KR100373384B1 - Polycarbonate Resin Composition - Google Patents

Abstract

Resin composition containing following (A)-(C):

(A) 90 to 10 parts by weight of a polycarbonate (PC) having a viscosity average molecular weight of 20,000 or more,

(B) 1 to 50 parts by weight of an aromatic vinyl / vinyl cyanide copolymer having a weight average molecular weight of 30,000 to 110,000, and

(C) 1 to 50 parts by weight of aromatic vinyl / vinyl cyanide / rubber polymer type copolymer.

The main object of the present invention is to provide a polycarbonate (PC) resin composition which can be molded thin while maintaining characteristics such as fluidity, chemical resistance, heat resistance and impact resistance.

Description

Polycarbonate resin composition

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

Polycarbonate (PC) resins and polymer mixtures blended with such resins and ABS (acrylonitrile-butadiene-styrene) resins are widely used in electrical and electronic devices, office automation equipment, and the like. In recent years, the demand for smaller and lighter weight is becoming stronger and there is a need for thinner walls and cabinets. To meet this need, novel molding methods have been tried and improvements have been made in terms of materials. For example, in order to obtain thinner walls, low molecular weight polycarbonate was used, and an attempt was made to increase the fluidity by increasing the mixing ratio of the ABS resin and the SAN resin (JP-A-83-46269). .

However, for example, if the molecular weight of the PC in the PC / ABS polymer mixture is reduced, defects such as product defects occur, including the tendency of edge cracks to progress during the molding process of products such as office automation equipment. In contrast, an increase in the blending ratio of the ABS resin and the SAN resin results in a drawback of decreasing heat resistance and strength. For this reason, it is an object of the present invention to provide a polycarbonate resin composition which allows thin-wall molding to be carried out while maintaining characteristics such as fluidity, chemical resistance, heat resistance and impact resistance. The present invention also has an object of providing excellent flame retardancy to polycarbonate resin compositions.

The inventors of the present invention conducted a thorough study of the polycarbonate resin composition, and as a result, by setting the molecular weight of the polycarbonate resin forming the matrix to a certain amount or more, by limiting the molecular weight of the aromatic vinyl / vinyl cyanide resin forming a dispersed phase It has been found that it is possible to obtain a resin composition having advantageous chemical resistance and various other properties, in particular fluidity, to achieve the object of the present invention.

In particular, the present invention

(A) 90 to 10 parts by weight of a polycarbonate resin having a viscosity average molecular weight of 20,000 or more,

(B) 1 to 50 parts by weight of a copolymer containing (a) an aromatic vinyl monomer component and (b) a vinyl cyanide monomer as a copolymer component, and having a weight average molecular weight of 30,000 to 110,000, and

(C) 1 to 50 parts by weight of a copolymer containing (a) an aromatic vinyl monomer component, (b) a vinyl cyanide monomer component, and (c) a rubber polymer as a copolymer component

It provides a resin composition containing.

The polycarbonate resins used in the present invention are aromatic polycarbonates produced by well-known phosgene methods or melting methods (see, for example, Japanese Patent Application Laid-Open No. 88-215763 and Japanese Patent Application Laid-open No. 90-124934). Reference). Examples of diphenyls used as raw materials include 2,2-bis (4-hydroxyphenyl) propane (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, 1,1-bis (4-hydroxyphenyl) decane, 1,4-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclodode CAN, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclododecane, 4,4-dihydroxydiphenyl ether, 4,4-thiodiphenol, 4,4-dihydroxy -3,3-dichloro diphenyl ether, and 4,4-dihydroxy-2,5-dihydroxydiphenyl ether. In addition, examples of precursors used to introduce carbonates include phosgene and diphenyl carbonate.

In the present invention, the polycarbonate resin should have a viscosity average molecular weight (Mv) of 20,000 or more, preferably 21,000 or more, particularly preferably 22,000 or more. If the molecular weight is too small, the chemical resistance is poor. There is no particular limitation on the upper limit of the viscosity average molecular weight, but for practical purposes the molecular weight should be 40,000 or less. In the present invention, the viscosity average molecular weight was measured by using the following Mark-Houwink viscosity formula (1) after measuring the intrinsic viscosity (limiting viscosity) in methylene chloride at 20 ° C:

Where

η is the limiting viscosity,

K and a are constants (K is 1.23 × 10 ⁻⁴ , a is 0.83),

M is the molecular weight.

