxy group, a hydroxy group, an aminoxy group, a phenoxy group, a thioalkoxy group or an amino group, a
Is an integer of 0, ¹ to 3, R ¹ and X ¹ bonded to a Si atom
And when each is two or more, they may be the same group or different groups.) Specific examples of the silane compound include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyl Alkoxysilanes such as diethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, methylchlorosilane, methyl Examples include chlorosilanes such as dichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, and diphenylchlorosilane. One or a mixture of two or more of these may be used. Can.

Examples of the polysiloxane (C) include, in addition to the above-mentioned condensation product of the silane compound, cyclic compounds such as octamethylcyclotetrasiloxane, octaphenylcyclosiloxane, hexamethylcyclotrisiloxane, and decamethylcyclopentasiloxane. Polymerization reaction products of silanes, alkali siliconates such as potassium methylsiliconate, methyl silicate 51 (manufactured by Mitsubishi Chemical Corporation: polymethoxysiloxane), ethyl silicate 40
A condensation reaction product of an alkoxysilane such as (Colcoat Co., Ltd .: polyethoxysiloxane) or the following general formula (3)

[0057]

Embedded image

Or the general formula (4)

[0059]

Embedded image

[In the general formulas (3) and (4), R ⁴
Is a monovalent hydrocarbon group selected from hydrogen, an alkyl group, an aryl group, and an aralkyl group; R ⁵ is a monovalent group selected from a hydroxy group, an alkoxy group, an acetoxy group, and an acyloxy group; And an integer of 1000, and R ⁴ and R ⁵ bonded to the Si atom may be the same or different groups.] Mixtures of more than one species can be used.

The ratio of the polysiloxane (C) is a solid content weight ratio with respect to the total amount of the polymer (A) having a carboxyl group and the ethylenic polymer (B) having a basic nitrogen atom-containing group. [(A) + (B)] :( C) = 100: 0.
Preferably, the ratio is 5 to 1: 1. The polysiloxane (C)
Is less than 0.5 part per 100 parts of [(A) + (B)], the effect of further improving the weather resistance and stain resistance cannot be obtained, while the ratio of the polysiloxane (C) is not obtained. However, when the amount exceeds 1 part, it is difficult to stably obtain an aqueous dispersion of the polymer particles [X].

The polymer particles [X] dispersed in the aqueous dispersion of the curable polymer are not particularly limited in their particle morphology, but are usually ethylenic polymers having a basic nitrogen atom-containing group ( B) constitutes the particle core, and the polymer (A) having a carboxyl group and the polysiloxane (C) constitute the particle shell (in this case, the polymer (A) and the polysiloxane (C) are polymer The chains may penetrate each other, or the polymer chains may be chemically bonded to each other.) A so-called core-shell type particle form, or the polymer (B) is a polymer (A) Or a form in which the polymer (B) and the polysiloxane (C) are dispersed in a matrix in a matrix composed of the polymer (A) or the polymer (A). And the like. Further, when the polymer (A) is dissolved or non-particulately dispersed in the aqueous medium, the polymer (B) and the polysiloxane (C) are present in the polymer (A) in a particulate form. There is also a form that does. In any of these particle forms, the carboxyl group of the polymer (A) stabilizes the dispersion of the polymer particles [X].

In the above embodiment, the polymer (B) constitutes the particle core, and the polymer (A) and the polysiloxane (C) constitute the particle shell (in this case, the polymer (A) The polysiloxane (C) may be such that the polymer chains may penetrate each other or the polymer chains may be chemically bonded to each other.) This is preferred because the properties and storage stability after the addition of the polyfunctional epoxy compound [Y] described below are improved, and the durability of the resulting film is further improved.

The aqueous dispersion of the curable polymer of the present invention has a pH of
Has a pH of 7 from the viewpoint of dispersibility, curability and storage stability.
It is preferably from 12 to 12. Since the dispersion of the polymer particles [X] in the dispersion liquid is stabilized by a carboxyl group, the carboxyl group is neutralized by a basic substance described later. From the viewpoint, the pH is preferably 7 or more. On the other hand, from the viewpoint of curability and storage stability of the curable polymer aqueous dispersion,
The pH of the curable polymer aqueous dispersion is preferably 12 or less.

The particle size of the polymer particles [X] dispersed in the aqueous dispersion of the curable polymer is not particularly limited, but the number average particle size is preferably 10 to 1000 nm.
It is preferable from the viewpoint of the film forming property of the film.

The aqueous dispersion of the curable polymer of the present invention contains the polymer particles [X] and the polyfunctional epoxy compound [Y] as constituents, but the polyfunctional epoxy compound [Y]
Is used to cure the film, and the polymer particles [X]
Reacts with a crosslinkable reactive group (a basic nitrogen atom-containing group and / or a carboxyl group) to improve various physical properties such as water resistance, solvent resistance and mechanical strength.

Specific examples of the polyfunctional epoxy compound [Y] include ethylene glycol diglycidyl ether,
Glycidyl ethers of aliphatic polyhydric alcohols such as propylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, cyclohexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether; polyethylene glycol Glycidyl ethers of polyalkylene glycol such as diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether; polyhydric alcohols [ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol,
Bis (hydroxymethyl) benzene etc.] and polyvalent carboxylic acid [oxalic acid, adipic acid, butanetricarboxylic acid, maleic acid, phthalic acid, terephthalic acid, isophthalic acid, benzenetricarboxylic acid, etc.] polyester polyglycidylated product, polycaprolactone Polyglycidylated products of polyesters such as polyglycidylated products of the above; polyvalent amines [ethylenediamine, diethylenetriamine, 1,4-cyclohexanediamine, isophoronediamine, tolylenediamine, etc.] and polycarboxylic acids [oxalic acid, adipic acid, butanetricarboxylic acid, Polyglycidylated polyamide with maleic acid, phthalic acid, terephthalic acid, isophthalic acid, benzenetricarboxylic acid, etc.

Bisphenol A epoxy resins such as condensates of bisphenol A and epichlorohydrin, ethylene oxide adducts of condensates of bisphenol A and epichlorohydrin, and propylene oxide adducts of condensates of bisphenol A and epichlorohydrin; phenol novolak resins, phenol novolaks Phenol novolak epoxy resins such as ethylene oxide adducts of resins and propylene oxide adducts of phenol novolak resins; epoxy urethane resins obtained by urethane modification of epoxy resins; various vinyl (co) polymers having epoxy groups in side chains; epoxy modification Silicone oil; Partial hydrolyzate of epoxy-containing alkoxysilane such as γ-glycidoxypropyltrimethoxysilane; in one molecule of epoxy-containing acrylic resin A compound having two or more epoxy groups. Among such polyfunctional epoxy compounds, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether , Polyglycerol polyglycidyl ethers, water-soluble epoxy compounds such as sorbitol polyglycidyl ether, or "Denacol EM-125"
(Nagase Kasei Kogyo Co., Ltd.), "Dick Fine EM
-100 "(manufactured by Dainippon Ink and Chemicals, Inc.)," ADEKARESIN EPE-0410, EPES-0425W "
Emulsified self-dispersible epoxy compounds such as (made by Asahi Denka Kogyo Co., Ltd.) or emulsified water-insoluble epoxy compounds (liquid or solid) with an emulsifier are polymer particles [X]. It is preferable from the viewpoint of compatibility with the polymer and curability.

The polyfunctional epoxy compound [Y] includes, in one molecule, an epoxy group and a reactive functional group other than the epoxy group (here, the reactive functional group refers to a polymer particle [X]). A reactive functional group capable of reacting with the reactive group or a reactive functional group capable of reacting with the reactive group). Epoxysilanes containing an epoxy group and a hydrolyzable silyl group or silanol group in the molecule are mentioned.

When a compound having both an epoxy group and a hydrolyzable silyl group and / or silanol group in one molecule is used, the durability of the cured product is remarkably improved, and the curability is further improved. Drying at room temperature alone is preferable because a cured product having desired performance can be obtained. It is also preferable because the adhesiveness to the inorganic base material is significantly improved.

Examples of the compound having both an epoxy group and a hydrolyzable silyl group and / or silanol group in one molecule include an ethylenic polymer having both of these types of reactive groups and an epoxy group. A typical example thereof is a silane coupling agent having the compound or a silicone resin having an epoxy group.

Here, the hydrolyzable silyl group or silanol group means a functional group represented by the following general formula (2).

In order to prepare these ethylenic polymers having both an epoxy group and a hydrolyzable silyl group and / or silanol group as described above, any of various well-known methods can be applied, but it is recommended. Examples of the method include a method in which various hydrolyzable silyl group-containing polymerizable monomers and various epoxy group-containing polymerizable monomers are solution-radical copolymerized. -Containing polymerizable monomers, various epoxy group-containing polymerizable monomers, and other polymerizable monomers copolymerizable therewith, a method of solution radical copolymerizing, γ-mercaptopropyltrimethoxy Silane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane or γ-mercaptopropyltriisopropenyloxysilane In the presence of various chain transfer agents containing a hydrolyzable silyl group, as described above, a monomer mixture containing various epoxy group-containing polymerizable monomers as an essential monomer component, Various methods such as a method in which solution radical (co) polymerization is performed, or a method in which the above method or the above method is combined with the above method are exemplified.

As the above-mentioned epoxy group-containing silane coupling agent, particularly typical ones include, for example,
γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane, β
-(3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl)
Various epoxysilane compounds such as ethylmethyldiethoxysilane or γ-glycidoxypropyltriisopropenyloxysilane; γ-isocyanatopropyltriisopropenyloxysilane or γ-isocyanatopropyltrimethoxysilane Adducts of various isocyanate silane compounds with glycidol; or adducts of various aminosilane compounds such as γ-aminopropyltrimethoxysilane with diepoxy compounds; or various epoxy silanes as described above Compounds obtained by partially hydrolyzing and condensing a compound and having both two or more epoxy groups and a hydrolyzable silyl group in one molecule are exemplified.

Further, a typical example of the silicone resin having an epoxy group is a cyclic tetrasiloxane, which is a compound represented by the following formula [5].

[0076]

Embedded image

In the formula (5), Gly represents a 3-glycidoxypropyl group.

The amount of the polyfunctional epoxy compound [Y] in the curable polymer aqueous dispersion is not particularly limited, but the curability of the curable polymer aqueous dispersion, the performance of the crosslinked film, and the like are not limited. From the viewpoint of storage stability of the curable polymer aqueous dispersion,
Basic nitrogen atom-containing group 1 contained in polymer particle [X] 1
It is preferable to use it in the range of 0.3 to 3.0 mol with respect to the mol.

Further, it is preferable to use a curing catalyst in combination with the aqueous dispersion of the curable polymer of the present invention, if necessary, from the viewpoint that the curability can be further improved.

[0080] Particularly typical examples of such a catalyst include various basic compounds such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and sodium methylate; tetraisopropyl titanate, tetra-n-butyl and the like. Titanate, tin octylate, lead octylate, cobalt octylate, zinc octylate, calcium octylate, zinc naphthenate, cobalt naphthenate, di-n-butyltin diacetate, di-n-butyltin dioctoate, di-n Metal-containing compounds such as -butyltin dilaurate and di-n-butyltin maleate; p-toluenesulfonic acid, trichloroacetic acid, phosphoric acid, monoalkyl phosphoric acid,
Various acidic compounds such as dialkylphosphoric acid, monoalkylphosphorous acid, and dialkylphosphorous acid are exemplified.

The solid component concentration of the curable polymer aqueous dispersion is
It is preferably 20 to 70% by weight. That is, by setting the solid component concentration to 70% by weight or less, an abnormal increase in the viscosity of the system at the time of production can be suppressed, and the stability of the curable polymer aqueous dispersion becomes good. 20% by weight
The above is preferable from the viewpoint of the thickness of the coating film when used in coating processing (paints, adhesives, paper, films, fiber processing agents, etc.), and the productivity of the aqueous curable polymer dispersion is also good. It becomes something. It is preferable that the solid content concentration is as described above from the viewpoint that the balance between them becomes good.

As described above, the aqueous curable polymer dispersion of the present invention can be produced with extremely small amounts of emulsifiers and dispersion stabilizers, or without using them at all.
The amounts of the emulsifier and the dispersion stabilizer in the dispersion can be extremely small. Specifically, the amount of the emulsifier and the dispersion stabilizer is preferably 1% by weight or less based on the solid content of the aqueous curable polymer dispersion. It is preferable in terms of properties and the like.

