JPH09235332A - Aqueous dispersion of curable polymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aqueous dispersion of a curable polymer excellent in water resistance, solvent resistance and mechanical strength, capable of reducing the use amount of an emulsifying agent or without using emulsifying agent at all. SOLUTION: A polymer article X to be dispersed into an aqueous medium consists of two phases of a phase A and a phase B. The polymer particle comprises the phase A composed of a carboxyl group-polymer A obtained by polymerizing a carboxyl group-containing ethylene unsaturated monomer such as methacrylic acid and another ethylenic unsaturated monomer and the phase B obtained by polymerizing an ethylenic unsaturated monomer containing a basic nitrogen atom-containing group such as dimethylaminoethyl methacrylate with another ethylenic unsaturated monomer. The polymer particle X and a polyfunctional epoxy-based compound Y such as glycerol polyglycidyl ether as essential components are made into an aqueous dispersion of curable polymer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curable polymer aqueous dispersion. More specifically, it is characterized in that it is composed of specific polymer particles [X] dispersed in an aqueous medium and a polyfunctional epoxy compound [Y] as essential components, and the water resistance of the emulsion film. Aqueous dispersions of curable polymers useful for paints, priming agents, adhesives, paper and textile finishing agents, film coating agents, etc., which give a cured film with markedly improved properties, solvent resistance, mechanical strength, etc. It is a thing.

[0002]

2. Description of the Related Art An aqueous polymer dispersion obtained by polymerizing various ethylenically unsaturated monomers is used as an emulsion binder in a wide range of applications such as paints, adhesives, paper and fiber processing. These polymer emulsions are usually produced by emulsion-polymerizing an ethylenically unsaturated monomer and a radical-forming catalyst in the presence of a surfactant (emulsifier).

Various methods have been studied so far for improving durability such as water resistance and solvent resistance of a film or a cured product of such a polymer emulsion. For example, a polymer emulsion having a reactive group is crosslinked. It has been attempted to achieve high durability by forming a crosslinked structure by adding an agent and reacting with a reactive group of the polymer, that is, by making the polymer thermosetting. Specifically, there is known a technique of improving various physical properties such as water resistance and solvent resistance by curing an amino group-containing polymer emulsion with an epoxy-based crosslinking agent.

[0004]

In the method of curing the above-mentioned amino group-containing polymer emulsion with an epoxy-based crosslinking agent, although it is possible to improve various physical properties such as water resistance and solvent resistance, A large amount of an emulsifier must be used in order to stably obtain a polymer emulsion containing an amino group, and as a result, a large amount of the emulsifier remains in the polymer emulsion even after the film is formed. There was a problem that water resistance and solvent resistance were not obtained, and mechanical strength was lowered.

The problem to be solved by the present invention is to reduce the amount of emulsifier used, or to use it at all.
An object of the present invention is to provide a curable polymer aqueous dispersion that gives a cured product having excellent water resistance, solvent resistance, and mechanical strength.

[0006]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a specific polymer particle [X] dispersed in an aqueous medium and a curing compound composed of a polyfunctional epoxy compound [Y] are used. It was found that an aqueous dispersion of a water-soluble polymer can solve the above-mentioned problems, and has completed the present invention.

That is, according to the present invention, in the curable polymer aqueous dispersion which exhibits curability, the polymer particles [X] dispersed in the aqueous medium are composed of at least two phases, phase A and phase B. And polymer particles of which phase A is composed of a polymer [A] containing a carboxyl group and phase B is composed of an ethylenic polymer [B] containing a basic nitrogen atom-containing group, A curable polymer aqueous dispersion comprising the polymer particles [X] and a polyfunctional epoxy compound [Y], and an aqueous medium containing the carboxyl group-containing polymer [A]. In, ethylenically unsaturated monomer (b-1) containing a basic nitrogen atom-containing group
Or a polyfunctional epoxy compound [Y] is added to the aqueous dispersion of the polymer particles [X] by polymerizing the monomer component (b) containing Alternatively,
Monomer component (b) containing an ethylenically unsaturated monomer (b-1) containing a basic nitrogen atom-containing group as an essential component
Is polymerized in the presence of a polyfunctional epoxy compound [Y] to obtain an aqueous dispersion of polymer particles [X], which relates to a method for producing a curable polymer aqueous dispersion.

The polymer particle [X] in the present invention is composed of two kinds of phases, A phase and B phase. That is, in the aqueous dispersion, the phase A is composed of the carboxyl group-containing polymer [A], and the carboxyl group in the carboxyl group-containing polymer [A] stabilizes the polymer particles [X] in an aqueous medium. It is used to disperse.

The carboxyl group in the carboxyl group-containing polymer [A] is a polyfunctional epoxy compound [Y].
An ethylenic polymer [B] forming a B layer with a polyfunctional epoxy compound [Y] as a crosslinkable reactive group with
It is used as a functional group that promotes the reaction with the basic nitrogen atom-containing group therein.

The content of the carboxyl group in the carboxyl group-containing polymer [A] is not particularly limited, but in order to stably disperse the polymer particles [X] in an aqueous medium, an acid value is required. It is preferably contained in an amount of 30 or more.

On the other hand, from the viewpoint of the water resistance of the obtained film, it is preferable to suppress the carboxyl group which imparts hydrophilicity to the carboxyl group-containing polymer [A] as much as possible. The carboxyl group-containing polymer [A] It is preferable that the acid value of the carboxyl group content is 300 or less. Therefore, the acid value is preferably 30 to 300 from the balance of these.

Further, the polymer particles [X] are A particles as described above.
The particles are composed of a layer and a layer B, and are dispersion-stabilized with the carboxyl group-containing polymer [A]. The acid value of the entire polymer particles [X] is preferably in the range of 5 to 70 from the viewpoint of dispersion stability of the particles and water resistance of the resulting film.

Here, the acid value is a numerical value representing the amount of carboxyl groups contained in the carboxyl group-containing polymer [A] or the polymer particles [X], and the carboxyl group-containing polymer [A] or the polymer particles. It is the mg number of potassium hydroxide required for neutralizing the free carboxyl group contained in 1 g of [X], and the measurement is carried out under the conditions shown in Examples described later.

The molecular weight of the carboxyl group-containing polymer [A] is not particularly limited, but from the viewpoint of preventing deterioration of the water resistance of the film due to the presence of a low molecular weight substance as a hydrophilic component, Weight average molecular weight of 10
It is preferably 10,000 or more.

Here, the weight average molecular weight is determined by dissolving the polymer constituting the carboxyl group-containing polymer [A] in a solvent (tetrahydrofuran) and measuring it by gel permeation chromatography (GPC method). The weight average molecular weight in terms of polystyrene is shown, and the measurement is carried out under the conditions shown in Examples below.

The weight average molecular weight of the carboxyl group-containing polymer [A] is preferably 100,000 or more. For example, even if the carboxyl group-containing polymer [A] is three-dimensionally crosslinked to increase the molecular weight. However, it is preferable that the gel fraction represented by the acetone-insoluble component of the carboxyl group-containing polymer [A] is 95% by weight or less.

That is, when the gel fraction of the carboxyl group-containing polymer [A] is 95% by weight or less, the stability during the polymerization of the monomer component (b) described below is improved, and the resulting film is obtained. The film forming property of is also good.

That is, the gel fraction of the carboxyl group-containing polymer [A] in the present invention is an index showing how much the polymer constituting the carboxyl group-containing polymer [A] is involved in cross-linking. Which is expressed by measuring the solvent insoluble content (% by weight) of the polymer.

Specifically, a polymer film is formed from a carboxyl group-containing polymer [A] or an aqueous dispersion containing the carboxyl group-containing polymer [A], and the polymer film is immersed in acetone so as not to participate in cross-linking. Elute the polymer,
It is carried out by measuring the remaining acetone-insoluble matter, and the measuring method includes a method of carrying out under the conditions shown in the Examples below.

The carboxyl group-containing polymer [A] constituting the phase A is reactive with a carboxyl group and, further, with a basic nitrogen atom-containing group in the ethylenic polymer [B] constituting the phase B described later. When it contains a group having a group, the phase A and the phase B are bound 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. This is preferable because various properties such as water resistance, especially solvent resistance are improved as a result.

The group having reactivity with the basic nitrogen atom-containing group is not particularly limited, but an epoxy group 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 phase A and the basic nitrogen atom-containing group in the phase B react with each other during the production of the curable polymer aqueous dispersion to give polymer particles. Although it may be crosslinked in [X], it remains uncrosslinked in the polymer particles before curing from the viewpoint of various physical properties such as film forming property, water resistance, solvent resistance, and mechanical strength. It is preferable to form a crosslinked film by reacting a reactive functional group during or after the film formation, because the physical properties are remarkably improved.

Depending on the field of application of the curable polymer aqueous dispersion, the film forming property of the film is often required for the purpose of application, and in that case, a carboxyl group containing a carboxyl group constituting phase A is used. The glass transition temperature (Tg) of the contained polymer [A] is preferably in the range of -60 to 30 ° C.

The carboxyl group-containing polymer [A] constituting the phase A is not specified, but it is an addition polymer of an ethylenically unsaturated monomer such as an acrylic polymer or a butadiene polymer ( Hereinafter, abbreviated as "ethylenic polymer"), a urethane polymer containing a polymer having urea and a urethane bond, a polyester polymer, and the like, and a mixture of these various polymers, such as an acrylic polymer / urethane polymer. Mixtures of polymers and grafted (blocked) products of various polymers, for example, products obtained by grafting an acrylic polymer on an unsaturated polyester polymer can also be used.

Particularly, a carboxyl group-containing polymer [A]
When designing considering the acid value, the adjustment of the molecular weight and the introduction of a reactive group having a crosslinkability with the basic nitrogen atom-containing group as described above, the design is easy and can be easily produced by the method described below. An ethylenic polymer is preferable because it can be produced.

Next, the ethylenic polymer [B] containing the basic nitrogen atom-containing group forming the phase B is a basic nitrogen atom as a crosslinkable reaction group with the polyfunctional epoxy compound [Y]. It has a containing group.

In particular, when the basic nitrogen atom-containing group in the ethylenic polymer [B] is a tertiary amino group, it has high reactivity with the polyfunctional epoxy compound [Y] and is subjected to mild heat treatment conditions. Even when it is cured by (1), the crosslinked density of the obtained cured product can be increased, and various physical properties such as water resistance, solvent resistance and mechanical strength can be remarkably improved, which is preferable.

The content of the basic nitrogen atom-containing group in the ethylenic polymer [B] is not particularly limited, but from the viewpoint of curability with the polyfunctional epoxy compound [Y], It is preferable that 1 g of the ethylenic polymer [B] contains 0.05 mmol or more of a basic nitrogen atom-containing group. In addition, the content of the basic nitrogen atom-containing group in the ethylenic polymer [B] is from the viewpoint of dispersion stability of the polymer particles [X], water resistance of the obtained cured product, and the like. It is preferable to make 2.0 mmol or less in 1 g of [B]. Therefore, from the balance of these, the amount is preferably 0.05 to 2.0 mmol in 1 g of the ethylenic polymer [B].

The content of the basic nitrogen atom-containing group in the whole polymer particles [X] is such that the curability with the polyfunctional epoxy compound [Y], the dispersion stability of the polymer particles [X], From the viewpoint of water resistance of the resulting cured product, polymer particles [X] 1
The basic nitrogen atom-containing group contained in g is 0.05 to 0.
It is preferably in the range of 7 mmol.

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

From the viewpoint of various properties such as water resistance of the resulting cured product, the carboxyl group-containing polymer [A] forming the A phase and the ethylenic group containing a basic nitrogen atom-containing group forming the B phase are used. The weight ratio of the polymer [B] is [A] /
The solid fraction of [B] is preferably 1/1 to 1/100. More specifically, from the viewpoint of excellent water resistance,
It is preferable that [A] / [B] = 3/7 to 1/100.

On the other hand, from the viewpoint of storage stability as an aqueous dispersion of a curable polymer, it contains a carboxyl group-containing polymer [A] constituting the A phase and a basic nitrogen atom-containing group constituting the B phase. The weight ratio of the ethylenic polymer [B] is
The solid fraction ratio of [A] / [B] is preferably 1/1 to 1/9. That is, [B] for 1 part by weight of [A]
By setting the ratio in terms of solid content of 9 parts by weight or less,
It is preferable because the storage stability of the curable polymer aqueous dispersion is remarkably improved.

That is, in view of the balance between the physical properties of the cured product and the storage stability as an aqueous dispersion of the curable polymer, the carboxyl group-containing polymer [A] constituting the A phase and the basic nitrogen constituting the B phase. The weight ratio of the ethylenic polymer [B] containing an atom-containing group is [A] / [B] solid fraction,
Most preferably, it is in the range of 3/7 to 1/9.

The polymer particle [X] dispersed in the curable polymer aqueous dispersion is not particularly specified in its phase structure, but is usually a so-called core having the B phase as the core and the A phase as the shell. -Shell structure, or a state in which the A phase is dissolved or dispersed in an aqueous medium in the form of particles, and the B phase is dispersed in the form of particles using the A phase as a matrix. In any of these dispersion states, the carboxyl group of phase A stabilizes the dispersion of the polymer particles.

