JPH09194721A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition having excellent flame-retardance, heat-resistance and impact strength and useful for OA and appliance field, car and vessel field, etc., by adding respective specific amounts of a polycarbodiimide and a flame-retardant to a thermoplastic resin. SOLUTION: The objective resin composition is produced by compounding (A) 30-99wt.% of a thermoplastic resin, (B) 70-1wt.% of a polycarbodiimide and (C) 1-50 pts.wt. (based on 100 pts.wt. of A+B) of a flame-retardant. A resin composition having considerably improved flame-retardance, heat-resistance and impact strength can be produced by curing the component B during the melt-kneading operation of the components A to C.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to flame retardancy, heat resistance,
The present invention relates to a flame-retardant resin composition having excellent 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, there is an increasing demand for plastics having excellent flame retardancy, heat resistance and impact resistance in order to improve product safety awareness. Conventionally, various flame retardants have been added to improve the flame retardancy of thermoplastic resins. However, due to the use of flame retardants,
There is a problem that heat resistance and impact resistance decrease. Also,
There are some concerns about the safety of antimony-based flame retardant aids used in combination with flame retardants, and it is desired to reduce the amount of use or to eliminate the use thereof. On the other hand, in order to improve heat resistance, various inorganic fillers such as glass fiber and mica are added to a thermoplastic resin and used, but it is sufficiently satisfactory in terms of combustion level and impact resistance. Not something you can do. Further, in order to improve impact resistance, various rubber components and elastomer components are used or increased in amount, but with the use of these components,
There is a problem that heat resistance and flame retardancy are reduced.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and has as its object to provide a flame-retardant resin composition having excellent flame retardancy, heat resistance and impact resistance. Aim.

[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) A flame-retardant resin composition containing 1 to 50 parts by weight of a flame retardant is provided.

[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-based monomer used in the monomer component 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 that case, 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 a vinyl cyanide compound, the chemical resistance of the rubber-reinforced styrene resin obtained is improved, but when it exceeds 45% by weight, the color tone of the rubber-reinforced styrene resin obtained becomes brown and the molding processability is improved. However, the thermal stability during molding becomes 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.

Acid anhydride type monomers Maleic anhydride, itaconic anhydride, citraconic anhydride and the like. Maleimide-based monomers Maleimide, N-methylmaleimide, N-butylmaleimide, N- (p-methylphenyl) maleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like. The above-mentioned monomers may be used alone.
Alternatively, two or more kinds can be used in combination.

Further, the rubber-like polymer is removed from the rubber-reinforced styrene resin by using an aromatic vinyl monomer and another functional group-containing monomer copolymerizable with 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 the functional group-containing monomer include unsaturated epoxy compounds such as glycidyl methacrylate and allyl glycidyl ether, unsaturated carboxylic acid amides such as acrylamide and methacrylamide, acrylamine, 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) improving the dispersibility of polycarbodiimide, forming a strong interface with polycarbodiimide,
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.

Examples of the polymerization initiator include organic hydroperoxides represented by cumene hydroxyperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide and the like, sugar-containing pyrophosphate formulations, sulfoxylate formulations and the like. A redox system in combination with a reducing agent, or a peroxide such as persulfate, azobisisobutyronitrile, benzoyl peroxide or the like 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 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 type monomer / (meth) acrylic acid ester type monomer / maleimide type monomer (7) Aromatic vinyl type monomer / vinyl cyanide type monomer / acid Anhydride-based monomer (8) Aromatic vinyl-based monomer / (meth) acrylic acid ester-based monomer / acid anhydride-based monomer (9) Aromatic vinyl-based monomer / vinyl cyanide-based Monomer / (meth) acrylic acid ester type monomer / acid anhydride type monomer

(10) Aromatic vinyl type monomer / maleimide type monomer / acid anhydride type monomer (11) Aromatic vinyl type monomer / vinyl cyanide type monomer / unsaturated group containing hydroxyl group Compound (12) Aromatic vinyl-based monomer / vinyl cyanide-based monomer / epoxy group-containing unsaturated compound (13) Aromatic vinyl-based monomer / vinyl cyanide-based monomer / oxazoline group-containing unsaturated Compound In the above combination, the unit derived from the aromatic vinyl-based 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 for copolymerization, the combination of the above (1) to (13) 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.

