JP3346128B2 - Aqueous crosslinked resin composition, method for producing the same, and material using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous crosslinked resin composition characterized by good water resistance, a method for producing the same, and a material using the same, and more particularly, fibers, paper, metal, plastic, and inorganic materials. The present invention relates to a water-based cross-linkable resin composition suitable as a surface coating agent or an adhesive for flocking or an adhesive for impregnation or bundling of paper or fiber, a method for producing the same, and a material using the same.

[0002]

2. Description of the Related Art Hitherto, as a water-based cross-linkable resin, a method of adding a polyfunctional epoxy resin as a cross-linking agent to a polymer having an amino group as a cross-linking agent to cross-link has been proposed, and is used for various purposes.

For example, in Japanese Patent Publication No. 55-30552, a polyepoxide compound is added to a polymer obtained by polymerizing an ethylenically unsaturated compound having a tertiary amino group and an ethylenically unsaturated compound having a carboxyl group as essential components. A water-soluble resin coating composition is disclosed.

However, in this technique, a large amount of an ethylenically unsaturated compound having a carboxyl group is copolymerized in order to make a polymer as a main agent water-soluble, so that when a polyepoxide compound is added and crosslinked, Also, there is a problem that the obtained film has low water resistance.

Further, as an aqueous cross-linkable resin composition using an epoxy resin as a cross-linking agent, Japanese Patent Application Laid-Open No. 4-65421 discloses a simple composition comprising a monomer containing a carboxyl group and a monomer containing a basic nitrogen atom. The polymer produced by emulsion polymerization of the monomer component, an epoxy resin crosslinking agent,
An aqueous crosslinking type resin composition to which an imidazole compound is added as a crosslinking accelerator is disclosed.

However, this technique has a drawback that the crosslink density between the main agent (polymer containing a carboxyl group) and the crosslinker (epoxy resin) is low, and the desired durability cannot be obtained.

The water-based cross-linkable resins disclosed in Japanese Patent Publication No. 55-30552 and Japanese Patent Application Laid-Open No. 4-65421 each have a drawback that water resistance is poor.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide an aqueous resin composition having excellent water resistance.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the prior art, and as a result, have found a resin composition which can achieve the above object and completed the present invention.

That is, the present invention provides an aqueous dispersion of polymer particles containing a basic nitrogen atom-containing ethylenically unsaturated monomer (a) and a carboxyl group-containing ethylenically unsaturated monomer (b) as main components ( A) and an aqueous crosslinked resin composition containing a polyfunctional epoxy resin (B) and a method for producing the same.

More specifically, the present invention relates to 3 to 15% by weight (% by weight based on the total ethylenically unsaturated monomer) of an ethylenically unsaturated monomer (a) containing a basic nitrogen atom, a) It is obtained by copolymerizing 1/10 to 1/2 mol of a carboxyl group-containing ethylenically unsaturated monomer (b) with another ethylenically unsaturated monomer (c) per 1 mol. ,
An aqueous crosslinked resin composition comprising an aqueous dispersion of polymer particles (A) and a polyfunctional epoxy resin (B) and having a system pH of 2 to 5, and a method for producing the same. .
Further, the present invention provides a material using the water-based crosslinked resin composition.

Further, the present invention relates to a method for producing an ethylenically unsaturated monomer containing a basic nitrogen atom (a) in an amount of 3 to 15% by weight (% by weight based on the total amount of the ethylenically unsaturated monomers). ) 1
1/10 to 1/2 mole of the carboxyl group-containing ethylenically unsaturated monomer (b) and the other ethylenically unsaturated monomer (c) are polymerized in an aqueous medium, Aqueous crosslinked resin comprising preparing an aqueous dispersion (A) of coalesced particles, adjusting the pH of the aqueous dispersion of polymer particles to 2 to 5, and then adding a polyfunctional epoxy resin (B). The present invention relates to a method for producing a composition.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Basic nitrogen atom-containing ethylenically unsaturated monomer (a) which is a constituent component in an aqueous dispersion of polymer particles which is the main component of the aqueous crosslinked resin composition of the present invention.
Is used as a cross-linkable reactive group when the basic nitrogen atom-containing group is cured with the polyfunctional epoxy resin (B) described later, and the basic nitrogen atom-containing group and ethylenically unsaturated There is no particular limitation as long as it has a group. For example, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate (Meth) acrylates such as N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethyl Aminopropyl (meth) acrylamide, N, N
(Meth) acrylamides such as -diethylaminopropyl (meth) acrylamide, and one or a mixture of two or more thereof can be used.

