JP2003055525A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition having easy processability because of excellent fluidity, and capable of providing a molded product having excellent rigidity, flame retardancy, impact resistance and molded appearance. SOLUTION: This thermoplastic resin composition comprises 100 pts.wt. thermoplastic resin constituted of [A] 5-80 pts.wt. rubber-reinforced resin obtained by polymerizing at least one kind of a monomer component selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound, a (meth)acrylic ester, an acid anhydride-based monomer and a maleimide-based compound, containing an acetone-soluble component having 60,000-200,000 weight average molecular weight and having 2.3-5 ratio Mw/Mn of the weight average molecular weight to the number average molecular weight, and [B] 20-95 pts.wt. polycarbonate resin having 16,000-32,000 viscosity average molecular weight, 1-30 pts.wt. condensed phosphorus-based flame retardant, 1-50 pts.wt. glass flakes and 0.1-5.0 pts.wt. lubricant.

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] [0001] The present invention relates to a rubber-reinforced resin,
Carbonate, phosphorus-based flame retardant, glass flake
More specifically, a thermoplastic resin composition containing an agent
Is easy to process due to its excellent fluidity,
Excellent in fire resistance, flame retardancy, impact resistance (surface impact) and molded appearance
The present invention relates to a thermoplastic resin composition. [0002] 2. Description of the Related Art Conventionally, ABS resin / polycarbonate
The resin material that made the alloy flame-retardant is
Widely used for parts of child copiers. Especially note
Computers are becoming thinner as products.
Materials used for the housing of the car must be thin and have high rigidity
It has become. To obtain thin and high rigidity, use glass fiber
Fiber, fibrous filler such as carbon fiber is compounded, especially
When these fibrous fillers are used, injection molded products
May cause warpage. Gala to avoid warpage
When using flake fillers such as flakes
However, the surface appearance of the molded product is poor,
There is a problem that a rib or the like is broken. Also,
Lakes can be compounded or molded in the same way as fibrous fillers.
Can be destroyed by shearing at the time, and the stiffness can be greatly reduced.
is there. [0003] SUMMARY OF THE INVENTION The present invention relates to a rigid
Properties, flame retardancy, fluidity, impact resistance (surface impact), surface appearance and
To provide a thermoplastic resin composition having excellent dimensional accuracy
With the goal. [0004] Means for Solving the Problems The present invention relates to [A] rubbery material.
In the presence of the polymer (a), an aromatic vinyl compound, cyanide
Vinyl compound, (meth) acrylate, acid anhydride
Selected from the group consisting of compound monomers and maleimide compounds
At least one monomer component (b) obtained by polymerization.
(Co) polymer resin (A1) or the (co) polymer resin
At least one selected from the group consisting of (A1) and the monomer component (b)
And (co) polymer (A2) obtained by polymerizing one type
It is composed of a mixture and has a weight-average molecular weight of acetone-soluble matter
M_wIs 60,000 to 200,000 and the weight is
Weight average molecular weight M_wAnd number average molecular weight M _nRatio M with_w/ M_n
5 to 80 parts by weight of a rubber reinforced resin having 2.3 to 5;
[B] With a viscosity average molecular weight of 16,000 to 32,000
And 20 to 95 parts by weight of a certain polycarbonate resin.
100 parts by weight of the thermoplastic resin to be formed [however, [A] +
[B] = 100 parts by weight], and the thermoplastic resin 10
[C] 1 to 30 parts by weight of condensed phosphorus-based flame retardant per 0 parts by weight
Parts, [D] 1 to 50 parts by weight of glass flakes, and
[E] Hardened castor oil, silicone oil and polyolefin
At least one member selected from the group consisting of
A thermoplastic resin composition containing 0.1 to 5 parts by weight of a lubricant
And melt flow rate (240 ° C, load 10k
g) is 30 g / 10 min or more, and the present composition
The residual average major axis of the glass flakes contained in is 50 to 30
A thermoplastic resin composition having a thickness of 0 μm.
To offer. [0005] BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail. 1. Rubber reinforced resin [A] The rubbery polymer forming the (co) polymer resin (A1)
The body (a) is a polymer exhibiting rubber elasticity. In this example
Polybutadiene, butadiene / styrene copolymer
Body, butadiene / acrylonitrile copolymer, styrene
・ Butadiene / styrene block copolymer, styrene
Isoprene / styrene block copolymer, isobutylene
・ Diene (co) polymers such as isoprene copolymers
Hydrogenated diene (co) polymer, ethylene
Pyrene / (non-conjugated diene) copolymer, ethylene / butene
-1 · (non-conjugated diene) copolymer, polyurethane rubber,
Acrylic rubber, silicone rubber, etc.
Of which, polybutadiene, butadiene / styrene copolymer
, Diene (co) polymer hydrogenated product, ethylene
Propylene / (non-conjugated diene) copolymer, acrylic rubber
And silicone rubber. These are one kind alone
Alternatively, two or more kinds can be used in combination. still,
When using silicone rubber, a vinyl group-containing rubber
Raft crossing agents (e.g., p-vinylphenylmethyldim
Toxisilane, 2- (p-vinylphenyl) ethylmethyl
Rudimethoxysilane, 2- (p-vinylphenyl) ethyl
Lenmethyldimethoxysilane, etc.)
