JPH09194741A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition consisting mainly of a thermoplastic resin and a thermosetting resin, excellent in both heat resistance and impact strength, and useful in the OA/home appliance field. SOLUTION: This resin composition consists mainly of (A) 30-99wt.% of a thermoplastic resin and (B) 70-1wt.% of a thermosetting resin. This composition is obtained by melt-kneading the components A and B in with the average diameter of the dispersed particles of the component B at <=50μm and pref. by curing the component B during the kneading process. The component A is pref. e.g. a rubber-reinforced styrene-based resin produced by emulsion polymerization of 100 pts.wt. of a rubbery polymer plus a monomer component in 80-130 pts.wt. of polymerization water at 30-110 deg.C, while the component B is pref. e.g. a polycarbodimide composed of recurring unit of the formula (R<1> is a divalent organic group).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition having excellent heat resistance and impact strength.

[0002]

2. Description of the Related Art With the advanced use of plastics,
In recent years, plastics having various characteristics have been provided in response to market needs. Above all, demand for plastics with excellent heat resistance and impact resistance is increasing due to market needs for light, thin, short, and small products. Conventionally, various inorganic fillers such as glass fiber and mica have been used to improve the heat resistance of thermoplastic resins and thermosetting resins. However, although the use of these improves the heat resistance, there is a problem that the impact resistance decreases. Further, in order to improve impact resistance, various rubber components and elastomer components have been used or increased in amount, but with the use of these components, there is a problem that heat resistance decreases. On the other hand, even if a thermoplastic resin and a thermosetting resin are simply compounded, it is difficult to obtain a resin composition that can be used because of the great difference in the resin characteristics between the two.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems of the prior art, and an object thereof is to provide a resin composition having excellent heat resistance and impact strength.

[0004]

The present invention provides (A) 30 to 99% by weight of a thermoplastic resin, and (B) a thermosetting resin 7.
The present invention provides a resin composition comprising 0 to 1% by weight as a main component, and the dispersed particles of the component (B) having an average particle size of 50 μm or less.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the resin composition of the present invention,
As the component (A), a known thermoplastic resin can be used without any limitation. Examples of the thermoplastic resin (A) include polyolefin resins such as polyethylene, polypropylene and polybutene-1, polyamides such as nylon 6, nylon 6,6, nylon 11, nylon 12 and nylon 4,6, polybutylene terephthalate, Polyester such as polyethylene terephthalate,
Polyether-based resins such as wholly aromatic polyester, polycarbonate, polyoxymethylene, and (modified) polyphenylene ether, styrene-based resins, styrene-based resins with impact resistance enhanced by rubber (hereinafter also referred to as "rubber-reinforced styrene-based resin"). ), Polyphenylene sulfide, polyamide elastomer, polyester elastomer, and thermotropic liquid crystal polyester. These (A) thermoplastic resins may be used alone,
Alternatively, two or more kinds can be used in combination.

Further, the thermoplastic resin (A) includes a carboxyl group, a hydroxyl group, an oxazoline group, an acid anhydride group,
A functional group such as an ester group, a carbonate group, an amino group, an amide group, an epoxy group, an isocyanate group, a urethane group and a urea group is contained singly or in combination of two or more.
It may be a functional group-containing thermoplastic resin. Also, (A)
The component may be a composition having any composition of a thermoplastic resin containing a functional group and a thermoplastic resin containing no functional group. When the functional group-containing thermoplastic resin is included as the component (A), the ratio of the functional group-containing thermoplastic resin is (A).
In the components, 1% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, particularly preferably 10% by weight or more.
90% by weight.

The preferred thermoplastic resin used as the component (A) is the above-mentioned polyolefin resin, polyamide, polyester, modified polyphenylene ether, polycarbonate, styrene resin, rubber-reinforced styrene resin, more preferably polyolefin resin, Styrene-based resins and rubber-reinforced styrene-based resins, particularly preferably rubber-reinforced styrene-based resins and styrene-based resins (hereinafter, rubber-reinforced styrene-based resins and / or styrene-based resins are also referred to as “(rubber-reinforced) styrene-based resins”). ).

The rubber-reinforced styrenic resin which is particularly preferably used as the component (A) of the resin composition of the present invention is obtained by, for example, graft-polymerizing an aromatic vinyl monomer to the rubber-like polymer (a). It can be obtained as a graft polymer. In this graft polymerization, selected from the group of vinyl cyanide monomers, (meth) acrylic acid ester monomers, acid anhydride monomers and maleimide monomers together with aromatic vinyl monomers. At least one other monomer (hereinafter, aromatic vinyl-based monomer and other monomer used as necessary are also collectively referred to as “monomer component”) It can be used in combination with an aromatic vinyl-based monomer. The rubber-reinforced styrene-based resin may be separately blended with an aromatic vinyl-based monomer and a copolymer obtained by polymerizing the above-mentioned other monomer used as necessary.

Examples of the rubber-like polymer (a) used in the rubber-reinforced styrene resin of the present invention include polybutadiene, polyisoprene, butyl rubber and styrene-butadiene copolymer (styrene content of 5 to 60% by weight is preferable). , Styrene-isoprene copolymer, acrylonitrile-butadiene copolymer, ethylene-α-olefin copolymer, ethylene-α-olefin-polyene copolymer, silicone rubber, acrylic rubber, butadiene- (meth) acrylic acid ester Copolymers, styrene-butadiene block copolymers, styrene-isoprene block copolymers, styrene-butadiene block copolymers, hydrogenated styrene-butadiene block copolymers, hydrogenated butadiene-based polymers, ethylene-based ionomers, etc. Can be mentioned.

The styrene-butadiene block copolymers and styrene-isoprene block copolymers include those having structures of AB type, ABA type, taper type, radial teleblock type, and the like. The hydrogenated butadiene-based polymer includes, in addition to the hydride of the block copolymer, a styrene block and a hydride of a styrene-butadiene random copolymer block, and a 1,2-vinyl bond in polybutadiene. 20% by weight
It includes the following blocks and hydrides of polymers composed of polybutadiene blocks having a 1,2-vinyl bond content of more than 20% by weight.

On the other hand, examples of the aromatic vinyl monomer used for the rubber-reinforced styrene resin include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene,
N, N-diethyl-p-aminoethylstyrene, N, N
-Diethyl-p-aminomethylstyrene, vinylpyridine, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, ethylstyrene, vinylnaphthalene and the like, and particularly styrene and α-methylstyrene are preferable. . These aromatic vinyl monomers may be used alone or in admixture of two or more. The amount of the aromatic vinyl monomer used is preferably 20 to 100% by weight, more preferably 30 to 90% by weight, particularly preferably 40 to 80% by weight, and less than 20% by weight in the monomer component. Then, sufficient moldability cannot be obtained.

