JP3424277B2 - Flame retardant resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant resin composition which is excellent in flame retardancy, greatly suppresses the occurrence of dripping phenomenon, and is excellent in heat resistance and impact resistance of molded articles.

[0002]

2. Description of the Related Art Conventionally, thermoplastic resins have been used in a wide variety of applications because of their excellent moldability. However, depending on the application, it is necessary to have flame retardancy. This is especially true when used as a household product, an electric product, an OA device, a product such as an automobile, or a building material. Known methods for rendering thermoplastics flame retardant consist of blending flame retardants, but often such flame retardants are halogen containing compounds such as brominated diphenyl oxide compounds and brominated polycarbonate compounds. Is. Further, as a flame retardant with less generation of dioxin and furan, which are toxic to the human body, there is a compound containing phosphorus and / or nitrogen. However, when these flame retardants are added, there is a drawback in that although a certain degree of flame retardancy can be imparted, melt dripping (dripping) during combustion cannot be prevented. Molten liquid dripping is dangerous because it will spread the fire in the event of a fire.

[0003]

DISCLOSURE OF THE INVENTION The object of the present invention is to solve the above-mentioned drawbacks of the prior art, to have excellent flame retardancy, to significantly suppress the occurrence of dripping phenomenon, and to improve the heat resistance and impact resistance of molded articles. It is to provide a flame-retardant resin composition having excellent properties.

[0004]

The present invention provides a component (A) containing at least one functional group selected from an epoxy group, a hydroxyl group, a carboxyl group, and an amide group, and N
-(B) component phenol resin 1 to 50 parts by weight, (C) component phosphorus-containing compound 1 to 50 parts by weight, and (D) component nitrogen-containing compound 0 to 100 parts by weight of the styrene-based resin having a substituted maleimide unit. 30 parts by weight, a flame-retardant resin composition prepared by blending 0 to 30 parts by weight of (E) functional group-containing oligomeric polymer, and a styrene resin in which (A) component has an N-substituted maleimide unit. (A-1) 5 to 95% by weight, styrene resin (A-2) 95 to 5 having at least one functional group selected from epoxy group, hydroxyl group, carboxyl group and amide group
There is provided the above flame-retardant resin composition consisting of wt%.

The present invention will be described in detail below. The styrene resin as the component (A) of the present invention contains at least one functional group selected from an epoxy group, a hydroxyl group, a carboxyl group, and an amide group, and has an N-substituted maleimide unit (rubber reinforced). It is a styrene resin.

The content of the functional group in the component (A), as the content of the functional group-containing monomer, is preferably 0.1 to 40% by weight, more preferably 1 to 30% by weight. By containing a functional group, more excellent flame retardancy can be obtained.
On the other hand, the content of the N-phenylmaleimide unit is preferably 1 to as the content of the N-substituted maleimide-based monomer.
It is 40% by weight, more preferably 3 to 25% by weight.

The component (A) is obtained by copolymerizing a functional group monomer, an N-substituted maleimide type monomer, an aromatic vinyl monomer and, if necessary, another monomer.

When the component (A) is to be reinforced with rubber, the above-mentioned monomer is polymerized in the presence of a rubber-like polymer,
A rubber-reinforced (A) component can be obtained. The content of the rubber-like polymer in the component (A) is preferably 5 to 50% by weight, more preferably 10 in order to obtain impact resistance.
-40% by weight.

The content of the aromatic vinyl monomer in the component (A) is preferably 30-98.9% by weight, more preferably 45-96% by weight. The content of the other monomer in the component (A) is preferably 0 to 70% by weight, more preferably 0 to 50% by weight.

Examples of the rubbery polymer include polybutadiene, styrene-butadiene copolymer, polyisoprene,
Butadiene-acrylonitrile copolymer, isobutylene-isoprene copolymer, ethylene-propylene- (non-conjugated diene) copolymer, acrylic rubber, styrene-butadiene-styrene block copolymer, styrene-butadiene-styrene radial tereblock copolymer Combined hydrogenated product, styrene-isoprene-styrene block copolymer, styrene-isoprene-styrene block copolymer hydrogenated product, polybutadiene random copolymer hydrogenated product, polyurethane rubber, silicone rubber, etc. Alternatively, they can be used in combination.

