JP2717339B2 - Thermoplastic resin composition - Google Patents

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, and more particularly, to a resin composition having high flame retardancy, rigidity and impact resistance, and having good fluidity capable of obtaining a thin molded product. The present invention relates to a carbon fiber reinforced thermoplastic resin composition having

[0002]

2. Description of the Related Art In recent years, miniaturization of office machines and electronic devices has demanded high-strength thin-walled products for housings, chassis and the like. For office machines and electronic devices,
High strength is generally required. Conventionally, it is generally known to mix carbon fibers with a thermoplastic resin. The compounding of the carbon fiber is performed for the purpose of obtaining a highly rigid molded article or the like.

[0003]

However, it is difficult to obtain a thermoplastic resin composition having flame retardancy, rigidity, fluidity and impact resistance only by simply blending carbon fibers with the thermoplastic resin. It is. The present invention has been made in view of the above circumstances, and has as its object to provide a thermoplastic resin composition having high flame retardancy, rigidity, impact resistance, and good fluidity capable of obtaining a thin molded product. To provide things.

[0004]

That is, the gist of the present invention resides in that the following components (A) to (H) are contained as essential components, and (A) to (A) to (C) are based on the total amount of the components. ) The ratio of the component is 30 to 90% by weight, and the ratio of the component (B) is 10 to
70% by weight, the proportion of the component (C) is 60% by weight or less (however, the total of (A) to (C) is 100% by weight),
The proportion of the component (D) is 1 to 30 parts by weight, and the proportion of the component (E) is 1 to 1 part by weight based on 100 parts by weight of the components (A) to (C).
2 parts by weight, the proportion of the component (F) is 1.0 part by weight or less,
(G) Component is 0.1 to 50 parts by weight, (A)
The ratio of the component (H) to 100 parts by weight of the components (G) to (G) is 1 to 20 parts by weight. (A) Aromatic polycarbonate resin (B) Graft copolymer obtained by polymerizing aromatic vinyl and a copolymerizable monomer in the presence of rubbery polymer (C) Aromatic vinyl and (A) Aromatic vinyl copolymer resin obtained by copolymerizing a copolymerizable monomer with (A) a bromine-containing flame-retardant organic compound (E) A flame-retardant auxiliary (F) A tetrafluoroethylene resin (G) Pitch-based carbon fiber (H) Copolyether / polyester heat containing 30 to 80% by weight of an aliphatic polyether chain and 70 to 20% by weight of an aromatic polyester chain and having a Vicat softening point of 100 ° C. or more Plastic elastomer

Hereinafter, the present invention will be described in detail. First, each raw material component (A) constituting the thermoplastic resin composition of the present invention
(H) will be described sequentially.

(A) Aromatic polycarbonate resin In the present invention, the aromatic polycarbonate resin is not particularly limited, and various resins can be used. For example, a solvent method, that is, a so-called phosgene method in which a dihydric phenol is reacted with a carbonate precursor such as phosgene in a solvent such as methylene chloride in the presence of a known acid acceptor and a molecular weight modifier, a divalent phenol and diphenyl Aromatic polycarbonate resins obtained by a transesterification method of reacting with a carbonate precursor such as carbonate are typical. Suitable dihydric phenols include bisphenols, and in particular, 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as “bis-phenol”).
Phenol A "). Also, screws
Phenol A may be obtained by partially or entirely substituting another dihydric phenol. From the viewpoints of mechanical strength and moldability, the aromatic polycarbonate resin preferably has a viscosity average molecular weight of 10,000 to 100,000, and particularly preferably 15,000 to 40,000.

(B) Graft Copolymer In the present invention, the graft copolymer is a graft copolymer obtained by polymerizing aromatic vinyl and a monomer copolymerizable therewith in the presence of a rubbery polymer. Use a copolymer. Preferred graft copolymers comprise from 40 to 80% by weight of an aromatic vinyl monomer, 20 to 40% by weight of a vinyl cyanide monomer and, if necessary, from 0 to 30% by weight of a vinyl monomer copolymerizable therewith. A graft copolymer obtained by polymerizing 30 to 80 parts by weight of the resulting monomer mixture (total 100% by weight) in the presence of 20 to 70 parts by weight of a rubbery polymer.

