JPH08127686A - Polycarbonate resin composition - Google Patents

Abstract

PURPOSE: To obtain a polycarbonate resin composition comprising a specific polycarbonate resin, a vinylic copolymer and a rubbery polymer-vinylic monomer copolymer, excellent in flowability, chemical resistance, heat resistance, impact resistance and thin-shaped product moldability, and useful for office automation equipments, etc. CONSTITUTION: This composition comprises (A) 90-10 pts.wt. of a polycarbonate resin having a viscosity-average mol.wt. of >=20000, (B) 1-50 pts.wt. of a copolymer having a weight-avarage mol.wt. of 30000-110000 and comprising a copolymer (e.g. SAN resin) containing an aromatic monomer component (BI) and a vinyl cyanide monomer component (BII) as the constituting components of the copolymer, and (C) 1-50 pts.wt. of a copolymer (e.g. ABS resin, AES resin, ACS resin or AAS resin) containing the component BI, the component BII and a rubbery polymer as the constituting components of the copolymer components.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition containing a polycarbonate resin.

[0002]

2. Description of the Related Art Polycarbonate (PC) resins and polymer alloys obtained by blending them with ABS (acrylonitrile-butadiene-styrene) resins have been widely used in electric and electronic products and OA equipment. There is. In recent years, there has been an increasing demand for miniaturization and weight reduction of these, and it has become necessary to reduce the thickness of housings and cabinets. In order to respond to this, new molding methods have been tried, and improvements have been made in terms of materials. For example, in order to achieve thinning, attempts have been made to adopt low-molecular weight polycarbonate and improve the fluidity by increasing the blending ratio of ABS resin and SAN resin (Japanese Patent Publication Sho 58).
-46269 publication).

However, for example, in PC / ABS polymer alloys, when the molecular weight of PC is lowered, the chemical resistance is lowered, and product defects such as edge cracks tend to occur when a product such as an OA equipment housing is molded. Brings the inconvenience of. On the other hand, if the compounding ratio of the ABS resin or SAN resin is increased, the heat resistance and strength will be reduced.

Therefore, an object of the present invention is to provide a polycarbonate resin composition which can be molded into a thin wall while maintaining properties such as fluidity, chemical resistance, heat resistance and impact resistance. Another object of the present invention is to provide a polycarbonate resin composition having excellent flame retardancy.

[0005]

Means for Solving the Problems As a result of intensive studies on the polycarbonate resin composition, the present inventors have found that
By specifying the molecular weight of the polycarbonate resin that forms the matrix to a certain level or more, and limiting the molecular weight of the aromatic vinyl / vinyl cyanide resin that forms the dispersed phase to a specific range, chemical resistance and various physical properties, especially fluidity The inventors have found that a resin composition having good properties can be obtained, and have reached the present invention.

That is, the present invention provides (A) viscosity average molecular weight
A copolymer containing 90 to 10 parts by weight of a polycarbonate resin having 20,000 or more, (B) (a) an aromatic vinyl monomer component and (b) a vinyl cyanide monomer component as constituents of the copolymer. And a weight average molecular weight of 30,000 to 110,000
1 to 50 parts by weight of a copolymer having, and (C) (a) an aromatic vinyl monomer component, (b) a vinyl cyanide monomer component and (c) a rubbery polymer, Provided is a resin composition containing 1 to 50 parts by weight of a copolymer contained as a constituent component.

The polycarbonate resin used in the present invention is an aromatic polycarbonate prepared by a known phosgene method or a melting method (for example, JP-A-63-2).
15763 and JP-A-2-124934). Examples of the diphenol used as a raw material include 2,2-bis (4-hydroxyphenyl) propane (so-called bisphenol A); 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane; 2,2 -Bis (3,5-dimethyl-4-hydroxyphenyl) propane; 1,1-bis (4-hydroxyphenyl) cyclohexane; 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane; 1-bis (4-hydroxyphenyl) decane; 1,4-bis (4-hydroxyphenyl) propane; 1,1-bis (4-hydroxyphenyl) cyclododecane; 1,1-bis (3,5-dimethyl- 4-hydroxyphenyl) cyclododecane; 4,4-dihydroxydiphenyl ether; 4,4-thiodiphenol; 4,4-dihydroxy
-3,3-dichlorodiphenyl ether; and 4,4-dihydroxy-2,5-dihydroxydiphenyl ether. Further, examples of the precursor for introducing the carbonate include phosgene and diphenyl carbonate.

