JPH0726093A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To obtain a highly flame-retardant resin compsn. without using a halogen-type flame retarder by compounding a specified phosphorous flame retarder with a specified polymer compsn. CONSTITUTION:This flame-retardant resin compsn. contains 3-50 pts.wt. component B to 100 pts.wt. of the below described component A. The component A consists of 0-100wt.% below described rubber-reinforced resin A1 and 100-0wt.% below described polymer A2 and wherein the intrinsic viscosity etaof the matrix resin in the component A is 0.1-1.5dtl/g. The resin A1 is a rubber- reinforced resin obtd. by polymerizing 95-30wt.% at least one monomer component (b) such as arom. vinyl compd. (meth) acrylate and maleimide compd. in the presence of 5-70wt.% rubbery polymer (a) and with a graft ratio of 5-150wt.%. The resin A2 is a polymer obtd. by polymerizing at least one monomer component selected from the above described A1-b. [B]is a phosphorous- contg. compd. of formulas I and II, in formula I, R1 and R2 are each a 1-20C hydrocarbon group and n is 0 or 1 and in formula II R1 to R3 are the same as R1 to R2 of formula I and q1 to q3 are 0 or 1.

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. By incorporating a phosphorus-based flame retardant having a specific molecular bond into a specific resin, the original resin To provide a flame-retardant resin composition having high flame retardancy without significantly impairing excellent characteristics and without using a halogen-based flame retardant, and further toughness,
An object is to provide a flame-retardant resin composition having excellent heat resistance.

[0005]

The present invention provides the following (A).
A flame-retardant resin composition (hereinafter also referred to as "first composition") containing 3 to 50 parts by weight of the component (B) is provided for 100 parts by weight of the 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 polymer (A-2) [(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.
A polymer composition which is 1 to 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. Polymer (A-2); by polymerizing 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. The resulting polymer.

Component (B): the following general formulas (I), (II),
At least one phosphorus-containing compound selected from the compounds represented by (III) and (IV).

[0007]

[Chemical 5]

(In the formula, R ₁ and R ₂ are independently of each other a hydrocarbon residue having 1 to 20 carbon atoms, and n is 0 or 1.)

[0009]

[Chemical 6]

(In the formula, R _{1 to} R ₃ are the same as the above R _{1 to} R ₂ , the hydrocarbon residue preferably has an aromatic group, and q 1 to q 3 are 0 or independently of each other. 1
Is. )

[0011]

[Chemical 7]

(R _{4 to} R ₁₁ are each independently a hydrogen atom or a hydrocarbon residue having 1 to 20 carbon atoms.)

[0013]

[Chemical 8]

(In the formula, R ₁₂ is the same as R ₄ above, X is an oxygen atom or a sulfur atom, and q1 is the same as q1 above.)

The present invention also provides the above-mentioned (A) components 5 to 95.
Wt% and (C) Polycarbonate 95-5 wt%
[However, total amount of (A) + (C) = 100% by weight] 1
Flame retardant resin composition containing 3 to 50 parts by weight of the component (B) with respect to 00 parts by weight (hereinafter also referred to as "second composition", the first composition and the second composition are collectively referred to as "composition." (Also referred to as "flame-retardant resin composition").

Hereinafter, the flame-retardant resin composition of the present invention is
The composition and the second composition will be described separately. First composition Component (A) used in the present invention is a rubber-reinforced resin (A-
1) and / or a polymer (A-2). The component (A-1) is 5 to 70% by weight, preferably 12 to 60% by weight of the rubber-like polymer (a),
More preferably, in the presence of 15 to 50% by weight, at least one monomer selected from the group consisting of aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid esters, maleic anhydride and maleimide compounds. Ingredient (b)
95 to 30% by weight, preferably 88 to 40% by weight, more preferably 85 to 50% by weight [(a) +
(B) = 100% by weight] is a rubber-reinforced resin obtained by polymerization. The component (A-2) is a polymer obtained by polymerizing the monomer component (b). The component (A-2) also includes, for example, a copolymer obtained by post-imidizing a maleic anhydride-styrene copolymer with an amine compound.

