JPH06271740A - Flame-retardant resin composition - Google Patents

Abstract

(57) [Summary] [Purpose] To provide a flame-retardant resin composition having excellent self-extinguishing property and being friendly to the global environment. [Structure] Phenolic resin 0.5 to 50 parts by weight and flame retardant 0.1 to 100 parts by weight of a specific rubber-reinforced resin.
5 to 95% by weight of a composition containing 30 to 30 parts by weight,
A flame-retardant resin composition containing 95 to 5% by weight of another resin material as a main component.

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 having excellent self-extinguishing property and being friendly to the global environment.

[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 included. When these flame retardants are blended with antimony trioxide, they exhibit an excellent flame retarding effect. However, when the above halogen-containing compound is added to the resin composition, harmful substances are generated during molding and burning. In particular, the generation of dioxins and furans, which are extremely toxic to the human body, has become a major problem.

As a method for eliminating such defects, it has been proposed to add a compound containing phosphorus and / or nitrogen, etc., to the thermoplastic resin, instead of the halogen-containing compound. However, these compounds are inferior to halogen-containing compounds in terms of flame retardancy. Therefore, in order to achieve a high level of flame retardancy, it is necessary to add a large amount of these compounds, in which case the physical properties such as impact resistance and heat resistance of the resin composition are significantly impaired.

[0004]

The present invention has been made against the background of the above-mentioned problems of the prior art. A resin composition obtained by adding a phenol resin and a flame retardant to a specific resin is added to another resin material. Flame retardant resin composition that achieves a high level of flame retardancy with a low halogen content and reduces the generation of harmful compounds such as dioxins and furans without compromising the original characteristics of other resin materials. Or a flame-retardant resin composition that achieves a high flame-retardant level with a phosphorus-based flame retardant without using a halogen-based flame retardant,
The purpose is to provide.

[0005]

The present invention provides the following (A).
5 to 95% by weight of a composition (E) containing 0.5 to 50 parts by weight of the component (B) and 0.1 to 30 parts by weight of the component (C) with respect to 100 parts by weight of the component, and (D) The flame-retardant resin composition is characterized by containing 95 to 5% by weight of the component (however, (E) + (D) = 100% by weight) as a main component. Component (A): 0 to 100% by weight of the following rubber-reinforced resin (A-1) and 100 to 0% by weight of the following copolymer (A-2).
[However, (A-1) + (A-2) = 100% by weight], and the intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the matrix resin in the component (A) is 0.1. A copolymer composition of about 1.5 dl / g. Rubber-reinforced resin (A-1); rubber-like polymer (a) 5 to 70
95% by weight of at least one monomer component (b) selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid esters, maleic anhydride and maleimide compounds in the presence of wt%. 30% by weight
(A) + (b) = 100% by weight], and a rubber-reinforced resin having a graft ratio of 5 to 150% by weight. Copolymer (A-2); at least one monomer component selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid esters, maleic anhydride and maleimide compounds is polymerized. The copolymer obtained as a result. (B) component; phenolic resin (C) component; flame retardant (D) component; other resin material

The component (A) used in the present invention is a composition containing a rubber-reinforced resin (A-1) and / or a copolymer (A-2). The component (A-1) is 5 to 70% by weight of the rubber-like polymer (a), preferably 12 to 6
At least one selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid esters, maleic anhydride and maleimide compounds in the presence of 0% by weight, more preferably 15 to 50% by weight. Monomer component (b) of 95 to 30% by weight, preferably 88 to 40% by weight, more preferably 85 to 50% by weight [however,
(A) + (b) = 100% by weight] is a rubber-reinforced resin obtained by polymerization. The component (A-2) is a copolymer obtained by polymerizing the monomer component (b).

Examples of the rubbery polymer (a) include polybutadiene, butadiene-styrene copolymer, polyisoprene, butadiene-acrylonitrile copolymer, ethylene-propylene- (non-conjugated diene) copolymer, isobutylene-isoprene copolymer. Polymer, acrylic rubber, styrene-
Butadiene-styrene block copolymer, styrene-butadiene-styrene radial teleblock copolymer, styrene-isoprene-styrene block copolymer, SE
Hydrogenated diene-based (block, random, and homo) polymers such as BS, polyurethane rubber, acrylic rubber,
Examples include silicone rubber. Among these, polybutadiene, butadiene-styrene copolymer, ethylene-propylene- (non-conjugated diene) copolymer, hydrogenated diene polymer and silicone rubber are preferable.