The production method of such an aqueous dispersion of a curable polymer is not particularly limited, and examples thereof include the following methods. That is, 1) a polymer (A) having a carboxyl group;
Ethylenic polymer having basic nitrogen atom-containing group (B)
And the polysiloxane (C) are separately produced, and once mixed, dispersed in an aqueous medium to obtain a dispersion of the polymer particles [X]. 2) producing a polymer (A) having a carboxyl group, dissolving or dispersing it in an aqueous medium, producing a polysiloxane (C) in the aqueous medium, and then producing the polysiloxane (C) A method of producing an ethylenic polymer (B) having a basic nitrogen atom-containing group therein and adding a polyfunctional epoxy compound [Y] thereto; 3) a polymer (A) having a carboxyl group; And dissolving or dispersing the same in an aqueous medium to produce a polysiloxane (C), and then producing an ethylenic polymer (B) having a basic nitrogen atom-containing group in the aqueous medium, There, multifunctional epo A method of adding a sheet-based compound [Y], 4) a polymer having a carboxyl group prepared in (A) carried out in an aqueous medium and then to produce a polysiloxane (C),
Next, a method of producing an ethylenic polymer (B) having a basic nitrogen atom-containing group in the aqueous medium, and adding a polyfunctional epoxy compound [Y] thereto,

5) Polymer having carboxyl group (A)
And the polysiloxane (C) were simultaneously dissolved or dispersed in an aqueous medium, and then an ethylenic polymer (B) having a basic nitrogen atom-containing group was produced in the aqueous medium. A method of adding a polyfunctional epoxy compound [Y] thereto, 6) simultaneously producing a polymer (A) having a carboxyl group and producing a polysiloxane (C) in an aqueous medium, A method in which an ethylenic polymer (B) having a basic nitrogen atom-containing group is produced in a medium, and a polyfunctional epoxy compound [Y] is added thereto. 7) A polymer having a carboxyl group (A) And then dissolving or dispersing it in an aqueous medium to produce an ethylenic polymer (B) having a basic nitrogen atom-containing group in the aqueous medium. C) Then, a polyfunctional epoxy compound [Y] is added thereto. 8) A polymer (A) having a carboxyl group is produced in an aqueous medium, and a basic nitrogen atom-containing group is produced in the aqueous medium. A method of producing an ethylenic polymer (B) having the same, then producing a polysiloxane (C) in the aqueous medium, and adding a polyfunctional epoxy compound [Y] thereto;

9) Polymer having carboxyl group (A)
And dissolving or dispersing the same in an aqueous medium, and then simultaneously producing an ethylenic polymer (B) having a basic nitrogen atom-containing group and a polysiloxane (C) in the aqueous medium, There, polyfunctional epoxy compound [Y]
10) A polymer (A) having a carboxyl group is produced in an aqueous medium, and an ethylenic polymer (B) having a basic nitrogen atom-containing group and a polysiloxane (C) are produced in the aqueous medium. )
And simultaneously adding a polyfunctional epoxy compound [Y] thereto. 11) Producing an ethylenic polymer (B) having a basic nitrogen atom-containing group, and adding it to an aqueous medium. After dissolving or dispersing, a polysiloxane (C) is produced in the aqueous medium, then a polymer (A) having a carboxyl group is produced in the aqueous medium, and a polyfunctional epoxy compound [ Y), 12) producing an ethylenic polymer (B) having a basic nitrogen atom-containing group, dissolving or dispersing it in an aqueous medium, and simultaneously producing a polysiloxane (C); Next, a method of producing a polymer (A) having a carboxyl group in the aqueous medium and adding a polyfunctional epoxy compound [Y] thereto, 13) an ethylenic polymer having a basic nitrogen atom-containing group (B) And a polysiloxane (C) are simultaneously dissolved or dispersed in an aqueous medium, and then a polymer (A) having a carboxyl group is produced in the aqueous medium. A method of adding an epoxy compound [Y], 14) simultaneously producing an ethylenic polymer (B) having a basic nitrogen atom-containing group and producing a polysiloxane (C) in an aqueous medium, There is a method in which a polymer (A) having a carboxyl group is produced therein, and a polyfunctional epoxy compound [Y] is added thereto.

Among these methods, in order to express desired physical properties such as water resistance, it is necessary to suppress the acid value of the polymer (A) having a carboxyl group to be low and to increase the molecular weight, From the viewpoint of increasing the molecular weight of the ethylenic polymer (B) having a functional nitrogen atom-containing group, the above methods 4), 6), 8) and 10) are preferred. further,
The particle morphology of the polymer particles [X] is determined based on the dispersion stability of the particles,
From the viewpoint of storage stability after the addition of the polyfunctional epoxy compound [Y] and durability of the obtained film, it is preferable to use the core-shell type as described above, and therefore, it will be described in detail below. It is preferable to produce by the production method of the present invention.

According to the production method of the present invention, the productivity of the aqueous dispersion of the curable polymer can be further increased.

The production method of the present invention comprises, in an aqueous medium containing a polymer (A) having a carboxyl group and a polysiloxane (C), an ethylenically unsaturated monomer having a basic nitrogen atom-containing group as an essential component. To obtain an aqueous dispersion of polymer particles [X], and then adding a polyfunctional epoxy compound [Y] to obtain an aqueous dispersion of a curable polymer. Is what you do.

The properties of the polymer (A) having a carboxyl group in the aqueous medium when producing the polymer particles [X] in the method for producing the aqueous dispersion of the curable polymer of the present invention are, in particular, The polymer is not limited, and the polymer (A) having a carboxyl group is completely dissolved in an aqueous medium, is semi-solubilized in an aqueous medium, or is dispersed as particles in an aqueous medium, and the like. Is mentioned. As described above, in order to improve various physical properties such as water resistance, the acid value of the polymer (A) having a carboxyl group should be suppressed as low as possible and the molecular weight should be increased.
Preferably, the polymer (A) having a carboxyl group having such characteristics is present in an aqueous medium in order to stably exist in the aqueous medium. It is preferably dispersed as particles.

The particle size of the polymer (A) having a carboxyl group dispersed as particles in an aqueous medium is not particularly limited, but the stability at the time of polymerization of the monomer (b) described later, From the viewpoint of the film forming properties of the finally obtained film,
It is preferable that the number average particle diameter is in the range of 5 to 1000 nm.

The method for producing the polymer (A) having a carboxyl group varies depending on the type of the polymer used, and is not particularly limited. For example, it is produced by free radical polymerization of an ethylenically unsaturated monomer. And by non-free radical addition polymerization or polycondensation.

Among these, the method of producing by free radical polymerization using an ethylenically unsaturated monomer as a raw material adjusts the acid value, molecular weight and gel fraction of the resulting polymer (A) having a carboxyl group. And a polymer component (A) having a carboxyl group, an ethylenic polymer (B) having a basic nitrogen atom-containing group, and a monomer component for obtaining the ethylenic polymer (B) This is preferred in that it has good compatibility with water and improves the stability of the production of the ethylenic polymer (B) in an aqueous medium.

Further, in the case of the production method using an ethylenically unsaturated monomer as a raw material, it is easy to introduce a reactive functional group other than the above-mentioned carboxyl group into the polymer (A) having a carboxyl group. It is also preferable from the viewpoint.

The method for producing the polymer (A) having a carboxyl group by free radical polymerization is not specified, but the carboxyl group-containing ethylenically unsaturated monomer (a-1) is an essential component. Monomers (a)
Depending on its properties, suspension polymerization, emulsion polymerization, bulk polymerization,
It can be produced by any method of solution polymerization. In particular, it is preferable to carry out the suspension polymerization or the emulsion polymerization performed in an aqueous medium because the weight average molecular weight of the polymer (A) having a carboxyl group can be easily increased to 100,000 or more. When the polymer (A) having a carboxyl group is produced in an aqueous medium, the step of dispersing the polymer (A) having a carboxyl group in the aqueous medium can be omitted, and the polymer (A) having a carboxyl group can be omitted. And the production process of the ethylenic polymer (B) can be performed continuously, which is also preferable in that the production process can be simplified.

Monomers (a) used for producing polymer (A) having a carboxyl group by free radical polymerization
Is a carboxyl group-containing ethylenically unsaturated monomer (a-
1) is an essential component. The carboxyl group-containing ethylenically unsaturated monomer (a-1) is not particularly limited as long as it has a carboxyl group and an ethylenically unsaturated group in the molecule. For example, (meth) acrylic acid, crotonic acid,
Itaconic acid, maleic acid, fumaric acid, β- (meth) acryloyloxyethyl hydrogen succinate, β-
(Meth) acryloyloxyethyl hydrogen phthalate, a half ester thereof, or a salt thereof, and the like, and one or a mixture of two or more thereof can be used.

As the monomers (a), in addition to the above-mentioned carboxyl group-containing ethylenically unsaturated monomer (a-1), an acid value is obtained by polymerizing a combination of other ethylenically unsaturated monomers. Is adjusted to the above-mentioned preferred range (acid value 10 to 200) to obtain a polymer (A) having a carboxyl group.

Other ethylenically saturated monomers include:
There is no particular limitation as long as it has copolymerizability with the ethylenically unsaturated monomer (a-1). For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i- Butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate,
(Meth) acrylates such as dodecyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, phenyl (meth) acrylate, and benzyl (meth) acrylate; 2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2,2
Fluorine-containing vinyl monomers such as 3,3, -tetrafluoropropyl (meth) acrylate and β- (perfluorooctyl) ethyl (meth) acrylate; vinyl acetate, vinyl propionate, vinyl butyrate, vinyl versatate, etc. Vinyl esters; methyl vinyl ether,
Vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, amyl vinyl ether and hexyl vinyl ether; nitriles of unsaturated carboxylic acids such as (meth) acrylonitrile; styrene, α-methylstyrene, vinyltoluene, vinylanisole, α-halostyrene, Vinyl compounds having an aromatic ring such as vinyl naphthalene and divinyl styrene; isoprene, chloroprene, butadiene, ethylene, tetrafluoroethylene, vinylidene fluoride, N-vinylpyrrolidone and the like, and one or a mixture of two or more thereof Can be used. Among these, (meth) acrylates are preferred because they are particularly easy to polymerize and have excellent physical properties such as water resistance of the resulting coating film.

As described above, if the polymer (A) having a carboxyl group contains a hydrolyzable silyl group and / or silanol group in addition to the carboxyl group, the polymer (A) having a carboxyl group ) Is linked to the polysiloxane (C) by the reactive group, whereby the mechanical strength and solvent resistance of the resulting emulsion film are improved.

Here, the hydrolyzable silyl group or silanol group means a functional group represented by the general formula (2).

As a method for introducing such a hydrolyzable silyl group and / or silanol group into the polymer (A) having a carboxyl group, the following ethylenically unsaturated groups containing a hydrolyzable silyl group and / or silanol group can be used. It is preferable to use a saturated monomer as the ethylenically unsaturated monomer (a-2), and specifically, for example, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxy Ethoxy) silane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltripropoxysilane, γ- (meth) acryloxypropyltributoxy Silane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ (Meth) acryloxy propyl methyl diethoxy silane, .gamma. (meth) acryloxypropyl dimethyl methoxy silane, .gamma. (meth) acryloxypropyl dimethyl ethoxysilane and the like,
One or a mixture of two or more of these can be used.

When the usage ratio of the monomer (a-2) is adjusted as described above, the polymer (A) having a carboxyl group is
Even when the polysiloxane (C) is composited, the gel fraction of the composite as a whole can be suppressed to 95% by weight or less, and the stability at the time of the production of the ethylenic polymer (B) described later is improved, which is preferable. .

Further, if necessary, as the other ethylenically unsaturated monomer, an ethylenically unsaturated monomer having a reactive functional group other than a carboxyl group can be used in combination. Such ethylenically unsaturated monomers include:
Although not particularly limited, for example, glycidyl (meth) acrylate, allyl glycidyl ether,
-Epoxy group-containing polymerizable monomers such as vinylcyclohexane monoepoxide; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, etc. Hydroxyl group-containing polymerizable monomers; amide group-containing polymerizable monomers such as (meth) acrylamide, N-monoalkyl (meth) acrylamide, N, N-dialkyl (meth) acrylamide; N-methylol (meth) acrylamide; A methylolamide group such as N-isopropoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide and a polymerizable monomer containing an alkoxylated product thereof; 2-aziridinylethyl (Meta) Aziridinyl group-containing polymerizable monomer such as acrylate; isocyanate group and / or blocked isocyanate group-containing polymerizable monomer such as phenol adduct of (meth) acryloyl isocyanate and (meth) acryloyl isocyanate ethyl; 2-isopropenyl Oxazoline group-containing polymerizable monomers such as -2-oxazoline, 2-vinyl-2-oxazoline and 2-oxazodinylethyl (meth) acrylate; cyclopentenyl group-containing polymerizable such as dicyclopentenyl (meth) acrylate Monomer

Carbonyl group-containing polymerizable monomers such as acrolein and diacetone (meth) acrylamide; acetoacetyl group-containing polymerizable monomers such as acetoacetoxyethyl (meth) acrylate; N, N-dimethylaminoethyl (meth) ) Acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N- [2- (meth) acryloyloxyethyl] piperidine , N- [2- (meth) acryloyloxyethyl] pyrrolidine, N- [2
-(Meth) acryloyloxyethyl] morpholine, 4
-[N, N-dimethylamino] styrene, 4- [N, N
-Diethylamino] styrene, 2-vinylpyridine, 4
A tertiary amino group-containing polymerizable monomer such as vinylpyridine;
N-methylaminoethyl (meth) acrylate, Nt
A polymerizable monomer having a secondary amino group such as -butylaminoethyl (meth) acrylate; aminomethyl acrylate,
Examples include primary amino group-containing polymerizable monomers such as aminoethyl acrylate, aminopropyl (meth) acrylate, amino-n-butyl (meth) acrylate, butylvinylbenzylamine, vinylphenylamine, and p-aminostyrene. And one or a mixture of two or more of these can be used.

Here, particularly as the other ethylenically unsaturated monomers in the monomers (a), of the ethylenically unsaturated monomers having a reactive functional group other than the above-mentioned carboxyl group, When an ethylenically unsaturated monomer containing a group having a reactivity with a basic nitrogen atom-containing group is used in combination as the ethylenically unsaturated monomer (a-3), a polymer having a carboxyl group (A) Polymer (B) can be crosslinked, the amount of non-crosslinked polymer remaining in the cured product when cured with the polyfunctional epoxy compound [Y] can be reduced, and various properties such as water resistance and solvent resistance can be reduced. This is preferable because physical properties can be improved.

That is, by using the monomer (a-3) in combination, the reactive functional group in the monomer and the basic nitrogen atom-containing group in the ethylenic polymer (B) undergo a crosslinking reaction. Thereby, the crosslink density of the cured product cured with the polymer particles [X] and the polyfunctional epoxy compound [Y] is increased,
Various physical properties such as water resistance of the cured product, particularly solvent resistance, are improved.

When the reactive functional group of the monomer (a-3) has reactivity with a carboxyl group, or when the reactive functional group of the monomer (a-3) reacts by itself. Is
It has the effect of increasing the molecular weight of the polymer (A) having a carboxyl group and improving various physical properties such as water resistance. However, as described above, the gel fraction of the polymer (A) having a carboxyl group is 95% by weight or less. It is preferable to use under the following conditions (selecting the type and amount of the reactive functional group, adjusting the reaction temperature during polymerization of the polymer (A) having a carboxyl group, the pH of the system during polymerization, and the like).

Such an ethylenically unsaturated monomer containing a group reactive with a basic nitrogen atom-containing group (a-
As 3), although not particularly limited, among the above compounds, for example, glycidyl (meth) acrylate, (β-methyl) glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) Epoxy group-containing polymerizable monomers such as acrylate, allyl glycidyl ether, 3,4-epoxyvinylcyclohexane, di (β-methyl) glycidyl malate, di (β-methyl) glycidyl fumarate; (meth) acryloyl isocyanate; Polymerizable monomers containing isocyanate groups and / or blocked isocyanate groups, such as phenol adducts of (meth) acryloyl isocyanate ethyl; polymerizable monomers containing acetoacetyl groups, such as acetoacetoxyethyl (meth) acrylate; . As the ethylenically unsaturated monomer (a-3), one or a mixture of two or more of these monomers can be used.

