JP2002179747A - Aqueous resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aqueous resin composition capable of bringing about uniform curing reaction, to obtain a resin powder comprising a polycondensation- based resin and an aqueous dispersion of a polycondensation-based resin, and to obtain a molding material composition comprising the aqueous resin composition and a molding obtained by molding it. SOLUTION: This thermosetting aqueous resin composition comprises a specified polycondensation-based resin (A) having an unsaturated dicarboxylic acid or its acid anhydride as at least one of constituting monomers, a polycondensation-based resin (B), a curing agent and water. The resin powder comprises an aqueous dispersion of the polycondensation-based resin (A) and a polycondensation-based resin (B). The molding material composition comprises the resin powder, the aqueous dispersion and the aqueous resin composition. The molding is obtained by molding the molding material composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting aqueous resin composition, an aqueous dispersion of a polycondensation resin, and a resin powder containing the polycondensation resin used for preparing the aqueous resin composition. The present invention relates to a molded article, a molding material composition containing the aqueous resin composition, and a molded article obtained by molding the same.

[0002]

2. Description of the Related Art As a molded article used for an automobile interior material or a building material, a base material such as fiber or wood is made of a phenol resin.
Adhesives such as urea resin and melamine resin (JP-A-7-16
No. 66) is often used,
There is a problem that formalin occurs. In addition, a polymer obtained by dissolving an unsaturated polyester resin and an organic peroxide in a polymerizable monomer such as styrene (Japanese Patent Application Laid-Open No. 10-36653), a product obtained by simply mixing an unsaturated polyester resin and an organic peroxide (see, However, there are problems such as the presence of odor of the monomer and the difficulty of uniform curing reaction.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides an aqueous resin composition which can improve environmental problems and cause a uniform curing reaction.
Used for preparing the aqueous resin composition, an aqueous dispersion of the polycondensation resin and a resin powder containing the polycondensation resin,
It is another object of the present invention to provide a molding material composition containing the water-based resin composition and a molded article obtained by molding the composition and having sufficient strength for practical use.

[0004]

That is, the gist of the present invention is as follows.
(1) An unsaturated dicarboxylic acid having a radical polymerizable unsaturated bond or an acid anhydride thereof is at least one of the constituent monomers, and has an acid value of 3 to 100 mgKOH / g.
A polycondensation resin (A) having an average particle size of 0.05 to 1 μm, an acid containing at least one kind of a monomer which is a radically polymerizable unsaturated dicarboxylic acid having an unsaturated bond or an acid anhydride thereof. The value is 3-100 mgKOH / g
And a thermosetting aqueous resin composition containing a polycondensation resin (B) having an average particle size of 5 to 500 μm, a curing agent and water, and (2) having a radical polymerizable unsaturated bond. An unsaturated dicarboxylic acid or an acid anhydride thereof is at least one of the constituent monomers, and has an acid value of 3 to 100 m.
Radical polymerization used for preparing a thermosetting water-based resin composition by mixing with an aqueous dispersion of a polycondensation resin (A) having an average particle size of 0.05 to 1 μm in gKOH / g. A polycondensation resin containing an unsaturated dicarboxylic acid having a possible unsaturated bond or an acid anhydride thereof as at least one of the constituent monomers, having an acid value of 3 to 100 mgKOH / g and an average particle size of 5 to 500 μm ( (3) a resin powder containing B), (3) an unsaturated dicarboxylic acid having a radically polymerizable unsaturated bond or an acid anhydride thereof as at least one of constituent monomers, and an acid value of 3 to 100.
mgKOH / g, which is used to prepare a thermosetting aqueous resin composition by blending with a resin powder containing a polycondensation resin (B) having an average particle size of 5 to 500 μm, An unsaturated dicarboxylic acid having an unsaturated bond capable of radical polymerization or an acid anhydride thereof is at least one of the constituent monomers, and has an acid value of 3 to 100 mgKOH / g.
, An aqueous dispersion of a polycondensation resin (A) having an average particle size of 0.05 to 1 µm, (4) a molding material composition containing the aqueous resin composition according to (1), and (5) A molded article obtained by molding the molding material composition according to (4).

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The aqueous resin composition of the present invention forms an aqueous dispersion in which resin particles and the like are uniformly dispersed in an aqueous medium. It contains resin fine particles, a curing agent and water. Further, the polycondensation resin has a specific acid value and an average particle size, respectively. When such an aqueous resin composition is used for a molding material composition, the resin fine particles are uniformly impregnated into a molding substrate, applied, mixed,
When the molding material composition can be adhered and molded (hot pressed), the polymerization reaction involving unsaturated bonds present in the polycondensation-based resin proceeds uniformly throughout the molding material composition,
An excellent effect is exhibited in which thermosetting occurs efficiently over the whole, and a molded article having practically sufficient strength is obtained. Further, in the aqueous resin composition of the present invention, an environmentally friendly molded article can be obtained because a phenol resin, a melamine resin, or the like that causes formalin generation is not used.