In the present invention, the polycarbonate resin has a viscosity average molecular weight (Mv) of 20,000 or more, preferably 21,000 or more, more preferably 22,000 or more.
If the molecular weight is too low, the chemical resistance is poor. The lower limit of the viscosity average molecular weight is not particularly limited, but is practically 40,000 or less. In the present invention, the viscosity-average molecular weight is measured by measuring the intrinsic viscosity (intrinsic viscosity) in methylene chloride at 20 ° C.
Mark-Houwink viscosity formula:

[0009]

## EQU1 ## [η] = KM ^a (where, [η] = intrinsic viscosity, K, a = constant (K = 1.
23 × 10 ⁻⁴ , a = 0.83), M = molecular weight).

Next, the component (B) is a copolymer containing (a) an aromatic vinyl monomer component and (b) a vinyl cyanide monomer component. The component (B) contributes to improving the moldability (flowability) of the resin composition.

(A) As the aromatic vinyl monomer component, for example, styrene, α-methylstyrene, o-, m- or p-
Methyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene, vinylnaphthalene, etc. can be mentioned, and one or more of them are used. To do. Styrene and α-methylstyrene are preferred.

(B) As the vinyl cyanide monomer component,
For example, acrylonitrile, methacrylonitrile, etc. can be mentioned, and these are used 1 type (s) or 2 or more types.
The composition ratio of these is not particularly limited and is selected according to the application.

The composition ratio of (a) / (b) is not particularly limited,
In the component (B), (a) is preferably 95 to 50% by weight, (b) is 5 to 50% by weight, and more preferably
(a) is 92 to 65% by weight, and (b) is 8 to 35% by weight.

Preferred examples of the component (B) copolymer include SAN resin (styrene-acrylonitrile copolymer).

The method for producing the component (B) copolymer is not particularly limited, and generally known methods such as bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization and emulsion polymerization can be used. It can also be obtained by blending separately copolymerized resins.

In the present invention, the weight average molecular weight (Mw) of the component (B) copolymer is 30,000 to 110,000, preferably 40,000 to 80,000. When the molecular weight of the component (B) copolymer is below the above range, the physical properties are deteriorated, and when it is above the above range, the fluidity is impaired.

Next, the component (C) will be described. (C) is
A copolymer containing (a) an aromatic vinyl monomer component, (b) a vinyl cyanide monomer component, and (c) a rubbery polymer.
As the aromatic vinyl monomer component (a) and the vinyl cyanide monomer component (b), those shown in the above component (B) can be mentioned. (c) The rubbery polymer includes polybutadiene, polyisoprene, styrene-butadiene random copolymers and block copolymers, hydrogenated products of the block copolymers, acrylonitrile-butadiene copolymers, butadiene-isoprene copolymers. Diene rubbers such as polymers, random copolymers and block copolymers of ethylene-propylene, random copolymers and block copolymers of ethylene-butene, copolymers of ethylene and α-olefins, ethylene-methacrylate , Copolymers with ethylene-unsaturated carboxylic acid esters such as ethylene-butyl acrylate, acrylic acid ester-butadiene copolymers, acrylic elastic polymers such as butyl acrylate-butadiene copolymer, ethylene-
Copolymers of ethylene and fatty acid vinyl such as vinyl acetate, ethylene-propylene-ethylidene norbornene copolymers, ethylene-propylene-hexadiene copolymers and other ethylene-propylene non-conjugated diene terpolymers, butylene-isoprene copolymers, Chlorinated polyethylene and the like can be used, and these are used alone or in combination of two or more. Preferred rubbery polymers are ethylene-propylene rubber, ethylene-propylene non-conjugated diene terpolymer, diene rubber and acrylic elastic polymer, and particularly preferred are polybutadiene and styrene-butadiene copolymer. The styrene content in the butadiene copolymer is preferably 50% by weight or less.

In the component (C), the composition ratio of the components (a), (b) and (c) is not particularly limited, and the components are blended according to the use.

