JPH09310001A - Flame retardant thermoplastic resin composition - Google Patents

Abstract

(57) [Abstract] [PROBLEMS] To provide a flame-retardant resin composition having excellent chemical resistance and slidability, which can be used in a wide range of applications. SOLUTION: (A) A non-diene rubber-reinforced polymer obtained by graft-polymerizing a monomer containing an aromatic vinyl compound and a vinyl cyanide compound as main components in the presence of a non-diene rubber polymer. A diene rubber-reinforced polymer (a-) obtained by graft-polymerizing (a-1) with a monomer containing an aromatic vinyl compound and a vinyl cyanide compound as main components in the presence of a diene rubber polymer. (B) 0.5 to 17 parts by weight of high-density polyethylene having a melt flow rate of 3 g / 10 min or more, and (C) modified polyethylene wax 0.1 to 100 parts by weight of a thermoplastic resin composition containing 2) as an essential component. To 7 parts by weight and (D) 2 to 40 parts by weight of a flame retardant, a flame-retardant thermoplastic resin composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame-retardant thermoplastic resin composition having excellent chemical resistance and slidability.

2. Description of the Related Art Flame-retardant ABS resin is used for molding surface appearance,
It has excellent molding processability and mechanical properties, and is widely used in the electrical and electronic fields and OA equipment fields. In recent years, the demand for chemical resistance and slidability of these products has increased. Particularly, alloying ABS resin and thermoplastic polyester resin has been conventionally performed in order to improve chemical resistance. Further, in order to improve slidability, it has been conventionally practiced to add polytetrafluoroethylene to ABS resin. However, when alloying the ABS resin and the thermoplastic polyester resin, in order to improve the chemical resistance, it is necessary to increase the blending amount of the thermoplastic polyester resin, and since both are difficult to mix, It is also practiced to use special compatibilizers. For this reason, it is difficult to impart flame retardancy, and there are problems that physical properties are deteriorated and cost is increased due to addition of a large amount of flame retardant. Further, there is a problem that the ABS resin obtained has a limit in chemical resistance. Further, in order to improve the slidability of the ABS resin, polytetrafluoroethylene has been conventionally added, but in order to develop the slidability, the blending amount increases and the cost also increases. There was a difficulty to end. The present invention
The object of the invention is to provide a flame-retardant thermoplastic resin composition having excellent chemical resistance and slidability which can be used in a wide range of applications.

[0002]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention In view of the present situation, the present inventors have studied the development of materials, and as a result, used a specific graft copolymer, a specific high-density polyethylene, and a modified polyethylene wax in specific amounts. By doing so, they have found that the above problems can be solved, and have completed the present invention.

[0003]

The present invention is obtained by graft-polymerizing a monomer containing an aromatic vinyl compound and a vinyl cyanide compound as main components in the presence of (A) a non-diene rubbery polymer. Non-diene rubber reinforced polymer (a-1)
And a diene rubber-reinforced polymer (a-, obtained by graft-polymerizing a monomer containing an aromatic vinyl compound and a vinyl cyanide compound as main components in the presence of a diene rubbery polymer.
2) an essential component, wherein the total amount of the non-diene rubbery polymer and the diene rubbery polymer is 2.5 to 35% by weight in the composition, and the non-diene rubber The weight ratio of the rubbery polymer to the diene rubbery polymer is 85:15 to 1
0.5 to 17 parts by weight of high-density polyethylene having a melt flow rate defined by JIS B6760 of 3 g / 10 min or more based on 100 parts by weight of the thermoplastic resin composition of 5:85, (C) modified A flame-retardant thermoplastic resin composition comprising 0.1 to 7 parts by weight of a polyethylene wax and 2 to 40 parts by weight of a flame retardant (D). Further, the present invention relates to the following compound (E) based on 100 parts by weight of the thermoplastic resin composition.
A flame-retardant thermoplastic resin composition comprising 0.1 to 5 parts by weight of polytetrafluoroethylene and / or (F) dimethyl silicone oil.