Further, among the above-mentioned constitutions, a constitution in which the A phase and the B phase form a so-called core-shell structure in which the A phase and the B phase are concentric with each other and the A phase is located on the outer side of the particles, the dispersion stability of the particles becomes good. Therefore, it is preferable.

In the curable polymer aqueous dispersion of the present invention, since the polymer particles [X] in the dispersion are dispersion-stabilized by the carboxyl group, the carboxyl group is neutralized by the basic substance described later. Is preferable from the viewpoint of dispersion stability of the polymer particles [X]. Therefore, the pH of the curable polymer aqueous dispersion 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, and therefore the pH is preferably 7 to 12 from the viewpoint of dispersibility, curability and storage stability.

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

The curable polymer aqueous dispersion of the present invention contains polymer particles [X] and a polyfunctional epoxy compound [Y] as constituent components, but the polyfunctional epoxy compound [Y] is used.
Is used for curing the film by reacting with the crosslinkable reactive group (basic nitrogen atom-containing group and / or carboxyl group) of the polymer particles [X], and has water resistance, solvent resistance, mechanical strength, etc. Improve various physical properties of.

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 glycols such as diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether; polyhydric alcohols [ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol,
Polyglycidylated polyester, polycaprolactone of 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.] Polyglycidylation products of polyesters such as polyglycidylation products; polyvalent amines [ethylenediamine, diethylenetriamine, 1,4-cyclohexanediamine, isophoronediamine, tolylenediamine, etc.] and polyvalent carboxylic acids [oxalic acid, adipic acid, butanetricarboxylic acid, Polyglycidyl derivative of polyamide with maleic acid, phthalic acid, terephthalic acid, isophthalic acid, benzenetricarboxylic acid, etc .; condensation product of bisphenol A and epichlorohydrin, condensation of bisphenol A and epichlorohydrin Ethylene oxide adducts, bisphenol A-based epoxy resins such as propylene oxide adducts of condensates of bisphenol A and epichlorohydrin; phenol novolac resins such as phenol novolac resins, ethylene oxide adducts of phenol novolac resins, and propylene oxide adducts of phenol novolac resins Epoxy resin; Epoxy urethane resin obtained by modifying the epoxy resin with urethane; Various vinyl (co) polymers having an epoxy group in the side chain; Epoxy modified silicone oil; Epoxy group-containing alkoxysilane such as γ-glycidoxypropyltrimethoxysilane A partial hydrolyzate of the above; a compound having two or more epoxy groups in one molecule such as an epoxy group-containing acrylic resin. Among such polyfunctional epoxy compounds, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ethers, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, glycerol polyglycidyl ethers, diglycerol polyglycidyl ether , Polyglycerol polyglycidyl ethers, water-soluble epoxy compounds such as sorbitol polyglycidyl ethers, or "Denacol EM-125" (manufactured by Nagase Kasei Co., Ltd.), "Dick Fine EM-100" (Dainippon Ink) Chemical Industry Co., Ltd., "Adeka Resin EPE-0410, EPE
S-0425W "(manufactured by Asahi Denka Kogyo Co., Ltd.) and the like are emulsified self-dispersing epoxy compounds, or water-insoluble epoxy compounds (liquid and solid) are emulsified with an emulsifier. It is preferable in terms of compatibility with the particle [X] and curability.

As the polyfunctional epoxy compound [Y], an epoxy group in one molecule and a reactive functional group other than the epoxy group (wherein the reactive functional group means the polymer particle [X]). It is preferable to have a reactive functional group capable of reacting with the reactive group or a reactive functional group capable of reacting with each other.) As such a compound, specifically, Epoxysilanes containing an epoxy group and a hydrolyzable silyl group or silanol group in the molecule can be mentioned.

When a compound containing an epoxy group and a hydrolyzable silyl group or silanol group in one molecule is used, various properties such as water resistance of the cured product, particularly solvent resistance, are remarkably improved. The curability is good, and a cured product having desired performance can be obtained only by drying at room temperature, which is preferable.

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

Here, the hydrolyzable silyl group is, for example, an alkoxy group, a substituted alkoxy group, a phenoxy group, a halogen atom, an isopropenyloxy group,
An atomic group containing a silicon atom to which an acyloxy group or iminooxy or the like is bonded, which is easily hydrolyzed to form a silanol group, is specifically referred to as, among them, for example, an alkoxy group. Examples thereof include a silyl group, a phenoxysilyl group, a halosilyl group, an isopropenyloxysilyl group, an acyloxysilyl group and an iminooxysilyl group.

In order to prepare these ethylenic polymers having both an epoxy group and a hydrolyzable silyl group or silanol group as described above, various known and conventional methods can be applied, but recommended methods are as follows. Is a method of solution radical copolymerizing various hydrolyzable silyl group-containing polymerizable monomers and various epoxy group-containing polymerizable monomers, as described above, hydrolyzable silyl group-containing polymerization Polymeric monomers, various epoxy group-containing polymerizable monomers, and a method of solution radical copolymerizing other polymerizable monomers copolymerizable therewith, γ-mercaptopropyltrimethoxysilane, of γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane or γ-mercaptopropyltriisopropenyloxysilane. Can, in the presence of various chain transfer agent containing a hydrolyzable silyl group, such as the supra,
Solution radical (co) polymerization of a monomer mixture containing various epoxy group-containing polymerizable monomers as essential monomer components, or a method combining the above method or the above method, etc. Various methods are available.

As a typical representative of the above-mentioned epoxy group-containing silane coupling agent, for example, γ
-Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, β-
Various epoxysilane compounds such as (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethylmethyldiethoxysilane or γ-glycidoxypropyltriisopropenyloxysilane; Addition products of various isocyanate silane compounds such as γ-isocyanatopropyltriisopropenyloxysilane or γ-isocyanatopropyltrimethoxysilane with glycidyl;
Or like γ-aminopropyltrimethoxysilane,
Addition products of various aminosilane compounds and diepoxy compounds; or 2 obtained in one molecule by partial hydrolysis condensation of various epoxysilane compounds as described above.
Examples thereof include compounds having both one or more epoxy groups and a hydrolyzable silyl group.

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 [I].

[0047]

Embedded image However, in the formula [I], 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 it depends on the curability of the curable polymer aqueous dispersion and the performance of the cured film. From the aspect of storage stability of the curable polymer aqueous dispersion,
Basic nitrogen atom-containing group 1 contained in polymer particles [X]
It is preferably used in the range of 0.3 to 3.0 mol, based on mol.

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

As typical examples of such a catalyst, various basic compounds such as lithium hydroxide, sodium hydroxide, potassium hydroxide and sodium methylate; tetraisopropyl titanate, tetra-n-butyl 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- Various metal-containing compounds such as butyltin dilaurate and di-n-butyltin maleate; p-toluenesulfonic acid, trichloroacetic acid, phosphoric acid, monoalkylphosphoric acid,
Examples thereof include various acidic compounds such as dialkyl phosphoric acid, monoalkyl phosphorous acid and dialkyl phosphorous acid.

The solid content concentration of the curable polymer aqueous dispersion is
It is preferably 20 to 70% by weight. That is, by setting the solid content 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
In the above, it is preferable from the viewpoint of the film thickness of the coating film when it is used in coating processing (paint, adhesive, paper, film, fiber processing agent, etc.), and productivity of curable polymer aqueous dispersion is also good. It will be Further, it is preferably 30 to 60% by weight from the viewpoint of good balance of these.

Further, as described above, the curable polymer aqueous dispersion of the present invention can be produced with an extremely small amount of the emulsifier and the dispersion stabilizer, or even without using it at all.
The amount of the emulsifier and the dispersion stabilizer present in the dispersion can be extremely small, and specifically, 1% by weight or less based on the solid content of the curable polymer aqueous dispersion, the water resistance of the cured product. It is preferable from the viewpoint of sex and the like.

Such a curable polymer aqueous dispersion is not particularly specified in its production method. For example, 1. a carboxyl group-containing polymer [A] and a basic nitrogen atom-containing group-containing ethylenic polymer Polymer (B) is produced separately,
A method in which these are once mixed and then dispersed in an aqueous medium to obtain a dispersion of polymer particles [X], and then a polyfunctional epoxy compound [Y] is added, 2. Carboxyl group-containing polymer [A] Is prepared, dissolved or dispersed in an aqueous medium, and then an ethylenically unsaturated monomer containing a basic nitrogen atom-containing group is polymerized in the aqueous medium, and then a polyfunctional epoxy system is prepared. Method of adding compound [Y], 3. Manufacturing carboxyl group-containing polymer [A], dissolving or dispersing this in an aqueous medium, and then adding polyfunctional epoxy compound [Y] in the aqueous medium. ] The method of polymerizing an ethylenically unsaturated monomer containing a basic nitrogen atom-containing group in the presence of [4], 4. producing an ethylenic polymer [B] containing a basic nitrogen atom-containing group, The water after being dissolved or dispersed in an aqueous medium A method of producing a carboxyl group-containing polymer [A] in a medium and then adding a polyfunctional epoxy compound [Y], 5. An ethylenic polymer [B] containing a basic nitrogen atom-containing group And a method for producing a carboxyl group-containing polymer [A] in the presence of a polyfunctional epoxy compound [Y] in the aqueous medium after dissolving or dispersing the same in an aqueous medium, In order to express desired physical properties such as water resistance, the acid value of the carboxyl group-containing polymer [A] is suppressed to a low level and the molecular weight is increased, and the basic nitrogen atom is used. Group-containing ethylenic polymer [B]
It is preferable to increase the molecular weight of the above, and for that purpose, the production method of the present invention described in detail below is preferable. Further, according to the production method of the present invention, storage stability and productivity can be further enhanced.

That is, in the production method of the present invention, the ethylenically unsaturated monomer (b-1) containing a basic nitrogen atom-containing group is added to an aqueous medium in which the carboxyl group-containing polymer [A] is present. Monomer component (b) as an essential component
To obtain an aqueous dispersion of polymer particles [X], and then add a polyfunctional epoxy compound [Y] to the aqueous dispersion, or an ethylenic group containing a basic nitrogen atom-containing group. Aqueous dispersion of polymer particles [X] by polymerizing a monomer component (b) containing an unsaturated monomer (b-1) as an essential component in the presence of a polyfunctional epoxy compound [Y]. It is characterized by obtaining a liquid.

The properties of the carboxyl group-containing polymer [A] in the aqueous medium at the time of producing the polymer particles [X] in the method for producing the curable polymer aqueous dispersion of the present invention are not particularly limited. Not, a carboxyl group-containing polymer [A]
May be completely dissolved in the aqueous medium, may be semi-solubilized in the aqueous medium, or may be dispersed as particles in the aqueous medium. In order to improve the physical properties, the acid value of the carboxyl group-containing polymer [A] is suppressed as low as possible and the molecular weight is increased, specifically, the weight average molecular weight is 100,
It is preferable that the carboxyl group-containing polymer [A] is dispersed in the aqueous medium as particles in order to make the carboxyl group-containing polymer [A] having such characteristics stably exist in the aqueous medium. Preferably.

The particle size of the carboxyl group-containing polymer [A] dispersed as particles in an aqueous medium is not particularly limited, but the stability during polymerization of the monomer component (b) described below and the final From the viewpoint of the film-forming property of the coating film obtained in general, the number average particle diameter is preferably in the range of 10 to 1000 nm.

The method for producing the carboxyl group-containing polymer [A] varies depending on the kind of the polymer used and is not particularly limited. For example, a method for producing by free radical polymerization of an ethylenically unsaturated monomer. Alternatively, it can be produced 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 can control the acid value, molecular weight and gel fraction of the obtained carboxyl group-containing polymer [A]. By the polymerization of the monomer component (b) in an aqueous medium in the presence of the carboxyl group-containing polymer [A] and the monomer component (b) and the carboxyl group-containing polymer [A]. It is preferable in terms of good compatibility with the polymer to be produced and improved stability during polymerization of the monomer component (b) carried out in an aqueous medium. Further, in the case of the production method using an ethylenically unsaturated monomer as a raw material, it is preferable from the viewpoint that it is easy to introduce a reactive functional group other than the carboxyl group described below into the carboxyl group-containing polymer [A]. .

The method for producing the carboxyl group-containing polymer [A] by free radical polymerization is not specified, but the carboxyl group-containing ethylenically unsaturated monomer component (a-1) is an essential component. Monomer component (a)
, Suspension polymerization, emulsion polymerization, bulk polymerization, depending on its properties,
Although it can be produced by any method of solution polymerization, in particular, since it is easy to set the weight average molecular weight of the carboxyl group-containing polymer [A] to 100,000 or more,
Preference is given to carrying out by suspension polymerization or emulsion polymerization carried out in an aqueous medium. Further, a carboxyl group-containing polymer [A]
In the aqueous medium, the step of dispersing the carboxyl group-containing polymer [A] in the aqueous medium can be omitted, and the step of producing the carboxyl group-containing polymer [A] and the polymerization of the monomer component (b) can be omitted. It is also preferable in that the manufacturing process can be simplified because the process can be performed continuously.