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

Examples of the aromatic vinyl monomer component (a) include styrene, α-methylstyrene, o-, m- or p-methylstyrene, vinyl xylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluoro Styrene, p-tert-butyl styrene, ethyl styrene, and vinylnaphthalene, and these materials may be used alone or in combination of two or more. Preferred materials are styrene and α-methylstyrene.

Examples of vinyl cyanide monomer component (b) include acrylonitrile and methacrylonitrile, and these materials may be used alone or in combination of two or more. There is no particular restriction on the compositional ratio of these substances, and they should be selected according to the use.

There is no particular restriction on the composition ratio of (a) / (b), and the preferred amounts in component (B) are (a) 95 to 50% by weight and (b) 5 to 50% by weight, particularly preferably (a) 92 to 65 weight percent and (b) 8 to 35 weight percent.

SAN resin (styrene-acrylonitrile copolymer) may be mentioned as a preferred example of the copolymer component (B).

There is no particular restriction on the method for producing the copolymer component (B), and conventional methods such as block polymerization, melt polymerization, block suspension polymerization, suspension polymerization and emulsion polymerization can be used. In addition, the copolymer may be obtained by separately blending the copolymer resin.

In the present invention, the weight average molecular weight (Mw) of the copolymer component (B) should be 30,000 to 110,000, preferably 40,000 to 80,000. If the molecular weight of the copolymer component (B) is less than the above-mentioned range, the physical properties are reduced, and if it exceeds the above-mentioned range, the fluidity is impaired.

(C) is a copolymer containing (a) an aromatic vinyl monomer component, (b) vinyl cyanide monomer component, and (c) a rubber polymer. Examples of aromatic vinyl monomer component (a) and vinyl cyanide monomer component (b) are as given in the description of component (B) above. Examples of the rubber polymer (c) include random copolymers and block copolymers of polybutadiene, polyisoprene and styrene-butadiene, hydrides of the block copolymers, diene rubbers such as acrylonitrile-butadiene copolymers and Butadiene-isoprene copolymers), ethylene-propylene random copolymers and block copolymers, ethylene-butene random copolymers and block copolymers, copolymers of ethylene and α-olefins, copolymers of ethylene-unsaturated carboxylic acid esters (e.g. ethylene Methacrylate and ethylene-butylacrylate), acrylic ester-butadiene copolymers (e.g. acrylic flexible polymers such as butylacrylate-butadiene copolymers), copolymers of ethylene and fatty acid vinyls (e.g. ethylene-vinyl acetate ), Ethylene-propylene nonconjugated diene terpolymers (e.g. ethylene-propylene-ethylidene norbornene copolymer Ethylene-propylene-hexadiene copolymer), butylene-isoprene and the copolymers, and chlorinated polyethylene, and these substances may be used alone or in combination of two or more. Examples of preferred rubber polymers include ethylene-propylene rubber, ethylene-propylene nonconjugated diene terpolymers, diene rubbers and acrylic flexible polymers, with polybutadiene and styrene-butadiene copolymers being particularly preferred, the styrene-butadiene The styrene content of the copolymer should preferably be 50% by weight or less.

There is no particular restriction on the composition ratio of components (a), (b) and (c) in component (C), and various components are blended according to the use.

In component (C), in addition to the above-mentioned components (a), (b) and (c), monomers (d) which can be copolymerized with the above components may be used in an amount which does not adversely affect the object of the present invention. have. Examples of such copolymerizable monomers include α, β-unsaturated carboxylic acids (eg acrylic acid and methacrylic acid), α, β-unsaturated carboxylic acid esters (eg methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) ) Acrylates, butyl (meth) acrylates, 2-ethyl (meth) acrylates and 2-ethylhexyl methacrylates), α, β-unsaturated dicarboxylic anhydrides such as maleic anhydride and itaconic anhydride, and imide compounds of α, β-unsaturated dicarboxylic acids (eg maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide and No-chlorophenylmaleimide), these monomers alone Or a combination of two or more thereof.

