JP3307591B2 - Polycarbonate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin composition containing a polycarbonate resin, and more particularly to a polycarbonate resin composition having excellent moisture resistance and little decrease in tensile properties.

[0002] Polycarbonate resin (PC) and A
Polymer alloys blended with BS (acrylonitrile-butadiene-styrene) resin are used in electrical and electronic products, O
Widely used for A equipment. In recent years, in these applications, demands for miniaturization and weight reduction of products have been increasing, and new molding methods have been tried, and thin resin molding performance, precision molding performance, high flame retardancy, and the like have been required for resins used. . In such applications, production and use in Southeast Asia has increased rapidly in recent years. They are used in high humidity environments, including Southeast Asia, and are used to store products, and there are many cases where deterioration of physical properties due to low moisture resistance of resin is feared.

[0003] Generally, polycarbonate resin (PC)
The moisture resistance of a polymer alloy blended with an ABS resin is not high. In particular, no flame-retardant resin composition has been obtained that maintains a high level of moisture resistance.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a resin composition which is improved in the moisture resistance of a polymer alloy blended with a polycarbonate resin (PC) or an ABS resin as compared with the prior art, and further has flame retardancy. Is to do.

[0005]

As a result of intensive studies on the polycarbonate resin composition to solve the above-mentioned problems,
The present inventors have found that the moisture resistance is improved by using an ABS copolymer having a low alkali metal content in a polycarbonate resin composition and further adding an epoxy stabilizer. As for the flame-retardant resin composition, a flame-retardant resin composition having particularly high moisture resistance can be obtained as compared with the conventional resin composition by using a phosphoric acid ester having a low acid value as a flame retardant to be used. Was found.

That is, an object of the present invention is to provide (A) 1 to 99 parts by weight of a polycarbonate resin having a viscosity average molecular weight of 10,000 to 100,000, and (B) (B-1) (a) aroma. Group vinyl monomer component,
(B) a copolymer containing each of a vinyl cyanide monomer component and (c) a rubbery polymer as a component of copolymerization, and / or (B-2) (a) an aromatic vinyl monomer (B) a vinyl cyanide monomer component as a component of the copolymer, wherein the copolymer (B)
-2) the weight average molecular weight of 30,000 to 200,0
A copolymer having an alkali metal content of 1 ppm or less from 99 parts by weight to 1 part by weight,
And (C) 1 to 40 parts by weight of a phosphoric ester compound having an acid value of 1 or less based on 100 parts by weight of the total of the component (A) and the component (B). The problem is solved by the polycarbonate resin composition described above.

[0007] Further, in this resin composition, 0 to 3 parts by weight of the epoxy stabilizer (E) is added to 100 parts by weight of the total of the component (A) and the component (B). (F) 0.01% of polytetrafluoroethylene per 100 parts by weight of the total of A) and component (B)
By blending from 3 parts by weight to 3 parts by weight, the present invention provides a polycarbonate-based resin composition having further excellent moisture resistance.

Hereinafter, each composition constituting the resin composition of the present invention will be described. The polycarbonate resin used in the present invention is an aromatic polycarbonate prepared by a known phosgene method or a melt method (for example, JP-A-63-215763 and JP-A-Hei. 2-1
24934). Examples of the diphenol used as a raw material include 2,2-bis (4-hydroxyphenyl) propane (so-called bisphenol A);
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 (3,5-dimethyl-4-hydroxyphenyl) cyclohexane; 1,1-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-
4,4-thiodiphenol; 4,4-dihydroxy-3,3-dichlorodiphenyl ether; and 4,4-dihydroxy-2,5-dihydroxydiphenyl ether;
Dihydroxydiphenyl ether and the like. Further, as a precursor for introducing a carbonate,
For example, phosgene, diphenyl carbonate and the like can be mentioned.

In the present invention, the polycarbonate resin has a viscosity average molecular weight (Mv) of 10,000 or more,
Preferably 21,000 or more, more preferably 22,000
000 or more. The upper limit of the viscosity average molecular weight is 100,
000 or less, and practically 40,000 or less. In the present invention, the viscosity average molecular weight is 20 ° C. in methylene chloride.
Measure the intrinsic viscosity (intrinsic viscosity) with the mark shown below.
Mark-Houwink viscosity formula: Intrinsic viscosity = Kma where K and a are constants, each K = 1.23E
-4, a = 0.83, calculated by calculation.