Those co-condensed with sun are preferred. The average particle size of the rubbery polymer (a) is preferably
Preferably 50 to 600 nm, more preferably 70 to 50 nm.
0 nm, more preferably 80 to 500 nm. this
If the average particle size is too small, the impact resistance decreases. on the other hand,
If it is too large, the surface appearance and flame retardancy of the molded article will be reduced.
In the present invention, two or more kinds having different average particle diameters are used.
It is also possible to use a combination of rubbery polymers,
Therefore, the balance of impact resistance, rigidity and flame resistance
improves. Polymerization in the presence of the rubbery polymer (a)
Of the aromatic vinyl compound among the monomer components (b)
Styrene, α-methylstyrene, o-methyls
Tylene, p-methylstyrene, vinyltoluene, methyl
-Α-methylstyrene, brominated styrene and the like.
You. Of these, styrene is preferred. These are one kind
Can be used alone or in combination of two or more
Wear. [0008] The vinyl cyanide compound includes
Lilonitrile, methacrylonitrile and the like,
Acrylonitrile is preferred. These are one kind alone
Alternatively, two or more kinds can be used in combination. the above
(Meth) acrylic acid esters include methyl acrylate
, Ethyl acrylate, butyl acrylate, methacryl
Methyl acrylate, ethyl methacrylate, butyl methacrylate, etc.
Of these, methyl methacrylate is
preferable. These may be used alone or in combination of two or more.
They can be used together. The above-mentioned acid anhydride-based monomers include
For example, formic acid, itaconic anhydride, citraconic anhydride, etc.
It is. Of these, maleic anhydride is preferred. this
Use one kind alone or two or more kinds in combination.
be able to. Further, as the maleimide compound
Is maleimide, N-methylmaleimide, N-phenyl
Maleimide, N- (2-methylphenyl) maleimide,
N- (4-hydroxyphenyl) maleimide, N-cyclo
Hexylmaleimide and the like.
Phenylmaleimide is preferred. These can be used alone
Alternatively, two or more kinds can be used in combination. In producing the above (co) polymer resin (A1)
Of the rubbery polymer (a) and the monomer component (b)
Preferably, the amount of the rubbery polymer (a) used is 20 to
70% by weight and 30 to 80% by weight of the monomer component (b)
%, More preferably 3% by weight of the rubbery polymer (a).
0 to 65% by weight and 35 to 70% of the monomer component (b)
% By weight, more preferably the above rubbery polymer (a)
Is 40 to 60% by weight and the monomer component (b) is 40 to 60% by weight.
60% by weight. However, (a) + (b) = 100 weight
%. The amount of the rubbery polymer (a) used is too small.
Or the amount of the monomer component (b) used is too large
And the impact resistance decreases, while the rubbery polymer (a)
Is too large or the monomer component (b)
If the amount is too small, delamination tends to occur and the flame retardancy
descend. The (co) polymer resin (A1) is a rubber
An aromatic vinyl compound and a shear agent in the presence of the porous polymer (a).
Vinyl compound, (meth) acrylate, acid-free
Selected from the group consisting of hydrate monomers and maleimide compounds.
At least one monomer component (b)
Is used in emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, etc.
It can be produced by carrying out calgraft polymerization. this
When the polymerization initiator, chain transfer agent (molecular weight regulator), water, etc.
In the case of emulsion polymerization, an emulsifier is further used.
You. In order to produce the (co) polymer resin (A1),
Rubbery polymer (a) and monomer component (b) used
Is to add monomer components all at once in the presence of the total amount of rubbery polymer.
It may be added and polymerized, divided or continuously added and polymerized
Is also good. In addition, by a method combining these,
Is also good. As the above polymerization initiator, cumene hydro
Peroxide, diisopropylbenzene hydropar
Oxide, paramenthane hydroperoxide, etc.
Representative organic hydroperoxides and sugar-containing pylori
Reducing agents represented by acid formulation, sulfoxylate formulation, etc.
Redox or persulfate
Persulfate such as lium, benzoyl peroxide, lau
Royl peroxide, t-butyl peroxylauray
Peroxidation of t-butyl peroxy monocarbonate, etc.
Things are used. Further, the above polymerization initiator is one of
They can be added together or continuously. Above polymerization
The amount of the initiator used is usually based on the total amount of the monomer component (b).
0.1-1.5% by weight, preferably 0.2-0.7% by weight
%. [0013] As the above chain transfer agent, octylmerca
Butane, n-dodecyl mercaptan, t-dodecyl mer
Captan, n-hexyl mercaptan, n-hexadec
Rumercaptan, n-tetradecyl mercaptan, t-
Mercaptans such as tetradecyl mercaptan, tarpi
Noren, dimers of α-methylstyrene and the like.
You. The amount of the chain transfer agent used is the total amount of the monomer component (b).