In particular, the basic nitrogen atom of the basic nitrogen atom-containing ethylenically unsaturated monomer (a) represented by the following general formula (1) is cross-linked with the epoxy group of the polyfunctional epoxy resin (B). As the water resistance of the film is greatly improved,
preferable.

[0015]

Embedded image

(Wherein, R ₁ , R ₂ and R ₃ represent a hydrogen atom or an alkyl group, and n is an integer of 1 to 8)

The amount of the basic nitrogen atom-containing ethylenically unsaturated monomer (a) used is from 3 to 3% of the total ethylenically unsaturated monomers.
It is necessary to use 15 parts by weight. If the amount is less than 3 parts by weight, the crosslinkability with a polyfunctional epoxy crosslinker described below will be low, and it will be difficult to obtain the desired durability. If the amount of the basic nitrogen atom-containing ethylenically unsaturated monomer (a) exceeds 15% by weight based on the total amount of the ethylenically unsaturated monomers, the water resistance of the obtained product is significantly reduced. Not preferred.

The carboxyl group-containing ethylenically unsaturated monomer (b) which is an essential component of the aqueous cross-linkable resin composition in the present invention is one having a carboxyl group and an ethylenically unsaturated group in the molecule. There is no particular limitation, and examples thereof include (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, a half ester thereof, a salt thereof and the like, and one or a mixture of two or more thereof is used. can do.

The carboxyl group-containing ethylenically unsaturated monomer (b) is 1/10 based on 1 mol of the basic nitrogen atom-containing ethylenically unsaturated monomer (a) in view of the polymerization stability of the polymer particles. It is necessary to use 〜 mole.

In the present invention, the above monomers (a) and (b)
In addition to the above, another ethylenically saturated monomer (c) is an essential component, and the monomer (c) is used in an amount of the monomer (a) and the monomer (b) in the polymer. Is not particularly limited as long as it is copolymerizable with the monomer (a) and the monomer (b). For example, methyl (meth) acrylate, ethyl (meth) acrylate, n- Butyl (meta)
Acrylate, i-butyl (meth) acrylate, t-
Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth)
Acrylic acid such as acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate Esters: 2,2,2-trifluoroethyl (meth)
Acrylate, 2,2,3,3-pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, β- (perfluorooctyl) Fluorine-containing vinyl monomers such as ethyl (meth) acrylate; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl versatate; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether;
Vinyl ethers such as amyl vinyl ether and hexyl vinyl ether; nitriles of unsaturated carboxylic acids such as (meth) acrylonitrile; aromatics such as styrene, α-methylstyrene, vinyltoluene, vinylanisole, α-halostyrene, vinylnaphthalene and divinylstyrene Vinyl compound having a ring; isoprene, chloroprene,
Epoxy group-containing polymerizable monomers such as butadiene, N-vinylpyrrolidone, glycidyl (meth) acrylate, and allyl glycidyl ether; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) ) Hydroxyl-containing polymerizable monomers such as acrylate and glycerol mono (meth) acrylate; aminoethyl (meth) acrylate, N-monoalkylaminoalkyl (meth) acrylate, N, N-dialkylaminoalkyl (meth)
Amino group-containing polymerizable monomer such as acrylate; N-methylol (meth) acrylamide, N-isopropoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth)
A methylolamide group such as acrylamide and an alkoxylated compound-containing polymerizable monomer; vinyltrichlorosilane,
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ
-(Meth) acryloxypropyltrimethoxysilane,
a silyl group-containing polymerizable monomer such as γ- (meth) acryloxypropylmethyldimethoxysilane; an aziridinyl group-containing polymerizable monomer such as 2-aziridinylethyl (meth) acrylate; (meth) acryloyl isocyanate;
Polymerizable monomers containing isocyanate groups and / or blocked isocyanate groups such as phenol adducts of (meth) acryloyl isocyanatoethyl; oxazolines such as 2-isopropenyl-2-oxazoline and 2-vinyl-2-oxazoline Group-containing polymerizable monomers; (meth) acrylamide, N-monoalkyl (meth) acrylamide,
Amide group-containing polymerizable monomers such as N, N-dialkyl (meth) acrylamide; cyclopentenyl group-containing polymerizable monomers such as dicyclopentenyl (meth) acrylate; carbonyl groups such as acrolein and diacetone (meth) acrylamide Containing polymerizable monomers; acetoacetyl group-containing polymerizable monomers such as acetoacetoxyethyl (meth) acrylate, and the like; one or a mixture of two or more of these can be used.

