JPH0790157A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To provide the title composition excellent in impact resistance, heat resistance and self-extinguishing properties. CONSTITUTION:The title composition comprises 100 pts.wt. composition comprising 10-100 pts.wt. maleic anhydride/styrene copolymer and/or syndiotactic polystyrene and/or alpha-methylstyrene-containing (rubber-reinforced) resin and 0-90wt.% styrene resin, 1-50 pts.wt. phosphorus-containing compound, 0-30 pts.wt. nitrogenous compound and 0-30 pts.wt. compatibilizer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a halogen-free flame-retardant resin composition having excellent heat resistance, self-extinguishing property and moldability (impact resistance).

[0002]

2. Description of the Related Art Conventionally, a thermoplastic resin imparted with impact resistance by a rubber-like polymer is well known as a resin generally referred to as ABS resin, but it has flame retardancy depending on its use. Is a necessary condition. 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. A
A known method for making rubber-reinforced thermoplastic resins such as BS resin flame-retardant consists of blending a flame retardant. In many cases, such a flame retardant is a brominated diphenyl oxide compound or bromine. A halogen-containing compound such as a modified polycarbonate compound. These flame retardants show an excellent flame retarding effect when blended with antimony trioxide. However, when the above halogen-containing compound is added to the resin composition, harmful substances are generated during molding and burning. However, the generation of dioxins and furans, which are extremely poisonous to the human body, has become a serious problem.

As a method for eliminating such drawbacks, a compound containing phosphorus and / or nitrogen instead of a halogen-containing compound is added to a rubber-reinforced thermoplastic resin such as ABS resin. Proposed. However, these compounds are inferior to halogen-containing compounds in terms of flame retardancy. In particular, the flame retarding effect on styrene-based rubber-reinforced thermoplastic resins such as ABS resin is low, and when such a resin is used,
A large amount of a compound containing phosphorus and / or nitrogen must be added, in which case the physical properties such as impact resistance and heat resistance of the resin composition are significantly impaired. Therefore, it has been desired to develop a resin composition that exhibits excellent flame retardancy without deteriorating the original properties such as impact resistance and heat resistance of the composition.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and provides a flame-retardant resin composition excellent in heat resistance, self-extinguishing property, moldability and impact resistance. The purpose is to provide.

[0005]

The present invention provides the following (A).
To 100 parts by weight of a composition consisting of 10 to 100% by weight of component and 0 to 90% by weight of component (B),
50 parts by weight, component (D) 1 to 50 parts by weight, component (E) 0
A flame-retardant resin composition containing 30 to 30 parts by weight and (F) component 0 to 30 parts by weight. Component (A): Maleic anhydride-styrene copolymer and / or syndiotactic polystyrene and / or α-methylstyrene-containing resin. Component (B): Styrene resin other than component (A). Component (C): Thermosetting resin. Component (D): phosphorus-containing compound. Component (E): nitrogen-containing compound. (F) component: Compatibilizer. And (A) component and / or (B) of claim 1.
A composition containing 100 parts by weight of a composition containing 0.1 to 50% by weight of a monomer having an epoxy group and / or a hydroxy group and / or a carboxy group and / or an amide group as a functional group. The flame-retardant resin composition of Hereinafter, the present invention will be described in detail.

The component (A) of the present invention will be described.
The component (A) is a maleic anhydride-styrene copolymer obtained by polymerizing a monomer in the presence or absence of a rubbery polymer and / or syndiotactic polystyrene and / or α-methylstyrene. It is a contained resin. The maleic anhydride-styrene copolymer is a copolymer of maleic anhydride and styrene, and can optionally be copolymerized with other copolymerizable monomers. As the copolymerizable monomer, vinyl cyanide such as acrylonitrile,
(Meth) acrylic acid and its derivatives, and aromatic vinyl compounds such as paramethylstyrene. The copolymer composition is preferably 1 to 90% by weight of maleic anhydride, further 10 to 99% by weight of styrene and 0 to 60 of other monomers.
% By weight.

