JP2001348473A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition excellent in rigidity, non-halogenous flame retardancy, fluidity, impact resistance (surface impact) and the appearance of molded articles. SOLUTION: The thermoplastic resin composition comprises (A) 4-39 pts.wt. of a rubber toughened resin, (B) 95-60 pts.wt. of an aromatic polyester and (C) 1-15 pts.wt. of polycarbonate, and further comprises, based on a total of 100 pts.wt. of (A)+(B)+(C), (D) 1-40 pts.wt. of a phosphorus flame-retardant, (E) 1-20 pts.wt. of a phenolic resin, (F) 0.1-5 pts.wt. of a flame-retardant assistant, and (G) 1-60 pts.wt. of a fibrous filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a rubber-reinforced resin, an aromatic polyester, a polycarbonate, a phosphorus-based flame retardant,
Regarding a thermoplastic resin composition containing a phenolic resin, a flame retardant aid and a fibrous filler, more specifically, rigidity,
The present invention relates to a thermoplastic resin composition having excellent halogen-free flame retardancy, fluidity, impact resistance, and molded appearance.

[0002]

2. Description of the Related Art Resin materials obtained by making ABS resin / polycarbonate resin materials flame-retardant are widely used in OA equipment, home electric appliances, personal computer housings, PPC parts and the like. In particular,
Notebook-type personal computers are becoming thinner as a product, and materials used for the housing of the product are required to be thinner and have higher rigidity. It is known to mix a fibrous filler such as carbon fiber in order to obtain a thin and high rigidity. However, when a fibrous inorganic filler is blended, there is a problem that the appearance of a molded product is inferior.

In order to improve the appearance of a molded product, it is conceivable to change the fibrous filler to a particulate filler such as talc, mica, and glass beads. The appearance can be improved by blending them, but there is a problem that the effect of improving rigidity is lower than that of the fibrous filler blending system. Therefore, in order to obtain the rigidity required in the market, a large amount of filler must be blended. Therefore, a resin material having practical impact strength and fluidity cannot be obtained.

In order to improve the appearance of a molded product, it is known that it is effective to incorporate a crystalline polymer such as nylon or polyester. However, when these crystalline polymers are blended, it is difficult to achieve non-halogenated flame retardancy in consideration of environmental issues.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and solves the above-mentioned problems and provides rigidity, non-halogen flame retardancy, fluidity, impact resistance and molding. An object is to provide a thermoplastic resin composition having excellent appearance.

[0006]

According to the present invention, there is provided an aromatic vinyl compound, a vinyl cyanide compound, a (meth) acrylic acid ester, an acid anhydride type monomer in the presence of (A) a rubbery polymer (a). Or a graft copolymer obtained by polymerizing at least one type of monomer component (b) selected from the group consisting of a monomer and a maleimide-based compound, or (G) of the graft copolymer and the monomer component (b). (A) The component (a) has a ratio of 5 to 60% by weight, and the component (b) has a ratio of 95 to 4% by weight.
4 to 39 parts by weight of a rubber reinforced resin which is 0% by weight [(a) + (b) = 100% by weight], 95 to 60 parts by weight of an aromatic polyester (B) and 1 to 15 parts by weight of a polycarbonate (C) [However, (A) + (B) + (C) = 1
00 parts by weight] (hereinafter, (A) to (C) components are also referred to as “resin components”) in a total amount of 100 parts by weight, (D) 1 to 40 parts by weight of phosphorus-based flame retardant, (E) phenol resin 1 to
The present invention relates to a thermoplastic resin composition comprising 20 parts by weight, (F) 0.1 to 5 parts by weight of a flame retardant auxiliary, and (G) 1 to 60 parts by weight of a fibrous filler. Where (G)
The fibrous filler is preferably a carbon fiber and the average residual fiber length of the carbon fiber in the composition is 0.05 to 0.70 mm.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION (A) A rubber-reinforced resin is prepared by preparing an aromatic vinyl compound, a vinyl cyanide compound, a (meth) acrylic acid ester, an acid anhydride monomer in the presence of a rubbery polymer (a). A graft copolymer obtained by polymerizing at least one monomer component (b) selected from the group consisting of a copolymer and a maleimide-based compound, or the graft copolymer and the monomer component ( It may be a blend of the (co) polymer of b).

Here, the rubbery polymer (a) includes polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, ethylene-propylene- (non-conjugated diene) copolymer, ethylene-butene-1
A hydrogenated diene (block, such as-(non-conjugated diene) copolymer, isobutylene-isoprene copolymer, acrylic rubber, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, SEBS, etc. Random and homo) polymers, polyurethane rubbers, silicone rubbers, among which polybutadiene, butadiene-styrene copolymer, ethylene-propylene- (non-conjugated diene) copolymer, acrylic rubber, hydrogenated Diene polymers and silicone rubber are preferred. When a silicone rubber is used, a graft-linking agent containing a vinyl group (for example, p-
Vinylphenylmethyldimethoxysilane, 2- (p-vinylphenyl) ethylmethyldimethoxysilane, 2-
(P-vinylphenyl) ethylmethyldimethoxysilane or the like) is preferably co-condensed with polyorganosiloxane.

