JPH09324086A - Thermoplastic resin composition - Google Patents

Abstract

(57) Abstract: A modified polycarbonate-based resin and polystyrene-based resin having flowability and impact strength comparable to ABS resin-blended polycarbonate-based resin are used as main materials. There is provided a thermoplastic resin composition which is harmless and has excellent flame retardancy, which is based on the polymer blend. SOLUTION: The thermoplastic resin composition comprises the following components (1) to (4), or further comprises the component (5). (1) Resin composition 10 comprising 30 to 95% by weight of a polycarbonate resin and 5 to 70% by weight of a polystyrene resin
0 parts by weight, (2) a block copolymer (C) comprising a polymer block (A) mainly containing a vinyl aromatic compound and a polymer block (B) mainly containing a conjugated diene compound in the same molecule, or 0.5 to 20 parts by weight of an epoxy-modified block copolymer (E) in which a double bond derived from a conjugated diene compound of the partially hydrogenated product is epoxidized, (3) an organic phosphorus compound 1 to 40 parts by weight, (4) ) Phenolic resin 0.1-1
0 parts by weight, (5) fluoroethylene polymer 0.05 to 5
Parts by weight

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition mainly composed of a polycarbonate-based resin and a polystyrene-based resin, which has excellent flame retardancy, moldability and impact resistance.
The present invention relates to a thermoplastic resin composition which is useful as a material for OA equipment, communication equipment, housings for home electric appliances, chassis and other members, or members for automobiles.

[0002]

2. Description of the Related Art Generally, home appliances and the like made of synthetic resin materials are required to have impact resistance. Among these synthetic resin materials, polycarbonate resin has excellent mechanical properties,
Since it has thermal properties, it is widely used industrially.
However, the fluidity at the time of molding required together with the mechanical strength is not sufficient, and it is often used as a polymer blend with another thermoplastic resin. For example, a polymer blend of a polycarbonate-based resin and an acrylonitrile-butadiene-styrene-based resin (ABS resin) was developed for the purpose of improving fluidity and cost reduction, and is currently used in the automobile field, OA equipment field, electronic field It is widely used in the electric field.

[0003]

On the other hand, in applications such as office automation equipment and home electric appliances, the synthetic resin materials used are required to have flame retardancy, and bromine- or chlorine-based halogen-based flame retardants are used as external flame retardants. It is commonly used. However, although these flame retardants have a relatively large flame retarding effect, they have the drawback that corrosive or toxic gases are generated during processing or combustion. Therefore, in recent years, with the increasing concern about environmental problems, development of a flame-retardant resin that does not use a bromine- or chlorine-based halogen compound is desired.

Further, there is a polystyrene resin as a synthetic resin used for home electric appliances and the like, but since the compatibility with the polycarbonate resin is poor, the resin composition composed of the both is inferior in mechanical properties and is therefore used much. Absent. However, if the properties of polystyrene resin having excellent impact resistance and moldability and good dimensional accuracy can be utilized, expansion of applications in such fields can be expected.

Under the above circumstances, it has been desired to develop a thermoplastic resin composition having fluidity and impact strength comparable to those of ABS resin blend polycarbonate resin, and having excellent flame retardancy and molding characteristics.

[0006]

Means for Solving the Problems The present inventors have found that when a flame retardant and a specific epoxy-modified block copolymer are blended with a resin composition comprising a polycarbonate resin and a polystyrene resin, impact resistance Further, they have found that a resin composition having extremely excellent flame retardancy and excellent fluidity can be obtained, and completed the present invention.