Syndiotactic polystyrene is a styrene polymer having a syndiotactic structure.
The syndiotactic structure here means that the stereochemical structure is mainly a syndiotactic structure, that is, a phenyl group or a substituted phenyl group, which is a side chain with respect to a main chain formed from a carbon-carbon bond, alternates in opposite directions. It has a steric structure located, and its tacticity is quantified by a nuclear magnetic resonance method ( ¹³ C-NMR method) using isotope carbon. ^The tacticity measured by the ¹³ C-NMR method is the proportion of a plurality of continuous constitutional units, for example, diad in the case of 2 and triad in the case of 3.
Although it can be represented by a pentad, the syndiotactic polystyrene is usually 75% or more, preferably 85% or more in a diad, or 36% or more in a pentad (racemic pentad), preferably 50% or more.
% Or more of syndiotacticity polystyrene, poly (alkoxystyrene), poly (halogenated styrene), poly (alkoxystyrene), poly (vinylbenzoic acid ester) and mixtures thereof, or containing them as the main components This refers to a copolymer.

Here, as the poly (alkylstyrene), there are poly (methylstyrene), poly (ethylstyrene), poly (isopropylstyrene), poly (tertiarybutylstyrene), etc., and poly (halogenated styrene) Examples include poly (chlorostyrene), poly (bromostyrene), poly (fluorostyrene), and the like. Examples of poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene). Among these, particularly preferred styrene-based polymers include polystyrene, poly (m-methylstyrene),
Poly (p-tertiary butyl styrene), Poly (p-
Examples thereof include chlorostyrene), poly (m-chlorostyrene), poly (p-fluorostyrene), and a copolymer of styrene and p-methylstyrene.

The syndiotactic polystyrene used in the present invention is not limited in its molecular weight, but preferably has a weight average molecular weight of 10,000 or more, and most preferably 50,000 or more. Here, if the weight average molecular weight is less than 10,000, the heat resistance and mechanical strength of this product are not sufficient, and sufficient improvement is not observed even after compounding. Further, the molecular weight distribution is not limited in width and width, and various kinds can be applied.

The α-methylstyrene-containing resin is a copolymer obtained by copolymerizing α-methylstyrene with another monomer, and if necessary, α-methylstyrene or the like may be added in the presence of a rubbery polymer. A rubber-reinforced material is also included by being polymerized. As the rubber-like polymer used for rubber reinforcement, polybutadiene, butadiene-styrene copolymer,
Polyisoprene, butadiene-acrylonitrile copolymer, ethylene-propylene- (non-conjugated diene) copolymer, isobutylene-isobrene copolymer, acrylic rubber, styrene-butadiene-styrene block copolymer, styrene-butadiene-styrene radialtere Block copolymers, styrene-isoprene-styrene block copolymers, hydrogenated diene (block, random, and homo) polymers such as SEBS, polyurethane rubber, acrylic rubber, silicone rubber, ethylene-butene-1- (non- Examples thereof include conjugated diene) copolymers. Among these, polybutadiene, butadiene-styrene copolymer, ethylene-propylene- (non-conjugated diene) copolymer, hydrogenated diene polymer and silicone rubber are preferable.

As the aromatic vinyl compound used for the α-methylstyrene-containing resin, in addition to α-methylstyrene, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-hydroxystyrene, (Α-ethylstyrene, methyl-α-methylstyrene), dimethylstyrene, bromostyrene, dibromostyrene, tribromostyrene, chlorostyrene, dichlorostyrene, trichlorostyrene, sodium styrenesulfonate, and the like.

Furthermore, examples of the vinyl cyanide compound used in the α-methylstyrene-containing resin include acrylonitrile and methacrylonitrile. Of these, acrylonitrile is preferred. Other copolymerizable monomers include (meth) acrylic acid esters and maleimide compounds. The composition of the α-methylstyrene-containing resin is preferably 0 to 90% by weight of a rubbery polymer, more preferably 0 to 60% by weight, α-methylstyrene 1 to 90% by weight, and an aromatic vinyl compound 10 to 90%.
% By weight, vinyl cyanide compound 0 to 90% by weight, more preferably 2 to 60% by weight.