Monomer component (a) used in producing the carboxyl group-containing polymer [A] by free radical polymerization
Is a carboxyl group-containing ethylenically unsaturated monomer (a-
1) is an essential component, but 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,
Examples thereof include β- (meth) acryloyloxyethyl hydrogen phthalate, half esters thereof, salts thereof, and the like, and one kind or a mixture of two or more kinds thereof can be used.

As the monomer component (a), in addition to the above-mentioned carboxyl group-containing ethylenically unsaturated monomer (a-1), another ethylenically unsaturated monomer is used in combination and polymerized to obtain an acid value. In the above-mentioned preferred range (acid value 30 to 300)
It is possible to obtain the carboxyl group-containing polymer [A] adjusted to.

Here, the other ethylenically saturated monomer is not particularly limited as long as it is copolymerizable 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) acrylic acid ester such as (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, phenyl (meth) acrylate, 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) ethyl (meth)
Fluorine-containing vinyl monomers such as acrylates; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl versatate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, amyl vinyl ether, hexyl vinyl ether, etc. Kind; (meta)
Nitriles of unsaturated carboxylic acids such as acrylonitrile;
Styrene, α-methylstyrene, vinyltoluene, vinylanisole, α-halostyrene, vinylnaphthalene,
A vinyl compound having an aromatic ring such as divinylstyrene;
Examples thereof include 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) acrylic acid esters are preferable because they are particularly easy to polymerize and the resulting coating film has excellent physical properties represented by water resistance.

If desired, an ethylenically unsaturated monomer containing a reactive functional group other than a carboxyl group may be used in combination as another ethylenically unsaturated monomer. As the ethylenically unsaturated monomer,
Although not particularly limited, for example, glycidyl (meth) acrylate, allyl glycidyl ether, 4
-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 monomer; amide group-containing polymerizable monomer such as (meth) acrylamide, N-monoalkyl (meth) acrylamide, N, N-dialkyl (meth) acrylamide; N-methylol (meth) acrylamide, Methylolamide groups such as N-isopropoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide and their alkoxylated-containing polymerizable monomers; vinyltrichlorosilane, vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltris (beta-methoxyethoxy)
Hydrolyzable silyl group- or silanol group-containing polymerizable monomers such as silane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane; 2-aziridinylethyl (meth ) Aziridinyl group-containing polymerizable monomer such as acrylate; isocyanate group and / or blocked isocyanate group-containing polymerizable monomer such as (meth) acryloyl isocyanate and phenol adduct of (meth) acryloyl isocyanate An oxazoline group-containing polymerizable monomer such as 2-isopropenyl-2-oxazoline, 2-vinyl-2-oxazoline, and 2-oxazodinylethyl (meth) acrylate; cyclo such as dicyclopentenyl (meth) acrylate Pentenyl group-containing polymerizable 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-dimethylaminopropyl (meth)
Acrylate, N, N-diethylaminopropyl (meth) acrylate, N- [2- (meth) acryloyloxyethyl] piperidine, N- [2- (meth) acryloyloxyethyl] pyrrolidine, N- [2- (meth) acryloyl Oxyethyl] morpholine, 4- [N, N-
Tertiary amino group-containing polymerizable monomers such as dimethylamino] styrene, 4- [N, N-diethylamino] styrene, 2-vinylpyridine, 4-vinylpyridine; N-methylaminoethyl (meth) acrylate, N- Secondary amino group-containing polymerizable monomers such as t-butylaminoethyl (meth) acrylate; aminomethyl acrylate, aminoethyl acrylate, aminopropyl (meth) acrylate,
Examples thereof include primary amino group-containing polymerizable monomers such as amino-n-butyl (meth) acrylate, butylvinylbenzylamine, vinylphenylamine, p-aminostyrene, etc., and one or more of these may be used. Mixtures can be used.

In the present invention, as the other ethylenically unsaturated monomer in the monomer component (a), among the ethylenic monomers containing a reactive functional group other than the above-mentioned carboxyl group, , An ethylenically unsaturated monomer containing a group having reactivity with a basic nitrogen atom-containing group is used as the ethylenically unsaturated monomer (a-2) in combination to polymerize the above-mentioned B phase. Can be cross-linked with the ethylenic polymer [B] forming the polymer, and the amount of the non-cross-linked polymer remaining in the cured product when cured with the polyfunctional epoxy compound [Y] can be reduced, resulting in water resistance and solvent resistance. It is preferable because various physical properties such as properties can be improved.

That is, when the monomer (a-2) is used 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. By doing so, the crosslink density of the cured product cured with the polymer particles [X] and the polyfunctional epoxy compound [Y] is increased, and various properties such as water resistance of the cured product, especially solvent resistance are improved. To do.

When the reactive functional group of the monomer (a-2) has reactivity with a carboxyl group, or when the reactive functional group of the monomer (a-2) self-reacts Is
Increase the molecular weight of the carboxyl group-containing polymer [A],
Although it has an effect of improving various physical properties such as water resistance, as described above, the condition that the gel fraction of the carboxyl group-containing polymer [A] is 95% by weight or less (selection of reactive functional group, amount,
The carboxyl group-containing polymer [A] is preferably used at the reaction temperature during polymerization, the pH of the system during polymerization and the like are adjusted.

An ethylenically unsaturated monomer (a- containing a group having reactivity with a basic nitrogen atom-containing group as described above).
2) is not particularly limited, but of the above-listed compounds, for example, glycidyl (meth) acrylate, (β-methyl) glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) Epoxy group-containing polymerizable monomer such as acrylate, allyl glycidyl ether, 3,4-epoxy vinyl cyclohexane, di (β-methyl) glycidyl malate, di (β-methyl) glycidyl fumarate; (meth) acryloyl isocyanate , (Meth) acryloyl isocyanatoethyl phenol adducts and other isocyanate groups and / or blocked isocyanate group-containing polymerizable monomers; acetoacetoxyethyl (meth) acrylate and other acetoacetyl group-containing polymerizable monomers Etc. As the ethylenically unsaturated monomer (a-2), one type of these monomers or a mixture of two or more types can be used.

Among them, glycidyl is particularly preferable because it has a significantly excellent reactivity with the 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, di 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 crosslinked with the above-mentioned various monomers and the carboxyl group-containing polymer [A] 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, as described above, it is preferable to use the gel fraction in a range not exceeding 95% 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, trimethylolpropane tri ( (Meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, allyl (meth) acrylate,
Examples thereof include diallyl phthalate and divinyl benzene.

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

Further, as other ethylenically unsaturated monomer, for the purpose of improving the stability during emulsion polymerization and the storage stability of the aqueous dispersion of the polymer particles [X], the water resistance of the film obtained is improved. Within a range that does not deteriorate the property, ethylenically unsaturated monomer containing sulfonic acid group and / or sulfate group (and / or salt thereof), phosphoric acid ester group-containing ethylenically unsaturated monomer, and nonionic A hydrophilic group-containing ethylenically unsaturated monomer or the like can be used in combination.

Specifically, for example, as an ethylenically unsaturated monomer containing a sulfonic acid group and / or a sulfate group (and / or a salt thereof), vinyl sulfonic acids such as vinyl sulfonic acid and styrene sulfonic acid, or a vinyl sulfonic acid thereof Allyl group-containing sulfonic acids such as salts, allylsulfonic acid, 2-methylallylsulfonic acid or salts thereof, (meth) acrylate group-containing sulfones such as 2-sulfoethyl (meth) acrylate and 2-sulfopropyl (meth) acrylate Examples thereof include acids or salts thereof, (meth) acrylamide group-containing sulfonic acids such as (meth) acrylamide-t-butylsulfonic acid or salts thereof, and 2-hydroxy group as a phosphoric acid ester group-containing ethylenically unsaturated monomer. 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, polyethylene glycol di (meth) acrylate, and the like. 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 used is such that the acid value of the carboxyl group-containing polymer [A] is as described above. It is preferable to use the carboxyl group-containing ethylenically unsaturated monomer (a-1) in a ratio such that it becomes 30 to 300, and the monomer component (b) described later.
It is preferable to select the type and amount in consideration of the compatibility with the produced polymer component.

Specifically, the ratio of the carboxyl group-containing ethylenically unsaturated monomer (a-1) to the other ethylenically unsaturated monomer used is the former / the latter = 3/9 on a weight basis.
7-50 / 50, more preferably the former / latter = 5
/ 95 to 30/70, and when used in this range, it is preferable from the viewpoint of stability during polymerization of the monomer component (b) and water resistance of the obtained emulsion film.

When an ethylenically unsaturated monomer (a-2) is used as the other ethylenically unsaturated monomer, the monomer (a-2) is a carboxyl group-containing ethylenically unsaturated monomer. When it has reactivity with the carboxyl group in the saturated monomer (a-1), the amount of the carboxyl group-containing ethylene used is from the viewpoint of stability during polymerization of the monomer component (b) and storage stability. The ethylenically unsaturated monomer (a-2) is contained in an amount of 0.1 to 0.
The amount is preferably in the range of 5 mol, and is also preferable from the viewpoint that the gel fraction of the carboxyl group-containing polymer [A] can be easily adjusted to 95% by weight or less.

When the monomer (a-2) has no reactivity with the carboxyl group in the carboxyl group-containing ethylenically unsaturated monomer (a-1), the carboxyl group-containing ethylenic It is preferable to use the ethylenically unsaturated monomer (a-2) in the range of 0.1 to 2.0 mol per 1 mol of the unsaturated monomer (a-1). It is preferable because the stability of the monomer component (b) during polymerization is improved.

When the carboxyl group-containing polymer [A] is produced from the monomer component (a) in an aqueous medium, it can be polymerized 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 of the resulting cured product is not deteriorated.

As the emulsifier, most known emulsifiers can be used, but anionic emulsifiers and nonionic emulsifiers such as cationic emulsifiers are preferred.

Examples of anionic emulsifiers include sulfuric acid esters of higher alcohols, alkylbenzene sulfonates, polyoxyethylene alkylphenyl sulfonates, and the like, and nonionic emulsifiers include polyoxyethylene alkyl ethers and polyoxyethylene alkyl phenyl sulfonates. Examples thereof include oxyethylene alkyl phenyl ether, polyoxyethylene-polyoxypropylene block copolymer, and the like, and one kind or a mixture of two or more kinds thereof can be used.

It is also possible to use an emulsifier having a polymerizable unsaturated group in the molecule, which is generally referred to as a reactive emulsifier, and having surface-active ability. For example, it has a sulfonic acid group and a salt thereof. "Latemur S-180" (Kao Corporation)
), "Eleminol JS-2", "Eleminol RS
-30 "(manufactured by Sanyo Kasei Co., Ltd.)," Aqualon HS-10, HS-20 "(manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) having a sulfate group and a salt thereof," Adecaria Soap SE-10 ".
N "(manufactured by Asahi Denka Kogyo Co., Ltd.)," New Frontier A-229E "having a phosphate group (Daiichi Kogyo Seiyaku Co., Ltd.)
"New Frontier N-177E" (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) having a nonionic hydrophilic group, such as "Aquaron RN-10, RN-20, RN-30, RN-5".
0 "(manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and the like, and one kind or a mixture of two or more kinds thereof can be used.

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

The above emulsifier and dispersion stabilizer are used for the purpose of improving stability during polymerization and storage stability.
From the viewpoint of water resistance of the emulsion film, it is necessary to minimize the amount used, and the amount used is preferably 2% by weight or less based on the solid content of the carboxyl group-containing polymer [A].

The aqueous medium for polymerizing the carboxyl group-containing polymer [A] is not particularly limited, but water alone may be used, or a mixed solution of water and a water-soluble solvent. May be used as. Examples of the water-soluble solvent used here include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethyl carbitol, ethyl cellosolve, and butyl cellosolve, and polar solvents such as N-methylpyrrolidone.
These 1 type, or 2 or more types of mixture can be used. The amount of the water-soluble solvent used when using a mixture of water and a water-soluble solvent can be arbitrarily selected from the viewpoint of stability during polymerization, the risk of ignition of the resulting polymer aqueous dispersion,
From the viewpoint of safety and hygiene, it is preferable to use the water-soluble solvent in the smallest possible amount. For these reasons, it is preferable to use water alone.

As a method for producing the carboxyl group-containing polymer [A] in an aqueous medium, water and a monomer component containing the carboxyl group-containing ethylenically unsaturated monomer (a-1) as an essential component ( a), a polymerization catalyst, and a method of collectively mixing (if necessary, an emulsifier and a dispersion stabilizer) for polymerization, a monomer dropping method of dropping the monomer component (a), water, a monomer component (a ), A so-called pre-emulsion method in which a mixture of emulsifiers is added dropwise can be used for the production.

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

At the time of polymerization, it is possible to add a hydrophilic solvent and a hydrophobic solvent and known additives, but the amount used is within a range that does not adversely affect the finally obtained cured product. It is preferable to suppress it.