The copolymer of component (C) should preferably be a graft copolymer prepared by graft copolymerizing other components in the presence of rubber polymer (c), and the preferred resin is ABS resin (acrylonitrile-butadiene). -Styrene copolymer), AES resin (acrylonitrile-ethylene-propylene-styrene copolymer), ACS resin (acrylonitrile-chlorinated polyethylene-styrene copolymer) and AAS resin (acrylonitrile-acrylic flexible polymer-styrene Copolymer).

The copolymer component (C) can be prepared using the same method as described for the copolymer (B).

The aforementioned components (A), (B) and (C) are blended in the following proportions. Specifically, these are (A) 90-10 weight part, (B) 1-50 weight part, and (C) 1-50 weight part with respect to a total of 100 weight part of (A)-(C), Preferably ( A) 85-20 weight part, (B) 1-40 weight part, and (C) 1-30 weight part. If the amount of (A) exceeds the above-mentioned range, the fluidity decreases, and if it is below the above-mentioned range, the heat resistance decreases. If the amount of (B) exceeds the above-mentioned range, the strength decreases, and if it is below the above-mentioned range, it has a detrimental effect on fluidity. If the amount of (C) exceeds the above-mentioned range, the rigidity will decrease, and if it is below the above-mentioned range, flame retardancy will decrease.

In addition to the components mentioned above, a composite rubber graft copolymer (D) prepared by grafting a vinyl monomer on a composite rubber containing polyorganosiloxane and polyalkyl (meth) acrylate is blended into the resin composition of the present invention. To improve flame retardancy. Component (D) is a composite rubber graft prepared by graft polymerizing one or more vinyl monomers onto a composite rubber having a composite single structure in which a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component are internally bonded to each other. Copolymers.

For example, the composite rubber graft copolymer can be prepared by the same method as described in the specification of Japanese Patent Application Laid-open No. 89-79257.

It is suitable to manufacture the composite rubber by emulsion polymerization method. Preferably, first, a latex is prepared from polyorganosiloxane rubber, and then the rubber particles of the polyorganosiloxane rubber latex are incorporated by using a monomer for synthesizing the alkyl (meth) acrylate rubber. The monomers for synthesis must be polymerized.

For example, the polyorganosiloxane rubber component can be prepared by emulsion polymerization using the organosiloxane and the crosslinking agent (I) described below, wherein the graft crosslinking agent (I) can be used together.

Examples of such organosiloxanes are chain organosiloxanes such as dimethylsiloxane. In addition, various cyclic organosiloxanes having three or more members, preferably 3 to 6 members, can also be used. Examples are hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylchlorohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane and octaphenylcyclotetrasiloxane. . The organosiloxanes may be used alone or in a mixture of two or more. Their amount should preferably be at least 50% by weight, particularly preferably at least 70% by weight, of the polygatosiloxane rubber component.

Trifunctional or tetrafunctional silane crosslinkers can be used as crosslinkers (I), examples of which are trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxy Silane and tetrabutoxysilane. Tetrafunctional crosslinkers are preferred, with tetraethoxysilane being particularly preferred. These crosslinkers can be used alone or in combination of two or more. The amount of crosslinker used should preferably be from 0.1 to 30% by weight of the polyorganosiloxane rubber component.

The graft crosslinker (I) must be a compound capable of forming the units represented by the formula (I-1, I-2 or I-3):

In the above formulas,

R ¹ is a lower alkyl group such as a methyl group, an ethyl group or a propyl group or a wasteyl group,

R ² is a hydrogen atom or a methyl group,

n is 0, 1 or 2,

p is an integer of 1-6.

Since the (meth) acryloyloxysiloxane capable of forming units of formula (I-1) has a high graft efficiency, it provides an advantage of forming an effective graft chain and exhibiting high impact resistance. In addition, methacryloyloxysiloxane is particularly preferred as a substance capable of forming units of formula (I-1). Examples of methacryloyloxysiloxanes include β-methacryloyloxyethyldimethoxymethylsilane, τ-methacryloyloxypropylmethoxydimethylsilane, τ-methacryloyloxypropyldimethoxymethylsilane, τ -Methacryloyloxypropyltrimethoxysilane, τ-methacryloyloxypropylethoxydiethylsilane, τ-methacryloyloxypropyldiethoxymethylsilane, and delta-methacryloyloxybutyldiethoxy Methylsilane. These materials may be used alone or in combination of two or more, and the amount of crosslinking agent should preferably be 0 to 10% by weight of the polyorganosiloxane rubber component.