The non-diene rubber-reinforced polymer (a-1) used in the present invention is a monomer containing an aromatic vinyl compound and a vinyl cyanide compound as main components in the presence of the non-diene rubber polymer. Is obtained by graft polymerization. Alternatively, a copolymer of one or more monomers selected from the above monomers (a
It is also possible to separately produce -3) and blend with the above graft copolymer. Examples of the non-conjugated diene rubber polymer of the present invention include ethylene-α olefin rubber polymers such as ethylene-α olefin copolymer and ethylene-α olefin-non-conjugated diene copolymer; styrene-isoprene block copolymer. Polymer hydrogenated product, acrylic-butadiene copolymer hydrogenated product, styrene-butadiene block copolymer hydrogenated product, butadiene copolymer hydrogenated product, styrene-butadiene random copolymer hydrogenated product And hydrogenated products of diene-based polymers, such as silicone rubber and acrylic rubber.
Among these, preferred non-diene rubbery polymers are ethylene-α-olefin rubbery polymers and hydrogenated products of diene polymers.

As the α-olefin of the ethylene-α-olefin rubbery polymer, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1
-Decene is mentioned. Of these, preferred α-olefins are propylene and 1-butene. Examples of non-conjugated dienes include cyclopentadiene, ethylidene norbornene, 1,4 hexadiene and 1,4 cyclopentadiene. The preferred weight ratio of ethylene to α-olefin is 90:10 to 20:80, more preferably 85:15 to 30:70. Examples of the diene polymer used for the hydrogenated product of the diene polymer include styrene-
Examples thereof include a butadiene block copolymer and a styrene-isoprene block copolymer. These include AB type,
Various materials such as those having an ABA type, a taper type, and a radial teleblock type structure can be used. Further, the hydrogenated product of a diene polymer is, in addition to the hydrogenated product of the above block copolymer, a hydrogenated product of a block copolymer composed of blocks such as a styrene block and a styrene-butadiene random copolymer, styrene- Hydrogenated products such as butadiene copolymers and styrene-isoprene copolymers, polybutadiene blocks having a 1,2-vinyl bond content of 20% by weight or less and polybutadiene blocks having a 1,2-vinyl bond content of more than 20% by weight in polybutadiene. Hydrides of the following polymers are included. The non-diene rubbery polymer may be used alone or in combination of two or more. Of these, as the non-diene rubbery polymer, the use of a hydrogenated product of an ethylene-α-olefinic rubbery polymer or a diene polymer provides a further excellent effect.

As the aromatic vinyl compound used in the graft polymerization, for example, styrene, α-methylstyrene and the like are used. As the vinyl cyanide compound, for example, acrylonitrile, methacrylonitrile and the like are used.
In the above graft polymer, if necessary, an unsaturated acid anhydride such as maleic anhydride; an unsaturated acid such as acrylic acid or methacrylic acid; an unsaturated dicarboxylic acid such as maleimide, N-phenylmaleimide or N-methylmaleimide. Imide compound of acid, methyl acrylate, ethyl acrylate,
(Meth) acrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate are used.

The content of the aromatic vinyl compound is (a-1)
The content of the components is preferably 45 to 93% by weight, more preferably 45 to 80% by weight, and particularly preferably 45 to 70% by weight. The content of the vinyl cyanide component in the component (a-1) is preferably 5 to 50% by weight, more preferably 5 to 40% by weight.
%, Particularly preferably 5 to 30% by weight. The content of the non-diene rubbery polymer component in the component (a-1) is preferably 2 to 70% by weight, more preferably 15 to 60% by weight, and particularly preferably 25 to 55% by weight.