That is, the present invention provides (1) 30 to 95% by weight of a polycarbonate resin and 5 to 7 of a polystyrene resin.
100 parts by weight of a resin composition consisting of 0% by weight, (2) consisting of a polymer block (A) mainly containing a vinyl aromatic compound and a polymer block (B) mainly containing a conjugated diene compound in the same molecule. 0.5 to 20 parts by weight of an epoxy-modified block copolymer (E) obtained by epoxidizing a double bond derived from a conjugated diene compound of the block copolymer (C) or its partially hydrogenated product (D), (3) Organic phosphorus compounds 1-4
The present invention provides a thermoplastic resin composition comprising 0 parts by weight and 0.1 to 10 parts by weight of (4) phenol resin. Further, the present invention provides a thermoplastic resin composition containing 0.05 to 5 parts by weight of a fluoroethylene polymer in the above thermoplastic resin composition. In addition, (1) 60 to 80% by weight of polycarbonate resin and 40 to 20 of polystyrene resin
100 parts by weight of a resin composition consisting of 1% by weight, (2) a block composed of a polymer block (A) mainly containing a vinyl aromatic compound and a polymer block (B) mainly containing a conjugated diene compound in the same molecule. Epoxy-modified block copolymer (E) in which the double bond derived from the conjugated diene compound of the copolymer (C) or its partially hydrogenated product (D) is epoxidized
1 to 5 parts by weight, (3) organophosphorus compound 5 to 20 parts by weight,
(4) A thermoplastic resin composition comprising 0.3 to 2 parts by weight of a phenol resin and (1) 0.1 to 1 part by weight of a fluoroethylene polymer (5) is provided. Hereinafter, the present invention will be described in detail.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION

(Polycarbonate Resin) As the polycarbonate resin used in the present invention, a resin produced by reacting a dihydric phenol with a carbonate precursor by a solution method or a melting method can be used. Typical examples of preferable dihydric phenols are 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A), bis (4-hydroxyphenyl) methane, and 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 can be mentioned. A particularly preferred dihydric phenol is a bis (4-hydroxyphenyl) alkane-based one, and particularly one containing bisphenol A as a main raw material. Further, preferred carbonate precursors include carbonyl halide, carbonyl ester, haloformate and the like,
Specific examples thereof include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and a mixture thereof. For the production of the polycarbonate resin, one or more of the above-mentioned dihydric phenols can be used, and two or more of the polycarbonate resins thus obtained may be mixed and used.

(Polystyrene Resin) The polystyrene resin used in the present invention is a polymer of an aromatic vinyl monomer, and the polymer may be a polymer modified with a rubbery polymer. . Examples of the monomer constituting the polystyrene resin include styrene, α-methylstyrene, halostyrene, vinyltoluene, and the like. In addition to these homopolymers, copolymers using two or more of the above monomers Good. Polystyrene resins preferably used in the present invention include polystyrene (GPPS) and high impact polystyrene (HIPS). There are no particular restrictions on the production of polystyrene-based resin, commonly used bulk polymerization,
Known methods such as solution polymerization, suspension polymerization and emulsion polymerization can be used.

(Epoxy-modified block copolymer (E))
Epoxy-modified block copolymer (E) used in the present invention
Is a block copolymer (C) composed of a polymer block (A) mainly containing a vinyl aromatic compound and a polymer block (B) mainly containing a conjugated diene compound in the same molecule.
Alternatively, the double bond derived from the conjugated diene compound of the partially hydrogenated product (D) is epoxidized.

As the "vinyl aromatic compound" constituting the block copolymer (A), styrene, α-methylstyrene, vinyltoluene, p-tertiarybutylstyrene, divinylbenzene, p-methylstyrene, 1,1. Examples thereof include diphenylstyrene, and styrene is particularly preferable. These can be used alone or in combination of two or more. As the "conjugated diene compound" constituting the block copolymer (B), butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3
Examples thereof include butadiene, piperylene, 3-butyl-1,3-octadiene, phenyl-1,3-butadiene and the like. Among these, one kind or a combination of two or more kinds can be used. Of these, butadiene, isoprene and combinations thereof are preferable.

The block copolymer (C) comprises a block copolymer (A) composed of a vinyl aromatic compound and a block copolymer (B) composed of a conjugated diene compound. Copolymerization of vinyl aromatic compounds and conjugated diene compounds (by weight)
The ratio is 5/9 for vinyl aromatic compound / conjugated diene compound.
5 to 70/30, especially 10/90 to 60 /
It is preferably in the range of 40.

The molecular structure of the block copolymer (C) may be linear, branched, radial or any combination thereof. For example, the block copolymer (A) and the block copolymer (B) are ABA and B.
-A-B-A, (A -B-) 4 Si, A-B-A-B-
A case having a structure such as A can be exemplified. The unsaturated bond derived from the conjugated diene compound of the block polymer (C) may be partially hydrogenated (D).