The polycondensation resin (A) contained in the aqueous resin composition of the present invention comprises at least one kind of a monomer which comprises a radically polymerizable unsaturated dicarboxylic acid having an unsaturated bond or an acid anhydride thereof. Price is 3-100mgKO
H / g, preferably 10-70 mg KOH / g,
Its average particle size is 0.05-1 μm.

On the other hand, the polycondensation resin (B) contained in the aqueous resin composition of the present invention contains at least one kind of a monomer which comprises an unsaturated dicarboxylic acid having an unsaturated bond capable of radical polymerization or an acid anhydride thereof. , Acid value is 3 ~ 100m
gKOH / g, preferably 10-70 mgKOH / g, and its average particle size is 5-500 μm.

In any of the polycondensation resins (A) and (B), if the acid value is less than 3 mgKOH / g, a stable aqueous dispersion cannot be obtained. If the acid value exceeds 100 mgKOH / g, the resin becomes water-soluble. When an oil-soluble curing agent or the like is internally added to the resin, the compatibility is reduced. In addition, when the polycondensation-based resins (A) and (B) have an average particle diameter within the above-specified ranges, an aqueous resin composition capable of exhibiting the desired effects of the present invention can be obtained. .

The polycondensation resins (A) and (B)
May be the same resin or different resins, except that each has an average particle size defined by each resin group.

The acid value is measured according to JIS K 0070, and the average particle size is determined, for example, by a laser diffraction type particle size distribution analyzer, SALD-2000J (manufactured by Shimadzu Corporation).
Measured by

As the polycondensation resin used in the present invention, ease of production of an aqueous resin composition which is an aqueous dispersion,
Polyesters and polyester polyamides are preferred from the viewpoint of adhesion to various substrates and not using formalin as a raw material. Therefore, the condensation polymerization resin (A),
An aqueous resin composition in which (B) is the same or different polyester or polyester polyamide is preferred.

The polycondensation resin used in the present invention, for example, the polyester can be produced by, for example, polycondensing an acid component listed below as a constituent monomer with a polyol component.

As the acid component, unsaturated dicarboxylic acids having radically polymerizable unsaturated bonds or acid anhydrides thereof include maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid and their acid anhydrides. And preferably maleic acid, fumaric acid, maleic anhydride and tetrahydrophthalic anhydride. These can be used alone or in combination of two or more. The content of these acid components is preferably 20 to 100 mol%, more preferably 50 to 100 mol%, based on the total acid components.

The acid component other than the above-mentioned acid component that can be used in the present invention is not particularly limited, and for example, the following polyvalent carboxylic acids or derivatives thereof can be used.

The polyvalent carboxylic acid or its derivative is not particularly limited, but is preferably a divalent or trivalent non-radical reactive carboxylic acid having 4 to 40 carbon atoms, such as phthalic acid, isophthalic acid, and the like. terephthalic acid, succinic acid, dimer acid, alkenyl succinic acid (C ₄ ~C _20),
Examples thereof include dicarboxylic acids such as cyclohexanedicarboxylic acid and naphthalenedicarboxylic acid, and trivalent carboxylic acids such as 1,2,4-benzenetricarboxylic acid, anhydrides thereof, and lower alkyl esters (C _{1 to} C ₄ ). In addition,
When a non-radical reactive acid component is used as the other acid component, the above-mentioned unsaturated dicarboxylic acid having a radical polymerizable unsaturated bond or an acid anhydride thereof is preferably used within the above-specified range.

On the other hand, the polyol component is not particularly limited, and is preferably ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, glycerin, pentaerythritol, trimethylolpropane, sorbitol, 1,6-hexane. Aliphatic polyols having 2 to 10 carbon atoms such as diols or aromatic polyols such as bisphenol A and hydrogenated bisphenol A and alkylene (C ₂ -C ₃ ) oxide adducts thereof (average number of moles = 2 to 10) And a propylene oxide adduct of bisphenol A is particularly preferred from the viewpoint of heat resistance and water resistance.

The polycondensation between the polyol component and the acid component can be carried out by a known method, for example, by reacting the polyol component and the acid component at a temperature of 180 to 250 ° C. in an inert gas atmosphere. The end point may be determined by tracking a softening point (Tm), an acid value, or the like, which is an index of the molecular weight.

The molar ratio between the polyol component and the acid component may be appropriately determined according to the acid value, number average molecular weight, glass transition point (Tg), etc. of the resulting polyester. The ratio is preferably 1: 1.5 (polyol component: acid component).

