JP2002371177A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition having high hydrolytic resistance, excellent moisture resistance, good flame retardance, mechanical strength, slidability and abrasion resistance. SOLUTION: This polycarbonate resin composition comprises (A) 30-90 pts.wt. of a polycarbonate resin having a viscosity-average molecular weight within the range of 10,000-100,000, (B) 1-50 pts.wt. of a styrene resin, (C) 0.5-30 pts.wt. of a slidability improver and (D) a phosphoric ester compound having <=1 acid value in an amount of 1-30 pts.wt. based on 100 pts.wt. of the total amount of the components (A), (B) and (C). The polycarbonate resin composition comprises further (E) a composite rubber graft copolymer prepared by grafting a vinyl monomer on a composite rubber containing a polyorganosiloxane and a polyalkyl (meth)acrylate in an amount of <=20 pts.wt. based on 100 pts.wt. of the total amount of the components (A), (B) and (C). Furthermore, (F) an epoxy stabilizer in an amount of 0.01-10 pts.wt. based on 100 pts.wt. of the total amount of the components (A), (B) and (C) may be contained.

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 suitable for applications requiring sliding and abrasion resistance of movable parts such as electric equipment and OA equipment, such as bearings of chassis and CD trays. About.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Polycarbonate resin (PC),
Alternatively, a polymer alloy obtained by blending a styrene-based resin, for example, an ABS resin (acrylonitrile-butadiene-styrene copolymer), is used in electric and electronic products, copiers,
It is widely used in OA equipment such as printers, facsimile machines, personal computers, notebook or portable computers, and communication equipment such as mobile phones. In recent years, there has been an increasing demand for smaller and lighter products for these applications.

For this reason, new molding methods have been tried to meet these demands, and the resin used has been required to have a thin-wall moldability, a precision moldability, and a high flame retardancy. I have. In order to improve such thin-wall moldability and precision moldability, it has been widely practiced to improve rigidity and dimensional stability by blending a reinforcing agent such as glass fiber, talc, or carbon fiber.

[0004] In recent years, production and use in Southeast Asia has been rapidly increasing. Here, use and storage of the product in an environment with high humidity are common, and there is often a fear that physical properties may be degraded due to low moisture resistance of the product resin. Therefore, it is essential to improve the moisture resistance of the product resin. Generally, it cannot be said that the moisture resistance of a polymer alloy blended with a polycarbonate resin (PC) or a styrene-based resin is high. In particular, the moisture resistance of the resin composition or the flame-retardant resin composition reinforced with a reinforcing agent such as carbon fiber was not at a high level.

The present applicant has invented a polycarbonate-based resin composition having excellent moisture resistance and good flame retardancy, and disclosed [A] a viscosity average molecular weight of 1 in JP-A-11-130954.
000 to 100,000 polycarbonate resin: 1 to 99 parts by weight, [B] (B-1) (a) an aromatic vinyl monomer component, (b) a vinyl cyanide monomer component and
(c) a copolymer containing a rubbery polymer as a copolymer component and / or (B-2) an (a) aromatic vinyl monomer component and (b) a vinyl cyanide monomer component. A copolymer containing as a component of the polymer, wherein the copolymer (B-2) has a weight-average molecular weight of 30,000 to 200,000 and an alkali metal content of 1 ppm or less. And [C] a phosphoric acid ester-based compound, and a total of 100 parts of the component [A] and the component [B].
A polycarbonate resin composition in which 0 to 40 parts by weight is blended with respect to parts by weight is proposed.

Further, the present applicant has disclosed in Japanese Patent Application Laid-Open No. 2000-191896 (A) 10 as a polycarbonate resin composition having excellent moisture resistance and good flame retardancy and excellent mechanical strength. Comprising 1 to 99 parts by weight of a polycarbonate resin having a viscosity average molecular weight of 2,000 to 100,000 and (B) 99 to 1 part by weight of a styrene resin.
And (C) acid value is 1 with respect to 100 parts by weight of (A) + (B) in total.
A resin composition containing 1 to 40 parts by weight of the following phosphoric acid ester compound, and further containing 1 to 100 parts by weight of (D) a reinforcing agent with respect to 100 parts by weight in total of (A) + (B) + (C) Suggesting things.