Next, the component (B) will be described. (B)
(B-1) is a copolymer containing (a) an aromatic vinyl monomer component, (b) a vinyl cyanide monomer component, and (c) a rubbery polymer.

(A) As the aromatic vinyl monomer component,
For example, styrene, α-methylstyrene, o-, m- or p
-Methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-ter-butylstyrene,
Ethyl styrene, vinyl naphthalene and the like can be mentioned, and one or more of these can be used. Preferably, it is alpha methyl styrene.

As the vinyl cyanide monomer component (b), for example, acrylonitrile, methacrylonitrile and the like can be mentioned, and one or more of these are used. These composition ratios are not particularly limited and are selected according to the application.

(C) The rubbery polymer includes polybutadiene, polyisoprene, random copolymers and block copolymers of styrene-butadiene, hydrogenated products of the block copolymers, acrylonitrile-butadiene copolymers, butadiene Diene rubbers such as isoprene copolymers, random copolymers and block copolymers of ethylene-propylene, copolymers of ethylene and alpha-olefins, ethylene such as ethylene-methacrylate and ethylene-butyl acrylate; Copolymers with unsaturated carboxylic acid esters, acrylic ester-butadiene copolymers such as acrylic elastic polymers such as butyl acrylate-butadiene copolymers, and copolymers of ethylene and fatty acid vinyl such as ethylene-vinyl acetate. Polymer, ethylene-propylene-hexadie Ethylene and copolymers - propylene nonconjugated Jienta - polymer -, butylene - Isoburen copolymers, chlorinated polyethylene and the like, to use them in one or two or more thereof. Preferred rubbery polymers are ethylene-propylene non-conjugated dienter polymers, diene rubbers and acrylic elastic polymers, particularly preferably polybutadienes and styrene-butadiene copolymers.

Component (B) includes the above components (a), (b),
In addition to (c), (d) monomers copolymerizable with these components can be used as long as the objects of the present invention are not impaired. Such copolymerizable monomers include acrylic acid, α, β-unsaturated carboxylic acids such as methacrylic acid,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth)
Acrylate, 2-ethyl (meth) acrylate, 2-
Α, β-unsaturated carboxylic acid esters such as ethylhexyl methacrylate; α, β-unsaturated dicarboxylic acid anhydrides such as maleic anhydride and itaconic anhydride; maleimide;
Imide compounds of α, β-unsaturated dicarboxylic acids, such as N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and No-chlorophenylmaleimide; Or used in two or more.

The component (B) copolymer is preferably a graft copolymer obtained by graft copolymerizing other components in the presence of a rubbery polymer (c), 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 body-styrene copolymer).

Component (B) B-2 is a copolymer containing (a) an aromatic vinyl monomer component and (b) a vinyl cyanide monomer component. B-2 contributes to improvement in the moldability (flowability) of the resin. (A) Examples of the aromatic vinyl monomer component include styrene, α-methylstyrene, o-, m- or p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, and fluorostyrene. , P-ter-butylstyrene, ethylstyrene, vinylnaphthalene, and the like, and one or more of these are used. Preferably, it is alpha methyl styrene.

(B) Examples of the vinyl cyanide monomer component include acrylonitrile, methacrylonitrile, etc., and one or more of these are used. These composition ratios are not particularly limited and are selected according to the application. The composition ratio of (a) / (b) is not particularly limited, but in the component (B), preferably (a) is from 95% by weight to 50% by weight, and (b) is from 5% by weight to 50% by weight.
More preferably, (a) is from 92% by weight to 65% by weight, and (b) is from 8% by weight to 35% by weight. Preferred examples of the component (B) copolymer include, for example, SAN resin (styrene-acrylonitrile copolymer).

In the present invention, the weight average molecular weight (Mw) of the component (B-2) copolymer is from 30,000 to 200,000.
000, preferably 30,000 to 110,0
00.