Among these rubber-like polymers, polybutadiene, styrene-butadiene copolymer, ethylene-propylene- (non-conjugated diene) copolymer, silicone rubber, ethylene-butene-1- (non-conjugated diene). Copolymers, hydrogenated products of random or block copolymers containing the above-mentioned butadienes are preferred.

Examples of the functional group-containing monomer include, for example,
Glycidyl methacrylate, glycidyl acrylate,
2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, p-hydroxystyrene, methacrylic acid, acrylic acid, 2-methacryloyloxyethyl succinic acid, 2 -Methacryloyloxyethyl phthalic acid, acrylamide, methacrylamide, etc. are mentioned, these being particularly preferred.

Examples of the N-substituted maleimide type monomer include a phenyl group, an alkyl group, an alicyclic hydrocarbon group, an alkyl group or an alicyclic hydrocarbon group, a phenyl group substituted with a hydroxyl group, a phenyl group or an aliphatic group. A maleimide monomer having a substituent selected from an alkyl group substituted with a cyclic hydrocarbon group, a phenyl group or an alicyclic hydrocarbon group substituted with an alkyl group, and / or an acid anhydride monomer A polymer obtained by post-imidizing the copolymer with a secondary amine or the like can be mentioned.

The N-substituted maleimide unit is preferably N-phenylmaleimide, Np-hydroxyphenylmaleimide or N-cyclohexylmaleimide.

Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, bromostyrene, dibromostyrene, tribromostyrene, chlorostyrene, dichlorostyrene, α-ethylstyrene. And the like, and preferably styrene and α-methylstyrene. These can be used alone or in combination of two or more.

The above "other copolymerizable monomer" can be copolymerized within a range that does not adversely affect various physical properties. Other copolymerizable monomers are preferably vinyl cyanide monomers, (meth) acrylic acid esters, acid anhydrides and the like. As vinyl cyanide monomer,
Examples thereof include acrylonitrile and methacrylonitrile. Of these, acrylonitrile is preferred.

Examples of the (meth) acrylic acid ester include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate and butyl methacrylate. Of these, methyl methacrylate and butyl acrylate are preferred. As the acid anhydride,
Maleic anhydride is preferred.

The method for producing the component (A) is not particularly limited, but preferable production methods include the following methods. The above-mentioned functional group-containing monomer, N-substituted maleimide-based monomer, aromatic vinyl monomer, and other monomer used as necessary in the presence or absence of a rubbery polymer. (A) of the present invention by polymerizing a monomer component consisting of
It is a method of obtaining components. A polymer obtained by polymerizing an N-substituted maleimide-based monomer, an aromatic vinyl monomer, and optionally other monomer in the presence or absence of a rubbery polymer. A unit consisting of (A-1) and a functional group-containing monomer, an aromatic vinyl monomer, and other monomer used as necessary in the presence or absence of a rubbery polymer. It is a method of appropriately blending a polymer (A-2) obtained by polymerizing a body component to obtain the component (A) of the present invention.

The mixing ratio of the above (A-1) and (A-2) is such that the component (A-1) is 5 to 95% by weight, preferably 10%.
~ 90 wt%, more preferably 20-80 wt%,
Component (A-2) is 95 to 5% by weight, preferably 90 to 1
It is 0% by weight, more preferably 80 to 20% by weight.
The above method is suitable for industrial production.

The styrene resin obtained in the above and / or the styrene resin composition obtained in the above is blended with a styrene resin which does not contain a functional group or an N-substituted maleimide monomer (rubber-reinforced). Of the present invention (A)
It is a method of obtaining components.