Further, as the aromatic vinyl compound,
Styrene, α-methylstyrene, o-methylstyrene,
m-methylstyrene, p-methylstyrene, p-hydroxystyrene, α-ethylstyrene, methyl-α-methylstyrene, dimethylstyrene, bromostyrene, dibromostyrene, tribromostyrene, chlorostyrene,
Examples thereof include dichlorostyrene, trichlorostyrene, sodium styrenesulfonate and the like. Among these,
Styrene, p-methylstyrene and α-methylstyrene are preferred.

Further, examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. Of these, acrylonitrile is preferred. Furthermore, examples of the (meth) acrylic acid ester include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like. Among these,
Methyl methacrylate and butyl acrylate are preferred.

Further, as the maleimide compound, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-phenylmaleimide, -(2-
Methylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (4-carboxyphenyl) maleimide, N- (4-hydroxyphenyl) maleimide, N- (4-bromophenyl) maleimide, tribromophenyl Maleimide, N- (4-chlorophenyl) maleimide and the like can be mentioned. Among these, N
-Phenylmaleimide, N-cyclohexylmaleimide and N- (4-hydroxyphenyl) maleimide, and tribromophenylmaleimide are preferred.

The rubber-reinforced resin (A-1) is used for obtaining a flame-retardant resin composition which requires impact resistance, but the rubber-like polymer (a) in the component (A-1) is used. If the content of) is less than 5% by weight, the impact resistance is insufficient, while
If it exceeds 0% by weight, the graft ratio, the surface gloss of the resin and the moldability will be deteriorated. The graft ratio of the rubber-reinforced resin (A-1) is 5 to 150% by weight, preferably 10 to 150.
%, 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 exhibited, and, for example, sufficient impact resistance cannot be obtained.
On the other hand, when it exceeds 150% by weight, dripping (melt dropping) during flame retardation is likely to occur. Here, the graft ratio (%) is the amount of the rubber component in 1 g of the component (A-1), x,
When the amount of methyl ethyl ketone insoluble matter in 1 g of the component (A-1) is y, it is a value obtained by the following equation. Graft ratio (%) = {(y−x) / x} × 100

The intrinsic viscosity [η] of the matrix resin in the component (A) (measured in methyl ethyl ketone at 30 ° C.) is
0.1-1.5 dl / g, preferably 0.3-1.0 d
1 / g. If the intrinsic viscosity [η] is less than 0.1 dl / g, the impact strength will not be sufficiently expressed, while 1.5 dl
If it exceeds / g, the moldability will decrease. Here, the matrix resin is a resin component other than the grafted rubber component in the component (A), and the intrinsic viscosity [η] is
Among the components (A), it is a value obtained by measuring the dissolved amount of methyl ethyl ketone according to a conventional method.

The component (A) is the rubber-reinforced resin (A-
1) and / or a copolymer (A-2), and a rubber-reinforced resin (A-1) and a copolymer (A-).
2) can be used alone. Further, when the rubber-reinforced resin (A-1) and the copolymer (A-2) are mixed and used, the content ratio of the rubber-reinforced resin (A-1) is 0.
To 100% by weight, preferably 0 to 95% by weight, more preferably 40 to 80% by weight, particularly preferably 45 to 70% by weight.
% By weight, and the copolymer (A-2) is 100 to 0% by weight, preferably 100 to 5% by weight, and more preferably 6%.
0 to 20% by weight, particularly preferably 55 to 30% by weight (however, (A-1) + (A-2) = 100% by weight). Within the above range, it is possible to obtain a flame-retardant resin composition having further excellent impact resistance and molding processability.