Separately, as a polycarbonate resin composition having excellent slidability, the present applicant has disclosed in
-101920 gazette, (A) viscosity average molecular weight 10,000-100,
30 to 90% by weight of PC resin having 000, (B) ABS resin 1 to 5
A resin composition comprising 0% by weight and (C) 0.5 to 30% by weight of a substance selected from the group consisting of low molecular weight polyolefin, silicone oil and silicone resin fine particles is proposed.

[0008]

An object of the present invention is to provide a polycarbonate having high hydrolysis resistance, excellent moisture resistance, good flame retardancy, excellent mechanical strength, and excellent slidability and abrasion resistance. An object of the present invention is to provide a resin composition.

[0009]

SUMMARY OF THE INVENTION The polycarbonate resin composition according to the present invention comprises (A) a polycarbonate resin having a viscosity average molecular weight in the range of 10,000 to 100,000;
(B) 1 to 50 parts by weight of the styrene resin, (C) 0.5 to 30 parts by weight of the slidability improver, (D) a phosphate compound having an acid value of 1 or less, A), (B), (C) 100 in total
It is characterized in that it is contained in an amount of 1 to 30 parts by weight based on parts by weight.

In the present invention, the (C) slidability improver is preferably at least one selected from the group consisting of polytetrafluoroethylene, polyolefin, silicone oil and silicone resin fine particles. Also,
The composition according to the present invention comprises (E) a composite rubber-based graft copolymer obtained by grafting a vinyl-based monomer onto a composite rubber containing a polyorganosiloxane and a polyalkyl (meth) acrylate, as (A) and (B). ) And (C) preferably in an amount of 20 parts by weight or less based on 100 parts by weight in total.

The content of the alkali metal contained in the styrene resin (B) used in the present invention is preferably 1 ppm or less, and the alkali metal contained in the styrene resin (B) is preferably sodium and / or sodium. Alternatively, it is preferably potassium. (B) Styrene resin is HIPS (impact polystyrene), ABS resin (acrylonitrile-butadiene-styrene copolymer), AES resin (acrylonitrile-ethylene-propylene-styrene copolymer), ACS resin (acrylonitrile-chlorine) It is preferably at least one selected from the group consisting of a polyethylene-styrene copolymer) and an AAS resin (acrylonitrile-acrylic elastic body-styrene copolymer).

Further, the resin composition according to the present invention comprises:
It is preferable that (F) an epoxy-based stabilizer: 0.01 to 10 parts by weight is contained based on 100 parts by weight in total of (A), (B) and (C). (F) 3,4-epoxy stabilizers
Epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate is preferred.

[0013]

DETAILED DESCRIPTION OF THE INVENTION The polycarbonate resin composition according to the present invention will be specifically described below. [(A) Polycarbonate resin] The (A) polycarbonate resin used in the present invention is an aromatic polycarbonate produced by a known phosgene method or a melting method. Such a polycarbonate resin is described in, for example, JP-A-63-215763. And JP-A-2-1249
No. 34 publication.

As the diphenol used as a raw material, 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; 1,1-bis (3,5-dimethyl-4-hydroxyphenyl)
Cyclohexane; 1,1-bis (4-hydroxyphenyl) decane; 1,4-bis (4-hydroxyphenyl) propane;
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 and the like. Examples of the precursor for introducing carbonate include phosgene and diphenyl carbonate.