Preferred styrene resins obtained by the above method include those obtained by polymerizing the following. (1) Rubber-like polymer / styrene / N-phenylmaleimide / glycidyl methacrylate (2) Rubber-like polymer / styrene / N-phenylmaleimide / methacrylic acid / acrylonitrile (3) Rubber-like polymer / styrene / N-phenylmaleimide / Acrylamide / acrylonitrile (4) rubbery polymer / styrene / N-phenylmaleimide / 2-hydroxyethylmethacrylate (5) styrene / N-phenylmaleimide / acrylic acid / acrylonitrile (6) styrene / N-phenylhydroxymaleimide /
Glycidyl methacrylate / acrylonitrile

The preferred method (A-
As the resin composed of the component 1) and the component (A-2),
The thing obtained by polymerizing the following is mentioned.

Component (A-1) (7) Rubber-like polymer / styrene / N-phenylmaleimide / acrylonitrile (8) Styrene / N-phenylmaleimide / acrylonitrile (8 ') styrene / N-phenylmaleimide / maleic anhydride (9) Rubber-like polymer / styrene / Np-hydroxyphenylmaleimide (A-2) component (10) Rubber-like polymer / styrene / glycidyl methacrylate (11) Rubber-like polymer / styrene / 2-hydroxyethyl methacrylate (12) Rubber-like polymer / styrene / acrylic acid / acrylonitrile (13) Styrene / acrylamide / acrylonitrile

The graft ratio of the rubber-like polymer in the component (A) is preferably 5-150%, more preferably 10-.
It is 130%. When the graft ratio is less than 5%, the effect of adding the rubber component is not sufficiently exerted and impact resistance cannot be sufficiently obtained. On the other hand, if it exceeds 150%, dripping tends to occur during combustion, which is not preferable.

Here, the graft ratio (%) is a value obtained by the following equation, where x is the amount of rubber component in 1 g of component (A) and y is the amount of methyl ethyl ketone insoluble component in 1 g of component (A). Graft ratio (%) = {(y−x) / x} × 100

The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the matrix resin in the component (A) is
It is preferably 0.1 to 1.5 dl / g, and more preferably 0.3 to 1.0 dl / g. Intrinsic viscosity [η] is 0.
When it is less than 1 dl / g, impact strength is not sufficiently expressed, while when it exceeds 1.5 dl / g, moldability is deteriorated, which is not preferable.

Here, the matrix resin is a resin component other than the grafted rubber component in the component (A), and the intrinsic viscosity [η] is the methyl ethyl ketone soluble component in the component (A). It is a value obtained by measuring according to the method.

The component (B) is a phenol resin. Examples of the phenol resin include novolac type phenol resin and resol type phenol resin. Of these, the novolac type phenolic resin is a polymer obtained by the condensation reaction of a substituted or unsubstituted phenol with an aldehyde. Specific examples thereof include phenol formaldehyde novolac resin, tertiary-butyl phenol formaldehyde novolac resin, phenol benzaldehyde novolac resin, copolymers thereof, and mixtures thereof. Phenol formaldehyde novolac resin is preferred.

The resol type phenol resin is a polymer having a relatively low molecular weight obtained by condensing a substituted or unsubstituted phenol with formaldehyde and the like, and has 3 to 20% by weight of a free methylol group. It is a thing. Specific examples of the substituted phenols include aryl-substituted phenols such as cresol, resorcinol and p-phenylphenol, and alkylated phenols such as pt-butylphenol, p-octylphenol and xylenol. In the present invention,
Resol-type phenolic resins using phenol, cresol, resorcinol and mixtures thereof are preferred. A preferred average molecular weight is in the range of 300 to 10,000.

Examples of the phosphorus-containing compound as the component (C) include organic phosphorus-containing compounds, red phosphorus, phosphazene compounds,
Examples thereof include ammonium polyphosphate. this house,
Examples of the organic phosphorus-containing compound include phosphates typified by triphenyl phosphate and phosphites typified by triphenyl phosphite.
These organic phosphorus-containing compounds may be used alone or in combination with 2
You may use it in mixture of 2 or more types. In the present invention,
As the organic phosphorus-containing compound, triphenyl phosphate, triphenyl thiophosphate, trixylenyl phosphate, trixylenyl thiophosphate, hydroquinone bis (diphenyl phosphate), resorcinool building (diphenyl phosphate), or 9,
10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (Sanko Chemical Co., Ltd., trade name H
CA) and derivatives having a substituent on the aromatic ring are preferred.

