JP2002121406A - Water-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-based resin composition capable of producing homogeneous curing reaction, a molding material composition comprising the water-based resin composition and provide a molded product having practically sufficient strength by molding the above composition. SOLUTION: This thermosetting water-based resin composition comprises a polycondensation resin (A) having 3-100 mgKOH/g acid value and containing an unsaturated dicarboxylic acid having radical-polymerizable unsaturated bond or its acid anhydride as at least one kind of component monomer, a curing agent, a curing accelerator and water. This water-based resin composition is used by using a water dispersion (C) in which the curing accelerator is internally added to the resin (A) and a water dispersion (B) in which the curing agent is internally added to the resin (A) and mixing the water dispersion (A) with the water dispersion (B) when used. This molding material composition comprises the above water-based resin composition. This molded product is obtained by molding the above molding material.

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 containing a curing agent, and used for preparing the aqueous resin composition. An aqueous dispersion of a polycondensation resin obtained by internally adding a curing accelerator,
The present invention also relates to a molding material composition containing the water-based 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]

SUMMARY OF THE INVENTION The present invention provides an aqueous resin composition capable of improving environmental problems and producing a uniform curing reaction, and internally adding a curing agent used for preparing the aqueous resin composition. An aqueous dispersion of a polycondensation resin obtained by internally adding a water dispersion of a polycondensation resin obtained by the method and a curing accelerator, a molding material composition containing the aqueous resin composition, and a molded material obtained by molding the same An object of the present invention is to provide a molded article having practically sufficient strength.

[0004]

That is, the gist of the present invention is as follows.
(1) A polycondensation resin (A) having an acid value of 3 to 100 mgKOH / g, comprising a radically polymerizable unsaturated dicarboxylic acid having an unsaturated bond or an acid anhydride thereof as at least one of the constituent monomers, a curing agent, A thermosetting aqueous resin composition containing a curing accelerator and water; (2) a polycondensation resin obtained by internally adding a curing agent to the polycondensation resin (A) described in (1) above; The polycondensation resin (A) described in (1) above, which is used for preparing a thermosetting aqueous resin composition by being blended with the aqueous dispersion of B), wherein a curing accelerator is internally added. Aqueous dispersion of polycondensation resin (C), (3) polycondensation resin (C) obtained by internally adding a curing accelerator to polycondensation resin (A) described in (1) above.
A polycondensation system obtained by internally adding a curing agent to the polycondensation resin (A) according to the above (1), which is used for preparing a thermosetting aqueous resin composition by being blended with the aqueous dispersion of (1). An aqueous dispersion of the resin (B), (4) an aqueous dispersion of the polycondensation resin (C) described in (2), and an aqueous dispersion of the polycondensation resin (B) described in (3). An aqueous resin composition used by mixing them at the time of use, (5) a molding material composition containing the aqueous resin composition according to the above (1) or (4), and (6) the above (5) The present invention relates to a molded article obtained by molding the molding material composition described in (1).

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The aqueous resin composition of the present invention is a system in which resin particles are uniformly dispersed in an aqueous medium, and includes a polycondensation resin having a specific acid value, a curing agent, and a curing accelerator. And water. Preferably, the curing agent and the curing accelerator are each internally added to the polycondensation resin. In such an aqueous resin composition, the polycondensation resin has a specific acid value, and forms a stable aqueous resin dispersion. When the aqueous resin composition is used for a molding material composition, the resin fine particles can uniformly impregnate, apply, mix, and adhere to a molding substrate. When the molding material composition is molded (hot-pressed), shrinkage occurs. The polymerization reaction involving unsaturated bonds present in the polymerized resin proceeds uniformly throughout the molding material composition, heat curing occurs efficiently throughout, and a molded article having practically sufficient strength can be obtained. An excellent effect is exhibited. 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.

[0006] The polycondensation resin (A) contained in the aqueous resin composition of the present invention is a resin comprising at least one unsaturated monomeric unsaturated dicarboxylic acid having a radically polymerizable unsaturated bond or an acid anhydride thereof. And the acid value is 3-100
mgKOH / g, preferably 10-70 mgKOH / g
It is. The form of the condensation polymerization resin (A) is fine particles, and the average particle size thereof is preferably 0.01 to 10%.
μm, more preferably 0.02 to 1 μm.

