JPH09194719A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition having excellent heat-resistance and impact strength. SOLUTION: This resin composition is produced by compounding 100 pts.wt. of a composition composed of 30-99wt.% of a thermoplastic resin and 70-1wt.% of a polycarbodiimide with 1-300 pts.wt. of at least one kind of substance selected from polyamide elastomer, polyester elastomer, acrylic rubber, silicone rubber, fluororubber, modified polyolefin and modified rubber.

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 Thermoplastic resins such as ABS resins, AS resins, (rubber-reinforced) styrene resins such as HIPS, polyamide resins such as nylon 6, nylon 6,6 and polyolefin resins such as polyethylene and polypropylene are electrically conductive. -Used in a wide range of fields including electronics, OA / home appliances, automobiles, building materials and housing equipment, and other fields. Conventionally, in order to improve the heat resistance of these thermoplastic resins, a method of incorporating various inorganic fillers such as glass fiber and mica has been adopted. However, although the use of these improves the heat resistance, there is a problem that the impact resistance decreases.

[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 excellent in heat resistance and impact strength.

[0004]

According to the present invention, (A) 30 to 99% by weight of a thermoplastic resin and (B) 70 to 1% by weight of polycarbodiimide are added to 100 parts by weight in total.
(C) Provided is a resin composition containing 1 to 300 parts by weight of at least one selected from the group consisting of polyamide elastomer, polyester elastomer, acrylic rubber, silicone rubber, fluororubber, modified polyolefin and modified rubber. It is a thing.

[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. As the thermoplastic resin (A), for example, ABS resin, AS resin, HIPS, PS,
(Rubber reinforced) styrene resins such as MBS, MS, AES and AAS, polyethylene, polypropylene, polybutene-1, ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl alcohol copolymer (EVOH) and other polyolefins Resin, polyamide resin, thermoplastic polyester resin, polycarbonate resin, wholly aromatic polyester, PPS resin, LCP, vinyl chloride resin (P
VC), polysulfone, polyether ether ketone,
(Modified) polyphenylene ether resin, polyoxymethylene (POM), polymethylmethacrylate (PMM)
A), polyurethane, urea resin and the like. These (A) thermoplastic resins may be used alone,
Alternatively, two or more kinds can be used in combination.

The polyamide resin used here is usually a linear resin represented by the general formula H ₂ N- (CH ₂ ) x-NH ₂ (wherein x represents an integer of 4 to 12). diamine and the general formula HO ₂ C- (CH ₂₎ (wherein, y is an integer of 2~12.) y-CO ₂ H linear represented by
Such as those prepared by polycondensation of dicarboxylic acids can be used.

Preferred examples of these polyamide resins include nylon 6,6, nylon 6,9 and nylon 6,
10, nylon 6,12, nylon 6, nylon 12,
Examples include nylon 11 and nylon 4 and 6. Also, nylon 6 / 6,6, nylon 6 / 6,10, nylon 6/12, nylon 6 / 6,12, nylon 6 /
Copolyamides such as 6,6 / 6,10 and nylon 6 / 6,6 / 12 can also be used.

Semi-aromatic polyamides obtained from aromatic dicarboxylic acids such as nylon 6/6, T (T: terephthalic acid component), terephthalic acid and isophthalic acid, and metaxylylenediamine, or alicyclic diamines. Polyamides, polyesteramides and the like obtained from metaxylylenediamine and the above linear dicarboxylic acid can also be used. The polyamide resin may be used alone, or two or more kinds may be used in combination.

Examples of the thermoplastic polyester resin include those obtained by polycondensing an aromatic dicarboxylic acid or its ester or ester-forming derivative and a diol by a known method. Examples of the aromatic dicarboxylic acid include naphthalene dicarboxylic acid such as naphthalene-2,6-dicarboxylic acid, terephthalic acid, isophthalic acid, p-hydroxybenzoic acid, adipic acid, sebacic acid, etc. Derivatives are also used in thermoplastic polyester resins. Examples of the diol include polymethylene glycol having 2 to 6 carbon atoms such as ethylene glycol, 1,4-butanediol, and 1,6-hexanediol, 1,4-cyclohexanediol, bisphenol A,
And their ester-forming derivatives.

Specific examples of the thermoplastic polyester resin include polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and bisphenol A isophthalate. Among them, PBT and PET are particularly preferable.
Is preferred. These thermoplastic polyester resins have 1
Species can be used alone or in combination of two or more.