When the rubber-like polymer (a) is used, when two or more kinds of graft copolymers having different rubber particle diameters are used, the thermoplastic resin composition of the present invention is more excellent in impact resistance and physical property balance. Is obtained. As preferred particle size,
It is preferable to use two kinds of the component (a) having different particle diameters of about 80 to 180 nm and about 180 to 480 nm. In this case, the monomer component (b) is added in the presence of the two rubbery polymers.
May be polymerized to synthesize the component (A), or two types of the component (A) having different rubber particle diameters may be blended.

The monomer component (b) is at least one selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound, a (meth) acrylate, an acid anhydride monomer and a maleimide compound. It is a monomer. As the monomer component (b), one type can be used alone, or two or more types can be used in combination.

As the aromatic vinyl compound, styrene,
α-methylstyrene, o-methylstyrene, p-methylstyrene, vinyltoluene, methyl-α-methylstyrene, brominated styrene and the like. Among them, styrene, α-methylstyrene and p-methylstyrene are preferred. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and acrylonitrile is preferable.

Examples of the (meth) acrylate include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, and butyl methacrylate. Methyl methacrylate and butyl acrylate are preferred. As the acid anhydride monomer, maleic anhydride is preferred. As maleimide monomers, maleimide, N-methylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide,
N- (4-hydroxyphenyl) maleimide and N-cyclohexylmaleimide are mentioned, and N-phenylmaleimide is preferred. In particular, when the maleimide monomer is copolymerized in the monomer component (b) in an amount of 20 to 80% by weight, the heat resistance of the thermoplastic resin composition of the present invention can be improved.

In the preparation of the graft copolymer of the present invention, the charge composition for graft polymerization of the monomer component (b) to the rubbery polymer (a) is preferably the component (a).
0-70% by weight, more preferably 25-65% by weight,
The content is particularly preferably 30 to 60% by weight, the component (b) is preferably 80 to 30% by weight, more preferably 75 to 35% by weight, and particularly preferably 70 to 40% by weight [where (a) + (b ) = 100% by weight]. In the graft copolymer obtained as described above, the monomer component (b) is not grafted to the rubbery polymer (a). (Co) polymer]. The (A) rubber-reinforced resin of the present invention is obtained by blending a (co) polymer obtained by (co) polymerizing the monomer component (b), in addition to the above graft copolymer. It may be something. Therefore, the final ratio of the component (a) and the component (b) in the rubber-reinforced resin (A) of the present invention is (a)
Component is 5 to 60% by weight, preferably 8 to 60% by weight, more preferably 10 to 50% by weight, and component (b) is 95 to 95% by weight.
40% by weight, preferably 92 to 60% by weight, more preferably 90 to 50% by weight [where (a) + (b) = 1
00% by weight]. If the content of the component (a) in the rubber-reinforced resin (A) is less than 5% by weight, the impact resistance is not sufficiently exhibited. On the other hand, if it exceeds 60% by weight, poor appearance and deterioration in molding processability occur. Not preferred.

The preferred graft ratio of the rubber-reinforced resin (A) is 30 to 200% by weight, more preferably 40 to 15% by weight.
0% by weight, particularly preferably 50 to 120% by weight.
If the graft ratio of the component (A) is less than 30% by weight, the thermoplastic resin composition of the present invention is not preferred because of poor appearance and reduced impact strength. On the other hand, if it exceeds 200% by weight,
Poor moldability.

The above graft ratio can be determined by the following formula, where x is a rubber component in 1 g of the component (A) and y is a methyl ethyl ketone insoluble component of the component (A). Graft ratio (%) = {(y−x) / x} × 100

The intrinsic viscosity [η] of the matrix resin (A) (measured in methyl ethyl ketone at 30 ° C.)
Is preferably 0.1 to 1.0 dl / g, more preferably 0.3 to 0.8 dl / g. When the intrinsic viscosity [η] is in this range, the thermoplastic resin composition of the present invention having an excellent balance between impact resistance and moldability (fluidity) can be obtained.

The graft copolymer or (co) polymer used for the rubber-reinforced resin (A) of the present invention can be produced by known emulsion polymerization, solution polymerization, suspension polymerization, or the like. Usually, the powder obtained by coagulation with a coagulant is purified by washing with water and drying.

As the radical initiator at the time of the graft polymerization, a general one can be used. Specific examples include cumene hydroperoxide, diisopropylbenzene hydroperoxide, potassium persulfate, AIBN, benzoyl peroxide, lauroyl peroxide, t-butylperoxylaurate, t-butylperoxymonocarbonate, and the like.

Regarding the compounding of the component (A), the resin (graft copolymer) of the component (A) alone or a blend of two or more resins of the component (A) may be used. Also,
When the (co) polymer of the monomer component (b) is separately added to the graft copolymer, the amount of the (co) polymer obtained by separately polymerizing only the component (b) [(A ) Component and (b)
(Copolymer) in which only the component is separately polymerized is taken as 100% by weight] is preferably 10 to 80% by weight, more preferably 15 to 60% by weight. Preferred combinations of the component (A) are described below.
The combinations are not limited to the following combinations as long as the gist is not exceeded.