An acid value of the polycondensation resin (A) is 3 mg KOH
/ G, a stable aqueous dispersion cannot be obtained.
When it exceeds KOH / g, the hydrophilicity of the resin increases, for example,
When an oil-soluble curing agent or the like is internally added to the resin, the compatibility decreases.

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

Specific examples of the condensation polymerization resin used in the present invention include polyester and polyester polyamide.

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 a radically polymerizable unsaturated bond or acid anhydrides thereof include maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid and acid anhydrides thereof. 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 polycarboxylic acids or derivatives thereof can be used.

The polyvalent carboxylic acid or derivative thereof 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, or the like. Terephthalic acid, succinic acid, dimer acid, alkenyl succinic acid (with 4 to 2 carbon atoms)
0), divalent carboxylic 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 thereof (having 1 to 4 carbon atoms). No. When a non-radical reactive acid component is used as the other acid component, the above-listed unsaturated dicarboxylic acid having a radically polymerizable unsaturated bond or an acid anhydride thereof may be used within the range specified above. is necessary.

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 alkylenes thereof (2 to 3 carbon atoms)
Oxide adducts (the number of moles added: n = 2 to 20) are preferred, and in particular, propylene oxide adducts and ethylene oxide adducts of bisphenol A are 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 in an inert gas atmosphere at a temperature of, for example, 180 to 250 ° C. The end point can be determined by tracking the softening point (Tm), the acid value and the like, which are indicators 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 the polycondensation, additives such as an esterification catalyst such as dibutyltin oxide and a polymerization inhibitor such as hydroquinone and t-butylcatechol can be used as appropriate.

The polyester polyamide, which is one of the preferred embodiments of the polycondensation resin used in the present invention, can 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. The amine derivative is not particularly limited,
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 acids such as ethanolamine and propanolamine Alcohols are mentioned, and methyl glycine, trimethyl glycine 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, for example, 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 size 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, if necessary, water. A step of adding a surfactant and the like, distilling off the organic solvent and performing a phase inversion to an aqueous system is performed, and at that time, it can be appropriately adjusted by changing conditions for phase inversion emulsification and the like.

The condensation polymerization resin used in the present invention includes a hydroxyl value (OH) based on JIS K 0070.
V) is preferably 1 to 50 mg KOH / g. Further, the resin has a glass transition point (Tg) (measured by a differential scanning calorimeter) of −50 to 100 ° C., a softening point (Tm) (measured by a flow tester method) of 180 ° C. or less, and a number average molecular weight (by GPC method). Polystyrene equivalent) is 1
It is preferably from 000 to 50,000. When the resin is a polyester polyamide, the AS
The amine value based on TM D2073 is 10 mgKOH /
g or less.

Further, the carboxyl group present in the polycondensation resin must be at least partially neutralized. For example, the neutralizing agent may be used before or when the aqueous resin composition of the present invention is prepared. 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 resin (A) in the aqueous resin composition of the present invention varies depending on the molding method.
From the balance between the required strength and the stability of the dispersion, the content is preferably 10 to 70% by weight, more preferably 30 to 60% by weight.

As the curing agent used in the aqueous resin composition of the present invention, for example, an organic peroxide, an azo-based polymerization initiator and the like can be mentioned, and an organic peroxide having high reactivity is preferable. In addition, it is preferable that such a curing agent is internally added to the polycondensation resin (A) from the viewpoint of the stability of the aqueous resin composition.

The organic peroxide includes diacyl peroxides, ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, peroxyesters. And the like. From the viewpoint that the amount of active oxygen is large and the activation energy is small, diacyl peroxides, hydroperoxides and ketone peroxides are preferred. Preferred specific examples include diacyl peroxides such as lauroyl peroxide, benzoyl peroxide, stearoyl peroxide and the like, and ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide and acetylacetone peroxide, and As the peroxides, t-amyl hydroperoxide, t-butyl hydroperoxide, 1,1,3,
Examples include 3-tetramethylbutyl hydroperoxide, cumene hydroperoxide and the like. Other peroxyketals include 1,1-di (t-hexylperoxy) 3,3,5-trimethylcyclohexane,
1,1-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 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-di (2-t-butylperoxyisopropyl) benzene and the like, and as peroxydicarbonates, bis (4-t-butylcyclohexyl) peroxydicarbonate and the like,
As peroxyesters, t-butylperoxy-
2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-
2-ethylhexyl monocarbonate, t-butylperoxybenzoate, bis (t-butylperoxy) isophthalate, di-t-butylperoxyhexahydroterephthalate, t-amylperoxy-3,5,5
-Trimethylhexanoate and the like.