The nitrogen-containing compound as the component (D) includes triazine, triazolysine, isocyanurate, urea,
Examples include glianidin, aminic acid, melamine and its derivatives. These nitrogen-containing compounds can be used alone or in combination of two or more. Preferred component (D) includes melamine and tris (hydroxyethyl) isocyanurate.

As the oligomeric polymer of the component (E), an epoxy resin, an isocyanate group-containing oligomer,
Examples thereof include bismaleimide-based oligomers and phenoxy resins. Preferred are epoxy resins and isocyanate group-containing oligomers.

Specific functional group-containing oligomeric polymers are listed below, but the present invention is not limited to the above unless it exceeds the gist thereof.
It is not limited to the following specific examples. Examples of the epoxy resin include bisphenol A-epichlorohydrin resin and alicyclic epoxy resin. Specifically, it is the YD series manufactured by Tohto Kasei. Examples of the hydroxyl group-containing resin include terpene-phenol resin, polyvinyl alcohol, epoxy-novolac resin and the like.

Examples of the isocyanate group-containing oligomer include MDI millionate (Nippon Polyurethane Industry Co., Ltd.). Examples of the amino group-containing resin include guanamine resin and bismaleimide resin. Examples of the bismaleimide-based oligomer include BT-resin manufactured by Mitsubishi Gas Chemical Company. Examples of the phenoxy resin include a bisphenol A oligomer whose terminal is sealed with a phenyl group. A specific example is the Tohsei Kasei YP series.

The blending ratios of the constituent components of the flame-retardant resin composition of claims 1 and 2 are shown below. The amount of component (B) used is
It is 1 to 50 parts by weight, preferably 3 to 25 parts by weight, and more preferably 8 to 20 parts by weight with respect to 100 parts by weight of the component (A). If the amount used exceeds 50 parts by weight, the heat resistance will be poor. The amount of the component (C) used is 1 to 50 parts by weight, preferably 8 to 40 parts by weight, relative to 100 parts by weight of the component (A),
More preferably 10 to 35 parts by weight, particularly preferably 1
It is 2 to 30 parts by weight. If the amount used is less than 1 part by weight, the flame retardancy is not sufficient, and if it exceeds 50 parts by weight, the heat resistance and impact resistance are significantly deteriorated, which is not preferable. The amount of the component (D) used is 30 parts by weight or less, preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight, and 30 parts by weight to 100 parts by weight of the component (A). If it is added in excess, it is not preferable because the impact resistance decreases.

The amount of the component (E) used is 100 parts of the component (A).
30 parts by weight or less with respect to parts by weight, preferably 0.5 to
30 parts by weight, more preferably 1 to 20 parts by weight. Three
If it exceeds 0 part by weight, impact resistance and heat resistance are deteriorated, which is not preferable. When the component (E) is used, flame retardancy is further improved.

Other resin materials may be added to the flame-retardant resin composition of the present invention, if necessary. AES resin, MB
S resin, HIPS, polystyrene, MS resin, polycarbonate, polyamide, PBT, PET, PPS, PP
At least one polymer selected from O, POM, polyacetal, polyetheresteramide, polyetherimide, polyimide, PEEK, polyarylate, polymethylmethacrylate, silicone resin and polyvinyl chloride can be mentioned. Among these, at least one polymer selected from polycarbonate, polyamide, PBT, PET, PPO and silicone resin is preferable.

By using a compatibilizing agent in order to improve the adhesiveness at the interface between the flame-retardant resin composition and another resin material, it is possible to impart even more excellent mechanical strength. The amount of the compatibilizer to be added is 100 parts by weight of the component (A),
It is 0.5 to 20 parts by weight. As the compatibilizing agent of the above resin composition, ethylene-glycidyl methacrylate copolymer polystyrene, acrylonitrile copolymer, polymethylmethacrylate graft copolymerization, styrene resin, polymethylmethacrylate polyester graft , Ethylene-glycidyl methacrylate copolymer, ethylene-maleic anhydride copolymer and the like are used.