The number average molecular weight of the block copolymer (C) is preferably 5,000 to 600,000, and particularly preferably 10,000 to 500,000. In addition, the molecular weight distribution [weight average molecular weight (Mw)
(Mw / Mn)] and the number average molecular weight (Mn) is 10
The following is preferred. This is because within this range, appropriate compatibility with each component can be obtained.

The epoxy-modified block copolymer (E) is
It can be obtained by reacting the block polymer (C) or partially hydrogenated product (D) with an epoxidizing agent such as hydroperoxides and peracids in an inert solvent. By blending the epoxy-modified block copolymer (E), appropriate impact resistance can be imparted to the thermosetting resin composition. The amount of the epoxidizing agent used in the epoxidation is not strictly limited, and is appropriately selected depending on the type of the epoxidizing agent, the desired degree of epoxidation, and the individual block copolymer (C) used.

(Organic Phosphorus Compound) The organic phosphorus compound used in the present invention is not particularly limited as long as it is an organic compound having a phosphorus atom. Preferably, an organic phosphorus compound having at least one ester oxygen atom directly bonded to a phosphorus atom is used. Organophosphorus compounds that can be used in the present invention include trimethyl phosphate, triethyl phosphate and 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-phenyl) Phenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate
, O-phenylphenyl dicresyl phosphate, dibutyl phosphate, monobutyl phosphate, di (2
-Ethylhexyl) phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl Examples thereof include orthophosphoric acid esters such as 2-methacryloyloxyethyl phosphate and their condensates. Of these, particularly preferred is triphenyl phosphate. Examples of the phosphite include triphenylphosphite, trisnonylphenylphosphite, tristridecylphosphite, dibutylhydrogenenephosphite, and condensates thereof. Further, other organic phosphorus compounds include triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate, diethyl phenylphosphonate, and the like. These organic phosphorus compounds may be used alone or in combination of two or more.

(Phenolic Resin) The phenolic resin used in the present invention is not limited, but a resin obtained by reacting phenols with aldehydes and / or ketones under an acidic or alkaline catalyst by a known method is used. can do. Examples of phenols include phenol, cresol, xylenol, ethylphenol, propylphenol, butylphenol, amylphenol, nonylphenol, phenylphenol, phenoxyphenol, hydroquinone, resorcinol, catechol, dihydroxydiphenyl, bis (hydroxyphenyl) pentane, dihydroxydiphenylmethane, bis. (Hydroxyphenyl) butane, dihydroxydiphenyl sulfone, dihydroxydiphenyl ketone, bis (hydroxyphenyl) propane, and the like, and mixtures thereof. Further, as the aldehydes, formaldehyde,
Paraformaldehyde, acetaldehyde, glyoxal, etc. are mentioned. Further, examples of the ketones include acetone. Further, as the phenol resin in the present invention, both a resol type and a novolac type can be used. Particularly preferred is a novolac type phenol resin.

(Fluoroethylene Polymer) In the present invention,
A fluoroethylene-based polymer can also be blended. The fluoroethylene polymer has a high molecular weight of Mn of 10,000 or more, a glass transition temperature of −30 ° C. or higher, more preferably 100 ° C. or higher, and a fluorine content of 65 to 76 wt%. It is particularly preferably 70 to 76% by weight. Furthermore, the average particle size is 0.05 to 1.0
00 μm, more preferably 0.08 to 20 μm,
The density is preferably 1.2 to 2.3 g / cm ³ . Examples of the fluoroethylene-based polymer that can be preferably used in the present invention include polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / hexafluoropropylene, and ethylene / tetrafluoroethylene copolymer. Particularly preferred is polytetrafluoroethylene. is there. These may be added alone or in combination of two or more.

(Blending Ratio of Thermoplastic Resin Composition) The blending ratio of each component in the thermoplastic resin composition of the present invention is shown below. The blending ratio of the polycarbonate-based resin and the polystyrene-based resin is 30 to 95 for the polycarbonate-based resin in the resin composition composed of the polycarbonate-based resin and the polystyrene-based resin (hereinafter referred to as “PC-PS resin composition”). It is preferably 50% by weight, more preferably 50 to 90% by weight, particularly preferably 60 to 80% by weight (based on the total of 100% by weight of both). If the blending amount of the polycarbonate-based resin is less than 30% by weight, the heat distortion temperature is inferior, while if it exceeds 95% by weight, moldability becomes insufficient.