As the azo-based 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 is determined from the viewpoint of the balance between the curing speed required for the material to be molded, the strength of the molded article, and the storage stability of the aqueous resin composition. Preferably 0.1 to 30 parts by weight based on 100 parts by weight of the polycondensation resin (A) contained in the resin composition.
Parts by weight, more preferably 0.5 to 20 parts by weight. When the curing agent is used by being internally added to the polycondensation resin (A), it may be internally added so that the content of the curing agent in the aqueous resin composition falls within the above range. The method of internal attachment is, for example,
A method of dissolving such a resin and a curing agent in an organic solvent, adding water and, if necessary, a surfactant and the like, distilling off the organic solvent, and inverting the phase to an aqueous phase can be used.

The curing accelerator used in the aqueous resin composition of the present invention is not particularly limited as long as the desired effect of the present invention is not impaired, but aniline derivatives, toluidine derivatives, metal soaps and thiourea Derivatives are preferred. In addition, such a curing accelerator may be added to water, but is preferably added internally to the polycondensation resin (A) from the viewpoint of the stability of the aqueous resin composition. However, in this case, it is preferable that both the curing agent and the curing accelerator are not internally added to the same resin particles in order to suppress a rapid curing reaction, that is, to secure the storage stability of the aqueous resin composition.

Preferred specific examples of the curing accelerator include N, N-dimethylaniline as an aniline derivative, p-toluidine as a toluidine derivative, and cobalt naphthenate as a metal soap. And thiourea derivatives such as Rongalit. These curing accelerators can be used alone or in combination of two or more.

The content of the curing accelerator in the aqueous resin composition of the present invention is determined from the viewpoint of the balance between the curing speed required for the material to be molded, the strength of the molded article, and the storage stability of the aqueous resin composition. It is preferably 0.01 to 100 parts by weight of the polycondensation resin (A) contained in the aqueous resin composition.
10 to 10 parts by weight, more preferably 0.05 to 5 parts by weight. When the curing accelerator is used by being internally added to the polycondensation resin (A), it may be internally added so that the content of the curing accelerator in the aqueous resin composition falls within the above range. Examples of the method of internal addition include, for example, a method of dissolving the resin and the curing accelerator in an organic solvent, adding water and, if necessary, a surfactant, etc., and distilling off the organic solvent to convert the phase to an aqueous phase. Is mentioned.

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.

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 heating and curing the molding material composition containing the aqueous resin composition of the present invention, in the heated molten state before curing, it is compatible with the polycondensation resin, and the melt viscosity of the resin is reduced. It has the effect of reducing, and also improves the strength of the molded article after curing by increasing the crosslink density due to the increase in the reactivity and the amount of unsaturated bonds due to the decrease in the melt viscosity of the resin, and the storage stability of the composition. From the viewpoint of the odor during molding and the like, a compound containing an allyl group is preferred. Specifically, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl maleate, diallyl itaconate, diallyl hexahydrophthalate, diallyl phthalate prepolymer,
Diallyl compounds such as diallyl isophthalate prepolymer and triallyl compounds such as triallyl 1,2,4-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, 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 aqueous resin composition of the present invention is preferably based on 100 parts by weight of the polycondensation resin from the viewpoints of increasing the strength of the molded article and improving heat resistance and water resistance. Is 0.5 to 80 parts by weight, more preferably 1 to 60 parts by weight. When an unsaturated bond compound is used by being internally added to the polycondensation resin (A), the condensation polymerization resin (A) is appropriately added so that the content of the unsaturated bond compound in the aqueous resin composition falls within the above range. A) may be added internally.

The water-based resin composition of the present invention may further contain a release agent 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. Good. As the release agent, low-molecular-weight polyethylene, polypropylene, long-chain fatty acids such as stearic acid, metal salts of long-chain fatty acids such as zinc stearate, paraffin wax, microcrystalline wax, petrolatum, waxes such as carnauba wax, and These emulsions and the like can be mentioned.