Examples of methods that can be used to prepare the latex of the polyorganosiloxane rubber component include those described in the specifications of US Pat. Nos. 2891920 and 3294725. In actual practice of the present invention, organosiloxanes and crosslinkers (e.g., by shear mixing with water, preferably using group nitriles or the like, in the presence of sulfonic acid emulsifiers such as alkylbenzene sulfonic acids or alkylsulfonic acids) 1-1) and, if necessary, a mixed solution of graft crosslinking agent (I-1). Alkylbenzenesulfonic acid is ideal, which acts as an polymerization initiator and simultaneously as an organosiloxane emulsifier. At this time, it is preferable to use together with the metal salt of alkylbenzene sulfonic acid, the metal salt of alkyl sulfonic acid, etc., because it has the effect of maintaining the stability of the polymer during the graft polymerization.

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

Examples of alkyl (meth) acrylates include alkyl acrylates (e.g. methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate) and alkyl methacrylates (e.g. Hexyl methacrylate, 2-ethylhexyl methacrylate and n-lauryl methacrylate), and it is preferable to use n-butyl acrylate.

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

Examples of graft crosslinkers (II) include arylmethacrylates, triarylcyanurates and triarylisocyanurates. Aryl methacrylate can also be used as a crosslinking agent. The crosslinking agent and the graft crosslinking agent may be used alone or in combination of two or more. The total amount of the crosslinker and graft crosslinker should preferably be from 0.1 to 20% by weight of the polyalkyl (meth) acrylate rubber component.

The polymerization of the polyalkyl (meth) acrylate rubber component is the aforementioned alkyl (meth) acrylate and crosslinking to the latex of the polyorganosiloxane rubber component neutralized by addition of an aqueous alkali solution (e.g., sodium hydroxide, potassium hydroxide or sodium carbonate). The binder and the graft crosslinking agent are added and the polyorganosiloxane rubber particles are incorporated, followed by the use of a conventional radical polymerization initiator. As the polymerization proceeds, polyorganosiloxane rubber crosslinks and polyalkyl (meth) acrylate rubber crosslinks internally bonded to each other are formed, thereby inherently inseparable polyorganosiloxane rubber components and polyalkyl (meth) acrylate rubber components. A synthetic rubber latex containing is obtained. In addition, in the actual practice of the present invention, the composite rubber preferably has a main chain of the polyorganosiloxane rubber component having a dimethylsiloxane repeating unit and a main chain of the polyalkyl (meth) acrylate rubber component having an n-butylacrylate repeating unit. Should be used.

Composite rubbers prepared in this manner by emulsion polymerization can be graft copolymerized with vinyl monomers. The gel content of the composite rubber, extracted and measured at 90 ° C. for 12 hours using triene, should preferably be at least 80% by weight.

In addition, in order to satisfy the condition that flame retardancy, impact resistance, appearance, etc. should be grouped, the ratio of the polyorganosiloxane rubber component and the polyalkyl (meth) acrylate rubber component in the above-described composite rubber is polyorganosiloxane rubber component 3 It should be 97 to 10% by weight of polyalkyl (meth) acrylate with respect to 90% by weight, and the average particle diameter of the composite rubber should preferably be 0.08 to 0.6 mu m.

Examples of vinyl monomers graft-polymerized into the above-mentioned composite rubber phase include various vinyl monomers such as aromatic alkenyl compounds such as styrene, α-methylstyrene and vinyl triene, methacrylic acid esters such as methyl methacryl Acrylate and 2-ethylhexyl methacrylate), acrylic esters such as methyl acrylate, ethyl acrylate and butyl acrylate, and vinyl cyanide compounds such as acrylonitrile and methacrylonitrile. May be used alone or in combination of two or more. Methyl methacrylate is particularly preferred as the vinyl monomer. The vinyl monomer should preferably be contained in an amount of 5 to 70% by weight relative to 30 to 95% by weight of the above-mentioned composite rubber.