As the component (C), in addition to the components (a), (b) and (c) described above, (d) a monomer copolymerizable with these components is not impaired for the purpose of the present invention. Can be used in a range. Examples of such copolymerizable monomers include α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth ) Acrylate, 2-ethyl (meth) acrylate, 2-ethylhexyl methacrylate and other α, β-unsaturated carboxylic acid esters; maleic anhydride, itaconic anhydride and other α,
β-unsaturated dicarboxylic acid anhydrides; maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, No-chlorophenylmaleimide and other α, β-unsaturated dicarboxylic acid imide compounds; These monomers can be used alone or in combination of two or more.

The component (C) copolymer is preferably a graft copolymer obtained by graft-copolymerizing (c) a rubbery polymer with other components, and more preferably ABS.
Resin (acrylonitrile-butadiene-styrene copolymer), AES resin (acrylonitrile-ethylene-propylene-styrene copolymer), ACS resin (acrylonitrile-chlorinated polyethylene-styrene copolymer), A
AS resin (acrylonitrile-acrylic elastic polymer-
Styrene copolymer).

Regarding the method for producing the component (C) copolymer,
The same method as in the above (B) copolymer can be used.

The above components (A), (B) and (C)
Are blended in the following ratios. That is, (A) to (C)
(A) 90 to 10 parts by weight,
(B) 1 to 50 parts by weight and (C) 1 to 50 parts by weight,
It is preferably (A) 85 to 20 parts by weight, (B) 1 to 40 parts by weight and (C) 1 to 30 parts by weight. When the amount of (A) is above the above range, the fluidity is lowered, and when it is below the above range, the heat resistance is lowered. When the amount of (B) is above the above range, the strength is lowered, and when it is below the above range, the fluidity is impaired. When the amount of (C) is above the above range, the rigidity is lowered, and when it is below the above range, the flame retardancy is lowered. The resin composition of the present invention further comprises, in addition to the above components, a composite rubber-based graft copolymer obtained by grafting a vinyl-based monomer onto a composite rubber containing (D) polyorganosiloxane and polyalkyl (meth) acrylate. A polymer may be blended to improve flame retardancy. Component (D) is a composite rubber having a structure in which a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component are alternately intertwined and composite-integrated, and one or more vinyl-based monomer It is a composite rubber-based graft copolymer obtained by graft-polymerizing a polymer.

For the production of such a composite rubber-based graft copolymer, for example, the method described in the specification of JP-A-64-79257 can be used.

It is suitable that such a composite rubber is produced by an emulsion polymerization method. First, a latex of polyorganosiloxane rubber is prepared, and then a monomer for synthesizing an alkyl (meth) acrylate rubber is impregnated into rubber particles of the polyorganosiloxane rubber latex. It is preferred to polymerize the monomer.

The polyorganosiloxane rubber component can be prepared by emulsion polymerization using, for example, the following organosiloxane and cross-linking agent (I), in which case a graft crossing agent (I) can be used in combination. .

Examples of the organosiloxane include chain organosiloxanes such as dimethylsiloxane. Further, various cyclic organosiloxanes having a 3-membered ring or more, preferably a 3 to 6-membered ring can also be used. Examples thereof include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane and octaphenylcyclotetrasiloxane. These organosiloxanes may be used alone or in admixture of two or more. The amount of these used is preferably 50% by weight or more, and more preferably 70% by weight or more in the polyorganosiloxane rubber component.

The cross-linking agent (I) may be trifunctional or tetrafunctional.
Functional silane-based crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetrabutoxysilane and the like can be used.
Particularly, a tetrafunctional crosslinking agent is preferable, and tetraethoxysilane is particularly preferable. The crosslinking agents may be used alone or in combination of two or more. The amount of the crosslinking agent used is 0.1 to 30% by weight in the polyorganosiloxane rubber component.
Is preferred.

The graft crossing agent (I) has the following formula:

[0029]

Embedded image CH ₂ ═C (R ² ) —COO— (CH ₂ ) _p —SiR ¹ _n O _{(3-n) / 2} (I-1)

[0030]

Embedded image CH ₂ ═CH—SiR ¹ _n O _{(3-n) / 2} (I-2) or

[0031]