In the above graft polymerization, vinyl cyanide type monomers, (meth) acrylic acid ester type monomers, acid anhydride type monomers, which can be used in combination with aromatic vinyl type monomers, Specific examples of the maleimide-based monomer are as follows.

Vinyl cyanide type monomers such as acrylonitrile and methacrylonitrile. Acrylonitrile is particularly preferred as the vinyl cyanide-based monomer. The amount of the vinyl cyanide-based monomer used in the monomer component is preferably 45 to 0% by weight, more preferably 40 to 10% by weight. By using the vinyl cyanide-based monomer, The chemical resistance of the obtained rubber-reinforced styrene resin is improved. However, when it exceeds 45% by weight, the color tone of the obtained rubber-reinforced styrene resin becomes brown, and the molding processability and the thermal stability at the time of molding become poor.

(Meth) acrylic acid ester type monomer Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate Acrylic ester such as; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, benzyl methacrylate and the like. Of these, butyl acrylate and methyl methacrylate are preferable.

Acid anhydride type monomers Maleic anhydride, itaconic anhydride, citraconic anhydride and the like.

Maleimide type monomers Maleimide, N-methylmaleimide, N-butylmaleimide, N- (p-methylphenyl) maleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like.

The above-mentioned monomers (1) to (4) can be used alone or in combination of two or more.

Further, the rubber-like polymer is removed from the rubber-reinforced styrene-based resin by removing other functional group-containing monomers copolymerizable with the aromatic vinyl-based monomer and any of the above-mentioned other monomers. It can be used at the time of graft polymerization so that 30% by weight or less, preferably 0.1 to 30% by weight, is copolymerized with the rest.

Examples of such functional group-containing monomers include unsaturated epoxy compounds such as glycidyl methacrylate and allyl glycidyl ether, unsaturated carboxylic acid amides such as acrylamide and methacrylamide, acrylic amine, aminomethyl methacrylate, and methacrylic acid. Amino group-containing unsaturated compounds such as aminoethyl, aminopropyl methacrylate, aminostyrene, hydroxystyrene,
3-hydroxy-1-propene, 4-hydroxy-1-
Butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, 3-hydroxy-2-
Hydroxyl group-containing unsaturated compounds such as methyl-1-propene, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate, unsaturated acids such as acrylic acid, methacrylic acid, itaconic acid and maleic acid, and oxazoline group such as vinyl oxazoline An unsaturated compound etc. are mentioned. These functional group-containing monomers may be used alone or in combination of two or more.

When these functional group-containing monomers are used in combination,
(B) The dispersibility of the thermosetting resin is improved, a strong interface is formed with the thermosetting resin, and the heat resistance and impact resistance are further improved. In particular, the use of a hydroxyl group-containing unsaturated compound or an unsaturated acid is preferable because the fluidity and the surface appearance of the molded product are improved. Further, it is preferable to use an unsaturated epoxy compound, an amino group-containing unsaturated compound, or an oxazoline group-containing unsaturated compound because the rib strength and the weld strength are improved.

The amount of the rubber-like polymer (a) in the rubber-reinforced styrene resin is preferably 5 to 80% by weight, more preferably 10 from the viewpoint of melt viscosity and impact resistance.
˜70% by weight, particularly preferably 20 to 55% by weight. The average particle size of the dispersed particles of the rubber-like polymer (a) in the rubber-reinforced styrene resin is preferably 0.01 to 50 μm, more preferably 0.05 to 50 μm from the viewpoint of melt viscosity and impact resistance. It is 30 μm.

The rubber-reinforced styrene resin used as the component (A) of the present invention is obtained by emulsifying a monomer component containing an aromatic vinyl monomer as a main component in the presence of the rubbery polymer (a). Radical graft polymerization can be performed by polymerization, suspension polymerization, solution polymerization, bulk polymerization, or the like. Preferably,
Emulsion polymerization. At this time, in the emulsion polymerization, a polymerization initiator,
Chain transfer agents (molecular weight modifiers), emulsifiers, water, etc. are used. The above monomers or monomer components can be added to the reaction system all at once or continuously.

As the polymerization initiator, organic hydroperoxides represented by cumene hydroxyperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide and the like and sugar-containing pyrophosphate prescription, sulfoxylate prescription and the like are represented. A redox system in combination with a reducing agent, or a peroxide such as persulfate, azobisisobutyronitrile, or benzoyl peroxide is used. Preferably, it is an oil-soluble initiator, and is a redox system obtained by combining a cumene hydroperoxide, a diisopropylbenzene hydroperoxide, a paramenthane hydroperoxide with a reducing agent represented by a sugar-containing pyrophosphate formulation, a sulfoxylate formulation, and the like. Is good. Moreover, you may combine the said oil-soluble initiator and a water-soluble initiator. When combined, the addition ratio of the water-soluble initiator is preferably 50% by weight or less, more preferably 25% by weight or less of the total amount. Further, the polymerization initiator can be added to the polymerization system all at once or continuously. The amount of the polymerization initiator to be used is generally 0.1 to 1.5% by weight, preferably 0.2 to 0.7% by weight, based on the monomer component.

As the chain transfer agent, mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, t-tetradecyl mercaptan, tetraethylthiuram sulfide, Hydrocarbons such as carbon tetrachloride, ethylene bromide and pentaphenylethane, or dimers of acrolein, methacrolein, allyl alcohol, 2-ethylhexyl thioglycolate, α-methylstyrene and the like can be mentioned. These chain transfer agents can be used alone or in combination of two or more. The method of using the chain transfer agent may be any of batch addition, divisional addition, and continuous addition. The amount of the chain transfer agent is usually about 0.05 to 2.0% by weight based on the monomer component.

As the emulsifier, an anionic surfactant,
Examples include nonionic surfactants and amphoteric surfactants. Among them, examples of the anionic surfactant include a higher alcohol sulfate, an alkylbenzene sulfonate, a fatty acid sulfonate, and a phosphoric acid type. As the nonionic surfactant, an alkyl ester type, an alkyl ether type, an alkyl phenyl ether type or the like of ordinary polyethylene glycol is used. Further, examples of the amphoteric surfactant include those having a carboxylate, a sulfate, a sulfonate, or a phosphate as an anion portion, and an amine salt, a quaternary ammonium salt, or the like as a cation portion. The amount of the emulsifier used is usually 0.
It is about 3 to 5.0% by weight.

The rubber-reinforced styrene resin is 80 to 1 with respect to 100 parts by weight of the rubber-like polymer and the monomer component.
50 parts by weight, preferably 80 to 130 parts by weight of polymerization water,
It is desirable to carry out emulsion polymerization under the conditions of a polymerization temperature of 10 to 120 ° C, preferably 30 to 110 ° C.