The content of the release agent in the aqueous resin composition is preferably from 0.05 to 10% by weight, from the viewpoint of the releasability between the molding machine and the molded article during molding and the water resistance of the molded article. Preferably it is 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.

Further, an isocyanate such as MDI can be added to increase the crosslink density of the resin after thermosetting.

Examples of the water used in the aqueous resin composition of the present invention include tap water, ion-exchanged water, distilled water and the like, 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. In the production of the aqueous resin composition, the curing agent and the curing accelerator are prevented from coming into direct contact from the viewpoint of storage stability. For example, the aqueous resin composition preferably includes at least the following components: (1) an aqueous dispersion of a polycondensation resin (B) obtained by internally adding a curing agent to the polycondensation resin (A) [hereinafter, water Dispersion (1)
And (2) an aqueous dispersion of a polycondensation resin (C) obtained by internally adding a curing accelerator to the polycondensation resin (A) [hereinafter referred to as an aqueous dispersion (2)]. It can be manufactured by mixing according to the method.

The polycondensation resin (B) and the polycondensation resin (C) represent another embodiment of the polycondensation resin (A).

Further, other components such as an unsaturated bond compound other than the condensation polymerization resin, the curing agent and the curing accelerator include:
At the time of such mixing, they may be appropriately added and mixed together.

If it is possible to prevent the curing agent and the curing accelerator from coming into direct contact with each other, for example, one of the curing agent and the curing accelerator is internally added to the polycondensation resin to be used. Alternatively, an aqueous dispersion of such a resin may be mixed with any one of a hardener and a hardening accelerator not added by a conventional method.

When the aqueous resin composition of the present invention is produced, for example, by mixing the aqueous dispersions (1) and (2) by a conventional method, the aqueous resin composition is a preparation obtained by mixing them in advance. Alternatively, the preparation can be obtained by mixing them immediately before use (aspect b) (aspect b).

The present invention also provides the aqueous dispersion (1) and the aqueous dispersion (2) used for preparing the aqueous resin composition of the present invention.

The water dispersion (1) is prepared in the following water dispersion (2)
Can be used to prepare the aqueous resin composition of the present invention.

The polycondensation resin (B) contained in the aqueous dispersion (1) is preferably prepared by adding the curing agent to the polycondensation resin (A) with respect to 100 parts by weight of the polycondensation resin. 1
To 30 parts by weight, more preferably 0.5 to 20 parts by weight. The content of the polycondensation resin (B) in the aqueous dispersion (1) is preferably 10 to 70% by weight, more preferably 30 to 60% by weight. As the water, those similar to the above-mentioned ones can be used, and the content thereof is adjusted to 100% by weight in total with the components other than water of the aqueous dispersion (1).

The water dispersion (2) is the same as the water dispersion (1).
Can be used to prepare the aqueous resin composition of the present invention.

The condensation polymerization resin (C) contained in the aqueous dispersion (2) is preferably such that the curing accelerator is added to the condensation polymerization resin (A) with respect to 100 parts by weight of the condensation polymerization resin. 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight. The content of the polycondensation resin (C) is preferably 10% in the aqueous dispersion (2).
７０70% by weight, more preferably 30-60% by weight. The same water as that described above can be used as the water, and the content thereof is adjusted to 100% by weight in total with the components other than water of the water dispersion (2).

Further, the present invention also provides an aqueous resin composition comprising the aqueous dispersion (1) and the aqueous dispersion (2) and mixing them at the time of use. Such an aqueous resin composition is one of the specific examples of the above embodiment b, and the aqueous dispersion (1) and the aqueous dispersion (2) are separately and independently provided until immediately before use of the aqueous resin composition. The water-based resin composition is provided at the same time as the aqueous resin composition, and both aqueous dispersions are mixed by an ordinary method for the first time when the water-based resin composition is used. In such an aqueous resin composition, the two kinds of aqueous dispersions are mixed at the time of providing the aqueous resin composition, and are in a separate and independent form before the aqueous dispersion, so that they are further excellent in storage stability.