The lower limit of the viscosity average molecular weight (Mv) of the polycarbonate resin (A) used in the present invention is 10.0 or less.
00, preferably 21,000, and more preferably 22,000. The upper limit is 10
And practically preferably 40,000.
It is. The viscosity average molecular weight (Mv) is
The intrinsic viscosity (intrinsic viscosity: [η]) is measured at 20 ° C., and the viscosity formula of Mark-Houwink is given as follows: [η] = K (Mv) ^a (where K = 1.23 × 10 ⁻⁴⁾ , A = 0.83). [(B) Styrene-based resin] The styrene-based resin used in the present invention has a structural unit derived from styrene, and (B-1) a styrene-containing graft polymer and / or (B-2) a styrene-based resin. It is a component composed of a polymer. In the present invention, (B-1) styrene-containing graft polymer, (B-2)
Styrene-based polymer may be used alone, or (B-
1) and (B-2) may be used as a mixture, but preferably
It is desirable to use (B-1).

(B-1) The styrene-containing graft polymer is
(A) an aromatic vinyl monomer component, and, if necessary,
It is obtained by grafting a mixture of this and (b) a copolymerizable vinyl monomer to (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,
Examples thereof include fluorostyrene, p-ter-butylstyrene, ethylstyrene, and vinylnaphthalene, and one or more of these may be used. Of these, α-methylstyrene is preferred.

(B) The copolymerizable vinyl monomers include, for example, acrylonitrile, methacrylonitrile, α, β-unsaturated carboxylic acids such as acrylic acid and methacrylic acid, methyl (meth) acrylate, ethyl (meth) Α, β such as acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethyl (meth) acrylate, 2-ethylhexyl methacrylate
-Unsaturated carboxylic esters; α, β-unsaturated dicarboxylic anhydrides such as maleic anhydride and itaconic anhydride;
Imide compounds of α, β-unsaturated dicarboxylic acids, such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and No-chlorophenylmaleimide; Use more than seeds. These composition ratios are not particularly limited,
It is 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-unsaturated carboxylic acids such as ethylene-methacrylate and ethylene-butyl acrylate Copolymers with acid esters, acrylate-butadiene copolymers, for example, acrylic elastic polymers such as butyl acrylate-butadiene copolymers, copolymers of ethylene and fatty acid vinyl such as ethylene-vinyl acetate, ethylene -Propylene-hexadie Propylene non-conjugated diene terpolymers, butylene - - Ethylene such copolymers Isoburen copolymers, chlorinated polyethylene and the like, used in these one or two or more. Preferred rubbery polymers are ethylene-propylene non-conjugated diene terpolymers, diene rubbers and acrylic elastic polymers,
Particularly preferred are polybutadiene and styrene-butadiene copolymer.

The composition ratio of the above (a), (b) and (c) is not particularly limited, and is appropriately selected according to the application. (B
-1) Preferably as a styrene-containing graft polymer,
HIPS (impact polystyrene), ABS resin (acrylonitrile-butadiene-styrene copolymer), AE
S resin (acrylonitrile-ethylene propylene-styrene copolymer), ACS resin (acrylonitrile-chlorinated polyethylene-styrene copolymer), and AAS resin (acrylonitrile-acrylic elastic body-styrene copolymer).

(B-2) As the styrene polymer component,
It can be obtained by polymerizing a mixture of (a) an aromatic vinyl monomer component and, if necessary, a (b) copolymerizable vinyl monomer by a known method. (B-2) contributes to the improvement of the moldability (fluidity) of the resin. (A) As the aromatic vinyl monomer component, the same substances as described above can be used. Preferably, styrene, α-
Methyl styrene can be used.

The same substances as described above can be used for the copolymerizable vinyl monomer component (b). One or more of these can be used, and the composition ratio thereof is not particularly limited, and is selected according to the application. Here, although the composition ratio of (a) / (b) is not particularly limited,
In the component (B-2), preferably, (a) is 95 to 50.
% By weight, and (b) is 5 to 50% by weight, more preferably (a) is 92 to 65% by weight, and (b) is 8 to 50% by weight.
35% by weight. (B-2) As a styrenic polymer,
Preferably, styrene resin and SAN resin (styrene-acrylonitrile copolymer) are used.