A radical polymerization initiator is used as a polymerization initiator used in the polymerization of the carboxyl group-containing polymer [A], and examples thereof include persulfates such as potassium persulfate and ammonium persulfate, benzoyl peroxide and cumene hydro. There are organic peroxides such as peroxides, hydrogen peroxide, etc., and radical polymerization is performed using only these peroxides, or the above peroxides are used in combination with a reducing agent such as sodium acid sulfite or sodium thiosulfate. Can also be polymerized with the redox polymerization initiator system described above, and an azo initiator such as 4,4′-azobis (4-cyanopentanoic acid) or 2,2′-azobis (2-amidinopropane) dihydrochloride is used. It is also possible to do so.

When it is necessary to adjust the molecular weight of the carboxyl group-containing polymer [A], a compound having chain transfer ability, such as lauryl, is used as a molecular weight regulator when synthesizing the carboxyl group-containing polymer [A]. Mercaptan,
Octyl mercaptan, dodecyl mercaptan, 2-mercaptoethanol, octyl thioglycolate, 3-
Mercaptans such as mercaptopropionic acid, or α
-Methylstyrene dimer or the like may be added.

The polymerization temperature at the time of polymerizing the carboxyl group-containing polymer [A] varies depending on the kind of the monomer used, the kind of the polymerization initiator, etc., but is usually 30 to 90 when the polymerization is carried out in an aqueous medium. A temperature range of ° C is preferred.

The carboxyl group of the carboxyl group-containing polymer [A] may be used as it is for the polymerization of the monomer component (b) without being neutralized, but it is stable during the polymerization of the monomer component (b). From the viewpoint of the above, a method of neutralizing a part of the carboxyl group with a basic substance and using it is preferable.

The degree of neutralization of the carboxyl group is not particularly limited, but the amount of the basic substance used is 10 mol% based on all the carboxyl groups in the polymer [A] from the viewpoint of stability during polymerization.
It is preferable to make the above.

As the basic substance used as the neutralizing agent, usual 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 Amine, diethanolamine,
Examples thereof include water-soluble organic amines such as triethanolamine, ethylenediamine, and diethylenetriamine, and one kind or a mixture of two or more kinds 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 scatter at room temperature or upon heating.

[0094] The carboxyl group-containing polymer [A] thus obtained forms phase A in the resin phase of the curable polymer aqueous dispersion of the present invention.

In the production method of the present invention, an ethylenically unsaturated monomer (b-1) containing a basic nitrogen atom-containing group is added in the presence of the carboxyl group-containing polymer [A] obtained as described above. ) An essential component of the monomer component (b)
To obtain an aqueous dispersion of polymer particles [X], and then add the polyfunctional epoxy compound [Y] to the aqueous dispersion (hereinafter abbreviated as “method”), or Monomer component (b) containing an ethylenically unsaturated monomer (b-1) containing a basic nitrogen atom-containing group as an essential component
Is polymerized in the presence of a polyfunctional epoxy compound [Y] to obtain an aqueous dispersion of polymer particles [X] (hereinafter,
Abbreviated as "method").

Here, the ethylenically unsaturated monomer (b-1) containing a basic nitrogen atom-containing group is 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, which is excellent in water resistance, solvent resistance, mechanical strength and the like. It is possible to exhibit excellent performance.

The ethylenically unsaturated monomer (b-1) containing 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]. No, for example, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (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
-Secondary amino group-containing polymerizable monomer such as butylaminoethyl (meth) acrylate; aminomethyl acrylate,
Examples thereof include primary amino group-containing polymerizable monomers such as aminoethyl acrylate, aminopropyl (meth) acrylate, amino-n-butyl (meth) acrylate, butylvinylbenzylamine, vinylphenylamine and p-aminostyrene. It is possible to use one kind or a mixture of two or more kinds thereof.

In addition, N-vinylformamide can also be used as one component of the polymerizable monomer. In this case, once the polymer is produced using N-vinylformamide, the polymer is hydrolyzed. To produce a polyvinylamine having a primary amino group to produce an ethylenic polymer [B]
It can be.

Among these, the ethylenically unsaturated monomer (b-1) containing a basic nitrogen atom-containing group is particularly excellent in reactivity with the polyfunctional epoxy compound [Y], and is a cured product. In terms of further improving the durability and water resistance of N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (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, - [N, N-diethylamino] styrene, 2-vinylpyridine, it is preferable to use a tertiary amino group-containing polymerizable monomer such as 4-vinylpyridine.

The monomer component (b) used in the present invention includes, in addition to the ethylenically unsaturated monomer (b-1) containing a basic nitrogen atom-containing group described in detail, the monomer (b). -1) and a copolymerizable ethylenically unsaturated monomer can be used in combination, 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). Acrylic esters such as acrylate, dicyclopentanyl (meth) acrylate, phenyl (meth) acrylate, 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) ethyl (meth) ac Fluorine-containing vinyl monomers such as rate; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl versatate; vinyl ethers such as methyl vinyl ether, 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 naphthalene, vinyl compounds having an aromatic ring such as divinylstyrene; 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.

If desired, an ethylenically unsaturated monomer containing a reactive functional group other than the basic nitrogen atom-containing group may be used in combination as the other ethylenically unsaturated monomer. As such ethylenically unsaturated monomer, although not particularly limited, for example, glycidyl (meth) acrylate, allyl glycidyl ether, epoxy group-containing polymerizable monomer such as 4-vinylcyclohexane monoepoxide Body; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate and other hydroxyl group-containing polymerizable monomers; (meth) acrylamide, N
An amide group-containing polymerizable monomer such as monoalkyl (meth) acrylamide, N, N-dialkyl (meth) acrylamide; N-methylol (meth) acrylamide, N-
Polymerizable monomer containing methylolamide group such as isopropoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide and its alkoxy compound; vinyltrichlorosilane, vinyltrimethoxysilane , Vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, etc. hydrolyzable silyl group or silanol group-containing polymerization Polymerizable monomer; aziridinyl group-containing polymerizable monomer such as 2-aziridinylethyl (meth) acrylate; (meth) acryloyl isocyanate, (meth)
2-Isopropenyl-2-, a polymerizable monomer containing an isocyanate group and / or a blocked isocyanate group, such as a phenol adduct of acryloyl isocyanate ethyl.
Oxazoline group-containing polymerizable monomers such as oxazoline, 2-vinyl-2-oxazoline and 2-oxazodinylethyl (meth) acrylate; dicyclopentenyl (meth)
Cyclopentenyl group-containing polymerizable monomers such as acrylates; Carbonyl group-containing polymerizable monomers such as acrolein and diacetone (meth) acrylamide; Acetoacetyl group-containing polymerizable monomers such as acetoacetoxyethyl (meth) acrylate; (Meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, β- (meth) acryloyloxyethyl hydrogen succinate, β- (meth) acryloyloxyethyl hydrogen phthalate, or their half-esters or salts thereof And the like, and one kind or a mixture of two or more kinds thereof can be used.

Further, if necessary, as another ethylenically unsaturated monomer, it has two or more ethylenically unsaturated groups for the purpose of crosslinking the ethylenic polymer [B] to increase the molecular weight. It is also possible to use a polyfunctional ethylenically unsaturated monomer in combination, and examples of the polyfunctional ethylenically unsaturated monomer include ethylene glycol di (meth) acrylate and 1,6-hexanediol diester. (Meth) acrylate, neopentyl glycol di (meth)
Examples thereof include acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, allyl (meth) acrylate, diallyl phthalate, and divinylbenzene.

Further, as another ethylenically unsaturated monomer, for the purpose of improving the stability during emulsion polymerization and the storage stability of the aqueous dispersion of polymer particles [X], the water resistance of the film obtained is improved. Within a range that does not deteriorate the property, ethylenically unsaturated monomer containing sulfonic acid group and / or sulfate group (and / or salt thereof), phosphoric acid ester group-containing ethylenically unsaturated monomer, and nonionic A hydrophilic group-containing ethylenically unsaturated monomer or the like can be used in combination.

Specifically, for example, as the ethylenically unsaturated monomer containing a sulfonic acid group and / or a sulfate group (and / or a salt thereof), a vinyl sulfonic acid such as vinyl sulfonic acid, styrene sulfonic acid or the like is used. Allyl group-containing sulfonic acids such as salts, allylsulfonic acid, 2-methylallylsulfonic acid or salts thereof, (meth) acrylate group-containing sulfones such as 2-sulfoethyl (meth) acrylate and 2-sulfopropyl (meth) acrylate Examples thereof include acids or salts thereof, (meth) acrylamide group-containing sulfonic acids such as (meth) acrylamide-t-butylsulfonic acid or salts thereof, and 2-hydroxy group as a phosphoric acid ester group-containing ethylenically unsaturated monomer. 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, polyethylene glycol di (meth) acrylate, and the like. Mixtures of two or more can be used.

The ethylenically unsaturated monomer (b-1) containing a basic nitrogen atom-containing group described above and the monomer (b-
The type of the ethylenically unsaturated monomer copolymerizable with 1) is selected in consideration of the curability with the polyfunctional epoxy compound [Y] and the compatibility with the carboxyl group-containing polymer [A]. The amount can be selected, but specifically, the monomer (b-
The use ratio of 1) and the ethylenically unsaturated monomer copolymerizable with the monomer is the former / the latter = 0.5 / 9 on a weight basis.
9.5 to 30/70 are various factors such as stability during polymerization of the monomer component (b), curability with the polyfunctional epoxy compound [Y], and water resistance of the obtained cured product. It is preferable in terms of physical properties. Further, as described above, the ethylenic polymer [B]
The content of the basic nitrogen atom-containing group in 1 g is 0.05 to
It is preferable to appropriately adjust the amount used so as to be 2.0 mmol.

Further, when the carboxyl group-containing polymer [A] has a reactive functional group other than the carboxyl group and the reactive functional group can react with the basic nitrogen atom-containing group, a unit amount of It goes without saying that the basic nitrogen atom-containing group in the body (b-1) may be crosslinked by the reaction with the reactive functional group in the carboxyl group-containing polymer [A].
Polyfunctional epoxy compound [Y] in polymer particles [X]
It is preferable to adjust the amount of the monomer (b-1) used so that the basic nitrogen atom-containing group capable of reacting with is left.

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

In the method and method, the method of polymerizing the monomer component (b) in the presence of the carboxyl group-containing polymer [A] is not specified, but it is usually emulsified in an aqueous medium. It can be performed by a polymerization method.

At that time, the carboxyl group-containing polymer [A]
The ratio of the monomer component (b) used relative to that of the carboxyl group-containing polymer [A] / monomer component (b) is from the viewpoint of stability during emulsion polymerization and water resistance of the resulting cured product. The weight is preferably 1/1 to 1/100.

That is, the carboxyl group-containing polymer [A] 1
When the weight ratio of the monomer component (b) to 1 part by weight is 1 part by weight or more, the resulting cured product has good water resistance, and a single amount per 1 part by weight of the carboxyl group-containing polymer [A]. When the weight ratio of the body component (b) is 100 parts by weight or less, the stability of the monomer component (b) during emulsion polymerization becomes good.

On the other hand, from the viewpoint of storage stability as an aqueous dispersion of a curable polymer, it contains a carboxyl group-containing polymer [A] which constitutes phase A and a basic nitrogen atom-containing group which constitutes phase B. The weight ratio of the ethylenic polymer [B] is
The solid fraction ratio of [A] / [B] is preferably 1/1 to 1/9. That is, [B] for 1 part by weight of [A]
By setting the ratio in terms of solid content of 9 parts by weight or less,
It is preferable because the storage stability of the curable polymer aqueous dispersion is remarkably improved.

That is, in view of the balance between the physical properties of the cured product and the storage stability as an aqueous dispersion of the curable polymer, the carboxyl group-containing polymer [A] constituting the A phase and the basic nitrogen constituting the B phase. The weight ratio of the ethylenic polymer [B] containing an atom-containing group is [A] / [B] solid fraction,
The range of 3/7 to 1/9 is most preferable, and specifically, the ratio of the monomer component (b) to the carboxyl group-containing polymer [A] is [A] / (on a weight basis. b)
Most preferably, it is in the range of 3/7 to 1/9.

It is also possible to use an emulsifier and a dispersion stabilizer for the purpose of improving the stability during emulsion polymerization and the storage stability. It is preferable to reduce the amount as much as possible, and in the emulsion polymerization, it is most preferable to emulsion-polymerize the monomer component (b) without newly adding an emulsifier or the like.

That is, when the emulsion polymerization of the monomer component (b) is carried out without using an emulsifier or other dispersion stabilizer, an ethylenic polymer obtained by the polymerization of the monomer component (b) [ B] is easily incorporated into the carboxyl group-containing polymer [A], and easily becomes a particle having a structure containing the carboxyl group-containing polymer [A] and the ethylenic polymer [B] in one particle. Is also preferable.