At the time of this polycondensation, additives such as an esterification catalyst such as dibutyltin oxide and a polymerization inhibitor such as hydroquinone monomethyl ether can be appropriately used.

The polyester polyamide, which is one of the preferred embodiments of the polycondensation resin used in the present invention, may be prepared by a known method, for example, an amine component in the component containing the acid component and the polyol used in the production of the polyester. The compound can be produced by condensation polymerization with the addition of a derivative. Such amine derivatives are not particularly limited, and polyamines such as ethylenediamine, hexamethylenediamine, diethylenetriamine and xylylenediamine; aminocarboxylic acids such as methylglycine, trimethylglycine, 6-aminocaproic acid, δ-aminocaprylic acid, and ε-caprolactam And amino alcohols such as propanolamine, and methylglycine, trimethylglycine and 6-aminocaproic acid are preferred from the viewpoint of solubility in organic solvents.

The molar ratio of the polyol component, the acid component, and the amine derivative in the polyester polyamide is appropriately determined according to the acid value, number average molecular weight, glass transition point, and the like of the polyester polyamide as in the case of the polyester. do it.

The acid value of the resulting polycondensation resin can be adjusted by adjusting the raw materials thereof, for example, the molar ratio of the acid component / polyol component, the reaction time and the like.

The average particle diameter is adjusted, for example, by adjusting the molecular weight, acid value, degree of neutralization, etc. of the resulting polycondensation resin, dissolving the resin in an organic solvent, and adding water and a surfactant. In addition, a step of evaporating the organic solvent and inverting the phase to an aqueous phase is performed, and at that time, it can be appropriately adjusted by changing the conditions of phase inversion emulsification and the like. Further, the obtained resin can be prepared by appropriately pulverizing the resin.

The condensation polymerization resins (A) and (B) used in the present invention preferably have a hydroxyl value (OHV) based on JIS K0070 of 1 to 50 mgKOH /
g. Further, the resin has a glass transition point (Tg) (measured by a differential scanning calorimeter) of 0 to 100 ° C and a softening point (Tg).
m) (measured by the flow tester method) is 30 to 180 ° C
And the number average molecular weight (value converted into polystyrene by the GPC method) is preferably 1,000 to 50,000. When the resin is a polyester polyamide, the amine value of the resin based on ASTM D2073 is preferably 10 mgKOH / g or less.

Further, it is preferable that at least a part of the carboxyl group present in the polycondensation resin is neutralized. For example, the neutralization may be carried out using a neutralizing agent before or during the preparation of the aqueous resin composition of the present invention, and the neutralization method is not particularly limited.

The neutralizing agent is not particularly limited as long as it can ionize a carboxyl group.
Hydroxides such as alkali metals and alkaline earth metals and various amines, particularly hydroxides of alkali metals, are used in an amount of 0.8 to 1 equivalent of a carboxyl group in the polycondensation resin. ~ 1.4 equivalents are preferred. The neutralizing agent may be used as it is, or may be used after being diluted and dissolved in a very small amount of water.

The content of the polycondensation resins (A) and (B) in the aqueous resin composition of the present invention varies depending on the molding method. However, from the balance between the required strength and the stability of the dispersion, polycondensation is carried out. System resin (A) is preferably 7.5 to 67.5.
% By weight, more preferably 10 to 60% by weight, still more preferably 15 to 50% by weight, and the condensation polymerization resin (B) is preferably 7.5 to 67.5% by weight, more preferably 10 to 60% by weight.
-60% by weight, more preferably 15-50% by weight. Further, the content ratio of the polycondensation-based resin (A) and (B) in the aqueous resin composition of the present invention is a weight ratio [(A) /
(B)], preferably 10/90 to 90/10, more preferably 10/60 to 60/10.

In the water-based resin composition of the present invention, in addition to the above-mentioned polycondensation resin, other resins may be used as appropriate within a range where the desired effects of the present invention are not impaired.

Examples of the curing agent used in the water-based resin composition of the present invention include organic peroxides and azo-based polymerization initiators, and organic peroxides having high reactivity are preferred. In addition, such a curing agent can be used by mixing with the polycondensation resin (B). Furthermore, from the viewpoint of uniform curability of the water-based resin composition, it is preferable to internally add the polycondensation resin (A).