The graft ratio of the rubber-reinforced styrene resin is
Preferably 5 to 200% by weight, more preferably 10 to
It is 150% by weight. If the graft ratio is less than 5% by weight,
The effect of adding the rubber component is not sufficiently exerted, and sufficient impact strength cannot be obtained. On the other hand, when it exceeds 200% by weight, moldability is deteriorated. Here, the graft ratio (% by weight) is
When the weight of the rubber component in 1 g of the rubber-reinforced styrene resin is x and the weight of the methyl ethyl ketone insoluble matter is y, the values are obtained by the following equation. Graft ratio (% by weight) = [(y−x) / x] × 100

The molecular weight of the rubber-reinforced styrene resin has an intrinsic viscosity [η] (methyl ethyl ketone soluble content) of preferably 0.1 to 2.5 dl / g, more preferably 0.2 to 2.0 dl / g. , Particularly preferably 0.2 to 1.
0 dl / g. This intrinsic viscosity [η] is 0.1 dl /
When it is less than g, a high balance of physical properties of rigidity and impact resistance cannot be obtained, while when it exceeds 2.5 dl / g, moldability is deteriorated.

When two or more monomer components are used in the graft polymerization, the preferred combinations are as follows. (1) Aromatic vinyl monomer / vinyl cyanide monomer (2) Aromatic vinyl monomer / (meth) acrylic acid ester monomer (3) Aromatic vinyl monomer / Vinyl cyanide monomer / (meth) acrylic acid ester monomer (4) Aromatic vinyl monomer / maleimide monomer (5) Aromatic vinyl monomer / vinyl cyanide monomer Polymer / maleimide monomer (6) Aromatic vinyl monomer / (meth) acrylic acid ester monomer / maleimide monomer (7) Aromatic vinyl monomer / vinyl cyanide monomer Monomer / acid anhydride monomer (8) Aromatic vinyl monomer / (meth) acrylic acid ester monomer / acid anhydride monomer (9) Aromatic vinyl monomer / Vinyl cyanide type monomer / (meth) acrylic acid ester type monomer / acid anhydride type monomer (10) Aroma Vinyl monomer / maleimide monomer /
In the above combination, the unit derived from the aromatic vinyl monomer is 1 in the graft chain grafted on the rubber-like polymer.
It occupies preferably from 100 to 100% by weight, preferably from 10 to 90% by weight.

On the other hand, the styrene resin preferably used as the component (A) of the composition of the present invention is obtained by homopolymerizing or copolymerizing the above aromatic vinyl monomer by a method known per se. Resin. Furthermore, the aromatic vinyl monomer, the vinyl cyanide monomer, a (meth) acrylic acid ester monomer,
A resin obtained by copolymerizing at least one monomer selected from the group of acid anhydride monomers and maleimide monomers by a method known per se is also included in the styrene resin. To be done.

Further, the styrene-based resin is obtained by adding the aromatic vinyl-based monomer and the above-mentioned other functional group-containing monomer copolymerizable with any of the above-mentioned monomers to the styrene-based resin. 30% by weight or less, preferably 0.
1 to 30% by weight may be copolymerized.

Specific examples of the aromatic vinyl-based monomer, the monomers (1) to (3), and the other copolymerizable functional group-containing monomer in the styrene-based resin are described in the case of the rubber-reinforced styrene-based resin. The present invention can be applied to styrenic resins including the preferable embodiments described above. Also, as a preferable combination in the case of copolymerization, the combination of the above (1) to (10) described in the rubber-reinforced styrene resin can be applied to this styrene resin.

In the repeating unit of styrene resin,
The unit derived from the aromatic vinyl monomer is preferably 1
˜100% by weight, more preferably 3 to 90% by weight. In addition, such a styrene resin can be used as the component (A) of the composition of the present invention in combination with the rubber-reinforced styrene resin. In this case, the rubber-like polymer (a) is preferably used in an amount of 1 to 80% by weight, more preferably 5 to 60% by weight, in the total amount of the rubber-reinforced styrene resin and the styrene resin. To be

Further, the functional group-containing (rubber-reinforced) styrene resin containing the functional group-containing monomer is preferably contained in the component (A) in an amount of preferably 1% by weight or more, more preferably 5% by weight or more, and further preferably Is preferably 10% by weight or more, particularly preferably 10 to 90% by weight. When the content of the functional group-containing (rubber-reinforced) styrene resin in the component (A) is less than 1% by weight, the effect of addition is not exhibited, which is not preferable.

As the thermosetting resin used in the component (B) of the present invention, known thermosetting resins can be used without any limitation. Examples of the thermosetting resin (B) include phenol resin, urea resin, melamine resin, epoxy resin, unsaturated polyester, and polycarbodiimide. These thermosetting resins should be used alone. Alternatively, two or more kinds may be mixed and used. Of these, phenol resins, urea resins, melamine resins, epoxy resins and polycarbodiimides are preferably used, more preferably urea resins, melamine resins and polycarbodiimides, particularly preferably polycarbodiimides.

The polycarbodiimide particularly preferably used as the component (B) of the present invention will be described below. Polycarbodiimide has the general formula (I) -N = C = N -R 1 - Table in · · · · · (I) [where in the formula (I), R ¹ represents a divalent organic group] Having a repeating unit that is

The method for synthesizing polycarbodiimide is not particularly limited, but, for example, organic polyisocyanate is reacted in the presence of a catalyst for promoting the carbodiimidization reaction of an isocyanate group (hereinafter, also referred to as "carbodiimidization catalyst"). As a result, polycarbodiimide can be synthesized.

As the organic polyisocyanate used for the synthesis of this polycarbodiimide, organic diisocyanate is preferable. Such organic diisocyanates include, for example, phenylene-1,3-diisocyanate,
Phenylene-1,4-diisocyanate, 1-methoxyphenylene-2,4-diisocyanate, 1-methylphenylene-2,4-diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3- Xylylene diisocyanate, 1,4-xylylene diisocyanate, biphenylene-4,4'-
Diisocyanate, 3,3'-dimethoxybiphenylene-4,4'-diisocyanate, 3,3'-dimethylbiphenylene-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethoxydiphenylmethane-4,4'-diisocyanate,
3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, naphthalene-1,5-diisocyanate, cyclobutylene-1,3-diisocyanate, cyclopentylene-1,3-diisocyanate, cyclohexylene-1,3-diisocyanate , Cyclohexylene-1,4-diisocyanate, 1-methylcyclohexylene-2,4-diisocyanate, 1-methylcyclohexylene-2,6-diisocyanate, 1-isocyanate-3,3,5-trimethyl-5-isocyanatomethyl Cyclohexane, cyclohexane-1,3-bis (methyl isocyanate), cyclohexane-1,4-
Bis (methyl isocyanate), isophorone diisocyanate, dicyclohexylmethane-2,4'-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, ethylene diisocyanate, tetramethylene-1,4-diisocyanate, hexamethylene-1,
6-diisocyanate, dodecamethylene-1,12-diisocyanate, lysine diisocyanate methyl ester and the like, and a terminal isocyanate prepolymer obtained by reacting a stoichiometric excess of these organic diisocyanates with a bifunctional active hydrogen-containing compound And the like. These organic diisocyanates can be used alone or in combination of two or more.