When a rubber-like polymer is used, the graft ratio affects the physical properties and flame retardancy of the flame-retardant resin composition. The preferable graft ratio is described below. In the case of α-methylstyrene-containing rubber-reinforced resin, the graft ratio is 5 to 150.
%, Preferably 10 to 150% by weight, more preferably 10 to 120% by weight. Graft ratio is 5% by weight
If the amount is less than the above, the effect of adding the rubber component is not sufficiently exhibited, and, for example, sufficient impact resistance cannot be obtained. On the other hand, if it exceeds 150% by weight, moldability becomes poor. Here, the graft ratio (%) was calculated by the following equation, where x is the amount of the rubber component in 1 g of the α-methylstyrene-containing rubber-reinforced resin and y is the amount of the methylethylketone-insoluble component in 1 g of the α-methylstyrene-containing rubber-reinforced resin. It is a value. Graft ratio (%) = {(y−x) / x} × 100

The intrinsic viscosity of a rubber-reinforced resin containing α-methylstyrene (measured in methyl ethyl ketone at 30 ° C.) is
0.1-1.5 dl / g, preferably 0.3-1.0 d
1 / g. When the intrinsic viscosity is less than 0.1 dl / g, the impact strength is not sufficiently expressed, while on the other hand, 1.5 dl / g
If it exceeds g, the moldability decreases. Here, the matrix resin is a resin component other than the grafted rubber component of the α-methylstyrene-containing rubber-reinforced resin, and the intrinsic viscosity is determined by the methyl ethyl ketone-soluble component of the α-methylstyrene-containing rubber-reinforced resin in a conventional manner. It is the value obtained by measuring according to.

Next, the component (B) of the present invention is a styrene resin other than the component (A), and is styrene alone, an aromatic vinyl compound (however, excluding α-methylstyrene) or another copolymerizable resin. Is a copolymer of various monomers,
It can be reinforced with rubber if necessary. Examples of the rubber-like polymer that can be used for rubber reinforcement include those mentioned above in the section for the component (A). Further, as the copolymerizable monomer, aromatic vinyl compounds such as paramethylstyrene (excluding α-methylstyrene), vinyl cyanide compounds such as acrylonitrile, (meth) acrylic acid ester, maleimide compounds And derivatives thereof. The composition of styrene resin is
Preferably rubbery polymer 0 to 90% by weight, styrene 5 to
100% by weight, more preferably 10 to 95% by weight, other aromatic vinyl compound 0 to 95% by weight, vinyl cyanide compound 0 to 95% by weight, further preferably 5 to 60% by weight, other monomer 0 ~ 80% by weight.

When a rubber-like polymer is used, the graft ratio affects the physical properties and flame retardancy of the flame-retardant resin composition. The preferable graft ratio is described below. The graft ratio of the rubber-reinforced styrene resin is 5 to 150% by weight, preferably 10 to 150% by weight, more preferably 10 to 120%.
% By weight. If the graft ratio is less than 5% by weight, the effect of adding the rubber component is not sufficiently exerted and, for example, sufficient impact resistance cannot be obtained. On the other hand, if it exceeds 150% by weight, moldability becomes poor. Here, the graft ratio (%) is x for the amount of the rubber component in 1 g of the rubber-reinforced styrene resin and y for the amount of methyl ethyl ketone insoluble matter in 1 g of the rubber-reinforced styrene resin.
Then, it is the value obtained by the following equation. Graft ratio (%) = {(y−x) / x} × 100

Intrinsic viscosity [η] of matrix resin in rubber-reinforced styrene resin (in methyl ethyl ketone, 30 ° C.)
Measured with 0.1) to 0.1-1.5 dl / g, preferably 0.
It is 3 to 1.0 dl / g. Intrinsic viscosity [η] is 0.1d
When it is less than 1 / g, impact strength is not sufficiently expressed, while when it exceeds 1.5 dl / g, moldability is deteriorated. Here, the matrix resin is a resin component other than the grafted rubber component in the rubber-reinforced styrene-based resin, and the intrinsic viscosity [η] is a rubber-reinforced styrene-based resin in which a methylethylketone-soluble component is usually used. It is the value obtained by measuring according to.