Examples of the organic peroxide include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, peroxyesters and the like. It is preferable that the active oxygen content is large and the activation energy is small. Preferred specific examples are ketone peroxides, methyl ethyl ketone peroxide, cyclohexanone peroxide,
Acetylacetone peroxide; and peroxyketals such as 1,1-di (t-hexylperoxy) 3,3,5-trimethylcyclohexane,
1-di (t-hexylperoxy) cyclohexane,
1,1-di (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 1,1-di (t-amylperoxy) 3,3 , 5-trimethylcyclohexane, 1,1
-Di (t-amylperoxy) cyclohexane, n-butyl-4,4-di (t-butylperoxy) valerate and the like. As hydroperoxides, t-
Amyl hydroperoxide, t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide and the like, and dialkyl peroxides such as dicumyl peroxide, 2,5 -Dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butylperoxide, 2,
5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 1,3-bis (t-butylperoxyisopropyl) benzene and the like, and as diacyl peroxides, lauroyl peroxide, benzoyl Peroxide, stearoyl peroxide and the like, and bis (4-
t-butylcyclohexyl) peroxydicarbonate; and peroxyesters such as t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, and t-butylperoxyisopropyl monocarbonate. , T-butyl peroxy-2-ethylhexyl monocarbonate,
t-butylperoxybenzoate, bis (t-butylperoxy) isophthalate, di-t-butylperoxyhexahydroterephthalate, t-amylperoxy-3,5,5-trimethylhexanoate and the like.

As the azo polymerization initiator, 2,2 ′
-Azobis-isobutyronitrile [1 minute half-life temperature (the same applies hereinafter): 116.0 ° C], 2,2'-azobis-2
-Methylbutyronitrile [119.0 ° C], 2,2'-
Azobis-2,4-dimethylvaleronitrile [104.
0 ° C.], 1,1′-azobis-1-cyclohexanecarbonitrile [141.0 ° C.], dimethyl-2,2′-azobisisobutyrate [119.0 ° C.], 1,1′-azobis- ( 1-acetoxy-1-phenylethane) [1
11.0 ° C.]. These curing agents can be used alone or in combination of two or more.

The content of the curing agent in the aqueous resin composition of the present invention depends on the curing rate required for the material to be molded and the balance between the strength of the molded article and the stability of the aqueous resin composition. 0.1 to 30 parts by weight, more preferably 0.5 to 100 parts by weight, based on 100 parts by weight of the polycondensation resin contained in the composition [total amount of the above condensation polymerization resins (A) and (B)]. 20 parts by weight. When a curing agent is used by being internally added to the polycondensation resin (A), the content of the curing agent in the aqueous resin composition falls within the above range.
What is necessary is just to add internally to the said condensation polymerization type resin (A) suitably. In addition,
The method of internal addition includes, for example, a method of dissolving such a resin and a curing agent in an organic solvent, adding water and, if necessary, a surfactant, removing the organic solvent, and inverting the phase to an aqueous phase. .

The aqueous resin composition of the present invention contains a compound having two or more radically polymerizable unsaturated bonds (hereinafter also referred to as an unsaturated bond compound) from the viewpoint of increasing the crosslinking density of the resin after thermosetting. Further, it is preferable to contain it. The unsaturated bond compound may be used by being internally added to the polycondensation resin (A) and / or (B).
The method of internal addition includes, for example, a method of dissolving the resin and the unsaturated bond compound in an organic solvent, adding water and, if necessary, a surfactant, removing the organic solvent, and inverting the phase to an aqueous system. No.

Examples of the unsaturated bond compound used in the present invention include one or more compounds selected from the group consisting of compounds having an allyl group, compounds having both terminal (meth) acryl groups, and compounds having a divinyl group. Can be
Among these, when the molding material composition containing the aqueous resin composition of the present invention is heated and cured, in the heated molten state before curing, it is compatible with the polycondensation resin and lowers the melting point of the resin. To improve the strength of the molded article after curing by increasing the cross-linking density due to the high reactivity associated with the decrease in the melting point of the resin and the amount of unsaturated bonds, the storage stability of the composition, and the molding. From the viewpoint of odor at the time, a compound having an allyl group is preferable. Specifically, diallyl compounds such as diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl maleate, diallyl itaconate, diallyl hexahydrophthalate, diallyl phthalate prepolymer, diallyl isophthalate prepolymer and 1,2,2 Triallyl compounds such as triallyl 4-benzenetricarboxylate are more preferred.

Compounds having a (meth) acrylic group at both terminals include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, and 1,3-butylene glycol. Dimethacrylate, 1,6-hexanediol dimethacrylate and the like, and triethylene glycol dimethacrylate,
Polyethylene glycol dimethacrylate and the like are preferred. As the compound having a divinyl group, divinylbenzene, divinylnaphthalene and the like are preferable. These unsaturated bond compounds may be used alone or in combination of two or more.

The content of the unsaturated bond compound in the water-based resin composition of the present invention is determined from the viewpoint of enhancing the strength of the molded article and improving heat resistance and water resistance. Total amount of A) and (B)] is preferably 5 to 80 parts by weight, more preferably 10 to 100 parts by weight.
60 parts by weight. When the unsaturated bond compound is used by being internally added to the polycondensation resin (A) and / or (B), the content of the unsaturated bond compound in the aqueous resin composition falls within the above range. What is necessary is just to add internally to the said condensation polymerization type resin (A) and / or (B) suitably.