In the present invention, the upper limit of the weight average molecular weight (Mw) of the (B-2) styrenic polymer is preferably 2
00,000, more preferably 110,000,
The lower limit is preferably 30,000. The method for producing the styrene resin as the component (B) is not particularly limited, and a commonly known method such as bulk polymerization, solution polymerization, bulk suspension polymerization, suspension polymerization, and emulsion polymerization is used. It is also possible to blend separately copolymerized resins. Preferably, bulk polymerization, solution polymerization, or bulk suspension polymerization is used.

In the present invention, the alkali metal content of the component (B) is preferably 1 ppm by weight or less, particularly preferably 0.5 ppm by weight or less, more preferably 0.1 ppm by weight or less. Further, among the alkali metals, the content of the sodium and / or potassium components in (B) is preferably 1 ppm by weight or less, particularly preferably 0.1 ppm by weight.
5 wt ppm or less, more preferably 0.1 wt ppm
It is as follows.

Such an alkali metal component is derived from a catalyst used in preparing the styrene resin (B), a raw material, and contamination from a polymerization facility. In the present invention, in order to remove such an alkali metal component,
The alkali-removing metal treatment in the styrene-based resin may be performed using an ion-exchange resin. [(C) Slidability improver] Next, the component (C) improves the slidability of the resin composition, and such a slidability improver can improve the slidability. If it is possible to use without any particular limitation, specifically, fluororesin,
It is at least one selected from low molecular weight polyolefin, silicone oil and silicone resin fine particles.

Any one of these may be selected, or two or more may be selected in combination. As the fluororesin, polytetrafluoroethylene is preferable. Particularly, polytetrafluoroethylene having a molecular weight of 300,000 or less is preferable. As the low molecular weight polyolefin, a polyolefin having a molecular weight of 10,000 or less is preferable. Examples of the polyolefin include polyethylene and polypropylene, and polyethylene is preferred. Molecular weight 1
Polyethylenes of 000 or less are particularly preferred. The silicone oil is not particularly limited, but includes, for example, dimethyl silicone oil, methylphenyl silicone oil and the like, among which dimethyl silicone oil is preferable. The silicone resin fine particles are silicone resin fine particles having a three-dimensional crosslinked structure. As such a silicone resin, a methyl silicone resin is preferable. The particle size of the silicone resin fine particles is preferably 0.
5 to 12 μm. Such silicone resin fine particles are available from Toshiba Silicone Co., Ltd. as "Tospearl".

The components (A) and (B) in the resin composition of the present invention
And (C), the amount of (A) 30 to 90 parts by weight, (B) 1 to
50 parts by weight and (C) 0.5 to 30 parts by weight. Preferably (A) 50 to 90 parts by weight, (B) 1 to 50 parts by weight and
(C) 0.5 to 20 parts by weight. If the proportion of the component (C) is too small, the effect of improving the slidability is not recognized, and if it is too large, the physical properties may be reduced.

[(D) Phosphate ester compound] The phosphate ester compound used in the present invention acts as a flame retardant. It is important that the acid value of the phosphoric acid ester is 1 or less, preferably 0.5 or less, more preferably 0.2 or less, and further preferably 0.1 or less. Those having an acid value as close to 0 as possible are particularly effective for the resin composition of the present invention having improved hydrolysis resistance. The acid value is a value representing the amount of free acid in fats, plasticizers, solvents and the like. Expressed in milligrams of KOH required to neutralize 1 gram of sample.

Examples of the phosphate compound include the following formula (I)

[0029]

Embedded image

[0030] ^{(wherein, R 1, R 2, R} 3 and R ⁴ each independently represent a hydrogen atom or an organic group, R ¹ =
Except when R ² = R ³ = R ⁴ = H. X represents a divalent or higher valent organic group, p is 0 or 1, q is an integer of 1 or more,
For example, r represents an integer of 30 or less, and r represents an integer of 0 or more. The compound represented by the formula (1) is preferably used, but is not limited thereto.