Next, the component (C) of the present invention will be described. The component (C) is a thermosetting resin, and examples thereof include novolac type phenol resin, resol type phenol resin, epoxy resin, urea resin, and melamine resin. Phenol resins are preferable, and novolac type phenol resins are particularly preferable. The novolac 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 no free methylol group. Regarding such novolac type phenolic resin, "Encyclopedia of Polymer"
r Science and Engineering
g, Vol. 11, pp, 45-95 ". Specific examples of substituted phenols include aryl-substituted phenols such as cresol, resorcinol, p-phenylphenol, and alkylated phenols such as pt-butylphenol, p-octylphenol, xylenol. In the present invention,
Preference is given to novolak type phenolic resins using phenol, cresol, resorcinol, and mixtures thereof.

Next, the component (D) in the present invention will be described. The component (D) is a phosphorus-containing compound, and examples of the phosphorus-containing compound include phosphates typified by triphenyl phosphate, phosphites typified by triphenyl phosphite, and the like. ) To (4) is a compound having at least one structural unit.

[0020]

[Chemical 1]

(In the formula, R _{1 to} R ₃ each represent a hydrocarbon residue which may be halogen-substituted, X ^{1 to} X ⁴ represent an oxygen atom or a sulfur atom, and q _{1 to} q ₃ represent 0 or 1. )

[0022]

[Chemical 2]

(In the formula, R _{1 to} R ₄ are each a hydrocarbon residue which may be substituted with halogen, R _{5 to} R ₈ are hydrogen atoms, halogen atoms or hydrocarbon residues, and X ^{1 to} X ⁶ are oxygen. Atom or sulfur atom, q _{1 to} q ₆ are 0 or 1, n
Indicates a number having a degree of polymerization of 1 to 30. )

[0024]

[Chemical 3]

(In the formula, R _{1 to} R ₅ are each a hydrocarbon residue which may be substituted with halogen, R _{6 to} R ₁₃ are hydrogen atoms, halogen atoms or hydrocarbon residues, and X ^{1 to} X ⁶ are oxygen. Atom or sulfur atom, q _{1 to} q ₇ are 0 or 1, n
Indicates a number having a degree of polymerization of 1 to 30. )

[0026]

[Chemical 4]

(Wherein R _{1 to} R ₆ are each a hydrocarbon residue which may be halogen-substituted, R _{7 to} R ₉ are hydrogen atoms, halogen atoms or hydrocarbon residues, and X ^{1 to} X ¹² are oxygen. Atom or sulfur atom, q _{1 to} q ₉ represent 0 or 1.)

These phosphorus-containing compounds may be used alone or in admixture of two or more. In the present invention, triphenyl phosphate, triphenyl thiophosphate represented by the following general formula (5), trixylenyl phosphate, trixylenyl thiophosphate, hydroquinone bis (diphenyl phosphate), resorcinol bis (diphenyl) is used as the phosphorus-containing compound. Phosphate) and the like are preferable.

[0029]

[Chemical 5]

Further, the following compounds having a phosphorus-water bond are also preferable.

[0031]

[Chemical 6]

Next, the component (E) of the present invention will be described. The component (E) is a nitrogen-containing compound, and specifically,
Triazine, triazolidine, urea melamine, guanidine, amino acids, peptides and salts or derivatives thereof. Preferred is melamine tris (hydroxyethyl) isocyanate.