Other organic polyisocyanates which may be optionally used together with the organic diisocyanate include, for example, phenyl-1,3,5-triisocyanate, diphenylmethane-2,4,4'-triisocyanate and diphenylmethane-2,5. , 4'-triisocyanate, triphenylmethane-2,4 ', 4 "-triisocyanate, triphenylmethane-4,4', 4"-
Triisocyanate, diphenylmethane-2,4
2 ', 4'-tetraisocyanate, diphenylmethane-2,5,2', 5'-tetraisocyanate, cyclohexane-1,3,5-triisocyanate, cyclohexane-1,3,5-tris (methylisocyanate), 3 , 5-Dimethylcyclohexane-1,3,5-
Tris (methyl isocyanate), 1,3,5-trimethylcyclohexane-1,3,5-tris (methyl isocyanate), dicyclohexylmethane-2,4,2 '
-Triisocyanate, dicyclohexylmethane-2,
By reacting a trifunctional or higher organic polyisocyanate such as 4,4'-triisocyanate or a stoichiometric excess of the trifunctional or higher organic polyisocyanate with a bifunctional or higher polyfunctional active hydrogen-containing compound The resulting terminal isocyanate prepolymer can be exemplified.

The above-mentioned other organic polyisocyanates can be used alone or in combination of two or more, and the amount thereof is usually 0-40 per 100 parts by weight of organic diisocyanate. Parts by weight, preferably 0 to 20 parts by weight.

Further, when synthesizing the polycarbodiimide, by adding an organic monoisocyanate as necessary, when the organic polyisocyanate contains the other organic polyisocyanate, the molecular weight of the obtained polycarbodiimide is appropriately regulated. Further, by using the organic diisocyanate in combination with the organic monoisocyanate, a polycarbodiimide having a relatively low molecular weight can be obtained.

Examples of such organic monoisocyanates include alkyl monoisocyanates such as methyl isocyanate, ethyl isocyanate, n-propyl isocyanate, n-butyl isocyanate, lauryl isocyanate and stearyl isocyanate, cyclohexyl isocyanate, 4-methylcyclohexyl isocyanate, Cycloalkyl monoisocyanates such as 2,5-dimethylcyclohexyl isocyanate, phenyl isocyanate, o-tolyl isocyanate, m
-Tolyl isocyanate, p-tolyl isocyanate,
Aryl monoisocyanates such as 2-methoxyphenyl isocyanate, 4-methoxyphenyl isocyanate, 2-chlorophenyl isocyanate, 4-chlorophenyl isocyanate, 2-trifluoromethylphenyl isocyanate, 4-trifluoromethylphenyl isocyanate, and naphthalene-1-isocyanate Can be mentioned.

These organic monoisocyanates may be used alone or in combination of two or more, and the amount thereof may be the desired molecular weight of polycarbodiimide, the above-mentioned other organic polyisocyanates. All organic polyisocyanate component 1
0 to 40 parts by weight, preferably 0 to 2 parts by weight, per 100 parts by weight
0 parts by weight.

As the carbodiimidization catalyst, for example, 1-phenyl-2-phosphorene-1-oxide, 1
-Phenyl-3-methyl-2-phospholene-1-oxide, 1-phenyl-2-phospholene-1-sulfide,
1-phenyl-3-methyl-2-phospholen-1-sulfide, 1-ethyl-2-phospholen-1-oxide,
1-ethyl-3-methyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-sulfide, 1
-Ethyl-3-methyl-2-phospholene-1-sulfide, 1-methyl-2-phospholene-1-oxide, 1-
Methyl-3-methyl-2-phospholene-1-oxide,
1-methyl-2-phospholene-1-sulfide, 1-methyl-3-methyl-2-phospholene-1-sulfide and phosphorene compounds such as 3-phospholene isomers thereof, iron pentacarbonyl, diiron nonacarbonyl, Metal carbonyl complexes such as tetracarbonyl nickel, hexacarbonyl tungsten, hexacarbonyl chromium, beryllium, aluminum, zirconium, chromium, acetylacetone complexes of metals such as iron, trimethyl phosphate, triethyl phosphate, triisopropyl phosphate, tri-t-butyl phosphate, Phosphate esters such as triphenyl phosphate and the like can be mentioned.

The above carbodiimidization catalysts can be used alone or in combination of two or more. The amount of the catalyst to be used is generally 0.001 to 30 parts by weight, preferably 0.01 to 10 parts by weight, per 100 parts by weight of all organic isocyanate components.

The polycarbodiimide synthesis reaction can be carried out without solvent or in a suitable solvent. The solvent may be any solvent that can dissolve the polycarbodiimide by heating during the synthesis reaction. For example, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-
Trichloroethane, 1,1,2-trichloroethane,
1,1,1,2-tetrachloroethane, 1,1,2,2
-Tetrachloroethane, pentachloroethane, hexachloroethane, 1,1-dichloroethylene, 1,2-dichloroethylene, trichloroethylene, tetrachloroethylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, 1,2,4-
Halogenated hydrocarbon solvents such as trichlorobenzene and trichloromethylbenzene, dioxane, anisole,
Ether solvents such as tetrahydrofuran, tetrahydropyran, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, and triethylene glycol monomethyl ether; Cyclohexanone, 2-acetylcyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone,
Cycloheptanone, 1-decalone, 2-decalone, 2,
4-dimethyl-3-pentanone, 4,4-dimethyl-2
-Pentanone, 2-methyl-3-hexanone, 5-methyl-2-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5
-Methyl-3-heptanone, 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone,
Ketone solvents such as -decanone and 4-decanone; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene and cumene; N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone and N-benzyl- 2
-Pyrrolidone, N-methyl-3-pyrrolidone, N-acetyl-3-pyrrolidone, N-benzyl-3-pyrrolidone, formamide, N-methylformamide, N, N-
Dimethylformamide, N-ethylformamide, N,
N-diethylformamide, acetamide, N, N-methylacetamide, N, N-dimethylacetamide, N
Amide solvents such as -methylpropionamide, aprotic polar solvents such as dimethyl sulfoxide, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-propoxyethyl acetate, 2-butoxyethyl acetate, 2-phenoxyethyl acetate; Diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate,
Acetate solvents such as diethylene glycol monobutyl ether acetate can be exemplified. These solvents can be used alone or in combination of two or more.

In the synthesis of polycarbodiimide, the concentration of the total organic isocyanate component in the solvent is usually 0.5.
６０60% by weight, preferably 5-50% by weight. If the concentration of all the organic isocyanate components is too low, the reaction rate will be slow and the productivity will be reduced, while if the concentration is too high, the polycarbodiimide to be formed may gel during the synthesis reaction.