Examples of the rubber-like polymer (a) include polybutadiene, butadiene-styrene copolymer, polyisoprene, butadiene-acrylonitrile copolymer, ethylene-propylene- (non-conjugated diene) copolymer, ethylene-butene-polymer. 1- (non-conjugated diene) copolymer, isobutylene-isoprene copolymer, acrylic rubber, styrene-butadiene-styrene block copolymer, styrene-butadiene-styrene radial teleblock copolymer, styrene-isoprene-styrene block copolymer Polymer, SEB
Examples thereof include hydrogenated diene-based (block, random, and homo) polymers such as S, polyurethane rubber, acrylic rubber, and silicone rubber. Among these, polybutadiene, butadiene-styrene copolymer, ethylene-propylene- (non-conjugated diene) copolymer, ethylene-
Butene-1- (non-conjugated diene) copolymer, hydrogenated diene polymer and silicone rubber are preferred.

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, examples of the maleimide compound include 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 particularly 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 polymer (A-2), which is a composition containing a rubber-reinforced resin (A-1) and a polymer (A-2).
Can be used alone. The content ratio of the rubber-reinforced resin (A-1) and the polymer (A-2) mixed is 0 to 10 for the rubber-reinforced resin (A-1).
0% by weight, preferably 0 to 95% by weight, more preferably 40 to 80% by weight, particularly preferably 45 to 70% by weight
And the polymer (A-2) is 100 to 0% by weight, preferably 100 to 5% by weight, more preferably 60 to 20% by weight, and particularly preferably 55 to 30% by weight [where (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 prepared by polymerizing the monomer component (b) in the presence of the rubber-like polymer (a), or 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 polymer (A-2)
Is the rubber-like polymer (a) in the above or the method, for example.
Is obtained by 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) used in the present invention is
It is at least one phosphorus-containing compound selected from the compounds represented by the above general formulas (I), (II), (III) and (IV). Specific examples of the compounds represented by formulas (I) to (IV) are shown below. That is, examples of the compound represented by the general formula (I) include tri (2,6-dimethylphenyl) phosphate, tri (xylenyl) phosphate, tri (2,6-diethylphenyl) phosphate and the like. Examples of the compound represented by the general formula (II) include triphenylthiophosphate, triphenylthiophosphine and tributylthiophosphine. The compound represented by the general formula (III) includes the following structural formula (V)
To (VI) are included, but the invention is not limited thereto.

[0026]

[Chemical 9]

[0027]

[Chemical 10]

As the compound represented by the general formula (IV),
Examples thereof include compounds represented by the following structural formulas (VII) to (VIII), but are not limited thereto.

[0029]

[Chemical 11]

[0030]

[Chemical 12]

These phosphorus-containing compounds (B) have a characteristic structure in the molecule. These characteristic structures impart effective flame retardancy to the resin composition. That is, in the compound represented by the general formula (I), the alkyl-substituted portion on the aromatic ring serves as a cross-linking point during combustion and promotes formation of a non-combustible film. In the compound represented by the general formula (II),
By introducing the phosphorus-sulfur double bond, the double bond is changed to a phosphorus-oxygen bond during combustion, so that oxidative decomposition of the resin is suppressed. In the compound represented by the general formula (III),
The hydrogen atom forming a phosphorus-hydrogen bond serves as an acid catalyst to promote the formation of a nonflammable film. In the compound represented by the general formula (IV), a hydroxyl group is present in the molecule, and the acid catalyst promotes the formation of a nonflammable film.

In the first composition of the present invention, the ratio of the (A) component to the (B) phosphorus-containing compound is 100 parts of the (A) component.
Component (B) is used in an amount of 3 to 50 parts by weight, preferably 5 to 40 parts by weight, more preferably 8 to 35 parts by weight, and particularly preferably 12 to 28 parts by weight. If the content of the phosphorus-containing compound (B) is less than 3 parts by weight, a resin having sufficient flame retardancy cannot be obtained, while if it exceeds 50 parts by weight, the impact resistance and molding appearance of the resin are poor.