Embedded image HS- (CH ₂ ) _p —SiR ¹ _n O _{(3-n) / 2} (I-3) (In the above formula, R ¹ is a lower alkyl group such as a methyl group,
Represents an ethyl group, a propyl group or the like or a phenyl group, R ²
Represents a hydrogen atom or a methyl group, and n is 0, 1 or 2
And p represents an integer of 1 to 6) is used. Since the (meth) acryloyloxysiloxane capable of forming the unit of the above formula (I-1) has high grafting efficiency, it is possible to form an effective graft chain, which is advantageous in that it exhibits high impact resistance. Is. In addition, methacryloyloxysiloxane is particularly preferable as a unit capable of forming the unit of the formula (I-1). Specific examples of methacryloyloxysiloxane include β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyl silane. Examples thereof include ethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane and δ-methacryloyloxybutyldiethoxymethylsilane. These may be used alone or in combination of two or more. The amount of the graft crossing agent used is preferably 0 to 10% by weight in the polyorganosiloxane rubber component.

The latex of the polyorganosiloxane rubber component can be produced by the method described in, for example, US Pat. Nos. 289,1920 and 3,294,725. In the practice of the present invention, for example, an organosiloxane, a cross-linking agent (I), and optionally a mixed solution of a graft crossing agent (I), an alkylbenzene sulfonic acid,
It is preferably produced by a method of shear mixing with water in the presence of a sulfonic acid-based emulsifier such as an alkyl sulfonic acid using, for example, a homogenizer. Alkylbenzene sulfonic acid is suitable because it acts as an emulsifier of the organosiloxane and at the same time serves as a polymerization initiator. At this time, it is preferable to use a metal salt of alkylbenzene sulfonic acid, a metal salt of alkyl sulfonic acid, or the like, because it is effective in maintaining the polymer stably during the graft polymerization.

Next, the polyalkyl (meth) acrylate rubber component constituting the above composite rubber may be synthesized by using the following alkyl (meth) acrylate, crosslinking agent (II) and graft crossing agent (II). it can.

As the alkyl (meth) acrylate,
Examples thereof include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, and hexyl methacrylate, 2-ethylhexyl methacrylate, alkyl methacrylates such as n-lauryl methacrylate, and particularly n-butyl. The use of acrylates is preferred.

Examples of the crosslinking agent (II) include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and 1,4-butylene glycol dimethacrylate.

Examples of the graft crossing agent (II) include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate and the like. Allyl methacrylate can also be used as a cross-linking agent. These crosslinking agents and graft crossing agents may be used alone or in combination of two or more. The total amount of the cross-linking agent and the graft crossing agent used is preferably polyalkyl (meth)
It is 0.1 to 20% by weight in the acrylate rubber component.

The polyalkyl (meth) acrylate rubber component is polymerized by adding the above alkyl (meth) acrylate into a latex of the polyorganosiloxane rubber component neutralized by the addition of an aqueous solution of an alkali such as sodium hydroxide, potassium hydroxide or sodium carbonate. ) An acrylate, a crosslinking agent and a graft crossing agent are added and impregnated into the polyorganosiloxane rubber particles, and then a normal radical polymerization initiator is allowed to act. As the polymerization proceeds, a crosslinked network of polyalkyl (meth) acrylate rubber entwined with each other is formed in the crosslinked network of polyorganosiloxane rubber, and it is practically impossible to separate.
A latex of a composite rubber of a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component is obtained. In the practice of the present invention, as the composite rubber, the main skeleton of the polyorganosiloxane rubber component has a repeating unit of dimethylsiloxane, and the main skeleton of the polyalkyl (meth) acrylate rubber component is a repeating unit of n-butyl acrylate. A composite rubber having is preferably used.

The composite rubber thus prepared by emulsion polymerization can be graft-copolymerized with a vinyl monomer. The gel content measured by extracting this composite rubber with toluene at 90 ° C. for 12 hours is preferably 80% by weight or more.

In order to satisfy the balance of flame retardancy, impact resistance, appearance and the like, the ratio of the polyorganosiloxane rubber component to the polyalkyl (meth) acrylate rubber component in the above composite rubber is 3 to The latter is preferably 97 to 10% by weight with respect to 90% by weight, and the average particle diameter of the composite rubber is preferably 0.08 to 0.6 μm.