The method for producing the component (B) copolymer is not particularly limited, and any known method such as bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization, and emulsion polymerization can be used. It is also possible to blend separately copolymerized resins.

In the present invention, the preferred production method (B) is bulk polymerization, solution polymerization, or bulk suspension polymerization. The alkali metal content of the component (B) is preferably 1 ppm or less, more preferably 0.5 ppm or less, even more preferably 0.1 ppm or less. Further, among the alkali metals, the content of sodium and / or potassium in the component (B) is preferably 1 ppm or less, more preferably 0.5 ppm or less, still more preferably 0.1 ppm or less.

The component (C) used in the present invention is a flame retardant.

[0022]

Embedded image (Where R1, R2, R3 and R4 each independently represent a hydrogen atom or an organic group, but R1 = R2 = R3
= R4 = H is excluded. X ′ represents a divalent or higher valent organic group, P is 0 or 1, Q is an integer of 1 or more, for example, an integer of 30 or less, and R represents an integer of 0 or more. Is mentioned. However, it is not limited to these.

In the above formula (Formula 1), examples of the organic group include an alkyl group, a cycloalkyl group and an aryl group which may or may not be substituted. When substituted, examples of the substituent include an alkyl group,
Examples thereof include an alkoxy group, an alkylthio group, a halogen, an aryl group, an aryloxy group, an arylthio group, and a halogenated aryl group, and a group obtained by combining these substituents (eg, an arylalkoxyalkyl group) or the substitution thereof. A group obtained by combining groups by bonding with an oxygen atom, a sulfur atom, a nitrogen atom, or the like (for example, an arylsulfonylaryl group) may be used as a substituent. In addition, a divalent or higher valent organic group is a group formed by removing one or more hydrogen atoms bonded to a carbon atom from the above organic group.
It means a group of valence or more. Examples include those derived from alkylene groups, and preferably (substituted) phenylene groups, polynuclear phenols, such as bisphenols,
The relative positions of the two or more free valences are arbitrary. Particularly preferred are hydroquinone, resorcinol, diphenylolmethane, diphenyloldimethylmethane,
Examples thereof include dihydroxydiphenyl, p, p'-dihydroxydiphenylsulfone, bisphenol A, bisphenol S, and dihydroxynaphthalene.

Specific examples of the phosphate compound 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) monooctyl phosphate, bisphenol A tetraphenyl diphosphate Bisphenol A tetra cresyl diphosphate, bisphenol A tetra xylylene diphosphate, hydroquinone tetraphenyl diphosphate, hydroquinone tetra cresyl diphosphate, hydroquinone tetra xylylene diphosphate, R
Bisphenol A bisphosphate, hydroquinone bisphosphate, resorcin bisphosphate, trioxybenzene triphosphate wherein 1, to R4 are alkoxy such as methoxy, ethoxy and propoxy, or preferably (substituted) phenoxy such as phenoxy, methyl (substituted) phenoxy. And preferably triphenyl phosphate and various bisphosphates.

The above component (C) is added when flame retardancy is required. The amount of addition is 1 to 40 parts by weight, preferably 3 to 30 parts by weight, based on 100 parts by weight of (A) + (B) in total. Parts, more preferably 5 to 20 parts by weight. If the amount of the component (C) is less than the above range, the effects of the present invention will not be sufficiently exhibited, and if it is more than the above range, heat resistance will be impaired. In the present invention, it is important that the phosphoric acid ester has an acid value of 1 or less. The acid value of the phosphate ester is
Preferably, it is 0.5 or less, more preferably,
Those having a value of 0.2 or less, more preferably 0.1 or less and as close as possible to 0 are effective for the resin composition of the present invention having improved hydrolysis resistance.

In the present invention, for the purpose of further improving the hydrolysis resistance, an epoxy stabilizer of the component (E) can be added. As the epoxy stabilizer, 3,
4-epoxycyclohexylmethyl '3-'4 epoxycyclohexanecarboxylate is preferred. This stabilizer is available as R-51 manufactured by Asahi Denka Kogyo KK and Celloxide 2021P manufactured by Daicel Chemical Industries, Ltd. The amount added is 0.01 to 10 parts by weight, preferably 0.1 to 0.5 parts by weight, based on 100 parts by weight of the total of the components (A) and (B). Also,
The epoxy-based stabilizer is not limited to those having the above structure.