The component (F) of the present invention is a compatibilizer, and specific examples thereof include polystyrene- (acrytonitrile-styrene block polymer), styrene-glycidyl methacrylate copolymer, and styrene-methacrylic acid copolymer. ,
A copolymer such as a styrene-acrylonitrile-methacrylic acid copolymer obtained by copolymerizing styrene with the above functional group-containing unsaturated compound and, if necessary, one or more vinyl monomers copolymerizable therewith is used. Can be mentioned. Further, ethylene-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate-vinyl acetate copolymer and the like,
Also included are copolymers obtained by copolymerizing ethylene with the above-mentioned functional group-containing unsaturated compound and, if necessary, one or more other vinyl monomers copolymerizable therewith. These copolymers also include those obtained by graft-reacting other polymers on these ethylene copolymers. Examples of the other polymer to be graft-reacted include radically polymerizable vinyl such as poly (meth) acrylic acid alkyl ester, polystyrene, styrene-acrylonitrile copolymer, and styrene- (meth) acrylic acid alkyl ester copolymer. The polymer polymerized using the monomer is mentioned. Specifically, it is MODIPER B-600 manufactured by NOF CORPORATION, but the present invention is not limited to the above specific examples as long as the gist thereof is not exceeded.

Next, the composition ratio of the flame-retardant resin composition according to claims 1 and 2 will be described. (A) component is 10-100
%, Preferably 30-80% by weight. When the content of the component (A) is less than 10% by weight, heat resistance is impaired.
The component (B) is 0 to 90% by weight, preferably 20 to 70% by weight. If the content of component (B) exceeds 90% by weight, heat resistance is impaired. The component (C) is 1 to 50 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the composition comprising the components (A) and (B). When the component (C) is less than 1 part by weight, a resin having sufficient flame retardancy cannot be obtained,
On the other hand, when it exceeds 50 parts by weight, heat resistance and impact resistance are impaired. The component (D) is 1 to 50 parts by weight with respect to 100 parts by weight of the composition comprising the components (A) and (B),
It is preferably 5 to 30 parts by weight. When the component (D) is less than 1 part by weight, sufficient flame retardancy cannot be obtained, and when it exceeds 50 parts by weight, heat resistance and impact resistance as a resin are impaired. The component (E) is 0 to 30 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the composition comprising the components (A) and (B). If the component (E) exceeds 30 parts by weight, the heat resistance and impact resistance of the resin will be impaired. The component (F) is 0 to 30 parts by weight, preferably 1 to 100 parts by weight of the composition comprising the components (A) and (B).
It is 0 to 20 parts by weight. When the component (F) exceeds 30 parts by weight, heat resistance, impact resistance, moldability and surface appearance are impaired.

With respect to claim 2, the component (A) and /
Alternatively, when the component (B) contains a monomer having an epoxy group and / or a hydroxy group and / or a carboxy group and / or an amide group, flame retardancy, particularly dripping resistance, is further improved. The content of the monomer containing an epoxy group and / or a hydroxy group and / or a carboxy group and / or an amide group is 0.1 to 0.1% in the composition comprising the component (A) and / or the component (B).
It is 50% by weight, preferably 0.1 to 30% by weight, particularly preferably 1 to 10% by weight.

The copolymerizable monomers having these functional groups include glycidyl methacrylate, glycidyl acrylate, 2-hydroxyethyl methacrylate and 2
-Hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, methacrylic acid, acrylic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl phthalic acid, acrylamide, methacrylamide, etc. There is.

The functional group-containing oligomeric polymer described below may be added to the flame-retardant resin composition of the present invention.
By adding these oligomeric polymers, more excellent flame retardancy can be obtained. Examples of the functional group include an amino group, an epoxy group, a hydroxyl group, an isocyanate group, a phenoxy group and an amide group. The repeating unit is preferably a 1- to 30-mer, more preferably a 3 to 25-mer. The molecular weight is preferably 5
0 to 10,000, more preferably 100 to 8,000
It is 0 (polystyrene conversion by GPC measurement).

Specific functional group-containing oligomeric polymers are listed below, but the present invention is not limited to the following specific examples as long as the gist thereof is not exceeded. 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 / phenolic resin, polyvinyl alcohol, epoxy / novolak resin and the like.
Examples of the isocyanate-containing oligomer include MDI silionate (Nippon Polyurethane Industry Co., Ltd.). Examples of the amino group-containing resin include guanamine resin and bismaleimide resin. Examples of the phenoxy resin include a bisphenol A oligomer whose terminal is sealed with a phenyl group.