In the above formula (I), examples of the organic group include an alkyl group which may or may not be substituted, 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, and a halogenated aryl group. (For example, an arylalkoxyalkyl group, etc.), or a group obtained by combining these substituents by bonding with an oxygen atom, a sulfur atom, a nitrogen atom, or the like (for example, an arylsulfonylaryl group, etc.) 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 groups. Examples include alkylene groups, and preferably (substituted) phenylene groups, those derived from polynuclear phenols, such as bisphenols, and the relative positions of two or more free valences are arbitrary. Particularly preferred are hydroquinone, resorcinol, diphenylolmethane, diphenyloldimethylmethane, dihydroxydiphenyl, p, p '
-Dihydroxydiphenylsulfone, bisphenol A, bisphenol S, dihydroxynaphthalene, and the like.

As a specific example of a phosphate compound,
Trimethyl phosphate, triethyl phosphate
Tributyl phosphate, trioctyl phosphate
Phosphate, tributoxyethyl phosphate, triphenyl
Phosphate, tricresyl phosphate, cresylph
Phenyl phosphate, octyl diphenyl phosphate
Diisopropylphenyl phosphate, tris
Loroethyl) phosphate, tris (dichloroprop
Le) phosphate, tris (chloropropyl) phosphate
, Bis (2,3-dibromopropyl) -2,3-dichloroprop
Propyl phosphate, tris (2,3-dibromopropyl)
Phosphate, bis (chloropropyl) monooctylho
Sulfate, bisphenol A tetraphenyl diphosph
, Bisphenol A tetracresyl diphosphate
G, bisphenol A tetraxylyl diphosphate,
Hydroquinone tetraphenyl diphosphate, hydroxy
Non-tetracresyl diphosphate, hydroquinone tet
Laxylyl diphosphate, R ¹~ R^FourWas alkoxy
For example, methoxy, ethoxy and propoxy, or
Or (substituted) phenoxy such as phenoxy, methyl
Bisphenol A bi which is (substituted) phenoxy
Phosphate, hydroquinone bisphosphate, reso
Lucine bisphosphate, trioxybenzene triphos
Fate and the like. Preferably triphenylphos
Fate and various bisphosphates are used.

The amount of the component (D) is (A) + (B) + (C)
Is 100 parts by weight, the upper limit is 30 parts by weight, preferably 20 parts by weight, and the lower limit is 1 part by weight, preferably 3 parts by weight, more preferably 5 parts by weight. Ingredient (D)
If the amount is less than the above lower limit, the effect of the present invention will not be sufficiently exhibited, and if it exceeds the above upper limit, heat resistance may be impaired. [(E) Composite rubber-based graft copolymer] The component (E) used in the present invention has a structure in which a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component are alternately entangled and are integrally integrated. To a composite rubber having
It is a composite rubber-based graft copolymer obtained by graft polymerization of one or more kinds of vinyl monomers.

Such a composite rubber-based graft copolymer can be produced, for example, by the methods disclosed in JP-A-64-79257, JP-A-7-207137 and JP-A-7-207132. it can. As the composite rubber, one produced by an emulsion polymerization method is preferably used. For example, a latex of a polyorganosiloxane rubber is prepared, and then a monomer for synthesizing an alkyl (meth) acrylate rubber is mixed with a polyorganosiloxane rubber latex. It is preferable that the rubber particles are produced by impregnating the rubber particles of the above and polymerizing a monomer for synthesizing the alkyl (meth) acrylate rubber.