Vinyl-based monomers to be graft-polymerized on the above composite rubber include styrene, α-methylstyrene,
Aromatic alkenyl compounds such as vinyltoluene; methacrylic acid esters such as methyl methacrylate and 2-ethylhexyl methacrylate; acrylic acid esters such as methyl acrylate, ethyl acrylate and butyl acrylate; vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. Examples thereof include vinyl monomers, which may be used alone or in combination of two or more. A particularly preferred vinyl monomer is methyl methacrylate. The vinyl-based monomer is the above-mentioned composite rubber 30-
It is preferably contained in a proportion of 5 to 70% by weight with respect to 95% by weight.

The composite rubber-based graft copolymer (D) is a composite rubber-based graft copolymer obtained by adding the above-mentioned vinyl-based monomer to the above-mentioned composite rubber latex and polymerizing it in a single stage or multiple stages by a radical polymerization technique. The combined latex can be separated and recovered by introducing it into hot water in which a metal salt such as calcium chloride or magnesium sulfate is dissolved, salting out and coagulating.

Such a composite rubber-based graft copolymer (D) is commercially available, for example, from Mitsubishi Rayon Co., Ltd. as METABLEN S-2001.

Component (D) is a total of 100 of (A) to (C).
The amount is preferably 0.5 to 40 parts by weight, more preferably 0.5 to 30 parts by weight, based on parts by weight. If the amount of (D) is above the above range, the rigidity tends to decrease, and if it is below the above range, the flame retardancy tends to decrease.

The resin composition of the present invention may further contain a component (E) phosphate compound in addition to the above components. Examples of such a phosphoric acid ester compound include the following formula:

[0045]

[Chemical 4] (Here, R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an organic group, and R ¹ = R ² =
Except when R ³ = R ⁴ = H. X'represents a divalent or higher valent organic group, p is 0 or 1, and q is 1 or more, for example, 30.
The following integers and r are integers of 0 or more. ). The compound shown by these is mentioned. However, it is not limited to these.

In the above formula, examples of the organic group include an alkyl group which may be substituted or not, a cycloalkyl group and an aryl group. When substituted, examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, a halogen, an aryl group, an aryloxy group, an arylthio group, a halogenated aryl group, and the like. A combined group (for example, an arylalkoxyalkyl group) or a group obtained by combining these substituents by an oxygen atom, a sulfur atom, a nitrogen atom or the like (for example, an arylsulfonylaryl group) may be used as a substituent. Good. The divalent or higher valent organic group means a divalent or higher valent group formed by removing one or more hydrogen atoms bonded to carbon atoms from the above-mentioned organic group. For example, an alkylene group, and preferably (substituted)
Examples include phenylene groups and polynuclear phenols such as those derived from bisphenols, and the relative positions of two or more free valences are arbitrary. Particularly preferred is
Examples thereof include hydroquinone, resorcinol, diphenylol methane, diphenylol dimethyl methane, dihydroxydiphenyl, p, p'-dihydroxydiphenyl sulfone and dihydroxynaphthalene.

Specific examples of phosphoric acid ester compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyl diphenyl. Phosphate,
Diisopropylphenyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate,
Bis (2,3-dibromopropyl) -2,3-dichloropropylphosphate, tris (2,3-dibromopropyl) phosphate and bis (chloropropyl) monooctylphosphate, R ^{1 to} R ⁴ are alkoxy such as methoxy, ethoxy and Propoxy, or preferably (substituted) phenoxy, such as phenoxy, methyl (substituted) phenoxy, bisphenol A bisphosphate, hydroquinone bisphosphate, resorcin bisphosphate, polyoxyphosphate such as trioxybenzene triphosphate, and the like, preferably triphosphate Phenyl phosphate and various polyphosphates.

The above component (E) is the component (A) to (C).
It is preferable to add 1 to 30 parts by weight to 100 parts by weight in total, and more preferably 3 to 20 parts by weight.

If the amount of component (E) is too small, flame retardancy tends to be insufficient, and if it is too large, heat resistance is impaired.