The water-based resin composition of the present invention may further contain a wax from the viewpoint of improving the releasability between the molding machine and the molded article during molding and improving the water resistance of the molded article. Examples of the wax include paraffin wax, microcrystalline wax, petrolatum, carnauba wax, and emulsions thereof.

The content of the wax in the aqueous resin composition is preferably from 0.05 to 10% by weight, more preferably from the viewpoint of the releasability between the molding machine and the molded article during molding and the water resistance of the molded article. 0.1 to 5% by weight.

The aqueous resin composition of the present invention may further contain, in addition to the above-mentioned components, various conventionally known additives, for example, ultraviolet absorbers such as benzotriazole and benzophenone, fungicides such as chloromethylphenol, and EDTA. And the like, and an oxygen absorbent such as a sulfite.

Examples of the water used in the aqueous resin composition of the present invention include tap water, ion-exchanged water and distilled water, but are not particularly limited as long as the desired effects of the present invention are not impaired. Absent. The content is adjusted so that the total amount becomes 100% by weight when the above components are contained.

Next, a method for producing the aqueous resin composition of the present invention will be described. The aqueous resin composition, for example,
At least the following components: (1) An unsaturated dicarboxylic acid having a radical polymerizable unsaturated bond or an acid anhydride thereof is at least one of the constituent monomers, and has an acid value of 3 to 100 mgKOH / g;
An aqueous dispersion of a polycondensation resin (A) having an average particle size of 0.05 to 1 μm; (2) at least a radical monomer capable of forming a radically polymerizable unsaturated dicarboxylic acid having an unsaturated bond or an acid anhydride thereof; One kind, acid value is 3-100
It can be produced by mixing a resin powder containing a polycondensation resin (B) having an average particle size of 5 to 500 μm in mgKOH / g and a curing agent (3) by a conventional method. .

Preferably, an aqueous dispersion of the polycondensation resin (A) of the present invention to be described later, a resin powder containing the polycondensation resin (B) and the above-mentioned curing agent are mixed by a conventional method. Other components other than the polycondensation resin and the curing agent may be appropriately added and mixed together during such mixing. The curing agent may be contained in the aqueous dispersion of the resin and / or the resin powder, and in such a case, it is not always necessary to add the curing agent during the mixing.

The aqueous resin composition of the present invention includes, for example, an aqueous dispersion of the polycondensation resin (A) of the present invention and a polycondensation resin (B).
When the resin powder containing and the above-mentioned curing agent are mixed and produced by a conventional method, they can be mixed in advance to obtain a preparation (aspect A), or they can be mixed immediately before use to prepare a preparation. (Aspect b).

Accordingly, the present invention relates to a resin powder containing an aqueous dispersion (hereinafter referred to as an aqueous dispersion) of a polycondensation resin (A) and a polycondensation resin (B), which are used in the above-mentioned embodiment (b). Hereinafter, referred to as resin powder).

The aqueous dispersion specifically includes an unsaturated dicarboxylic acid having a radically polymerizable unsaturated bond or an acid anhydride thereof as at least one of the constituent monomers.
It is an aqueous dispersion of a polycondensation resin (A) having an acid value of 3 to 100 mgKOH / g and an average particle size of 0.05 to 1 μm. It can be used to prepare a composition.

The condensation polymerization resin (A) contained in the aqueous dispersion is the same as the condensation polymerization resin (A). Its content is preferably 7.5 to 6 in the aqueous dispersion.
It is 7.5% by weight, more preferably 10 to 60% by weight. Such an aqueous dispersion may further contain the curing agent, and the content thereof is preferably 0.1 to 30% by weight.
It is. It is preferable that a curing agent is internally added to the polycondensation resin (A) from the viewpoint of the stability of the aqueous dispersion. The water to be used is the same as described above, and the content is adjusted so as to be 100% by weight in total with the components other than water of the aqueous dispersion. In addition, as an internal addition method, for example, in a manufacturing process of an aqueous dispersion described below, a curing agent is present together with a polycondensation resin to carry out phase inversion emulsification. Is taken in.

The aqueous dispersion is preferably produced by phase inversion emulsification or the like. For example, the polycondensation resin, if desired, the curing agent and the unsaturated bond compound are dissolved in an organic solvent, and after adding the water or the surfactant, the organic solvent is distilled off and the phase is changed to an aqueous phase. It is manufactured by The phase inversion may occur when water is added, but it is preferable that the phase inversion occur during the distillation of the organic solvent from the viewpoint of obtaining a stable aqueous dispersion of the resin.