The temperature of the polycarbodiimide synthesis reaction is
The temperature is usually 20 to 200 ° C., though it is appropriately selected depending on the types of the organic isocyanate component and the carbodiimidization catalyst. In the synthesis reaction of the polycarbodiimide, the organic isocyanate component may be added in its entirety before the reaction, or a part or all thereof may be added continuously or stepwise during the reaction.

Further, a compound capable of reacting with an isocyanate group is added at an appropriate reaction stage from the initial stage to the latter stage of the polycarbodiimide synthesis reaction to seal the terminal isocyanate group of the polycarbodiimide to obtain a polycarbodiimide obtained. The molecular weight can be adjusted, and the molecular weight of the obtained polycarbodiimide can be regulated to a predetermined value by adding it at a later stage of the polycarbodiimide synthesis reaction. Examples of the compound capable of reacting with such an isocyanate group include alcohols such as methanol, ethanol, isopropanol and cyclohexanol, and amines such as dimethylamine, diethylamine and benzylamine.

The polycarbodiimide synthesized as described above is separated from the solution if necessary. In this case, as a method for separating polycarbodiimide, for example, a polycarbodiimide solution is added to a non-solvent inert to the polycarbodiimide, and the resulting precipitate or oil is separated and collected by filtration or decantation. , A method of separating and collecting by spray drying, a method of separating and collecting by utilizing a change in solubility of the obtained polycarbodiimide with respect to the solvent used in the synthesis, that is, a polycarbodiimide dissolved in the solvent immediately after synthesis. When is precipitated by lowering the temperature of the system, a method of separating and collecting the suspension from the suspension by filtration and the like can be mentioned, and these separation and collecting methods can be appropriately combined.

The polystyrene equivalent number average molecular weight (Mn) of the polycarbodiimide of the present invention determined by gel permeation chromatography (GPC) is generally 400 to 500,000, preferably 1,000 to.
200,000, more preferably 2,000 to 10
It is 0000.

In the present invention, the polycarbodiimide used as the component (B) is a compound (hereinafter also referred to as "reactive compound") containing a graft-reactive group and a carboxylic acid anhydride group, if necessary. Resin grafted with at least one species (hereinafter also referred to as "modified polycarbodiimide"),
Alternatively, by using the modified polycarbodiimide in combination with the epoxy compound (b), the curing characteristics are improved, the rigidity of the obtained resin composition of the present invention is improved, and the resistance to the use of the inorganic filler is improved. Impact resistance is further improved.

Here, the reactive compound used for the synthesis of the modified polycarbodiimide is a compound having a graft reactive group and a carboxylic acid anhydride group, and an aromatic compound,
It can be an aliphatic compound or an alicyclic compound. Among these, the alicyclic compound may be a carbocyclic compound or a heterocyclic compound. The graft-reactive group in the reactive compound means a group that reacts with polycarbodiimide to give a modified polycarbodiimide in which a residue of the reactive compound having a carboxylic anhydride group is grafted. Such a graft reactive group may be any functional group having active hydrogen, such as a carboxyl group or a primary group.
Grade or secondary amino groups can be mentioned. In this reactive compound, one or more same or different graft-reactive groups can be present, and one or more carboxylic anhydride groups can be present.

Examples of such reactive compounds include trimellitic acid anhydride, benzene-1,2,3-tricarboxylic acid anhydride, naphthalene-1,2,4-tricarboxylic acid anhydride and naphthalene-1,4. , 5-tricarboxylic acid anhydride, naphthalene-2,3,6-tricarboxylic acid anhydride, naphthalene-1,2,8-tricarboxylic acid anhydride,
4- (4-carboxybenzoyl) phthalic anhydride, 4
-(4-carboxyphenyl) phthalic anhydride, 4-
(4-carboxyphenoxy) aromatic tricarboxylic anhydrides such as phthalic anhydride, pyromellitic monoanhydride monomethyl ester, 3,3 ', 4,4'-benzophenonetetracarboxylic monoanhydride monomethyl ester,
Aromatic tetracarboxylic monoanhydride monoalkyl esters such as 3,3 ', 4,4'-biphenyltetracarboxylic monoanhydride monomethyl ester, 3-carboxymethylglutaric anhydride, butane-1,2,4 Aliphatic tricarboxylic anhydrides such as tricarboxylic acid-1,2-anhydride and propene-1,2,3-tricarboxylic acid-1,2-anhydride; 3-amino-4-cyano-5-methylphthalic acid Anhydride, 3-amino-4-cyano-5,6-diphenylphthalic anhydride, 3-methylamino-4-cyano-5
Aminoaromatic dicarboxylic anhydrides such as -methylphthalic anhydride, 3-methylamino-4-cyano-5,6-diphenylphthalic anhydride; aminosuccinic anhydride;
-Amino-1,2-butanedicarboxylic anhydride, 4-aminohexahydrophthalic anhydride, N-methylaminosuccinic anhydride, 4-methylamino-1,2-butanedicarboxylic anhydride, 4-methyl Examples thereof include amino aliphatic dicarboxylic anhydrides such as aminohexahydrophthalic anhydride. Among these reactive compounds, trimellitic anhydride is particularly preferred. The above-mentioned reactive compounds can be used alone or in combination of two or more.

The modified polycarbodiimide is obtained by adding at least one reactive compound to a polycarbodiimide having a repeating unit represented by the above general formula (I) at a suitable temperature in the presence or absence of a suitable catalyst. Can be synthesized by grafting (hereinafter also referred to as "modification reaction") with. In this case, the polycarbodiimides can be used alone or as a mixture of two or more.

The amount of the reactive compound used in the modification reaction is appropriately adjusted depending on the type of the polycarbodiimide, the compound, the use of the resin composition, etc., and is represented by the above general formula (I) of the polycarbodiimide. The graft reactive group in the reactive compound is 0.01 per mol of the repeating unit.
It is used in an amount of 1 to 1 mol, preferably 0.02 to 0.8 mol. In this case, the proportion of graft-reactive groups is 0.
If it is less than 01 mol, heating for a long time is required to cure the polycarbodiimide, while if it exceeds 1 mol,
There is a possibility that the original properties of polycarbodiimide may be impaired. In the above modification reaction, the reaction between the graft reactive group of the reactive compound and the repeating unit represented by the general formula (I) of the polycarbodiimide progresses quantitatively, and a graft reaction commensurate with the amount of the compound used is achieved. Is done.

The modification reaction can be carried out without solvent, but it is preferably carried out in a suitable solvent. Such a solvent is not particularly limited as long as it is inert to the polycarbodiimide and the reactive compound and can dissolve them. As this solvent,
Examples thereof include the above-mentioned ether solvents, amide solvents, ketone solvents, aromatic hydrocarbon solvents, aprotic polar solvents and the like used in the synthesis of polycarbodiimide. These solvents can be used alone or in combination of two or more. When the solvent used during the synthesis of the polycarbodiimide can be used for the modification reaction, the polycarbodiimide solution obtained by the synthesis can be used as it is.