Second Composition The second composition is obtained by further improving the toughness and heat resistance of the composition obtained by adding the above-mentioned first composition containing the above-mentioned component (A) and the phosphorus-containing compound (B) as main components. Therefore, it is a flame-retardant resin composition containing (C) polycarbonate. Here, the (C) polycarbonate used in the present invention is obtained by a reaction of various dihydroxyaryl compounds with phosgene (phosgene method), or obtained by transesterification reaction of a dihydroxyaryl compound and diphenyl carbonate. The thing (transesterification method) is mentioned. A typical polycarbonate is a polycarbonate obtained by reacting 2,2'-bis (4-hydroxyphenyl) propane with phosgene.

The dihydroxyaryl compound used as the raw material for the polycarbonate is bis (4-hydroxyphenyl) methane, 1,1'-bis (4-hydroxyphenyl) ethane, 2,2'-bis (4-hydroxy). Phenyl) propane, 2,2'-bis (4-hydroxyphenyl) butane, 2,2'-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2'-bis (4 -Hydroxy-3-
Methylphenyl) propane, 2,2'-bis (4-hydroxy-3-t-butylphenyl) propane, 2,2-
Bis (4-hydroxy-3-bromophenyl) propane, 2,2'-bis (4-hydroxy-3,5-dichlorophenyl) propane, 1,1'-bis (4-hydroxyphenyl) cyclopentane, 1,1 ′ -Bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-
3,3'-dimethyldiphenyl ether, 4,4'-dihydroxyphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethylphenyl sulfide, 4,4 '
-Dihydroxyphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethylphenyl sulfide, 4,
4'-dihydroxydiphenyl sulfoxide, 4,4 '
-Dihydroxy-3,3'-dimethylphenyl sulfoxy-4,4'-dihydroxyphenyl sulfone, 4,
4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, hydroquinone, resorcin and the like can be mentioned, and these can be used alone or in combination of two or more. Particularly preferred is 2,2'-bis (4-hydroxyphenyl)
Propane, bisphenol A.

The weight average molecular weight of the (C) polycarbonate is preferably 15,000 to 40,000, more preferably 17,000 to 35,000, and particularly preferably 18,000 to 30,000.

In the second composition of the present invention, first, (A)
The ratio of the component to the (C) polycarbonate is 5 to 95% by weight of the (A) component, preferably 10 to 80% by weight, more preferably 20 to 70% by weight, and 95 to 5% by weight of the (C) polycarbonate, preferably 70 to 20% by weight, more preferably 80 to 30% by weight (however, (A) + (C)
= 100% by weight]. If the amount of the (C) polycarbonate used is less than 5% by weight, the heat resistance and toughness cannot be sufficiently improved, whereas if it exceeds 95% by weight, the moldability becomes poor.

The amount of the (B) phosphorus-containing compound used is
3 to 50 parts by weight, preferably 5 to 5 parts by weight based on 100 parts by weight of the total amount of the component (A) and the polycarbonate (C).
40 parts by weight, more preferably 8 to 35 parts by weight, particularly preferably 12 to 28 parts by weight. If the amount of the phosphorus-containing compound (B) is less than 3 parts by weight, a resin having sufficient flame retardancy cannot be obtained, while if it exceeds 50 parts by weight, impact resistance and molding appearance as a resin are impaired.

Other Additives In addition, an antimony-containing compound may be added to the flame-retardant resin composition of the present invention in order to improve the flame-retardant effect of the above (B) phosphorus-containing compound. The amount of the antimony-containing compound used to obtain the effect of addition is (A) component 10
0 part by weight, or preferably 0.5 per 100 parts by weight of the total amount of the component (A) and the polycarbonate (C).
-20 parts by weight, more preferably 1-15 parts by weight. Examples of the antimony-containing compound include antimony trioxide, antimony tetraoxide, (colloidal) antimony pentoxide, sodium antimonate, antimony phosphate, and the like, among which antimony trioxide is preferable.