The properties of the graft copolymer are such that the graft ratio is 10 to 200% and the specific viscosity is 0.04 to 0.1.
It is preferably 15. Examples of the rubbery polymer include butadiene homopolymer, a copolymer comprising butadiene and a vinyl monomer copolymerizable therewith, an acrylate homopolymer, an acrylate ester and a vinyl monomer copolymerizable therewith. A copolymer composed of a body is used. As the vinyl monomer which can be copolymerized with the above-mentioned aromatic vinyl monomer and vinyl cyanide monomer, the monomers listed in (C) Aromatic vinyl copolymer described below are used. You can do it.

In the method for producing the graft copolymer, any generally known polymerization technique can be employed. For example,
Aqueous heterogeneous polymerization such as suspension polymerization and emulsion polymerization, bulk polymerization,
Solution polymerization, heterogeneous precipitation polymerization performed in a non-solvent of the produced polymer, and polymerization in combination thereof can be adopted.

(C) Aromatic vinyl copolymer The aromatic vinyl copolymer is obtained by copolymerizing aromatic vinyl and a monomer copolymerizable therewith. Preferred aromatic vinyl copolymers are aromatic vinyl monomers 40 to
80% by weight and a vinyl monomer 20 copolymerizable therewith
~ 60% by weight of an aromatic vinyl copolymer.
In the present invention, a mixture of two or more aromatic vinyl copolymers can be used.

As the aromatic vinyl monomer, styrene,
Styrene monomers such as α-methylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene and the like and their substituted monomers are exemplified. In particular, styrene or α-methylstyrene is preferably used.

Examples of monomers copolymerizable with the aromatic vinyl monomer include acrylonitrile, methacrylonitrile, α
-Vinyl cyanide monomers such as methacrylonitrile, acrylate monomers such as methyl acrylate, ethyl acrylate and butyl acrylate, and methacrylates such as methyl methacrylate and ethyl methacrylate. Monomer, vinyl carboxylic acid monomer such as acrylic acid and methacrylic acid, maleimide monomer such as maleimide, N-methylmaleimide and N-phenylmaleimide, maleic anhydride, acrylic amide, methacrylamide, acenaphthylene , N-vinylcarbazole and the like. In particular, acrylonitrile, acrylate, methacrylate, maleimide, N-methylmaleimide or N-phenylmaleimide is preferably used.

(D) Bromine-Containing Flame-Retardant Organic Compound In the present invention, the bromine-containing flame-retardant organic compound is nonvolatile during production and processing of the thermoplastic resin composition of the present invention and is thermally non-volatile. Compounds that are stable are used. Specific examples of the bromine-containing flame-retardant organic compound include the compounds listed in the following (1) to (3). (1) Oligocarbonate from decabromodiphenyl ether, octabromodiphenyl, octabromodiphenyl ether or tetrabromobisphenol A and its high molecular weight bromine compound (2) Oligomer and high molecular weight copolymer of tetrabromobisphenol A and epoxy ( 3) Compound in which the terminal of the oligomer or high molecular weight compound described in (2) is sealed with alkyl or the like Among the above, the compounds described in (2) and (3) are particularly preferably used.

(E) Flame retardant aid In the present invention, the flame retardant aid includes antimony trioxide, antimony carbonate, bismuth trioxide, bismuth carbonate,
Antimony pentoxide or the like can be used. In particular, antimony trioxide is preferably used. (F) Tetrafluoroethylene resin As the tetrafluoroethylene resin, commercially available polytetrafluoroethylene, for example, “Polyflon F201” manufactured by Daikin Industries, Ltd. can be used as it is.