The organosiloxane rubber component can be prepared, for example, by emulsion polymerization using the following organosiloxane and a crosslinking agent (II-1). At this time, if necessary, a graft crosslinking agent (II-2) ) Can be used together. As the organosiloxane, for example,
A chain organosiloxane such as dimethylsiloxane, or various cyclic organosiloxanes having three or more members, preferably three to six members, can be used. For example,
Examples include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, and octaphenylcyclotetrasiloxane. These organosiloxanes can be used alone or in combination of two or more. It is desirable that the amount of the organosiloxane used is preferably 50% by weight or more, more preferably 70% by weight or more in the polyorganosiloxane rubber component.

As the crosslinking agent (II-1), trifunctional or tetrafunctional silane crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n- Propoxysilane, tetrabutoxysilane, or the like can be used. Particularly, a tetrafunctional crosslinking agent is preferable, and among them, 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 0.1% in the polyorganosiloxane rubber component.
30% by weight is preferred. The following formula is used as the graft crossing agent (II-2): CH ₂ ＣC (R ² ) —COO— (CH ₂ ) _p —SiR ¹ _n O _{(3-n) / 2)} (II-2-1 _{) ^{) CH 2 = CH-SiR 1}} n O (3-n) / 2 ... (II-2-2) HS— (CH ₂ ) _p —SiR ¹ _n O _{(3-n) / 2} (II-2-3) (wherein R ¹ is a lower alkyl group such as a methyl group, Represents an ethyl group, a propyl group, or a phenyl group,
R ² represents a hydrogen atom or a methyl group; n represents 0, 1 or 2; and p represents an integer of 1 to 6).

(Meth) acryloyloxysiloxane capable of forming the unit of the above formula (II-2-1) has a high grafting efficiency, so that an effective graft chain can be formed, and high impact resistance can be obtained. It is preferable in that it is expressed. Note that methacryloyloxysiloxane is particularly preferable as a unit capable of forming the unit of the formula (II-2-1). Specific examples of methacryloyloxysiloxane include β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-
Methacryloyloxypropyltridimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane, δ-methacryloyloxybutoxybutyldiethoxymethylsilane, and the like. . These may be used alone or in combination of two or more.
The amount of the graft crosslinking agent used is preferably 0 to 10% by weight in the polyorganosiloxane rubber component.

The production of this polyorganosiloxane rubber component latex is described, for example, in US Pat. No. 2,891,920.
No. 3,294,725 can be used. In the practice of the present invention, for example, a mixed solution of an organosiloxane, a crosslinking agent (II-1) and, if desired, a graft crosslinking agent (II-2) is mixed in the presence of a sulfonic acid emulsifier such as alkylbenzenesulfonic acid or alkylsulfonic acid. For example, it is desirable to manufacture by a method of shear mixing with water using a homogenizer or the like.
Alkyl benzene sulfonic acid is particularly preferred because it functions as an emulsifier for the organosiloxane and also serves as a polymerization initiator. At this time, it is preferable to use a metal salt of an alkylbenzene sulfonic acid, a metal salt of an alkyl sulfonic acid, or the like in combination, since it has an effect of keeping the polymer constant during graft polymerization.

Next, the polyalkyl (meth) acrylate rubber component constituting the composite rubber is prepared by using the following alkyl (meth) acrylate, a crosslinking agent (III-1) and a graft crossing agent (III-2). Can be synthesized.
Examples of the alkyl (meth) acrylate include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate, and alkyls such as hexyl methacrylate, 2-ethylhexyl methacrylate, and n-lauryl methacrylate. Methacrylate is mentioned, and it is particularly preferable to use n-butyl acrylate.

Examples of the crosslinking agent (III-1) include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate and the like. Examples of the graft crosslinking agent (III-2) include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate and the like. Allyl methacrylate can also be used as a crosslinking agent. These cross-linking agents and graft crossing agents may be used alone or in combination of two or more. The total amount of the crosslinking agent and the graft crosslinking agent used is preferably 0.1 to 0.1 in the polyalkyl (meth) acrylate rubber component.
20% by weight.