The rubber-reinforced resin (A-1) is obtained by polymerizing the monomer component (b) in the presence of the rubber-like polymer (a), for example, in the presence of the rubber-like polymer (a). , Part of the monomer component (b) is polymerized, and the remaining monomer component (b) is separately polymerized,
It can be obtained by a production method such as a graft blending method in which these are blended. Further, the above copolymer (A-
2) is the rubber-like polymer (a) in the above method or
Is obtained by using a manufacturing method which does not use. A typical composition of the component (A) may be a rubber-reinforced resin composition composed of an ABS resin and styrene and an acrylonitrile copolymer (AS resin), and the preferable composition of each component is as follows. 5 to 70% by weight, the latter 95 to
It is 30% by weight.

Next, the component (B) of the present invention is a phenolic resin. Examples of the phenolic resin include novolac type phenolic resin and resol type phenolic resin. Among these, the novolac type phenolic 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 the substituted phenols include cresol, resorcinol, aryl-substituted phenols such as p-phenylphenol, and pt-butylphenol, p-phenylphenol.
-Alkylated phenols such as octylphenol, xylenol and the like. In the present invention, a novolac type phenol resin using phenol, cresol, resorcinol and a mixture thereof is preferable.

The resol type phenolic resin is a polymer having a relatively low molecular weight obtained by condensing substituted or unsubstituted phenols with formaldehyde and having 3 to 20% by weight of 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.

The content of the phenolic resin (B) is
0.5 to 50 parts by weight based on 100 parts by weight of the component (A),
Preferably 5 to 45 parts by weight, more preferably 8 to 40
Parts by weight, particularly preferably 9 to 35 parts by weight. If the amount of the phenolic resin (B) is less than 0.5 parts by weight, sufficient flame retardancy cannot be obtained, while if it exceeds 50 parts by weight, impact resistance and molding appearance as a resin are impaired.

As the flame retardant (C), those used as flame retardants for polymers such as general rubbers and resins can be used. Examples thereof include halogen-containing compounds and phosphorus-containing compounds. Examples thereof include compounds, nitrogen-containing compounds, silicon-containing compounds, antimony-containing compounds and the like.

Specific examples of the halogen-containing compound include tetrabromobisphenol A, tetrabromobisphenol A-bis (2-hydroxyethyl ether) and tetrabromobisphenol A-bis (2,3-).
Tetrabromobisphenol A derivative such as dibromopropyl ether), hexabromodiphenyl ether,
Octabromodiphenyl ether, decabromodiphenyl ether, bis (tribromophenoxy) ethane, hexabromocyclododecane and the like can be mentioned.

Further, it is selected by polymerizing monobromophenol, tribromophenol, pentabromophenol, tribromocresol, dibromopropylphenol, tetrabromobisphenol S, cyanuric chloride or the like, or selected from the group of the above halogen compounds. Oligomer type halogen compounds obtained by copolymerizing with at least one kind of halogen compound are also included.

Further, there may be mentioned a polycarbonate oligomer of tetrabromobisphenol A, a polycarbonate oligomer of tetrabromobisphenol A and bisphenol A, a polycarbonate oligomer of tetrabromobisphenol S, a polycarbonate oligomer of tetrabromobisphenol S and bisphenol S, and the like.

Further, halogenated epoxy oligomers represented by the following general formula (I) are also included.

[0023]

[Chemical 1]

[In the general formula (I), m is an average degree of polymerization represented by an integer of 1 to 100, X's independently represent a hydrogen atom, a chlorine atom or a bromine atom, and i, j, k And p are each an integer of 1 to 4, R and R'are the same or different and each is a hydrogen atom or a group represented by the following general formula (II) or (III). ]

[0025]

[Chemical 2]

[0026]

[Chemical 3]

(Here, Y represents a bromine atom or a chlorine atom, and q is an integer of 0 to 5.) Examples of the phosphorus-containing compound include organic phosphorus-containing compounds, red phosphorus, phosphazene-based compounds, and polyphosphoric acid. Examples thereof include ammonium. Among these, examples of the organic phosphorus-containing compound include phosphates typified by triphenyl phosphate, phosphites typified by triphenyl phosphite, and the like. For example, the following general formula (IV)
It is a compound having at least one structural unit represented by (VII).