(G) Pitch-based carbon fiber Pitch-based carbon fiber is a so-called chopped strand fiber using coal coal tar as a raw material. After spraying or applying a sizing agent to the carbon fiber surface, It is obtained by bundling, drying and cutting carbon fibers. In the present invention, the epoxy sizing agent 1 to 10
Pitch-based carbon fibers which are bundled in a weight% and cut to a fiber length of 1.5 mm to 20 mm are preferably used. The diameter of the single fiber is usually in the range of 5 to 20 μm.
The reasons for using pitch-based carbon fibers in the thermoplastic resin composition of the present invention are as follows. That is, in a PAN-based carbon fiber using polyacrylonitrile as a raw material, the volatile matter at a high temperature is large, and it is difficult to impart flame retardancy to the obtained thermoplastic resin composition. In addition, with metal fibers or the like, desired flame retardancy cannot be obtained,
When using only inorganic reinforcing materials such as glass fiber and mica,
This is because the desired rigidity and impact resistance cannot be obtained.

(H) Copolyether / polyester thermoplastic elastomer In the present invention, the copolyether / polyester thermoplastic elastomer includes 30 to 80% by weight of an aliphatic polyether chain and 70 to 20% by weight of an aromatic polyester. A copolyether / polyester thermoplastic elastomer having a chain and having a Vicat softening point of 100 ° C. or higher (measured in accordance with JIS K-72016) is used. By blending the above specific copolyether / polyester thermoplastic elastomer, the thermoplastic resin composition of the present invention can improve impact resistance without impairing other properties. As the thermoplastic elastomer, a block copolymer composed of two types of blocks, an aliphatic polyether chain and an aromatic polyester chain, is preferable. Copolymers obtained by random copolymerization of monomers constituting the polyether chain and the polyester chain are not preferred because desirable physical properties cannot be obtained.

The aliphatic polyether chains are derived from alkylene oxide or alkylene glycol. Specific examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran. Further, as a specific example of the alkylene glycol, a compound having a structure in which a hydroxy group is bonded to both ends of a methylene having 2 to 10 carbon atoms is preferable. Specifically, ethylene glycol, 1,4-
Butanediol, 1,5-pentanediol, 1,6-
Hexanediol and the like are mentioned, and ethylene glycol or 1,4-butanediol is particularly preferable.

[0018] The aromatic polyester chains are derived from aromatic dicarboxylic acids and alkylene glycols. Specific examples of the aromatic dicarboxylic acid include terephthalic acid, naphthalene-1,4-dicarboxylic acid, and naphthalene-1,5-dicarboxylic acid.
Examples thereof include dicarboxylic acids, and specific examples of the alkylene glycol include the same compounds as described above.

Particularly preferred copolyether / polyester thermoplastic elastomers include polyethylene terephthalate-polytetramethylene glycol block copolymer, polytetramethylene terephthalate-polytetramethylene glycol block copolymer and the like.

Next, the mixing ratio of each of the raw material components (A) to (H) will be described. The ratio of the component (A) to the total amount of the components (A) to (C) is 30 to 90% by weight,
The proportion of the component (B) is 10 to 70% by weight, the proportion of the component (C) is 60% by weight or less (however, the total of (A) to (C) is 100% by weight), and (A) to (C) )) 100 parts by weight of the component, the proportion of the component (D) is 1 to 30 parts by weight,
The proportion of the component (E) is 1 to 12 parts by weight, the proportion of the component (F) is 1.0 part by weight or less, and the proportion of the component (G) is 0.1 to 50 parts by weight.
Parts by weight, and the ratio of the component (H) to 100 parts by weight of the components (A) to (G) must be 1 to 20 parts by weight.