The polymerization of the polyalkyl (meth) acrylate rubber component is carried out by adding the above-mentioned polyorganosiloxane rubber component into a latex neutralized by adding an aqueous solution of an alkali such as sodium hydroxide, potassium hydroxide or sodium carbonate. Alkyl (meth) acrylate, crosslinking agent (III-
After adding 1) and the graft-linking agent (III-2) and impregnating the polyorganosiloxane rubber particles, the reaction is carried out by the action of a usual radical polymerization initiator. As the polymerization proceeds, a cross-linked network of polyalkyl (meth) acrylate rubber entangled with the cross-linked network of polyorganosiloxane rubber is formed, and the polyorganosiloxane rubber component and the polyalkyl (meth) acrylate rubber component are substantially inseparable. Latex of the composite rubber 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 the following is preferably used.

The composite rubber thus prepared by emulsion polymerization can be graft-copolymerized with a vinyl monomer. The gel content of this composite rubber measured by extracting 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, etc., the ratio of the polyorganosiloxane rubber component to the polyalkyl (meth) acrylate rubber component in the composite rubber is 3 to 90% by weight. %, And the latter is preferably 97 to 10% by weight, and the composite rubber preferably has an average particle size of 0.08 to 0.6 μm.

The vinyl monomers to be graft-polymerized on the composite rubber include styrene, α-methylstyrene,
Aromatic alkenyl compounds such as vinyl toluene; methacrylates such as methyl methacrylate and 2-ethylhexyl methacrylate; acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate; various types of vinyl cyanide compounds such as acrylonitrile and methacrylonitrile Vinyl monomers are mentioned, and these can be used alone or in combination of two or more. A particularly preferred vinyl monomer is methyl methacrylate. The vinyl monomer is a composite rubber 3 as described above.
It is preferable that the content is contained in a ratio of 5 to 70% by weight to 0 to 95% by weight.

The composite rubber-based graft copolymer (E) is obtained by adding the above-mentioned vinyl monomer to the above-mentioned composite rubber latex,
Separate the composite rubber-based graft copolymer latex obtained by polymerizing in one or multiple stages by radical polymerization technology into hot water in which metal salts such as calcium chloride or magnesium sulfate are dissolved, salting out and coagulating. ,
Can be recovered.

Such a composite rubber-based graft copolymer
(E) is commercially available, for example, from Mitsubishi Rayon Co., Ltd. as Metablen S-2001. component
(E) has an upper limit of 20 parts by weight, preferably 10 parts by weight, particularly preferably 6 parts by weight, and a lower limit of 0 part by weight based on 100 parts by weight of (A) + (B) + (C) in total. It is sufficient that the amount is more than part by weight (it is sufficient if it is contained even a little), preferably 1 part by weight, particularly preferably 2 parts by weight. If (E) exceeds the above upper limit, moldability may be impaired. [(F) Epoxy stabilizer] In the present invention, an epoxy stabilizer can be added as a component (F) for the purpose of further improving hydrolysis resistance. The epoxy stabilizer includes 3,4-epoxycyclohexylmethyl-3 ′, 4′-
Epoxycyclohexanecarboxylate is preferred.
This stabilizer is available as R-51 manufactured by Asahi Denka Kogyo Co., Ltd. and Celloxide 2021P manufactured by Daicel Chemical Industries, Ltd. (A) + (B) + (C) total 1
The upper limit is 10 parts by weight, preferably 0.5 parts by weight, and the lower limit is 0.01 parts by weight, preferably 0.1 parts by weight, based on 00 parts by weight. If it exceeds the upper limit, mechanical strength cannot be obtained, and if it is less than the lower limit, improvement in hydrolysis resistance cannot be achieved. The epoxy-based stabilizer is not limited to the above structure.