Is usually 0.05 to 2.0% by weight. The above emulsifier used in the case of emulsion polymerization is
For example, higher alcohol sulfates,
Alkylbenzene such as sodium rubenzenesulfonate
Aliphatic sulfonates such as sulfonates and sodium lauryl sulfate
Anions such as folate, higher aliphatic carboxylate, and phosphoric acid
On-active surfactant, alkyl of polyethylene glycol
Nonionic surfactants such as ester type and alkyl ether type
Sexual agents. The amount of the emulsifier used is usually a single
Usually, 0.3 to 5 parts by weight per 100 parts by weight of the body component (b).
Parts by weight. In the case of production by emulsion polymerization, usually coagulation
The powder obtained by coagulation with an agent is washed with water and then dried
Purified by This coagulant includes calcium chloride
, Magnesium sulfate, magnesium chloride, sodium chloride
Use of inorganic salts such as lium and acids such as sulfuric acid and hydrochloric acid
Can be. In the presence of the rubbery polymer (a),
(Co) polymer resin obtained by polymerizing monomer component (b)
In (A1), the monomer component (b) is a rubbery polymer
(A) Graft copolymerization component grafted onto the above monomer
Component (b) is not grafted on rubbery polymer (a)
Ungrafted component [(co) polymerization of monomer component (b)
Body] is included. The (co) polymer resin (A1) is a single
Even if it is a (co) polymer resin of composition, two or more
It may be a blend of the above (co) polymer resins. Also,
As the rubber-reinforced resin [A] according to the present invention,
In addition to the (co) polymerized resin (A1),
(A) polymer (A) obtained by (co) polymerizing the component (b)
It may be a mixture with 2). The above (co) polymer (A
The monomer component (b) for forming 2) is the simple monomer exemplified above.
Using a single monomer alone or in combination of two or more
Can be The above-mentioned (co) polymerized rubber-reinforced resin [A]
Resin (A1) and the above (co) polymer (A2)
Forming the (co) polymer (A2) when
The amount of component (b) used is preferably 30 to 90% by weight,
More preferably, it is 40 to 80% by weight. The above (co) weight
The union (A2) is a (co) polymer having a single composition,
A blend of two or more (co) polymers with different compositions.
May be. The above-mentioned (co) polymerized rubber-reinforced resin [A]
A mixture of the resin (A1) and the (co) polymer (A2)
In some cases, the content ratio (A1) / (A2) is (A1)
When the total of (A2) is 100% by weight, preferably
5 to 95/5 to 95 (% by weight), more preferably
10-90 / 10-90 (% by weight), more preferably 2
0 to 80/20 to 80 (% by weight). The above (co) weight
If the content of the synthetic resin (A1) is too small, the impact resistance decreases.
I do. Graft ratio of the (co) polymer resin (A1)
Is preferably 10% or more, more preferably 20 to 15%.
0%, more preferably 30 to 130%. here,
The graft ratio (%) refers to the grafting rate of the rubbery polymer (a).
Is the ratio of the monomer component (b),
Value. Graft ratio (%) = 100 × (TS) / S [However, as for T, the (co) polymer resin (A1) is put into acetone.
The weight of the insoluble matter obtained by separating the insoluble matter and the soluble matter,
S is the weight of the rubbery polymer in the (co) polymer resin (A1)
Represent. ] The above graft ratio (%) is determined by
Polymerization initiator and chain transfer when polymerizing resin (A1)
Type and amount of emulsifier, emulsifier, solvent, etc.
It can be controlled by changing the temperature and the like. The above (co) polymer resin (A1) can be acetone
Weight average molecular weight M_wIs 60,000-200,
000, preferably 70,000 to 180,00.
0, more preferably 80,000 to 150,000
You. Also, the weight average molecular weight M _wAnd number average molecular weight M_nWith
Ratio M_w/ M_nIs 2.3 to 5, preferably 2.4
-5, more preferably 2.5-5. Above acetone
Weight average molecular weight of soluble matter M_wIs too large for moldability
On the other hand, if too small, the impact resistance decreases.
I do. In addition, M of the acetone-soluble component_w/ M_nIs the above range
Outside of the range, the balance between impact resistance and moldability deteriorates. 2. Polycarbonate resin [B] The above polycarbonate resin constituting the above thermoplastic resin
[B] includes various dihydroxyaryl compounds
Obtained by reaction with phosgene, or dihydro
S of xyaryl compound and diphenyl carbonate
Examples include those obtained by a tell exchange reaction. Poly
Dihydroxyaryl compounds as carbonate raw materials
As bis (4-hydroxyphenyl) methane,
1,1′-bis (4-hydroxyphenyl) ethane,
2,2'-bis (4-hydroxyphenyl) propane,
2,2'-bis (4-hydroxyphenyl) butane,
2,2'-bis (4-hydroxyphenyl) octane,
Bis (4-hydroxyphenyl) phenylmethane, 2,
2'-bis (4-hydroxy-3-methylphenyl) p
Lopan, 2,2'-bis (4-hydroxy-3-tert-butyl
Tylphenyl) propane, 2,2′-bis (4-hydro
(Xy-3-bromophenyl) propane, 2,2'-bis
(4-hydroxy-3,5-dichlorophenyl) propa
1,1'-bis (4-hydroxyphenyl) cyclo
Pentane, 1,1'-bis (4-hydroxyphenyl)
Cyclohexane, 4,4'-dihydroxydiphenyl
-Tel, 4,4'-dihydroxy-3,3'-dimethyl
Diphenyl ether, 4,4'-dihydroxyphenyl
Sulfide, 4,4'-dihydroxy-3,3'-dim
Tylphenyl sulfide, 4,4'-dihydroxyphen
Nylsulfide, 4,4'-dihydroxy-3,3'-
Dimethylphenyl sulfide, 4,4'-dihydroxy
Diphenylsulfoxide, 4,4'-dihydroxy-
3,3'-dimethylphenylsulfoxide, 4,4'-
Dihydroxyphenyl sulfone, 4,4'-dihydroxy
C-3,3'-dimethyldiphenyl sulfone, hydroxy
And resorcinol, which are used alone or
They are used in combination of two or more. Particularly preferred
Is 2,2'-bis (4-hydroxyphenyl) propa
(Also known as "bisphenol A"). Polycar above
Polycarbonate obtained from the above raw materials is used as the carbonate resin.