Examples of the organic solvent include ketone solvents having 3 to 8 carbon atoms, such as acetone, methyl ethyl ketone and diethyl ketone, and carbon atoms having 4 carbon atoms, such as tetrahydrofuran (THF).
To 8 are preferable, and acetone, methyl ethyl ketone and THF are more preferable. The amount of the organic solvent used is preferably 100 to 600 parts by weight of the organic solvent based on 100 parts by weight of the polycondensation resin used in the aqueous dispersion of the present invention.

The amount of the water used is preferably 100 to 1000 parts by weight based on 100 parts by weight of the polycondensation resin used in the aqueous dispersion of the present invention. In this case, acetylene glycol compound, various anions,
Nonionic surfactants, especially higher alcohol sulfates, polyoxyethylene alkyl ether sulfates, dialkyl sulfosuccinates, β-naphthalenesulfonic acid formalin condensate salts, etc. are added in an amount of 1 to 20 parts by weight per 100 parts by weight of the polycondensation resin. It is preferable to further add about parts by weight because the average particle diameter of the resin fine particles can be reduced and the resin concentration can be increased. Examples of the water-soluble initiator include water-soluble peroxides such as sodium persulfate, potassium persulfate, and ammonium persulfate, 2,2-azobis (2-amidinopropane) dihydrochloride, and 4,4′-azobis (4 When a water-soluble azo compound such as -cyanovaleric acid) or 2,2-azobisisobutyramide dihydrate is added, the compound is heated at the time of molding to generate radicals from the compound, thereby further promoting the thermosetting reaction. It is preferred. The water-soluble initiator may be added when mixing the molding base and the aqueous resin composition.

In the present invention, the distillation of the organic solvent is preferably carried out, for example, at 30 to 70 ° C. under reduced pressure, and the content of the organic solvent is preferably 1% by weight or less, more preferably 0.1% by weight. It is desirable to adjust as follows. Further, it is more preferable to adjust the pH of the obtained processing solution to 6 to 10. For the adjustment of pH, the above-described neutralizing agent and the like can be used.

The average particle size of the polycondensation resin (A) contained in the aqueous dispersion varies, for example, the molecular weight, acid value, degree of neutralization, phase inversion emulsification conditions and the like of the polycondensation resin used. This can be adjusted as appropriate.

The water dispersion is preferably of a self-dispersion type, but is formed by adding a surfactant and dispersing the mixture with a forced stirring disperser such as a homomixer or a fill mix and an emulsifier such as an attritor. May be done.

The resin powder of the present invention specifically includes an unsaturated dicarboxylic acid having an unsaturated bond capable of radical polymerization or an acid anhydride thereof as at least one of the constituent monomers, and has an acid value of 3 to 100 mgKOH / g, a resin powder containing a polycondensation resin (B) having an average particle size of 5 to 500 μm, which is blended with the aqueous dispersion to prepare the aqueous resin composition of the present invention. Can be used.

The condensation polymerization resin (B) used for the resin powder is the same as the condensation polymerization resin (B). Its content is preferably 7.5 to 6 in the resin powder.
It is 7.5% by weight, more preferably 10 to 60% by weight. Such a resin powder may further contain the curing agent, and the content is preferably 0.1 to 30% by weight.
It is.

The resin powder is obtained, for example, by pulverizing the polycondensation resin used with a jet mill or the like to obtain fine particles of the polycondensation resin (B) having the desired average particle size. It can be manufactured by appropriately mixing.

When the aqueous resin composition of the present invention is prepared using the aqueous dispersion of the present invention and the resin powder, the aqueous dispersion and the resin powder are mixed with the condensation polymerization resin ( The weight ratio of (A) and (B) [(A) / (B)] is preferably 10
/ 90-90 / 10, more preferably 10 / 60-60
What is necessary is just to mix by a conventional method so that it may become / 10.

The aqueous resin composition of the present invention not only has excellent thermosetting properties, but also can impart heat resistance, water resistance and the like to the molded article according to the composition. Useful. Further, when the aqueous resin composition is prepared by mixing the resin powder of the present invention and the aqueous dispersion, it is possible to increase the concentration of the solid content. The aqueous resin composition of the present invention is impregnated into a molding substrate or the like, applied, mixed, adhered, for example, by spray coating, foam coating, etc.
A molding composition can be obtained.

The molding base is not particularly limited, and inorganic fibers such as glass fibers and carbon fibers, organic fibers such as synthetic fibers and natural fibers, inorganic powders such as silica, alumina, clay, calcium carbonate and talc, and pulp. Flour, wood flour, wood chips and the like can be used.

If necessary, catalysts, oligomers and prepolymers having unsaturated bonds, and other hardening aids having low odor at room temperature, crosslinking accelerators, amide waxes, synthetic waxes, synthetic latexes, fatty acid metal salts, etc. And a filler such as talc, silica, calcium carbonate, clay, and aluminum hydroxide, known additives, fillers, and extenders. These agents may be added, for example, when mixing the molding base and the aqueous resin composition.