If desired, the flame-retardant resin composition of the present invention may be mixed with other resin materials. Other resin materials include polyamides such as nylon 6, polyesters such as polybutylene terephthalate (PBT) and polyethylene terephthalate (PET), polyphenylene sulfide (PPS), polyphenylene oxide (PP).
O), polyacetal such as polyoxymethylene (POM), polyether ester amide, polyether imide, polyimide, polyether ether ketone (PEE)
K), polyarylate, polymethylmethacrylate, silicone resins, vinyl chloride resins (PVC) and other chlorine-based polymers, fluorine-based polymers, epoxy resins, polyurethanes, unsaturated polyesters, and thermoplastic elastomers. One polymer is mentioned. Among these, polyamide, PBT, PET,
At least one polymer selected from the group of PPS and PPO is preferred.

The blending ratio of the other resin material is preferably 30 to 90% by weight of the flame-retardant resin composition of the present invention and 70 to 10% by weight of the other resin material. When the other resin material is in this numerical range, the effect of adding the other resin material can be obtained.

In producing the flame-retardant resin composition of the present invention or a mixture of the flame-retardant resin composition and another resin material, a compatibilizing agent may be used to improve compatibility between polymers. Impact resistance and surface appearance of molded products 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 such as styrene-glycidyl methacrylate copolymer, styrene-maleic anhydride copolymer, styrene-methacrylic acid copolymer and styrene-acrylonitrile-methacrylic acid copolymer. 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, Additives such as 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 and the like can be added. . Among these, the glass fiber and the carbon fiber preferably have a fiber diameter of 6 to 60 μm and a fiber length of 30 μm or more. The amount of these additives added is 0.01 to 100 parts by weight of the flame-retardant resin composition of the present invention.
About 100 parts by weight is preferable.

Preparation of flame-retardant resin composition The flame-retardant resin composition of the present invention is preferably used in various extruders, Banbury mixers, kneaders, rolls, etc.
It can be obtained by kneading each component in the range of ℃ to 350 ℃. 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.

[0046]

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 3 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 was carried out in the same manner as in the graft copolymer (a-1) except that the monomers shown in Table 1 were used to complete the reaction and the graft copolymer A polymer (a-2) was obtained.

[0049]

[Table 1]

Polymer (b-1): In a separable flask equipped with a reflux condenser, a thermometer and a stirrer, 250 parts of deionized water, 3.0 parts of potassium rosinate, 75 parts of styrene.
Parts, acrylonitrile 25 parts and t-dodecyl mercaptan 0.1 part, then sodium ethylenediamine tetraacetate 0.05 part, ferrous sulfate heptahydrate 0.002 part and sodium formaldehyde sulfoxylate 0.1 part. Was added to a solution dissolved in 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 polymer latex to coagulate, washed with water and dried to obtain a polymer (b-1). Polymer (b-2): Polymerization is carried out in the same manner as in the polymer (b-1) except that 55 parts of styrene and 45 parts of acrylonitrile are used to complete the reaction and obtain a polymer (b-2). It was Polymer (b-3): Polymerization is carried out in the same manner as in Polymer (b-1) except that 45 parts of styrene, 28 parts of acrylonitrile and 27 parts of N-phenylmaleimide are used to complete the reaction, and then polymer. (B-3) was obtained.