ABS resin ABS resin / AS resin AES resin / AS resin Silicone rubber reinforced resin / AS resin

Typical (A) rubber-reinforced resins include A
BS resin, AES resin and the like can be mentioned. Typical resins when the monomer component (b) is polymerized alone include AS resin, styrene-methyl methacrylate copolymer, styrene-N-phenylmaleimide copolymer, styrene-N-phenyl And maleimide-acrylonitrile copolymer. Among them, AS resin is preferable.

The preferred amount of the ABS resin or AES resin is 20 to 65% by weight, more preferably 2 to 65% by weight.
5 to 55% by weight, preferably 50 to 130% by weight, more preferably 60 to 120% by weight, and the preferred intrinsic viscosity [η] of the matrix resin is 0.1 to 1.0%.
dl / g.

As the AS resin, the copolymerization amount of acrylonitrile is preferably 15 to 45% by weight, more preferably 20 to 35% by weight, and particularly preferably 23 to 32% by weight, and the preferred intrinsic viscosity [η] is 0.1%. 3 to 0.8 dl /
g, more preferably 0.4 to 0.7 dl / g.

The component (A) may be copolymerized with a functional group-containing vinyl monomer. Examples of the functional group include an epoxy group, a hydroxyl group, a carboxylic acid group, an amino group, an amide group, and an oxazoline group. Specific examples of the functional group-containing vinyl monomer include glycidyl methacrylate, glycidyl acrylate, and 2-hydroxyethyl. Examples include methacrylate, 2-hydroxyethyl acrylate, acrylamide, acrylic acid, methacrylic acid, and vinyl oxazoline. By copolymerizing these functional group-containing vinyl monomers, the interfacial adhesion (compatibility) when (B) the aromatic polyester or another thermoplastic resin is blended can be increased. In consideration of the compatibility with the component (B), an epoxy group and a hydroxyl group are preferred. More preferably, it is an epoxy group. This is because the epoxy group can react with the terminal hydroxyl group of the aromatic polyester (B). The copolymerization amount of these functional group-containing vinyl monomers is preferably 0.1 to 15% by weight in the component (A),
More preferably, it is 0.5 to 12% by weight.

Next, as the aromatic polyester (B), those obtained by known condensation polymerization of an aromatic dicarboxylic acid, an ester, or an ester-forming derivative thereof and a diol can be used.

Examples of aromatic dicarboxylic acids include naphthalene dicarboxylic acids such as naphthalene-2,6-dicarboxylic acid, terephthalic acid, isophthalic acid, p-hydroxybenzoic acid, adipic acid and sebacic acid, and their ester-forming derivatives. Is mentioned.

Examples of the diol include polymethylene glycol having 2 to 6 carbon atoms such as ethylene glycol, 1,4-butanediol and 1,6-hexanediol, or 1,4-cyclohexanediol, bisphenol -A and their ester-forming derivatives.

Specific examples of the aromatic polyester thus obtained include polyethylene terephthalate (P
ET), polybutylene terephthalate (PBT), bisphenol-A isophthalate and the like, among which polybutylene terephthalate (PBT) is preferable.

(B) Preferred intrinsic viscosity of aromatic polyester (measured in o-chlorophenol solvent at 25 ° C.)
Is from 0.5 to 1.4 dl / g, more preferably from 0.6 to 1.2 dl / g. When the intrinsic viscosity is low, the appearance of molding and the fluidity are favorable, but the impact resistance tends to be inferior.

Next, (C) the polycarbonate is blended in the composition of the present invention as a compatibilizer for compatibilizing the components (A) and (B). Examples of the (C) polycarbonate include those obtained by reacting various dihydroxyaryl compounds with phosgene (phosgene method) and those obtained by transesterification of dihydroxyaryl compound with diphenyl carbonate (ester exchange method). . A typical polycarbonate is an aromatic polycarbonate obtained by reacting 2,2'-bis (4-hydroxyphenyl) propane with phosgene. Aliphatic polycarbonates are not preferred because of poor heat stability.

Here, as the dihydroxyaryl compound (C) as a raw material of the polycarbonate, bis (4-
(Hydroxyphenyl) methane, 1,1'-bis (4-hydroxyphenyl) ethane, 2,2'-bis (4-hydroxyphenyl) propane, 2,2'-bis (4-hydroxyphenyl) butane, 4,4 '-Dihydroxy-
3,3'-dimethyldiphenyl ether, 4,4'-dihydroxyphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-
Known ones such as 3,3'-dimethyldiphenylsulfone, hydroquinone, resorcin and the like can be mentioned.

The weight average molecular weight of the polycarbonate (C) used in the present invention is preferably 15,000 to 3
5,000, more preferably 17,000-28,000
00, particularly preferably 18,000 to 26,000. Within these ranges, a thermoplastic resin composition of the present invention having excellent moldability can be obtained. As described above, the (C) polycarbonate is blended to compatibilize the component (A) and the component (B). However, if the blending of the component (C) is insufficient, the polycarbonate is mixed. Furthermore, EGMA-gr-
An AS resin (manufactured by Nippon Oil & Fats Co., Ltd., trade name: MODIPER) or the like can be appropriately blended.