As another ethylenically unsaturated monomer (c), a polymer having two or more ethylenically unsaturated groups for the purpose of increasing the molecular weight by crosslinking polymer particles and improving durability. It is also possible to use a functional ethylenically unsaturated monomer in combination. Examples of the polyfunctional ethylenically unsaturated monomer include ethylene glycol di (meth) acrylate and 1,6-hexanediol di ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate,
Examples thereof include polypropylene glycol di (meth) acrylate, allyl (meth) acrylate, diallyl phthalate, and divinylbenzene.

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

The method for producing the aqueous crosslinked resin composition of the present invention is produced by free radical polymerization of an ethylenically unsaturated monomer, and the method may be any of suspension polymerization and emulsion polymerization depending on its properties. It can also be manufactured by a method.

In particular, since it is necessary to stably disperse the polymer particles in water under the condition of minimizing the amount of the highly hydrophilic crosslinkable reactive group, which is the means of the present invention, the reaction is carried out in an aqueous medium. It is preferable to produce by a suspension polymerization method or an emulsion polymerization method.Moreover, from the viewpoint of the stability of the particles during polymerization and the storage stability of the obtained aqueous dispersion of polymer particles, it is preferable to use an emulsion polymerization method. .

When producing the polymer particles in an aqueous medium, the polymerization can be carried out without using any emulsifier or other dispersion stabilizer, but the dispersion stability of the particles during the polymerization and the obtained polymer From the viewpoint of the stability of the aqueous dispersion, an emulsifier and other dispersion stabilizers can be used as necessary.

The emulsifier is not particularly limited, and known emulsifiers such as a cationic emulsifier, a nonionic emulsifier, a nonionic reactive emulsifier, and an amphoteric emulsifier can be used. For example, examples of the cationic emulsifier include alkyl ammonium chloride (Arcade 12-50, manufactured by Lion Corporation).

Examples of the nonionic emulsifier include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene-polyoxypropylene block copolymer and the like.

Further, as the nonionic reactive emulsifier,
Aqualon RN-10, RN-2 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
0, RN-50 and Adekaria Soap NE-10, NE-20, NE-30 manufactured by Asahi Denka Kogyo KK.

As the emulsifier, one or a mixture of two or more of these can be used. In particular, it is preferable to use a nonionic emulsifier from the viewpoint of stability during production of the polymer aqueous dispersion.

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

The above-mentioned emulsifier and dispersion stabilizer are used for the purpose of improving stability during polymerization and storage stability.
It is necessary to minimize the amount of the emulsion film from the viewpoint of water resistance and the like, and the amount is preferably 5% by weight or less based on the solid content of the polymer particles.

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

As a method for producing the polymer particles in an aqueous medium, water, a basic nitrogen atom-containing ethylenically unsaturated monomer (a), and a carboxyl group-containing ethylenically unsaturated monomer (b) are essential. A method of collectively mixing and polymerizing a polymerizable monomer mixture and a polymerization catalyst (an emulsifier and a dispersion stabilizer as necessary) as a component of the above-mentioned method, and a method in which water, a polymerizable monomer, and an emulsifier are previously mixed are dropped. So-called pre-emulsion method,
It can be produced by a method such as a monomer dropping method.

Particularly, from the viewpoint of stability during production, it is preferable to carry out the method by a monomer pre-emulsion method.