Among them, glycidyl is particularly preferred in that it has remarkably excellent reactivity with a basic nitrogen atom-containing group in the ethylenic polymer (B) described later and further improves the water resistance and solvent resistance of the cured product. (Meth) acrylate, (β-methyl) glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, allyl glycidyl ether, 3,4-epoxyvinylcyclohexane, di (β-methyl) glycidyl malate, It is preferable to use an epoxy group-containing polymerizable monomer such as (β-methyl) glycidyl fumarate.

Further, if necessary, other ethylenically unsaturated monomers may be used, in addition to the various monomers described above, to crosslink polymer (A) having a carboxyl group to increase the molecular weight. It is also preferable to use a polyfunctional ethylenically unsaturated monomer having two or more ethylenically unsaturated groups in combination. However, in this case, the gel fraction was 9 as described above.
It is preferable to use it in a range not exceeding 5% by weight. Examples of the polyfunctional ethylenically unsaturated monomer include ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and trimethylolpropane tri ( Examples thereof include (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, allyl (meth) acrylate, diallyl phthalate, and divinylbenzene.

As the other ethylenically unsaturated monomers, one or a mixture of two or more of the above-mentioned monomers can be used.

Further, as other ethylenically unsaturated monomers, for the purpose of improving the stability during polymerization in an aqueous medium and the storage stability of the polymer particles [X],
Sulfonic acid groups and / or sulfate groups (and / or salts thereof) as long as the water resistance of the resulting film is not reduced.
, An ethylenically unsaturated monomer containing a phosphate ester group, an ethylenically unsaturated monomer containing a nonionic hydrophilic group, and the like.

Specifically, examples of the ethylenically unsaturated monomer containing a sulfonic acid group and / or a sulfate group (and / or a salt thereof) include vinyl sulfonic acids such as vinyl sulfonic acid and styrene sulfonic acid; Allyl group-containing sulfonic acids such as salts, allylsulfonic acid and 2-methylallylsulfonic acid or salts thereof, and (meth) acrylate group-containing sulfones such as (meth) acrylate 2-sulfoethyl and (meth) acrylate 2-sulfopropyl Acids or salts thereof, (meth) acrylamide-containing sulfonic acids such as (meth) acrylamide-t-butylsulfonic acid, and salts thereof, and the like. Ethyl (meth) acryloyl phosphate, nonionic hydrophilic group-containing ethylenic Examples of the saturated monomer include hydroxypolyethylene glycol mono (meth) acrylate, methoxypolyethylene glycol mono (meth) acrylate, phenoxypolyethylene glycol mono (meth) acrylate, and polyethylene glycol di (meth) acrylate. Mixtures of two or more can be used.

The ratio of the carboxyl group-containing ethylenically unsaturated monomer (a-1) to the other ethylenically unsaturated monomer is determined by the acid value of the carboxyl group-containing polymer (A) as described above. It is preferable to use the carboxyl group-containing ethylenically unsaturated monomer (a-1) in such a ratio that the amount becomes 10 to 200, and the amount of the monomer (b) and the polymer component produced therefrom described below are used. It is preferable to select the type and amount in consideration of compatibility.

Specifically, the ratio of the use of the carboxyl group-containing ethylenically unsaturated monomer (a-1) to the other ethylenically unsaturated monomer is 1/9 on a weight basis.
9-50 / 50, more preferably the former / latter = 2
/ 98 to 30/70, and when used in this range, it is preferable in terms of stability during polymerization of the monomer (b) and water resistance of the obtained emulsion film.

In the case where a hydrolyzable silyl group and / or silanol group-containing ethylenically unsaturated monomer (a-2) is used as another ethylenically unsaturated monomer, the monomer (a The amount of -2) used is such that 1 g of the polymer (A) having a carboxyl group has a hydrolyzable silyl group and / or
Alternatively, the use as a silanol group so as to be contained in the range of 0.02 to 0.5 mmol may increase the reactivity with the polysiloxane (C), the dispersion stability of the polymer particles [X],
Further, it is preferable from the viewpoint of film formability of the obtained film.

On the other hand, when an ethylenically unsaturated monomer (a-3) containing a group reactive with a basic nitrogen atom-containing group is used as the other ethylenically unsaturated monomer, The amount of the monomer (a-3) used is such that the monomer (a-3) has a reactivity with the carboxyl group in the carboxyl group-containing ethylenically unsaturated monomer (a-1). In view of the stability at the time of production of the ethylenic polymer (B) and the storage stability of the aqueous polymer dispersion, the amount used is based on 1 mol of the carboxyl group-containing ethylenically unsaturated monomer (a-1). The ethylenically unsaturated monomer (a-2) is 0.1 to
It is preferably in the range of 0.5 mol, and is also preferable in that the gel fraction of the polymer (A) having a carboxyl group can be easily adjusted to 95% by weight or less.

If the monomer (a-3) has no reactivity with the carboxyl group in the carboxyl group-containing ethylenically unsaturated monomer (a-1), It is preferable to use the ethylenically unsaturated monomer (a-3) in a range of 0.1 to 2.0 mol per 1 mol of the unsaturated monomer (a-3). It is preferable because the stability during the production of the ethylenic polymer (B) is improved.

The polymer (A) having a carboxyl group is
When producing from the monomers (a) in an aqueous medium, the polymerization can be carried out without using any emulsifier or other dispersion stabilizer. If necessary, an emulsifier and other dispersion stabilizers can be used as long as the water resistance and the like of the obtained cured product are not reduced.

As the emulsifier, most of known ones can be used, and among them, anionic emulsifier and nonionic emulsifier are preferably used.

Examples of the anionic emulsifier include a sulfate of a higher alcohol, an alkylbenzene sulfonate, a polyoxyethylene alkylphenyl sulfonate, and the like. Examples of the nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene and the like. Examples thereof include ethylene alkyl phenyl ether and polyoxyethylene-polyoxypropylene block copolymer.
Species or a mixture of two or more can be used.

An emulsifier having a polymerizable unsaturated group in the molecule and having a surfactant activity, which is generally called a reactive emulsifier, can also be used. For example, an emulsifier having a sulfonic acid group and a salt thereof can be used. "Latemul S-180" (Kao Corporation)
"Eleminol JS-2", "Eleminol RS"
-30 "(manufactured by Sanyo Kasei Kogyo Co., Ltd.)," Aqualon HS-10, HS-20 "having a sulfate group and a salt thereof (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)," Adecaria Soap SE-10
N "(manufactured by Asahi Denka Kogyo Co., Ltd.) and" New Frontier A-229E "having a phosphate group (Daiichi Kogyo Pharmaceutical Co., Ltd.)
New Frontier N-177E "having a nonionic hydrophilic group (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)," Aqualon RN-10, RN-20, RN-30, RN-5 "
0 "(manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and one or a mixture of two or more of these.

Examples of other dispersion stabilizers other than emulsifiers include polyvinyl alcohol, cellulose ether, starch, maleated polybutadiene, maleated alkyd resin, polyacrylic acid (salt), polyacrylamide, and water-soluble acrylic resin. And the like, or a synthetic or natural water-soluble polymer substance, and one or a mixture of two or more thereof can be used.

The above-mentioned emulsifiers and dispersion stabilizers are used for the purpose of improving stability during polymerization and storage stability.
It is necessary to minimize the amount of the emulsion film in terms of water resistance and the like, and the amount is preferably 2% by weight or less based on the solid content of the polymer (A) having a carboxyl group.

The aqueous medium for polymerizing the polymer (A) having a carboxyl group is not particularly limited, but may be water alone, or a mixture of water and a water-soluble solvent. It may be used as a solution. Examples of the water-soluble solvent used herein include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethyl carbitol, ethyl cellosolve, and butyl cellosolve, and polar solvents such as N-methylpyrrolidone. Mixtures of two or more can be used. When using a mixture of water and a water-soluble solvent, the amount of the water-soluble solvent used can be arbitrarily selected from the viewpoint of stability during polymerization, but the danger of ignition of the resulting polymer aqueous dispersion, It is preferable to minimize the amount of the water-soluble solvent used from the viewpoint of safety and health. For these reasons, it is particularly preferable to use water alone.

As a method for producing the polymer (A) having a carboxyl group in an aqueous medium, water- and carboxyl group-containing ethylenically unsaturated monomers (a-1) are used as essential components. (A), a method of collectively mixing and polymerizing a polymerization catalyst and, if necessary, an emulsifier and a dispersion stabilizer, a method of dropping a monomer (a), a method of dropping a monomer, and a method of mixing water and a monomer (a). It can be manufactured by a method such as a so-called pre-emulsion method in which an emulsifier is previously mixed and dropped.

Of these, the production by the monomer dropping method or the pre-emulsion method is particularly preferred from the viewpoint of stability during polymerization.

In the polymerization, a hydrophilic solvent and a hydrophobic solvent can be added, and known additives can be added. However, the amount used is within a range that does not adversely affect the finally obtained cured product. It is preferable to suppress.

As the polymerization initiator used in the polymerization of the polymer (A) having a carboxyl group, a radical polymerization initiator is used. For example, persulfates such as potassium persulfate and ammonium persulfate, benzoyl peroxide, cumene hydrochloride and the like. There are organic peroxides such as peroxides, hydrogen peroxide, etc., and radical polymerization is performed using only these peroxides, or the peroxide is used in combination with a reducing agent such as sodium acid sulfite or sodium thiosulfate. Azo initiators such as 4,4'-azobis (4-cyanopentanoic acid) and 2,2'-azobis (2-amidinopropane) dihydrochloride. It is also possible.

When it is necessary to adjust the molecular weight of the polymer (A) having a carboxyl group, a compound having a chain transfer ability as a molecular weight modifier when synthesizing the polymer (A) having a carboxyl group may be used. For example, mercaptans such as lauryl mercaptan, octyl mercaptan, dodecyl mercaptan, 2-mercaptoethanol, octyl thioglycolate, and 3-mercaptopropionic acid, or α-methylstyrene dimer may be added.

The polymerization temperature at the time of polymerizing the polymer (A) having a carboxyl group varies depending on the type of the monomer used, the type of the polymerization initiator, and the like. A temperature range of 90 ° C. is preferred.

The carboxyl group of the polymer (A) having a carboxyl group may be produced as it is without neutralizing the ethylenic polymer (B). From the viewpoint of properties, a method in which a part of the carboxyl group is neutralized with a basic substance and used is preferable.

Although the degree of neutralization of the carboxyl group is not particularly limited, the amount of the basic substance used is adjusted to 10 mol% based on the total carboxyl groups in the polymer (A) from the viewpoint of stability during polymerization.
It is preferable to make the above.

As the basic substance to be used as the neutralizing agent, ordinary substances can be used, for example, sodium hydroxide,
Alkali metal compounds such as potassium hydroxide; alkaline earth metal compounds such as calcium hydroxide and calcium carbonate; ammonia; monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dimethylpropylamine, monoethanol Amines, diethanolamine,
Examples thereof include water-soluble organic amines such as triethanolamine, ethylenediamine, and diethylenetriamine. One or a mixture of two or more thereof can be used.

In order to further improve the water resistance of the cured product, it is preferable to use low-boiling amines such as ammonia, monomethylamine, dimethylamine, and trimethylamine which are scattered at room temperature or when heated.

The thus obtained polymer (A) having a carboxyl group forms the outermost shell of the polymer particles [X] of the aqueous dispersion of the curable polymer of the present invention.

Next, a method for producing the polysiloxane (C) in the present invention will be described. In the method for producing an aqueous dispersion of a curable polymer according to the present invention, the polysiloxane (C) is preferably present in an aqueous medium together with the polymer (A) having a carboxyl group. Examples of a method for producing siloxane (C) include the following method.

Specifically, in the step of producing the polymer (A) having a carboxyl group in an aqueous medium, 1) a radical polymerization reaction of ethylenically unsaturated monomers,
A method of producing a polysiloxane (C) by performing a condensation reaction of a silane compound at the same time; 2) producing a polysiloxane (C) by carrying out a condensation reaction of a silane compound first and then producing an ethylenically unsaturated monomer; 3) a method of performing a radical polymerization reaction; 3) a method of performing a radical polymerization reaction of ethylenically unsaturated monomers first to produce a polymer (A) having a carboxyl group, followed by a condensation reaction of a silane compound to perform polysiloxane ( C).

In the above-mentioned production method, in the production step of the polymer (A) having a carboxyl group, a radical polymerization reaction of an ethylenically unsaturated monomer and a condensation reaction of a silane compound are carried out at the same time to obtain a polysiloxane ( The method of producing C) is preferable because the stability at the time of production and the storage stability of the finally obtained aqueous polymer dispersion are improved. It is also preferable from the viewpoint of excellent durability.

In the production process of the polymer (A) having a carboxyl group, the method of simultaneously performing the radical polymerization reaction of the ethylenically unsaturated monomer and the condensation reaction of the silane compound at the same time is as follows. ) A method in which ethylenically unsaturated monomers and a silane compound are simultaneously or sequentially introduced into a reaction system. 2) A silane compound is introduced into a reaction system in advance or sequentially, and then ethylene is introduced. Introducing unsaturated monomers,
Alternatively, 3) the ethylenically unsaturated monomers are introduced into the reaction system in advance or sequentially introduced, and then the silane compound is introduced.
Alternatively, there is a method of sequentially introducing, and it is possible to combine and carry out each method as necessary.

Next, a method for producing the ethylenic polymer (B) having a basic nitrogen atom-containing group will be described. In the production method of the present invention, the production of the ethylenic polymer (B) having a basic nitrogen atom-containing group comprises the production of the carboxyl-containing polymer (A) obtained as described above and the polysiloxane (C). In an aqueous medium containing, a monomer (b) containing an ethylenically unsaturated monomer (b-1) having a basic nitrogen atom-containing group as an essential component can be polymerized.

Here, the ethylenically unsaturated monomer (b-1) having a basic nitrogen atom-containing group is the same as the monomer (b-
The basic nitrogen atom-containing group of 1) reacts with a polyfunctional epoxy compound [Y] to be described later at the time of curing to form a crosslinked structure, thereby providing excellent water resistance, solvent resistance, mechanical strength, and the like. That is, it is possible to exhibit the performance that has been achieved.