The composite rubber graft copolymer (D) is obtained by adding the above-described vinyl monomer to the above-mentioned composite rubber latex, and hot water (calcium chloride) of the composite rubber graft copolymer latex obtained by single or multi-stage copolymerization through a radical polymerization technique. Or a metal salt such as magnesium sulfate is dissolved) and then isolated and recovered by salting out and solidifying.

For example, a composite rubber graft copolymer (D) of this type is commercially available from Mitsubishi Rayon Co., Ltd. in the form of Methaprene S-2001. You can buy it at

Component (D) should be mixed in an amount of 0.5 to 40 parts by weight, more preferably 0.5 to 30 parts by weight, based on 100 parts by weight of (A) to (C) total. If the amount of (D) exceeds the above-mentioned range, the stiffness decreases, and if it is below the above-mentioned range, the flame retardancy tends to decrease.

The resin composition of the present invention may further contain a phosphate ester component (E) in addition to the above-mentioned components. Examples of the phosphate ester component are compounds represented by the following general formula (4).

Where

R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or an organic group except when H is

X 'is a divalent or higher organic group,

p is 0 or 1,

q is an integer of 1 or more (e.g. 30 or less),

r is an integer of 0 or more.

However, there is no particular limitation on the material.

Wherein the organic group may be a substituted or unsubstituted alkyl group, a cycloalkyl group, an aryl group, or the like. Further, if the group is 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 or a halogenated aryl group, or a group consisting of a combination of the above substituents (e.g., aryl Alkoxyalkyl groups), or combination groups (e.g., arylsulphylaryl groups) prepared by combining the substituents with an oxygen atom, a sulfur atom or a nitrogen atom. In addition, a divalent or more organic group represents the divalent or more group obtained by removing 1 or more hydrogen atoms couple | bonded with the carbon atom from the above-mentioned organic group. Examples are alkylene groups, or preferably (substituted) phenylene groups, and materials derived from bisphenols (eg multinuclear phenols) having two or more free valences in any relative structure. Examples of particularly preferred materials are hydroquinone, resorcinol, diphenylol methane, diphenylol dimethylmethane, dihydroxy diphenyl, p, p'-dihydroxydiphenyl sulfone and dihydroxy naphthalene.

Examples of specific phosphate ester compounds include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl phenyl phosphate, octyl diphenyl phosphate, and diisopropyl. Phenylphosphate, 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, bisphenol A bisphosphate [R ¹ to R ⁴ is alkoxy (e.g. methoxy, ethoxy or propoxy), or preferably (substituted) phenoxy (Eg, phenoxy or methyl (substituted) phenoxy)], and polyphosphates (eg, hydroquinone bisphosphates, res) Zorcinol bisphosphate, trioxybenzene triphosphate), triphenylphosphate and various polyphosphates are preferred.

Component (E) should be added in an amount of 1 to 30 parts by weight, preferably 3 to 20 parts by weight, based on 100 parts by weight of (A) to (C) total.

If the amount of component (E) is too small, the flame retardancy tends to be insufficient, and too much has a detrimental effect on heat resistance.

In addition, the resin composition of the present invention may also contain a drip prevention agent. Fluorinated polyolefins that can be used as the anti-dropping agent can be purchased commercially or prepared by well known methods. For example, the antidropping agent is a free radical catalyst (e.g. sodium peroxydisulfate, potassium peroxydisulfate or aluminum peroxydi) in an aqueous medium at a pressure of 100 to 1,000 psi, 0 to 200 ° C, preferably 20 to 100 ° C. Sulfate), to give a white solid obtained by polymerizing tetrafluoroethylene. See US Pat. No. 2,393,967 to Brubaker, which is incorporated herein by reference, for details. Although not necessary, it is preferable to use a resin in the form of relatively large particles (eg, particles having an average diameter of 0.3 to 0.7 mm (mainly 0.5 mm)). This is more advantageous than polytetrafluoroolefin powder having a particle diameter of 0.05 to 0.55 mm, which is commonly used. Materials with relatively large particle diameters are preferred because they can be easily dispersed in the polymer and tend to bond the polymers to form a fibrous material. This kind of optimal polytetrafluoroolefin is called the third type by ASTM, which is actually E. coli. children. Commercially available in the form of Teflon 6 from E. I. Dupont de Nemours and Company. Alternatively, it is commercially available in the form of Teflon 30J from Mitsui Dupont Fluorochemical Co. The fluorinated polyolefin should be used in an amount of 0.01 to 2 parts by weight, preferably 0.05 to 1.0 parts by weight, based on 100 parts by weight of component (A).