Next, the phosphorus-based flame retardant (D) used in the present invention will be described in detail. Recently, phosphorus-based flame retardants have been used in place of conventional brominated flame retardants in view of environmental problems. However, flame retardancy of crystalline polymers such as nylon and polyester is difficult to achieve with phosphorus-based flame retardants. In the prior art, high flame retardancy has been obtained by blending red phosphorus or the like as a phosphorus-based flame retardant. However, if red phosphorus is blended, phosphine gas is likely to be generated during combustion, which is not preferable in terms of environmental problems. In addition, since the color becomes red, there is a restriction on the development of the resin material.

The present inventors have conducted intensive studies and found that (D)
It has been found that high flame retardancy can be obtained by combining an organic phosphorus-based flame retardant and (E) a phenol resin.
(D) Examples of the phosphorus-based flame retardant include monophenyl-type phosphorus-based flame retardants such as triphenyl phosphate, trixylenyl phosphate, tricresyl phosphate, and trixylenyl thiophosphate. Examples of the flame retardant include hydroquinone bis (diphenyl phosphate), resorcinol bis (diphenyl phosphate), resorcinol bis (dixylenyl phosphate), oligomers of triphenyl phosphate, bisphenol-A bis (diphenyl phosphate), bisphenol-A bis (Dixylenyl phosphate) and the like. Among these, triphenyl phosphate, resorcinol bis (dixylenyl phosphate), oligomers of triphenyl phosphate, and bisphenol-A bis (diphenyl phosphate) are preferred. The monomolecular phosphorus-based flame retardant has higher flame retardancy than the oligomer-type phosphorus-based flame retardant, but may cause mold contamination during molding. In this regard, the use of the oligomer-type phosphorus-based flame retardant is preferred.

(D) The preferred phosphorus concentration of the phosphorus-based flame retardant is 4 to 30% by weight, more preferably 6 to 25% by weight.
It is. Further, a preferred melting point is 40 to 140C, preferably 45 to 130C. (D) As the phosphorus-based flame retardant, a liquid one at room temperature (23 ° C.) can be used. When melt-kneading these liquid phosphorus-based flame retardants with an extruder, it is desirable to feed them in the middle.
When feeding midway, the phosphorus-based flame retardant is 40 to 70 ° C.
It is desirable to feed before and after heating.

Next, the phenol resin (E) will be described in detail. The feature of the present invention is that by blending the component (E),
An object of the present invention is to obtain high flame retardancy in a system containing (D) a phosphorus-based flame retardant without using red phosphorus or the like.

As the phenolic resin (E), a novolak-type phenolic resin, a resol-type phenolic resin and the like can be used. Among them, a novolak-type phenolic resin is preferable. When a resol type phenol resin is used, the resol resin hardens depending on the molding conditions and may reduce the impact strength and the fluidity of the thermoplastic resin composition of the present invention. Therefore, the use of a novolak type phenol resin is preferred.

The novolak type phenol resin includes phenol-formaldehyde novolak resin, t
-Butylphenol-formaldehyde novolak resin, p-octylphenol-formaldehyde novolak resin, p-cyanophenol-formaldehyde novolak resin and the like are preferable, and among them, phenol-formaldehyde novolak resin is preferable.

A novolak resin having no substituent such as an alkyl group on the aromatic ring of phenol is particularly preferred. As a feature of the present invention, as a non-halogenated flame retardant mechanism by a combination of (D) a phosphorus-based flame retardant and (E) a phenol resin, formation of a non-combustible film (Char) by a crosslinking reaction on a phenol aromatic ring is important. It is. The presence of a substituent on the aromatic ring is not preferred because it not only suppresses the crosslinking reaction but also causes the substituent to become a combustion component.

When a resol type phenol resin is used, it is preferable that the content of the reactive methylol group is 3 to 15% by weight. When the content of the methylol group exceeds 15% by weight, a crosslinking reaction occurs rapidly, and the impact strength and fluidity of the thermoplastic resin composition of the present invention are impaired.

(E) The preferred average molecular weight of the phenol resin is 300 to 10,000, more preferably 400.
~ 5,000. The number of phenols in one molecule is 2
~ 15 nuclei are preferred. The preferred softening point of the phenol resin is 70 to 140 ° C, more preferably 90 to 120 ° C.
° C. When the softening point is less than 70 ° C., when the thermoplastic resin composition of the present invention is pelletized, biting failure in a hopper is likely to occur. On the other hand, when the temperature exceeds 140 ° C,
Poor moldability.

Next, as (F) a flame retardant auxiliary, for example,
Polytetrafluoroethylene (PTFE). Polytetrafluoroethylene is blended in the composition of the present invention in order to prevent dripping (drip of melt) during combustion. Preferred molecular weight is 500,000 or more,
More preferably, it is one million or more. The preferred average particle size is 90 to 600 μm, more preferably 100 to 50 μm.
0 μm, particularly preferably 120 to 400 μm. Preferred specific gravities are 1.5 to 2.5, 2.1 to 2.3. Preferred bulk density is 0.5-1.0 g / ml, more preferably 0.6-0.9 g / ml. When polytetrafluoroethylene is blended, dripping during combustion can be prevented, so that a higher flame retardant level can be achieved. Solvents such as water or lubricants (polyethylene wax,
Organic acids, organic metal salts such as magnesium stearylate)
Can also be used.