The component (a-2) used in the present invention is obtained by graft-polymerizing a monomer containing an aromatic vinyl compound and a vinyl cyanide compound as main components in the presence of a diene rubbery polymer. The component (A) of the present invention is the above (a-1),
Although it contains (b-1), these (a-
1) and 1) selected from the above monomers in addition to (b-1)
It is also possible to use a blend obtained by separately polymerizing or copolymerizing one or more kinds of monomers (a-3). Although the graft polymerization method is not particularly limited, it can be produced by usual emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization, or the like. Examples of the diene rubbery polymer include polybutadiene, styrene-butadiene copolymer, styrene-isoprene copolymer, butadiene-acrylic copolymer, styrene-butadiene block copolymer and the like. As the aromatic vinyl compound used for the graft polymerization, for example, styrene, α-methylstyrene and the like are used. As the vinyl cyanide compound, for example, acrylonitrile, methacrylonitrile and the like are used. In the above graft polymer, if necessary, unsaturated acid anhydride such as maleic anhydride; unsaturated acid such as acrylic acid or methacrylic acid; unsaturated such as maleimide, N-phenylmaleimide or N-methylmaleimide. Dicarboxylic acid imide compounds (meth) acrylic acid esters such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate are used.

The content of the aromatic vinyl compound is (a-2)
The content of the components is preferably 45 to 93% by weight, more preferably 45 to 80% by weight, and particularly preferably 45 to 70% by weight. The content of the vinyl cyanide component in the component (a-2) is preferably 5 to 50% by weight, more preferably 5 to 40%.
%, Particularly preferably 5 to 30% by weight. The content of the diene rubbery polymer component in the component (a-2) is preferably 2 to 70% by weight, more preferably 15 to 60% by weight, and particularly preferably 25 to 55% by weight. The total amount of the non-diene rubbery polymer and the diene rubbery polymer in the thermoplastic resin composition (A) is 2.5 to 35% by weight, preferably 3 to 30% by weight, more preferably 3. 5-27
%, Particularly preferably 4 to 25% by weight. 2.5
When it is less than 35% by weight, impact strength is lowered, and when it exceeds 35% by weight, rigidity and combustibility are poor. The weight ratio of the non-diene rubbery polymer to the diene rubbery polymer is 85:15.
15:85, preferably 80:20 to 20:80, and more preferably 75:25 to 22:78. When the amount of the non-diene rubbery polymer is less than this range, the high-density polyethylene cannot be compatibilized and slidable. The kinematics cannot be improved, and in many cases, flammability is poor. The graft ratio of the components (a-1) and (a-2) is preferably 5 to 150 weights, more preferably 10 to 120 weights. Also, (a-1), (a
-2) and (a-3) component methyl ethyl ketone (ME
The intrinsic viscosity (30 ° C., MEK) of the K) soluble component is preferably 0.2 to 1.5, more preferably 0.3 to 1 dl / g. The above-mentioned component (a-3) is prepared in advance from (a-1), (a
-2) or may be added in the mixing step for obtaining the composition of the present invention.

The high-density polyethylene (B) used in the present invention is a polyethylene having a density of 0.924 g / cm ³ or more, and has a melt flow rate defined by JIS K6760 of 3 g / 10 min or more, preferably 5 g / 10 min or more, more preferably A polyethylene having a value of 6 to 30 g / 10 min. The melt flow rate measurement condition was 19
It is 0 ° C. × 2.16 kgf. Melt flow rate is 3
If it is less than g / 10 min, sufficient slidability cannot be obtained. Further, even so-called low-density polyethylene cannot obtain sufficient slidability. The component (B) is 0.5 to 17 parts by weight, preferably 1 to 15 parts by weight, and more preferably 1,5 to 13 parts by weight, relative to 100 parts by weight of the component (A). 0.
If it is less than 5% by weight, the effect of improving the slidability is insufficient, and the amount of wear increases in particular. On the other hand, if it exceeds 17% by weight, heat resistance and combustibility are deteriorated.