The resin composition of the present invention may further contain an anti-dripping agent together with the addition of a flame retardant. This is the component (F) polytetrafluoroethylene. 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 can be used, for example, at a pressure of 100 to 1000 psi and 0 to 1000 psi in an aqueous medium using a free radical catalyst (eg, sodium, potassium or ammonium peroxydisulfate).
It is a white solid obtained by polymerizing tetrafluoroethylene at a temperature of 200C to 200C, preferably 20C to 100C. For more information, see Brubaker
U.S. Pat. No. 2,939,967.

Although not essential, relatively large particles, for example an average particle size of 0.3 to 0.7 mm (mainly 0.5 m
It is preferable to use the resin in the state of particles of m). This is better than regular polytetrafluoroethylene powders having a particle size of 0.05-0.5 mm. The reason that such relatively large particle size materials are particularly preferred is that they disperse readily in the polymer and tend to combine the polymers to form a fibrous material. Such a suitable polytetrafluoroethylene is what is referred to as type 3 according to ASTM and is in fact DuPont (EI D
upont de Nemoursand Company), Teflon 6 (Tef
lon 6 (trade name) is commercially available. Or, Teflon 3 of Mitsui DuPont Fluorochemicals Co., Ltd.
It can be obtained commercially as 0J (trade name).
Fluorinated polyolefin is (A) + (B) total 100
It is preferably used in an amount of 0.01 to 1 part by weight, more preferably 0.05 to 1.0 part by weight based on part by weight. Other flame-retardant aids and anti-dripping agents, such as polysiloxane, may be added in an amount of 0.1 parts by weight based on 100 parts by weight of the total of the components (A) and (B).
1 to 20 parts by weight can be used.

The thermoplastic resin composition according to the present invention may contain, in addition to the above-mentioned components, other materials commonly used in mixing resins, molding, etc., depending on the purpose, as long as the physical properties are not impaired. Additives such as pigments, dyes, reinforcing agents (talc, mica, clay, glass fiber, glass flake, milled glass, carbon fiber, silica, glass beads, metal fiber, wollastonite, etc.), coloring agents (carbon black) , Titanium oxide, etc.), heat-resistant agents, antioxidant inhibitors, weathering agents (ultraviolet absorbers), lubricants, release agents, crystal nucleating agents,
Well-known additives such as plasticizers, flow improvers, antistatic agents, inorganic and organic antibacterial agents can be blended. Specific examples of the ultraviolet absorber, the stabilizer, and the release agent are shown below.

Any of the resin compositions of the present invention can contain a phosphorus-based stabilizer as an optional component. As such a phosphorus-based stabilizer, for example, any of those commercially available from various stabilizer manufacturers as an antioxidant can be used. Specifically, triphenyl phosphite, diphenyl nonyl phosphite, tris (2,4-di-t-butyl phenyl) phosphite, tris nonyl phenyl phosphite, diphenyl isooctyl phosphite, 2, 2'-
Methylenebis (4,6-di-t-butylphenyl) octyl phosphite, diphenyl isodecyl phosphite, diphenyl mono (tridecyl) phosphite, 2,
2′-ethylidenebis (4,6-di-t-butylphenol) fluorophosphite, phenyldiisodecylphosphite, phenyldi (tridecyl) phosphite,
Tris (2-ethylhexyl) phosphite, tris (isodecyl) phosphite, tris (tridecyl) phosphite, dibutyl hydrogen phosphite, trilauryl trithiophosphite, tetrakis (2,4-
Di-t-butylphenyl) -4,4'-biphenylenediphosphonite, 4,4'-isopropylidenediphenolalkyl (C12-C15) phosphite, 4,4 '
-Butylidenebis (3-methyl-6-t-butylphenyl) ditridecyl phosphite, bis (2,4-di-t
-Butylphenyl) pentaerythritol diphosphite, bus (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, distearyl-pentaerythritol diphosphite Phosphite, phenyl-bisphenol A pentaerythritol diphosphite, tetraphenyldipropylene glycol diphosphite, 1,1,3-tris (2-methyl-4-
Di-tridecylphosphite-5-t-butylphenyl) butane, 3,4,5,6-dibenzo-1,2-oxaphosphane-2-oxide and the like can be used. Adeka stub PEP-
36, PEP-24, PEP-4C, PEP-8 (all trade names, manufactured by Asahi Denka Kogyo KK), Irgafos
168 (trade name, manufactured by Ciba Geigy), Sandst
ab P-EPQ (trade name, Sandoz)
Chelex L (trade name, Sakai Chemical Industry Co., Ltd.)
3P2S (trade name, Ihara Chemical Industry Co., Ltd.)
Mark 329K, Mark P (all trade names, manufactured by Asahi Denka Kogyo Co., Ltd.), and Weston 6
18 (trade name, manufactured by Sanko Chemical Co., Ltd.). The amount of the phosphorus-based stabilizer to be added is not particularly limited, but is preferably 0.0001 to 5 parts by weight based on 100 parts by weight of the total of the components (A) and (B).