Next, examples of the fibrous filler (G) include carbon fibers such as PAN-based carbon fibers and pitch-based carbon fibers, and glass fibers. Among these,
Carbon fibers are particularly preferred.

The PAN-based carbon fiber is obtained by sintering polyacrylonitrile fiber (PAN) as a raw material.
It is a carbon fiber. Preferred carbon fiber diameter is 5 to 15
μm, and more preferably 6 to 10 μm. The preferred tensile modulus is 100 to 700 GPa, more preferably 200 to 500 GPa.

The pitch-based carbon fiber is a pitch-based carbon fiber obtained by spinning pitch as a raw material and heat-treating.
The preferred carbon fiber diameter is 5 to 15 μm, more preferably 8 to 12 μm. The preferred tensile modulus is 1
0 to 900 GPa, more preferably 30 to 600 GPa
a. The amount of the carbon fiber sizing agent used is 3 to 9% by weight.
It is about.

The glass fiber is obtained by spinning general C glass or E glass. The preferred glass fiber diameter is 7 to 18 μm, more preferably 8 to 15 μm, and particularly preferably 10 to 13 μm. The preferred amount of the glass fiber sizing agent is 0.1 to 3% by weight, more preferably 0.5 to 1.5% by weight. As the type of the sizing agent of the component (G), acrylic resin type, urethane resin type,
Epoxy resin, AS resin and the like can be used. Among them, acrylic resin, epoxy resin, and AS resin are preferable.

(G) About the compounding of the fibrous filler,
The component (G) is fed on the way by an axial extruder to be kneaded with the thermoplastic resin of the present invention. When two kinds of fibrous fillers are used, even if each of them is fed halfway by a twin-screw extruder, two kinds of (G) components are previously blended by a tumbler, and a blended product of the (G) components is obtained. May be fed on the way. In the case of blending with a tumbler, the speed is 1 to 20 revolutions / minute, which is about 1 to 3 minutes. If the number of rotations is too high or the blending time is too long, the component (G) is undesirably defibrated. Furthermore, when tumbling and blending only carbon fibers, if a lubricant such as polyethylene wax and hardened castor oil is blended, it is possible to prevent the fibrillation of the component (G) at the time of blending and feeding by a twin screw extruder. it can.

The thermoplastic resin composition of the present invention comprises, as resin components, (A) 4-39 parts by weight of a rubber-reinforced resin, (B) 60-95 parts by weight of an aromatic polyester,
(C) 1 to 15 parts by weight of polycarbonate, preferably 7 to 22 parts by weight of component (A), 75 to 93 parts by weight of component (B), 3 to 13 parts by weight of component (C), more preferably component 10 To 15 parts by weight, 80 to 90 parts by weight of the component (B), and 5 to 10 parts by weight of the component (C).
(A) + (B) + (C) = 100 parts by weight]. When the amount of the component (A) is less than 4 parts by weight, the impact strength is poor.
When the component (A) exceeds 39 parts by weight, the flame retardancy is poor.
When the component (B) is less than 60 parts by weight, the appearance of a molded product,
When the flame retardancy is poor, on the other hand, when it exceeds 95 parts by weight, the fluidity is poor. When the amount of the component (C) is less than 1 part by weight, the impact strength is inferior because the compatibility between the component (A) and the component (B) is poor.
On the other hand, if it exceeds 15 parts by weight, the appearance of the molded product is inferior.

(D) The compounding amount of the phosphorus-based flame retardant is based on 100 parts by weight of the resin component [(A) to (C) component] and (D)
Component is 1 to 40 parts by weight, preferably 10 to 35 parts by weight, more preferably 20 to 30 parts by weight. If the component (D) is less than 1 part by weight, the effect of imparting flame retardancy is small, while if it exceeds 40 parts by weight, the impact strength and thermal deformation temperature of the thermoplastic resin composition are impaired.

The amount of the phenolic resin (E) is based on 100 parts by weight of the resin component [(A) to (C) component].
(E) Component is 1 to 20 parts by weight, preferably 3 to 15 parts by weight, more preferably 5 to 12 parts by weight. When the component (E) is less than 1 part by weight, the effect of imparting flame retardancy is small,
On the other hand, if it exceeds 20 parts by weight, the impact strength of the thermoplastic resin composition is impaired.

The compounding amount of the (F) flame retardant aid is based on 100 parts by weight of the resin component [(A) to (C) component], and
0.1 to 5 parts by weight of components, preferably 0.3 to 3 parts by weight,
More preferably, it is 0.5 to 2 parts by weight. When the component (F) is less than 0.1 part by weight, the auxiliary effect of flame retardancy is small. On the other hand, when it exceeds 5 parts by weight, processability at the time of extrusion (pelletizing step) is poor.