The ethylenically unsaturated monomer (b-1) having a basic nitrogen atom-containing group is not particularly limited as long as it can react with the epoxy group of the polyfunctional epoxy compound [Y]. For example, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N -[2- (meth) acryloyloxyethyl] piperidine, N- [2- (meth)
Acryloyloxyethyl] pyrrolidine, N- [2-
(Meth) acryloyloxyethyl] morpholine, 4-
[N, N-dimethylamino] styrene, 4- [N, N-
[Diethylamino] styrene, 2-vinylpyridine, 4-
Tertiary amino group-containing polymerizable monomers such as vinylpyridine; N
-Methylaminoethyl (meth) acrylate, Nt-
Secondary amino group-containing polymerizable monomers such as butylaminoethyl (meth) acrylate; aminomethyl acrylate, aminoethyl acrylate, aminopropyl (meth) acrylate, amino-n-butyl (meth) acrylate,
Butylvinylbenzylamine, vinylphenylamine,
Primary amino group-containing polymerizable monomers such as p-aminostyrene can be exemplified, and one or a mixture of two or more thereof can be used.

In addition, N-vinylformamide can be used as one component of the ethylenically unsaturated monomer.
In this case, once a polymer is produced using N-vinylformamide, the polymer is hydrolyzed to produce a polyvinylamine having a primary amino group, thereby obtaining an ethylenic polymer (B). it can.

Among these, as the ethylenically unsaturated monomer (b-1) having a basic nitrogen atom-containing group,
From the point that the reactivity with the polyfunctional epoxy compound [Y] is remarkably excellent, and the durability and water resistance of the cured product are further improved,
It is preferable to use the tertiary amino group-containing polymerizable monomer.

The monomers (b) used in the present invention include, in addition to the ethylenically unsaturated monomer (b-1) having a basic nitrogen atom-containing group described in detail, and the monomer (b- 1) can be used in combination with an ethylenically unsaturated monomer copolymerizable with
For example, methyl (meth) acrylate, ethyl (meth)
Acrylate, n-butyl (meth) acrylate, i-
Butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
Hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate Acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; 2,
2,2-trifluoroethyl (meth) acrylate,
2,2,3,3-pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, β- (perfluorooctyl)
Fluorine-containing vinyl monomers such as ethyl (meth) acrylate; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl versatate; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, amyl vinyl ether, hexyl Vinyl ethers such as vinyl ether; nitriles of unsaturated carboxylic acid such as (meth) acrylonitrile; vinyl having an aromatic ring such as styrene, α-methylstyrene, vinyltoluene, vinylanisole, α-halostyrene, vinylnaphthalene and divinylstyrene Compounds: isoprene, chloroprene, butadiene,
Examples thereof include ethylene, tetrafluoroethylene, vinylidene fluoride, and N-vinylpyrrolidone, and one or a mixture of two or more of these can be used.

As described above, when the ethylenic polymer (B) having a basic nitrogen atom-containing group contains a hydrolyzable silyl group or a silanol group in addition to the basic nitrogen atom-containing group, It is preferable because the ethylenic polymer (B) and the polysiloxane (C) are linked by the reactive group, and the mechanical strength and solvent resistance of the obtained emulsion film are improved.

As a method for introducing such a hydrolyzable silyl group and / or silanol group into the ethylenic polymer (B), an ethylenically unsaturated monomer containing a hydrolyzable silyl group or silanol group is converted into an ethylenically unsaturated monomer. Unsaturated monomer (b
-2) is preferably used. The compounds described above can be used as the hydrolyzable silyl group or silanol group-containing ethylenically unsaturated monomer.

If necessary, an ethylenically unsaturated monomer containing a reactive functional group other than a basic nitrogen atom-containing group may be used in combination as the other ethylenically unsaturated monomer. Such an ethylenically unsaturated monomer is not particularly limited, for example, the epoxy group-containing polymerizable monomer, hydroxyl group-containing polymerizable monomer,
Amide group-containing polymerizable monomer, methylolamide group and its alkoxylated product-containing polymerizable monomer, aziridinyl group-containing polymerizable monomer, isocyanate group and / or blocked isocyanate group-containing polymerizable monomer, Oxazoline group-containing polymerizable monomer, cyclopentenyl group-containing polymerizable monomer, carbonyl group-containing polymerizable monomer, acetoacetyl group-containing polymerizable monomer, (meth) acrylic acid, crotonic acid, itaconic acid, Maleic acid, fumaric acid, β- (meth)
Acryloyloxyethyl hydrogen succinate,
β- (meth) acryloyloxyethyl hydrogen phthalate, or a half ester thereof or a salt thereof, and the like, and one or a mixture of two or more thereof can be used.

Further, if necessary, other ethylenically unsaturated monomers have two or more ethylenically unsaturated groups for the purpose of increasing the molecular weight by crosslinking the ethylenic polymer (B). It is also possible to use a polyfunctional ethylenically unsaturated monomer in combination, and examples of the polyfunctional ethylenically unsaturated monomer include the compounds described above.

Further, other ethylenically unsaturated monomers may be used to improve the stability during emulsion polymerization and the storage stability of the aqueous dispersion of the polymer particles [X]. As long as the acidity is not reduced, ethylenically unsaturated monomers containing sulfonic acid groups and / or sulfate groups (and / or salts thereof), phosphate group-containing ethylenically unsaturated monomers, and nonionic monomers A hydrophilic group-containing ethylenically unsaturated monomer or the like can be used in combination.

Examples of the ethylenically unsaturated monomer containing a sulfonic acid group and / or a sulfate group (and / or a salt thereof) include the compounds described above.

An ethylenically unsaturated monomer (b-1) having a basic nitrogen atom-containing group described in detail, and the monomer (b-
The ethylenically unsaturated monomer copolymerizable with 1) is selected from the group consisting of the curability with the polyfunctional epoxy compound [Y] and the compatibility with the polymer (A) having a carboxyl group. Type and quantity can be selected. Specifically, the ratio of the monomer (b-1) to the ethylenically unsaturated monomer copolymerizable with the monomer is (former / latter = 0.
The ratio of 5 / 99.5 to 30/70 means that the monomer (b) is stable during polymerization, the curability with the polyfunctional epoxy compound [Y], the water resistance of the obtained cured product, and the like. Is preferred from the viewpoint of various physical properties. Further, as described above, the content of the basic nitrogen atom-containing group in 1 g of the ethylenic polymer (B) is 0.1 g.
It is preferable to appropriately adjust the amount to be used so as to be from 0.05 to 2.0 mmol.

Further, the polymer (A) having a carboxyl group has a reactive functional group other than the carboxyl group,
And, when the reactive functional group can react with the basic nitrogen atom-containing group, the basic nitrogen atom-containing group in the monomer (b-1) is converted into a polymer (A) having a carboxyl group. Needless to say, the polymer may be crosslinked by reaction with the reactive functional group, but a basic nitrogen atom-containing group capable of reacting with the polyfunctional epoxy compound [Y] is contained in the polymer particle [X]. It is preferable to adjust the amount of the monomer (b-1) to be used so as to remain.

Specifically, a monomer having a basic nitrogen atom-containing group (b-based) is used per mole of a reactive group capable of reacting with a basic nitrogen atom-containing group in the polymer (A) having a carboxyl group. It is preferable to use 1) in a ratio of 1.2 to 100 mol.

The method for polymerizing the monomers (b) in the presence of the polymer (A) having a carboxyl group is not specified, but is carried out in an aqueous medium by a usual emulsion polymerization method. be able to.

In this case, the proportion of the monomer (b) to the polymer (A) having a carboxyl group is determined based on the viewpoint of stability during emulsion polymerization and water resistance of the obtained cured product. The ratio is preferably from 1: 1 to 1: 100 based on the weight of the polymer (A) and the monomers (b).

That is, the weight ratio of the monomer (b) to 1 part by weight of the polymer (A) having a carboxyl group was 1%.
When the amount is not less than 1 part by weight, the obtained cured product has good water resistance, and the weight ratio of the monomer (b) to 1 part by weight of the polymer (A) having a carboxyl group is 1 part by weight.
When the amount is not more than 00 parts by weight, the stability of the monomer (b) at the time of emulsion polymerization becomes good.

On the other hand, as described above, from the viewpoint of storage stability as an aqueous dispersion of a curable polymer, the polymer (A) having a carboxyl group and the ethylenic polymer (B) having a basic nitrogen atom-containing group are preferred. ) Is preferably from 1: 1 to 1:20 in terms of solid fraction ratio of (A) :( B).

It is also possible to use emulsifiers and dispersion stabilizers for the purpose of improving the stability during emulsion polymerization and the storage stability. It is preferable to minimize the amount, and in the emulsion polymerization, it is most preferable to carry out the emulsion polymerization of the monomer (b) without newly adding an emulsifier or the like.

That is, when the emulsion polymerization of the monomer (b) is carried out without using an emulsifier or other dispersion stabilizer, the ethylenic polymer ( B) is a polymer (A) having a carboxyl group
Having a structure containing a polymer (A) having a carboxyl group, a polysiloxane (C), and an ethylenic polymer (B) in one particle. It is also preferable from the viewpoint of easily becoming particles.

The specific method of emulsion-polymerizing the monomers (b) is not particularly limited, and includes, for example, 1) a method of preparing a polymer (A) having a carboxyl group and a polysiloxane (C). A method in which the monomers (b) and the polymerization catalyst are mixed and mixed together in an existing aqueous medium, and 2) a polymer having water, the monomers (b), and a carboxyl group in the aqueous medium ( A) a so-called pre-emulsion method in which a pre-mixed mixture of polysiloxane (C) (a small amount of emulsifier if necessary) is added. 3) Carboxyl-containing polymer (A) and polysiloxane (C) are present. A monomer dropping method of dropping the monomer (b) into an aqueous medium, 4) adding the monomer (b) in the presence of the polymer (A) having a carboxyl group and the polysiloxane (C) Polymer having a carboxyl group (A ) And the polysiloxane (C) are swollen with the monomers (b), and then a polymerization is performed by adding a polymerization initiator.

Among the above polymerization methods, particularly, the emulsion polymerization of the monomer (b) can be carried out without using an emulsifier or other dispersion stabilizer, or can be carried out without using it at all. From the viewpoint of the stability of the polymerization of the monomer (b), it is preferable to carry out the method by the monomer dropping method 3).

As a specific method of polymerizing the monomer (b) by the monomer dropping method, for example, an aqueous medium, a polymerization initiator and a polymer having a carboxyl group are placed in a stirred reactor equipped with a dropping funnel. (A), polysiloxane (C)
(In this case, the polymer (A) and the polysiloxane (C)
The polymer chains may penetrate each other,
Then, the temperature of the reactor is raised to the polymerization temperature, and the monomer (b) is dropped from the dropping funnel.

At this time, the inside of the reactor may be an open system, but it is preferable that the inside of the reactor is replaced with an inert gas such as nitrogen.

The polymerization temperature varies depending on the type of the monomer used, the type of the polymerization initiator, and the like.
A temperature range of ~ 90 ° C is suitable, more preferably 40 ° C.
C. to 80C.

The dropping rate of the monomer (b) is determined by the ratio of the polymer (A) having a carboxyl group to the monomer (b),
It is preferable to appropriately adjust the concentration depending on the solid component concentration of the obtained aqueous polymer dispersion.

In the emulsion polymerization of the monomers (b), a hydrophilic solvent and a hydrophobic solvent can be added, and known additives can be added, as long as the effects of the present invention are not impaired. .

The polymerization initiator used here is not particularly limited, and a usual radical polymerization initiator is used, and examples thereof include the above-mentioned compounds. When it is necessary to adjust the molecular weight of the ethylenic polymer (B) obtained by emulsion polymerization of the monomers (b), when the monomer (b) is polymerized, a chain is used as a molecular weight regulator. A compound having mobility can be added.

The molecular weight of the ethylenic polymer (B) having a basic nitrogen atom-containing group thus obtained is not particularly limited, but the weight average molecular weight is 100,00.
It is preferably 0 or more from the viewpoint of various physical properties such as water resistance, solvent resistance and mechanical strength of the cured product.

In the present invention, the polymer particles [X] containing a specific functional group reactive with an epoxy group, obtained as described above, are combined with the polyfunctional epoxy compound [Y]. Thereby, a functional bond is exhibited between the particles during the formation of the polymer particles [X], and the performance of the cured product can be significantly improved. Here, as a method of using the polyfunctional epoxy compound [Y], 1) a method of producing the polymer particles [X] and then adding the polyfunctional epoxy compound [Y] to the aqueous dispersion. ,
2) A method for producing the polymer particles [X] in the presence of the polyfunctional epoxy compound [Y] may be mentioned, but the stability at the time of producing the polymer particles [X] and the curable polymer aqueous dispersion From the viewpoint of storage stability as described above, the method 1) is preferred.

In this method, depending on the properties of the polyfunctional epoxy compound [Y], a water-soluble epoxy compound [Y] may be added as it is, or may be added after diluting in water. Water-insoluble substances can be added as they are, or can be added after being dispersed in water using an emulsifier or the like.

Further, depending on the properties of the polyfunctional epoxy compound [Y], aggregates may be formed when the multifunctional epoxy compound [Y] is added to the aqueous dispersion of the polymer particles [X]. Neutralizing the carboxyl group in the above with the above-mentioned basic substance improves the dispersion stability of the polymer particles [X] and also improves the stability when the polyfunctional epoxy compound [Y] is added, which is preferable. .

In particular, the pH of the aqueous dispersion of the polymer particles [X] before the addition of the polyfunctional epoxy compound [Y] is 7 to 12
When neutralized using a basic substance so as to be in the range of
It is preferable because the stability of the aqueous dispersion of the curable polymer is improved.

Further, a polyfunctional epoxy compound [Y]
The addition time of the polyfunctional epoxy compound [Y] is determined by the curability of the resulting cured product and the properties of the cured product such as water resistance, solvent resistance, and mechanical strength. It is preferable to add it immediately before using the combined aqueous dispersion.

When used as a paint or a finish coating agent, the polyfunctional epoxy compound [Y]
Is preferably added and used immediately before coating.

The amount of the polyfunctional epoxy compound [Y] in the curable polymer aqueous dispersion is not particularly limited, but the curability of the curable polymer aqueous dispersion, the performance of the crosslinked film, and the like are not limited. From the viewpoint of storage stability of the curable polymer aqueous dispersion,
Basic nitrogen atom-containing group 1 contained in polymer particle [X] 1
It is preferable to use it in the range of 0.3 to 3.0 mol with respect to the mol.