[0028]

[Chemical 4]

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

[0030]

[Chemical 5]

(Where R₁~ R_FourIs a halogen storage
Optionally substituted hydrocarbon residue, R _Five~ R₈Is hydrogen
Child, halogen atom or hydrocarbon residue, X¹~ X⁸Is acid
Elementary atom or sulfur atom, q₁~ Q₆Is 0 or 1, n
Indicates a number having a degree of polymerization of 1 to 30. )

[0032]

[Chemical 6]

(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 ⁸ 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. )

[0034]

[Chemical 7]

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

[0037]

[Chemical 8]

[0038]

[Chemical 9]

Examples of the nitrogen-containing compound include melamine and its derivatives. Further, examples of the above-mentioned silicon-containing compound include general organosiloxanes, and specific examples thereof include silicone oil and silicone resin. Also, aluminum silicate,
Also included are sodium silicate, silicon dioxide and the like. Further, examples of the antimony-containing compound include antimony trioxide, antimony tetraoxide, (colloidal) antimony pentoxide, sodium antimonate, and antimony phosphate. Among them, antimony trioxide is preferable. These flame retardants (B) may be used alone or in 2
Combinations of more than one species can be used.

The flame retardant (C) is a bromine-containing compound,
Chlorine-containing compounds, phosphorus- and / or nitrogen-containing compounds are preferable, and phosphorus- and / or nitrogen-containing compounds are preferable because they do not generate toxic gases such as dioxins. Particularly, triphenyl phosphate and triphenyl thiophosphate are typical. Preferred are phosphates, hydroquinone bis (diphenyl phosphate), phosphate oligomers typified by hydroquinone bis (dicresyl phosphate), ammonium polyphosphate, red phosphorus, and melamine.

The feature of the present invention is that the use of the component (B) improves the flame retardancy of the composition, achieves a high flame retardance level with a low halogen content, and produces harmful compounds such as dioxins and furans. And further (B)
It is because of the synergistic action of the components and the phosphorus-based flame retardant, that a high flame retardation level is achieved without using a halogen-based flame retardant. That is, according to the present invention, it is possible to obtain a resin composition to which the above-mentioned high level of flame retardancy is imparted, without impairing the original performance and characteristics of the other resin material (D) component.

The content of the flame retardant (C) is 10 parts of the component (A).
0.1 to 30 parts by weight, preferably 0.
5 to 30 parts by weight, more preferably 3 to 30 parts by weight, and particularly preferably 5 to 25 parts by weight. Flame retardant (C)
If it is less than 0.1 part by weight, a resin having sufficient flame retardancy cannot be obtained, while if it exceeds 30 parts by weight, the impact resistance and molding appearance of the resin are impaired.

Other resin materials which are the component (D) of the present invention include polycarbonate, polyamide such as nylon 6, polyester such as polybutylene terephthalate (PBT) and polyethylene terephthalate (PET), polyphenylene sulfide (PPS), polyphenylene. Polyacetals such as oxide (PPO) and polyoxymethylene (POM), polyether ester amide, polyether imide, polyimide, polyether ether ketone (PEEK), polyarylate, polymethyl methacrylate, silicone resin, vinyl chloride resin (PVC) )
And at least one polymer selected from the group consisting of chlorine-based polymers, fluorine-based polymers, epoxy resins, polyurethanes, unsaturated polyesters, and thermoplastic elastomers. Among these are polycarbonate, polyamide, PBT, PET, PPS and PPO.
At least one polymer selected from the group of is preferable.

The blending ratio of the other resin material (D) is 5 to 95% by weight, preferably 30 to 90% by weight, more preferably 30 to 90% by weight of the composition (E) comprising the components (A) to (C) of the present invention. 40-80% by weight, other resin material (D) 95-5% by weight, preferably 70-10% by weight, more preferably 6
It is 0 to 20% by weight. When the content of the component (D) is less than 5% by weight, the original characteristics of the other resin material (D) such as impact resistance, heat resistance and chemical resistance are impaired. On the other hand, when the content of the other resin material (D) exceeds 95% by weight, sufficient flame retardancy cannot be obtained due to the flame retarding effect of the composition (E) including the components (A) to (C).