As a specific method for synthesizing polymer particles by the monomer pre-emulsion method, for example, an aqueous medium is placed in a stirred reactor equipped with a dropping funnel, and then the reactor is heated to the polymerization temperature. After that, a polymerization initiator is added, and a basic nitrogen atom-containing ethylenically unsaturated monomer (a), a carboxyl group-containing ethylenically unsaturated monomer (b), and other ethylenically unsaturated monomers are added through a dropping funnel. A method of dropping a mixture of the body (c) and the emulsifier is exemplified.

The basic nitrogen atom of the monomer (a) may be used for polymerization as it is without neutralization. However, from the viewpoint of stability during polymerization, a part of the basic nitrogen atom is neutralized with an acidic substance. The method of using them in combination is preferred.

The amount of the acidic substance used for the neutralization is not particularly limited, but from the viewpoint of stability during polymerization, the amount of the basic nitrogen atom in the basic nitrogen atom-containing ethylenically unsaturated monomer (a) is 50%.
It is preferably neutralized to 100 mol%.

However, in the present invention, since the carboxyl group-containing ethylenically unsaturated monomer (b) capable of neutralizing the basic nitrogen atom-containing ethylenically unsaturated monomer (a) is used, The amount of the acidic substance necessary for the addition of the basic substance is reduced by the amount by which the basic nitrogen atom-containing ethylenically unsaturated monomer (a) is neutralized with the carboxyl group-containing ethylenically unsaturated monomer (b). Is preferred.

As the acidic substance used as the neutralizing agent,
Usually, inorganic acids and organic acids can be used. Examples of the inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. Examples of the organic acids include formic acid, acetic acid, propionic acid, lactic acid, and oxalic acid. , Malonic acid, succinic acid, citric acid,
Examples thereof include organic acids such as tartaric acid and malic acid, and one or a mixture of two or more thereof can be used.

In order to further improve the water resistance of the emulsion film, it is preferable to use an acidic substance having a low boiling point, such as hydrochloric acid or formic acid, which evaporates easily at normal temperature or by heating.

When an acidic substance having a low boiling point is used for an application in which odor becomes a problem, it is preferable to use an acidic substance having low volatility such as citric acid, tartaric acid, malic acid and lactic acid.

The inside of the reactor used for the polymerization may be an open system, but is preferably replaced with an inert gas such as nitrogen.

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

In addition, during the emulsion polymerization of the polymer particles, it is possible to add a hydrophilic solvent and a hydrophobic solvent, and to add known additives, as long as the effects of the present invention are not impaired.

As the polymerization initiator used in the polymerization of the polymer particles, a radical polymerization initiator is used. Examples of the radical polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate; organic peroxides such as benzoyl peroxide and cumene hydroperoxide; and hydrogen peroxide. Radical polymerization can be carried out by using only these peroxides, or by a redox polymerization initiator system using the peroxide together with a reducing agent such as sodium acid sulfite and sodium thiosulfate,
4,4'-azobis (4-cyanopentanoic acid), 2,
It is also possible to use a water-soluble azo compound such as 2'-azobis (2-amidinopropane) dihydrochloride.

In particular, the use of a water-soluble azo compound is preferred because of good stability during polymerization.

If it is necessary to adjust the molecular weight of the polymer particles, a compound having a chain transfer ability, for example, a mercaptan, may be added as a molecular weight modifier when synthesizing the polymer particles.

The solid content concentration of the aqueous dispersion of the curable polymer is preferably from 20 to 70% by weight, more preferably from 20 to 60% by weight.

That is, by setting the solid component concentration to 70% by weight or less, an abnormal increase in the viscosity of the system during the polymerization can be suppressed, and the heat generated during the polymerization of the monomer can be easily and stably removed. An aqueous polymer dispersion becomes easier to produce. Further, it is preferable that the solid component concentration be 60% by weight or less, because the viscosity of the aqueous curable polymer dispersion can be obtained in a range practically required for various uses.

The pH of the polymerized aqueous crosslinked resin composition is as follows:
It needs to be 2-5. By adjusting the pH, the pot life when the polyfunctional epoxy resin (B) described below is added to the aqueous crosslinked resin composition can be extended.