The aqueous dispersion of a curable polymer of the present invention thus obtained is crosslinked at room temperature or by heating to form a crosslinked film having good water resistance and solvent resistance. If necessary, a water-soluble or water-dispersible cross-linking agent other than the polyfunctional epoxy compound [Y] can be added for use. Examples of the cross-linking agent include a polyfunctional melamine compound and a polyfunctional melamine compound. Polyamine compound, polyfunctional polyethyleneimine compound, polyfunctional (block)
Examples thereof include an isocyanate compound and a metal salt compound, and these can be used as one kind or as a mixture of two or more kinds.

In addition to the above-mentioned crosslinking agents, a water-soluble or water-dispersible thermosetting resin, for example, a phenol resin, a urea resin, a melamine resin, a urethane resin, or the like can be used as a mixture.

If necessary, fillers, pigments, pH adjusters, film-forming auxiliaries, leveling agents, thickeners, water repellents, defoamers, etc., as long as the desired effects of the present invention are not impaired. Known substances can be appropriately added and used.

The aqueous dispersion of a curable polymer of the present invention gives a cured product having excellent water resistance, solvent resistance and mechanical strength, and its application is wide-ranging. It is useful in the fields where properties are required, such as paint, primer treatment agent, adhesive, film coating agent, resin for textile industry (binder for nonwoven fabric, binder for flocking, etc.), resin for paper processing, glass fiber processing Resin (glass fiber sizing agent, glass paper binder, etc.), mortar modifying resin, etc. Especially,
Paint, film coating, adhesive, resin for textile industry,
In applications used in coating processing in application fields, such as paper processing resins, extremely excellent effects are exhibited as described above.

Further, when the aqueous dispersion of the curable polymer of the present invention is used as a paint or a finishing coating agent, a coated film excellent in various physical properties such as weather resistance, stain resistance and bending resistance can be obtained. .

The paint or finishing coating composition of the present invention can be used in the form of a clear paint or a component usually added to or blended with an aqueous paint, such as a pigment, a filler, an aggregate, a dispersant, a wetting agent,
Thickener, rheology control agent, defoamer, plasticizer,
A film-forming aid, an organic solvent, a preservative, a fungicide, an antioxidant, an ultraviolet absorber, an ultraviolet stabilizer, and the like can be selected according to each use and purpose, and can be used in combination.

[0183]

The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to these examples.

Hereinafter, unless otherwise specified, "%" indicates% by weight and "parts" indicates "parts by weight".

Reference Example AC-1 <Production of Polymer (A) Having Carboxyl Group and Polysiloxane (C)> A reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel was removed. Ionized water 250
The temperature was raised to 80 ° C. while blowing nitrogen.
Under stirring, 0.5 part of ammonium persulfate was added, followed by 49 parts of n-butyl acrylate, 30 parts of methyl methacrylate, and 20 parts of methacrylic acid (as a carboxyl group-containing monomer (a-1)). A mixture [monomer (a)], 30 parts of methyltrimethoxysilane (as a silane compound), 1 part of γ-methacryloxypropyltrimethoxysilane [hydrolyzable silyl group-containing ethylenically unsaturated monomer (a -2) was dropped from a separate dropping funnel over 60 minutes to polymerize. During this time, the temperature inside the reaction vessel was kept at 80 ± 2 ° C.
After the completion of the dropwise addition, the mixture was stirred at the same temperature for 60 minutes.

Thereafter, the content was cooled, and the solid content concentration became 2%.
It was adjusted to 0.0% with deionized water, and filtered through a 100 mesh wire mesh. The aqueous dispersion of the obtained polymer is
Solid content concentration 20.0%, pH 2.3, viscosity 10 cps
(Measured at 25 ° C. with a BM viscometer), and the agglomerates that did not pass through the 100 mesh wire mesh were 0.1% or less (ratio to the generated dispersion). This polymer aqueous dispersion is referred to as [AC-
1].

The polymer particles contained in this [AC-1] are composed of a mixture of the polymer (A) having a carboxyl group and the polysiloxane (C), and have an acid value of the polymer (A) having a carboxyl group. 130 [calculated from the charged ratio of the monomers (a)], and the gel fraction of the polymer particles as a whole was 7
5.0%, and the particle diameter of the polymer particles was 95 nm.
Regarding the weight average molecular weight of [AC-1], the polymer was not completely dissolved in tetrahydrofuran used as an eluent for GPC and a sample dissolving solution, and the molecular weight as a whole could not be measured because of a large amount of gel.

Reference Example AC-2 <Production of polymer (A) having carboxyl group and polysiloxane (C)> A reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen introduction pipe, a thermometer, and a dropping funnel was removed. Ionized water 250
The temperature was raised to 80 ° C. while blowing nitrogen.
Under stirring, 0.5 part of ammonium persulfate is added, followed by 50 parts of n-butyl acrylate, 30 parts of methyl methacrylate, and 20 parts of methacrylic acid [as a carboxyl group-containing monomer (a-1)]. The mixture [monomer (a)] was added dropwise from a dropping funnel over 60 minutes to polymerize. During this time, the temperature inside the reaction vessel was kept at 80 ± 2 ° C.

After completion of the dropwise addition, the mixture was stirred at the same temperature for 60 minutes. [Production of polymer (A) having a carboxyl group] Here, sampling was performed to measure the acid value and the weight average molecular weight of the polymer (A) having a carboxyl group.

Subsequently, under stirring, 30 parts of methyltrimethoxysilane (as a silane compound) was dropped from the dropping funnel over 30 minutes to condense the reaction vessel. During this time, the temperature inside the reaction vessel was kept at 80 ± 2 ° C.

After completion of the dropwise addition, the mixture was stirred at the same temperature for 60 minutes. [Production of polysiloxane (C)] Thereafter, the content was cooled, adjusted with deionized water to a solid content concentration of 20.0%, and filtered through a 100 mesh wire mesh.

The resulting aqueous dispersion of the polymer had a solid content of 20.0%, a pH of 2.3, a viscosity of 20 cps (measured at 25 ° C. with a BM type viscometer), and was not passed through a 100 mesh wire mesh. Agglomerates were 0.5% (to the resulting dispersion ratio). This polymer aqueous dispersion is referred to as [AC-2].

The polymer particles contained in [AC-2] consist of a mixture of the polymer (A) having a carboxyl group and the polysiloxane (C), and the acid value of the polymer (A) having a carboxyl group is 130 (calculated from the charged ratio of the monomers (a)), and the gel fraction of the polymer particles as a whole was 4
3.0%, and the particle diameter of the polymer particles was 120 nm.
Polymer (A) having a carboxyl group in [AC-2]
Had a weight average molecular weight of 560,000.

Reference Example AC-3 <Production of Polymer (A) Having Carboxyl Group and Polysiloxane (C)> In the same reaction vessel as Reference Example AC-1,
Add 250 parts of deionized water, and use Adecaria Soap SE-1025N [manufactured by Asahi Denka Co., Ltd .; α-sulfo-
ω- (1- (nonylphenoxy) methyl-2- (2-propenyloxy) ethoxy-poly- (oxy-1-2-
Aqueous solution of ammonium salt of ethanediyl), solid content 25
%] (Solid part 0.3 part) was added, and the temperature was raised to 80 ° C. while blowing nitrogen with stirring to dissolve the emulsifier.

Thereafter, polymerization was carried out in the same manner as in Reference Example 1. An aqueous dispersion [AC-3] of a polymer was obtained in the same manner as in Reference Example AC-1, except that the above-mentioned emulsifier was added and a monomer mixture shown in Table 1 below was used.

The acid value of the polymer (A) having a carboxyl group contained in [AC-3], the gel fraction of the whole polymer particles, and the particle size of the polymer particles are also shown in Table 1 (1). It was as it was.

REFERENCE EXAMPLES AC-4 and AC-5 <Production of Polymer (A) Having Carboxyl Group and Polysiloxane (C)> Glycidyl methacrylate [monomer and basic nitrogen atom-containing group as a monomer mixture] As a monomer (a-3) containing a reactive group having the formula:
Aqueous dispersions [AC-4] and [AC-5] of the polymer were obtained in exactly the same manner as in Reference Example 3 except that those shown in the table were used.
I got

The acid value of the polymer (A) having a carboxyl group contained in [AC-4] and [AC-5], the gel fraction of the whole polymer particles, and the particle size of the polymer particles are as follows. As shown in Table 2 below.

Reference Example AC-6 <Production of polymer (A) having carboxyl group and polysiloxane (C)> In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel, isopropyl was added. 100 parts of alcohol was added, and the temperature was raised to 80 ° C. while blowing nitrogen.

Under stirring, a monomer composed of 90 parts of acrylic acid [as the carboxyl group-containing monomer (a-1)], 10 parts of n-dodecyl mercaptan, and 1 part of 2,2'-azobisisobutyronitrile The mixture [monomer (a)] was mixed with 120
It was dropped over a period of minutes and polymerized. During this time, the temperature inside the reaction vessel was kept at 80 ± 2 ° C.

After the completion of the dropwise addition, the mixture was stirred at the same temperature for 120 minutes. Thereafter, the content is cooled, and the solid concentration is 50.2%.
A solution of the polymer was obtained. The obtained polymer solution was neutralized by adding 75 parts of 28% ammonia water and 100 parts of deionized water to obtain a polymer aqueous solution.

The solid concentration was adjusted to 20.0% with deionized water, and the mixture was filtered through a 100 mesh wire mesh. The obtained aqueous polymer solution had a solid content of 20.0% and a pH of 8.
5, viscosity 100 cps (measured at 25 ° C. with a BM viscometer), acid value 700, weight average molecular weight 9,000, 100
Aggregates that did not pass through the mesh wire mesh were 0.1% or less (ratio to the resulting dispersion). [Production of polymer (A) having carboxyl group] The polymer aqueous solution 200 obtained above was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel.
The temperature was raised to 80 ° C. while blowing nitrogen.

Under stirring, 20 parts of methyltrimethoxysilane (as a silane compound) were added dropwise from a dropping funnel over 30 minutes to condense. During this time, the temperature inside the reaction vessel was 80 ± 2.
C. was maintained.

After completion of the dropwise addition, the mixture was stirred at the same temperature for 60 minutes. (Production of polysiloxane (C))
The mixture was adjusted to 0% with deionized water, and filtered with a 100 mesh wire mesh.

The obtained aqueous polymer solution had a solid concentration of 2
0.0%, pH 8.3, viscosity 120 cps (measured at 25 ° C. with a BM type viscometer), and the amount of aggregates that did not pass through a 100 mesh wire mesh was 2.0% (the ratio of the produced dispersion liquid). This polymer aqueous solution is referred to as [AC-6].

The acid value of the polymer (A) having a carboxyl group contained in [AC-6] and the gel fraction of the polymer particles as a whole are as shown in Table 1-3.

Reference Example AC-7 <Production of polymer (A) having carboxyl group and polysiloxane (C)> A reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel was charged with isopropyl. 100 parts of alcohol was added, and the temperature was raised to 80 ° C. while blowing nitrogen.

With stirring, 50 parts of n-butyl acrylate,
A monomer mixture comprising 20 parts of styrene, 20 parts of methyl methacrylate, 10 parts of methacrylic acid [as the carboxyl group-containing monomer (a-1)], and 2 parts of t-butyl peroxybenzoate is dropped and polymerized over 180 minutes. I was sorry. During this time, the temperature inside the reaction vessel was kept at 80 ± 2 ° C. After completion of the dropwise addition, the mixture was stirred at the same temperature for 120 minutes.

Thereafter, the content was cooled, and the solid concentration was 5%.
A 0.5% polymer solution was obtained. Next, the obtained polymer solution was neutralized by adding 7 parts of 28% aqueous ammonia, and then 370 parts of deionized water was added over 60 minutes to obtain an aqueous dispersion of the polymer. The solid content was adjusted to 20.0% with deionized water and filtered through a 100 mesh wire mesh.

The resulting aqueous polymer dispersion had a solid content of 20.0%, a pH of 8.5, a viscosity of 100 cps (measured at 25 ° C. with a BM type viscometer), an acid value of 65 and a weight average molecular weight of 4
It was 7,000, and the agglomerate that did not pass through the 100 mesh wire mesh was 1.0% (the ratio of the generated dispersion liquid). [Production of polymer (A) having carboxyl group] The polymer aqueous solution 200 obtained above was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel.
The temperature was raised to 80 ° C. while blowing nitrogen.

Under stirring, 20 parts of methyltrimethoxysilane (as a silane compound) were added dropwise from a dropping funnel over 30 minutes to condense. During this time, the temperature inside the reaction vessel was 80 ± 2.
C. was maintained.

After the completion of the dropwise addition, the mixture was stirred at the same temperature for 60 minutes. [Production of polysiloxane (C)] The solid concentration was adjusted to 20.0% with deionized water, and the mixture was filtered through a 100-mesh wire mesh.

The obtained polymer aqueous dispersion had a solid content of 20.0%, a pH of 8.4, a viscosity of 110 cps (measured at 25 ° C. with a BM type viscometer), and was agglomerated without passing through a 100 mesh wire mesh. The product was 3.5% (ratio to the resulting dispersion). The aqueous dispersion of this polymer is referred to as [AC-7].

The acid value, the weight average molecular weight, the gel fraction of the polymer particles as a whole, and the particle size of the polymer particles of the polymer (A) having a carboxyl group contained in [AC-7] are as follows.
As shown in Table 3 below.

The acid value, weight average molecular weight, gel fraction, and particle size in Tables 1 to 3 in Table 1 were measured by the following methods. <Acid value> A sample was applied on a glass plate with a 3 mil applicator and dried at room temperature for 1 hour to form a semi-dry film.
The obtained film was peeled off from the glass plate, 1 g was precisely weighed and dissolved in 100 g of tetrahydrofuran to obtain a measurement sample.

The measurement was performed by a neutralization titration method using an aqueous solution of potassium hydroxide. Two drops of phenolphthalein were added to the tetrahydrofuran solution in which the sample was dissolved, and 0.1
A point at which the color of the solution changes from colorless to light pink by dropping an aqueous solution of potassium hydroxide N was taken as an end point. The consumption of potassium hydroxide at that time was measured, and the mg was used as the polymer (A) having a carboxyl group. Acid value.