Further, a hindered phenol-based antioxidant, an epoxy-based stabilizer, a sulfur-based stabilizer and the like can be added. As the hindered phenolic antioxidant, for example, n-octadecyl-3- (3 ′, 5′-
Di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-tert-butyl-4-hydroxymethylphenol, 2,2′-methylenebis (4-methyl-6
-T-butylphenol) and pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate. Examples of the epoxy stabilizer include epoxidized soybean oil, epoxidized linseed oil, phenylglycidyl ether, allyl glycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, and the like. The addition amount of these stabilizers is not particularly limited, but is preferably 0.0001 to 5 parts by weight based on 100 parts by weight of the total of components (A) and (B).

For the purpose of improving the releasability, a release agent can be added. Preferred release agents include silicone release agents such as methylphenyl silicone oil, pentaerythritol tetrastearate, glycerin monostearate, montanic acid wax, ester release agents such as polyalphaolefin, and olefin release agents. It is.
The amount of these additives is not particularly limited, but is preferably 0.0001 relative to the total of 100 parts by weight of the components (A) + (B).
To 5 parts by weight.

As the UV absorber, any UV absorber commonly used in PC resin compositions can be used. For example, a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a salicylate-based ultraviolet absorber and the like can be mentioned. Examples of the benzotriazole-based ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- ( 2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3' , 5'-Di-amylphenyl) benzotriazole, 2- (2'-hydroxy-3'-dodecyl-5 '
-Methylphenyl) benzotriazole, 2- (2'-
Hydroxy-3 ′, 5′-dicumylphenyl) benzotriazole, 2,2′-methylenebis [4- (1,1,
3,3-Tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol]. The benzotriazole-based ultraviolet absorber is commercially available as, for example, UV5411 from American Cyanamid. The benzophenone-based UV absorber is commercially available as UV531 from Synamid. Examples of the salicylate-based ultraviolet absorber include phenyl salicylate, pt-butylphenyl salicylate, p-
Octylphenyl salicylate and the like. The amount of these additives is not particularly limited, but is preferably 0.0001 relative to the total of 100 parts by weight of the components (A) + (B).
To 5 parts by weight.

Further, a compatibilizer can be added to the thermoplastic resin composition according to the present invention. Examples of the compatibilizer include a copolymer in which an acrylonitrile-styrene copolymer is grafted on a polycarbonate and a copolymer in which a polystyrene resin is grafted on a polycarbonate. For example, MODEIPER CH430, L43 manufactured by NOF Corporation
0D, L150D. Polymethyl methacrylate (PMMA) can also be used as a compatibilizer. The amount of these additives is not particularly limited, but is preferably from 0.1 to 30 parts by weight based on 100 parts by weight of the total of the components (A) and (B).

The method for producing the resin composition of the present invention is not particularly limited, and ordinary methods can be used satisfactorily. However, generally the melt mixing method is preferred. The use of small amounts of solvents is possible but generally not necessary. Examples of the apparatus include an extruder, a Banbury mixer, a roller, a kneader, and the like. These devices can be operated batchwise or continuously. The order of mixing the components is not particularly limited.