As the acidic substance used as the pH adjuster, inorganic acids and organic acids can be usually used. As the inorganic acids, for example, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and the like can be used. For example, organic acids such as formic acid, acetic acid, propionic acid, lactic acid, oxalic acid, malonic acid, succinic acid, citric acid, tartaric acid, malic acid, and the like, and one or a mixture of two or more thereof may be used. Can be.

In order to further improve the water resistance of the emulsion film, it is preferable to use an acidic substance having a low boiling point, such as hydrochloric acid or formic acid, which evaporates easily at normal temperature or by heating.

By using an acidic substance having a low boiling point, citric acid,
It is preferable to use an acidic substance having low volatility such as tartaric acid, malic acid, and lactic acid.

On the other hand, when the curable polymer aqueous dispersion of the present invention is used in coating processing for use (paint, adhesive, paper processing agent, etc.), the polymer aqueous dispersion is used in view of the film thickness of the coating film. The solid content concentration is preferably 20% by weight or more,
Further, from the viewpoint of productivity in terms of economy, it is preferable that the solid component concentration be 20% by weight or more.

The particle size of the polymer particles dispersed in the curable polymer aqueous dispersion is not particularly limited, but it is necessary that the number average particle size is 30 to 500 nm. It is preferable from the point of view.

Glass transition temperature (Tg) of polymer particles comprising monomer (a), monomer (b) and monomer (c)
Is not particularly limited, but -60 to 30 ° C
It is preferable to be within the range.

The polyfunctional epoxy resin (B) in the present invention
Is not particularly limited as long as it has a polyfunctional glycidyl group in the molecule, utilizing a basic nitrogen atom and a carboxyl group in the polymer particles as a crosslinking reaction point, for example, neopentyl glycol diglycidyl ether, Polypropylene diglycidyl ether, phthalic acid diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, dimer acid diglycidyl ether, triglycidyl isocyanurate, tetraglycidylaminodiphenylmethane, (poly) ethylene glycol diglycidyl ether, (poly ) Propylene glycol diglycidyl ether, butanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether, (poly) gly Roll polyglycidyl ether, tetra pentaerythritol polyglycidyl ether, 1,6
Examples thereof include hexanediol diglycidyl ether, and an emulsion of these epoxy resins using an emulsifier or a protective colloid. These epoxy resins are usually used alone or in combination of two or more.

As the polyfunctional epoxy resin, a water-soluble epoxy resin is preferable. The water solubility of this epoxy resin is 50
% Or more is preferable. The water solubility of the epoxy resin refers to the dissolution rate when 10 parts of the epoxy resin is dissolved in 90 parts of water at room temperature.

The aqueous dispersion of a curable polymer of the present invention itself forms a cured film having good water resistance and solvent resistance by self-crosslinking at room temperature or by heating. A water-soluble or water-dispersible crosslinking agent can be added and used. Examples of the crosslinking agent include a polyfunctional epoxy compound, a polyfunctional melamine compound, a polyfunctional polyamine compound, and a polyfunctional polyethyleneimine. Examples include compounds, polyfunctional (blocked) isocyanate compounds, dihydrazine compounds, metal salt compounds, and the like, and these can be used as one kind or as a mixture of two or more kinds.

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

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

The aqueous dispersion of a curable polymer of the present invention provides a cured product having excellent water resistance, solvent resistance and mechanical strength, and its use is diversified. It is useful in the field where solvent properties are required, and is used for paints, adhesives, resins for the textile industry (binders for nonwoven fabrics, flocking, etc.), resins for paper processing, resins for glass fiber processing (glass fiber sizing agents) , A binder for glass paper, etc.) and a mortar modifying resin. In particular, in applications used in coatings in application fields such as paints, adhesives, resins for the textile industry, resins for paper processing, etc., extremely excellent effects are exhibited as described above.

[0063]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the scope of the present invention is not limited to these Examples. Hereinafter, unless otherwise specified in the examples, "%" indicates% by weight and "parts" indicates "parts by weight".