The content of the molding substrate in the molding material composition is preferably from 1 to 99.5% by weight, more preferably from 20 to 9 from the viewpoint of the specific gravity of the molding and the strength of the molding.
8% by weight.

The content of the aqueous resin composition of the present invention in the molding material composition is preferably from 0.5 to 99% by weight, more preferably from 2 to 80% by weight, from the viewpoint of the strength of the molded article and the specific gravity of the molded article. %.

The method for molding the molding material composition of the present invention having such a constitution is not particularly limited, and known methods such as press molding with heating, compression molding, lamination molding, injection molding and extrusion molding are used. be able to. Further, the molding material composition may be subjected to molding after preheating. Further, after molding once, molding (secondary molding) may be performed again.

The molded article obtained by such a method has sufficient strength without causing environmental problems. That is,
There is no odor originating from the constituents of the molded body, and
When measured by the method shown in Examples described later, it is preferably flexural strength 25 N / mm ² or more, more preferably 40N / mm ² or more, the peel strength is preferably 0.3 N / mm ² or more, more preferably Is 0.45 N / m
m ² or more. Such a molded article can be suitably used for an automobile interior material, a building material, and the like.

[0064]

EXAMPLES Examples of resin production Bisphenol A (propylene oxide) average 2.1
1021 g of molar adduct, 398 g of ethylene glycol,
560 g of hydrogenated bisphenol A, 1380 fumaric acid
g (100 mol% in acid component), hydroquinone 0.3 g
And 8.4 g of dibutyltin oxide in a nitrogen stream at 160
The mixture was stirred for 4 hours. Thereafter, the temperature was raised to 200 ° C., and the reaction was carried out at normal pressure for 1 hour and at a reduced pressure of 9.33 kPa for another 1 hour. The resulting polyester resin had an acid value (AV) of 27.6 mgKOH / g and a hydroxyl value (O
HV) is 18.2 mg KOH / g and softening point (Tm) is 1.
The solid was a solid having a temperature of 03 ° C., a glass transition point (Tg) of 53.5 ° C., and a number average molecular weight of 3,300.

The softening point was measured using a Koka type flow tester (manufactured by Shimadzu Corporation) with a load of 20 kgf (196
N), orifice diameter 1 mm, orifice length 1 mm, 3
The temperature was measured under a heating condition of ° C./min, and the temperature at which a half amount flowed out was taken.
In addition, the glass transition point was measured by a differential scanning calorimeter DSC20 (manufactured by Seiko Denshi) under a heating condition of 10 ° C./min and determined by a tangential method.

Example 1 (1) Preparation of Resin Powder (B-1) The resin obtained in the above resin production example was pulverized to an average particle size of 50 μm.
Is obtained, and this is referred to as a resin powder (B-1).

(2) Preparation of Resin Powder (B-2) A benzoyl peroxide (manufactured by NOF CORPORATION, trade name: Niiper B) was added to the above resin powder (B-1) as a curing agent.
W) was added to 5 g with respect to 100 g of (B-1), and mixed uniformly. This is designated as resin powder (B-2).

(3) Preparation of Resin Powder (B-3) 1,3-Bis (t-butylperoxyisopropyl) benzene (Kakuyaku Akzo Co., Ltd.) was added to the above resin powder (B-1) as a curing agent. Product name: Parkadox 14R-P)
Was added to 100 g of (B-1) and uniformly mixed. This is referred to as a resin powder (B-3).

Example 2 (1) Preparation of Aqueous Dispersion of Resin (A-1) 300 g of the resin obtained in the above resin production example and 50 g of benzoyl peroxide were dissolved in 500 g of methyl ethyl ketone, and 16.0 g of triethylamine was dissolved. 20 g of ion-exchanged water containing water is added for neutralization, 800 g of ion-exchanged water is added under stirring, and methyl ethyl ketone is distilled off at 40 ° C. under reduced pressure to adjust the water content. A polyester resin (average particle size: 0.075 μm, solid content: 40% by weight) was obtained. This was used as an aqueous dispersion of resin (A-
1).

(2) Preparation of Resin Aqueous Dispersion (A-2) 300 g of the resin obtained in the above resin production example, 50 g of benzoyl peroxide and 60 g of diallyl phthalate were dissolved in 500 g of methyl ethyl ketone. In the same manner as in the case of 1, a thermosetting self-dispersible aqueous polyester resin (average particle size: 0.083 μm, solid content: 40% by weight) was obtained. This is referred to as a resin aqueous dispersion (A-2).

Example 3 The resin powder prepared in Example 1 and the aqueous dispersion prepared in Example 2 were mixed according to the composition shown in Table 1, respectively.
A thermosetting aqueous resin composition (solid content 58% by weight) was prepared. In the table, the numbers in parentheses indicate the weights of the mixed resin powder and aqueous dispersion.