The preferred thermoplastic resin used as the component (A) is the above-mentioned polyolefin resin, polyamide resin,
Thermoplastic polyester resin, modified polyphenylene ether, polycarbonate, (rubber reinforced) styrene resin, more preferably polyolefin resin, (rubber reinforced) styrene resin, particularly preferably (rubber reinforced) styrene resin .

The (rubber-reinforced) styrene resin which is particularly preferably used as the component (A) of the resin composition of the present invention is
In the presence or absence of a rubber-like polymer, an aromatic vinyl compound or a monomer component comprising an aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound is polymerized. (Graft) polymer.

The rubber-like polymer used here includes
For example, polybutadiene, polyisoprene, butyl rubber,
Styrene-butadiene copolymer (styrene content 5-60
% By weight), a styrene-isoprene copolymer,
Acrylonitrile-butadiene copolymer, ethylene-α
-Olefin copolymer, ethylene-α-olefin-
Polyene copolymer, silicone rubber, acrylic rubber, butadiene- (meth) acrylic acid ester copolymer, styrene-butadiene block copolymer, styrene-isoprene block copolymer, styrene-butadiene block copolymer, hydrogenated styrene -Butadiene block copolymer, hydrogenated butadiene-based polymer, ethylene-based ionomer and the like.

The styrene-butadiene block copolymers and styrene-isoprene block copolymers include those having AB type, ABA type, taper type and radial teleblock type structures. 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. These rubbery polymers can be used alone or in combination of two or more.

As the (rubber-reinforced) styrene resin, from the viewpoint of impact resistance, a rubber-reinforced styrene resin obtained in the presence of a rubber-like polymer or a rubber obtained in the presence of a rubber-like polymer. It is preferable to use a mixture of a reinforced styrenic resin and a styrenic resin obtained by polymerization in the absence of a rubbery polymer.

As the aromatic vinyl compound used in the (rubber-reinforced) styrene resin, 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, etc. Styrene and α-methylstyrene are particularly preferred. These aromatic vinyl compounds can be used alone or
Used as a mixture of more than one species. The amount of the aromatic vinyl compound used is preferably 20 to 100% by weight in the monomer component,
More preferably 30 to 90% by weight, particularly preferably 4
It is 0 to 80% by weight, and if it is less than 20% by weight, sufficient moldability cannot be obtained.

Other vinyl monomers include vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amino acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl. Acrylic esters such as acrylate, cyclohexyl acrylate, dodecyl acrylate, octadecyl acrylate, phenyl acrylate, benzyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate,
Butyl methacrylate, amino methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate, methacrylic acid esters such as benzyl methacrylate; maleic anhydride, itaconic anhydride, citraconic anhydride, etc. Unsaturated acid anhydrides; unsaturated acids such as acrylic acid and methacrylic acid; maleimide, N-methylmaleimide, N-butylmaleimide;
Α, such as N- (p-methylphenyl) maleimide, N-phenylmaleimide and N-cyclohexylmaleimide;
an imide compound of β-unsaturated dicarboxylic acid; an epoxy group-containing unsaturated compound such as glycidyl methacrylate or allyl glycidyl ether; an unsaturated carboxylic acid amide such as acrylamide or methacrylamide;
Amino group-containing unsaturated compounds such as aminomethyl methacrylate, aminoether methacrylate, aminopropyl methacrylate, and aminostyrene; 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2- Butene, trans-4-hydroxy-2-
Butene, 3-hydroxy-2-methyl-1-propene,
Examples include a hydroxyl group-containing unsaturated compound such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and hydroxystyrene; and an oxazoline group-containing unsaturated compound such as vinyl oxazoline. These other vinyl monomers can be used alone or in combination of two or more.

In addition, in a (graft) polymer of an aromatic vinyl compound and an imide compound of an α, β-unsaturated dicarboxylic acid, a copolymer of the aromatic vinyl compound and the unsaturated acid anhydride is treated with Those which are imidized (completely or partially) are also included in the (rubber-reinforced) styrenic resin of the present invention. The amount of these other vinyl monomers used is preferably 80 to 0% by weight, more preferably 7% by weight in the monomer component.
It is 0 to 10% by weight, particularly preferably 60 to 20% by weight.