The specific method for emulsion-polymerizing the monomer component (b) is not particularly limited, but for example, as a polymerization method in the method, 1. The presence of the carboxyl group-containing polymer [A] is present. A method in which the monomer component (b) and the polymerization catalyst are mixed together in an aqueous medium and polymerized, 2. Water, the monomer component (b) and the carboxyl group-containing polymer [A] ( A so-called pre-emulsion method in which a mixture of a small amount of an emulsifier) is added in advance, 3. A monomer addition in which the monomer component (b) is added in an aqueous medium in which the carboxyl group-containing polymer [A] is present. Law etc. are mentioned.

4. In the presence of the carboxyl group-containing polymer [A], the monomer component (b) was added to allow the carboxyl group-containing polymer [A] to swell with the monomer component (b) and then polymerized. A method of polymerizing by adding an initiator, and the like. Next, as a polymerization method in the method,

5. A method in which the monomer component (b) and the polymerization catalyst are mixed together in an aqueous medium in which the carboxyl group-containing polymer [A] and the polyfunctional epoxy compound [Y] are present to perform polymerization, 6. A method in which the monomer component (b), the polyfunctional epoxy compound [Y] and the polymerization catalyst are mixed together in an aqueous medium in which the carboxyl group-containing polymer [A] is present, and polymerized. A mixture of water, a monomer component (b), a carboxyl group-containing polymer [A] (a small amount of an emulsifier if necessary) and a polyfunctional epoxy compound [Y] is dropped into a medium, which is so-called. Pre-emulsion method, 8. Monomer dropping method in which the monomer component (b) is dropped into an aqueous medium in which the carboxyl group-containing polymer [A] and the polyfunctional epoxy compound [Y] are present.

9. A monomer dropping method in which a mixture obtained by previously mixing the monomer component (b) and the polyfunctional epoxy compound [Y] is dropped into an aqueous medium in which the carboxyl group-containing polymer [A] is present, 10. The monomer component (b) is added to an aqueous medium in which the carboxyl group-containing polymer [A] and the polyfunctional epoxy compound [Y] coexist to prepare a single amount of the carboxyl group-containing polymer [A]. A method of polymerizing by adding a polymerization initiator after swelling with the body component (b), and the like.

Among the above-mentioned polymerization methods, particularly the emulsion polymerization of the monomer component (b) can be carried out by further reducing the amount of the emulsifier or other dispersion stabilizer used, or without using it at all. From the viewpoint of the stability of the polymerization of the monomer component (b), it is preferable to carry out the monomer dropping method in the method 3 and the monomer dropping method in the methods 8 and 9.

The monomer component (b) is prepared by the monomer dropping method.
As a specific method of polymerizing, for example, a stirring reactor equipped with a dropping funnel, an aqueous medium, a polymerization initiator, a carboxyl group-containing polymer [A], and in the method 8. Of the polymerizable epoxy compound [Y], then the temperature of the reactor is raised to the polymerization temperature, and the monomer component (b) (in the method 9., the polyfunctional epoxy compound [Y] is further added through the dropping funnel). Mixture mixed with monomer (b))
The method of dropping is mentioned.

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

The polymerization temperature varies depending on the type of monomer used, the type of polymerization initiator, etc., but is usually 30.
A temperature range of up to 90 ° C is suitable, more preferably 40
The range of 80 ° C to 80 ° C is mentioned.

The dropping rate of the monomer component (b) is the ratio of the carboxyl group-containing polymer [A] to the monomer component (b),
And it is preferable to appropriately adjust the concentration of the solid content of the resulting polymer aqueous dispersion.

Further, in the emulsion polymerization of the monomer component (b), it is possible to add a hydrophilic solvent and a hydrophobic solvent and to add known additives within a range that does not impair the effects of the present invention.

The polymerization initiator used here is not particularly limited, and a usual radical polymerization initiator is used, and examples thereof include persulfates such as potassium persulfate and ammonium persulfate, benzoyl peroxide and cumene hydro. There are organic peroxides such as peroxides, hydrogen peroxide, etc., and radical polymerization is performed using only these peroxides, or the above peroxides are used in combination with a reducing agent such as sodium acid sulfite or sodium thiosulfate. Can also be polymerized with the redox polymerization initiator system described above, and an azo initiator such as 4,4′-azobis (4-cyanopentanoic acid) or 2,2′-azobis (2-amidinopropane) dihydrochloride is used. It is also possible to do so.

When it is necessary to adjust the molecular weight of the ethylenic polymer [B] obtained by emulsion polymerization of the monomer component (b), the molecular weight is adjusted when the monomer component (b) is polymerized. A compound having a chain transfer ability as an agent, for example, mercaptans such as lauryl mercaptan, octyl mercaptan, dodecyl mercaptan, 2-mercaptoethanol, octyl thioglycolate, and 3-mercaptopropionic acid, or α-methylstyrene dimer is added. May be. No.

The ethylenic polymer [B] thus obtained forms the B phase in the polymer particles [X] of the curable polymer aqueous dispersion of the present invention. The molecular weight of the phase B ethylenic polymer [B] is not particularly limited,
A weight average molecular weight of 100,000 or more is preferable from the viewpoint of physical properties such as water resistance, solvent resistance and mechanical strength of the cured product.

In the present invention, the polyfunctional epoxy compound [Y] may be added (method) after the polymer [B] is produced and the polymer particles [X] are obtained as described above. ,
Further, as shown in 5. to 10., the polymer [B] may be produced in the presence of the polyfunctional epoxy compound [Y], but the stability of the monomer component (b) during polymerization is stable. Alternatively, from the viewpoint of storage stability of the curable polymer aqueous dispersion, a method of producing an aqueous dispersion of polymer particles [X] and then adding a polyfunctional epoxy compound [Y] to the aqueous dispersion is preferable.

In the case of this method, the method of adding the polyfunctional epoxy compound [Y] is as follows. Depending on the properties of the polyfunctional epoxy compound [Y], a water-soluble one is added as it is or a water-soluble one is added after dilution. However, a water-insoluble substance can be added as it is, or can be added by dispersing it in water using an emulsifier or the like.

Further, depending on the properties of the polyfunctional epoxy compound [Y], aggregates may be generated when added to the aqueous dispersion of the polymer particles [X], but the polymer particles [X] It is preferable to neutralize the carboxyl group therein with the above-mentioned basic substance because the dispersion stability of the polymer particles [X] is improved and the stability when the polyfunctional epoxy compound [Y] is added is also improved. .

In particular, when a basic substance is used for neutralization so that the pH of the aqueous dispersion of the polymer [X] before the addition of the polyfunctional epoxy compound [Y] is in the range of 7 to 12, it is cured. It is preferable because the stability of the water-soluble polymer dispersion is improved.

Furthermore, the addition timing of the polyfunctional epoxy compound [Y] is excellent in the curability of the resulting cured product and the various properties such as water resistance, solvent resistance and mechanical strength of the cured product. The polyfunctional epoxy compound [Y] is preferably added immediately before using the curable polymer aqueous dispersion.

The amount of the polyfunctional epoxy compound [Y] in the curable polymer aqueous dispersion is not particularly limited, but it depends on the curability of the curable polymer aqueous dispersion and the performance of the cured film. From the aspect of storage stability of the curable polymer aqueous dispersion,
Basic nitrogen atom-containing group 1 contained in polymer particles [X]
It is preferably used in the range of 0.3 to 3.0 mol, based on mol.

The curable polymer aqueous dispersion of the present invention thus obtained is itself crosslinked at room temperature or by heating to form a cured 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 and used. Examples of the cross-linking agent include polyfunctional melamine compounds and polyfunctional melamine compounds. Polyamine compound, polyfunctional polyethyleneimine compound, polyfunctional (block)
Examples thereof include isocyanate compounds and metal salt compounds, and these can be used alone or as a mixture of two or more kinds.

In addition to the above-mentioned cross-linking agent, a water-soluble or water-dispersible thermosetting resin such as phenol resin, urea resin, melamine resin or urethane resin may be mixed and used.

If necessary, a filler, a pigment, a pH adjusting agent, a film-forming aid, a leveling agent, a thickener, a water repellent, a defoaming agent, etc. may be added as long as the desired effects of the present invention are not impaired. Known materials can be appropriately added and used.

The curable polymer aqueous dispersion of the present invention gives a cured product excellent in water resistance, solvent resistance and mechanical strength, and although its use is versatile, it is It is useful in fields where solvent resistance is required, such as paints, primer treatment agents, adhesives, film coating agents, textile industry resins (nonwoven fabric binders, flocking binders, etc.), paper processing resins, glass It can be used as a resin for fiber processing (glass fiber sizing agent, binder for glass paper, etc.), resin for mortar modification, and the like. Especially,
Paint, film coating, adhesion, textile industry resin,
As described above, it exerts an extremely excellent effect in applications used for coating processing in application fields such as resins for paper processing.

[0138]

EXAMPLES 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, "%" means% by weight and "part" means part by weight.

Reference Example A-1 <Production of Carboxyl Group-Containing Polymer [A-1]> 250 parts of deionized water was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer and a dropping funnel. The temperature was raised to 80 ° C. while blowing nitrogen. Under stirring, 0.5 part of ammonium persulfate was added, followed by a monomer mixture consisting of 50 parts of n-butyl acrylate, 25 parts of styrene and 25 parts of methacrylic acid (as carboxyl group-containing monomer (a-1)). (Monomer component (a)) was added dropwise for 60 minutes while maintaining the temperature at 80 ± 2 ° C. for polymerization. After the completion of dropping, the mixture was stirred at the same temperature for 60 minutes. After that, the contents are cooled and adjusted with deionized water so that the solid content concentration becomes 20.0%,
The mixture was filtered through a 100 mesh wire mesh.

The obtained polymer aqueous dispersion had a solid content concentration of 20.0%, a pH of 2.3, and a viscosity of 10 cps (measured with a BM type viscometer at 25 ° C.), and did not pass through a 100 mesh wire mesh. The content was 0.1% or less (ratio of generated dispersion liquid). Aqueous dispersion of this carboxyl group-containing polymer is [A
-1]. The polymer contained in this [A-1] had an acid value of 130, a gel fraction of 43.0%, and a particle diameter of 105 nm. The weight average molecular weight of [A-1] is such that the polymer is GPC.
It was not completely dissolved in tetrahydrofuran used as the eluent and the sample solution, and the total molecular weight could not be measured because the gel content was large.

Reference Example A-2 <Production of carboxyl group-containing polymer [A-2]> Carboxyl group was prepared in the same manner as in Reference Example 1 except that the monomer mixture shown in Table 1 below was used. An aqueous dispersion [A-2] of the group-containing polymer was obtained. The acid value, the weight average molecular weight, the gel fraction, and the particle diameter of the polymer contained in this [A-2] were as described in 1 of Table 1.

Reference Example A-3 <Production of Carboxyl Group-Containing Polymer [A-3]> 250 parts of deionized water was placed in the same reaction vessel as in Reference Example 1, and Levenol WZ (manufactured by Kao Corporation; as an emulsifier; Sodium polyoxyethylene alkylphenyl ether sulfonate, solid content 25%) 2 parts (solid content 0.5 parts) are added,
The temperature was raised to 80 ° C. while blowing nitrogen under stirring to dissolve the emulsifier. Then, polymerization was performed in the same manner as in Reference Example 1. Aqueous dispersion of a carboxyl group-containing polymer [A-3] in the same manner as in Reference Example 1 except that the above emulsifier was added and the monomer mixture shown in Table 1 below was used.
I got

The acid value of the polymer contained in this [A-3],
The weight average molecular weight, gel fraction and particle size were as described in 1 of Table 1.

Reference Examples A-4 and A-5 <Production of Carboxyl Group-Containing Polymers [A-4] and [A-5]> Glycidyl methacrylate (reactive with basic nitrogen atom-containing group as a monomer mixture) Aqueous dispersion of a carboxyl group-containing polymer [as in Reference Example 3 except that the one shown in Table 1 below containing a monomer (a-2) having a reactive group) was used. A-4], [A
-5] was obtained. The acid value, the weight average molecular weight, the gel fraction, and the particle size of the polymers contained in [A-4] and [A-5] are as shown in Table 1-2.

Reference Example A-6 <Production of Carboxyl Group-Containing Polymer [A-6]> 100 parts of isopropyl alcohol was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
The temperature was raised to 80 ° C. while blowing nitrogen. With stirring, 90 parts of acrylic acid, 10 parts of n-dodecyl mercaptan,
A monomer mixture consisting of 1 part of 2,2′-azobisisobutyronitrile was added while maintaining the temperature inside the reaction vessel at 80 ± 2 ° C.
The mixture was added dropwise over 20 minutes for polymerization. After completion of dropping, the mixture was stirred at the same temperature for 120 minutes. Then, the content was cooled to obtain a polymer solution having a solid content concentration of 50.2%. To the obtained polymer solution, 75 parts of 28% ammonia water, deionized water 1
00 parts was added and neutralized to obtain a polymer aqueous solution. Adjust with deionized water so that the solid concentration becomes 20.0%, and
It was filtered through a 0 mesh wire mesh.