Bonate resin alone or in combination of two or more
Can be used. In addition, (B1) and (B
2) Even if the same polycarbonate resin is different
It may be. The above-mentioned polycarbonate constituting the above-mentioned thermoplastic resin
The carbonate resin [B] has a viscosity average molecular weight of 16,000.
~ 32,000, preferably 17,000-3
1,000, more preferably 18,000 to 30,00
0. In the present invention, the viscosity average component within the above range
Combination of two or more types of polycarbonate resin
It is preferable to use a mixture of these. Two types with different viscosities
By using the above polycarbonate resin,
The balance between fluidity and impact resistance can be improved
It has the effect of being able to do it. Two types with different viscosity average molecular weight
Polycarbonate resin [(B1) and (B2)
You. Is used, the viscosity average molecule of the component (B1) is used.
The amount is preferably between 13,000 and 19,000,
More preferably, it is 14,000 to 18,000. Ma
The component (B2) preferably has a viscosity average molecular weight of 2
3,000 to 35,000, more preferably 2
1,000 to 33,000. The above component (B1) having a different viscosity average molecular weight
The content of (B2) and (B2) is preferably the above component (B1).
3 to 50% by weight, more preferably 5 to 40% by weight,
More preferably, the content is 10 to 35% by weight.
2) is preferably 50 to 97% by weight, more preferably 6% by weight.
0 to 95% by weight, more preferably 65 to 90% by weight.
You. If the content of the component (B1) is too small or
If the content of the component (B2) is too large, the moldability is low.
On the other hand, is the content of the component (B1) too large?
Or if the content of the above component (B2) is too small, the impact resistance may be reduced.
Is reduced. The above-mentioned rubber reinforcement constituting the above-mentioned thermoplastic resin
Resin [A] and polycarbonate resin [B] contained
The ratio [A] / [B] is 5 to 80/20 to 95 (weight
%), Preferably 10 to 75/25 to 90 (weight
%), More preferably 15 to 70/30 to 85 (weight)
%). Low content of the rubber reinforced resin [A]
Include or contain the above polycarbonate resin [B]
If the amount is too large, the moldability deteriorates, while the rubber
Content of the fluorinated resin [A] is too large or
If the content of the carbonate resin [B] is too small, heat resistance,
Impact resistance and flame retardancy are reduced. 3. Condensed phosphorus flame retardant [C] The condensed phosphorus-based flame retardant [C] is not particularly limited,
For example, a condensed phosphate represented by the following general formula (I)
Is preferably used. Embedded image (However, R¹  , R²  , R³  And R⁴  Each
Phenyl or xylenyl groups independently selected from each other
X is a divalent resorcinol residue or bisphenol
Represents an A residue, and n is 0.5 to 1.2. ) R above¹  ~ R⁴  Phenyl or xylenyl group in
Means that the hydrogen atom of the aromatic ring is
It may be replaced. X is a dihydroxylated compound
Derived from the compound resorcinol or bisphenol A
It is a derived group. Mixed with the above condensed phosphorus flame retardant [C]
In the case of a product, the value of n
(Average degree of polymerization). The average degree of polymerization n is 0.5
~ 1.2, preferably 0.7 ~ 1.2, more preferably
0.9 to 1.1. When the average degree of polymerization n is less than 0.5
In this case, the problem of mold contamination is likely to occur. On the other hand, the average degree of polymerization
Condensed phosphoric acid esters in which n exceeds 1.2 are difficult to produce
Therefore, it is expensive and difficult to use economically. General above
The condensed phosphoric ester represented by the formula (I) may be used singly.
Or two or more types can be used in combination
You. The amount of the condensed phosphorus-based flame retardant [C] is as follows:
The rubber reinforced resin [A] and the polycarbonate resin
1 to 30 parts by weight based on 100 parts by weight in total of [B]
Preferably 3 to 25 parts by weight, more preferably 5 to 2 parts by weight.
0 parts by weight. Insufficient flame retardancy if the amount is small
On the other hand, if it is too much, the heat resistance decreases. The above condensed phosphorus-based flame retardant [C] and other
Flame retardants may be used in combination, for example, halogen-based flame retardants,
Examples include antimony compounds and metal hydroxides. the above
As a halogen-based flame retardant, tetrabromobisphenol
Oligomer of Ru-A (terminal is epoxy group,
Enol), post-brominated polystyrene
Ren, brominated polycarbonate oligomer, tetrab
Lomobisphenol-A, chlorinated polystyrene, aliphatic
Chlorine compounds and the like. In addition, the above antimony compound
Antimony trioxide, antimony pentoxide, etc.