Preparation of Component (B) As the phosphorus-containing compound (B), tri (xylenyl) phosphate [compound represented by general formula (I)], triphenylthiophosphate [compound represented by general formula (II)] ], A compound represented by the structural formula (V) [hereinafter also referred to as "compound (V)") [a compound represented by the general formula (III), manufactured by Sanko Chemical Co., Ltd., HCA], the structural formula ( VIII)
Compound represented by (hereinafter also referred to as "compound (VIII)")
[Compound represented by the general formula (IV), manufactured by GLC, CN-
1137] was used. Preparation of component (C) As a polycarbonate, Panlite L-1125 manufactured by Teijin Chemicals Ltd. was used. Preparation of Other Resin Material As another resin material, polybutylene terephthalate (P
BT) [PBT-120 manufactured by Kanebo Ltd.] was used.

Production and Evaluation of Flame Retardant Resin Composition Each component shown in Tables 2 to 4 was melt-kneaded at a temperature of 190 to 240 ° C. with an extruder having an inner diameter of 50 mm to prepare pellets. The obtained pellets were molded with a 5oz injection molding machine at a molding temperature of 200 to 240 ° C to prepare a test piece, and its physical properties were evaluated. The results are shown in Tables 2-4.

The evaluation of the 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 )

[0054]

[Table 2]

[0055]

[Table 3]

[0056]

[Table 4]

* 1) Unit: [η] (dl / g) * 2) notV; UL-94, V-flame does not disappear at the time of test execution, flame reaches sample jig or drips This is the case where the fire remains in the sample even after occurrence of, and burning continues. Even when the flame disappears without dripping, if the time until disappearance exceeds 30 seconds, it is determined as notV. As is clear from Tables 2 and 3, the flame-retardant resin compositions of the present invention of Examples 1 to 6 have been obtained as the object of the present invention. On the other hand, as is clear from Table 4, Comparative Example 1 is an example using a flame retardant that does not correspond to the (B) phosphorus-containing compound of the present invention, and is inferior in flame retardancy and heat resistance. Comparative Example 2 is an example in which the amount of the (B) phosphorus-containing compound used exceeded the range of the present invention, and the impact resistance was poor. Comparative Example 3 is (B)
This is an example in which the amount of the phosphorus-containing compound used is less than the range of the present invention, and the flame retardancy is poor.

[0058]

EFFECTS OF THE INVENTION According to the flame-retardant resin composition of the present invention, the flame-retardant resin composition has excellent flame-retardant properties even when a halogen-containing flame-retardant is not used, and moreover, harmful substances are generated during molding and combustion. It is difficult and 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 front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location C08L 55/02 LME C09K 21/12 21/14 (72) Inventor Yoichi Kamoshida Tsujiji, Chuo-ku, Tokyo No. 11-24 Japan Synthetic Rubber Co., Ltd.

Claims (2)

[Claims] 1. To 100 parts by weight of the following component (A),
A flame-retardant resin composition containing 3 to 50 parts by weight of component (B). Component (A); 0 to 100% by weight of the following rubber-reinforced resin (A-1) and 100 to 0% by weight of the following polymer (A-2) [(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.
A polymer composition which is 1 to 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. Polymer (A-2); by polymerizing 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. The resulting polymer. Component (B): at least one phosphorus-containing compound selected from compounds represented by the following general formulas (I), (II), (III) and (IV). [Chemical 1] (In the formula, R ₁ and R ₂ independently of each other have 1 to 2 carbon atoms.
0 is a hydrocarbon residue and n is 0 or 1. ) [Chemical 2] (Wherein, R ₁ to R ₃ are as defined above R ₁ ~R _2, q1~q
3 is 0 or 1 independently of each other. ) [Chemical 3] (R _{4 to} R ₁₁ are each independently a hydrogen atom or a hydrocarbon residue having 1 to 20 carbon atoms.) (In the formula, R ₁₂ is the same as R ₄ above, X is an oxygen atom or a sulfur atom, and q1 is the same as q1 above.) 2. A total amount of 100 parts by weight of (A) component 5 to 95% by weight and (C) polycarbonate 95 to 5% by weight [where (A) + (C) = 100% by weight] according to claim 1. On the other hand, a flame-retardant resin composition containing 3 to 50 parts by weight of the component (B) according to claim 1.