The resulting polymer aqueous solution had a solid content of 2
The viscosity was 0.0%, pH 8.5, and viscosity 150 cps (measured with a BM type viscometer at 25 ° C.). This polymer aqueous solution is designated as [A-6]. The acid value, the weight average molecular weight, and the gel fraction of the polymer contained in this [A-6] were as shown in Table 1-2.

Reference Example A-7 <Production of Carboxyl Group-Containing Polymer [A-7]> 100 parts of isopropyl alcohol was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer and a dropping funnel.
The temperature was raised to 80 ° C. while blowing nitrogen. A monomer mixture consisting of 50 parts of n-butyl acrylate, 20 parts of styrene, 20 parts of methyl methacrylate, 10 parts of methacrylic acid, and 2 parts of t-butyl peroxybenzoate was stirred while maintaining the temperature in the reaction vessel at 80 ± 2 ° C. It was added dropwise over 180 minutes for polymerization.

After completion of dropping, the mixture was stirred at the same temperature for 120 minutes. Then, the contents are cooled and the solid content concentration is 50.5%.
A polymer solution of Next, 2
7 parts of 8% ammonia water was added for neutralization, and then 370 parts of deionized water was added over 60 minutes to obtain an aqueous dispersion of the polymer. The solid content concentration was adjusted to 20.0% with deionized water, and filtered through a 100-mesh wire net.

The obtained polymer aqueous dispersion had a solid content concentration of 20.0%, a pH of 8.5, a viscosity of 100 cps (measured with a BM type viscometer at 25 ° C.), and a 100-mesh wire mesh non-aggregation. The product was 1.0% (ratio of product dispersion liquid). The aqueous dispersion of this polymer is designated as [A-7]. The acid value, the weight average molecular weight of the polymer contained in this [A-7],
The gel fraction and the particle size were as described in Table 1-2.

The acid value, the weight average molecular weight, the gel fraction, and the particle diameter in 1 and 2 in Table 1 were measured by the following methods. <Acid value> The acid value is a numerical value representing the amount of carboxyl groups contained in the carboxyl group-containing polymer [A], and is for neutralizing the free carboxyl groups contained in 1 g of the carboxyl group-containing polymer [A]. It is the number of mg of potassium hydroxide required.

A sample was coated 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, 1 g was precisely weighed and dissolved in 100 g of tetrahydrofuran to give a measurement sample.

The measuring method was a neutralization titration method using an aqueous potassium hydroxide solution. To the tetrahydrofuran solution in which the sample was dissolved, 2 drops of phenolphthalein was added,
An aqueous solution of N-potassium hydroxide was added dropwise to make the end point a point where the color of the solution changed from colorless to light pink, and the consumption amount of potassium hydroxide at that time was measured, and the mg number was measured to obtain the carboxyl group-containing polymer [A]. The acid value was used.

For the sample which was not dissolved in tetrahydrofuran, the measurement by this method is impossible. Therefore, it was determined from the charged amount of the carboxyl group-containing monomer used during the production of the carboxyl group-containing polymer [A]. The calculated value was calculated as the acid value of the carboxyl group-containing polymer [A].

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

A sample was coated 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.

As a measuring device, a high performance liquid chromatograph LC-08 type manufactured by Nippon Analytical Industry Co., Ltd. was used. The column is
Showa Denko KK packed columns A-800P, A-8
06, A-805, A-803, and A-802 were used in combination.

As a standard sample, standard polystyrene (Molecular weight: 4.48 million, manufactured by Showa Denko KK and Toyo Soda Co., Ltd.,
4.25 million, 2.88 million, 2.75 million, 18.50 million, 8.60 million, 4
50,000, 411,000, 355,000, 190,000, 160,000, 9.
640,000, 37,900, 198,000, 196,000,
5570, 4000, 2980, 2030, 500) to prepare a calibration curve.

Tetrahydrofuran was used as the eluent and the sample solution, the flow rate was 1 mL / min, and the sample injection rate was 50.
The weight average molecular weight was measured using an RI detector with 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
The sample was coated so that it had a thickness of 7 mm, dried at room temperature for 7 days, and then the film was peeled from the glass plate.
The test piece was cut into 0 mm square. Next, the weight (G ₀ ) of the test piece before being immersed in acetone was measured in advance, and the acetone-insoluble portion of the test piece after being immersed in the acetone solution at room temperature for 24 hours was separated, and the test piece was dried at 110 ° C. The weight (G ₁ ) after drying for an hour was measured, and the gel fraction was determined according to the following method.

[0160]

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

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

[0162]

[Table 1]

[0163]

[Table 2]

[The amounts of the polymerizable monomer and the emulsifier used in 1 and 2 of Table 1 are shown in parts by weight of the solid content. The agglomerates in 1 and 2 of Table 1 are the amounts of a 100-mesh wire mesh non-passing agglomerates after the completion of the polymerization when the carboxyl group-containing polymer [A] was polymerized in an aqueous medium. It was expressed as a weight percentage of the dispersion liquid ratio.

The acid value * in Table 1 indicates that the acid value of the carboxyl group-containing polymer [A] could not be measured, and therefore the calculated value obtained from the composition ratio of the raw materials used is described. . The official names of the abbreviations in Table 1 are shown below.

BA; n-butyl acrylate St; styrene MAA; methacrylic acid D-SH; n-dodecyl mercaptan EA; ethyl acrylate MMA; methyl methacrylate GMA; glycidyl methacrylate THF; tetrahydrofuran
]

Reference Example B-1 <Production of Polymer Aqueous Dispersion [B-1]> 70 parts of deionized water in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer and a dropping funnel. 125 parts (25 parts of solid content) of the aqueous dispersion [A-1] of the carboxyl group-containing polymer obtained in Example A-1 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 50 parts of n-butyl acrylate, 48 parts of methyl methacrylate and dimethylaminoethyl methacrylate (a monomer (b containing a basic nitrogen atom-containing group). −
1) as a monomer mixture consisting of 2 parts (monomer component (b)) while maintaining the reaction vessel internal temperature at 80 ± 2 ° C.
The mixture was added dropwise over 0 minutes for polymerization.

After completion of dropping, the mixture was stirred at the same temperature for 60 minutes.
Then, the content was cooled, adjusted with deionized water so that the solid content concentration was 40.0%, and filtered through a 100-mesh wire net.

The obtained polymer aqueous dispersion had a solid content concentration of 40.0%, a pH of 4.8, a viscosity of 30 cps (measured with a BM type viscometer at 25 ° C.), and a 100-mesh wire mesh non-aggregation. The product was 5.0% (ratio of generated dispersion liquid).
This polymer aqueous dispersion is designated as [B-1].

This polymer aqueous dispersion [B-1] was obtained by using the carboxyl group-containing polymer [A] constituting the A phase of the polymer particles having an acid value of 163 and the ethylenic polymer [B] constituting the B phase. ] The content of the basic nitrogen atom-containing group is 0.13 mg per 1 g of the ethylenic polymer [B] (monomer component (b)).
(B-1) containing a basic nitrogen atom-containing group in
Calculated from the charged amount). Further, when the acid value and the content of the basic nitrogen atom-containing group of the entire polymer aqueous dispersion are calculated from the charged amounts of the carboxyl group-containing polymer [A] and the monomer component (b), the polymer aqueous dispersion is obtained. The acid value is 33 and the basic nitrogen atom-containing group content is 0.10 mg per 1 g of the solid content of the dispersion.

Reference Example B-2 <Production of Polymer Aqueous Dispersion [B-2]> 50 parts of deionized water in the same reaction vessel as in Reference Example B-1 and the carboxyl group obtained in Reference Example A-1. Aqueous dispersion of polymer containing [A-
1] 125 parts (solid content 25 parts) was added, a mixture of 1.5 parts of 28% ammonia water and 20 parts of deionized water was added over 1 hour to adjust the pH of the system to 6, and then, A monomer mixture consisting of 50 parts of n-butyl acrylate, 48 parts of methyl methacrylate and 2 parts of dimethylaminoethyl methacrylate was added while maintaining the temperature inside the reaction vessel at 80 ± 2 ° C.
Polymerization was performed by dropwise addition over a period of time, and an aqueous polymer dispersion was obtained in the same manner as in Reference Example B-1.

The obtained polymer aqueous dispersion had a solid content concentration of 40.0%, a pH of 5.8, a viscosity of 40 cps (measured with a BM type viscometer at 25 ° C.), and a 100-mesh wire mesh non-aggregation. The product was 0.1% (ratio of product dispersion liquid).
This polymer aqueous dispersion is designated as [B-2].

This polymer aqueous dispersion [B-2] was obtained by using the carboxyl group-containing polymer [A] constituting the A phase of the polymer particles to have an acid value of 163 and the B phase constituting the ethylenic polymer [B]. ] The content of the basic nitrogen atom-containing group is 0.13 mg per 1 g of the ethylenic polymer [B] (monomer component (b)).
(B-1) containing a basic nitrogen atom-containing group in
Calculated from the charged amount). Further, when the acid value and the content of the basic nitrogen atom-containing group of the entire polymer aqueous dispersion are calculated from the charged amounts of the carboxyl group-containing polymer [A] and the monomer component (b), the polymer aqueous dispersion is obtained. The acid value is 33 and the basic nitrogen atom-containing group content is 0.10 mg per 1 g of the solid content of the dispersion.

Reference Examples B-3 to B-9 <Production of Polymer Aqueous Dispersions [B-3] to [B-9]> In Reference Example B-2, the amount of the aqueous dispersion of the carboxyl group-containing polymer. And the kind (Reference Examples A-1 to A-7) and the kind of the monomer mixture as shown in Tables 1 to 3 below, the same procedure as in Reference Example B-2 was performed. Liquids [B-3] to [B-9] were obtained.

The pH of [B-3] to [B-9], 10
The amount of aggregates that did not pass through the 0-mesh wire mesh was as shown in Tables 1 to 3 together. In addition, [B-3] to [B-
The acid value and the content of the basic nitrogen atom-containing group calculated from the charged amount of the raw material [9] are shown in Tables 1 and 2.

Reference Example B-10 <Production of Polymer Aqueous Dispersion [B-10]> Stirrer, reflux condenser, nitrogen inlet tube, thermometer, dropping funnel for dropping monomer mixture, dropping funnel for dropping polymerization catalyst. 130 parts of deionized water, Aqualon HS-10 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .; ammonium propoxy group-containing polyoxyethylene alkylphenyl ether sulfonate, solid content 1)
(00%) 0.3 part, 80 ° C while blowing nitrogen
Temperature.

With stirring, 0.2 part of ammonium persulfate was added, and then a monomer mixture consisting of 10 parts of n-butyl acrylate, 5 parts of styrene, 2 parts of glycidyl methacrylate and 3 parts of methacrylic acid was added to the reaction vessel at an internal temperature. 80 ± 2 ℃
While maintaining the temperature at 60 ° C., it was added dropwise for 60 minutes to polymerize. (Production of Carboxyl Group-Containing Polymer [A]) After completion of dropping, the mixture was kept at the same temperature for 60 minutes.

After that, 3 parts of 5% aqueous ammonia was added dropwise at the same temperature over 30 minutes. Subsequently, the monomer mixture consisting of 35 parts of 2-ethylhexyl acrylate, 25 parts of styrene, 17 parts of methyl methacrylate, and 3 parts of dimethylaminoethyl methacrylate and 30 g of a 10% ammonium persulfate aqueous solution were separately added from a dropping funnel to raise the temperature inside the reaction vessel. While maintaining the temperature at 80 ± 2 ° C., the mixture was added dropwise over 180 minutes for polymerization. (Production of Ethylenic Polymer [B] Containing Basic Nitrogen Atom-Containing Group) After completion of dropping, the mixture was maintained at the same temperature for 60 minutes. Then, the content was cooled, adjusted with deionized water so that the solid content concentration was 40.0%, and filtered through a 100-mesh wire net.

The obtained polymer aqueous dispersion had a solid content concentration of 40.0%, a pH of 6.5, a viscosity of 30 cps (measured with a BM type viscometer at 25 ° C.), and a 100-mesh wire mesh non-aggregation. The product was 0.1% (ratio of product dispersion liquid).
This polymer aqueous dispersion is designated as [B-10].

The acid value and the content of the basic nitrogen atom-containing group calculated from the charged amount of the raw material [B-10] are shown in Tables 1 and 2.

Reference Example 11 130 parts of deionized water and Aqualon HS-10 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .; ammonium propoxy group-containing polyoxyethylene alkylphenyl ether sulfonate, solid type) in the same reaction vessel as in Reference Example 10 0.3 part) was added and the temperature was raised to 80 ° C. while blowing nitrogen.

With stirring, 0.5 part of 25% aqueous ammonia and 0.2 part of ammonium persulfate were added, followed by 10 parts of n-butyl acrylate and 5 parts of t-butyl methacrylate.
Part, γ-methacryloxypropyltrimethoxysilane 1
Part, 1 part of glycidyl methacrylate, and 3 parts of methacrylic acid were added dropwise for 60 minutes to polymerize while maintaining the internal temperature of the reaction vessel at 80 ± 2 ° C. (Production of Carboxyl Group-Containing Polymer [A]) After completion of dropping, the mixture was kept at the same temperature for 60 minutes.