As a preferable (rubber-reinforced) styrenic resin, an aromatic vinyl compound and a vinyl cyanide compound and, if necessary, another copolymerizable vinyl-based monomer in the presence of a rubber-like polymer are used. Examples thereof include a combination of a rubber-reinforced styrene-based resin obtained by polymerization, an aromatic vinyl compound, a vinyl cyanide compound, and a styrene-based resin made of another vinyl-based monomer copolymerizable as necessary.

The functional group-containing (rubber-reinforced) styrenic resin of the present invention is an acrylic ester, a methacrylic ester, or an unsaturated ester in the copolymer component of the (rubber-reinforced) styrenic resin of the component (A). At least one selected from the group of acid anhydrides, unsaturated acids, epoxy group-containing unsaturated compounds, unsaturated carboxylic acid amides, amino group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, and oxazoline group-containing unsaturated compounds. Examples thereof include those obtained by copolymerizing the functional group-containing vinyl monomer. The amount of the functional group-containing vinyl-based monomer in the functional group-containing (rubber-reinforced) styrene-based resin used is preferably 0.1 to 30% by weight in the monomer component. In addition, the functional group-containing (rubber-reinforced) styrenic resin is 1% in the component (A).
It is preferable to mix it by weight% or more.

When these functional group-containing vinyl monomers are used in combination, the dispersibility of the polycarbodiimide (B) is improved, a strong interface is formed with the polycarbodiimide, 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, an epoxy group-containing unsaturated compound, an amino group-containing unsaturated compound,
The use of the oxazoline group-containing unsaturated compound, rib strength,
It is preferable because the weld strength is improved.

The amount of the rubber-like polymer 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 in the rubber-reinforced styrene resin is preferably 0.05 to 30 μm from the viewpoint of melt viscosity and impact resistance.

The (rubber-reinforced) styrenic resin used as the component (A) of the present invention emulsifies a monomer component containing an aromatic vinyl compound as a main component in the presence or absence of a rubber-like polymer. Radical (graft) polymerization can be performed by polymerization, suspension polymerization, solution polymerization, bulk polymerization, or the like. Preferably, it is emulsion polymerization. At this time, a polymerization initiator, a chain transfer agent (molecular weight regulator), an emulsifier, water and the like are used for the emulsion polymerization. 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, tetraethyl thiuram 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, a phosphoric acid, and a fatty acid salt. 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. Furthermore, as the amphoteric surfactant,
Examples thereof include those having a carboxylate salt, a sulfuric acid ester salt, a sulfonate salt, and a phosphoric acid ester salt as the anion portion, and those having an amine salt, a quaternary ammonium salt or the like as the cation portion. The amount of the emulsifier used is usually, with respect to the monomer component,
It is about 0.3 to 5.0% by weight.

The (rubber-reinforced) styrene resin is preferably emulsion polymerized 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 150% by weight, more preferably 10 to 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, if it exceeds 150% by weight,
Moldability decreases. Here, graft ratio (% by weight)
Is a value obtained by the following equation, where x is the weight of the rubber component in 1 g of the rubber-reinforced styrenic resin and y is the weight of the methyl ethyl ketone insoluble matter. Graft ratio (% by weight) = [(y−x) / x] × 100

The molecular weight of the (rubber-reinforced) styrenic resin has an intrinsic viscosity [η] (methyl ethyl ketone soluble content, 3
0 ° C.) is preferably 0.3 to 2.0 dl / g. When the intrinsic viscosity [η] is less than 0.3 dl / g, a high balance of physical properties between rigidity and impact strength cannot be obtained, while 2.
If it exceeds 0 dl / g, the moldability will deteriorate.

When two or more monomer components are used in the (graft) polymerization, the preferred combinations are as follows. (1) Aromatic vinyl compound / vinyl cyanide compound (2) Aromatic vinyl compound / (meth) acrylate (3) Aromatic vinyl compound / vinyl cyanide compound /
(Meth) acrylic acid ester (4) aromatic vinyl compound / imide compound of α, β-unsaturated dicarboxylic acid (5) aromatic vinyl compound / vinyl cyanide compound /
Imide compound of α, β-unsaturated dicarboxylic acid (6) Aromatic vinyl compound / (meth) acrylic acid ester / Imide compound of α, β-unsaturated dicarboxylic acid (7) Aromatic vinyl compound / Vinyl cyanide compound / Unsaturated acid anhydride (8) Aromatic vinyl compound / (meth) acrylic acid ester / Unsaturated acid anhydride (9) Aromatic vinyl compound / Vinyl cyanide compound /
(Meth) acrylic acid ester / unsaturated acid anhydride (10) aromatic vinyl compound / imide compound of α, β-unsaturated dicarboxylic acid / unsaturated acid anhydride (11) aromatic vinyl compound / vinyl cyanide compound /
Hydroxyl-containing unsaturated compound (12) aromatic vinyl compound / vinyl cyanide compound /
Epoxy group-containing unsaturated compound (13) Aromatic vinyl compound / vinyl cyanide compound /
Oxazoline group-containing unsaturated compound In the above combination, the unit derived from the aromatic vinyl compound (in the graft chain grafted on the rubbery polymer) is 1
It occupies preferably from 100 to 100% by weight, preferably from 10 to 90% by weight.

Next, the polycarbodiimide 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 that accelerates the carbodiimidization reaction of the 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 may 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, an organic monoisocyanate is added, if necessary, so that when the organic polyisocyanate contains the other organic polyisocyanate, the molecular weight of the obtained polycarbodiimide is appropriately controlled. 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 used may be the desired molecular weight of the polycarbodiimide and the above-mentioned other organic polyisocyanates. All organic polyisocyanate component 1
0 to 40 parts by weight, preferably 0 to 20 parts by weight
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 may be used alone or in combination of two or more. The amount of the catalyst used is usually 0.001 to 30 parts by weight, preferably 0.01 to 10 parts by weight, based on 100 parts by weight of the total organic isocyanate component.

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, and to obtain the 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 in 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 and / or the unmodified polycarbodiimide in combination with an epoxy compound, the curing properties are improved, the rigidity of the obtained resin composition of the present invention is improved, and the inorganic filler is further improved. Impact resistance during use 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 a reactive compound 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 prepared by adding at least one reactive compound to a polycarbodiimide having a repeating unit represented by the 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 according to 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.

[0055] 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 and heating with an epoxy compound described below, even without using a curing catalyst due to the action of the carboxylic acid anhydride group in the modified polycarbodiimide, it is usually 100 to 100%.
It has the property of easily curing at a temperature of 350 ° C, preferably 150 to 300 ° C.

The epoxy compound used in the polycarbodiimide as the component (B) of the present invention is a compound having at least one epoxy group in the molecule and may have 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, 3,4-epoxycyclohexyl methacrylate and various epoxy resins. Further, those in which a part of the epoxy compound is substituted with a halogen atom are also preferably used.

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 3 parts by weight per 100 parts by weight of polycarbodiimide.
00 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 polycarbodiimide as a cured product tends to decrease. .

The polycarbodiimide (B) of the present invention is thermosetting, and it is preferable to use a non-thermosetting one when it is melt-kneaded with other components, but a partially cured one, or A completely cured product may be used.
Further, the polycarbodiimide (B) of the present invention is preferably dispersed as dispersed particles in the component (A).
The component (C) may be dispersed in the component (A), in the component (B), or in both components (A) to (B). Therefore, the dispersed particles (B) are
When the component (B) is used alone, the component (B) may contain other components.

The average particle size of the dispersed particles of the component (B) in the resin composition of the present invention is preferably 500 μm or less, more preferably 100 μm or less, and particularly preferably 0.01 to.
50 μm. The average particle size as used herein is a weight average, and this average particle size can be measured by a method of observing a section of the composition with an electron microscope. Here, the weight average particle diameter is calculated by the following equation. The weight average particle diameter _{(R) = Σn 1 R 1} 4 / Σn 1 R 1 3 n 1; dispersed particles number R _1; particle size of n ₁ [particle size, at least 500 or more (n ₁ ≧ 500) is measured . The dispersed particle diameter observed by an electron microscope does not always maintain a perfect circle, and the average value of the longest diameter and the shortest diameter of the particle is defined as the particle diameter. This average particle size is determined by the component (A),
Amount of use of component (B), component (C), component (A) / (B)
It can be easily adjusted by the melt viscosity of the component / (C), the shearing force at the time of kneading, the addition order of each component, and the like.

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 / 60-98 / 2, more preferably 50 / 50-95 / 5, particularly preferably 6
It is 0/40 to 95/5. The amount of component (A) used is 30
If it is less than wt% [(B) component exceeds 70 wt%],
Impact strength is lowered, which is not preferable. On the other hand, when it exceeds 99% by weight [(B) component is less than 1% by weight], the effect of improving heat resistance is not observed.

Next, the component (C) includes at least one selected from the group consisting of polyamide elastomers, polyester elastomers, acrylic rubbers, silicone rubbers, fluororubbers, modified polyolefins and modified rubbers.

The polyamide elastomer used here includes a hard segment (X) composed of an aminocarboxylic acid or lactam having 6 or more carbon atoms, or a nylon mn salt having m + n of 12 or more, and a polyol such as poly (alkylene). (Oxide) glycol and other soft segments (Y). Here, the ratio of X and Y is preferably X / Y = 95/5 to 5/95% by weight.

Aminocarboxylic acid or lactam having 6 or more carbon atoms, or nylon mn having m + n of 12 or more
As the hard segment (X) composed of salt, ω-
Aminocarboxylic acids such as aminocaproic acid, ω-aminoenoic acid, ω-aminocaprylic acid, ω-aminobergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid and 12-aminododecanoic acid; lactams such as caprolactam and laurolactam Nylon 6,6, nylon 6,10, nylon 6,12, nylon 11,6, nylon 11,10, nylon 12,6, nylon 11,1
2. Nylon salts such as 2, nylon 12,10 and nylon 12,12 can be mentioned.

As the soft segment (Y) such as polyol, polyethylene glycol, poly (1,
2- and 1,3-propylene oxide) glycol,
Examples thereof include poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, a block or random copolymer of ethylene oxide and propylene oxide, and a block or random copolymer of ethylene oxide and tetrahydrofuran. Also,
As the soft segment (Y) such as polyol, those containing dihydric phenol such as bisphenol A and hydroquinone can also be used. The number average molecular weight (Mn) of these soft segments (Y) by gel permeation chromatography (GPC) is preferably 200 to 6,000, more preferably 250 to 4,0.
00.

In the present invention, both terminals of the poly (alkylene oxide) glycol (Y) may be aminated or carboxylated before use. The bond between the component (X) and the component (Y) may be an ester bond or an amide bond with respect to the terminal group of each component. Also,
When forming such a bond, a third component such as dicarboxylic acid or diamine may be added.

Examples of the dicarboxylic acid used here include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid and diphenyl-4,4-dicarboxylic acid. , Diphenoxyethanedicarboxylic acid, aromatic dicarboxylic acids such as sodium 3-sulfoisophthalate, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, aliphatic dicarboxylic acids such as dicyclohexyl-4,4-dicarboxylic acid , Succinic acid, oxalic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid and other aliphatic dicarboxylic acids, and mixtures of these dicarboxylic acids, among which terephthalic acid, isophthalic acid, 1,4
-Cyclohexanedicarboxylic acid, sebacic acid, adipic acid and dodecanedicarboxylic acid are preferably used from the viewpoint of polymerizability, color tone and physical properties.

Examples of diamines include aliphatic diamines such as hexamethylenediamine, tetramethylenediamine and metaxylylenediamine, and aromatic diamines such as phenylenediamine.

Reduced viscosity η of polyamide elastomer
_{sp / c} (0.5 g / 100 ml in formic acid solution, measured at 25 ° C.) is preferably 0.5 to 3.0.

Further, as the polyester elastomer, polycondensation of a dicarboxylic acid compound and a dihydroxy compound, polycondensation of an oxycarboxylic acid compound, ring-opening polycondensation of a lactone compound, or polycondensation of a mixture of these components, etc. It is a block copolymer in which the obtained polyester is a hard segment and the polyol is a soft segment. The hard segment may be either homopolyester or copolyester.

Examples of the dicarboxylic acid compound used for the polyester elastomer include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenylethanedicarboxylic acid, cyclohexanedicarboxylic acid, adipic acid and sebacic acid. And these alkyls,
Alkoxy or halogen substitution products are also included. In addition, these dicarboxylic acid compounds can also be used in the form of a derivative capable of forming an ester, for example, a lower alcohol ester such as dimethyl ester. These dicarboxylic acid compounds may be used alone,
Alternatively, two or more kinds can be used in combination.

The dihydroxy compound used in the polyester elastomer is ethylene glycol, propylene glycol, butanediol, neopentyl glycol, butenediol, hydroquinone, resorcin, dihydroxydiphenyl ether, cyclohexanediol, 2,2-bis (4 -Hydroxyphenyl) propane and the like, and also includes polyoxyalkylene glycol and alkyl, alkoxy or halogen-substituted products thereof. These dihydroxy compounds can be used alone or in combination of two or more.

Further, examples of the oxycarboxylic acid compound used for the polyester elastomer include oxybenzoic acid, oxynaphthoic acid, diphenyleneoxycarboxylic acid and the like, and their alkyl, alkoxy and halogen substitution products are also included. These oxycarboxylic acid compounds may be used alone or in combination of two or more. Further, a lactone compound such as ε-caprolactone can be used for the production of the polyester elastomer.

As the polyol used for the soft segment of the polyester elastomer, all the polyols used for producing the above polyamide elastomer can be used. Further, the polyester as the hard segment and the polyol as the soft segment can be bonded by the method described for the polyamide elastomer. The intrinsic viscosity [η] of polyester elastomer (o-chlorophenol, measured at 35 ° C.) is
0.5 to 2.5 is preferable.

As the acrylic rubber, silicone rubber and fluororubber used as the component (C), all known ones can be used.

The modified polyolefin used as the component (C) may be a polyolefin rubber or a polyolefin resin modified with a functional group. Here, the polyolefin rubber is an α-olefin copolymer. As the α-olefin used here, ethylene, propylene, butene-1, 3
-Methylbutene-1, 3-methylpentene-1, 4-methylpentene-1 and the like. A preferred polyolefin rubber is a copolymer of ethylene and another α-olefin (ethylene-α-olefin rubber), and examples thereof include a block copolymer and a random copolymer. Another particularly preferred α-olefin is propylene. The ethylene content of the ethylene-α-olefin rubber is 10 to 90% by weight, preferably 20 to 8%.
It is 0% by weight, more preferably 30 to 70% by weight.

On the other hand, examples of the above polyolefin resin include homopolymers of the above α-olefins and copolymers thereof. Typical examples are high-density, medium-density or low-density polyethylene, linear low-density polyethylene, ultra-high-density polyethylene, propylene homopolymer, propylene-ethylene block copolymer or random copolymer, propylene homopolymer. Polymers, polypropylenes such as propylene-ethylene block copolymers and random copolymers, polypropylenes such as propylene-ethylene-diene compound copolymers, polybutene-1, poly-4-methylpentene-1 and the like can be mentioned. Among them, crystalline polyethylene and crystalline polypropylene are preferable,
Crystalline polypropylene is particularly preferable.

Examples of crystalline polypropylene include crystalline isotactic polypropylene and
Copolymerization part consisting of ethylene-propylene random copolymer having a low ethylene unit content or homopolymerization part consisting of propylene homopolymer and ethylene-propylene random copolymer having a relatively high ethylene unit content Commercially available as a so-called propylene block copolymer, a substantially crystalline block copolymer of propylene and ethylene, or each homopolymerization or copolymerization part of this block copolymer. However, a substantially crystalline propylene-ethylene-α-olefin copolymer or the like, which is composed of a copolymer of α-olefin such as butene-1, is preferable. The polyolefin resin used here has a melt index (MI) of 0.5 to 60 g.
/ 10 minutes is preferred.

The functional group used for modifying the above-mentioned polyolefin rubber or polyolefin resin is an ester group, a carboxyl group, an acid anhydride group, an epoxy group,
Examples thereof include an amide group, an amino group, a hydroxyl group and an oxazoline group. Examples of the functional group-containing vinyl monomer used for this modification include various functional group-containing vinyl monomers used for the functional group-containing (rubber-reinforced) styrene resin. As the modification method, the functional group-containing vinyl-based monomer is modified by copolymerizing the polyolefin-based rubber or the polyolefin-based resin during polymerization, the polyolefin-based rubber or the polyolefin-based resin, and the functional group-containing vinyl. Examples include a method of modifying by heating and melting in the presence of a system monomer and, if necessary, a peroxide, a method of modifying by oxidizing a polyolefin rubber or a polyolefin resin, and the like.

As the modified rubber used as the component (C), a functional group-modified rubber of the above rubber-like polymer is used.
Examples of the modification method include the method used in the above modified polyolefin. In the above modification methods ~, the amount of the functional group-containing vinyl-based monomer used for modification is
0.1 to 3 in modified polyolefin or modified rubber
The range of 0% by weight is preferable, and the polyolefin or rubber modified by the method is preferably one having one or more functional groups added per molecule on average. The above-mentioned component (C) can be used alone or in combination of two or more.

The amount of the component (C) used in the resin composition of the present invention is 1 to 300 parts by weight, preferably 1 to 250 parts by weight, based on 100 parts by weight of the total amount of the components (A) + (B). It is more preferably 5 to 200 parts by weight. In a region where the amount is less than 1 part by weight or exceeds 300 parts by weight, the impact strength is poor. The component (C) of the present invention can be used by appropriately blending the above rubbery polymer.

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, potassium titanate whiskers, and cellulosic materials may be used alone or in combination. The above may be mixed and used. Among these fillers, glass fibers and carbon fibers preferably have a fiber diameter of 6 to 60 μm and a fiber length of 30 μm or more. 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.

In addition, the resin composition of the present invention includes known coupling agents, antibacterial / antifungal agents, foaming agents, flame retardants, antioxidants, plasticizers, colorants, lubricants, weathering agents and antistatic agents. ,
Additives such as extending oils, metallic pigments, fluororesins and silicone oils can be added.

The resin composition of the present invention is used in various extruders,
It can be obtained by kneading each component using a Banbury mixer, a kneader, a Brabender, a roll, a Henschel mixer, a feeder ruder and 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. The kneading is done with an extruder,
It may be kneaded with a kneader, a Banbury mixer, a roll, a Brabender, etc., and then pelletized with an extruder.

At the time of kneading, the polycarbodiimide as the component (B) can be added and used in a cured, semi-cured or uncured state as described above. At this time,
The average particle size of the component (B) is preferably 500 μm or less,
It is more preferably 100 μm or less, and particularly preferably 0.1 μm or less.
You may use what was pulverized to 01-50 micrometers.

A preferred method of using the component (B) is
This is a method of curing the component (B) during melt-kneading of the components (A) and (C). By curing the component (B) during the melt-kneading of the components (A) and (C), a resin composition with more excellent heat resistance and impact resistance can be obtained. (B) at this time
As the component, uncured or semi-cured one 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 components (A) and (C), the component (B) may be used in combination with the above-mentioned uncured and / or semi-cured component. The component (B) can be used in the component (B) in an amount of preferably 99% by weight or less, more preferably 90% by weight or less, and particularly preferably 10 to 80% by 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 can be used for various molded products 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 articles obtained by the above-mentioned molding method, utilizing the excellent properties, are used as interior / exterior agents in the vehicle field and O
A. It can be used for various parts, housings, chassis, etc. in a wide range of fields such as home appliances, building materials / household equipment, sports / leisure, sanitary, and miscellaneous goods.

[0090]

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 box-shaped molded product obtained by heat-resistant injection molding was left in a gear oven at 100 ° C. for 1 hour, then taken out and examined for change in shape and evaluated. ；: Little deformation. ×: large deformation. Impact strength According to ASTM D648, thickness 1/4 ", notched, Izod impact (IZ) at 23 ° C ambient temperature
Was measured. The unit is kgf · cm / cm.

Reference Example Each component used in Examples and Comparative Examples of the present invention is as follows. Preparation of Rubbery Polymers (a) -1 to (a) -5 As the rubbery polymers used in the (rubber-reinforced) styrene resin which is the component (A) of the present invention, those shown in Table 1 were used. (Rubber reinforced) styrene resin and modified (rubber reinforced) su
Preparation of ethylene resin (A) -1 to (A) -11 In the presence of the rubber-like polymers (a) -1 to (a) -5,
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. (A) -1, (A) -3, (A) -6, (A)-
8, (A) -10 is emulsion polymerization, and (A) -2, (A)-
4, (A) -5, (A) -7, and (A) -11 were obtained by solution polymerization. Further, (A) -11 was obtained by polymerizing styrene and a maleic anhydride copolymer, and then imidizing a part of maleic anhydride with aniline.