The amount of the epoxy-modified block copolymer (E) compounded is 100 parts by weight of the PC-PS resin composition.
5 to 20 parts by weight, particularly preferably 1 to 5 parts by weight.
If it is less than 0.5 part by weight, the effect of improving the compatibility between the polycarbonate resin and the polystyrene resin is not sufficient,
The mechanical properties of the obtained thermoplastic resin composition may be inferior. On the other hand, when the amount exceeds 20 parts by weight, the flame retardancy is adversely affected, and the flexural modulus and the heat deformation temperature may be reduced.

The compounding amount of the organic phosphorus compound is 1 to 40 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the PC-PS resin composition. If it is less than 1 part by weight, the flame retardant effect is not sufficient, and if it exceeds 40 parts by weight, the mechanical properties of the obtained thermoplastic resin composition are impaired.

The amount of the phenol resin compounded is 0.1 to 10 parts by weight, preferably 0.3 to 2 parts by weight, based on 100 parts by weight of the PC-PS resin composition. If it is less than 0.1 part by weight, the flame retardant effect is not sufficient and the surface impact strength effect is not sufficient. On the other hand, if it exceeds 10 parts by weight, the mechanical properties of the thermoplastic resin composition may be impaired.

When the fluoroethylene-based polymer is blended in the thermoplastic resin composition of the present invention, it is preferably 0.05 to 5 parts by weight, particularly preferably 100 parts by weight of the PC-PS resin composition. It is preferably 0.1 to 1 part by weight. When the blending amount of the fluoroethylene-based polymer is in this range, dripping due to plasticization of the resin due to the addition of the organic phosphorus compound can be sufficiently prevented, and the mechanical properties of the obtained resin composition can be impaired. Absent. Even when the fluoroethylene-based polymer is not blended, a thermoplastic resin composition having practical flame retardancy and excellent fluidity and impact resistance can be obtained.

(Method for Producing Thermoplastic Resin Composition) For producing the thermoplastic resin composition of the present invention, known means can be applied. For example, a predetermined amount of each component is premixed with a mixer such as a Henschel mixer, a tumbler blender, a kneader, and then kneaded with an extruder, or melt-kneaded with a heating roll or a Banbury mixer, and then pelletized or crushed. It can be manufactured by doing. At that time, if necessary, various additives that can be used in the polycarbonate-based resin or the polystyrene-based resin, for example, fillers, lubricants, reinforcing agents, stabilizers, light stabilizers, ultraviolet absorbers, plasticizers, antistatic agents, hues. You may add a modifier etc.

The thermoplastic resin composition of the present invention is excellent in moldability, impact resistance, thermal stability and flame retardancy, and is used for OA equipment, communication equipment, housings for home electric appliances, chassis and other members, or automobiles. It can be used as a thermoplastic resin composition which is a material for a member for use.

[0026]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples.

(1) Impact strength (unit: kg · cm / c
m) Impact strength was evaluated on a 1/4 inch thick test piece using the notched Izod impact strength as a scale. (2) Surface impact strength (Dupont impact strength, unit kgf ·
cm) 1 kg load used for Dupont impact strength, punch diameter R =
It was evaluated on a 1/4 inch, 2 mm thick test specimen. (3) Flame retardancy (UL94) As a flame retardancy evaluation scale, in accordance with the vertical flammability test (94V-0) defined in UL94 of the US UL standard,
The test piece (bar sample) having a thickness of 1/16 inch was evaluated. In the table below, B represents burning. (4) Fluidity (unit: mm) Spiral flow (section shape: thickness 2 mm, width 20 m
The flow length (mm) of m) was measured. Cylinder temperature: 2
50 ° C, mold temperature: 60 ° C, injection pressure: 500 kg / c
It was set to m ² .