Subsequently, n-butyl acrylate 35
Parts, t-butyl methacrylate 25 parts, methyl methacrylate 17 parts, dimethylaminoethyl methacrylate 3
The monomer mixture consisting of 10 parts and 30 g of a 10% aqueous solution of ammonium persulfate were separately added through a dropping funnel, and the temperature inside the reaction vessel was adjusted to 8
While maintaining the temperature at 0 ± 2 ° C., the mixture was added dropwise over 180 minutes for polymerization. (Production of Ethylenic Polymer [B] Containing Basic Nitrogen Atom-Containing Group) After completion of dropping, the mixture was maintained at the same temperature for 60 minutes. Then, the content was cooled, adjusted with deionized water so that the solid content concentration was 40.0%, and filtered through a 100-mesh wire net.

The obtained polymer aqueous dispersion had a solid content concentration of 40.0%, a pH of 6.5, a viscosity of 100 cps (measured with a BM type viscometer at 25 ° C.), and a 100-mesh wire mesh did not pass through. The product was 0.1% (ratio of product dispersion liquid). This polymer aqueous dispersion is designated as [B-11].

The acid value and the content of basic nitrogen atom-containing groups calculated from the charged amount of the raw material [B-11] are shown in Tables 1 and 2.

Comparative Reference Example C-1 <Preparation of Comparative Polymer Aqueous Dispersion [C-1]> To prepare a pre-emulsion of the monomer mixture, 30 parts of deionized water was placed in a pre-emulsion mixing container. Then, 4 parts of an emulsifier Emulgen 950 (manufactured by Kao Corporation; polyoxyethylene alkylphenyl ether, solid content 100%) was added and dissolved by stirring. 50 parts of n-butyl acrylate, 47 parts of methyl methacrylate, and 3 parts of dimethylaminoethyl methacrylate were sequentially added to the container, and stirred to prepare a pre-emulsion of the monomer mixture.

100 parts of deionized water was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel, and the temperature was raised to 80 ° C. while blowing nitrogen. With stirring, 0.3 part of ammonium persulfate was added, and then the pre-emulsion of the monomer mixture was added dropwise over 120 minutes while maintaining the pre-emulsion of the monomer mixture for polymerization. After the completion of dropping, the mixture was stirred at the same temperature for 60 minutes. Then, a polymer aqueous dispersion [C-1] was obtained by the same operation as in Reference Example B-1.

The pH of this [C-1] and the amount of aggregates that did not pass through the 100-mesh wire net were as shown in 6 of Table 2. The acid value and the content of the basic nitrogen atom-containing group calculated from the charged amount of the raw material of [C-1] are shown in Table 3-2.

[0190]

[Table 3]

[0191]

[Table 4]

[0192]

[Table 5]

The amounts of the carboxyl group-containing polymer [A] and the monomer component (b) used in Tables 1 to 3 are shown in parts by weight of the solid content. The agglomerates in 1 to 3 of Table 2 are the amounts of a 100-mesh wire mesh non-passaged agglomerates after the completion of the polymerization when the monomer component (b) was polymerized in an aqueous medium. It was expressed in% by weight of liquid ratio.

The official names of the abbreviations in Tables 1 to 3 are shown below. BA; n-butyl acrylate MMA; methyl methacrylate DMAEMA; dimethylaminoethyl methacrylate St; styrene 2-EHA; 2-ethylhexyl acrylate t-BMA; t-butyl methacrylate GMA; glycidyl methacrylate MAPTMA; γ-methacryloxypropyltrimethoxysilane Em -950; Emulgen 950 (manufactured by Kao Corporation; emulsifier)]

[0195]

[Table 6]

[0196]

[Table 7]

Example 1 <Production of Curable Polymer Aqueous Dispersion [E-1]> Stirrer,
In a mixing container equipped with a thermometer, 100 parts of the polymer aqueous dispersion [B-1] obtained in Reference Example B-1 (as an aqueous dispersion containing polymer particles [X]) was placed, and 25 Denacol EX-313 (manufactured by Nagase Kasei Co., Ltd .; glycerol polyglycidyl ether) (1.0 part) (as a polyfunctional epoxy compound [Y]) was added at 30 ° C., and the mixture was stirred for 30 minutes to obtain a solid component concentration of It was adjusted to 40.0% with deionized water and filtered through a 100-mesh wire net to obtain a curable polymer aqueous dispersion.

The obtained curable polymer aqueous dispersion had a solid content concentration of 40.0%, a pH of 4.8 and a viscosity of 250 cps (B
It was measured with an M-type viscometer at 25 ° C.), and the agglomerates that did not pass through the 100-mesh wire net was 5.0% (ratio to generated dispersion liquid). This curable polymer aqueous dispersion is designated as [E-1].

Example 2 <Production of Curable Polymer Aqueous Dispersion [E-2]> Example 1
100 parts of the polymer aqueous dispersion [B-1] obtained in Reference Example B-1 was placed in a mixing container similar to the above, and 2 parts of 25% aqueous ammonia was added to adjust the pH of the polymer aqueous dispersion. It was adjusted to 9.0.

Then, at 25 ° C., Denacol EX-313
Add 1.0 part and stir for 30 minutes until the solid content concentration is 4
It was adjusted to be 0.0% with deionized water and filtered through a 100-mesh wire net to obtain a curable polymer aqueous dispersion.

The resulting curable polymer aqueous dispersion had a solid content concentration of 40.0%, a pH of 8.9 and a viscosity of 1500 cps.
(Measured with a BM type viscometer at 25 ° C.), and the agglomerates that did not pass through the 100 mesh wire net were 0.1% or less (ratio to generated dispersion liquid). This curable polymer aqueous dispersion is [E-
2].

Examples 3 to 18 <Production of Curable Polymer Aqueous Dispersion [E-3] to [E-18]> In Example 1 or 2, polymer aqueous dispersion (polymer particles [X]). Types (reference examples B-1 to B-1
1), the curable weight was the same as in Example 1 or 2, except that the pH of the polymer aqueous dispersion, the type and amount of the polyfunctional epoxy compound [Y] were as shown in Table 4 below. Combined aqueous dispersions [E-3] to [E-18] were obtained.

The pH of [E-3] to [E-10], 1
The amount of agglomerates that did not pass through a 00 mesh wire mesh is 1 to 3 in Table 4.
Was also described in.

Comparative Example 1 <Production of Comparative Polymer Aqueous Dispersion [F-1]> Example 1
100 parts of the polymer aqueous dispersion [C-1] obtained in Comparative Reference Example C-1 was placed in a mixing container similar to that described above, and 1.5 parts of 25% aqueous ammonia was added to add the polymer aqueous dispersion. PH was adjusted to 9.0.

Then, at 25 ° C., Denacol EX-313
Add 1.0 part and stir for 30 minutes until the solid content concentration is 4
It was adjusted to be 0.0% with deionized water and filtered through a 100-mesh wire net to obtain a curable polymer aqueous dispersion.

The obtained curable polymer aqueous dispersion had a solid content concentration of 40.0%, a pH of 9.0 and a viscosity of 520 cps (B
It was measured by an M-type viscometer at 25 ° C.), and the agglomerates that did not pass through 100 mesh wire net was 0.1% or less (ratio of generated dispersion liquid). This curable polymer aqueous dispersion is [F-
1].

Comparative Examples 2 to 5 In Comparative Example 1, the type of polymer aqueous dispersion (Reference Example B) was used.
-5 to B-7, Comparative Reference Example C-1), except that the pH of the polymer aqueous dispersion, the presence / absence and type of the polyfunctional epoxy compound [Y], and the amount are as shown in Table 4 below. Is a curable polymer aqueous dispersion [F-2] in the same manner as in Comparative Example 1.
~ [F-5] were obtained.

The pH of [F-2] to [F-5], 10
The amount of aggregates that did not pass through the 0-mesh wire mesh was as described in 4 of Table 4.

[0209]

[Table 8]

[0210]

[Table 9]

[0211]

[Table 10]

[0212]

[Table 11]

[Aggregates 1 to 4 in Table 4 are the 100 mesh generated when the polyfunctional epoxy compound [Y] is added to the aqueous polymer dispersion containing the polymer particles [X]. This is the amount of aggregates that did not pass through the wire mesh and was expressed as the weight% of the ratio of dispersion liquid to product.

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 KK; glycerol polyglycidyl ether) Denacol EX-614B (manufactured by Nagase Kasei Kogyo KK;
Sorbitol polyglycidyl ether) Denacol EX-512 (manufactured by Nagase Kasei Co., Ltd .; polyglycerol polyglycidyl ether) A-187 (manufactured by Nippon Unicar Co., Ltd .; γ-glycidoxypropyltrimethoxysilane) A-186 (Japan Unicar Co., Ltd .; 2- (3 ', 4'
-Epoxycyclohexyl) ethyltrimethoxysilane) Dick Fine EM-100 (manufactured by Dainippon Ink and Chemicals, Inc .; aqueous dispersion of bisphenol A type solid epoxy resin: solid content 50%)]

Example 19 <Production of Curable Polymer Aqueous Dispersion [E-19]> 70 parts of deionized water in a reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, dropping funnel, reference Aqueous dispersion [A-5] 1 of the carboxyl group-containing polymer obtained in Example A-5
25 parts (solid content of 25 parts) were added, and the temperature was raised to 80 ° C. while blowing nitrogen.

With stirring, 0.3 part of ammonium persulfate was added, followed by 50 parts of n-butyl acrylate, 47 parts of methyl methacrylate, 3 parts of dimethylaminoethyl methacrylate, and Denacol EX-211 (manufactured by Nagase Chemicals Co., Ltd.). A monomer mixture consisting of 3 parts (neopentyl glycol diglycidyl ether) (as a polyfunctional epoxy compound [Y]) was added dropwise over 120 minutes to carry out polymerization while maintaining the reaction vessel internal temperature at 80 ± 2 ° C. .

After completion of dropping, the mixture was stirred at the same temperature for 60 minutes.
Then, the content was cooled, adjusted with deionized water so that the solid content concentration was 40.0%, and filtered through a 100-mesh wire net.

The obtained polymer aqueous dispersion had a solid content concentration of 40.0%, a pH of 6.8, a viscosity of 150 cps (measured with a BM type viscometer at 25 ° C.), and a 100-mesh wire mesh non-aggregation. The product was 0.8% (ratio of product dispersion). This polymer aqueous dispersion is referred to as a curable polymer aqueous dispersion [E-19].

This curable polymer aqueous dispersion [E-19]
Is an acid value of the carboxyl group-containing polymer [A] constituting the A phase of the polymer particles is 97, and the content of the basic nitrogen atom-containing group of the ethylenic polymer [B] constituting the B phase is ethylenic. 0.19 mg per 1 g of the polymer [B] (a monomer (b) containing a basic nitrogen atom-containing group in the monomer component (b))
-1) calculated from the charged amount). Further, the acid value is 19 and the content of the basic nitrogen atom-containing group is 0.15 mg per 1 g of the solid content of the polymer aqueous dispersion.

Example 20 <Production of Curable Polymer Aqueous Dispersion [E-20]> 70 parts of deionized water and Reference Example A- in the same reaction vessel as in Example 19.
125 parts (solid content: 25 parts) of the aqueous dispersion of the carboxyl group-containing polymer [A-5] obtained in Example 5 was added, and the temperature was raised to 80 ° C. while blowing nitrogen.

With stirring, 0.3 part of ammonium persulfate was added, followed by 50 parts of n-butyl acrylate, 47 parts of methyl methacrylate, 3 parts of dimethylaminoethyl methacrylate, A-187 (manufactured by Nippon Unicar Co., Ltd .; γ. −
A monomer mixture consisting of 2 parts of glycidoxypropyltrimethoxysilane) (as a polyfunctional epoxy compound [Y]) was added dropwise for 120 minutes to carry out polymerization while keeping the temperature inside the reaction vessel at 80 ± 2 ° C. .

After completion of dropping, the mixture was stirred at the same temperature for 60 minutes.
Then, the content was cooled, adjusted with deionized water so that the solid content concentration was 40.0%, and filtered through a 100-mesh wire net.

The obtained polymer aqueous dispersion had a solid content concentration of 40.0%, a pH of 6.7, a viscosity of 320 cps (measured with a BM type viscometer at 25 ° C.), and a 100-mesh wire mesh non-aggregation. The product was 0.8% (ratio of product dispersion). This polymer aqueous dispersion is referred to as a curable polymer aqueous dispersion [E-20].

This curable polymer aqueous dispersion [E-20]
Is an acid value of the carboxyl group-containing polymer [A] constituting the A phase of the polymer particles is 97, and the content of the basic nitrogen atom-containing group of the ethylenic polymer [B] constituting the B phase is ethylenic. 0.19 mg per 1 g of the polymer [B] (a monomer (b) containing a basic nitrogen atom-containing group in the monomer component (b))
-1) calculated from the charged amount). Further, the acid value is 19 and the content of the basic nitrogen atom-containing group is 0.15 mg per 1 g of the solid content of the polymer aqueous dispersion.