The amount of the solvent used in the modification reaction is usually 10 to 10,000 per 100 parts by weight of the total amount of the reaction raw materials.
0 parts by weight, preferably 50 to 5,000 parts by weight.
The temperature of the modification reaction is appropriately selected depending on the types of the polycarbodiimide and the reactive compound.
Hereinafter, it is preferably −10 to + 80 ° C. The number average molecular weight (Mn) in terms of polystyrene of the modified polycarbodiimide obtained as described above determined by gel permeation chromatography (GPC) is usually 500.
~ 1,000,000, preferably 1,000-40
000, more preferably 2,000 to 200,0
00.

The modified polycarbodiimide thus obtained is usually used by separating it from the solution. As a method for separating the modified polycarbodiimide obtained as a solution at the time of the synthesis from the solvent, a method similar to the above-described method for separating polycarbodiimide can be exemplified.

[0060] modified polycarbodiimide of the present invention, the repeating units of the graft reactive group of the reactive compound is a polycarbodiimide (-N = C = N-R 1 -) react with a carboxylic acid anhydride of the compound It has a structure in which a residue having a group is grafted, and has a structure essentially different from that of the polycarbodiimide before the modification reaction. Therefore, the modified polycarbodiimide has different properties from the polycarbodiimide before the modification reaction,
By mixing with an epoxy compound (b) described below and heating, it is usually 10 even without using a curing catalyst due to the action of the carboxylic acid anhydride group in the modified polycarbodiimide.
It has the property of being easily cured at a temperature of 0 to 350 ° C, preferably 150 to 300 ° C.

The epoxy compound (b) used in the modified polycarbodiimide of the component (B) of the present invention is a compound having at least one epoxy group in the molecule and has a functional group other than the epoxy group. The molecular weight is not particularly limited, but is, for example, 70 to 20,000.
Examples of such epoxy compounds include glycidol, glycidyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexyl acrylate,
Examples thereof include 3,4-epoxycyclohexyl methacrylate and various epoxy resins. Further, a part of the epoxy compound may be substituted with a halogen atom.

A preferred epoxy compound is an epoxy resin, and examples thereof include glycidyl ether type epoxy resins represented by bisphenol type epoxy resin, novolac type epoxy resin, cresol novolac type epoxy resin, and glycidyl ester type epoxy resin. Examples thereof include aromatic glycidyl amine type epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, liquid rubber-modified epoxy resins and the like.

The above epoxy compounds may be used alone or in combination of two or more. The amount used is usually 5 to 500 parts by weight, preferably 10 to 100 parts by weight of the modified polycarbodiimide.
~ 300 parts by weight. In this case, if the amount of the epoxy compound used is less than 5 parts by weight, the effect of improving the curing rate tends to decrease, while if it exceeds 500 parts by weight, the heat resistance of the resin composition tends to decrease.

The average particle size of the dispersed particles of the component (B) in the resin composition of the present invention is 50 μm or less, preferably 0.01.
˜50 μm, more preferably 0.01 to 30 μm, and particularly preferably 0.01 to 10 μm. The average particle diameter here is a weight average, and is measured by observing the resin composition with an electron microscope. If the average particle size exceeds 50 μm, the filling effect in the resin composition is reduced, and stress concentration is likely to occur, and the heat resistance and impact resistance of the resulting composition are reduced, which is not preferable.

This average particle size is determined by the melt-kneading mixing degree or the mechanical kneading method, or by making the component (A) functional group-containing,
By using a modified product as the component (B),
It can be easily adjusted.

The weight ratio [(A) / (B)] of the components (A) and (B) in the resin composition of the present invention is 30/7.
0-99 / 1, preferably 40 / 60-97 / 3, more preferably 50 / 50-95 / 5, particularly preferably 6
0/40 to 90/10. The amount of component (A) used is 3
When it is less than 0% by weight [the content of the component (B) exceeds 70% by weight], the impact resistance is lowered, which is not preferable, while when it exceeds 99% by weight [the content of the component (B) is less than 1% by weight], the heat resistance is poor. .

The resin composition of the present invention contains glass fiber, carbon fiber, metal fiber, metal flake, glass beads, wollastonite, rock filler, calcium carbonate, talc, mica, for the purpose of improving mechanical properties. Fillers such as glass flakes, milled fibers, kaolin, barium sulfate, graphite, molybdenum disulfide, magnesium oxide, zinc oxide whiskers and potassium titanate whiskers may be used alone or in combination of two or more. Can also be used. Among these fillers, the shape of glass fiber and carbon fiber is 6 to 60 μm.
Those having a fiber diameter of 30 μm and a fiber length of 30 μm or more are preferable. These fillers are usually used in the range of 5 to 150 parts by weight with respect to 100 parts by weight of the resin composition of the present invention.

Next, in the resin composition of the present invention, known flame retardants, antibacterial agents, wood powder, coupling agents, antioxidants, plasticizers, colorants, lubricants, antistatic agents, silicone oils, foams. Additives such as agents can be added. Can be granted. As the flame retardant, general rubber, those used as flame retardants for polymers such as resins can be used, and examples thereof include halogen-containing compounds, phosphorus-containing compounds, nitrogen-containing compounds, silicon-containing compounds and the like. Can be mentioned. When using a flame retardant, the amount of flame retardant used is
It is usually 1 to 60 parts by weight, preferably 3 to 50 parts by weight, and more preferably 4 to 40 parts by weight based on 100 parts by weight of the total amount of the components (A) to (B). If it is less than 1 part by weight, the flame retardant effect is not exhibited, while if it exceeds 60 parts by weight, the weld appearance and weld strength are poor.

As the flame retardant aid, antimony-containing compounds such as antimony trioxide, antimony tetroxide, (colloidal) antimony pentoxide, sodium antimonate and antimony phosphate, chlorinated polyethylene, polyorganosiloxane polymer, Tetrafluoroethylene or the like is used, and these may be used alone or in combination of two or more.

Here, the tetrafluoroethylene polymer has an average particle size of 0.05 to 1,000 μm,
Those having a density of 1.2-2.3 g / cm ³ and a fluorine content of 65-76% by weight are preferred. Further, those obtained by emulsion polymerization or suspension polymerization are preferably used.
The preferred amount of the flame retardant aid used is generally 0.1, based on 100 parts by weight of the components (A) to (B) and the total amount of the flame retardant.
It is 1 to 20 parts by weight, more preferably 0.5 to 15 parts by weight.

As the antibacterial agent, an organic / inorganic silver compound, an inorganic substance carrying a silver compound and / or a silver complex salt, an inorganic substance having an ion-exchange ability to ion-exchange silver ions, Examples include boric acid-based glass containing a silver compound. Examples of the silver compound used here are silver oxide, silver chloride, silver nitrate, silver sulfate, silver acetate, silver chlorate, silver bromide, silver fluoride, silver picrate, protein silver, colloidal silver, and silver carboxylic acid. salt,
Examples thereof include a silver salt of an alkyl ester, a phenyl ester or an alkylphenyl ester of phosphoric acid or phosphorous acid.

Examples of the silver salt of carboxylic acid include the following silver salts of carboxylic acid. Aliphatic saturated monocarboxylic acid having 1 to 30 carbon atoms, preferably 2 to 22, for example, acetic acid, propionic acid, butyric acid, valeric acid, lauric acid, myristic acid, palmitic acid, stearic acid, docosanoic acid, carbon number 2 to 34 , Preferably 2-8 aliphatic saturated dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, suberic acid, sebacic acid, unsaturated aliphatic carboxylic acids such as oleic acid, erucic acid, maleic acid, fumaric acid, carbon Cyclic carboxylic acids such as benzoic acid, phthalic acid, cinnamic acid, hexahydrobenzoic acid, abietic acid, hydrogenated abietic acid, hydrocarboxylic acids such as lactic acid, malic acid, citric acid, salicylic acid, aminocarboxylic acids such as aspartic acid , Glutamic acid.

In the present invention, the preferred silver salt of a carboxylic acid is a silver salt of an aliphatic saturated monocarboxylic acid, particularly silver laurate, silver stearate, a silver salt of an aliphatic unsaturated carboxylic acid, especially silver oleate, and The silver salts of carbocyclic carboxylic acids, particularly silver benzoate and hydrogenated silver abietic acid.
In addition, a homopolymer or copolymer of methacrylic acid or acrylic acid in which the carboxylic acid moiety is a silver salt is also included in the antibacterial agent.

Examples of the inorganic substance carrying a silver compound and / or a silver complex salt include silica gel, activated carbon, hydrotalcite, and calcium-based ceramics such as calcium phosphate, calcium carbonate, calcium silicate, and hydroxyapatite. Zeolites, zirconium phosphate and the like are mentioned as the inorganic substance having an ion exchange ability. As the zeolite, both natural products and synthetic products can be used.

The boric acid-based glass is not particularly limited, but is one containing a boron oxide (B ₂ O ₃ ). The content of B ₂ O ₃ is 5 to 70% by weight, preferably 10 to 60% by weight, more preferably 15 to 60% by weight.
% By weight. Boric acid-based glass is usually used in addition to SiO ₂
In addition, M ₂ O (M is Li, Na, K, etc.) may be contained. The specific composition is preferably as follows. SiO ₂ 25 to 60 wt% B ₂ O ₃ 18-60 wt% Al ₂ O ₃ 0 to 20 wt% M ₂ O 8 to 30 wt% (M; Li, Na, K) M'O 0~20 wt% (M '; Ca, Mg, Z
n, Ba) The above boric acid-based glass may contain the above silver compound, but silver oxide is particularly preferable. The preferred silver oxide content is 0.1 to 10% by weight. The average particle size of the inorganic material and boric acid glass is preferably 50 μm or less, more preferably 20 μm or less, and particularly preferably 10 μm or less.

The amount of silver and silver compound contained in the above inorganic substance is preferably in the range of 0.01 to 10% by weight. In addition, these antibacterial agents include zinc oxide,
Those with improved antibacterial properties are included. A particularly preferable antibacterial agent is at least one selected from zeolite in which silver ions are ion-exchanged, boric acid glass, and boric acid glass / silver oxide.

When the antibacterial agent is used, the amount of the antibacterial agent used is usually 0.01 to 10 parts by weight, preferably 0.05 to 100 parts by weight of the total amount of the components (A) and (B).
-5 parts by weight, more preferably 0.1-5 parts by weight. If the amount is less than 0.01 part by weight, the antibacterial property and antifungal property are poor, while if the amount is more than 10 parts by weight, the surface appearance of the molded product is poor.

Polyethylene glycol, polyethylene oxide chain-containing copolymer, antistatic agent and the like are added to the resin composition of the present invention, preferably 100 parts by weight of the total amount of the components (A) and (B) is added to the resin composition. For 0.5 to
By adding 20 parts by weight, the chain antibacterial property and antifungal property can be improved.

The wood flour is not particularly limited to the kind of tree, and pine trees such as spruce, Todo pine and larch, hemlock, cherry, cedar, oak, cypress, linden,
Examples include beech, rawan and fir. As wood flour,
Sawdust, sawdust, strips, and the like generated when cutting and sawing these raw logs can be used. As these wood flours, powders of 50 mesh or less are usually used. When wood flour is added, the coefficient of linear expansion decreases,
Effects such as improvement of vibration damping property and improvement of appearance of the molded product of the resin composition can be obtained. When using wood flour, the amount of wood flour used is
With respect to 100 parts by weight of the total amount of the components (A) and (B),
Usually, 1 to 500 parts by weight, preferably 1 to 30 parts by weight,
More preferably, it is 1 to 100 parts by weight, and if it is less than 1 part by weight, the effect of adding wood powder is not exhibited, while if it exceeds 500 parts by weight, the surface appearance of the molded product is poor.

The resin composition of the present invention can be used in various extruders,
It is obtained by kneading each component using a Banbury mixer, kneader, roll, feeder ruder, or the like. The kneading temperature is preferably 100 to 350 ° C, more preferably 150 to 300 ° C. Moreover, when kneading each component, you may knead each component collectively, and may add and knead several times. Kneading may be carried out in a multi-stage addition type using an extruder,
It is also possible to knead with a Banbury mixer, a kneader or the like, and then pelletize with an extruder.

At the time of kneading, the thermosetting resin as the component (B) can be added and used in a cured, semi-cured or uncured state. At this time, the average particle diameter of the component (B) is preferably 500 μm or less, more preferably 10 μm or less.
Finely divided particles of 0 μm or less, particularly preferably 0.01 to 50 μm, may be used.

The preferred use of the component (B) is (A)
This is a method of curing the component (B) during melt-kneading of the components. By curing the component (B) during melt-kneading of the component (A), a resin composition having more excellent heat resistance and impact resistance can be obtained. As the component (B) at this time, an uncured or semi-cured component can be used, and a mixture thereof may be used. By using the uncured component (B), it is easy to control the dispersion form of the component (B) in the resulting composition during melt-kneading, and further to introduce a third component capable of reacting with the component (B). It is preferable because it is easy. As a result, the resin composition of the present invention has suitable mechanical properties. Use of the semi-cured component (B) is preferable because the component (B) in the obtained composition has a relatively uniform particle shape and the dispersibility of the component (B) is further improved.

When the component (B) is cured during the melt-kneading of the component (A), the above-mentioned uncured and / or
Alternatively, in combination with a semi-cured resin, the other cured component (B) is preferably contained in the component (B) in an amount of 99% by weight or less, more preferably 90% by weight or less, and particularly preferably 10 to 80% by weight.
It can be used in the range of weight%.