The amount of the fibrous filler (G) is based on 100 parts by weight of the resin component [(A) to (C) component] and 100 parts by weight of (G).
Component is 1 to 60 parts by weight, preferably 15 to 50 parts by weight, more preferably 25 to 45 parts by weight. When the component (G) is less than 1 part by weight, the effect of imparting rigidity is small.
If it exceeds 60 parts by weight, the impact strength of the thermoplastic resin composition will be impaired.

The preferred weight ratio of component (A) to component (B) is 5-30 / 95-70 (% by weight /% by weight),
More preferably, it is 10-20 / 90-80. Within this range, the thermoplastic resin composition of the present invention having excellent balance between high flame retardancy and appearance of a molded product can be obtained.

Further, the fluidity (MFR value: 240 ° C., 10 kg load; AS) of the thermoplastic resin composition of the present invention is preferable.
TM D1238) is 50 to 250 g / 10 mi.
n. , More preferably 100 to 200 g / 10 mi.
n. It is. Within this range, the case of an A4 size notebook personal computer having a thickness of 1.0 mm can be formed even with pin gates having about 1 to 5 points.

Further, when carbon fibers are used as the fibrous filler (G) of the thermoplastic resin composition of the present invention, the average residual fiber length in the carbon fiber composition is from 0.05 to 0.05.
0.70 mm, more preferably 0.10 to 0.50 m
m, particularly preferably 0.15 to 0.40 mm. If the average residual fiber length is less than 0.05 mm, the effect of imparting rigidity is small, while if it exceeds 0.70 mm, the fluidity is poor.

Here, the average residual fiber length is a value measured for pellets of the thermoplastic resin composition of the present invention. As a measuring method, the pellet is dissolved in dichloromethane (or methyl ethyl ketone, strong acid, o-chlorophenol) and only the component (G) is separated. Then, only the component (G) is photographed with an electron microscope, and the photograph is analyzed by image processing. (G) The number of extracted components is 200 to 50.
There are zero.

(G) In order to increase the average residual fiber length of the fibrous filler, it is most effective to increase the processing temperature in a twin-screw extruder. The preferred processing temperature is 2
30 to 270 ° C, more preferably 240 to 260 ° C
It is. The screw dimension of the twin-screw extruder is preferably one having few kneaded parts. The position for feeding the component (G) is preferably closer to the tip (die side) of the twin-screw extruder.

Known fillers can be added to the thermoplastic resin composition of the present invention for the purpose of further imparting rigidity. Examples of the filler include wollastonite, talc, mica, zinc oxide whiskers, calcium titanate whiskers, and glass beads. Among these inorganic fillers, talc and mica are preferred, and talc is particularly preferred.

The preferred average particle size of talc is 0.5 to 2
0 μm, more preferably 1 to 15 μm, particularly preferably 1.3 to 13 μm. If the average particle size is less than 0.5 μm, agglomeration occurs during kneading and the appearance of the molded product is inferior, while if it exceeds 20 μm, physical properties such as impact resistance and appearance are impaired.

As these inorganic fillers, those whose surfaces have been treated with a silane coupling agent can also be used. The amount of the silane coupling agent is from 0.1 to 5% by weight, preferably from 0.5 to 3% by weight, based on the inorganic filler. As silane coupling agents, epoxy groups, amino groups, vinyl groups,
Those having a functional group such as a hydroxyl group can be used. Particularly, those having an epoxy group or an amino group are preferable.

Further, an inorganic phosphorus compound can be blended in the thermoplastic resin composition of the present invention. The inorganic phosphorus compounds include sodium dihydrogen phosphate, disodium monohydrogen phosphate and hydrates thereof. When these inorganic phosphorus compounds are blended, the thermal stability during molding can be improved. Usually, the residual emulsifier, coagulant, etc. in ABS cause a decrease in the molecular weight of the polycarbonate,
The physical properties of the alloy material are reduced. The decomposition reaction of polycarbonate in the composition of the present invention remarkably proceeds particularly at a high temperature (such as during molding). By blending the inorganic phosphorus compound, the decomposition reaction of the polycarbonate can be suppressed even at a high temperature. The amount of the resin component of the present invention [(A)
Component (C)] is 0.1 to 3 parts by weight, preferably 0.2 to 2 parts by weight, per 100 parts by weight.

Further, the thermoplastic resin composition of the present invention includes:
Known additives such as a weathering agent, an antioxidant, a plasticizer, a lubricant, a coloring agent, an antistatic agent, and silicone oil can be blended. The weathering agent is preferably a phosphorus-based or sulfur-based organic compound, or an organic compound containing a hydroxyl group or a vinyl group. Examples of the antistatic agent include polyether and a sulfonate having an alkyl group. The preferred amount of these additives is 100 parts of the resin component (components (A) to (C)).
The amount is 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight, relative to parts by weight.

Further, the thermoplastic resin composition of the present invention may contain other polymers (other thermoplastic resins and thermosetting resins) according to the required use. As other polymers, polypropylene, polysulfone, polyethersulfone, polyphenylene sulfide, liquid crystal polymer, styrene-vinylidene acetate copolymer, polyamide elastomer, polyester elastomer, polyetheresteramide and the like can be appropriately blended. The amount of these other polymers is determined by the resin component [(A)
To (C) component], preferably 1 to 100 parts by weight.
It is 150 parts by weight, more preferably 5 to 100 parts by weight.