Synthesis Example 1 <Production of aqueous dispersion of polymer containing basic nitrogen atom-containing group and carboxyl group> A reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, and a dropping funnel was removed. 300 parts of deionized water is added, and Emulgen 950 is used as an emulsifier.
3 parts (manufactured by Kao Corporation; polyoxyethylene alkyl phenyl ether, solid content: 100%) were added, and the temperature was raised to 80 ° C. while blowing nitrogen with stirring to dissolve the emulsifier.

Under stirring, 0.2 parts of 2,2′-azobis (2-amidinopropane) dihydrochloride was added, followed by 90 parts of methyl methacrylate and 90 parts of n-butyl acrylate.
Part, basic nitrogen atom-containing ethylenically unsaturated monomer (a)
18 parts of dimethylaminoethyl methacrylate neutralized with 4 parts of acetic acid, and a monomer mixture consisting of 2 parts of methacrylic acid as the carboxyl group-containing ethylenically unsaturated monomer (b) at a temperature of 80 ± The solution was added dropwise over 6 hours while maintaining the temperature at 2 ° C.

After completion of the dropwise addition of the monomer mixture, 0.1 part of 2,2'-azobis (2-amidinopropane) dihydrochloride was added, and the mixture was stirred at the same temperature for 2 hours to react the remaining monomer. I let it.

Thereafter, the content is cooled, and the solid component concentration becomes 4%.
After adjusting to 0.0% with deionized water, the mixture was filtered through a 100 mesh wire mesh. The resulting polymer aqueous dispersion is
The solid content concentration was 39.8%, the pH was 5.4, and the aggregates that did not pass through the 100-mesh wire mesh were 0.1% (relative to the generated dispersion). This aqueous dispersion is designated as [A-1].

Synthesis Examples 2 to 8 <Preparation of Aqueous Dispersion 8 of Polymer Containing Basic Nitrogen Atom-Containing Group and Carboxyl Group> Synthesis was performed except that the monomer mixture shown in Table 1 was used. An aqueous dispersion of a carboxyl group-containing polymer [A-
2] to [A-8] were obtained.

The compositions, solid contents and pH of the polymers contained in [A-2] to [A-8] were as shown in Table 1. Example 1 Aqueous dispersion [A-1] 500 of a polymer containing a basic nitrogen atom-containing group and a carboxyl group obtained in Synthesis Example 1
5 parts by weight of acetic acid was added to the parts by weight to adjust the pH of the aqueous dispersion of the polymer to 4.5 or less.

Next, 10 parts of Denacol EX-313 (manufactured by Nagase Kasei Kogyo Co., Ltd .; glycerol polyglycidyl ether; water solubility 99%, epoxy equivalent 140) was added as a polyfunctional epoxy resin (B) to give an aqueous crosslinked resin. It was set as composition [B-1].

Examples 2 to 4 and Comparative Examples 1 to 4 Aqueous dispersions of polymers containing basic nitrogen atom-containing groups and carboxyl groups obtained in Synthesis Examples 2 to 8 [A-2] to
[A-8] To 500 parts by weight of acetic acid, 5 parts by weight of acetic acid was added to adjust the pH of the aqueous dispersion of the polymer to 5.0 or less.

Next, 10 parts of Denacol EX-313 was added as a polyfunctional epoxy resin (D) to obtain aqueous crosslinked resin compositions [B-2] to [B-8] using a 3 mil applicator. Apply to glass plate and dry at room temperature 12
The mixture was treated at 0 ° C. for 5 minutes, immersed in water for 24 hours, and observed for whitening.

After 24 hours, the sample which did not whiten at all was evaluated as "5", and the one which whitened and swollen was evaluated as "1". Application Example 1 <Flocking Method Using Electrostatic Flocking Machine> The flocking method was performed by an up method. In the up method, electrodes are arranged on the upper and lower sides, a pile is placed on the lower electrode, and the aqueous cross-linkable resin composition [B
-1] to [B-8] are attached with the coated side down to the soft PVC. The distance between the electrodes is 10c
m, voltage was 45 kV for 10 seconds, and 120 ° C. for 5 minutes.