The composition of the present invention is preferably used in various extruders, Banbury mixers, kneaders, rolls, etc., preferably 20
It can be obtained by kneading each component in the range of 0 to 300 ° C. When kneading, each component may be kneaded together, or after kneading any components,
It is also possible to employ a multi-stage divided kneading method in which the remaining components are added and kneaded. A preferable kneading method is a method performed by an extruder, and a twin-screw co-rotating extruder is particularly preferable as the extruder.

The addition amount is preferably 0. 0 with respect to 100 parts by weight of the composition comprising the components (A) and (B).
The amount is 1 to 40 parts by weight, more preferably 0.5 to 30 parts by weight.

The flame-retardant resin composition of the present invention contains, if necessary, antioxidants, stabilizers such as ultraviolet absorbers, silicone oil, silane coupling agents, lubricants such as low molecular weight polyethylene, calcium carbonate, talc. , Clay, titanium oxide, antimony oxide, iron oxide, copper oxide, zinc oxide, chromium oxide, zinc borate, magnesium oxide, aluminum hydroxide, magnesium hydroxide, magnesium carbonate, carbon black, barium sulfate, calcium oxide, aluminum oxide , Mica, glass beads, glass fibers, carbon fibers, aramid fibers, glass flakes, thermally expansive graphite, iron lactate, ferrocene, aluminum oxide, fillers such as metal fillers, dispersants, foaming agents, colorants, etc. are added. be able to. Of these, the shapes of the glass fiber and the carbon fiber are 6 to 60 μm and 30 μm.
Those having a fiber length of m or more are preferable. The amount of these additives added is 100 parts by weight of the composition of the present invention.
About 0.01 to 150 parts by weight is preferable.

The flame-retardant resin composition of the present invention is produced by extrusion molding,
Molded by injection molding, compression molding or other molding means, these molded products are excellent in flame retardancy, impact resistance, heat resistance and practical moldability, and have a good surface appearance. It is extremely useful as an article such as household articles, electric equipment, office automation equipment, an article such as an automobile, or a building material.

[0043]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. In the examples, parts and% are based on weight unless otherwise specified.

[Explanation of Components Used in Examples and Comparative Examples] Maleic anhydride-styrene copolymer (A-1): As maleic anhydride-styrene copolymer, Idemitsu Petrochemical's Moamax UG461 is used. I was there. Syndiotactic polystyrene (A-2): Syndiotactic polystyrene polymerizes styrene using a titanium compound and a condensation product of water and a trialkylaluminum as a catalyst in an inert hydrocarbon solvent such as toluene or in the presence of a solvent. Was used to produce syndiotactic polystyrene having a triad of 85% syndiotacticity. α-Methylstyrene-containing ABS (A-3): The composition produced in the laboratory is 15.3% butadiene rubber, 43% α-methylstyrene, 16.7% styrene, and 25% acrylonitrile.

ABS (B-1): AB produced in the laboratory
S was used. The composition is 41% butadiene rubber and 4 styrene.
4%, acrylonitrile 15%, graft ratio 5
5%, and the matrix [η] is 0.45. AS (B-2-): AS manufactured in the laboratory was used.
The composition was 71% styrene and 29% acrylonitrile, and [η] was 0.62. AS (B-2-): Modified A consisting of 60% styrene, 12% para-methylstyrene and 28% acrylonitrile
S resin was used. [Η] was 0.60 dl / g. Epoxy group-containing AS (B-3): 190 parts of ion-exchanged water, 1.5 parts of potassium laurate, styrene 7 in a reaction vessel
0 parts, acrylonitrile 25 parts, and glycidyl methacrylate 5 parts were added, and the reaction system was heated to 40 ° C., after which ethylenediaminetetraacetic acid sodium 0.067 parts, ferrous sulfate 7
A solution prepared by dissolving 0.002 parts of a hydrate and 0.13 part of sodium aldehyde sulfoxylate in 15 parts of ion-exchanged water and 0.1 part of diisopropylbenzene peroxide and polymerized were used. Hydroxy group-containing AS (B-4): A hydroxy group-containing AS produced in the laboratory was used. The production was performed by a method similar to (B-3). Composition is styrene 67%, acrylonitrile 23%, 2-hydroxyethyl methacrylate 1
It is 0%. The intrinsic viscosity was 0.48 (in methyl ethyl ketone, 30 ° C.). Carboxy group-containing AS (B-5): A carboxy group-containing AS manufactured in the laboratory was used. The production was performed by a method similar to (B-3). The composition is styrene 47%, α-methylstyrene 25%, acrylonitrile 18%, and methacrylic acid 10%.