The following inorganic and organic compounds may be added to the present invention as flame retardant aids. These substances include antimony compounds such as antimony trioxide and antimony pentoxide, borate compounds such as zinc borate and barium metaborate, metal hydroxides such as magnesium hydroxide and aluminum hydroxide, iron-based compounds such as ferrocene and iron oxide. Compound,
Examples thereof include fluorine-based compounds such as polytetrafluoroethylene, and silicon-based compounds such as silicone resins and silicone rubber.

Further, if necessary, the flame-retardant resin composition of the present invention contains a stabilizer such as an antioxidant and an ultraviolet absorber,
Silicone oil, lubricant such as low molecular weight polyethylene, calcium carbonate, talc, clay, titanium oxide, silica,
Add fillers such as copper oxide, zinc oxide, magnesium oxide, magnesium carbonate, carbon black, barium sulfate, calcium oxide, aluminum oxide, mica, glass beads, glass fibers, metal fillers, dispersants, foaming agents, colorants, etc. can do.

Of these, the glass fiber and carbon fiber preferably have a fiber diameter of 6 to 60 μm and a fiber length of 30 μm or more.

The blending amount of these additives is preferably about 0.01 to 100 parts by weight with respect to 100 parts by weight of the flame-retardant resin composition of the present invention.

As an apparatus for melt-mixing the respective components used in producing the flame-retardant resin composition of the present invention, there are an open type mixing roll, a non-open type Banbury mixer, an extruder, a kneader, a continuous mixer and the like. Preferably 1
It is desirable to produce by kneading each component in the range of 80 to 280 ° C. At the time of kneading, each component may be kneaded at once, or a multi-stage divided kneading method in which after kneading arbitrary components, the remaining components are added and kneading can be adopted. A preferable kneading method is a method performed by an extruder, and a twin-screw co-directional extruder is particularly preferable as the extruder.

The flame-retardant resin composition of the present invention is molded by extrusion molding, injection molding, compression molding, etc., and these molded articles have flame retardancy, impact resistance and practical use. Since it is excellent in property formation and has a good surface appearance, it is extremely useful as an article such as household articles, electric equipment, OA equipment, parts such as automobiles, or a building material.

[0045]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. A in the text and table
"-" Indicates a rubber-reinforced copolymer, and "a-" indicates other copolymers. Adjustment of component (A) The following was used as the component (A).

Graft copolymer (A-) In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, 40 parts by weight of polybutadiene rubber latex as an initial component in terms of solid content and 65 parts of ion-exchanged water.
Parts by weight, rosin acid soap 0.35 parts by weight, styrene 1
5 parts by weight and 5 parts by weight of acrylonitrile were added, and then 0.2 parts by weight of sodium pyrophosphate, 0.01 parts by weight of ferrous sulfate heptahydrate and 0.4 parts by weight of glucose were added to 20 parts by weight of deionized water. Added to the dissolved solution. Then, 0.07 part by weight of cumene hydroperoxide was added to start polymerization, and after polymerization for 1 hour, 45 parts by weight of ion-exchanged water as an increment component, 0.7 part by weight of rosin acid soap, 30 parts by weight of styrene. , Acrylonitrile 10 parts by weight and cumene hydroperoxide 0.
01 parts by weight was continuously added over 2 hours, and the reaction was completed by further polymerizing for 1 hour.

Sulfuric acid was added to the obtained copolymer latex to coagulate, washed with water and dried to obtain a graft copolymer (A-).

Graft Copolymer (A-) Using the polymerization method of the graft copolymer A-, an N-phenylmaleimide-containing graft copolymer A-was obtained with the following monomer composition. (A-) initial component: 40 parts by weight of polybutadiene latex solid content, N-phenylmaleimide 1.7
Parts by weight, 13.3 parts by weight of styrene, acrylonitrile 5
Parts by weight. Increment component: N-phenylmaleimide 3.3 parts by weight, styrene 26.7 parts by weight, acrylonitrile 10
Parts by weight.