The aqueous dispersions (1) and (2) are preferably produced by phase inversion emulsification or the like. For example, the polycondensation resin, the curing agent or the curing accelerator, and if desired, the unsaturated bond compound is dissolved in an organic solvent, and after adding the water or the surfactant, the organic solvent is distilled off. It is produced by inverting the phase to an aqueous system. 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 curing agent include water-soluble persulfate 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-azobisisobutylamide 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 curing agent may be added when mixing the molding base and the aqueous resin composition.

The distillation of the organic solvent is preferably performed, 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 or less.
It is desirable to adjust it to not more than weight%. 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 contained in the aqueous dispersion may be appropriately adjusted by, for example, changing the molecular weight, acid value, degree of neutralization, phase inversion emulsification conditions and the like of the polycondensation resin used. Can be adjusted.

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 water-based resin composition of the present invention is not only excellent in thermosetting properties but also excellent in storage stability. According to the composition, heat resistance, water resistance and the like are imparted to the molded article. Therefore, it is useful as a raw material of a molded article. A molding material composition can be obtained by applying, impregnating, spray-coating, foam-coating, etc. the molding resin or the like based on the aqueous resin composition of the present invention.

The molding base is not particularly limited, and inorganic fibers such as glass fibers and rock wool, carbon fibers,
Organic fibers such as synthetic fibers and natural fibers, inorganic powders such as silica, aluminum hydroxide, alumina, clay, calcium carbonate, and talc, pulp powder, wood powder, and wood chip chips can be used.

Further, if necessary, a catalyst, a curing aid having a low odor at room temperature such as an oligomer or a prepolymer having an unsaturated bond, a crosslinking accelerator, and talc, silica, calcium carbonate, clay, aluminum hydroxide And a known additive such as a flame retardant may be used. These agents may be added internally to the resin, for example, or may be added when the molding base and the aqueous resin composition are mixed.

The content of the molding substrate in the molding material composition is preferably from 1 to 99.5 from the viewpoint of the strength of the molded article.
%, More preferably 20 to 98% by weight.

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

Since the molded article obtained by such a method does not cause environmental problems and has sufficient strength, it can be suitably used for automobile interior materials, building materials and the like.

[0066]

EXAMPLES Preparation of Resin 1 Preparation of Polyester Resin 1021 g of bisphenol A propylene oxide adduct (average number of moles added: 2.2 mol), 398 g of ethylene glycol, 560 g of hydrogenated bisphenol A, 1380 g of fumaric acid (100 mol in all acid components) %), 0.3 g of hydroquinone and 8.4 g of dibutyltin oxide were reacted at 160 ° C. for 4 hours under a nitrogen stream. Then 200 ° C
Thereafter, the reaction was carried out at normal pressure for 1 hour and at a reduced pressure of 9.33 kPa for 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. This is referred to as resin (1). The softening point is high flow type flow tester (manufactured by Shimadzu Corporation)
Was measured under a heating condition of 20 kgf, orifice diameter 10 mm, orifice length 1 mm, and 3 ° C./min. The glass transition point is
It was measured by a differential scanning calorimeter, DSC200 (manufactured by Seiko Instruments Inc.) under a heating condition of 10 ° C./min, and determined by a tangential method.

Example 1 (1) Preparation of Resin Aqueous Dispersion (B-1) 300 g of the above resin (1) and 10 g of Niper BW (benzoyl peroxide, manufactured by NOF Corporation) were dissolved in 500 g of methyl ethyl ketone. 16 g of triethylamine
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. Polyester resin (average particle size: 0.065
μm, solid content: 40% by weight) [Aqueous dispersion of resin (B-1)].

(2) Preparation of Resin Aqueous Dispersion (B-2) 300 g of the resin (1), 7 g of Permec N (methyl ethyl ketone peroxide, manufactured by NOF Corporation) and 60 g of diallyl phthalate were dissolved in 500 g of methyl ethyl ketone. In the same manner as in B-1, a thermosetting self-dispersible aqueous polyester resin (average particle size: 0.061 μm, solid content:
(Aqueous dispersion of resin (B-2)).

Example 2 (1) Preparation of Resin Aqueous Dispersion (C-1) After dissolving 300 g of the resin (1) and 4 g of dimethylaniline in 500 g of methyl ethyl ketone, ion-exchanged water containing 16.0 g of triethylamine was used. 20 g was added for neutralization, 800 g of ion exchange water was added under stirring, and methyl ethyl ketone was distilled off under reduced pressure at 40 ° C. to adjust the water content, and a thermosetting self-dispersible water-based polyester resin (average) Particle size: 0.050 μm, solid content: 40% by weight) [Aqueous dispersion of resin (C-1)].