[0217] The sample obtained by simultaneously producing the polymer (A) having a carboxyl group and the polysiloxane (C) and the sample in which the polymer (A) was not dissolved in tetrahydrofuran were measured by this method. Is impossible, the calculated value obtained from the charged amount of the carboxyl group-containing monomer (a-1) used in the production of the polymer (A) having a carboxyl group is calculated based on the amount of the polymer (A) having a carboxyl group. Calculated as acid value.

<Weight average molecular weight> The weight average molecular weight was measured by gel permeation chromatography (GPC method).

A sample was applied on a glass plate with a 3 mil applicator and dried at room temperature for 1 hour to form a semi-dry film. The obtained film was peeled from the glass plate, and the film 0.4
g was dissolved in 100 g of tetrahydrofuran to obtain a measurement sample.

A high performance liquid chromatograph LC-08 manufactured by Nippon Kagaku Kogyo KK was used as a measuring device. The column is
Packed columns A-800P, A-8 manufactured by Showa Denko KK
06, A-805, A-803, and A-802 were used in combination.

As a standard sample, standard polystyrene manufactured by Showa Denko KK and Toyo Soda Co., Ltd. (molecular weight: 4.48 million,
4.25 million, 28.88 million, 2.75 million, 1.85 million, 860,000
50,000, 411,000, 35.5 million, 190,000, 160,000, 9.
640,000, 50,000, 3.79, 1.98, 1.96,
5570, 4000, 2980, 2030, 500).

Using tetrahydrofuran as an eluent and a sample dissolving solution, a flow rate of 1 mL / min and a sample injection amount of 50
The weight average molecular weight was measured using an RI detector at 0 μL and a sample concentration of 0.4%.

<Gel Fraction> The gel fraction was measured as acetone-insoluble matter. The film thickness after drying on a glass plate is 0.5
mm, and dried at room temperature for 7 days. The film was peeled off from the glass plate.
The test piece was cut into a square of 0 mm. Next, the weight (G ₀ ) of the test piece before immersion in acetone was measured in advance, and the acetone-insoluble portion of the test piece after immersion in an acetone solution for 24 hours at room temperature was separated. The weight (G ₁ ) after drying for a time was measured, and the gel fraction was determined according to the following method.

[0224]

(Equation 1) G ₀ : Weight of test piece before immersion in acetone G ₁ : Dry weight of insoluble portion of test piece after immersion in acetone

<Particle Size> The particle size was measured using a submicron particle analyzer; Coulter N4 (manufactured by Coulter)
And the value of the number average particle diameter was shown as the particle diameter.

[0226]

[Table 1]

[0227]

[Table 2]

[0228]

[Table 3]

The aggregates in Tables 1 to 3 in Table 1 are the amount of aggregates that have not passed through a 100-mesh wire net after the completion of polymerization of the polymer (A) having a carboxyl group in an aqueous medium. Yes, expressed as% by weight of the ratio of dispersion to product.

The acid values in Tables 1 to 3 in Table 1 indicate the acid value of only the polymer (A) having a carboxyl group, and the asterisks indicate the actual measurement of the acid value of the polymer (A) having a carboxyl group. This indicates that the calculated values obtained from the composition ratios of the raw materials used are described.

The weight average molecular weight in Tables 1 to 3 in Table 1 indicates the weight average molecular weight of only the polymer (A) having a carboxyl group, and the weight average molecular weight of the polymer (A) having a carboxyl group and the polysiloxane (C). The molecular weight was not measured for the reference examples produced simultaneously.

The formal names of the abbreviations in Tables 1 to 3 are shown below. BA; n-butyl acrylate MAA; methacrylic acid MMA; methyl methacrylate MAPTMS; γ-methacryloxypropyl trimethoxysilane MTMS; methyltrimethoxysilane MTES; methyltriethoxysilane CHMA; cyclohexyl methacrylate MTES; methyltriethoxysilane GMA; glycidyl methacrylate AA; acrylic acid D-SH; n-dodecyl mercaptan St; styrene THF; tetrahydrofuran rear soap SE1025;
25N (Asahi Denka Co., Ltd. emulsifier)

Reference Example B-1 <Production of ethylenic polymer (B) having a basic nitrogen atom-containing group> A reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen introduction pipe, a thermometer, and a dropping funnel was removed. 70 parts of ion water,
Aqueous dispersion of the polymer obtained in Reference Example AC-1 [AC-
1] 125 parts (solid part: 25 parts) were added, and the temperature was raised to 80 ° C. while blowing nitrogen.

Under stirring, 0.3 part of ammonium persulfate was added, followed by 43 parts of n-butyl acrylate, 55 parts of methyl methacrylate, and 2 parts of dimethylaminoethyl methacrylate [monomer having basic nitrogen atom-containing group ( b
A monomer mixture [monomer (b)] was dropped over 120 minutes and polymerized. During this time, the temperature inside the reaction vessel was kept at 80 ± 2 ° C. After the completion of the dropwise addition, the mixture was stirred at the same temperature for 60 minutes.

Thereafter, the content was cooled, and the solid concentration was 4%.
It was adjusted to 0.0% with deionized water, and filtered through a 100 mesh wire mesh. The obtained polymer aqueous dispersion had a solid content concentration of 40.0%, a pH of 4.5, and a viscosity of 180 cps.
(Measured at 25 ° C. with a BM viscometer), and the agglomerates that did not pass through the 100-mesh wire mesh were 5.0% (the ratio of the generated dispersion liquid). The aqueous dispersion of this polymer is referred to as [B-1].

This polymer aqueous dispersion [B-1] was prepared such that the content of the basic nitrogen atom-containing group in the ethylenic polymer (B) was 0.13 mg [single amount] in 1 g of the ethylenic polymer (B). Monomer (b) having a basic nitrogen atom-containing group in the class (b)
-1) calculated from the charged amount].

The acid value and the content of the basic nitrogen atom-containing group in the whole polymer aqueous dispersion are calculated from the charged amounts of the polymer (A) having a carboxyl group and the monomer (b). The acid value per 1 g of the solid content of the polymer aqueous dispersion was 25, and the content of the basic nitrogen atom-containing group was 0.10 mg.
Becomes

Further, when the content of the polysiloxane (C) was calculated from the charged amount of the silane compound (calculated on the assumption that the silane compound was completely condensed), the total amount of the polymer (A) and the polymer (B) was calculated. The weight of the polysiloxane (C) per 100 parts by weight is about 3.0 parts.

Reference Example B-2 <Production of ethylenic polymer (B) having basic nitrogen atom-containing group> In a reaction vessel similar to Reference Example B-1, 50 parts of deionized water, Reference Example AC-1 125 parts (solid part: 25 parts) of the aqueous dispersion [AC-1] of the polymer obtained in the above was added,
A mixture of 1.5 parts of 28% aqueous ammonia and 20 parts of deionized water was added over 1 hour to adjust the pH of the system to 6, followed by 43 parts of n-butyl acrylate, 55 parts of methyl methacrylate, and dimethylamino. A monomer mixture [monomer (b)] consisting of 2 parts of ethyl methacrylate [as monomer (b-1) having a basic nitrogen atom-containing group] was mixed with 120 parts of
The mixture was dropped and polymerized over a period of minutes to obtain a polymer aqueous dispersion in the same manner as in Reference Example B-1.

The obtained polymer aqueous dispersion had a solid content of 40.0%, a pH of 6.5, and a viscosity of 270 cps (measured at 25 ° C. with a BM type viscometer). The product was 0.1% (relative to product dispersion). This polymer aqueous dispersion is referred to as [B-2].

The aqueous polymer dispersion [B-2] was prepared such that the content of the basic nitrogen atom-containing group in the ethylenic polymer (B) was 0.13 mg [single amount] in 1 g of the ethylenic polymer (B). Monomer (b) having a basic nitrogen atom-containing group in the class (b)
-1) calculated from the charged amount].

Further, the acid value and the content of the basic nitrogen atom-containing group in the whole aqueous polymer dispersion are calculated from the charged amounts of the polymer (A) having a carboxyl group and the monomers (b). The acid value per 1 g of the solid content of the polymer aqueous dispersion was 25, and the content of the basic nitrogen atom-containing group was 0.10 mg.
Becomes

Further, when the content of the polysiloxane (C) was calculated from the charged amount of the silane compound (calculated on the assumption that the silane compound was completely condensed), the total amount of the polymer (A) and the polymer (B) was calculated. The weight of the polysiloxane (C) per 100 parts by weight is about 3.0 parts.

Reference Examples B-3 and B-4 <Production of ethylenic polymer (B) having a basic nitrogen atom-containing group> As a monomer mixture, γ-methacryloxypropyltrimethoxysilane [hydrolyzable As a silyl group-containing monomer (b-2)], an aqueous polymer dispersion [B-3] was prepared in exactly the same manner as in Reference Example B-2, except that the one shown in Table 1 below was used. ] And [B-4].

The pH of [B-3] and [B-4] was 10
The amount of agglomerates that did not pass through the 0-mesh wire mesh was as described in 1 of Table 2. The acid value, the content of the basic nitrogen atom-containing group, and the content of the polysiloxane calculated from the charged amounts of the raw materials [B-3] and [B-4] are shown in Table 3-1.

Reference Examples B-5 to B-10 <Production of Ethylenic Polymer (B) Having Basic Nitrogen-atom-Containing Group> In Reference Example B-2 or B-3, Amount and type (Reference Examples AC-2 to AC-
7) In the same manner as in Reference Example B-2 or B-3 except that the kind of the monomer mixture is as shown in Tables 2 and 3 in Table 2, the aqueous polymer dispersions [B-5] to [B-10] was obtained.

The pH of [B-5] to [B-10],
The amount of aggregates that did not pass through the 00 mesh wire mesh was as described in Tables 2 and 3. Also, [B-5] to [B-
The acid value, the content of the basic nitrogen atom-containing group, and the content of the polysiloxane calculated from the charged amounts of the raw materials in [10] are shown in Tables 1 and 2 in Table 3.

Reference Example B-11 <Production of Polymer Aqueous Dispersion [B-11]> Stirrer, reflux condenser, nitrogen inlet tube, thermometer, dropping funnel for dropping monomer mixture, dropping funnel for dropping polymerization catalyst 130 parts of deionized water and Adecaria Soap SE as emulsifier
-1025N [manufactured by Asahi Denka Co., Ltd .; α-sulfo-ω- (1
-Aqueous solution of ammonium salt of (nonylphenoxy) methyl-2- (2-propenyloxy) ethoxy-poly- (oxy-1--2-ethanediyl), solid content 25%] 1.
2 parts were added, and the temperature was raised to 80 ° C. while blowing nitrogen with stirring to dissolve the emulsifier. Under stirring, 0.2 part of ammonium persulfate was added, followed by 7.5 parts of n-butyl acrylate, 8 parts of cyclohexyl methacrylate, and 2 parts of glycidyl methacrylate [containing a reactive group reactive with a basic nitrogen atom-containing group. Monomer (a-3)), 2 parts of methacrylic acid (as a carboxyl group-containing monomer (a-1)) [monomer (a)] and methyltrimethoxy A monomer mixture consisting of 10 parts of silane (as a silane compound) and 0.5 part of γ-methacryloxypropyltrimethoxysilane [as a hydrolyzable silyl group-containing ethylenically unsaturated monomer (a-2)] The polymerization was carried out by dropping from a separate dropping funnel over 60 minutes, and the temperature inside the reaction vessel was kept at 80 ± 2 ° C.

After the completion of the dropwise addition, the temperature was maintained at the same temperature for 60 minutes. [Production of Polymer (A) Having Carboxyl Group and Polysiloxane (C)] Thereafter, 3 parts of 5% aqueous ammonia were added dropwise at the same temperature over 30 minutes.

Subsequently, 28 parts of 2-ethylhexyl acrylate, 35 parts of cyclohexyl methacrylate, 14 parts of methyl methacrylate, and 3 parts of dimethylaminoethyl methacrylate [as monomer (b-1) having a basic nitrogen atom-containing group] The monomer mixture [monomer (b)] and 30 g of a 10% aqueous ammonium persulfate solution were dropped from separate dropping funnels over 180 minutes to polymerize. During this time, the temperature inside the reaction vessel was kept at 80 ± 2 ° C.

After the completion of the dropwise addition, the temperature was maintained at the same temperature for 60 minutes. [Production of Ethylenic Polymer (B) Having Basic Nitrogen Atom-Containing Group] Then, the content was cooled, and the solid content was adjusted with deionized water so as to have a concentration of 40.0%. And filtered.

The obtained aqueous polymer dispersion had a solid content concentration of 40.0%, a pH of 6.5, a viscosity of 300 cps (measured at 25 ° C. with a BM type viscometer), and did not pass through a 100 mesh wire mesh. The product was 1.0% (relative to the resulting dispersion). This polymer aqueous dispersion is referred to as [B-11].

Table 2 in Table 3 shows the acid value, the content of the basic nitrogen atom-containing group, and the content of the polysiloxane calculated from the charged amounts of the raw materials [B-11].

Comparative Reference Example C-1 <Preparation of Comparative Polymer Aqueous Dispersion> To prepare a pre-emulsion of a monomer mixture, 30 parts of deionized water was placed in a pre-emulsion mixing container, and emulgen was used as an emulsifier. 950 [manufactured by Kao Corporation; polyoxyethylene alkylphenyl ether, solid content 100%] 4 parts were added,
Stir to dissolve.

The container is charged with n-butyl acrylate 40
Parts, 57 parts of cyclohexyl methacrylate and 3 parts of dimethylaminoethyl methacrylate were sequentially added and stirred to prepare a pre-emulsion of a monomer mixture.

In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel, 100 parts of deionized water was charged, and the temperature was raised to 80 ° C. while blowing nitrogen. Under stirring, 0.3 part of ammonium persulfate was added, and then a pre-emulsion of the monomer mixture and 10 parts of methyltrimethoxysilane were added dropwise from separate dropping funnels over 180 minutes to polymerize. During this time, the temperature inside the reaction vessel was 80 ± 2.
C. was maintained. After the completion of the dropwise addition, the mixture was stirred at the same temperature for 60 minutes.

Thereafter, a polymer aqueous dispersion [C-1] was obtained in the same manner as in Reference Example B-1. The p of this [C-1]
H, the amount of aggregates not passing through the 100 mesh wire mesh is 4 in Table 2
It was as described in addition.