Copolymer (a-) In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, 250 parts by weight of deionized water, 3.0 parts by weight of potassium rosinate, 75 parts by weight of styrene, 25 parts by weight of acrylonitrile. Parts and 0.1 parts by weight of t-dodecyl mercaptan, then 0.05 parts by weight of sodium ethylenediaminetetraacetate, 0.002 parts by weight of ferrous sulfate heptahydrate and 0.1 parts by weight of sodium formaldehyde sulfoxylate. Was added to a solution dissolved in 8 parts by weight of ion-exchanged water. Then, 0.1 part by weight of diisopropylbenzene hydroperoxide was added to initiate polymerization, and the polymerization was completed for about 1 hour to complete the reaction.

Sulfuric acid was added to the obtained copolymer latex to coagulate it, followed by washing with water and drying to obtain a copolymer a-. The polymerization method of the typical copolymers of the copolymers a- to is shown below.

Maleimide Monomer Copolymer (a-) In a glass flask having an internal volume of 7 liter equipped with a stirrer, 100 parts by weight of deionized water, 0.5 parts by weight of sodium dodecylbenzenesulfonate, potassium hydroxide were added. 0.0
1 part by weight was added, and the temperature was raised to 40 ° C. with stirring.

100 parts by weight of deionized water, 1 part by weight of sodium dodecylbenzenesulfonate, 0.02 part by weight of potassium hydroxide, 0.1 part by weight of t-dodecyl mercaptan, 0.2 part of diisopropylbenzene hydroperoxide.
By weight, a mixture of increment polymerization components consisting of 27 parts by weight of N-phenylmaleimide, 55 parts by weight of styrene and 18 parts by weight of acrylonitrile was continuously added to the flask over 3 hours, and the reaction was continued.

While adding the increment component, 0.1 part by weight of sodium ethylenediaminetetraacetate, sulfuric acid first
Simultaneous addition of 0.003 parts by weight of iron heptahydrate, 0.2 parts by weight of sodium formaldehyde sulfoxylate dihydrate and 15 parts by weight of ion-exchanged water, and 0.1 parts by weight of diisopropylbenzene hydroperoxide. did.

After completion of the addition, the reaction was continued for 1 hour with further stirring, and then 0.2 part by weight of 2,2-methylene-bis- (4-ethylene-6-t-butylphenol) was added to give a reaction product. It was taken out of the flask.

Then, the product was coagulated with 2 parts by weight of potassium chloride, dehydrated, washed with water and dried to obtain a powdery copolymer a-.

Epoxy group-containing copolymer (a-) Epoxy group-containing copolymers a- and ′ were obtained with the following monomer composition by the method of polymerizing the copolymer a-. a-; 12 parts by weight of glycidyl methacrylate, 63 parts by weight of styrene, and 25 parts by weight of acrylonitrile. a- ': 65 parts by weight of glycidyl methacrylate, 25 parts by weight of styrene, 10 parts by weight of acrylonitrile.

Using the method of polymerizing the amide group / hydroxyl group-containing copolymer copolymer a-, hydroxyl group-containing copolymers a- and a-'were obtained with the following monomer compositions. a-; 2-hydroxyethyl methacrylate 15 parts by weight, styrene 60 parts by weight, acrylonitrile 20 parts by weight, acryloamide 5 parts by weight. a- '; 60 parts by weight of 2-hydroxyethyl methacrylate, 20 parts by weight of styrene, 15 parts by weight of acrylonitrile, 5 parts by weight of acryloamide.

A hydroxyl group-containing copolymer a-was obtained with the following monomer composition by the method of polymerizing the methacrylic acid copolymer copolymer a-. a-: 10 parts by weight of methacrylic acid, 65 parts by weight of styrene, 25 parts by weight of acrylonitrile.

A hydroxyl group / maleimide-containing copolymer a-was obtained with the following monomer composition by the method of polymerizing a hydroxyl group / maleimide copolymer copolymer a-. a-; 2-hydroxyethyl methacrylate 10 parts by weight, N-phenylmaleimide 25 parts by weight, styrene 55
Parts by weight, 10 parts by weight of acrylonitrile.