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 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 above-mentioned 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 may be the desired molecular weight of polycarbodiimide, the above-mentioned other organic polyisocyanate. 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 may 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 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 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 as 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 the epoxy compound (b), the curing characteristics are improved, and the rigidity of the obtained resin composition of the present invention is further improved. Impact resistance when using an inorganic filler 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 prepared 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 according to the type of polycarbodiimide and the compound, the use, etc., but 1 mol of the repeating unit represented by the general formula (I) of the polycarbodiimide is used. On the other hand, the amount of the graft reactive group in the reactive compound is 0.01 to 1 mol, preferably 0.02 to 0.8 mol.
In this case, if the proportion of the graft-reactive group is less than 0.01 mol, long-time heating is required to cure the polycarbodiimide, while if it exceeds 1 mol, the original properties of the 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.

[0059] 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 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. Well, 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, 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 resulting composition tends to decrease.

The average particle size of the dispersed particles of the component (B) in the flame-retardant 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 here is a weight average, and the particle size of the dispersed particles 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 flame-retardant resin composition of the present invention is 30 /
70 to 99/1, preferably 40/60 to 97/3, more preferably 50/50 to 95/5, particularly preferably 60/40 to 90/10. When the amount of the component (A) used is less than 30% by weight [the amount of the component (B) exceeds 70% by weight], the impact resistance is lowered, which is not preferable. %], Flame retardancy and heat resistance are poor.

As the flame retardant (C) of the present invention, all known flame retardants can be used, but preferably a halogen flame retardant, a phosphorus flame retardant, and phosphorus and a halogen are simultaneously contained in the molecule. Examples include flame retardants. this house,
Examples of the halogen-based flame retardant include halogen-containing compounds represented by the following chemical formula 1 and having epoxy groups at both ends.

[0066]

Embedded image

(Wherein X is a bromine atom or a chlorine atom,
a to d are natural numbers of 1 to 4, and p is 0 or a natural number. The halogen-containing compound represented by Chemical Formula 1 is obtained as a reaction product of halogen-containing bisphenol A and a halogen-containing bisphenol A type epoxy resin.

Examples of the halogen-containing bisphenol A include tetrabromobisphenol A, dichlorobisphenol A, tetrachlorobisphenol A and dibromobisphenol A. Examples of the halogen-containing bisphenol A type epoxy resin include diglycidyl ether of tetrabromobisphenol A, diglycidyl ether of tetrachlorobisphenol A, diglycidyl ether of dichlorobisphenol A, and diglycidyl ether of dibromobisphenol A. . Particularly preferred is a reaction product of tetrabromobisphenol A and a diglycidyl ether of tetrabromobisphenol A.

Further, as a halogen-based flame retardant,
A halogen-containing compound represented by

[0070]

Embedded image

(In Chemical Formula 2, X and a to d are the same as those in Chemical Formula 1, and q is a natural number of 1 to 5.) The flame retardant of Chemical Formula 2 is a halogenated bisphenol A which constitutes the flame retardant of Chemical Formula 1. -Type epoxy resin and halogenated phenols such as tribromophenol, dibromophenol, trichlorophenol and dichlorocresol are heated and reacted in the presence of a chlorine-containing catalyst.

Further, as the halogen-based flame retardant, brominated polystyrene represented by the following chemical formula 3 can be cited.