The thermoplastic resin composition of the present invention is preferably kneaded by using an extruder (preferably a twin-screw extruder) and feeding the component (G) to the extruder on the way. A processing method such as a banbury roll or a roll is not preferable because the fiber length of the carbon fiber is broken.

The thermoplastic resin composition of the present invention can be formed into various molded products by injection molding, sheet extrusion, vacuum molding, profile extrusion, foam molding and the like. Various molded products obtained by the molding method described above are used for housing materials of OA products and home electric appliances, especially for personal computers, DVDs, CD-ROM housing materials, various tray materials, etc. by utilizing their excellent properties. Can be. In particular, it is suitable for personal computer housing materials. Further, the thermoplastic resin composition of the present invention can be printed and marked by using a laser marking method.

[0066]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the scope of the present invention is not limited to the following Examples unless it exceeds the gist of the invention. . Parts and% in Examples are parts by weight and% by weight unless otherwise specified. In addition, various measurement items in the examples were as follows.

The average particle diameter of the dispersed particles was confirmed by an electron microscope that the particle diameter of the latex synthesized in advance in an emulsified state directly indicates the particle diameter of the dispersed particles in the resin. Was measured by a light scattering method. The measuring instrument used was LPA-3100 manufactured by Otsuka Electronics Co., Ltd.
The particle diameter was measured using the cumulant method by integrating 0 times.

Graft ratio Details are described in the text. Dissolve the sample in methyl ethyl ketone, a limiting viscosity solvent,
It was measured with a Ubbelohde viscometer at a temperature of 0 ° C.

The Izod impact strength was measured according to ASTM D256. Measured with notch. Fluidity (Melt Flow Rate) Measured according to ASTM D1238. Measurement temperature is 2
At 40 ° C., the load is 10 kg. The heat distortion temperature was measured according to ASTM D1238. The flexural modulus was measured according to ASTM D790. Combustion test (flame retardancy ) It complies with the UL-94 V test. The thickness is 1.0mm
It is.

Evaluation of molded product surface A flat molded product of 150 × 150 × 2 mm was molded, and (G)
The surface roughness state derived from the components was visually inspected. Finally, coating was performed, and it was determined whether or not the surface roughness due to the component (G) was conspicuous. ：: After coating, surface roughness is not conspicuous at all. ：: After coating, the surface roughness was hardly noticeable, but was partially noticeable. Δ: Surface roughness is noticeable after coating. X: The surface roughness is remarkable before painting.

Evaluation of Surface Impact Strength Using a Dupont impact measuring device, a load of 200 gr
Was dropped every 10 cm at a height of 10 to 50 cm, and the height at the time when the test piece was cracked was evaluated. Cracked height is 30cm
The above is preferred. The sample thickness is 2.4 mm. Average residual fiber length of carbon fiber

Preparation of Component (A) A-1; Preparation of ABS Resin 100 parts of ion-exchanged water, 1.5 parts of sodium dodecylbenzenesulfonate, 1.5 parts of t-dodecyl mercaptan were placed in a 7-liter glass flask equipped with a stirrer. 0.1 part, 40 parts of polybutadiene (a) having an average particle size of 320 nm (in terms of solid content), 15 parts of styrene and 5 parts of acrylonitrile were added, and the mixture was heated while stirring. When the temperature reaches 45 ° C., it consists of 0.1 part of sodium ethylenediaminetetraacetate, 0.003 part of ferrous sulfate, 0.2 part of formaldehyde sodium sulfoxylate dihydrate and 15 parts of ion-exchanged water. An activator aqueous solution and 0.1 part of diisopropylbenzene hydroperoxide were added, and the reaction was continued for 1 hour.

Thereafter, an incremental polymerization comprising 50 parts by weight of ion-exchanged water, 1 part of sodium dodecylbenzenesulfonate, 0.1 part of t-dodecylmercaptan, 0.2 part of diisopropyl hydroperoxide, 30 parts of styrene and 10 parts of acrylonitrile. The components were continuously added over 3 hours to continue the polymerization reaction. After the addition was completed, stirring was further continued for 1 hour, and 2,2-methylene-bis- (4-ethylene-6-t-butylphenol) 0.2
And the reaction product was taken out of the flask.

The latex of the reaction product is coagulated with sulfuric acid,
After thoroughly washing the reaction product with water, it was dried at 75 ° C. for 24 hours to obtain a white powder. The polymerization conversion was 97.2%, the graft ratio was 75%, and the intrinsic viscosity was 0.44 dl / g.