No. Examples of the metal hydroxide include magnesium hydroxide
Cium, aluminum hydroxide and the like. The flame retardant [C] contains a flame retardant auxiliary.
Is preferred. As the flame retardant aid, for example, poly
Tetrafluoroethylene is mentioned. Polytetraflu
Oroethylene is dripping during combustion (the melt dripping)
Has the effect of preventing. The preferred weight average molecular weight is 50
It is 10,000 or more, more preferably 1,000,000 or more. Politet
When mixing and kneading lafluoroethylene with other components
The preferred average particle size is from 90 to 600 μm, more preferably
100 to 500 μm, more preferably 120 to 40
0 μm. In addition, polytet after kneading with other components
Lafluoroethylene has an average particle diameter of 0.1 to 100 μm.
m, or dispersed as finer fibrous material
Is done. Also, polytetrafluoroethylene is used as another component.
The preferred specific gravity when mixing with 1.5 to 2.5, more
It is preferably 2.1 to 2.3, and the preferred bulk density is
0.5-1 g / ml, more preferably 0.6-0.9 g
/ Ml. Compounding polytetrafluoroethylene
As it can prevent dripping during combustion,
High flame retardant levels can be achieved. Polytetraf
Fluoroethylene or the like with a solvent such as water or a lubricant (polyethylene)
Such as renwax, organic acid, magnesium stearylate, etc.
Dispersion-type polyester dispersed in an organic metal salt)
Trafluoroethylene can also be used. When the flame retardant aid is used, the amount of the
Reinforced resin [A] and the above polycarbonate resin [B]
Is usually 0 to 20 parts by weight relative to 100 parts by weight of
, Preferably 0 to 18 parts by weight, more preferably 0 to 1 part by weight.
5 parts by weight. If the compounding amount is too large, impact resistance and heat resistance
Decreases. 4. Glass flake [D] Commercially available glass flakes [D]
Can be used as it is, but the preferred shape is scale
And the preferred average major axis is 100 to 800 μm,
More preferably, it is 150 to 700 μm, more preferably, 15 to 700 μm.
0 to 600 μm, and the aspect ratio (average major axis and
Thickness ratio) is preferably 5 or more, more preferably 10 or more.
Above, more preferably 30 or more. The above glass frame
If the average length of [D] is too large, classification will occur during compounding.
And it may be difficult to mix uniformly with the resin.
Deteriorates the surface appearance. Also, the aspect ratio is too small
Insufficient improvement in the heat distortion temperature of the molded product
Impact resistance decreases. The amount of the glass flake [D] is
The rubber reinforced resin [A] and the above polycarbonate resin
1 to 50 parts by weight with respect to 100 parts by weight in total of [B]
Preferably 5 to 45 parts by weight, more preferably 10 to 45 parts by weight.
45 parts by weight. Insufficient rigidity when the amount is too small
On the other hand, if it is too large, the impact resistance and molding processability are low.
Down. 5. Lubricant [E] Examples of the lubricant [E] include hardened castor oil and silicone oil.
Selected from the group consisting of yl and polyolefin wax
At least one kind is used. Amount of the above lubricant [E]
Is the rubber-reinforced resin [A] and the polycarbonate
0.1 to 5.0 based on 100 parts by weight of resin [B] in total.
Parts by weight, preferably 0.2 to 4 parts by weight, more preferably
Or 0.3 to 4 parts by weight. If the amount is too small
Molding processability and mold releasability decrease, while if too large,
Heat resistance and thermal stability decrease. The heat of the present invention containing the above [A] to [E]
Melt flow rate of the thermoplastic resin composition (240 ° C, load
(Weight 10kg) is more than 30g / 10min.
At least 40 g / 10 min, more preferably 50 g / min.
10 minutes or more. Melt flow rate is too low
Glass flakes are greatly destroyed during kneading,
Heat resistance tends to decrease. Further, the thermoplastic resin composition of the present invention will be described later.
As can be obtained by kneading each component,
During this kneading, the above glass flakes [D] are crushed.
And The remaining average major axis of the glass flakes after kneading is 5
0 to 300 μm, preferably 100 to 200 μm
It is. If the remaining average major axis is too short, the glass flakes
If the goal cannot be achieved,
Poor surface appearance of the shape. In addition, the thermoplastic resin composition of the present invention
The residual emulsifier, coagulant, etc. in the rubber reinforced resin [A]
At high temperatures (such as during molding)
The decomposition reaction of the resin [B] occurs, and the physical properties of the composition decrease.