Curable polymer aqueous dispersions [E-1] to [E-2] obtained in Examples 1 to 20 and Comparative Examples 1 to 5.
0] and [F-1] to [F-5] were evaluated for the following items.

Evaluation Method <Film Water Resistance> Curable polymer aqueous dispersions [E-1] to [E-2] obtained in Examples 1 to 20 and Comparative Examples 1 to 5.
0] and [F-1] to [F-5] on a glass plate for 3 m.
It was applied with an il applicator and dried at room temperature for 7 days to form a film. From the glass plate coating films obtained, 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 as test pieces. The test piece is immersed in room temperature water for 7 days, the turbidity of the test piece before and after water immersion is measured with a turbidimeter, and the degree of change in the turbidity is determined as a W value, and the film is degraded by immersion in water. (Whitening) was evaluated. Turbidimeter: NDH-300 Turbidimeter manufactured by Nippon Denshoku Industries Co., Ltd.
A measurement light source; halogen lamp, light receiving element; silicon photocell according to JIS K7105 Measurement area; transmission 12φ Turbidity and degree of change in turbidity before and after immersion in water were calculated according to the following formulas.

[0227]

(Equation 1) TL: Total transmittance (%) DF: Diffuse transmittance (%)

[0228]

(Equation 2) H ₀ : Turbidity of test piece before immersion in water H ₁ : Turbidity of test piece after immersion in water The degree of change in turbidity W value was evaluated according to the following three grades.

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

<Water absorption rate and elution rate of film> Examples 1 to 1
20, the curable polymer aqueous dispersions [E-1] to [E-20] and [F-1] to [F-, obtained in Comparative Examples 1 to 5
5] on a glass plate, the film thickness after drying is 0.5 m.
The film was peeled off from the glass plate after being coated so as to have a thickness of m and dried at room temperature for 7 days. From the obtained films, those dried only at room temperature and those dried at room temperature for 20 minutes at 110 ° C. were prepared as test pieces. The film was cut into 20 mm square and the weight was measured (W ₀ ) to obtain a test film. The test film was dipped in room temperature water for 7 days, pulled up, lightly wiped off water on the film surface, and then weighed (W ₁ ). Furthermore, the film 11
It was dried at 0 ° C. for 1 hour, allowed to cool, and then weighed (W ₂ ).
The water absorption rate and the elution rate of the film were calculated by the following formulas.

[0231]

(Equation 3)

[0232]

(Equation 4)

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 and drying

<Film Solvent Resistance> Aqueous dispersions of curable polymers obtained in Examples 1 to 20 and Comparative Examples 1 to 5 [E-
1] to [E-20] and [F-1] to [F-5] are coated on a glass plate with a 3 mil applicator, and are applied at room temperature for 7 hours.
It was dried for a day to form a film. From the glass plate coating films obtained, ones that were only dried at room temperature and those that were subjected to heat treatment at 110 ° C. for 20 minutes after being dried at room temperature were prepared as test pieces.

The resin-coated surface of the obtained test piece was rubbed 100 times with a cotton swab soaked with an acetone or toluene solution, and the presence or absence of deterioration of the coated surface was observed. ○: There is no abnormality in the film.

Δ: There is deterioration on the surface and inside of the film, and there is some detachment from the glass plate. X: The inside of the film is deteriorated and the detachment is remarkable.

<Film Strength> Curable polymer aqueous dispersions obtained in Examples 1 to 20 and Comparative Examples 1 to 5 [E-
1] to [E-20] and [F-1] to [F-5] were coated on a glass plate so that the film thickness after drying would be 0.5 mm, and dried at room temperature for 7 days. The film was peeled from the glass plate. From the obtained film, only dry at room temperature,
After being dried at room temperature, heat treatment was performed at 110 ° C. for 20 minutes to prepare test pieces. These films are JIS3
A punched test piece was used in a No. dumbbell mold, and the breaking strength in a tensile test was measured under the following conditions. Tensile tester; Shimazu Autograph AG-5000
C Pulling speed (cross head speed): 200 mm / min Distance between chucks: 50 mm

<Evaluation of Storage Stability of Polymer Aqueous Dispersion>
Curable polymer aqueous dispersions [E-1] to [E-20] and [F-] obtained in Examples 1 to 20 and Comparative Examples 1 to 5.
Regarding 1] to [F-5], the viscosity immediately after production and the viscosity after storage at 25 ° C. for 48 hours after production were measured at 25 ° C. with a BM type viscometer.

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

[0240]

[Table 12]

[0241]

[Table 13]

[0242]

[Table 14]

[0243]

[Table 15]

[0244]

[Table 16]

[0245]

[Table 17]

[0246]

[Table 18]

[0247]

[Table 19] * In the polymer aqueous dispersions E-19 and E-20 of Examples 19 and 20, the polyfunctional epoxy compound [Y] is added at the time of producing the polymer particles [X]. E-19: Denacol EX-211 (manufactured by Nagase Kasei Co., Ltd .; neopentyl glycol diglycidyl ether) E-20: A-187 (manufactured by Nippon Unicar Co., Ltd .; γ-glycidoxypropyltrimethoxysilane)

[0248]

[Table 20]

[Details of the compound used as the polyfunctional epoxy compound [Y] in Tables 1 to 5 are shown below. EX-313 (Denacol EX-313) (manufactured by Nagase Kasei Kogyo KK; glycerol polyglycidyl ether) EX-614B (Denacol EX-614B) (manufactured by Nagase Kasei KK; sorbitol polyglycidyl ether) EX-512 ( Denacol EX-512) (manufactured by Nagase Kasei Co., Ltd .; polyglycerol polyglycidyl ether) A-187 (manufactured by Nippon Unicar Co., Ltd .; γ-glycidoxypropyltrimethoxysilane) A-186 (Japan Unicar Co., Ltd.) Made; 2- (3 ', 4'
-Epoxycyclohexyl) ethyltrimethoxysilane) EM-100 (Dick Fine EM-100) (manufactured by Dainippon Ink and Chemicals, Inc .; water dispersion of bisphenol A type solid epoxy resin: solid content 50%)]

[0250]

According to the method of the present invention, the amount of emulsifier and other dispersion stabilizers used is reduced to a very small amount, and a crosslinking agent-curable polymer emulsion can be stably obtained without using it at all. , Performance deterioration due to conventional emulsifiers can be avoided, the resulting cured product has water resistance, solvent resistance,
A curable polymer aqueous dispersion having excellent physical properties such as mechanical strength can be obtained.

The curable polymer aqueous dispersion of the present invention has extremely excellent properties such as adhesiveness and heat resistance in addition to water resistance, solvent resistance and mechanical strength.

Claims (27)

[Claims] 1. A curable polymer aqueous dispersion that exhibits curability, and polymer particles [X] dispersed in an aqueous medium.
Is a polymer having at least two kinds of phases A and B, and the phase A contains a carboxyl group [A]
Is a polymer particle composed of an ethylenic polymer [B] having a basic nitrogen atom-containing group, the polymer particle [X] and a polyfunctional epoxy compound [Y]. ] The curable polymer aqueous dispersion characterized by being comprised from these. 2. The curable polymer aqueous dispersion according to claim 1, wherein the basic nitrogen atom-containing group of the ethylenic polymer [B] constituting the B phase of the polymer particle [X] is a tertiary amino group. liquid. 3. The curable polymer aqueous dispersion according to claim 1, wherein the acid value of the carboxyl group-containing polymer [A] constituting the phase A of the polymer particles [X] is 30 to 300. 4. The weight average molecular weight of the carboxyl group-containing polymer [A] is 100,000 or more, and the gel fraction (acetone insoluble matter) is 95% by weight or less.
The curable polymer aqueous dispersion according to any one of 3 to 3. 5. The curable polymer aqueous dispersion according to any one of claims 1 to 4, wherein the carboxyl group-containing polymer [A] is an ethylenic polymer. 6. The ethylenic polymer [B] has a basic nitrogen atom-containing group of 0.1 g in 1 g of the ethylenic polymer [B].
It is contained in a ratio of about 2.0 mmol.
The curable polymer aqueous dispersion according to any one of items 1 to 5. 7. The weight ratio of the carboxyl group-containing polymer [A] constituting the A phase and the ethylenic polymer [B] constituting the B phase is [A] / [B] = as a solid fraction. 1 / 1-1 /
The curable polymer aqueous dispersion according to any one of claims 1 to 6, which is 100. 8. The weight ratio of the carboxyl group-containing polymer [A] constituting the A phase and the ethylenic polymer [B] constituting the B phase is [A] / [B] = solid fraction. 1 / 1-1 /
9. The curable polymer aqueous dispersion according to claim 1, which is 9. 9. The curable polymer aqueous dispersion according to claim 1, wherein the polymer particles [X] have an acid value of 5 to 70. 10. Polymer particles [X] have a basic nitrogen atom-containing group in an amount of 0.05 to 0.1% in 1 g of the polymer particles [X].
It is contained at a ratio of 7 mmol.
The curable polymer aqueous dispersion according to any one of 1. 11. The polymer particles [X] have an acid value of 5 to 70.
And the basic nitrogen atom-containing group contained in 1 g of the polymer particles [X] is 0.05 to 0.7 mmol, and the curable polymer according to any one of claims 1 to 10. Aqueous dispersion. 12. The carboxyl group-containing polymer [A] is
The curable polymer aqueous dispersion according to any one of claims 1 to 11, which contains, in addition to a carboxyl group, a group having reactivity with a basic group nitrogen atom-containing group. 13. The curable polymer aqueous dispersion according to claim 12, wherein the group reactive with the basic nitrogen atom of the carboxyl group-containing polymer [A] is an epoxy group. 14. A polyfunctional epoxy compound [Y],
The curable polymer aqueous dispersion according to any one of claims 1 to 13, which is a compound containing an epoxy group and a hydrolyzable silyl group or a silanol group in one molecule. 15. The pH of the curable polymer aqueous dispersion is 7
The curable polymer aqueous dispersion according to any one of claims 1 to 14, which is -12. 16. A monomer containing an ethylenically unsaturated monomer (b-1) containing a basic nitrogen atom-containing group as an essential component in an aqueous medium in which the carboxyl group-containing polymer [A] is present. The polymer component (b) is polymerized to obtain an aqueous dispersion of polymer particles [X], and then a polyfunctional epoxy compound [Y] is added to the aqueous dispersion, or a basic nitrogen atom-containing group is added. An ethylenically unsaturated monomer containing (b-
A monomer component (b) containing 1) as an essential component is polymerized in the presence of a polyfunctional epoxy compound [Y] to obtain an aqueous dispersion of polymer particles [X]. A method for producing an aqueous dispersion of a curable polymer. 17. The carboxyl group-containing polymer [A] is a particle, and the number average particle diameter thereof is 10 to 1000.
17. The manufacturing method according to claim 16, which is nm. 18. A carboxyl group-containing polymer [A] is
Carboxyl group-containing ethylenically unsaturated monomer (a-1)
The production method according to claim 16 or 17, which is obtained by polymerizing a monomer component (a) containing as an essential component in an aqueous medium. 19. The production method according to claim 16, 17, or 18, wherein the acid value of the carboxyl group-containing polymer [A] is 30 to 300. 20. The carboxyl group-containing polymer [A] has a weight average molecular weight of 100,000 or more and a gel fraction (acetone insoluble matter) of 95% by weight or less.
The manufacturing method according to any one of 6 to 19. 21. The ethylenically unsaturated monomer (b-1) containing a basic nitrogen atom-containing group is a tertiary amino group-containing ethylenically unsaturated monomer (b-1 ′). 16-
20. The manufacturing method according to any one of 20. 22. The ratio of the monomer component (b) used to the carboxyl group-containing polymer [A] is [A] on a weight basis.
22 (/ b) = 1/1 to 1/100
The manufacturing method according to any one of the above. 23. The ratio of the monomer component (b) used to the carboxyl group-containing polymer [A] is [A] on a weight basis.
/ (B) = 1/1 to 1/9, The manufacturing method according to any one of claims 16 to 22. 24. The carboxyl group-containing polymer [A] is
24. The production method according to claim 16, wherein 10 mol% or more of all carboxyl groups in the polymer are neutralized with a basic substance. 25. The monomer component (a) is a monomer (a-
25. In addition to 1), it has an ethylenically unsaturated monomer (a-2) containing a group reactive with a basic nitrogen atom-containing group, The method according to any one of claims 16 to 24. Production method. 26. An ethylenically unsaturated monomer (a-2) containing a group having reactivity with a basic nitrogen atom-containing group,
26. The production method according to claim 25, which is an epoxy group-containing ethylenically unsaturated monomer (a-2 ′). 27. The polyfunctional epoxy compound [Y] is
27. A compound containing an epoxy group and a hydrolyzable silyl group or silanol group in one molecule.
The curable polymer aqueous dispersion according to any one of 1.