The modified polyethylene wax (C) used in the present invention is, for example, a modified polyethylene wax having a functional group introduced therein. Among these, those modified with a carboxyl group are preferable. Examples of the modification method include modification by copolymerization of ethylene with an unsaturated carboxylic acid and / or a functional group-containing unsaturated compound such as an anhydride thereof,
Examples thereof include a method of oxidizing polyethylene or a decomposed product of polyethylene. As the unsaturated carboxylic acid and its anhydride, acrylic acid, monocarboxylic acid such as methacrylic acid, maleic acid, fumaric acid, dicarboxylic acid such as itaconic acid, maleic anhydride, dicarboxylic acid anhydride such as itaconic anhydride and the like. Can be mentioned. Those modified with a carboxyl group can be obtained by, for example, copolymerizing polyethylene with a carboxyl group-containing unsaturated compound, or by post-oxidizing a decomposed product of polyethylene. The polyethylene wax has an average molecular weight of 500 to 10,000, preferably 700 to 7,000, and more preferably 1,000 to 50.
The range is 00. The compounding amount of the component (C) is 0.1 to 7 parts by weight, preferably 0.1 part by weight, based on 100 parts by weight of the component (A).
It is 2 to 6 parts by weight, more preferably 0.5 to 5 parts by weight. If it is less than 0.1 parts by weight, the slidability, especially the improvement of the dynamic friction coefficient is insufficient, and if it exceeds 7 parts by weight, heat resistance, Flame retardance is reduced.

The flame retardant (D) used in the present invention is, for example, tetrabisphenol A and its derivative, tetrabromophthalic anhydride, brominated diphenyl ether, brominated polycarbonate oligomer and its derivative, brominated epoxy resin and its terminal modification, and product. , Halogenated flame retardants such as brominated polystyrene, brominated phenoxy resin, tris dibromophosphate, chlorinated polyethylene,
Examples include phosphorus-based flame retardants such as trisphenyl phosphate and red phosphorus. These flame retardants are used alone or in combination of two or more. Among them, tetrabisphenol A, brominated epoxy resin and its terminal modified product are preferable.
The compounding amount of the component (D) is 2 to 40 parts by weight, preferably 3
To 35 parts by weight, more preferably 5 to 30 parts by weight. By blending the component (D), the required flammability can be exhibited. However, excessive use is negative in terms of cost and physical properties. Further, in order to improve flame retardancy, it is also effective to use an antimony oxide compound in combination as a flame retardant aid.

Further, by adding (E) tetrafluoroethylene or (F) dimethyl silicone oil to the composition of this patent, the slidability can be further improved. The (E) tetrafluoroethylene is not particularly limited, but one having a molecular weight of 1,000,000 or less, which is generally used as a slidability improving agent, is preferable. When the molecular weight exceeds 1,000,000 and becomes large, the flow processability is deteriorated. The compounding amount of (E) is preferably 0.1 to 5 parts by weight, more preferably 0.1.
2 to 4.5 parts by weight, particularly preferably 0.5 to 4 parts by weight. Although the effect is exhibited in this range, the slidability does not change even if the amount exceeds 5 parts by weight, and the cost increases.
(F) Dimethyl silicone oil is not particularly limited, but one having a viscosity of 100,000 centistokes or less,
It is preferable in terms of the effect of improving the slidability. The compounding amount of (F) is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 4.5 parts by weight, and particularly preferably 0.5 to 4 parts by weight. Although the effect is exhibited in this range, when it is blended with the resin in an amount of more than 5 parts by weight, the screw slips on the extruder in the granulation process and causes a problem in actual production. The components (E) and (G) can be used in combination.

The resin composition of the present invention contains fillers such as glass fibers, carbon fibers, glass beads, talc, mica, and kaolin, as well as known coupling agents, antioxidants, plasticizers, coloring agents, lubricants, and charging agents. Additives such as inhibitors can be blended. Further, the resin composition of the present invention, other polymers depending on the required performance, for example, polyamide,
Polycarbonate, polysulfone, polyvinylidene fluoride, polyamide elastomer, polyester resin and the like can be appropriately blended. The thermoplastic resin composition of the present invention can be obtained by kneading the components using various extruders, Bavary mixers, kneaders, rolls and the like. When kneading the components, the components may be kneaded at once, or may be kneaded by a multi-stage addition method. The resin composition of the present invention thus obtained can be formed into various molded products by injection molding, sheet extrusion, vacuum molding, foam molding, or the like.