Sometimes However, it contains inorganic phosphorus compounds
By doing, polycarbonate tree at high temperature
The decomposition reaction of fat can be suppressed. As this inorganic phosphorus compound
Is sodium dihydrogen phosphate, disodium hydrogen phosphate
And hydrates thereof. The amount
100 parts by weight of thermoplastic resin (combination of the above [A] and [B]
Weighing), usually 0.1 to 3 parts by weight, preferably
0.2 to 2 parts by weight. The thermoplastic resin composition of the present invention contains
Agents, weathering agents, antistatic agents, antioxidants, plasticizers, coloring agents
And a coupling agent and the like. Above charge
Fillers include glass fiber, carbon fiber, wollastonite
, Talc, mica, glass flake, milled fiber
ー, zinc oxide whiskers, calcium titanate whiskers
-And the like. These may be used alone or in combination of two or more.
The above can be used in combination. Glass fiber and
The preferred size of the carbon fiber is a fiber diameter of 6 to 20 μm,
The fiber length is 30 μm or more (usually, the upper limit is 50 μm)
You. Examples of the weathering agent include organic phosphorus compounds, organic sulfur
Based compounds and organic compounds containing hydroxyl groups are preferred.
No. Further, the antistatic agent has an alkyl group
Sulfonate and the like. The thermoplastic resin composition of the present invention can be prepared by various extrusions.
Machine, Banbury mixer, kneader and roll etc.
It is obtained by kneading each component under heating.
A preferred production method is a method using a twin-screw extruder. each
When kneading the components, even if they are kneaded all at once,
It may be kneaded by addition. Two types with different viscosity average molecular weight
When compounding the above polycarbonate resin,
After mixing, it may be kneaded with other components, or
These may be previously melt-kneaded and then kneaded with other components. The thermoplastic resin composition of the present invention is prepared by injection molding.
For shape, sheet extrusion, vacuum molding, profile extrusion and foam molding
Therefore, electronic products such as personal computers, CD-ROMs, and DVDs
Various molded products including housing can be obtained
You. The product obtained by using the thermoplastic resin composition of the present invention
Of the molded article to be measured under the measurement conditions in the following examples
The flexural modulus is preferably between 35,000 and 80000 k
g / cm², More preferably 36000 to 70000k
g / cm²It is. Also, the warpage of the molded product is preferably
0.5 mm or less, more preferably 0.3 mm or less
be able to. [0041] EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples.
Although described in detail, the scope of the present invention does not exceed the gist thereof.
It is not limited by the following examples.
No. In the following Examples and Comparative Examples, parts and% are
Unless otherwise specified, parts and percentages are by weight. 1. Evaluation method The evaluation method used in this example is as follows.
is there. (1) Average particle size The average particle size of the dispersed particles was synthesized in advance in an emulsified state.
Particles of the dispersed particles in the resin with the particle size of the latex unchanged
The diameter was confirmed by an electron microscope.
The particle size of the dispersed particles therein was measured by a light scattering method. Measuring machine
The vessel used was LPA-3100 manufactured by Otsuka Electronics Co., Ltd.
The particle diameter was measured using the cumulant method by integrating 0 times. (2) Graft ratio of (co) polymer resin Details are described in the text. (3) Intrinsic viscosity 25 g of acetone was added to 0.8 g of the (co) polymer resin,
Shake for a time, then distant at 15,000 rpm
Separation was performed to separate soluble and insoluble components. Soluble 0.25
g in methyl ethyl ketone and at a temperature of 30 ° C.
It was measured with an Ubbelohde viscometer. (4) Acetone of (co) polymer resin [A]
Molecular weight of dissolved matter About the acetone-soluble matter obtained in the above (3), the following
Gel Permeation Chromatography (GP
C) Measure and determine the weight average molecular weight M_w, Number average molecular weight M
_nAnd their ratio M_w/ M_nI asked. 20 mg of sample
Dissolved in 10 ml of solvent tetrahydrofuran and used for liquid chromatography
After filtration with a pretreatment disk, Tosoh Corporation HLC-
Using 8120 gel permeation chromatography
The molecular weight was measured by GPC. The calibration curve is a police
It was prepared using a standard material of styrene. The column is TSKg
el GMHHR-H (30) and TSKgel Mu
column temperature by directly using ltipore HXL-M
The temperature was measured at 40 ° C. (5) Fluidity (melt flow rate) The measurement was performed according to ASTM D1238. Measurement temperature is 2
At 40 ° C., the load is 10 kg. (6) Combustion test Compliant with UL-94 V test. The thickness of the sample piece was 1.
0 mm. (7) Residual average major axis of glass flakes Dissolve the molded product in dichloromethane
Fat (B) only, and 200-500 glass flour
The work was extracted and photographed by an electron microscope. this
The residual average major axis was measured by image analysis of the photograph.
Was. (8) Evaluation of molded product surface Using an injection molding machine, molding temperature 240 ° C, mold temperature 50 ° C
To obtain a 150 × 150 × 2 mm flat molded product,
Painted and noticed surface roughness from glass flake [D]
Judged whether to stand. The criteria are as follows:
You. ：: After coating, surface roughness is not conspicuous at all. ：: After coating, the surface roughness was almost inconspicuous, but was partially
Stand out. Δ: After coating, surface roughness is noticeable. X: The surface roughness is remarkable before painting. (9) Warpage Molding temperature 240 ° C, mold temperature 50 ° C, 150 × 150
× 2mm flat plate molded product was obtained at 23 ° C and humidity of 50%.