Table 3 in Table 3 shows the acid value, the content of the basic nitrogen atom-containing group, and the content of the polysiloxane calculated from the charged amounts of the raw materials [C-1]. Comparative Reference Example C-2 <Production of Comparative Polymer Aqueous Dispersion> A reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, a dropping funnel for dropping a monomer mixture, and a dropping funnel for dropping a polymerization catalyst. In addition, 130 parts of deionized water, Adecaria Soap SE- as an emulsifier
1025N [manufactured by Asahi Denka Co., Ltd .; α-sulfo-ω- (1-
Aqueous solution of ammonium salt of (nonylphenoxy) methyl-2- (2-propenyloxy) ethoxy-poly (oxy-1--2-ethanediyl), solid content 25%] 1.2
The mixture was heated to 80 ° C. while blowing nitrogen under stirring to dissolve the emulsifier.

Under stirring, 0.2 part of ammonium persulfate was added, and then a monomer mixture comprising 8 parts of n-butyl acrylate, 8 parts of cyclohexyl methacrylate, 2 parts of glycidyl methacrylate and 2 parts of methacrylic acid was added dropwise to the dropping funnel. For 60 minutes to polymerize. During this time,
The temperature inside the reaction vessel was kept at 80 ± 2 ° C. After completion of the dropwise addition, the temperature was maintained at the same temperature for 60 minutes.

Thereafter, 3 parts of 5% aqueous ammonia was dropped at the same temperature over 30 minutes. Subsequently, a monomer mixture comprising 28 parts of 2-ethylhexyl acrylate, 35 parts of cyclohexyl methacrylate, 14 parts of methyl methacrylate, and 3 parts of dimethylaminoethyl methacrylate,
30 g of 0% ammonium persulfate aqueous solution was added dropwise from separate dropping funnels over 180 minutes to polymerize. During this time, the temperature inside the reaction vessel was kept at 80 ± 2 ° C. After the completion of the dropwise addition, the mixture was stirred at the same temperature for 60 minutes.

Thereafter, the content was cooled and the solid content concentration was reduced to 4%.
It was adjusted to 0.0% with deionized water, and filtered through a 100 mesh wire mesh. The pH of this [C-2] and the amount of agglomerates that did not pass through a 100-mesh wire mesh were as shown in Table 2-4.

Table 3 in Table 3 shows the acid value, the content of the basic nitrogen atom-containing group, and the content of the polysiloxane calculated from the charged amounts of the raw materials [C-2].

[0263]

[Table 4]

[0264]

[Table 5]

[0265]

[Table 6]

[0266]

[Table 7]

The aggregates in Tables 1 to 3 in Table 2 are defined as 100% after polymerization of the monomer (b) in the aqueous medium.
The amount of agglomerates that did not pass through the mesh wire mesh, and was expressed in terms of% by weight based on the ratio of the resulting dispersion.

The formal names of the abbreviations in Tables 1 to 3 are shown below. BA; n-butyl acrylate MMA; methyl methacrylate DMAEMA; dimethylaminoethyl methacrylate MAPTMS; γ-methacryloxypropyltrimethoxysilane CHMA; cyclohexyl methacrylate HEMA; 2-hydroxyethyl methacrylate GMA; glycidyl methacrylate 2-EHA; 2-ethylhexyl acrylate Em -950; Emulgen 950 (manufactured by Kao Corporation; emulsifier)

[0269]

[Table 8]

[0270]

[Table 9]

[0271]

[Table 10]

Example 1 <Production of curable polymer aqueous dispersion> 100 parts of the polymer aqueous dispersion [B-1] obtained in Reference Example B-1 was placed in a mixing vessel equipped with a stirrer and a thermometer. (As an aqueous dispersion containing the polymer particles [X]), 1.5 parts of Denacol EX-313 [manufactured by Nagase Kasei Kogyo Co., Ltd .; glycerol polyglycidyl ether] at 25 ° C. with stirring (polyfunctional) And then stirred for 30 minutes, adjusted with deionized water to a solid concentration of 40.0%, and filtered through a 100-mesh wire mesh to obtain a curable composition. An aqueous polymer dispersion was obtained.

The obtained aqueous dispersion of curable polymer had a solid content of 40.0%, a pH of 4.8, and a viscosity of 150 cps (B
(Measured at 25 ° C. with an M-type viscometer), and the amount of agglomerates that did not pass through the 100-mesh wire mesh was 5.0% (the ratio of the produced dispersion liquid).

Example 2 <Preparation of curable polymer aqueous dispersion> 100 parts of the polymer aqueous dispersion [B-1] obtained in Reference Example B-1 was placed in the same mixing vessel as in Example 1. Put, 25% ammonia water 1.8
Was added to adjust the pH of the aqueous polymer dispersion to 8.5.

Thereafter, under stirring at 25 ° C., Denacol E
Add 1.5 parts of X-313, stir for 30 minutes, adjust the solid content concentration to 40.0% with deionized water, filter through a 100-mesh wire gauze, and disperse the curable polymer aqueous solution. A liquid was obtained.

The obtained aqueous dispersion of curable polymer had a solid content of 40.0%, a pH of 8.5, and a viscosity of 230 cps (B
(Measured with an M-type viscometer at 25 ° C.), and the amount of aggregates that did not pass through a 100-mesh wire mesh was 0.1% or less (the ratio of the generated dispersion liquid).

Examples 3 to 18 <Production of aqueous dispersion of curable polymer> In Examples 1 and 2, the type of aqueous dispersion of polymer (polymer particles [X]) (Reference Examples B-1 to B- 11), p of the aqueous polymer dispersion
H, a curable polymer aqueous dispersion was obtained in the same manner as in Example 1 or 2, except that the kind and amount of the polyfunctional epoxy compound [Y] were as shown in Table 4 below.

The pH of the obtained aqueous dispersion of curable polymer was
The amount of agglomerates that did not pass through the 100 mesh wire mesh was 1 to 4 in Table 4.
No. 3 was used.

Comparative Example 1 <Production of Comparative Curable Polymer Aqueous Dispersion> In the same mixing container as in Example 1, the polymer aqueous dispersion [C-1] obtained in Comparative Reference Example C-1 was placed. 7. Add 100 parts and add 1.5 parts of 25% aqueous ammonia to adjust the pH of the aqueous polymer dispersion to 8.
Adjusted to 7.

Thereafter, under stirring at 25 ° C., Denacol EX
-313 1.5 parts was added, followed by stirring for 30 minutes, adjusting the solid content concentration to 40.0% with deionized water, filtering through a 100 mesh wire mesh, and setting the aqueous curable polymer aqueous solution. A dispersion was obtained.

The obtained aqueous dispersion of curable polymer had a solid content of 40.0%, a pH of 8.7, and a viscosity of 520 cps (B
(Measured with an M-type viscometer at 25 ° C.), and the amount of aggregates that did not pass through a 100-mesh wire mesh was 0.1% or less (the ratio of the generated dispersion liquid).

Comparative Examples 2 to 5 <Preparation of Comparative Curable Polymer Aqueous Dispersion> In Comparative Example 1, the types of the polymer aqueous dispersions (Comparative Reference Examples C-2, B-8, B-10 , B-11), the pH of the aqueous polymer dispersion, and the type, amount and presence or absence of the polyfunctional epoxy compound [Y] as shown in Table 4 below, in the same manner as in Comparative Example 1. A curable polymer aqueous dispersion was obtained.

The pH of the obtained aqueous dispersion of curable polymer was
The amount of agglomerates that did not pass through the 100-mesh wire mesh was as shown in Table 4-4.

[0284]

[Table 11]

[0285]

[Table 12]

[0286]

[Table 13]

[0287]

[Table 14]

The aggregates in Tables 1 to 4 are 100-mesh wire nets generated when the polyfunctional epoxy compound [Y] is added to the aqueous polymer dispersion containing the polymer particles [X]. The amount of unagglomerated agglomerates, expressed as a percentage by weight of the resulting dispersion
Displayed with.

The details of the compound used as the polyfunctional epoxy compound [Y] in Tables 1 to 4 are shown below. Denacol EX-313 [manufactured by Nagase Kasei Kogyo; glycerol polyglycidyl ether] Denacol EX-614B [manufactured by Nagase Kasei Kogyo; sorbitol polyglycidyl ether] KBM-403 [manufactured by Shin-Etsu Chemical Co., Ltd .; Glycidoxypropyltrimethoxysilane] Dick Fine EM-100 [manufactured by Dainippon Ink and Chemicals, Inc .; aqueous dispersion of bisphenol A type solid epoxy resin: solid content 50%] KBE-402 [Shin-Etsu Chemical Co., Ltd.] [Gamma] -glycidoxypropylmethyldiethoxysilane] KBM-303 [Shin-Etsu Chemical Co., Ltd .; 2- (3 ', 4'-epoxycyclohexyl) ethyltrimethoxysilane]

Example 19 <Production of curable polymer aqueous dispersion> A reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer and a dropping funnel was charged with 70 parts of deionized water, Reference Example AC-4. 125 parts (solid part: 25 parts) of the aqueous polymer dispersion [AC-5] obtained in the above was added, and the temperature was raised to 80 ° C. while blowing nitrogen.

Under stirring, 0.3 part of ammonium persulfate was added, followed by 43 parts of n-butyl acrylate, 55 parts of methyl methacrylate, 2 parts of dimethylaminoethyl methacrylate, and Denacol EX-211 [manufactured by Nagase Kasei Kogyo Co., Ltd.] Neopentyl glycol diglycidyl ether], and a monomer mixture consisting of 3 parts (as a polyfunctional epoxy compound [Y]) was dropped and polymerized over 120 minutes. During this time, the temperature inside the reaction vessel was kept at 80 ± 2 ° C.
After the completion of the dropwise addition, the mixture was stirred at the same temperature for 60 minutes.

Thereafter, the content was cooled, and the solid component concentration became 4%.
It was adjusted to 0.0% with deionized water, and filtered through a 100 mesh wire mesh. The resulting polymer aqueous dispersion had a solid content of 40.0%, a pH of 6.8, and a viscosity of 250 cps.
(Measured at 25 ° C. with a BM viscometer), and the agglomerates that did not pass through the 100 mesh wire mesh were 3.5% (the ratio of the generated dispersion liquid). This aqueous polymer dispersion is referred to as an aqueous curable polymer dispersion [E-19].

This curable polymer aqueous dispersion [E-19]
Means that the acid value of the polymer (A) having a carboxyl group is 6
5. The content of the basic nitrogen atom-containing group in the ethylenic polymer (B) is 0.13 mg per 1 g of the ethylenic polymer (B).
[Calculated from the charged amount of the monomer (b-1) having a basic nitrogen atom-containing group in the monomers (b)].

Further, the acid value and the content of the basic nitrogen atom-containing group of the whole aqueous polymer dispersion are calculated from the charged amounts of the polymer (A) having a carboxyl group and the monomer (b). The acid value per 1 g of the solid content of the aqueous polymer dispersion is 13, and the content of the basic nitrogen atom-containing group is 0.10 m.
g, the content of the polysiloxane (C) is 3.8 parts based on 100 parts by weight of the total amount of the polymer (A) and the polymer (B).

Example 20 <Preparation of Curable Polymer Aqueous Dispersion> In the same reaction vessel as in Example 19, 70 parts of deionized water, the polymer aqueous dispersion obtained in Reference Example AC-4 [AC- 4] 125 parts (solid part 2
5 parts) and heated to 80 ° C. while blowing nitrogen.

While stirring, 0.3 part of ammonium persulfate was added, followed by 43 parts of n-butyl acrylate, 55 parts of methyl methacrylate, 2 parts of dimethylaminoethyl methacrylate, and KBE-403 [manufactured by Shin-Etsu Chemical Co., Ltd .;
[Gamma-glycidoxypropyltriethoxysilane] 2 parts (as polyfunctional epoxy compound [Y]) was dropped and polymerized over 120 minutes. During this time, the temperature inside the reaction vessel was kept at 80 ± 2 ° C. After the completion of the dropwise addition, the mixture was stirred at the same temperature for 60 minutes.

Thereafter, the content was cooled, and the solid concentration was 4%.
It was adjusted to 0.0% with deionized water, and filtered through a 100 mesh wire mesh. The resulting aqueous polymer dispersion had a solid content of 40.0%, a pH of 6.7, and a viscosity of 320 cps.
(Measured at 25 ° C. with a BM viscometer), and the agglomerates that did not pass through the 100 mesh wire mesh were 0.8% (ratio to the generated dispersion). This aqueous polymer dispersion is referred to as an aqueous curable polymer dispersion [E-20].

This curable polymer aqueous dispersion [E-20]
Means that the acid value of the polymer (A) having a carboxyl group is 6
5. The content of the basic nitrogen atom-containing group in the ethylenic polymer (B) is 0.13 mg per 1 g of the ethylenic polymer (B).
[Calculated from the charged amount of the monomer (b-1) having a basic nitrogen atom-containing group in the monomers (b)]. Further, when the acid value and the content of the basic nitrogen atom-containing group in the entire polymer aqueous dispersion are calculated from the charged amounts of the polymer (A) having a carboxyl group and the monomers (b), the polymer is obtained. The acid value per 1 g of the solid content of the aqueous dispersion was 13, the content of the basic nitrogen atom-containing group was 0.10 mg, and the total amount of the polysiloxane (100) by weight of the polymer (A) and the polymer (B) was 100 parts by weight. The content of C) is 3.8 parts.

The performances of the aqueous curable polymer dispersions obtained in Examples 1 to 20 and Comparative Examples 1 to 5 were evaluated for the following items.

Evaluation Method <Coating Water Resistance> The curable polymer aqueous dispersions obtained in Examples 1 to 20 and Comparative Examples 1 to 5 were applied on a glass plate with a 3 mil applicator, and were allowed to stand at room temperature for 7 days. Dried to form a film.

[0301] From the obtained glass plate coated films, ones dried only at room temperature and ones dried at room temperature and then heat-treated at 110 ° C for 20 minutes were prepared, and each was used as a test piece. The test piece was immersed in water at 25 ° C. for 7 days, the turbidity of the test piece before and after immersion in water was measured with a turbidimeter, and the degree of change in the turbidity was determined by W
The deterioration (whitening) of the film due to water immersion was evaluated. Turbidity meter: Nippon Denshoku Industries Co., Ltd. turbidity meter NDH-300
A Measurement light source; Halogen lamp Light receiving element; Silicon photocell conforming to JIS K7105 Measurement area; Transmission 12φ The turbidity and the degree of change in turbidity before and after immersion in water were determined according to the following equations.