The resin composition of the present invention may further contain an anti-dripping agent. The fluorinated polyolefin that can be used as such an anti-dripping agent is commercially available or can be produced by a known method. It is, for example, 100 to 10 in aqueous medium using a free radical catalyst (eg sodium, potassium or ammonium peroxydisulfate).
It is a white solid obtained by polymerizing tetrafluoroethylene at a pressure of 00 psi and a temperature of 0 to 200 ° C, preferably 20 to 100 ° C. See Brubaker US Pat. No. 2,393,967 for more information. Although not essential, it is preferred to use a resin in the form of relatively large particles, for example particles having an average particle size of 0.3 to 0.7 mm (mainly 0.5 mm). This is 0.05 ~
Better than regular polytetrafluoroethylene powder with a particle size of 0.5 mm. The reason why such a relatively large particle size material is particularly preferred is that it tends to disperse readily in the polymer and bind the polymers together to form a fibrous material. Such a suitable polytetrafluoroethylene is referred to as Type 3 according to ASTM and is actually commercially available as Teflon 6 from EIDupont de Nemours and Company.
Alternatively, Teflon 30 from Mitsui DuPont Fluorochemicals
Commercially available as J. The fluorinated polyolefin is preferably 0.01 to 100 parts by weight of the component (A).
2 parts by weight, more preferably 0.05 to 1.0 parts by weight is used.

In addition to the above-mentioned components, the resin composition of the present invention may contain other conventional additives such as pigments at the time of resin mixing and molding, depending on the purpose, as long as the physical properties are not impaired. Dyes, reinforcing agents (glass fiber, carbon fiber, etc.),
Add fillers (carbon black, silica, titanium oxide, etc.), heat-resistant agents, antioxidants, weathering agents, lubricants, release agents, crystal nucleating agents, plasticizers, fluidity improvers, antistatic agents, etc. You can

There is no particular limitation on the method for producing the resin composition of the present invention, and ordinary methods can be satisfactorily used. However, melt mixing is generally preferred. The use of small amounts of solvent is possible, but generally not required. Examples of the apparatus include extruders, Banbury mixers, rollers, kneaders, etc., which are operated batchwise or continuously. The order of mixing the components is not particularly limited.

[0053]

In the present invention, PC and aromatic vinyl /
By making the molecular weight of the vinyl cyanide-based resin a combination within a specific range, it was possible to obtain a resin composition having an excellent balance of various properties and capable of being molded into a thin wall. Furthermore, by adding the flame retardant components (D) and (E), a resin composition having excellent flame retardancy can be obtained.

[0054]

The present invention will be described in more detail by the following examples. The following components were used in the examples. Component (A) (PC (3) used in Comparative Example) PC (1): Polycarbonate of bisphenol A (trademark; Lexan, manufactured by Nippon GE Plastics Co., Ltd.), intrinsic viscosity measured at 20 ° C. in methylene chloride. 0.4
6 dl / g, Mv = about 20,000 (calculated value) PC (2): Polycarbonate of bisphenol A (trademark; Lexan, manufactured by Nippon GE Plastics Co., Ltd.), intrinsic viscosity 0.5 measured at 20 ° C. in methylene chloride.
0 dl / g, Mv = approximately 22,000 (calculated value) PC (3): polycarbonate of bisphenol A (trademark; Lexan, manufactured by Nippon GE Plastics Co., Ltd.), intrinsic viscosity 0.4 measured at 20 ° C. in methylene chloride
2 dl / g, Mv = about 18,000 (calculated value) Component (B) (SAN (1) was used in Comparative Example) SAN (1): SAN resin, trademark SR 30B (manufactured by Ube Saikon Corporation), Mw = 117,000 , SAN (2): SAN resin, trademark SR 05B (manufactured by Ube Saikon Corporation), Mw = 63,000 component (C) ABS: ABS resin, trademark UX 050 (manufactured by Ube Saikon Corporation) ingredient (D) Metabrene S-2001 : Trademark, methylmethacrylate-butylacrylate-dimethylsiloxane copolymer, component (E) CR733S manufactured by Mitsubishi Rayon Co., Ltd .: Trademark, phenylresorcin polyphosphate,
Optional component Teflon 30J manufactured by Daihachi Chemical Co., Ltd .: Trademark, polytetrafluoroethylene, manufactured by Mitsui DuPont Fluorochemical Co., Ltd. Examples 1 to 5 and Comparative Examples 1 to 4 , 240 ℃,
It was extruded with a twin-screw extruder (30 mm) set at 150 rpm to prepare pellets. Then, this pellet is set to a set temperature of 25
Injection molding was performed at 0 ° C and a mold temperature of 60 ° C. Izod impact strength and melt viscosity (MV, Melt
Viscosity) was measured and tested for chemical resistance. Moreover, about Examples 3-5 and Comparative Examples 3-4, flame retardancy was also evaluated. The results are shown in Table 1.