Thermoplastic resin (A) -12 transparent ABS resin, # 58 manufactured by Japan Synthetic Rubber Co., Ltd.
Was used. Nylon 6 [Amilan CM1017 manufactured by Toray Industries, Inc.] was used as the thermoplastic resin (A) -13 polyamide resin. Thermoplastic resin (A) -14 As a thermoplastic polyester resin, polybutylene terephthalate (PBT) [PBT-12 manufactured by Kanebo Ltd.]
4] was used. Panlite L-1225 manufactured by Teijin Chemicals Ltd. was used as the thermoplastic resin (A) -15 polycarbonate.

Polycarbodiimide (B) -1 to (B)-
Preparation 3 (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.

Preparation of Component (C) (C) -1; Polyamide Elastomer Polyamide 6 Oligomer / Polyethylene Glycol (P
EG1500) = 50/50% multi-block copolymer, formic acid (25 ° C, concentration 0.5g / 100m)
The one having a reduced viscosity of 2.0 measured in 1) was used. (C) -2; Polyester elastomer PBT oligomer / polytetramethylene glycol = 4
Consisting of 0/60% multiblock copolymer, intrinsic viscosity 1.5 measured at 35 ° C. in o-chlorophenol solvent
Was used.

(C) -3; Modified ethylene-propylene copolymer rubber Ethylene-propylene copolymer rubber [Nippon Synthetic Rubber Co., Ltd.]
Manufactured, EP-01P] to 100 parts of maleic anhydride 1
Part, organic peroxide [Kayahexa AD manufactured by Kayaku Nouri Co., Ltd., 0.3 part] are mixed and melt-kneaded by an extruder.
An ethylene-propylene copolymer rubber to which maleic anhydride was added was used. (C) -4: Modified polypropylene 100 parts of polypropylene [block type polypropylene BC-3 manufactured by Mitsubishi Chemical Co., Ltd.], 1 part of maleic anhydride, organic peroxide [Kayahexa, manufactured by Kayaku Nouri Co., Ltd.] AD] Maleic anhydride-modified polypropylene obtained by mixing 0.3 parts of AD] and melt-kneading with an extruder was used. (C) -5; Acrylic rubber (n-butyl acrylate homopolymer) (C) -6; Silicone rubber (polydimethylsiloxane rubber)

Examples 1 to 24, Comparative Examples 1 to 4 The resin compositions were prepared by drying the above components to a water content of 0.1% or less, mixing the ingredients according to the formulations shown in Tables 3 to 7, and using a kneader. The mixture was melt-kneaded at a set temperature of 200 ° C., and then pelletized with a feeder ruder. The obtained pellets,
After drying to a water content of 0.1% or less, a test piece was prepared with an injection molding machine and evaluated by the above evaluation method. The evaluation results are shown in Tables 3-7.
Shown in

As is clear from Tables 3 to 6, Examples 1 to 1
All of 24 have excellent heat resistance and impact resistance.
On the other hand, as is clear from Table 7, in Comparative Example 1,
A large proportion of the component (A) is outside the scope of the present invention,
This is an example in which the amount of the component used is small outside the range of the present invention, and the heat resistance is poor. Comparative Example 2 is an example in which the compounding ratio of the component (A) is too small outside the range of the present invention, and the amount of the component (B) used is too large outside the range of the present invention, and the impact resistance is poor. Comparative Example 3 is an example in which the amount of the component (C) used in the obtained composition was small outside the range of the present invention, and the impact strength was poor. Comparative Example 4 is an example in which the amount of the component (C) used in the present invention is large outside the range of the present invention, and the impact strength is poor.

[0101]

[Table 1]

[0102]

[Table 2]

[0103]

[Table 3]

[0104]

[Table 4]

[0105]

[Table 5]

[0106]

[Table 6]

[0107]

[Table 7]

[0108]

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.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C08L 33/08 LJA C08L 33/08 LJA 51/04 LKY 51/04 LKY 67/00 LPA 67/00 LPA 77/00 LQS 77/00 LQS 83/04 LRY 83/04 LRY

Claims (2)

[Claims] 1. (A) 30 to 99% by weight of a thermoplastic resin,
And (B) selected from the group consisting of (C) polyamide-based elastomer, polyester-based elastomer, acrylic rubber, silicone rubber, fluororubber, modified polyolefin and modified rubber with respect to 100 parts by weight of the total amount of 70 to 1% by weight of polycarbodiimide. A resin composition containing 1 to 300 parts by weight of at least one kind. 2. The resin composition according to claim 1, which is obtained by curing the component (B) during melt-kneading of the components (A) to (C).