In addition to the aforementioned components of the resin composition of the present invention, additives may also be added upon mixing or molding, depending on the use, provided these additives do not impair the physical properties of the present invention, examples being pigments, dyes, reinforcing agents. (Glass fibers, carbon fibers, etc.), fillers (carbon black, silica, titanium oxide, etc.), heat resistant agents, antioxidants, weathering agents, lubricants, mold release agents, crystal nucleating agents, plasticizers, fluidity improving agents, antistatic agents and the like.

There is no particular limitation on the method used to prepare the resin composition of the present invention, and any conventional method can be satisfactorily used. However, melt mixing methods are generally preferred. It is also possible to use small amounts of solvent, but this is generally not necessary. Examples of equipment used are extruders, Banbury mixers, rollers and kneaders, which can be operated in batch or continuous processes. There is no particular limitation on the order of mixing of the components.

In the present invention, by mixing PC and aromatic vinyl / vinyl cyanide resin in a specific molecular weight range, it is possible to obtain a resin composition suitable for thin molding, in which various properties are well balanced. Moreover, it is possible to obtain the resin composition which shows the outstanding flammability by adding flame retardant component (D) and (E).

Example

The following describes the present invention in detail by way of examples. The following ingredients were used in the examples.

Component (A) (PC (3) was used in the comparative example)

PC (1): Bisphenol A polycarbonate (trade name: LEXAN), Nihon Paper. this. Plastic case. Nihon G. E. Plastics K. K., intrinsic viscosity 0.46 dl / g (measured in methylene chloride at 20 ° C), Mv approximately 20,000 (calculated).

PC (2): Bisphenol A polycarbonate (trade name Lexan), Nihon Paper. this. Plastic case. K. Preparation, intrinsic viscosity 0.50 dl / g (20 degreeC, measured in methylene chloride), Mv about 22,000 (calculated value).

PC (3): Bisphenol A polycarbonate (trade name: Lexan), Nihon Paper. this. Plastic case. K. Preparation, intrinsic viscosity 0.42 dl / g (20 DEG C, measured in methylene chloride), Mv about 18,000 (calculated).

Component (B) (SAN (1) was used in the comparative example)

SAN (1): SAN resin, brand name: SR 30B [Ube Psycon K. Manufactured by Ube Cycon K. K.], MW 117,000.

SAN (2): SAN resin, trade name: SR 05B (manufactured by Ube Psycon K. K.), Mw 63,000.

Ingredient (C)

ABS ABS resin, brand name: UX 050 (manufactured by Ube Psycon K. K.)

Ingredient (D)

Trade name: Metaprene LS-2001 (Methyl methacrylate-butylacrylate-dimethylsiloxane copolymer, Mitsubishi Rayon Company, Limited)

Ingredient (E)

Brand Name: CR 733S. Phenylresorcin polyphosphate [Oya, inaccurate range] Kagaku k. K. Produce]

Arbitrary ingredients

Trade name: Teflon 30J (manufactured by Polytetrafluoroethylene, Mitsui Dupont Fluorochemical Company)

Examples 1-5 and Comparative Examples 1-4

Various components were mixed at the ratios (weight ratios) shown in Table 1 and extruded with a twin screw extruder (30 mm) set at 240 ° C. and 150 rpm to produce pellets. The pellet was then injection molded at a set temperature of 250 ° C. and a metal forming temperature of 60 ° C. The molded article obtained was tested for Izod impact strength and melt viscosity (Mv) and also for chemical resistance. In addition, flame retardance was also evaluated in Examples 3 to 5 and Comparative Examples 3 to 4. The results are shown in Table 1.

Evaluation test of the resin composition was carried out as follows.

(1) Izod impact strength (Kg-cm / cm)

A 1/8 inch thick, notched test piece was measured according to ASTM D 256.

(2) melt viscosity (Mv)

The viscosity was measured at a shear rate of 260 ° C., 1500 sec ⁻¹ using a capillary rheometer.