[0073]

Embedded image

(Wherein X is a bromine atom or a chlorine atom,
e is a natural number of 1 to 5, and n is a natural number. The flame retardant of Chemical formula 3 is preferably brominated polystyrene obtained by polymerizing brominated or brominated styrene after polystyrene, and the bromine content is 68 to 72% by weight.
Is preferable, and more preferably 68 to 70% by weight. Moreover, the weight average molecular weight in terms of gel permeation chromatography (GPC) is 1,500 to 1.
It is preferably in the range of 5,000.

Further, as the halogen-based flame retardant, a brominated phthalimide represented by the following chemical formula 4 can be mentioned.

[0076]

Embedded image

(Wherein X is a bromine atom or a chlorine atom,
f and g are natural numbers of 1 to 4. )

Examples of other halogen-based flame retardants include aromatic halogen compounds, halogenated polycarbonates, halogenated polycarbonate oligomers, halogenated cyanurate resins, halogenated polyphenylene ethers, etc., preferably decabromodiphenyl oxide, octabromodiphenyl. Oxides, tetrabromobisphenol A, polycarbonate oligomers of tetrabromobisphenol A, brominated bisphenol-based phenoxy resin, brominated bisphenol-based polycarbonate, brominated polyphenylene ether, decabromodiphenyl oxalide condensate, halogen-containing phosphoric acid ester, etc. .

Examples of the phosphorus flame retardant include inorganic phosphates such as ammonium polyphosphate, aromatic phosphates such as triphenyl phosphate, alkyl phosphates such as triethyl phosphate, acidic phosphates, phosphonitrile chloride derivatives. Examples thereof include nitrogen-containing phosphorus compounds such as, vinyl phosphate, polymerizable phosphorus compounds such as allyl phosphonate, and red phosphorus flame retardants.
These (C) flame retardants may be used alone or
Alternatively, two or more kinds can be used in combination.

Among the above (C) flame retardants, the halogen-based flame retardants represented by the above chemical formula 1 having epoxy groups at both ends are particularly preferable in terms of dispersion in the resin, and phosphorus is preferable in terms of processability. Flame retardants are preferred. The amount of the halogen-based flame retardant represented by Chemical Formula 1 is preferably 1 to 10 in (C) the flame retardant.
0% by weight, more preferably 10 to 100% by weight, and particularly preferably 20 to 80% by weight.

The amount of the flame retardant (C) used is 1 to 50 parts by weight, preferably 3 to 50 parts by weight, and more preferably 4 per 100 parts by weight of the total amount of the components (A) and (B).
４０40 parts by weight. If it is less than 1 part by weight, the effect of improving flame retardancy is not observed, while if it exceeds 50 parts by weight, heat resistance and impact resistance are poor.

A flame retardant aid may be used in combination with the (C) flame retardant. Examples of the flame retardant aid include antimony trioxide, antimony tetroxide, antimony pentoxide, chlorinated polyethylene, polyorganosiloxane-based polymer, tetrafluoroethylene polymer, and the like, and these may be used alone. Alternatively, two or more kinds can be used in combination. Here, the tetrafluoroethylene polymer has an average particle size of 0.05 to 1,000 μm.
Those having a density of 2 to ^2.3 g / cm ³ and a fluorine content of 65 to 76% by weight are preferred. Further, those obtained by emulsion polymerization or suspension polymerization are preferably used. The amount of the flame retardant aid used is 100 in total of the components (A) to (B).
0.1 to 20 parts by weight, preferably 0.5
To 10 parts by weight.

The composition of the present invention contains glass fiber, carbon fiber, metal fiber,
Metal flakes, glass beads, wollastonite, glass milled fiber, rock filler, glass flakes, calcium carbonate, talc, mica, kaolin, barium sulfate, graphite, molybdenum disulfide, magnesium oxide, zinc oxide whiskers, potassium titanate whiskers Fillers such as glass balloons and ceramic balloons may be used alone or in combination of two or more. Among these fillers, those having a fiber diameter of 6 to 60 μm and a fiber length of 30 μm or more are preferable as the shape of glass fiber or carbon fiber.
These fillers are usually used in the range of 1 to 200 parts by weight based on 100 parts by weight of the resin composition of the present invention.