When the mixing ratio of the raw material components (A) to (C) is out of the above range, a thermoplastic resin composition having an excellent balance of physical properties such as rigidity, heat resistance and impact resistance can be obtained. Absent. When the amount of the bromine-containing flame-retardant organic compound is less than 1 part by weight, the desired flame retardancy cannot be obtained. When the amount exceeds 30 parts by weight, the heat stability becomes poor or other physical properties deteriorate. I do. When the amount of the flame retardant aid is less than 1 part by weight,
If the desired flame retardancy cannot be obtained, and if it exceeds 12 parts by weight, the thermal stability becomes poor or other physical properties deteriorate.
When the amount of the tetrafluoroethylene resin is more than 1.0 part by weight, the thermal stability is deteriorated and other physical properties are deteriorated. When the blending amount of the copolyether / polyester-based thermoplastic elastomer is less than 1 part by weight, the practical impact strength of the obtained composition is not sufficiently improved, and when it exceeds 20 parts by weight, the heat resistance of the obtained composition is increased. And the rigidity is reduced.

The thermoplastic resin composition of the present invention can be used in combination with glass fibers, flat glass flakes, milled glass, and the like that are bundled with a sizing agent such as epoxy, acrylic, or urethane. It is also possible to use an inorganic substance such as talc.

[0023]

EXAMPLES Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. In the following examples, “parts” means “parts by weight”. In the following examples, the following raw material components were used.

(A) Aromatic polycarbonate resin (P
C) An aromatic polycarbonate resin based on bisphenol A and having a relative viscosity of 1.29 (average molecular weight: 23000).

(B) Graft copolymer ABS (specific viscosity = 0.048, graft ratio = 30%) obtained by the following production method was used as the graft copolymer.
That is, potassium persulfate is used as an initiator, and a particle size of 0.25
A mixed monomer (61% by weight) having a styrene / acrylonitrile ratio of 70/30% by weight is copolymerized with 39% by weight of a styrene-butadiene rubber latex of μm.

(C) Aromatic vinyl copolymer resin (A
S) Styrene / acrylonitrile = 70/30 weight ratio copolymer (relative viscosity 1.4)

(D) Bromine-containing flame-retardant organic compound A bromine compound in which a terminal epoxy group of a copolymer of tetrabromobisphenol A and propylene oxide (weight average molecular weight: 2,000) is sealed with tribromophenol.

(E) Flame retardant assistant Antimony trioxide (F) Tetrafluoroethylene resin (PTFE) Polytetrafluoroethylene (“Polyflon F201” manufactured by Daikin Industries, Ltd.)

(G) Pitch-based carbon fiber (CF) Fiber diameter 10 μm bundled with 5% by weight of epoxy-based sizing agent,
Pitch-based carbon fiber with a fiber length of 6 mm ("Dialead K223" (G ') manufactured by Mitsubishi Chemical Corporation) polyacrylonitrile-based carbon fiber (PAN-C
F) Polyacrylonitrile-based carbon fiber having a fiber diameter of 7 μm and a fiber length of 6 mm bundled with 5% by weight of an epoxy-based sizing agent

(H) Copolyether / polyester thermoplastic elastomer ("HYTRELR4056", manufactured by DuPont, USA) (I) Glass fiber (GF) Fiber diameter 13 μm using epoxy sizing agent, fiber length 3 m
m glass monofilament

Examples 1 to 3 and Comparative Examples 1 to 6 Each of the above-mentioned raw material components (A) to (H) was weighed according to the mixing ratio (parts by weight) shown in Tables 1 and 2, and mixed by a tumbler. The resulting mixture is kneaded using a vented twin-screw extruder while removing volatile matter, and pitch-based carbon fiber (G) or polyacrylonitrile-based carbon fiber (G ′) and glass single fiber ( And H) to prepare pellets of the resin composition.

Test pieces for measuring physical properties were formed from the above-mentioned pellets by an injection molding method, and flexural modulus, Izod impact strength (with notch), and deflection temperature under load (HDT) were measured. In addition, a fluidity test and a combustion test according to UL regulations were performed. The results are shown in Tables 1 and 2.