[0302]

(Equation 2) TL; total transmittance (%) DF; diffuse transmittance (%)

[0303]

(Equation 3) H ₀ ; turbidity of the test piece before immersion in water H ₁ : turbidity of the test piece after immersion in water

○: Turbidity change degree W value is less than 5. Δ: The turbidity change degree W value is 5 or more and less than 30. X: The turbidity change degree W value is 30 or more.

<Film Water Absorption Rate and Elution Rate>
20, the film thickness after drying the curable polymer aqueous dispersion obtained in Comparative Examples 1 to 5 on a glass plate is 0.5 m
m and dried at room temperature for 7 days, after which the film was peeled off from the glass plate. From the obtained films, ones which were dried only at room temperature and those which were dried at room temperature and then heat-treated at 110 ° C. for 20 minutes were prepared, and each was used as a test piece. The film was cut into a square of 20 mm and the weight was measured (W ₀ ) to obtain a test film. The test film was immersed in water at 25 ° C. for 7 days, pulled up, lightly wiped off the water on the film surface, and weighed (W ₁ ). Further, the film was dried at 110 ° C. for 1 hour, allowed to cool, and then weighed (W ₂ ).
did. The water absorption and dissolution rate of the film were determined by the following formulas.

[0306]

(Equation 4)

[0307]

(Equation 5)

W ₀ : Weight of test film before immersion in water W ₁ : Weight of test film after immersion in water W ₂ : Weight of test film after immersion in water

<Solvent Resistance to Film> The aqueous dispersion of the curable polymer obtained in each of Examples 1 to 20 and Comparative Examples 1 to 5 was coated on a glass plate with a 3 mil applicator and dried at room temperature for 7 days. To form a film.

[0310] From the obtained coated films of glass plates, ones dried only at room temperature and ones dried at room temperature and then heat-treated at 110 ° C for 20 minutes were prepared, and each was used as a test piece. The resin-coated surface of the obtained test piece was rubbed 100 times with a cotton swab impregnated with an acetone or toluene solution, and the deterioration of the coated surface was observed.

A: No abnormality was found in the film. Δ: Deterioration was observed on the surface and inside of the film, and desorption from the glass plate was slightly observed. ×: Degraded to the inside of the film and markedly desorbed.

<Film Strength> The curable polymer aqueous dispersions obtained in Examples 1 to 20 and Comparative Examples 1 to 5 were coated on a polypropylene plate so that the film thickness after drying was 0.3 mm. After drying at room temperature for 7 days, the film was peeled off from the glass plate.

From the obtained films, a film dried at room temperature and a film dried at room temperature and then heat-treated at 110 ° C. for 20 minutes were prepared, and each was used as a test piece. These films were punched out into a JIS No. 3 dumbbell mold, and the breaking strength in a tensile test was measured under the following conditions. Tensile tester; Autograph AG-5000 manufactured by Shimadzu Corporation
C Pulling speed (crosshead speed): 200 mm / min. Distance between chucks: 50 mm

<Evaluation of Storage Stability of Polymer Aqueous Dispersion>
For the aqueous dispersions of the curable polymers obtained in Examples 1 to 20 and Comparative Examples 1 to 5, the viscosity immediately after the production and the
After storage at 5 ° C for 48 hours, the viscosity was measured using a BM type viscometer.
It was measured at 5 ° C.

The results of measurement of the coating water resistance, film water absorption and elution rate, coating solvent resistance and film strength according to the above evaluation methods are shown in Tables 1 to 4 below, and the storage stability is shown in Table 6. 1 to 5.

[0316]

[Table 15]

[0317]

[Table 16]

[0318]

[Table 17]

[0319]

[Table 18]

[0320]

[Table 19]

[0321]

[Table 20]

[0322]

[Table 21]

[0323]

[Table 22] * In the polymer aqueous dispersions E-19 and E-20 of Examples 19 and 20, the polyfunctional epoxy compound [Y] was added during the production of the polymer particles [X]. E-19: Denacol EX- 211 [manufactured by Nagase Kasei Kogyo; neopentyl glycol diglycidyl ether] E-20: KBE-403 [Shin-Etsu Chemical Co., Ltd .; γ-glycidoxypropyltriethoxysilane]

[0324]

[Table 23]

The details of the compound used as the polyfunctional epoxy compound [Y] in Tables 1 to 5 are shown below. EX-313 (Denacol EX-313) [Nagase Kasei Kogyo Co., Ltd .; glycerol polyglycidyl ether] EX-614B (Denacol EX-614B) [Nagase Kasei Kogyo Co., Ltd .; sorbitol polyglycidyl ether] KBM-403 [ Shin-Etsu Chemical Co., Ltd .; γ-glycidoxypropyltrimethoxysilane] Dick Fine EM-100 [Dainippon Ink Chemical Industry Co., Ltd .; Aqueous dispersion of bisphenol A type solid epoxy resin: solid component 50%] KBE-402 [manufactured by Shin-Etsu Chemical Co., Ltd .; γ-glycidoxypropylmethyldiethoxysilane] KBM-303 [manufactured by Shin-Etsu Chemical Co., Ltd .; 2- (3 ′, 4′-epoxycyclohexyl) Ethyltrimethoxysilane]

Example 21 The curable polymer aqueous dispersion obtained in Example 9 was formed into a paint with the following composition, and the coating film performance was evaluated. "Painting composition"<Pigmentdispersion> Taipaque CR-97 (* 1) 100.0 parts High Metrolose 90SH-15000 (* 2) 0.6 parts Primal 850 (* 3) 1.0 parts 5% of sodium tripolyphosphate Aqueous solution 2.0 parts Adecanol SX-568 (* 4) 2.5 parts Ethylene glycol 10.0 parts Water 35.2 parts 28% ammonia water 1.0 parts The above-mentioned composition is dispersed by a high-speed disperser, and pigment dispersion is performed. John was blended. <Letdown component> Aqueous dispersion of curable polymer 400.0 parts Texanol 6.6 parts Adekanol UH-420 (* 5): water = 1: 2 Mixing amount adjusted by paint viscosity (* 1) Ishihara Sangyo Co., Ltd. Rutile-type titanium oxide (* 2) Shin-Etsu Chemical Co., Ltd .; Methylcellulose (* 3) Rohm and Haas (USA); Polycarboxylic acid-type dispersant (* 4) Asahi Denka Kogyo Co., Ltd. Defoamer (* 5) Asahi Denka Kogyo KK; Thickener A paint was prepared by mixing a letdown component with the above pigment dispersion.

Examples 22 to 25 A coating material was prepared in the same manner as in Example 21 except that the kind of the aqueous dispersion of the curable polymer was changed as shown in Table 7 below. The performance was evaluated.

Comparative Examples 6 and 7 A coating material was prepared in the same manner as in Example 21 except that the kind of the aqueous dispersion of the curable polymer was changed as shown in Table 7 below. The performance was evaluated.

The coating properties of the paints obtained in Examples 21 to 25 and Comparative Examples 6 and 7 were evaluated for the following items.

Method of evaluating coating film <Weather resistance> The coating materials obtained in Examples 21 to 25 and Comparative Examples 6 and 7 were applied on an aluminum plate with a 3 mil applicator and dried at room temperature for 14 days. A membrane coupon was formed.

The specular reflectance (%) of the coating film specimen was measured at 60 ° to 60 °, and was measured as an initial gloss value. (This is referred to as a gloss value at the start of the test.) Next, an exposure test of the coating film was performed using the following sunshine type weather meter. Exposure tester; Ducycle Sunshine Super Long Life Weather Meter WEL-SUN-D
CH-B [manufactured by Suga Test Instruments Co., Ltd.] Rain cycle: 18 minutes / 120 minutes Black panel temperature; 63 ° C. UV irradiation; 60 ° -60 ° after continuous exposure 3,000 hours Final specular reflectance (%) It was measured as a typical gloss value. The gloss retention was determined by the following formula and used as an index of weather resistance. Here, the larger the value of the gloss retention, the better the weather resistance.

[0332]

(Equation 6)

G ₀ : Gloss after 3000 hours of exposure test G ₁ : Initial gloss

<Hardness> Examples 21 to 25, Comparative Examples 6 and 7
Was applied on an aluminum plate with a 3 mil applicator and dried at room temperature for 14 days to form a coating film specimen.

The pencil hardness of the coated sample was measured in a thermostat at 20 ° C. in accordance with JIS K-5400. Pencil: Mitsubishi Uni [Mitsubishi Pencil Co., Ltd.] <Bending resistance> The paints obtained in Examples 21 to 25 and Comparative Examples 6 and 7 are applied on a 0.1 mm thick aluminum plate with a 3 mil applicator. And dried at room temperature for 14 days to form a coating film sample.

The coated sample was placed in a thermostat at 20 ° C.
It was bent to 3 mmφ / 180 degrees, and the state of the coating film at the bent portion was visually evaluated. ；: No abnormality in the coating film.

Δ: The coating film is cracked but not peeled. X: The crack and peeling of a coating film are remarkable.

Table 7 below shows the measurement results of the weather resistance, hardness and flex resistance of the coating film by the above evaluation method.

[0339]

[Table 24]

In Table 7, "-" in the column of the aqueous dispersion of the curable polymer used indicates the aqueous dispersion of the curable polymer obtained in the Example, and "-" indicates the comparative example. Means the aqueous dispersion of the curable polymer obtained in the above.

[0341]

The aqueous dispersion of a curable polymer according to the present invention has excellent physical properties such as water resistance, solvent resistance and mechanical strength of the obtained cured product. Since the use amount of the emulsifier can be reduced to a very small amount, or the polymer emulsion can be stably produced without using the emulsifier at all, the performance deterioration caused by the emulsifier, which has conventionally been a problem, can be avoided.

Further, by using the aqueous dispersion of the curable polymer of the present invention as an aqueous paint or a finishing coating agent, the weather resistance, stain resistance, water resistance, solvent resistance, hardness, flex resistance, It is possible to provide a paint or a finish coating agent which forms a crosslinked coating film having excellent properties such as adhesion to a material.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 83/04 C08L 83/04 101/02 101/02 101/06 101/06 C09D 201/02 C09D 201/02 // C08L 33 / 00 C08L 33/00 43/00 43/00 C09D 133/00 C09D 133/00 143/00 143/00

Claims (17)

[Claims] 1. A polymer particle [X] composed of a polymer (A) having at least a carboxyl group, an ethylenic polymer (B) having a group containing a basic nitrogen atom, and a polysiloxane (C). A curable polymer aqueous dispersion comprising a functional epoxy compound [Y]. 2. The polysiloxane (C) is represented by the following general formula (1): (R ¹ ) _a —Si— (X ¹ ) _4-a (1) (wherein R ¹ is a hydrogen atom or An organic group having 1 to 20 carbon atoms, X ¹ is a monovalent group selected from a halogen atom, an alkoxy group, an acyloxy group, a hydroxy group, an aminoxy group, a phenoxy group, a thioalkoxy group or an amino group, a
Is an integer of 0, ¹ to 3, R ¹ and X ¹ bonded to a Si atom
Are each the same or different, when they are two or more, respectively.) The aqueous curable polymer dispersion according to claim 1, which is a condensate of an alkoxysilane represented by the following formula: 3. The aqueous dispersion of a curable polymer according to claim 1, wherein the basic nitrogen atom-containing group of the ethylenic polymer (B) having a basic nitrogen atom-containing group is a tertiary amino group. 4. The method according to claim 1, wherein the polyfunctional epoxy compound [Y] is 1
The curable polymer aqueous dispersion according to any one of claims 1 to 3, which is a compound having an epoxy group and a hydrolyzable silyl group and / or silanol group in a molecule. 5. A polymer (A) having a carboxyl group
Is a polymer having a hydrolyzable silyl group and / or a silanol group. The curable polymer aqueous dispersion according to any one of claims 1 to 4, wherein 6. A polymer having a carboxyl group (A)
Is a polymer having a group reactive with a basic nitrogen atom-containing group. The curable polymer aqueous dispersion according to any one of claims 1 to 5, wherein 7. The aqueous dispersion of a curable polymer according to claim 6, wherein the group having reactivity with the basic nitrogen atom of the polymer (A) having a carboxyl group is an epoxy group. 8. The method according to claim 1, wherein the ethylenic polymer (B) having a basic nitrogen atom-containing group is a polymer having a hydrolyzable silyl group and / or a silanol group.
Item 10. The aqueous dispersion of a curable polymer according to item 8. 9. The aqueous dispersion of a curable polymer according to claim 1, wherein the acid value of the polymer (A) having a carboxyl group is from 10 to 200. 10. A polymer having a carboxyl group (A)
The curable polymer aqueous dispersion according to any one of claims 1 to 9, having a weight average molecular weight of 100,000 or more and a gel fraction (acetone-insoluble content) of 95% by weight or less. 11. A polymer (A) having a carboxyl group
And the weight ratio of the ethylenic polymer (B) having a basic nitrogen atom-containing group is (A) :( B) = 1:
The curable polymer aqueous dispersion according to any one of claims 1 to 10, wherein the ratio is 1 to 1:20. 12. The polysiloxane (C) is a solid component weight ratio to the total amount of the polymer (A) having a carboxyl group and the ethylenic polymer (B) having a group containing a basic nitrogen atom. [(A) + (B)] :( C) = 100: 0.5
The curable polymer aqueous dispersion according to any one of claims 1 to 11, wherein the ratio is from 1 to 1. 13. The polymer particle [X] having an acid value of 3 to 50.
The aqueous dispersion of a curable polymer according to any one of claims 1 to 12, wherein 14. A curable polymer aqueous dispersion having a pH of 7
The curable polymer aqueous dispersion according to any one of claims 1 to 13, which is an aqueous dispersion of the curable polymer. 15. A polymer (A) having a carboxyl group
And an aqueous medium containing a polysiloxane (C), and polymerizing monomers having an ethylenically unsaturated monomer having a basic nitrogen atom-containing group as an essential component, to thereby obtain an aqueous dispersion of polymer particles [X]. A method for producing an aqueous dispersion of a curable polymer, which comprises obtaining a liquid and then adding a polyfunctional epoxy compound [Y]. 16. A polymer (A) having a carboxyl group
19. The curable polymer according to claim 18, wherein the curable polymer is obtained by polymerizing a monomer having a carboxyl group-containing ethylenically unsaturated monomer as an essential component in an aqueous medium. A method for producing an aqueous dispersion. 17. A paint containing the curable polymer aqueous dispersion according to claim 1. Description: