JPH09217000A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To modify a polymer blend composed mainly of a polycarbonate resin and a polystyrene resin to a thermoplastic resin compsn. having fluidity and impact strength comparable to a polycarbonate resin blended with an ABS resin and to provide a harmless, flame retarded thermoplastic resin compsn. based on the modified compsn. SOLUTION: This thermoplastic resin compsn. comprises: 100 pts.wt. resin blend comprising 30 to 95wt.% polycarbonate resin (a) and 5 to 70wt.% polystyrene resin (b) and 0.1 to 10 pts.wt. ethylene/carbon monoxide/(meth)acrylic alkyl ester copolymer incorporated into the blend. Further, 1 to 40 pts.wt. organophosphorus compd. (d) and 0.05 to 5 pts.wt. fluoroethylene polymer (e) are added.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition which is a raw material for office automation equipment, communication equipment, housings for home appliances, chassis and other members, members for automobiles and the like. More specifically, it relates to a thermoplastic resin composition having a polycarbonate-based resin and a polystyrene-based resin as a main material and excellent in moldability, impact resistance, and thermal stability, and a flame retardant resin composition thereof. is there.

[0002]

2. Description of the Related Art Polycarbonate resins are widely used industrially because they have excellent mechanical properties and thermal properties. However, a large number of polymer blends with other thermoplastic resins have been developed in order to improve molding processability, particularly fluidity. Among them, a polymer blend with an acrylonitrile-butadiene-styrene (ABS) resin is widely used in the fields of automobiles, OA equipment, electronics and electricity for the purpose of improving fluidity and reducing costs. In contrast, polymer blends with polystyrene have poor mechanical properties due to poor compatibility and are currently rarely used.

Further, mainly for use in OA equipment and home electric appliances, synthetic resin materials to be used must have flame retardancy, and bromine or chlorine-based halogen-based flame retardants are generally used as externally added flame retardants. Have been. Such a flame retardant has a relatively large flame-retarding effect, but has the disadvantage that corrosive or toxic gases are generated during processing or combustion. In recent years, with increasing interest in environmental issues, development of a flame-retardant resin that does not use bromine or a chlorine-based halogen compound has been desired as a method of solving these drawbacks.

The present invention relates to a thermoplastic resin having fluidity and impact strength, which is a polymer blend composed mainly of a polycarbonate resin and a polystyrene resin, which is comparable to an ABS resin blend polycarbonate resin. It is an object of the present invention to modify a resin composition and to provide a harmless flame-retardant thermoplastic resin composition based on the modified composition.

[0005]

[Means for Solving the Problems] That is, the present invention is
(A) Polycarbonate-based resin 30 to 95% by weight,
(B) Polystyrene-based resin 0.1 to 10 parts by weight of (c) ethylene / carbon monoxide / alkyl (meth) acrylate copolymer is added to 100 parts by weight of a resin mixture consisting of 5 to 70% by weight. The thermoplastic resin composition according to the second aspect of the present invention is the thermoplastic resin composition according to claim 1, further comprising (d) 1 to 40 parts by weight of an organic phosphorus compound, and (e) Fluoroethylene polymer 0.05 ~
A flame-retardant thermoplastic resin composition obtained by adding 5 parts by weight is presented.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The polycarbonate resin as the component (a) of the present invention is produced by reacting a divalent phenol with a carbonate precursor by a solution method or a melting method. It is what is done. To give a representative example of divalent phenol,
2,2-bis (4-hydroxyphenyl) propane (bisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxy) -3,5-Dimethylphenyl) propane, 2,2-bis (4-hydroxy-)
3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) sulfide, bis (4
-Hydroxyphenyl) sulfone and the like. A preferred divalent phenol is a bis (4-hydroxyphenyl) alkane type, especially bisphenol A as a main raw material. Further, as a carbonate precursor, carbonyl halide, carbonyl ester or haloform
And phosgene, diphenyl carbonate, dihaloformate of divalent phenol and a mixture thereof. In producing the polycarbonate resin, one or more of these divalent phenols can be used. In addition, the thus obtained polymer
It is also possible to use a mixture of two or more of the binder resins.

The polystyrene resin as the component (b) of the present invention is a polymer obtained by polymerizing an aromatic vinyl monomer, and the polymer is modified with a rubbery polymer. The above-mentioned polymer is also included.

Examples of the aromatic vinyl monomer used in the present invention include styrene, α-methylstyrene, halostyrene and vinyltoluene. Examples of the rubbery polymer include polybutadiene, polyisoprene, and styrene-butadiene copolymer rubber (including random and block). The method for producing polystyrene is not particularly limited, and known methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be used. The polystyrene resin preferably used in the present invention is polystyrene (GPPS), high impact polystyrene (HIPS), or the like.

The ethylene / carbon monoxide / (meth) acrylic acid alkyl ester copolymer which is the component (c) of the present invention is ethylene / carbon monoxide and (meth) acrylic acid alkyl ester copolymer, The term “(meth) acrylic acid alkyl ester” as used herein means an ester of acrylic acid or methacrylic acid, but usually has 1 to 1 carbon atoms.
A linear or branched alkyl ester of about 8, preferably about 1 to 8, is preferable. More specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, se
c-butyl, t-butyl, isobutyl, n-hexyl,
Examples thereof include esters such as 2-ethylhexyl and n-octyl. In the ethylene / carbon monoxide / (meth) acrylic acid alkyl ester copolymer, the amount of ethylene is 30 to 90% by weight, preferably 40 to 80% by weight, and the amount of carbon monoxide is 1 to 40% by weight, preferably 5-3
It is desirable that the (meth) acrylic acid alkyl ester is contained in an amount of 5 to 60% by weight, preferably 20 to 50% by weight, in an amount of 0% by weight. It is also possible to copolymerize.

In order to produce such a copolymer, for example, ethylene, carbon monoxide and (meth) acrylic acid, which are monomers, are respectively added to t-butylperoxyisobutyrate and azobisisobutybutyro. Like nitrile,
It may be supplied together with a radical initiator into a high-speed stirring reactor at a predetermined ratio, and mixed at high temperature (for example, 160 to 250 ° C.) and high pressure (for example, 160 to 300 MPa) under high speed stirring for copolymerization. Further, the ethylene / carbon monoxide / (meth) acrylic acid alkyl ester copolymer may be grafted with a polyamide oligomer or graft-copolymerized with an unsaturated carboxylic acid or an anhydride thereof.

The organic phosphorus compound which is the component (d) of the present invention is not particularly limited as long as it is an organic compound having a phosphorus atom, but preferably has at least one ester oxygen atom directly bonded to the phosphorus atom. An organic phosphorus compound is used. Examples of such compounds include orthophosphoric acid esters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate. , Trioleyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, tris (o-phenylphenyl) phosphate , Tris (p-
Phenylphenyl) phosphate, trinaphthylphosphate, cresyldiphenylphosphate, xylenyldiphenylphosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenylphosphate , O-phenylphenyl dicresyl phosphate, dibutyl phosphate, monobutyl phosphate, di (2-ethylhexyl) phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid. Orthophosphoric acid esters such as phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate and their condensates are Can be mentioned.

Examples of the phosphite include triphenyl phosphite, trisnonyl phenyl phosphite, tris tridecyl phosphite, dibutyl hydrogen phosphite and condensates thereof.

Other organic phosphorus compounds include:
Examples thereof include triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate and diethyl phenylphosphonate. These organic phosphorus compounds may be used alone or in combination of two or more.

The fluoroethylene-based polymer which is the component (e) of the present invention is a high molecular weight Mn of 10,000 or more, and has a glass transition temperature of -30 ° C. or more, preferably 100 ° C. or more, 65 to 65. Fluorine content of 76% by weight, more preferably 70-76% by weight, 0.05-1, 00
It has an average particle size of 0 μm, preferably 0.08 to 20 μm and a density of 1.2 to 2.3 g / cm ³ .
Suitable fluoroethylene-based polymers include polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / hexafluoropropylene and ethylene / tetrafluoroethylene copolymers, and these are added alone or in combination. . In the resin composition of the present invention, the amount of the polycarbonate resin as the component (a) is 30 to 95% by weight, preferably 50 to 90% by weight.
%, More preferably 60 to 80% by weight. If the blending amount is less than 30% by weight, the heat distortion temperature is poor,
On the other hand, if it exceeds 95% by weight, moldability is insufficient.

The blending amount of the polystyrene resin as the component (b) is 5 to 70% by weight, preferably 10 to 50% by weight, more preferably 20 to 40% by weight. The blending amount is 5
If it is less than wt%, the moldability is insufficient, while
If it exceeds 70% by weight, the heat distortion temperature tends to be poor.

The blending amount of the ethylene / carbon monoxide / (meth) acrylic acid alkyl ester copolymer as the component (c) is
Component (a) + component (b) = 0.1 per 100 parts by weight
10 to 10 parts by weight, preferably 1 to 5 parts by weight. If the blending amount is less than 0.1 parts by weight, the effect of improving the compatibility between the components (a) and (b) is insufficient, resulting in poor mechanical properties. On the other hand, if it exceeds 10 parts by weight, the flame retardancy is adversely affected. In addition to giving, mechanical strength decreases.

The amount of the organic phosphorus compound as the component (d) is 1 to 4 with respect to 100 parts by weight of the component (a) + the component (b) = 100 parts by weight.
0 parts by weight, preferably 5 to 20 parts by weight. If the blending amount is less than 1 part by weight, the flame retardant effect is not sufficient, and 40
When it exceeds the weight part, the mechanical properties of the composition are impaired.

The amount of the fluoroethylene polymer as the component (e) to be blended is 0.05 to 5 parts by weight, preferably 0.1 to 1 part by weight, relative to 100 parts by weight of the component (a) + the component (b). It is a department. The compounding amount of fluorinated polyolefin is 0.0
If it is less than 5 parts by weight, the function of preventing dripping due to plasticization of the resin, which occurs when the organic phosphorus compound is added, is not sufficient. On the other hand, if it exceeds 5 parts by weight, the mechanical properties are impaired and the cost increases. As a method for producing the resin composition of the present invention, all known means can be applied. For example, a predetermined amount of each component (a) to (e) is premixed with a mixer such as a Henschel mixer, a tumbler blender, or a kneader, and then kneaded with an extruder, or melt-kneaded with a heating roll or a Banbury mixer. Then, it can be manufactured by pelletizing or pulverizing. At this time, if necessary, various additives that can be used in the polycarbonate-based resin or the polystyrene-based resin,
For example, a filler, a lubricant, a reinforcing agent, a stabilizer, a light resistance stabilizer, an ultraviolet absorber, a plasticizer, an antistatic agent, a hue improver and the like may be added.

[0019]

EXAMPLES The present invention will be described in more detail below by showing Examples and Comparative Examples, but the scope of the present invention is not limited to these Examples.

The thermoplastic resin compositions and flame-retardant thermoplastic resin compositions of the following Examples and Comparative Examples were evaluated in the following manner.

(1) Impact resistance strength The impact resistance strength was evaluated by using a notched Izod impact strength as a scale and a 1/4 inch thick test piece.

(2) Flame retardance As a flame retardancy evaluation scale, in accordance with the vertical flammability test (94V-0) prescribed in UL94 of the US UL standard,
The test piece (bar sample) having a thickness of 1/16 inch was evaluated.

(3) Fluidity Spiral flow (section: thickness 2 mm, width 20 m
The flow length of m) was measured. Cylinder temperature: 250 ° C,
Mold temperature: 60 ° C., injection pressure: 500 kg / cm ² Examples 1 to 5, Comparative Examples 1 to 6 Daicel Styrol S81 (trade name: product of Daicel Chemical Industries, Ltd.), which is high-impact polystyrene as a polystyrene resin. Tufflon FN-2700 (trade name: product of Idemitsu Petrochemical Co., Ltd.) as a polycarbonate resin, and Elvalloy EP4051 as an ethylene / carbon monoxide / (meth) acrylic acid alkyl ester copolymer
(Product name: Mitsui DuPont Polychemical Co., Ltd. product),
ABS resin as SEVIAN-V520 (trade name: product of Daicel Chemical Industries, Ltd.), triphenyl phosphate as organic phosphorus compound, PX-130, PX-200 (product name: product of Daihachi Chemical Industry Co., Ltd.), fluoroethylene type Teflon 6-J (trade name: Dupont Mitsui Fluorochemicals Co., Ltd.) as a polymer was blended in a tumbler blender with the composition shown in Table 1 and melt-kneaded with an extruder to obtain a pelletized resin composition. It was Next, a test piece for general physical properties was prepared with an injection molding machine (cylinder temperature 250 ° C., mold temperature 60 ° C.), and physical properties were measured according to standard methods. Table 1 shows the results.

[0024]

[Table 1] Evaluation of Test Results The thermoplastic resin composition according to the present invention, which is mainly composed of a polycarbonate resin and a polystyrene resin, has almost the same impact strength as that of the ABS resin blend polycarbonate resin. The fluidity (molding workability) is superior.

The flame-retardant thermoplastic resin composition of the present invention comprises
Compared with a resin composition containing a polycarbonate-based resin and an ABS-based resin as a main material in a considerable amount, the impact resistance is at the same level, and the flame retardancy and fluidity (molding processability) are Furthermore, it has an advantage.

This effect can be obtained only when the ethylene / carbon monoxide / (meth) acrylic acid alkyl ester copolymer and the fluoroethylene polymer are used in combination.

[0027]

As described above, a polymer blend of a polycarbonate-based resin and a polystyrene-based resin,
By adding the ethylene / carbon monoxide / (meth) acrylic acid alkyl ester copolymer, a thermoplastic resin composition having excellent moldability with significantly improved compatibility and excellent impact strength was obtained. Furthermore, in addition to this, by adding an organic phosphorus compound and a fluoroethylene polymer, there is no generation of corrosive or toxic gas during processing or combustion, and excellent flame resistance and impact resistance and molding processing. It was possible to obtain a novel non-bromine / non-chlorine flame-retardant thermoplastic resin composition with added properties. According to the present invention, a polystyrene blend, which has been a difficult problem in the prior art, has become possible in place of an ABS resin for the purpose of modifying a polycarbonate resin. The value of is very large.

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Claims (2)

[Claims] (A) Polycarbonate-based resin (30) to (9)
5% by weight, (b) polystyrene resin 5 to 70% by weight
A thermoplastic resin composition obtained by mixing 0.1 to 10 parts by weight of (c) ethylene / carbon monoxide / (meth) acrylic acid alkyl ester copolymer with 100 parts by weight of the resin mixture consisting of. 2. The thermoplastic resin composition according to claim 1, further comprising 1 to 40 parts by weight of (d) an organophosphorus compound and 0.05 to 5 parts by weight of a (e) fluoroethylene polymer. Flame-retardant resin composition obtained by adding.