[0036]

The present invention will be further disclosed below with reference to examples. Materials used in carrying out the thermoplastic resin composition according to the present invention are as follows.

The polycarbonate of component (A) is polycarbonate LEXAN (trade name; manufactured by Nippon GE Plastics Co., Ltd.) using bisphenol A.
N141 was used. (Intrinsic viscosity measured in methylene chloride at 20 ° C. 0.50 dl / g, Mv = about 23,000
0 (calculated value))

The following components were used for the other components. Ingredient (B) ABS resin: Santac AT-07 (trade name; manufactured by Mitsui Chemicals, Inc.) Ingredient (B) ABS resin: UX050 (trade name; manufactured by Ube Sicon Co., Ltd.) Ingredient (C) Resorcinol diphosphate: CR73
3S (trade name; manufactured by Daihachi Chemical Co., Ltd.) Acid value 0.03 Component (C) Bisphenol A-diphosphate: CR
741, CR741S (trade name; manufactured by Daihachi Chemical Co., Ltd.)
Acid value 1.6, Acid value 0.64, Acid value 0.03 Component (D) SAN resin: SR05B (trade name; manufactured by Ube Sicon Co., Ltd.) Component (E) Epoxy stabilizer: 3,4 epoxycyclohexyl Methyl-3'-4 'epoxycyclohexanecarboxylate celloxide 2021P (trade name; manufactured by Daicel Chemical Industries, Ltd.) Optional component (F) polytetrafluoroethylene: Teflon 30J (trade name; DuPont Mitsui Fluorochemicals, Inc.) Made

Using each of the above materials, a twin-screw extruder
The extrusion was performed under the conditions of a screw rotation speed of 200 rpm and a barrel set temperature of 270 to 280 ° C., followed by cutting to produce pellets.

Using the pellets thus produced, test pieces were molded by an 80t injection molding machine manufactured by Toyo Kikai Metal Co., Ltd. The molding conditions were set at a barrel temperature of 240 ° C. and a mold temperature of 60 ° C.

Mechanical properties such as Izod impact strength and tensile strength were evaluated in accordance with standard ASTM.

The flame retardancy test was performed according to UL94 / V0, VI, VII
The test was performed according to. Five specimens were tested at a 1/16 inch thickness according to the test method set forth in Underwriters Laboratories Ink's Bulletin 94 "Burning Test for Material Classification" (hereinafter UL-94). According to this test method, the test material was rated to any of UL-94 V-0, VI, and V-II based on the results of five materials.

Component (B) The determination of the alkali metals in the ABS resin was carried out by ICP method and atomic absorption method after the sample was incinerated and dissolved in pure water. Table 1 shows the measured values.

The moisture resistance was evaluated at 60 ° C./85% R
The test pieces were evaluated by tensile strength and tensile elongation after leaving the test pieces in a high-temperature and high-humidity oven at 95 ° C./98% RH. Tables 2, 3, and 4 show the compositions and evaluation results of Comparative Examples and Examples.

The acid value of the phosphoric acid ester of the component (C) is measured according to ASTM D974. Alternatively, it is measured by the following method.

(Method for Evaluating Phosphate Acid Value) Evaluation is made by dissolving a sample in a mixed solution of ethyl alcohol and water and then titrating with a N / 10 sodium hydroxide solution using a bromthymol blue solution as an indicator. Reagent: (1) Ethyl alcohol / water mixed solution Ethyl alcohol (special reagent grade) and ion-exchanged water 9: 1
Mix at a volume ratio of. (2) Bromthymol blue solution Bromthymol blue (special grade reagent) 95V to 0.10g
Add 20 ml of% ethyl alcohol (special grade reagent) and dilute to 100 ml with water. (3) N / 10 sodium hydroxide solution