(2) Preparation of Resin Aqueous Dispersion (C-2) 300 g of the resin (1), 3 g of cobalt naphthenate,
60 g of diallyl phthalate in 500 g of methyl ethyl ketone
And a thermosetting self-dispersible aqueous polyester resin (average particle size: 0.064 μm,
(Solid content: 40% by weight) [Aqueous dispersion of resin (C-
2)].

Example 3 Preparation of Thermosetting Aqueous Resin Composition Resin Aqueous Dispersion (B-1) and Resin Aqueous Dispersion (C-1)
Are mixed in the same amount to obtain a thermosetting aqueous resin sample-1.
The same amount of (B-2) and (C-2) were mixed to prepare a thermosetting aqueous resin sample-2.

Example 4 Rawn wood chips were defibrated and made into Rawan fibers, which was used as a molding base. The above sample-1 (solid content: 40% by weight) 480 per 1 kg (absolute dry weight) of Rawan fibers
g was mixed while being applied by spraying, and dried through a flash dryer until the water content became 7% by weight to obtain a molding fiber (resin content: 13% by weight).

Next, 220 g of molding fiber was put into a mold frame of 10 cm long × 25 cm wide and pressed to form a fiber mat for molding, and a hot press machine in which the upper and lower hot plates were heated to 200 ° C. In the above, a 12 mm width spacer is sandwiched, and hot-pressed under the conditions of a pressure of 2.9 MPa and a molding time of 2 minutes, and a wood board (medium fiber board (MDF) type)
Sample a was prepared. The board specific gravity was 0.74. The board sample was evaluated according to JIS A 5905, the bending strength is 46N / mm ^2, the peel strength is 0.47N / mm ^2, and had a sufficient strength.

Example 5 A wood board (medium fiber board (MDF type)) sample b was prepared in the same manner as in Example 4 except that Sample-1 used in Example 4 was changed to Sample-2. The board specific gravity was 0.72. This board sample is
When evaluated according to A 5905, the flexural strength was 50
A N / mm ^2, the peel strength is 0.50 N / mm ^2, and had a sufficient strength.

In this example, there is no formaldehyde emission.
It can be seen that a wood board having sufficient strength can be obtained.

[0076]

According to the present invention, environmental problems can be improved,
An aqueous resin composition capable of producing a uniform curing reaction is obtained, and a molded article having practically sufficient strength can be obtained by molding a molding material composition containing the aqueous resin composition.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F071 AA43 AA57 AC08 AC12 AC13 AE02 AE03 BA03 BC07 4J002 AA061 CF031 CL081 DE028 EG087 EK006 EN067 EV127 FD146 FD157 HA07

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 of a condensation polymerization resin (A), a curing agent, a curing accelerator and water. 2. The aqueous resin composition according to claim 1, further comprising a compound having two or more radically polymerizable unsaturated bonds. 3. The curing agent is at least one selected from the group consisting of diacyl peroxides, hydroperoxides and ketone peroxides, and the curing accelerator is an aniline derivative, a toluidine derivative, a metal soap and a thiourea. 3. The aqueous resin composition according to claim 1, which is at least one selected from the group consisting of derivatives. 4. A thermosetting aqueous resin composition which is blended with an aqueous dispersion of a polycondensation resin (B) obtained by internally adding a curing agent to the polycondensation resin (A) according to claim 1. 2. An aqueous dispersion of a polycondensation resin (C) obtained by internally adding a curing accelerator to the polycondensation resin (A) according to claim 1, which is used for preparing a polymer. 5. A polycondensation resin (C) obtained by internally adding a curing accelerator to the polycondensation resin (A) according to claim 1.
2. A polycondensation resin obtained by internally adding a curing agent to the polycondensation resin (A) according to claim 1, which is used for preparing a thermosetting aqueous resin composition by being blended with an aqueous dispersion of The aqueous dispersion of (B). 6. An aqueous dispersion of the polycondensation resin (C) according to claim 4 and an aqueous dispersion of the polycondensation resin (B) according to claim 5, which are mixed and used at the time of use. Aqueous resin composition. 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.