As the other component (A), the following polymer synthesized by emulsion polymerization and solution polymerization was used. A-2; ABS resin composition = butadiene / styrene / acrylonitrile = 40
/ 45/15 (%) Intrinsic viscosity = 0.38 dl / g Graft ratio = 50% A-3; AS resin composition = styrene / acrylonitrile = 75/25 (%) Intrinsic viscosity = 0.47 dl / g

Preparation of Component (B) (Aromatic Polyester) B-1; Polyplastics, Duranex 10
1 EP, [η] = 0.50 dl / g B-2; Polyplastics, DURANEX 60
0FP, [η] = 1.00 dl / g

Preparation of Component (C) (Polycarbonate) C-1; Teflon FN2200, manufactured by Idemitsu Petrochemical (weight average molecular weight: 22,000)

Preparation of Component (D) D-1; Resorcinol bis (dixinenylphosphate) [PX200, manufactured by Daihachi Chemical Industry Co., Ltd.] D-2: Bisphenol-A bis (diphenylphosphate) [Asahi FP600 manufactured by Denka Kogyo Co., Ltd.]

(E) Preparation of Component E-1; Novolak-type phenol resin [PSM4326, manufactured by Gunei Chemical Industry Co., Ltd.] E-2; Novolak-type phenol resin [Mitsui Chemicals Co., Ltd.]
Manufactured, 1000WS, softening point 99-105 ° C]

Preparation of Component (F) F-1; manufactured by Hoechst, TF1620 (average particle size = 22)
0 μm, bulk density = 0.85 g / dl)

Preparation of Component (G) PAN-based carbon fiber; HTA-C, manufactured by Toho Rayon Co., Ltd.
6

Other Additives Inorganic phosphorus compound; sodium dihydrogen phosphate dihydrate

Examples 1 to 4 and Comparative Examples 1 to 5 The components (A) to (G) and other components were mixed in the proportions shown in Tables 1 and 2 at a temperature of 230 to 250 ° C. using a twin-screw extruder. The mixture was melt-kneaded and pelletized. Carbon fiber is
Feeding was performed halfway by a twin screw extruder. The obtained pellet is
An evaluation sample was obtained by injection molding (molding temperature: 230 ° C.). When compounding D-2 as a phosphorus-based flame retardant, the D-2 component was heated to about 50 to 60 ° C., and liquid was added using a twin-screw extruder. The results are shown in Tables 1 and 2.

[0084]

[Table 1]

[0085]

[Table 2]

As is clear from Table 1, the compositions of the present invention (Examples 1 to 3) all had excellent rigidity, fluidity,
It showed impact resistance (surface impact strength) and non-halogen flame retardancy. In Example 4, since the average remaining fiber length of the carbon fibers is less than the range defined in claim 2 of the present invention, high flame retardancy and good molded appearance can be obtained while lowering rigidity and impact strength. (Example 4 was obtained by repeating the extrusion process five times using a twin-screw extruder.) On the other hand, as is clear from Table 2, Comparative Example 1
The component (E) is lacking, and the flame retardancy is poor. Comparative Example 2
The component (E) exceeds the range of the present invention, and the rigidity and impact strength are poor. In Comparative Example 3, the component (D) exceeds the range of the present invention, and the impact strength and the heat distortion temperature are inferior. Comparative Example 4
The component (B) is less than the range of the present invention, and the heat distortion temperature and the appearance of the molded product are inferior. In Comparative Example 5, the component (G) exceeds the range of the present invention, and the impact strength is poor.

[0087]

According to the thermoplastic resin composition of the present invention, it is excellent in rigidity, non-halogen flame retardancy, fluidity, impact resistance and molded appearance, and is used as a housing material for OA products and home electric appliances. It is particularly useful for applications such as housing materials for personal computers, DVDs and CD-ROMs, and various tray materials.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) C08L 69:00 C08L 69:00 61:04 61:04 101: 00) 101: 00) (72) Inventor Fumihiko Usui Techno Polymer Co., Ltd. 1-1-18 Kyobashi, Chuo-ku, Tokyo (72) Inventor Masahiko Noro 1-118 Kyobashi Kyobashi, Chuo-ku, Tokyo F-term (reference) 4J002 BC062 BD155 BN062 BN122 BN152 BN162 BN172 BN212 CC044 CF041 CF061 CF071 CG013 CG023 DA017 DL007 EW046 FA047 FD135 FD136 GQ00

Claims (2)

[Claims] (1) In the presence of (A) a rubbery polymer (a),
Aromatic vinyl compound, vinyl cyanide compound, (meth)
A graft copolymer obtained by polymerizing at least one monomer component (b) selected from the group consisting of an acrylate ester, an acid anhydride monomer and a maleimide compound; A (co) polymer of the monomer component (b), and the proportion of the component (a) is 5 to 60% by weight;
The proportion of the component (b) is 95 to 40% by weight [however, (a)
+ (B) = 100% by weight].
Parts by weight, (B) 95 to 60 parts by weight of an aromatic polyester, and (C) 1 to 15 parts by weight of a polycarbonate [provided that
(A) + (B) + (C) = 100 parts by weight].
(D) 1 to 40 parts by weight of a phosphorus-based flame retardant, (E) 1 to 20 parts by weight of a phenol resin, (F) 0.1 to 5 parts by weight of a flame retardant auxiliary, and (G) fiber A thermoplastic resin composition comprising 1 to 60 parts by weight of a filler in the form of a thermoplastic resin. (G) The fibrous filler is a carbon fiber, and the average residual fiber length of the carbon fiber in the composition is 0.02.
The thermoplastic resin composition according to claim 1, which has a thickness of 5 to 0.70 mm.