Amide group / maleimide copolymer In the same manner as in copolymer a-, the following monomer composition was used:
An amide group- and maleimide-containing copolymer a- was obtained. a-; 5 parts by weight of acrylamide, 25 parts by weight of N-phenylmaleimide, 55 parts by weight of styrene, 15 parts by weight of acrylonitrile.

The monomer composition of the component (A) is shown in Table 1.
The numbers in the table are parts by weight. Component (B): Phenolic resin (Gunei Chemical Industry Co., Ltd.,
(PSM-4307, softening point 122 ° C.) (C) component: trixylenyl phosphate (Dahachi Chemical Industry Co., Ltd.) (D) component: Melamine (Nissan Chemical Co., Ltd.) (E) component: Epoxy resin (Toto Kasei YD- 927H /
Epoxy equivalent 2091 (g / eq), softening point 127 ° C)

[Table 1]

The above compounds were blended in the proportions shown in Table 2 to prepare a twin-screw extruder (PCM-4 manufactured by Ikegai Tekko Co., Ltd.).
5. Cylinder temperature: 240 ° C.) to pelletize. Then, a test piece was formed by a molding machine at a cylinder temperature of 240 ° C. The results of measuring the flame retardancy of the blend using this sample are shown in Table 2. The numbers in the table are
Parts by weight.

[Table 2]

The evaluation method is as follows. 1. Flame-retardant measurement method Flame-retardant measurement was performed based on the vertical test method of UL-94 standard. NC indicates non-standard. Specimen dimensions; 1/16 "× 1/2" × 5 "2. heat resistance (thermal deformation ^{temperature) ASTM D648 (18.6Kg / cm 2} ) specimen dimensions; 1/2" × 1/2 " × 5 ″ 3. Impact resistance (Izod impact strength) ASTM D256 (1/4 ", 23 ° C, notched)

As is clear from Table 2, the flame-retardant resin compositions of Examples 1 to 7 of the present invention have a flame retardancy of V-0, and therefore do not have dripping and are also flame-retardant. Excellent and what is the object of the present invention has been obtained. On the other hand, the compositions of Comparative Examples 1 to 4 have flame retardance outside the scope of the present invention, which does not have either the N-substituted maleimide-based monomer or the functional group monomer in the component A. Since it is a resin composition, the desired flame retardancy or original characteristics of the resin are not obtained.

[0065]

INDUSTRIAL APPLICABILITY The resin composition of the present invention improves heat resistance without lowering impact resistance, prevents dripping (melt dripping) during combustion, and has excellent flame retardancy. is there. In addition, it is unlikely that harmful substances such as dioxins will be generated during molding and combustion, and also has high-level impact resistance and heat resistance at a practical level.

Therefore, it is possible to mold large moldings and complicated moldings such as office equipment such as office automation equipment and electric equipment, and it is a material excellent in practical use, has an extremely large industrial value, and is extremely useful in industry. is there.

Front page continuation (72) Inventor Seiichi Gomori 2-11-24 Tsukiji, Chuo-ku, Tokyo Within Japan Synthetic Rubber Co., Ltd. (56) References JP-A-4-45143 (JP, A) (58) Field (Int.Cl. ⁷ , DB name) C08L 1/00-101/16

Claims (2)

(57) [Claims] 1. A component (A) containing at least one functional group selected from an epoxy group, a hydroxyl group, a carboxyl group, and an amide group, and N
-(B) component phenol resin 1 to 50 parts by weight, (C) component phosphorus-containing compound 1 to 50 parts by weight, and (D) component nitrogen-containing compound 0 to 100 parts by weight of the styrene-based resin having a substituted maleimide unit. A flame-retardant resin composition comprising 30 parts by weight and 0 to 30 parts by weight of the functional group-containing oligomeric polymer (E). 2. The styrene resin (A-1) 5 to 95, wherein the component (A) in claim 1 has an N-substituted maleimide unit.
The flame-retardant resin composition according to claim 1, which comprises 95 to 5% by weight of a styrene resin (A-2) having at least one functional group selected from an epoxy group, a hydroxyl group, a carboxyl group, and an amide group.