[0016]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. In the examples, parts and% are by weight unless otherwise specified. Also, various evaluations in the examples,
It measured as follows. The heat distortion temperature specified in heat resistance ASTM D-648 was measured. Impact High-speed impact tester made by Shimadzu Corporation Servo pulsar EHF-2H
The breaking energy of a test piece having a thickness of 50 × 80 × 2.4 mm was measured using -20 L under the following conditions. Test piece cradle diameter 3
0φ, striking rod tip is 12.7R, striking speed 3.1 m / s chemical resistance 35 × 180 × 1.8 mm thick test piece is molded and
4 The test piece was fixed to an elliptical metal jig, dioctyl phthalate was applied to the test piece in a state in which the test piece was continuously strained, and the maximum strain amount without cracking due to the chemical after 24 hours was measured. Sliding property A Suzuki type sliding tester was used, and S45C was used as a mating material. The test piece used was a hollow cylinder having an outer diameter of 25.6 mm and an inner diameter of 20.0 mm, and the mating member had the same shape. The wear amount was measured under conditions of 23 ° C., humidity of 50% and load of 0.
It was measured at 5 kg and a running speed of 50 cm / sec. The dynamic friction coefficient was calculated by the following formula. μ = [3 × F × R × (r ₂ ² −r ₁ ² )] / [P × (r ₂ ³ −
r ₁ ^3)] (wherein, mu is the dynamic friction coefficient, F is applied to the load cell force,
P is the load, R is the arm length up to the load cell, r ₁ is the inner diameter, r ₂ is the outer diameter) Flammability 5 ″ × 1/12 ″ according to the method specified in UL94
A vertical combustion test method was performed on a test piece of 1/10 ". Ethylene-propylene rubbery polymer and diene rubber.
Quality polymer preparation of the present invention of (A) ethylene used in Component - propylene-based rubbery polymer and a diene-based rubbery polymer are shown in Table 1.

[0017]

[Table 1]

Preparation of thermoplastic resin (A) In the presence of rubbery polymers (a) '-1 and -2, a resin obtained by polymerizing styrene and an acrylonitrile monomer component, and styrene and an acrylonitrile monomer component alone are used. A polymerized resin was obtained. The resin compositions of these are shown in Table 2.

[0019]

[Table 2] (A-1) and (a-3) were obtained by solution polymerization, and (a-2) was obtained by emulsion polymerization.

As the preparation (B) -1 of high- density polyethylene (B), HJ390 manufactured by Mitsubishi Chemical Co., Ltd., which is high-density polyethylene, was used. (Melt flow rate is 28g
/ 10 min) As (B) -2, HJ560 manufactured by Mitsubishi Chemical Corporation, which is a high-density polyethylene, was used. (The melt flow rate is 7 g /
For comparison, a high density polyethylene HJ340 manufactured by Mitsubishi Chemical Corporation was used as (B) -3. (The melt flow rate is 1.5 g / 10 min.) As (B) -4, low density polyethylene LF660H manufactured by Mitsubishi Chemical Corporation was used. (The melt flow rate is 7g
/ 10 min)

As the preparation (C) -1 of modified polyethylene wax (C), a number average molecular weight of 2000 and an oxidation degree of 20 was used. As (C) -2, a number average molecular weight of 3000 and an oxidation degree of 20 was used. As the preparation (D) -1 of the flame retardant (D), a brominated epoxy resin, Plasam EC-20, manufactured by Dainippon Ink and Chemicals, Inc. was used. As (D) -2, antimony trioxide which is a flame retardant aid was used. As a preparation (E) -1 of polytetrafluoroethylene (E), L169J manufactured by Asahi IC Eye Fluoropolymers was used. Preparation of dimethyl silicone oil (F) As (F) -1, dimethyl silicone oil having a viscosity of 10,000 centistokes was used.