In the production of the mixture of the composition (E) and the other resin material (D), the impact resistance and the impact resistance are improved by using a compatibilizing agent in order to improve the compatibility between the polymers. The surface appearance of the molded product can be improved.
As the compatibilizing method, a functional group-containing unsaturated compound having at least one functional group selected from the group consisting of an acid anhydride group, a hydroxyl group, an amino group, an epoxy group, an oxazoline group, and an imide group during kneading, And a method of allowing a peroxide to be present if necessary, a method of using another polymer having the above functional group, and the like. The polymer having the functional group is a random, block or graft copolymer of the unsaturated compound having the functional group and another vinyl monomer copolymerizable therewith.

Specific examples of the compatibilizer include styrene-glycidyl methacrylate copolymer, styrene-maleic anhydride copolymer, styrene-methacrylic acid copolymer, styrene-acrylonitrile-methacrylic acid copolymer and the like. And a copolymer obtained by copolymerizing the above-mentioned functional group-containing unsaturated compound and, if necessary, one or more vinyl monomers copolymerizable therewith. In addition, ethylene-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate-vinyl acetate copolymer and the like, ethylene and the functional group-containing unsaturated compound and other vinyl monomers copolymerizable therewith as necessary. A copolymer obtained by copolymerizing with one or more kinds may also be mentioned. These copolymers also include those obtained by graft-reacting other polymers on these ethylene copolymers. Other polymers to be graft-reacted include, for example, radically polymerizable vinyl monomers 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 body is mentioned.

In the flame-retardant resin composition of the present invention, if necessary, antioxidants, stabilizers such as ultraviolet absorbers, silicone oil, lubricants such as low molecular weight polyethylene, calcium carbonate, talc, clay, Titanium oxide, antimony oxide, iron oxide, copper oxide, zinc oxide, zinc borate, magnesium oxide, aluminum hydroxide, magnesium hydroxide, magnesium carbonate, carbon black, barium sulfate, calcium oxide, aluminum oxide, mica, glass beads, Fillers such as glass fibers, carbon fibers, aramid fibers, glass flakes, thermally expansive graphite, iron lactate, ferrocene, aluminum oxide, and metal fillers, dispersants, foaming agents, and colorants can be added. Among these, the shapes of glass fiber and carbon fiber are 6 to 6
Those having a fiber diameter of 0 μm and a fiber length of 30 μm or more are preferable. 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 composition of the present invention.

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 ° C to 350 ° C. At the time of kneading, the respective components may be kneaded at once, or a multi-stage divided kneading method in which after kneading arbitrary components and then adding the remaining components and kneading can be adopted. 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 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 goods, electric equipment, office automation equipment, parts such as automobiles, or a building material.

[0050]

The present invention will be described in more detail 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. In the examples, parts and% are based on weight unless otherwise specified.

Examples 1 to 6 and Comparative Examples 1 to 5 Preparation of Component (A) The following components were used as the component (A). Graft copolymer (a-1); 40 parts of polybutadiene rubber latex as an initial component in terms of solid content, 65 parts of ion-exchanged water, and rosin acid soap in a separable flask equipped with a reflux condenser, a thermometer and a stirrer. .3
5 parts, 15 parts of styrene and 5 parts of acrylonitrile were added, then 0.2 parts of sodium pyrophosphate, 7 parts of ferrous sulfate.
0.01 part of hydrate and 0.4 part of glucose were added to a solution prepared by dissolving 20 parts of ion-exchanged water. Then, 0.07 part of cumene hydroperoxide was added to start polymerization, and polymerization was started for 1 hour. After polymerization for 1 hour, 45 parts of ion-exchanged water as an increment component, 0.7 part of rosin acid soap, 30 parts styrene, 1 acrylonitrile
0 part and 0.01 part of cumene hydroperoxide were 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-1).

Graft copolymer (a-2): Polymerization is carried out in the same manner as in the graft copolymer (a-1) except that the monomers shown in Table 1 are used to complete the reaction, and the graft copolymer (a-2) is obtained. A polymer (a-2) was obtained.

