JP2003261761A - Flame retardant thermoplastic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve sliding property of a polyphenylene ether-based resin and impart flame retardant property thereto. <P>SOLUTION: This flame retardant thermoplastic resin composition excellent in sliding property consists of (a) 100 pts.wt. polyphenylene ether-based resin or a thermoplastic resin consisting of the same and a styrene-based resin, (b) 2-50 pts.wt. graft copolymer consisting of 5-95 wt.% &alpha;-olefinic polymer and 95-5 wt.% vinylic polymer consisting of at least 1 kind of vinyl monomer, (c) 10-40 pts.wt. aromatic phosphoric acid ester-based flame retardant and (d) 0-150 pts.wt. inorganic filler. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyphenylene ether flame-retardant thermoplastic resin composition having excellent slidability.

[0002]

2. Description of the Related Art Polyphenylene ether resin compositions are widely used in the field of office equipment, information equipment and the like because they are excellent in heat resistance, flame retardancy, dimensional stability and electrical characteristics. In recent years, the processing speed has increased significantly in the office equipment field and the information equipment field, so that the drive unit becomes faster. Since polyphenylene ether-based resin is inferior in wear and abrasion resistance,
When the driving part is operated at high speed, frictional noises are likely to be generated at the contact points with metal or resin, and the size of the product is changed due to wear, which shortens the product life, which is a problem. In order to solve these problems, a material having excellent slidability is required. Therefore,
Naturally, polyphenylene ether resins, which are widely used in the field of office equipment and information equipment, are required to have slidability.

As a method for improving the slidability of a polyphenylene ether resin, Japanese Patent Application Laid-Open No. 166560/1985 discloses a technique of blending a polyamide elastomer. However, although such a technique reduces the amount of wear, it has little effect on the reduction of the friction coefficient. Patent No. 3049784
In the publication, there is disclosed a technique for producing a thermoplastic resin having excellent slidability by blending a thermoplastic resin having a multi-phase structure composed of a non-polar α-olefin (co) copolymer and a vinyl (co) polymer. It is disclosed. However, although the slidability is improved by such a technique, the flame retardancy deteriorates to the extent that it cannot be estimated from the decrease due to the styrene resin that is usually added. The deterioration of flame retardancy is further greatly promoted when the inorganic filler is added.

This is a serious problem because it is required to have flame retardancy in most cases used in the field of office equipment and information equipment.
Although the publication describes that a flame retardant may be added, it does not indicate the proper range of the flame retardant thermoplastic resin composition having excellent slidability.

[0005]

An object of the present invention is to provide a flame-retardant thermoplastic resin composition having excellent slidability, which can be effectively used in the fields of office equipment and information equipment.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies for the purpose of imparting slidability to a polyphenylene ether resin without impairing its inherent properties such as flame retardancy. We have achieved the object by discovering that flame retardancy is significantly improved by adding an aromatic phosphate ester type flame retardant and that deterioration due to an inorganic filler can be prevented. That is, the present invention is: (A) 100 parts by weight of a polyphenylene ether resin, or 100 parts by weight of a thermoplastic resin containing the same, and (b) a vinyl resin containing 5 to 95% by weight of an α-olefin polymer and at least one vinyl monomer. Polymer 9
2 to 50 parts by weight of a graft copolymer composed of 5 to 5% by weight and (c) an aromatic phosphate ester-based flame retardant 10 to 40
A flame-retardant thermoplastic resin composition having excellent slidability consisting of parts by weight is provided.

2. (A) 100 parts by weight of a polyphenylene ether-based resin or a thermoplastic resin composed of the polyphenylene ether-based resin and a styrene-based resin, (b) an α-olefin-based polymer 5 to 9
2 to 50 parts by weight of a graft copolymer composed of 5% by weight and 95 to 5% by weight of a vinyl polymer composed of at least one vinyl monomer, (c) an aromatic phosphate ester flame retardant 1
2. A flame-retardant thermoplastic resin composition having an excellent slidability, which comprises 0 to 40 parts by weight and (d) an inorganic filler of 5 to 150 parts by weight. The flame-retardant thermoplastic resin composition according to claim 1 or 2, wherein the component (b) is a graft copolymer composed of polyethylene and poly (styrene-alkyl methacrylate-hydroxyalkyl methacrylate copolymer). To do.

The polyphenylene ether resin which is the component (a) of the present invention means the following general formula (1),

[0009]

[Chemical 1]

(Wherein R1, R2, R3, R4, R5,
R6 is a monovalent residue such as an alkyl group having 1 to 4 carbon atoms, an aryl group, halogen and hydrogen, and R5 and R6 are not hydrogen at the same time) and the constitutional unit is represented by the formula [1]. A homopolymer or copolymer of a] and [b] can be used.

A typical example of a homopolymer of a polyphenylene ether resin is poly (2,6-dimethyl-1,4).
-Phenylene) ether, poly (2-methyl-6-ethyl 1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl- 1,4-phenylene) ether, poly (2,6-di-n-propyl-1,4-phenylene) ether, poly (2-methyl-6-n-butyl-)
1,4-phenylene) ether, poly (2-ethyl-6)
-Isopropyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly ( Homopolymers such as 2-methyl-6-chloroethyl-1,4-phenylene) ether are mentioned.

The polyphenylene ether copolymer is 2,
Copolymer of 6-dimethylphenol and 2,3,6-trimethylphenol or copolymer of o-cresol or 2,3,6-trimethylphenol and o-
It includes a polyphenylene ether copolymer mainly composed of a polyphenylene ether structure such as a copolymer with cresol. Further, in the polyphenylene ether-based resin of the present invention, as long as it does not violate the gist of the present invention, other various phenylene ether units which have been proposed to be present in the conventional polyphenylene ether resin may be used as a partial structure. You may include it. As an example of what is proposed to coexist in a small amount, Japanese Patent Application No. 63-12
6-98 and JP-A-63-301222, 2- (dialkylaminomethyl) -6-
Examples thereof include a methylphenylene ether unit and a 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit.

Also included are those in which a small amount of diphenoquinone or the like is bound to the main chain of the polyphenylene ether resin.
Further, for example, JP-A-2-276823 and JP-A-63-
It also includes polyphenylene ether modified with a compound having a carbon-carbon double bond, as described in 108059 and JP-A-59-59724. In addition to the polyphenylene ether-based resin, the component (a) can include a polystyrene-based resin in an arbitrary ratio. The polystyrene resin is a polymer obtained by polymerizing a styrene compound or a compound copolymerizable with the styrene compound in the presence or absence of a rubbery polymer.

The styrene compound is represented by the general formula [2]

[0015]

[Chemical 2]

(Wherein R represents hydrogen, lower alkyl or halogen, Z is selected from the group consisting of vinyl, hydrogen, halogen and lower alkyl, and p is an integer of 0 to 5). Means a compound.

Specific examples of these include styrene and α-
Methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, ethylstyrene and the like can be mentioned. Examples of the compound copolymerizable with the styrene compound include methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; and acid anhydrides such as maleic anhydride. And used with styrenic compounds.

Examples of the rubbery polymer include a conjugated diene rubber, a copolymer of a conjugated diene and an aromatic vinyl compound, a hydrogenated product thereof, or an ethylene-propylene copolymer rubber. Suitable styrenic resins for the present invention are polystyrene and rubber reinforced polystyrene. The graft copolymer which is the component (b) of the present invention means a vinyl polymer 95 comprising 5 to 95% by weight of an α-olefin polymer and at least one vinyl monomer.
It is a graft copolymer composed of about 5% by weight.

Examples of the α-olefin polymer include polyethylene, polypropylene, ethylene-propylene copolymer and the like. The α-olefin-based polymer may be mixed and used. Vinyl monomers include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-t
styrene compounds such as ert-butyl styrene and ethyl styrene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid and itaconic anhydride α, β- An unsaturated carboxylic acid and its metal salt are mentioned.

Further, methyl acrylate and acrylic acid n-
Butyl, isobutyl acrylate, methyl methacrylate,
Α, β-Unsaturated carboxylic acid esters such as ethyl methacrylate, vinyl acetates such as vinyl acetate, vinyl propionate and vinyl caproate, unsaturated glycidyl group-containing monomers such as glycidyl acrylate and glycidyl methacrylate. Is mentioned. The vinyl polymer is a homopolymer of these or a copolymer of at least two vinyl monomers.

As the component (c) of the present invention, an aromatic phosphate ester flame retardant is used in order not to impair the slidability. As an aromatic phosphate ester-based flame retardant, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, dixylenyl phenyl phosphate, and hydroxy are used because they do not impair the slidability. Non-bisphenol, resorcinol bisphosphate,
Triphenyl-substituted type phosphoric acid esters such as bisphenol A bisphosphate are preferably used. These may be used alone or in combination of two or more.

The inorganic filler which is the component (d) of the present invention is added when it is necessary to improve the rigidity and dimensional stability of the resin composition. The filler type can be arbitrarily selected depending on the purpose, but glass fiber, glass flakes, mica, talc, etc. are generally used. In the present invention, the added amount of the graft copolymer which is the component (b) is 2 to 5 with respect to 100 parts by weight of the component (a) from the viewpoint of sliding effect and layer peeling.
It is selected from the range of 0 parts by weight.

In the present invention, the amount of the aromatic phosphate ester type flame retardant which is the component (c) is 10 to 4 with respect to 100 parts by weight of the component (a) from the viewpoint of flame retardancy and heat resistance.
It is selected from the range of 0 parts by weight. In the present invention, (d)
The addition amount of the inorganic filler, which is a component, is (a) component 100.
5 to 5 parts by weight from the viewpoint of moldability, physical properties and surface properties.
It is selected from the range of 150 parts by weight.

If desired, stabilizers such as antioxidants, ultraviolet absorbers, heat stabilizers, etc., colorants, release agents, etc. may be added to the resin composition of the present invention. The method for preparing the composition of the present invention is not particularly limited, but an extruder is preferably used for stably producing a large amount of the resin composition.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail based on Examples, but the present invention is not limited to these Examples. The parts used below are parts by weight, and% is% by weight. (B) in Examples and Comparative Examples
As a graft copolymer as a component, NOF Corporation
MODIPER A1511, which is a graft copolymer composed of polyethylene and poly (styrene-alkyl methacrylate-hydroxyalkyl methacrylate), was used.

Each measured value in Examples and Comparative Examples was determined by the following method. (1) Sliding property (dynamic friction coefficient, wear depth) Orientec Co., Ltd. reciprocating sliding tester AFT-15
Using M, the pin / disk friction coefficient was measured under the following conditions. Pin: SUS304 5 mm diameter steel ball, load: 0.5 k
g, moving speed: 30 mm / sec, one-way distance: 20 m
m, number of reciprocations: 10,000, measurement temperature: 23 ° C. The wear depth indicates the depth after 10,000 reciprocations. The coefficient of kinetic friction also shows the value measured after 10,000 reciprocations.

(2) Flame retardancy (flammability) A test piece having a thickness of 1.6 mm was used to measure the number of seconds of combustion based on the UL94 test method, and is shown as the average number of seconds of combustion.

[0028]

Example 1 33 parts of poly (2,6-dimethyl-1,4-phenylene) ether having an intrinsic viscosity of 0.43 dl / g (measured in chloroform solvent at 30 ° C.) and polystyrene H9302 manufactured by A & M Styrene Co., Ltd. 30 parts, 5 parts of MODIPER A1511, 12 parts of bisphenol A bisphosphate and 20 parts of talc were used with a PCM30 twin-screw extruder manufactured by Ikegai Iron Works Co., Ltd., kneading disk L: 2, kneading disk R: A resin pattern was obtained by melt-kneading with a screw pattern having three seals and one cylinder at a cylinder temperature of 300 ° C. and a screw rotation speed of 100 rpm. The results of the physical property test of the composition are shown in Table 1.

[0029]

Comparative Example 1 Example 1 was repeated except that 12 parts of bisphenol A bisphosphate of Example 1 was replaced with 9 parts, 5 parts of Modiper A1511 was replaced with 0 parts, and 30 parts of polystyrene H9302 was replaced with 38 parts. A resin composition was obtained. The results of the physical property test of the composition are shown in Table 1.

[0030]

Comparative Example 2 12 parts of bisphenol A bisphosphate of Example 1 was added to 9 parts, and 30 parts of polystyrene H930 was used.
Example 1 was repeated except that 2 parts was replaced with 33 parts to obtain a resin composition. The results of the physical property test of the composition are shown in Table 1.

[0031]

[Example 2] 45 parts of the same poly (2,6-dimethyl-1,4-phenylene) ether used in Example 1, 20 parts of polystyrene 685 manufactured by A & M Styrene Co., Ltd., Modiper A1
7 parts of 511, 8 parts of triphenyl phosphate and 20 parts of glass fiber having a diameter of 13 μm were melt-kneaded under the same conditions as in Example 1 to obtain a resin composition. The results of the physical property test of the composition are shown in Table 2.

[0032]

Comparative Example 3 8 parts of triphenyl phosphate of Example 2 was added to 4 parts, and 7 parts of Modiper A1511 was added to 0 part.
A resin composition was obtained by repeating Example 2 except that 0 part of polystyrene 685 was replaced with 31 parts. The results of the physical property test of the composition are shown in Table 2.

[0033]

Comparative Example 4 A resin composition was obtained by repeating Example 2 except that 8 parts of triphenyl phosphate in Example 2 was replaced with 4 parts and 20 parts of polystyrene 685 was replaced with 24 parts. The results of the physical property test of the composition are shown in Table 2.

[0034]

[Table 1]

[0035]

[Table 2]

[0036]

The flame-retardant thermoplastic resin composition of the present invention has excellent slidability and can be effectively used in the field of office equipment and information equipment.

Claims (3)

[Claims] 1. (a) Polyphenylene ether resin,
Alternatively, a thermoplastic resin 1 comprising this and a styrene resin
00 parts by weight, (b) Graft copolymer 2 comprising 5 to 95% by weight of α-olefin polymer and 95 to 5% by weight of vinyl polymer comprising at least one vinyl monomer
50 parts by weight and (c) aromatic phosphate ester flame retardant 1
A flame-retardant thermoplastic resin composition comprising 0 to 40 parts by weight. 2. (a) a polyphenylene ether resin,
Alternatively, a thermoplastic resin 1 comprising this and a styrene resin
00 parts by weight, (b) Graft copolymer 2 comprising 5 to 95% by weight of α-olefin polymer and 95 to 5% by weight of vinyl polymer comprising at least one vinyl monomer
50 parts by weight, 10- (c) aromatic phosphate ester flame retardant
The flame-retardant thermoplastic resin composition according to claim 1, which comprises 40 parts by weight and (d) 5 to 150 parts by weight of the inorganic filler. 3. The flame-retardant thermoplastic resin according to claim 1, wherein the component (b) is a graft copolymer composed of polyethylene and poly (styrene-alkyl methacrylate-hydroxyalkyl methacrylate copolymer). Composition.