Novolak resin (C-1): Novolak resin PSM-4307 manufactured by Gunei Chemical Co., Ltd. was used. Phosphorus-containing compound (D-1): Triphenyl phosphate manufactured by Daihachi Chemical Co., Ltd. was used. Nitrogen-containing compound (E-1): THEIC manufactured by Nissan Kagaku was used. Compatibilizer (F-1): Polystyrene-AS manufactured by NOF CORPORATION
Copolymer Modiper B-600 was used. The composition is 70% polystyrene and 30% AS, and the composition of AS is 70% styrene and 30 acrylonitrile.
%. MDI silionate manufactured by Nippon Polyurethane Industry Co., Ltd. was used as the functional group-containing oligomeric polymer.

Next, the production and evaluation of the flame-retardant resin composition will be described. The test pieces were produced by blending the components shown in Table 1 with a Henschel mixer, melt-kneading the mixture with an extruder having an inner diameter of 50 mm at a temperature in the range of 200 to 240 ° C., and then producing the pellets at 50 z. Molding was performed at a molding temperature of 180 to 240 ° C. using an injection molding machine. The evaluation of physical properties is as follows. Combustion test: Conforms to UL-94 (V-test). Test pieces:
1/16 "x 1/2" x 5 ". Impact resistance test: Izod impact strength, ASTM D256
(1/4 ", 23 ° C, with notch). Heat distortion temperature: ASTM D648. Molding workability: Judged by ease of molding during molding.

[Examples 1 to 7, Comparative Examples 1 to 4] Example 1
.About.7 and Comparative Examples 1 to 4 are shown in Table 1. Example 1
Nos. 7 to 7 are compositions within the scope of the present invention, and the effects intended by the present invention are obtained. On the other hand, Comparative Example 1 does not contain the component (A) of the present invention and is inferior in heat resistance. Also,
Comparative Example 2 does not contain the novolac resin, which is an essential component of the present invention, and is inferior in flame retardancy. In Comparative Examples 3 and 4, the addition amount of the novolac resin or the phosphorus-containing compound exceeds the upper limit of the range of the present invention, and the impact resistance and heat resistance of the resin are poor.

[0049]

[Table 1]

[0050]

According to the flame retardant resin composition of the present invention, excellent flame retardancy can be obtained without using a halogen-containing compound as a flame retardant. Moreover, it is unlikely that harmful substances such as dioxins will be generated during molding and combustion, and also has high level of impact resistance and heat resistance at a practical level.

Front page continuation (72) Inventor Yoichi Kamoshida 2-11-24 Tsukiji, Chuo-ku, Tokyo Inside Nippon Synthetic Rubber Co., Ltd.

Claims (2)

[Claims] 1. 1 to 50 parts by weight of (C) component and (D) component to 100 parts by weight of a composition comprising 10 to 100% by weight of the following component (A) and 0 to 90% by weight of (B) component. 1
˜50 parts by weight, component (E) 0 to 30 parts by weight, and component (F) 0 to 30 parts by weight, a flame-retardant resin composition. Component (A): Maleic anhydride-styrene copolymer and / or syndiotactic polystyrene and / or α-methylstyrene-containing resin. Component (B): Styrene resin other than component (A). Component (C): Thermosetting resin. Component (D): phosphorus-containing compound. Component (E): nitrogen-containing compound. (F) component: Compatibilizer. 2. At least one selected from an epoxy group, a hydroxy group, a carboxy group and an amide group as a functional group in 100 parts by weight of the composition comprising the component (A) and / or the component (B) of claim 1. Monomer containing seed 0.1
The flame-retardant resin composition according to claim 1, which comprises -50% by weight.