(Examples 1 to 6 and Comparative Examples 1 to 8) As a polycarbonate resin (Idemitsu Petrochemical Co., Ltd. product: "Taflon FN-2700"), as a polystyrene resin, high-impact polystyrene (Daicel Chemical Industries Ltd.) )
(Manufactured by: “Daicel Styrol S81”), as an epoxy-modified block copolymer (manufactured by Daicel Chemical Industries, Ltd .:
"ESBS420"), ABS resin (manufactured by Daicel Chemical Industries, Ltd .: "Cebian-V520"), triphenyl phosphate and trixylenyl phosphate as organic phosphorus compounds ("PX-130" manufactured by Daihachi Chemical Industry Co., Ltd.) , An organic phosphorus compound represented by the following chemical formula (1) (“PX-200” manufactured by Daihachi Chemical Industry Co., Ltd.), and a fluoroethylene polymer (“Teflon 6-manufactured by DuPont Mitsui Fluorochemical Co., Ltd.”
J ”), a special phenol resin (“ Bellpearl S-890 ”manufactured by Kanebo Co., Ltd.) and a novolac type phenol resin (“ Sumilite Resin PR-53195 ”manufactured by Sumitomo Dures Co., Ltd.) as phenol resins. In the blending ratio (parts by weight) shown in -2, the mixture was mixed with a tumbler blender and melt-kneaded with an extruder to obtain a pellet-shaped resin composition. Next, injection molding machine (cylinder temperature 250 ℃, mold temperature 6
At 0 ° C.), a test piece for general physical properties was prepared, and each physical property was measured according to standard methods. The results are shown in Tables 1 and 2.

[0029]

Embedded image

[0030]

[Table 1]

[0031]

[Table 2]

(Test Results) The thermoplastic resin composition of the present invention is extremely excellent in flame retardancy and fluidity (molding processability).
In particular, when compared with a resin composition containing a polycarbonate-based resin and an ABS-based resin as main materials, it is equivalent in impact resistance, but is excellent in fluidity, flame retardancy, and impact resistance. This effect was remarkable when the epoxy-modified block copolymer and the phenol resin were used in combination.

[0033]

EFFECT OF THE INVENTION The thermoplastic resin composition of the present invention has impact resistance and phenol resin by blending a composition of polycarbonate resin and polystyrene resin with a specific epoxy-modified block copolymer. A thermoplastic resin composition having excellent flame retardancy and molding processability, which does not generate corrosive or toxic gas at the time of processing or burning by blending with and an organic phosphorus compound.

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Claims (3)

[Claims] 1. A thermoplastic resin composition comprising the following components (1) to (4). (1) Resin composition 10 comprising 30 to 95% by weight of a polycarbonate resin and 5 to 70% by weight of a polystyrene resin
0 parts by weight, (2) a block copolymer (C) comprising a polymer block (A) mainly containing a vinyl aromatic compound and a polymer block (B) mainly containing a conjugated diene compound in the same molecule.
Or 0.5 to 20 parts by weight of an epoxy-modified block copolymer (E) in which a double bond derived from a conjugated diene compound of the partially hydrogenated product (D) is epoxidized, (3) an organic phosphorus compound 1 to 40 parts by weight Parts, (4) phenol resin 0.1 to 10 parts by weight 2. A thermoplastic resin composition comprising the following components (1) to (5). (1) Resin composition 10 comprising 30 to 95% by weight of a polycarbonate resin and 5 to 70% by weight of a polystyrene resin
0 parts by weight, (2) a block copolymer (C) comprising a polymer block (A) mainly containing a vinyl aromatic compound and a polymer block (B) mainly containing a conjugated diene compound in the same molecule.
Or 0.5 to 20 parts by weight of an epoxy-modified block copolymer (E) in which a double bond derived from a conjugated diene compound of the partially hydrogenated product (D) is epoxidized, (3) an organic phosphorus compound 1 to 40 parts by weight Parts, (4) phenol resin 0.1 to 10 parts by weight, (5) fluoroethylene polymer 0.05 to 5 parts by weight 3. A thermoplastic resin composition comprising the following components (1) to (5). (1) Resin composition 1 comprising 60 to 80% by weight of polycarbonate resin and 40 to 20% by weight of polystyrene resin
00 parts by weight, (2) a block copolymer (C) comprising a polymer block (A) mainly containing a vinyl aromatic compound and a polymer block (B) mainly containing a conjugated diene compound in the same molecule.
Alternatively, 1 to 5 parts by weight of an epoxy-modified block copolymer (E) obtained by epoxidizing a double bond derived from a conjugated diene compound of the partially hydrogenated product (D), (3) 5 to 20 parts by weight of an organic phosphorus compound, (4) 0.3 to 2 parts by weight of phenolic resin, (5) 0.1 to 1 part by weight of fluoroethylene polymer