<Evaluation Method of Flocking Strength of Flocked Fabric> A flocking strength test was conducted in accordance with JIS L 1084, and the flocking strength when dry and the flocking strength when wet with water were measured. The sample for measuring the flocking strength at the time of drying is left in a test room of JIS Z 8703 in a standard temperature and humidity class 2 (temperature: 20 ° C. ± 2 ° C., relative humidity: 65 ± 2%) to reach a water equilibrium and measure. The sample for measuring the flocking strength when wet with water was measured in a wet state after the test piece was immersed in water for 15 minutes.

<Method of Measuring Flocking Strength of Flocked Cloth> The method of measuring flocking strength of a flocked cloth was performed by a friction tester method.
The friction tester method includes an edge method and a flat method. The edge method includes a 1.5R method and a 45R method. In the former method, two friction cloths (Cotton Kanakin No. 3) are stacked and mounted on an arc surface using a friction tester for a color fastness test. A test piece of 2 × 6 cm was attached to a friction element having a radius of curvature of 1.5 mm, and a total load of 3.92 N
(400 gf) at a reciprocating speed of 30 times per minute on the friction cloth, and the number of times of friction until a part of the adhesive layer of the test piece is exposed is measured. The latter has a radius of curvature of 45 mm and a total load of 4.9.
A test piece having a size of 2 × 7 cm is attached to a 0N (500 gf) friction element. Other methods conform to the 1.5R method.
The flat method uses a friction tester for testing color fastness and uses a 3 ×
A 22 cm specimen is mounted on the arc surface. Attach Cotton No. 3 cloth to the friction element and apply a total load of 4.90 N (500 g
In f), the test piece was rubbed at a reciprocating speed 30 times per minute, and the number of times of friction until a part of the adhesive layer of the test piece was exposed was measured.

The results are shown in Tables 1 and 2.

[0077]

[Table 1]

In the table, the number of the flocking strength indicates the number of times until a part of the adhesive layer of the test piece is exposed, and DM; N, N-dimethylaminoethyl methacrylate MAA; BA methacrylate; A methyl methacrylate. ADEKA NOL UH-46
2 is a nonionic thickener [manufactured by Asahi Denka Kogyo KK].

[0079]

[Table 2]

Examples 5 to 10 and Comparative Example 5 The aqueous cross-linkable resin composition [B-1] obtained in Example 1 and the basic nitrogen atom-containing group and carboxyl group obtained in Synthesis Example 1 were contained. Aqueous dispersion of polymer [A-1] 5
Denacol EX- was used as a polyfunctional epoxy resin (B) in a mixture of 00 parts in which the amount of acetic acid was changed from 0 to 5 parts, and tartaric acid and lactic acid in an equimolar amount to 5 parts of acetic acid. The aqueous crosslinked resin compositions [B-9] to [B-15] were obtained by adding 2 parts of 313. Next, the aqueous cross-linkable resin compositions [B-9] to [B-15] were applied to a glass plate with a 3 mil applicator, dried at room temperature, and dried at 120 ° C.
The mixture was treated in 5 minutes and immersed in water for 24 hours to observe whitening.

After 24 hours, a sample which did not whiten at all was evaluated as “5”, and a sample which swollen and bleached was evaluated as “1”. The change with time of the viscosity of the aqueous cross-linkable resin compositions [B-9] to [B-15] was placed in a constant temperature water bath at 40 ° C., and after 1 day and 2 days.
The viscosity after one day was measured by a BM type viscometer.

The flocking strength was measured in accordance with Application Example 1. The results are shown in Tables 3 and 4.

[0083]

[Table 3]

In the table, the number of flocking strength indicates the number of times until a part of the adhesive layer of the test piece is exposed, and DM; N, N-dimethylaminoethyl methacrylate MAA; BA methacrylate; MMA butyl acrylate A methyl methacrylate. ADEKA NOL UH-46
2 is a nonionic thickener [manufactured by Asahi Denka Kogyo KK].

[0085]

[Table 4]

In the table, the number of the flocking strength indicates the number of times until a part of the adhesive layer of the test piece is exposed, and DM; N, N-dimethylaminoethyl methacrylate MAA; methacrylic acid BA; butyl acrylate MMA A methyl methacrylate. ADEKA NOL UH-46
2 is a nonionic thickener [manufactured by Asahi Denka Kogyo KK].