The measuring method and the test method are as follows. (1) Flexural modulus (Kg / cm2) Measured according to JIS K7113. (2) Izod impact strength (with notch) (Kg · cm /
cm) Measured according to JIS K7110 (with notch). (3) Deflection temperature under load (HDT) (° C.) Measured in accordance with JIS K7207 A method (without annealing). (4) Fluidity Using a FS80 type injection molding machine manufactured by Nissei Resin Industry Co., Ltd., a resin temperature of 260 mm was formed in a screw-shaped mold having a thickness of 1 mm and a width of 8 mm.
Injection was performed at 910 kg / cm 2 at 910 ° C., and the spiral flow length (cm) was measured.

[0034]

[Table 1]

[0035]

[Table 2]

The following becomes clear from Tables 1 and 2.
That is, the thermoplastic resin composition of the present invention has good flame retardancy, rigidity, fluidity, and impact resistance, retains the excellent impact resistance of a non-reinforced resin, and exhibits high rigidity (Examples). 1-3) On the other hand, a system containing no copolyether / polyester thermoplastic elastomer (Comparative Example 1) does not improve the impact resistance. The systems without the pitch-based carbon fibers (Comparative Examples 2 to 4) do not have the desired flame retardancy.
Further, the resin composition obtained outside the scope of the present invention has a disadvantage that the balance between impact resistance, rigidity and fluidity is poor (Comparative Examples 5 and 6).

[0037]

As described above, the present invention has the following special and remarkable effects, and its industrial utility value is extremely large. (1) Since the thermoplastic resin composition of the present invention contains a filler such as carbon fiber, it has excellent dimensional stability, has both high heat resistance and high rigidity, and has excellent molding processability. Has the appearance. (2) The thermoplastic resin composition of the present invention impairs other properties by containing a bromine-based flame retardant and by containing pitch-based carbon fibers as a reinforcing agent. It can exhibit flame-retardant properties with a thin wall. (3) The thermoplastic resin composition of the present invention maintains high rigidity and flame retardancy by containing a thermoplastic resin composition comprising a polycarbonate resin and an aromatic vinyl-based copolymer resin. Since it contains an ether-polyester thermoplastic elastomer, it also exhibits high impact properties.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C08L 69/00 C08L 69/00 // (C08L 51/04 25:00 69:00 67:02 27:18) (C08L 25/00 51:04 69:00 67:02 27:18) (C08L 69/00 25:00 51:04 67:02 27:18)

Claims (1)

(57) [Claims] Claims: 1. An ingredient comprising the following components (A) to (H) as essential components, based on the total amount of the components (A) to (C):
The proportion of the component (A) is 30 to 90% by weight, the proportion of the component (B) is 10 to 70% by weight, and the proportion of the component (C) is 60% by weight.
The following (however, the total of (A) to (C) is 100% by weight)
With respect to 100 parts by weight of the components (A) to (C),
The proportion of the component (D) is 1 to 30 parts by weight, the proportion of the component (E) is 1 to 12 parts by weight, the proportion of the component (F) is 1.0 part by weight or less, and the proportion of the component (G) is 0.1. ~ 50 parts by weight,
A thermoplastic resin composition, wherein the ratio of the component (H) is 1 to 20 parts by weight based on 100 parts by weight of the components (A) to (G). (A) Aromatic polycarbonate resin (B) Graft copolymer obtained by polymerizing aromatic vinyl and a copolymerizable monomer in the presence of rubbery polymer (C) Aromatic vinyl and (A) Aromatic vinyl copolymer resin obtained by copolymerizing a copolymerizable monomer with a monomer (D) Bromine-containing flame-retardant organic compound (E) Flame-retardant auxiliary (F) Tetrafluoroethylene resin (G) Pitch-based carbon fiber (H) Copolyether / polyester heat containing 30 to 80% by weight of an aliphatic polyether chain and 70 to 20% by weight of an aromatic polyester chain and having a Vicat softening point of 100 ° C. or more Plastic elastomer