(3) flame retardancy test

UL 94 / V0, VI, VII tests

Five test strips 1/16 inch thick according to the test method presented in Underwriters Laboratories Corporation's report 94 ["Combustion Tests for Materials Classification"] (referred to below as UL-94). Tested against. Using this test method, the sample material was classified into grades of UL-94 V-0, V-I and V-II based on the results for five samples. The criteria for the various V grades of UL-94 are summarized briefly below.

V-0: The average flame holding time after removing the ignition flame is 5 seconds or less, and the fine flame which can ignite the absorbent cotton does not fall from all samples.

V-I: The average flame holding time after removing the ignition flame is 25 seconds or less, and the fine flame which can ignite the absorbent cotton does not fall from all samples.

V-II: The average flame holding time after removing the ignition flame is 5 seconds or less, and the fine flame which can ignite the absorbent cotton falls from the sample.

In addition, UL-94 states that unless all test rods meet the requirements for a particular group V, they cannot be assigned to that group. If the above requirements are not met, five test bars are assigned to the group of test bars with the worst results. For example, if one test bar is classified as V-II, the group of all five test bars is V-II.

UL94 / 5V (5VB) Test (5-Inch Flame Test)

According to Method A (rod test), the test piece was brought into contact with the burner five times and the following items were observed: (1) burn time and glow time, (2) length of the burning part of the test piece, (3) drip the presence of drips, and (4) strain and physical strength. In addition, the thickness of the test piece was 2.5 mm. The evaluation criteria for passing 5 VB are as follows: after 5 application of the test flame, no test pieces burn time or burning time exceed 60 seconds. Also, none of the specimens showed a drop.

(4) chemical resistance

The 1/8 inch thick molded article is fixed using a dedicated jig, a strain of 1% is applied, the liquid is applied to the surface (phenylresorcinol polyphosphate), and the specimen is left for 48 hours. The surface state was observed. The number of cracks or frays in five samples is shown (see Table 1).

The resin composition of the present invention has a good balance of fluidity, chemical resistance, heat resistance and impact resistance, and can also be thin molded. Moreover, it is also possible to obtain the resin composition which shows the outstanding flame retardance by adding a flame retardant. Therefore, the resin composition of the present invention can greatly contribute to miniaturization and weight reduction of various machinery, and can be used for applications such as exterior materials and cabinets for small and light weight devices (for example, notebook computers and laptop computers).

Table 1

Claims (7)

(A) 90 to 10 parts by weight of a polycarbonate resin having a viscosity average molecular weight of 20,000 or more, (B) 1 to 50 parts by weight of a copolymer containing (a) an aromatic vinyl monomer component and (b) a vinyl cyanide monomer component as a copolymer component, and having a weight average molecular weight of 30,000 to 110,000, and (C) a copolymer containing (a) an aromatic vinyl monomer component, (b) a vinyl cyanide monomer component, and (c) a rubber polymer as a copolymer component 1 to 50 parts by weight of coalescing Resin composition containing. The method of claim 1, The polycarbonate resin (A) has a viscosity average molecular weight of 21,000 or more Resin composition. The method of claim 1, The copolymer (B) has a weight average molecular weight of 40,000 to 80,000 Resin composition. The method of claim 3, wherein The copolymer (B) is a SAN resin (styrene-acrylonitrile copolymer) Resin composition. The method of claim 4, wherein The copolymer (C) is an ABS resin (acrylonitrile-butadiene-styrene copolymer), AES resin (acrylonitrile-ethylene-propylene-styrene copolymer), ACS resin (acrylonitrile-chlorinated polyethylene-styrene copolymer) ) And AAS resin (acrylonitrile-acrylic flexible polymer-styrene copolymer) Resin composition. The method of claim 5, 0.5 to 40 parts by weight of the composite rubber graft copolymer (D), based on 100 parts by weight of the total of the aforementioned components (A) to (C), contains a polyorganosiloxane and a polyalkyl (meth) acrylate. Produced by grafting a vinyl monomer onto a composite rubber Resin composition. The method of claim 6, Further comprising 1 to 30 parts by weight of the phosphate ester compound (E) based on 100 parts by weight of the aforementioned components (A) to (C) in total. Resin composition.