In addition, the composition of the present invention includes known coupling agents, antibacterial agents, antifungal agents, antioxidants, weathering (light resistance) agents, plasticizers, colorants (pigments, dyes, etc.), lubricants, Additives such as metal powder can be blended.

The flame-retardant resin composition of the present invention can be obtained by kneading the components using various extruders, Banbury mixers, kneaders, rolls, feeder ruders and the like. The kneading temperature is preferably 100 to 350.
C., more preferably 150 to 300.degree. Also,
When kneading each component, each component may be kneaded collectively or may be added and kneaded several times. The kneading may be carried out in a multi-stage addition type with 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 polycarbodiimide 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 100 μm or less, and particularly preferably 0.01 to 50 μm.
May be used.

A preferred method of using 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 the melt-kneading of the component (A), a resin composition having further excellent flame retardancy, 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 preferable because the dispersion form of the component (B) can be easily controlled during melt-kneading in the resulting composition, and further the third component that can react with the component (B) can be easily introduced. 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), as the component (B), the 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%. Further, it is preferable that all or part of the component (C) coexist during the above kneading, because the flame retardancy is further improved.

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 flame-retardant resin composition of the present invention thus obtained can be used in various forms 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 into a molded product. 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.

[0091]

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.

The number average molecular weight (Mn) was determined by gel permeation chromatography (GPC) in terms of polystyrene.

The combustion state after the flame contact with the flame-retardant test piece was observed and evaluated. ○: disappeared naturally. X: continued burning. The heat-resistant box-shaped molded product was allowed to stand 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].

Polycarbodiimide (B) -1 to (B)-
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 polycarbodiimide solution, 3.8 g of trimellitic anhydride was added as a reactive compound, and the mixture was reacted at 20 ° C. for 3 hours to obtain a solution of 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 ).

[0097] (B) -3; strange in combination an epoxy compound
A polycarbodiimide was obtained as follows. 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; Tetrabromobisphenol A was used. (C) -2; Tetrabromobisphenol A and epichlorohydrin were obtained by reaction, and epoxy having both ends and a molecular weight of about 2,000 was used. (C) -3: Triphenyl phosphate was used as a phosphorus-based flame retardant.

Examples 1 to 13 and Comparative Examples 1 to 4 Using the compounding recipes shown in Tables 3 to 4, melt kneading was performed at a preset temperature of 200 ° C. using a kneader, and then pelletized with 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. As is clear from Table 3, Examples 1 to 1
All of 13 have excellent flame retardancy, heat resistance and impact resistance. On the other hand, Comparative Example 1 is an example in which the components (A) to (B) have too high a proportion of the component (A) and too low a proportion of the component (B). Inferior to. Comparative Example 2 is an example in which, of the components (A) to (B), the blending ratio of the component (A) is too small and the blending ratio of the component (B) is too large, and the impact resistance is poor. Comparative Example 3 is an example in which the component (C) is large outside the scope of the present invention, and is poor in heat resistance and impact resistance. Comparative Example 4 is an example in which the amount of the component (C) is less than the range of the present invention, and the flame retardancy is poor.

[0100]

[Table 1]

[0101]

[Table 2]

[0102]

[Table 3]

[0103]

[Table 4]

[0104]

The flame-retardant resin composition of the present invention has flame-retardant properties,
It has excellent heat resistance and impact resistance, and is used in a wide range of fields such as OA / home appliances, vehicles, ships, housing-related fields such as furniture / construction materials, sanitary fields, toys / sports fields, and other miscellaneous goods. Can be used.

Claims (2)

[Claims] 1. (A) 30 to 99% by weight of a thermoplastic resin,
And (B) 1 to 50 parts by weight of the flame retardant (C) with respect to 100 parts by weight of the polycarbodiimide (70 to 1% by weight) in total. 2. The flame-retardant resin composition according to claim 1, wherein the component (B) is cured during melt-kneading of the components (A) to (B).