The evaluation test of the resin composition was conducted as follows. (1) Izod impact strength (Kg-cm / cm) Measured according to ASTM D 256 with a thickness of 1/8 inch and a notch. (2) Melt viscosity (MV) Using a capillary rheometer, temperature 260 ℃, shear rate
The viscosity at 1500 sec- ¹ was measured. (3) Flame retardance test UL94 / V0, VI, VII test Five test rods are shown in Bretin 94 "Combustion test for material classification" (hereinafter referred to as UL-94) of Underwriters Laboratories Corporation. The test was performed at a thickness of 1/16 inch according to the test method. According to this test method, the test material was evaluated to any of UL-94 V-0, VI and V-II based on the results of five samples. The criteria for each V rating for UL-94 are as follows. V-0: Average flame holding time after removing the ignition flame is 5
It is less than a second, and all the samples do not fall the fine flame igniting the absorbent cotton. VI: Average flame holding time after removing the ignition flame is 25
It is less than a second, and all the samples do not fall the fine flame igniting the absorbent cotton. V-II: Average flame holding time after removing the ignition flame
It is less than 25 seconds, and these samples fall into a fine flame igniting absorbent cotton.

UL-94 also stipulates that all test rods must be classified in a particular V grade if they do not pass the grade. If this condition is not met, the 5 test rods will be given the grade of the worst performing 1 test rod. For example, if one test rod is classified as V-II, the rating for all five test rods is V-II. UL94 / 5V (5VB) test (5 inch Framtes
The preparative) A method (bar test), by applying five times the test piece to the burner, the presence or absence of (1) burn time and glowing time, (2) burning distance of the specimen, (3) drips (drip) , (4) Deformation and physical strength were observed. The thickness of the test piece was 2.5 mm. 5VB acceptance criterion: No burning time and / or growing time after applying a test flame 5 times to any test piece exceeds 60 seconds. And none of the test pieces were dripping. (4) Chemical resistance A molded product with a thickness of 1/8 inch is fixed to a special jig, applied with a strain of 1%, coated with liquid (phenylresorcin polyphosphate) on the surface, and left for 48 hours. The condition was observed. The number of cracks or phrases (small cracks) in the 5 samples was represented.

[0057]

[Table 1]

[0058]

EFFECTS OF THE INVENTION The resin composition of the present invention is excellent in various properties such as fluidity, chemical resistance, heat resistance and impact resistance in a well-balanced manner, and is capable of thin-wall molding. Further, by adding a flame retardant, a resin composition having excellent flame retardancy can be obtained. Therefore, it can greatly contribute to downsizing and weight saving of various devices, and is useful for housings and cabinets of small and lightweight devices such as notebook type and laptop type.

Claims (7)

[Claims] 1. A composition comprising (A) 90 to 10 parts by weight of a polycarbonate resin having a viscosity average molecular weight of 20,000 or more, (B) an aromatic vinyl monomer component and (b) a vinyl cyanide monomer component, A copolymer containing 1 to 50 parts by weight of a copolymer having a weight average molecular weight of 30,000 to 110,000, and (C) (a) an aromatic vinyl monomer component, (b) Copolymers 1 to 50 containing vinyl cyanide monomer component and (c) rubbery polymer as constituents of the copolymer
A resin composition containing parts by weight. 2. The resin composition according to claim 1, wherein the polycarbonate resin (A) has a viscosity average molecular weight of 21,000 or more. 3. The weight average molecular weight of the copolymer (B) is 40,000.
The resin composition according to claim 1 or 2, which has -80,000. 4. The resin composition according to claim 1, wherein the (B) copolymer is a SAN resin. 5. The (C) copolymer is an ABS resin or AES.
The resin composition according to any one of claims 1 to 4, which is selected from a resin, an ACS resin, and an AAS resin. 6. A total of the components (A) to (C)
0.5 to 40 parts by weight of a composite rubber-based graft copolymer obtained by grafting a vinyl-based monomer onto a composite rubber containing (D) polyorganosiloxane and polyalkyl (meth) acrylate, relative to 100 parts by weight. Item 6. The resin composition according to any one of items 1 to 5. 7. The total of the components (A) to (C)
100 parts by weight of (E) phosphate compound 1
The resin composition according to any one of claims 1 to 6, which comprises -30 parts by weight.