Left for one day, put it on a horizontal desk,
The gap formed between them was measured. (10) Evaluation of surface impact strength Using a DuPont impact measuring device, load 200g
Drop the test piece every 10 cm at a height of 10 to 50 cm,
Was evaluated based on the height at the time of cracking. Sample thickness is 2.4m
m. (11) Evaluation of releasability 4mm inside diameter 7mm outside diameter on a flat plate of 60 × 300 × 2mm
Using a molded product with 12 bosses with a height of 30 mm
evaluated. Of the six protruding pins (diameter 5 mm) of the mold
Attach a pressure sensor to one tip, and when protruding
The pressure applied to the ejection pin was measured. At the time of injection molding
The injection molding pressure of
Was. 2. Preparation of rubber reinforced resin In a 7-liter glass flask equipped with a stirrer
100 parts of ion-exchanged water, sodium dodecylbenzenesulfonate
Thorium 1.5 parts, t-dodecyl mercaptan 0.1
Parts, rubbery polymer a shown in Table 1₁And a₂, Each
8 parts and 32 parts, styrene 15 parts, acrylonitrile 5
Then, the mixture was heated while stirring. The temperature reaches 45 ° C
At that time, sodium ethylenediaminetetraacetate 0.1
Part, ferrous sulfate 0.003 part, formaldehyde sodium
0.2 parts of umsulfoxylate dihydrate and ion exchange
Activator aqueous solution consisting of 15 parts of water replacement, and diisopropyl
0.1 part of benzene hydroperoxide was added,
The reaction was continued for hours. After that, 50 parts of ion exchange water
1 part of sodium silbenzenesulfonate, t-dodecyl
0.1 part of mercaptan, diisopropyl hydroperoxy
0.2 parts of side, 30 parts of styrene and acrylonitrile
Delivery of 10 parts of incremental polymerization component over 3 hours
And the polymerization reaction was continued. After the addition is complete
After stirring for 1 hour, 2,2-methylene-bis-
(4-ethylene-6-t-butylphenol) 0.2 part
Was added and the reaction product was taken out of the flask. Reaction student
The resulting latex is coagulated with 2 parts of calcium chloride and reacted.
After thoroughly washing the product with water, drying at 75 ° C. for 24 hours
A color powder (co) polymer resin (A1-1) was obtained. Polymerization conversion
Rate is 97.2%, graft rate is 75%, intrinsic viscosity is 0.1%.
It was 44 dl / g. Sets shown in Table 2 in the same manner as above
The resulting (co) polymer resin (A1-2-3) was produced. Ma
Acrylonitrile / styrene resin having the composition shown in Table 2
(A2-1-2) was obtained by solution polymerization. The above (co) weight
Resin (A1-1-3) or, if necessary, acrylonitrile
Tables 3 to 5 show the tolyl styrene resins (A2-1 and A2).
The rubber mixture is used as a rubber reinforced resin and the composition is manufactured.
Used for [0052] [Table 1] [0053] [Table 2] 3. Polycarbonate resin The following were used. B-1; manufactured by Mitsubishi Engineering-Plastics Co., Ltd.
Product name "NOVAREX 7022PJ-LH1" (viscosity flat
(Equivalent molecular weight: 14,500) B-2: Made by Mitsubishi Engineering-Plastics Co., Ltd.
Product name "NOVAREX 7022PJ-LH1" (viscosity flat
(Equivalent molecular weight: 21,000) B-3; manufactured by Idemitsu Petrochemical Co., Ltd., trade name "Toughlon FN2"
200 "(viscosity average molecular weight: 22,000) B-4; manufactured by Mitsubishi Engineering-Plastics Corporation
Product name "NOVAREX 7022PJ-LH1" (viscosity flat
(Equivalent molecular weight: 30,000) 4. Condensed phosphorus flame retardant The following condensed phosphate esters were used. C-1: resorcinol and dixylenyl phosphate
And n in the general formula (I) is 1.0
Equivalent. C-2: bisphenol-A and diphenylphospho
And n in the general formula (I) is 1.1
Equivalent to 5. Flame retardant aid F-1 as a product name “TF1620” manufactured by Hoechst
(Average particle size: 220 μm, bulk density: 0.85 g / dl)
Was used. 6. Glass flake The following were used. D-1; manufactured by Nippon Sheet Glass Co., Ltd., trade name "Freka REFG
−101 ”(average major axis 600 μm, average thickness 5 μm) D-2: manufactured by Nippon Sheet Glass Co., Ltd., trade name "Freka REFG
−301 ”(average major axis 140 μm, average thickness 5 μm) D-3; manufactured by Nippon Sheet Glass Co., Ltd., trade name "FLECA REFG
−401 ”(average major axis 300 μm, average thickness 5 μm) 7. Lubricant The following were used. E-1: Hardened castor oil, manufactured by Kao Corporation, trade name "KAO"
WAX 85P " E-2: Silicone oil, Dow Corning Toray
Product name "SH200" E-3; polyolefin wax, manufactured by Sanyo Chemical Co., Ltd.
Product name "171-P" 8. Examples 1 to 9, Comparative Examples 1 to 6 The above components [A] to [F] were mixed in the mixing ratios shown in Tables 3 to 5.