[0053]

[Table 1]

Copolymer (b-1): In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, 250 parts of ion-exchanged water, 3.0 parts of potassium rosinate and 7 parts of styrene.
5 parts, 25 parts of acrylonitrile and 0.1 part of t-dodecyl mercaptan were added, followed by 0.05 part of sodium ethylenediaminetetraacetate, ferrous sulfate heptahydrate 0.002
Parts and 0.1 parts of sodium formaldehyde sulfoxylate were added to a solution prepared by dissolving 8 parts of ion-exchanged water.
Then, 0.1 part of diisopropylbenzene hydroperoxide was added to start the polymerization, and the reaction was completed by polymerizing for about 1 hour. Sulfuric acid was added to the obtained copolymer latex to coagulate, washed with water and dried to obtain a copolymer (b-1).

Copolymer (b-2): Copolymer (b-) except that 55 parts of styrene and 45 parts of acrylonitrile are used.
Polymerization was carried out in the same manner as in 1) to complete the reaction and obtain a copolymer (b-2). Preparation of component (B) As the component (B), a novolac type phenol resin [Tamanor PA110 manufactured by Arakawa Chemical Industry Co., Ltd.] was used. Preparation of component (C) Triphenyl phosphate and triphenyl thiophosphate were used as the flame retardant (C). Preparation of component (D) As another resin material (D), polycarbonate or polybutylene terephthalate (PBT) was used.

Production and Evaluation of Flame Retardant Resin Composition Each component shown in Table 2 was heated at a temperature of 19 with an extruder having an inner diameter of 50 mm.
Melt kneading was carried out in the range of 0 to 240 ° C. to prepare pellets. The obtained pellets were treated with a 50z injection molding machine,
A test piece was prepared by molding at a molding temperature of 200 to 240 ° C., and its physical properties were evaluated. The results are shown in Table 2. In addition,
The evaluation of physical properties is as follows. Flammability O. I. (Oxygen index) Test piece: 1/8 "x 1/2" x 5 "Flammability test based on UL-94 Test piece: 1/8" x 1/2 "x 5" Izod impact strength ASTM D256 ( 1/4 ", 23 ° C, notched) Heat distortion temperature ASTM D648 (18.6 kg / cm ² )

[0057]

[Table 2]

As is clear from Table 2, the flame-retardant resin compositions of the present invention of Examples 1 to 6 have been obtained which are the objects of the present invention. On the other hand, the compositions of Comparative Examples 1 to 5 are flame-retardant resin compositions in which the content of the component (D) is outside the range of the present invention, and the desired flame retardancy or the original characteristics of the resin are obtained. Has not been done.

[0059]

EFFECTS OF THE INVENTION According to the flame-retardant resin composition of the present invention, the flame-retardant resin composition has a low halogen content or excellent flame retardancy even when a halogen-containing flame retardant is not used. It is unlikely that harmful substances such as dioxins will be generated, and also has high level of 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.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Reference number within the agency FI Technical display location C08L 33/20 LJN 7921-4J 35/00 LHS 7921-4J LJW 7921-4J 55/02 LMF 7308-4J // (C08L 55/02 61:06) (72) Inventor Yoichi Kamoshida 2-11-24 Tsukiji, Chuo-ku, Tokyo Within Nippon Synthetic Rubber Co., Ltd.

Claims (1)

[Claims] 1. To 100 parts by weight of the following component (A),
Component (B) 0.5 to 50 parts by weight and component (C) 0.1
5 to 95% by weight of the composition (E) containing from 30 to 30 parts by weight and 95 to 5% by weight of the component (D) [however, (E) +
(D) = 100% by weight] as a main component, a flame-retardant resin composition. Component (A): 0 to 100% by weight of the following rubber-reinforced resin (A-1) and 100 to 0% by weight of the following copolymer (A-2).
[However, (A-1) + (A-2) = 100% by weight], and the intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the matrix resin in the component (A) is 0.1. A copolymer composition of about 1.5 dl / g. Rubber-reinforced resin (A-1); rubber-like polymer (a) 5 to 70
95% by weight of at least one monomer component (b) selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid esters, maleic anhydride and maleimide compounds in the presence of wt%. 30% by weight
(A) + (b) = 100% by weight], and a rubber-reinforced resin having a graft ratio of 5 to 150% by weight. Copolymer (A-2); at least one monomer component selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid esters, maleic anhydride and maleimide compounds is polymerized. The copolymer obtained as a result. (B) component; phenolic resin (C) component; flame retardant (D) component; other resin material