The above "uncured", "semi-cured",
The definition of "curing" is no different than that common to those in the industry and to the general public. That is, uncured refers to a state in which the component does not form a three-dimensional crosslinked structure and is soluble in a solvent. The term "semi-cured" means that the extraction amount (elution amount) when a solvent in which a three-dimensional crosslinked structure is partially or mostly formed and the uncured portion is soluble is preferably 0.1% by weight.
Above, more preferably 0.5% by weight or more, particularly preferably 1% by weight or more. Further, curing means that the amount of extraction with the above solvent is preferably less than 0.1% by weight, more preferably less than 0.5% by weight, and particularly preferably less than 1% by weight.

The resin composition of the present invention thus obtained is used in various moldings by injection molding, sheet extrusion, vacuum molding, profile extrusion molding, blow molding, foam molding, injection press molding, gas injection molding and the like. It can be molded. Various molded products obtained by the above molding method are used for various parts, housings, chassis, etc. in the OA / home electric appliance field, electric / electronic field, miscellaneous goods field, sanitary field, automobile field, etc. by utilizing their excellent properties. be able to.

[0086]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples unless it exceeds the gist of the invention. In the examples, parts and% are by weight unless otherwise specified. Various evaluations in the examples are values measured as follows.

Number average molecular weight (Mn ) It was determined by gel permeation chromatography (GPC) in terms of polystyrene. The average particle size resin composition is sectioned and observed with a transmission electron microscope,
The measurement was performed using an image analysis device manufactured by Nippon Avionics Co., Ltd.

The heat-resistant box-shaped molded product was left in a gear oven at 100 ° C. for 1 hour, then taken out and examined for change in shape and evaluated. ○: Does not deform. X: Deformed. According to the impact resistance ASTM D256, it was determined Izod Impact (IZ). The unit is kgf · cm / cm.

The components used in the examples and comparative examples of the present invention are as follows. Rubber-like polymer (a) -1 to (a) -3 As the rubber-like polymer (a) used in the thermoplastic resin (A) of the present invention, those shown in Table 1 were used. Preparation of thermoplastic resins (A) -1 to (A) -6 In the presence of the rubber-like polymers (a) -1 to (a) -3,
A resin obtained by graft polymerization of various monomer components and a resin obtained by polymerizing only the monomer components without the presence of a rubbery polymer were obtained. Table 2 shows the compositions of these resins. In addition, (A) -1, (A) -2 and (A) -6 were obtained by emulsion polymerization, and (A) -3, (A) -4 and (A) -5 were obtained by solution polymerization. Thermoplastic resins (A) -7 to (A) -9 (A) -7; Nylon 6 [Kanebo Co., Ltd., Mc10
0LY] (A) -8; polycarbonate [Idemitsu Petrochemical Co., Ltd.
Manufactured by FN2200] (A) -9; polybutylene terephthalate [manufactured by Kanebo Ltd., PBT-124].

Thermosetting resins (B) -1 to (B) -7 (B) -1; polycarbodiimide was obtained by the following method. 50 g of diphenylmethane-4,4'-diisocyanate (MDI) and 3.1 g of phenylisocyanate
And 1-phenyl- in 200 g of cyclohexanone
0.044 3-methyl-2-phospholene-1-oxide
The reaction was carried out at 80 ° C. for 4 hours in the presence of g to obtain a solution of polycarbodiimide (P-MDI) (Mn = 3,500). Then, it was separated and dried.

(B) -2: A modified polycarbodiimide was obtained by the following method. To the above polycarbodiimide solution, 3.8 g of trimellitic anhydride was added as a reactive compound and reacted at 20 ° C. for 3 hours to obtain a solution of a modified polycarbodiimide having Mn of 3,800. Thereafter, it was separated and dried. As a result of infrared spectroscopy, the modified polycarbodiimide was found to have an infrared absorption characteristic of a carbodiimide unit (wave number 2,150 to 2,100 cm ^-1 ) and an infrared absorption characteristic of a carboxylic anhydride (wave number 1,850 to 1,1). 780
cm ^-1 ).

(B) -3: A modified polycarbodiimide combined with an epoxy compound was obtained in the following manner. In the modified polycarbodiimide solution, as an epoxy compound,
After adding 20 g of an epoxy resin consisting of a diglycidyl ether derivative of bisphenol A [Epicote 828, manufactured by Yuka Shell Epoxy Co., Ltd.] to 20 g of the modified polycarbodiimide solid content in the above solution, the pore diameter was 1 μm.
The mixture was filtered under pressure using a filter of m, and cyclohexanone was added so that the total solid concentration in the solution was 20% to prepare a solution. Then, it was degassed under vacuum to obtain a paste-like resin.

(B) -4; Phenolic resin [PR-53195, manufactured by Sumitomo Dures Co., Ltd.] (B) -5; Epoxy resin [Okaka Shell Epoxy Co., Ltd.]
Manufactured by Epicoat 1001] (B) -6; urea resin (obtained from urea and formaldehyde by a known method) (B) -7; melamine resin (obtained from melamine and formaldehyde by a known method).

Examples 1 to 14 and Comparative Examples 1 to 3 According to the formulation shown in Tables 3 to 4, melt kneading was performed at a preset temperature of 200 ° C. using a kneader, and then pelletized by a feeder ruder. Using the pellets, test specimens were prepared with an injection molding machine and evaluated by the above-described evaluation methods. The evaluation results are shown in Tables 3-4. In addition, it was confirmed that each of the components (B) in these resin compositions had an average particle diameter of 50 μm or less unless otherwise noted. Also, (B)-
4 is phenol resin 1 when using phenol resin
To 00 parts, 10 parts of hexamine were added during the melt-kneading. As is clear from Table 3, Examples 1-14
Have excellent heat resistance and impact resistance. On the other hand, Comparative Example 1 has a large blending ratio of the component (A) and is inferior in heat resistance and impact resistance. Comparative Example 2 has a low proportion of the component (A) and is inferior in impact resistance. Comparative Example 3 is an example in which the component (B) in the obtained composition has a large average particle size of 150 μm and is inferior in heat resistance and impact resistance.

[0095]

[Table 1]

[0096]

[Table 2]

[0097]

[Table 3]

[0098]

[Table 4]

[0099]

INDUSTRIAL APPLICABILITY The resin composition of the present invention is excellent in heat resistance and impact strength, and is used in a wide range of fields, for example, OA / home appliances field, vehicles, marine fields, housing-related fields such as furniture / building materials, sanitary fields, It can be used in a wide range of fields such as toys and sports, and other miscellaneous goods.

Claims (2)

[Claims] 1. (A) 30 to 99% by weight of a thermoplastic resin,
And (B) a thermosetting resin of 70 to 1% by weight as a main component, and an average particle size of dispersed particles of the component (B) is 50 μm or less. 2. The resin composition according to claim 1, wherein the component (B) is cured during melt-kneading of the components (A) to (B).