(Titration of N / 10 sodium hydroxide solution titer) Sulfamic acid (standard reagent) was dried in a vacuum sulfuric acid desiccator, and 0.2 to 0.3 g of the dried product was dried.
Weigh correctly in a ml Erlenmeyer flask, add about 25 ml of water to dissolve, and titrate with bromthymol blue solution as an indicator with N / 10 sodium hydroxide solution. Titer = (S × P) / (0.9709 × A
S) Sulfamic acid weighed amount (g) P: Sulfamic acid purity (%) A: N / 10 sodium hydroxide solution titration (ml)

Operation : (1) 40 ml of a mixed solution of ethyl alcohol and water is put into a 200 ml Erlenmeyer flask with a measuring cylinder. (2) Add 1 ml of bromthymol blue solution with a female pipette, and titrate until the color of the N / 10 sodium hydroxide solution is confirmed to be blue-green. (3) Sample 10 was added to this 200 ml Erlenmeyer flask.
g is weighed using an electronic precision balance and read to one decimal place. (4) Titrate with N / 10 sodium hydroxide solution until the same blue-green color as in (2) is confirmed.

Acid value (KOH mg / g) = (A × F
× 5.61) / S A: Number of ml of N / 10 sodium hydroxide required for titration of sample F: Potency of N / 10 sodium hydroxide solution S: Sample (g)

[0050]

[Table 1]

[0051]

[Table 2]

[0052]

[Table 3]

[0053]

[Table 4]

[0054]

As shown in Table 2, the system using the ABS resin having a low alkali metal content has a higher retention of tensile strength after aging under humidity, and has a significantly improved moisture resistance. Further, as shown in Table 3, the use of a phosphoric acid ester having an acid value lower than 1 and lower than 0.1 can significantly improve the moisture resistance. Further, as shown in Table 4, it is shown that the addition of the epoxy stabilizer can significantly improve the moisture resistance even under severe high temperature and high humidity aging.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08L 33/20 C08L 33/20 55/02 55/02

Claims (9)

(57) [Claims] (A) a viscosity average molecular weight of 10,000 to
(B) (B-1) (a) an aromatic vinyl monomer component, comprising 1 to 99 parts by weight of a polycarbonate resin which is 100,000;
(B) a copolymer containing each of a vinyl cyanide monomer component and (c) a rubbery polymer as a component of copolymerization, and / or (B-2) (a) an aromatic vinyl monomer (B) a vinyl cyanide monomer component as a component of the copolymer, wherein the copolymer (B)
-2) the weight average molecular weight of 30,000 to 200,0
A copolymer having an alkali metal content of 1 ppm or less from 99 parts by weight to 1 part by weight,
And (C) 1 to 40 parts by weight of a phosphate compound having an acid value of 1 or less based on 100 parts by weight of the total of the components (A) and (B). A polycarbonate-based resin composition characterized in that: 2. The polycarbonate resin composition according to claim 1, wherein the alkali metal contained in the component (B) is sodium and / or potassium. 3. The component (B) according to claim 1, wherein the component (B) is a copolymer selected from an ABS resin, an AES resin, an ACS resin and an AAS resin. Polycarbonate resin composition. 4. A total of 100 of the components (A) and (B)
(E) epoxy-based stabilizer relative to parts by weight.
The polycarbonate-based resin composition according to any one of claims 1 to 3, wherein the composition is added in an amount of from 01 part by weight to 10 parts by weight. 5. The composition according to claim 1, wherein the component (E) is an epoxy stabilizer.
The polycarbonate resin composition according to claim 4, wherein the composition is epoxycyclohexylmethyl-3'-4 'epoxycyclohexanecarboxylate. 6. The polycarbonate resin composition according to claim 1, wherein the component (A) is a polycarbonate resin obtained by a melt polymerization method. 7. The polycarbonate resin composition according to claim 1, wherein an alkali metal content in the entire polycarbonate resin composition is 1 ppm or less. 8. The content of sodium and potassium in the entire polycarbonate resin composition is 1 p.
The polycarbonate resin composition according to any one of claims 1 to 6, wherein the polycarbonate resin composition is not more than pm. 9. A total of 100 of the components (A) and (B)
The polycarbonate resin composition according to any one of claims 1 to 8, wherein 0.01 to 3 parts by weight of (F) polytetrafluoroethylene is further blended with respect to part by weight.