[0072]

[Table 1]

Example 4 Raw materials obtained by defibrating rawan wood chips into rawan fibers were used as a molding base, and 300 kg of the above sample-1 was mixed with 1 kg (absolute dry weight) of rawan fibers while being sprayed and mixed. The mixture was dried through a flash dryer until the water content reached 7% to obtain molding fibers (resin content: 13% by weight).

Then, 120 g of the molding fiber was placed in a mold frame of 10 cm long × 25 cm wide to form a fiber mat for molding by embossing, and the hot press machine was heated to 200 ° C. in the upper and lower plates. And the pressure is 30kgf / c
Heating was performed under the conditions of m ² (2.94 MPa) and a molding time of 2 minutes to prepare a wood board (medium fiber board (MDF) type) sample a (board specific gravity: 0.74). When this board sample was evaluated according to JISA 5905, the flexural strength was 46 N / mm ² and the peel strength was 0.4 N / mm ² .
It was 47 N / mm ² and had sufficient strength.

Examples 5 to 7 In the same manner as in Example 4, wooden boards (medium fiber board (MDF) type) samples b to d were prepared using Samples 2 to 4, and evaluated in the same manner as in Example 4. Was done. Table 2 summarizes the results.

[0076]

[Table 2]

From the results in Table 2, it can be seen that the moldings (wood boards) obtained by molding the molding material composition containing the aqueous resin composition of the present invention have a bending strength of 46 N / mm ² or more.
The peel strength was 0.47 N / mm ² or more, indicating that the film had sufficient strength. In addition, these wood boards have no odor derived from monomers and are environmentally friendly.

[0078]

According to the present invention, environmental problems can be improved,
An aqueous resin composition capable of producing a uniform curing reaction is provided. Further, a molding material composition containing the water-based resin composition and a molded article obtained by molding the same and having sufficient strength for practical use are provided.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F071 AA49 AA54 AA81 AA85 AA86 AF01 AF58 AH03 AH11 BA03 BB13 BC07 4J027 AB02 AB06 AB07 AB08 AD01 CD01

Claims (8)

[Claims] An unsaturated dicarboxylic acid having an unsaturated bond capable of radical polymerization or an acid anhydride thereof is at least one of the constituent monomers, and has an acid value of 3 to 100 mg KOH.
/ G, a polycondensation resin (A) having an average particle size of 0.05 to 1 μm, an unsaturated dicarboxylic acid having an unsaturated bond capable of radical polymerization or an acid anhydride thereof is at least one of constituent monomers. , Acid value 3-100mgKOH
/ G, a thermosetting aqueous resin composition comprising a polycondensation resin (B) having an average particle size of 5 to 500 µm, a curing agent and water. 2. The content ratio of the polycondensation resin (A) to (B) is from 10/90 to 90/10 by weight ratio ((A) / (B)).
The aqueous resin composition according to claim 1, which is 3. The composition according to claim 1, further comprising a compound having two or more radically polymerizable unsaturated bonds.
The aqueous resin composition according to the above. 4. The aqueous resin composition according to claim 1, wherein the polycondensation resins (A) and (B) are the same or different polyesters or polyester polyamides. 5. An unsaturated dicarboxylic acid having an unsaturated bond capable of radical polymerization or an acid anhydride thereof is at least one of the constituent monomers, and has an acid value of 3 to 100 mg KOH.
/ G, used for preparing a thermosetting water-based resin composition by blending with an aqueous dispersion of a polycondensation resin (A) having an average particle diameter of 0.05 to 1 μm, capable of being radically polymerizable. An unsaturated dicarboxylic acid having an unsaturated bond or an acid anhydride thereof as at least one of the constituent monomers, an acid value of 3 to 100 mgKOH / g, and an average particle size of 5 to 100 mgKOH / g.
A resin powder containing a polycondensation resin (B) having a size of 500 μm. 6. An unsaturated dicarboxylic acid having an unsaturated bond capable of radical polymerization or an acid anhydride thereof is at least one of constituent monomers, and has an acid value of 3 to 100 mg KOH.
/ G, a radical used for preparing a thermosetting aqueous resin composition by blending with a resin powder containing a polycondensation resin (B) having an average particle size of 5 to 500 μm. Condensation polymerization comprising an unsaturated dicarboxylic acid having a polymerizable unsaturated bond or an acid anhydride thereof as at least one of the constituent monomers, having an acid value of 3 to 100 mgKOH / g and an average particle size of 0.05 to 1 μm. An aqueous dispersion of the resin (A). 7. A molding material composition comprising the aqueous resin composition according to claim 1. 8. A molded article obtained by molding the molding material composition according to claim 7.