Examples 1 to 12 and Comparative Examples 1 to 12 The ingredients shown in Table 3 were mixed in a mixer for 3 minutes to obtain 50
It was melt-extruded at a cylinder temperature of 180 to 210 ° C. using a mm extruder to obtain pellets. The pellets were injection molded at a cylinder temperature of 200 ° C. and a mold temperature of 50 ° C. to obtain various test pieces for evaluation. Table 3 shows the evaluation results of these test pieces.
Shown in

[0023]

[Table 3]

[0024]

[Table 4]

As is clear from Examples 1 to 12 in Tables 3 and 4, the resin composition of the present invention is excellent in chemical resistance, slidability, heat resistance, impact resistance and combustion resistance. Comparative Example 1 is a case where the amount of the rubbery polymer as the component (A) is outside the range of the present invention, but the impact resistance is poor. In Comparative Example 2, the amount of the rubbery polymer as the component (A) is outside the range of the present invention, but the flammability is poor. Comparative Example 3 is a case where the amount of the ethylene-propylene rubber polymer as the component (A) is out of the range of the present invention, but the impact resistance, chemical resistance and slidability are poor. Comparative Example 4 is a case where the amount of the ethylene-propylene rubber polymer as the component (A) is out of the range of the present invention, but the slidability and flammability are poor. Comparative Example 5 is a case where the component (B) is not used outside the range of the present invention, but the chemical resistance and slidability are poor. In Comparative Example 6, the amount of the component (B) is large outside the range of the present invention, but the heat resistance and the flammability are poor. In Comparative Example 7, the amount of the component (C) is out of the range of the present invention, but the heat resistance and the flammability are inferior. In Comparative Example 8, the component (B) is out of the range of the present invention and the melt flow rate is 1.5 g / 10 min, but the slidability is poor.
Comparative Example 9 is a case where the component (B) is low density polyethylene outside the range of the present invention, but the slidability is poor. Comparative Example 10 does not use components (B) and (C) outside the scope of the present invention,
The component (E) is also in a large amount outside the scope of the present invention, but the impact resistance and chemical resistance are poor.

[0026]

The flame-retardant thermoplastic resin composition of the present invention comprises:
It has excellent chemical resistance and slidability and is useful in a wide range of applications.

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Claims (2)

[Claims] 1. A non-diene rubber-reinforced polymer obtained by graft polymerizing a monomer containing an aromatic vinyl compound and a vinyl cyanide compound as main components in the presence of (A) a non-diene rubber polymer. A diene rubber reinforced polymer (a) obtained by graft-polymerizing the polymer (a-1) and a monomer containing an aromatic vinyl compound and a vinyl cyanide compound as main components in the presence of the diene rubber polymer. -2) as an essential component, wherein the total amount of the non-diene rubbery polymer and the diene rubbery polymer is 2.5 to 35% by weight in the composition, and the non-diene rubbery polymer is used. (B) JISK6760 based on 100 parts by weight of the thermoplastic resin composition in which the weight ratio of the rubbery polymer and the diene rubbery polymer is 85:15 to 15:85.
0.5 to 17 parts by weight of high-density polyethylene having a melt flow rate of 3 g / 10 min.
A flame-retardant thermoplastic resin composition comprising 0.1 to 7 parts by weight of a modified polyethylene wax (C) and 2 to 40 parts by weight of a flame retardant (D). 2. The thermoplastic resin composition 100 according to claim 1.
A flame-retardant thermoplastic resin composition comprising 0.1 to 5 parts by weight of the following compound (E) and / or (F) with respect to parts by weight. (E) Polytetrafluoroethylene (F) Dimethyl silicone oil