Examples 11 to 13 The aqueous cross-linkable resin composition [B-1] obtained in Example 1 and the polymer having a basic nitrogen atom-containing group and a carboxyl group obtained in Synthesis Example 1 were prepared. Aqueous dispersion [A-1] 5
After adding 5 parts of acetic acid to 00 parts, Denacol EX-911 (produced by Nagase Kasei Kogyo; propylene glycol diglycidyl ether; water solubility 75%, epoxy equivalent 150) as a polyfunctional epoxy resin (B), Denacol EX-211 (manufactured by Nagase Kasei Kogyo Co., Ltd .; neopentyl glycol diglycidyl ether; water solubility 26%, epoxy equivalent 140), CR-5L (manufactured by Dainippon Ink and Chemicals, Inc .; sorbitol polyglycidyl ether; water solubility) Aqueous crosslinked resin compositions [B-16] to [B-18] to which 10 parts of 85% and an epoxy equivalent of 170) were added were applied to a glass plate with a 3 mil applicator, and dried at room temperature.
The mixture was treated at 0 ° C. for 5 minutes, immersed in water for 24 hours, and observed for whitening.

After 24 hours, a sample that did not whiten at all was evaluated as “5”, and a sample that swollen and bleached was evaluated as “1”. In addition, the flocking strength was measured according to Application Example 1.

Table 5 shows the results.

[0090]

[Table 5]

In the table, the number of the flocking strength indicates the number of times until a part of the adhesive layer of the test piece is exposed. DM; N, N-dimethylaminoethyl methacrylate MAA; BA methacrylate; MMA butyl acrylate A methyl methacrylate. ADEKA NOL UH-46
2 is a nonionic thickener [manufactured by Asahi Denka Kogyo KK].

From the above results, it can be seen that the film made of the aqueous crosslinked resin composition of the present invention has excellent water resistance.

[0093]

The aqueous crosslinked resin composition of the present invention has excellent water resistance and is of a non-formalin type.
It is suitable as a surface coating agent such as fiber, paper, metal, plastic, or inorganic material or an adhesive for flocking or an adhesive for impregnation or bundling of paper or fiber.

──────────────────────────────────────────────────の Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 33/06-33/26 C08L 63/00-63/10 C08L 57/00-57/12 C09J 133 / 06-133/26 C09J 163/00-163/10 C09J 157/00-157/12 WPI (DIALOG)

Claims (6)

(57) [Claims] (1) 3 to 15% by weight of an ethylenically unsaturated monomer (a) containing a basic nitrogen atom, and 1/10 to 1/2 mol of a carboxyl group per 1 mol of the monomer (a). Aqueous dispersion (A) of polymer particles containing copolymerized ethylenically unsaturated monomer (b) and other ethylenically unsaturated monomer (c), and a polyfunctional epoxy resin (B) ), And the pH of the system is 2 to 5. 2. The aqueous cross-linkable resin composition according to claim 1, wherein the basic nitrogen atom-containing ethylenically unsaturated monomer (a) is a compound represented by the following general formula (1). object. (Wherein, R ₁ , R ₂ , and R _{3 represent} a hydrogen atom or an alkyl group, and n is an integer of 1 to 8). 3. The aqueous crosslinked resin composition according to claim 1, wherein the polyfunctional epoxy resin (B) is a water-soluble epoxy resin. 4. An ethylenically unsaturated monomer containing a basic nitrogen atom (a) in an amount of 3 to 15% by weight and 1/10 to 1/2 mol of a carboxyl group per 1 mol of the monomer (a). The aqueous ethylenically unsaturated monomer (b) and the other ethylenically unsaturated monomer (c) are polymerized in an aqueous medium to produce an aqueous dispersion of polymer particles. PH of liquid 2
A method for producing a water-based crosslinked resin composition, which comprises adding a polyfunctional epoxy resin (B) after adjusting the composition to ~ 5. 5. An adhesive comprising the aqueous cross-linkable resin composition according to claim 1 as a main component. 6. A flocking binder comprising the aqueous cross-linkable resin composition according to claim 1 as a main component.