Using a twin-screw extruder under a temperature condition of 230 to 250 ° C.
The mixture was melt-kneaded to obtain pellets. Except for Comparative Example 3,
Russ flakes were fed in the middle of a twin screw extruder. Comparison
Example 3 feeds all components from the raw material hopper at once.
Was. When blending C-2 as a condensed phosphorus-based flame retardant,
Is to heat the C-2 component to around 70-80 ° C,
Liquid was added at the output machine. Injection molding of the obtained pellet
(Molding temperature: 240 ° C.) to obtain an evaluation sample. This
The above various evaluations were performed using the evaluation samples of
Also described in 5. [0059] [Table 3] [0060] [Table 4][0061] [Table 5]9. Effects of the embodiment From Table 5, Comparative Example 1 shows the blending amount of the polycarbonate resin.
Was out of the range of the present invention and was inferior in fluidity. Liquidity
Therefore, the warpage of the molded article was large. Also gala
Stiffness is inferior due to small residual average major diameter of flakes
Was. In Comparative Example 2, the blending amount of the polycarbonate resin was
It was small outside the range of the invention and inferior in surface impact strength. Ma
Moreover, the flammability was poor. Comparative Example 3 is a glass flake
Is fed from the hopper, but in the composition
Small residual average major axis and low rigidity. Also contains lubricant
As a result, the releasability was poor. Comparative Example 4 has an average viscosity
No polycarbonate resin with small molecular weight is blended
Therefore, the surface appearance of the molded product was inferior. Also contains lubricant
Therefore, the releasability is poor. Furthermore, due to poor fluidity,
Large warpage. Since Comparative Example 5 does not contain a lubricant, it is released.
Sex was inferior. Comparative Example 6 shows only one type of polycarbonate.
In this case, the surface impact strength was inferior. one
In Examples 1 to 10 shown in Tables 3 and 4,
Excellent rigidity, fluidity, impact resistance (surface impact strength), heat resistance
Properties, molded product surface appearance, flame retardancy, small warpage, and
It showed releasability. Especially, the content of glass flake is large
Have high flexural modulus and excellent rigidity.
However, those with flame retardant additives show excellent flammability.
Was. In Examples 1 to 5, the compounding amount of the rubber reinforced resin was polycarbonate.
Nitrate resin, more flame retardant additives
The bending modulus was high (except for Example 5).
V) was achieved in the evaluation of flammability (Example 3
-1). Also, the warpage is 0.3mm,
It was excellent. In Examples 6 to 9, the amount of the rubber-reinforced resin
Less flame retardant than that of carbonate resin
Is not blended, and reaches V-2 in flammability evaluation
And the warpage is 0.3mm, which is excellent in dimensional stability.
Was. [0063] The thermoplastic resin composition of the present invention has a high rubber strength.
Resin consisting of activated resin and polycarbonate resin
Condensed phosphorus-based flame retardant, glass flake, lubricant, etc.
It has excellent fluidity and can be obtained using it.
Excellent rigidity, flame retardancy, impact resistance and molded appearance of molded products
You.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08L 83/04 C08L 83/04 91/00 91/00 (72) Inventor Fumihiko Usui 1-18 Kyobashi, Kyobashi, Chuo-ku, Tokyo No.1 Techno Polymer Co., Ltd. F-term (reference) 4J002 AE033 AE053 BB003 BN13W BN14W BN21W CG01X CG02X CP033 DL007 EW046 FA017 FD010 FD136 FD173 GC00 4J026 AA45 AA68 AA69 AB02 AB44 AC01 BA03 AC04 DB14 DB24 FA04 GA01 GA09

Claims (1)

Claims: [A] In the presence of a rubbery polymer (a),
Aromatic vinyl compound, vinyl cyanide compound, (meth)
A (co) polymer resin (A) obtained by polymerizing at least one monomer component (b) selected from the group consisting of acrylic acid esters, acid anhydride monomers and maleimide compounds;
1) or a mixture of the (co) polymer resin (A1) and a (co) polymer (A2) obtained by polymerizing at least one member selected from the group of the monomer components (b). , The weight average molecular weight _{Mw of} the acetone-soluble component is from 60,000 to 2
Is 00,000, and a rubber-reinforced resin 5-80 parts by weight ratio _M w / _{M n} of the weight-average molecular weight _{M w} of the number-average molecular weight _{M n} is from 2.3 to 5, [B] The viscosity average Molecular weight 1
A thermoplastic resin 10 comprising 20 to 95 parts by weight of a polycarbonate resin of 6,000 to 32,000.
0 parts by weight [provided that [A] + [B] = 100 parts by weight], and, based on 100 parts by weight of the thermoplastic resin, [C] 1 to 30 parts by weight of a condensed phosphorus-based flame retardant, [D] glass A thermoplastic resin composition comprising 1 to 50 parts by weight of flakes and 0.1 to 5 parts by weight of (E) at least one lubricant selected from the group consisting of hardened castor oil, silicone oil and polyolefin wax, Melt flow rate (2
A thermoplastic resin composition characterized in that the glass flakes contained in the present composition have a residual average major axis of 50 to 300 μm at 40 ° C. and a load of 10 kg) of 30 g / 10 min or more.