The resin composition of the present invention may further contain component (G) a fluorinated polyolefin as an anti-dripping agent. Preferably, polytetrafluoroethylene can be used. Polytetrafluoroethylene is a white solid, commercially available, or can be produced by known methods. For example,
Free radical catalysts (eg, sodium peroxydisulfate,
Potassium or ammonium) in an aqueous medium at a pressure of 100-1000 psi and 0-20
It is obtained by polymerizing tetrafluoroethylene at a temperature of 0 ° C, preferably 20 to 100 ° C. For more information, see U.S. Pat.
No. 967.

Although not essential, tetrafluoroethylene is a relatively large particle, for example, having an average particle size of 0.3 to 0.1.
It is desirable to use particles in a state of particles of 7 mm (mainly 0.5 mm). This is 0.05-0.5
Better than normal polytetrafluoroethylene powder with a particle size of mm. The reason that such relatively large particle size materials are particularly preferred is that they readily disperse 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 the ASTM and is in fact EIDupont de Nemours an.
d Company) as Teflon 6 (Teflon 6). Alternatively, it is commercially available as Teflon (R) 30J of Mitsui DuPont Fluorochemicals.
(G) The compounding amount of the fluorinated polyolefin is (A) + (B) + (C)
Is preferably 3.0 with respect to 100 parts by weight in total.
Parts by weight, more preferably 1.0 part by weight, and the lower limit is preferably 0.01 part by weight, more preferably 0.05 part by weight.

As other flame retardant aids and anti-dripping agents, polysiloxanes and the like are preferably used in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the total of (A) + (B) + (C). You can also. The resin composition of the present invention, in addition to the above components, as long as the physical properties are not impaired, at the time of mixing the resin according to the purpose, other additives commonly used at the time of molding,
For example, pigments, dyes, heat stabilizers, stabilizers (antioxidants),
Well-known additives such as weathering agents (ultraviolet absorbers), lubricants, mold release agents, crystal nucleating agents, plasticizers, flow improvers, antistatic agents, inorganic and organic antibacterial agents can be blended.

Examples of the stabilizer include phosphorus stabilizers which are commercially available from various stabilizer manufacturers as antioxidants. Specifically, triphenyl phosphite, diphenyl nonyl phosphite, tris (2,4-
Di-t-butylphenyl) phosphite, trisnonylphenyl phosphite, diphenylisooctyl phosphite, 2,2′-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, diphenylisodecyl 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'-biphenylene phosphonite, 4,4'-isopropylidenediphenol alkyl (C ₁₂ -C ₁₅₎ phosphite, 4,4'-butylidene bis (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 Fight, 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.

As commercial products, ADK STAB PEP-36, PEP
-24, PEP-4C, PEP-8 (trade names, manufactured by Asahi Denka Kogyo Co., Ltd.), Irgafos168 (trade name, manufactured by Ciba Geigy), SandstabP-EPQ (trade name, manufactured by Sandoz) , Chelex L (trade name, manufactured by Sakai Chemical Industry Co., Ltd.), 3P
2S (trade name, manufactured by Ihara Chemical Industry Co., Ltd.), Mark32
9K, Mark P (all trade names, manufactured by Asahi Denka Kogyo Co., Ltd.), and Weston 618 (trade name, manufactured by Sanko Chemical Co., Ltd.).

Other stabilizers include hindered phenolic antioxidants, epoxy stabilizers, sulfur stabilizers and the like. As the hindered phenolic antioxidant, for example, n-octadecyl-3- (3 ′, 5 ′)
-Di-t-butyl-4-hydroxyphenyl) propionate,
2,6-di-t-butyl-4-hydroxymethylphenol, 2,
2'-methylenebis (4-methyl-6-t-butylphenol), 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) + (B) + (C). As the release agent, preferably, a silicone release agent such as methylphenyl silicone oil, an ester release agent such as pentaerythritol tetrastearate, glycerin monostearate, montanic acid wax, poly α-olefin or an olefin release agent. Agents and the like. The addition amount of these release agents is not particularly limited, but preferably, the components (A) + (B) +
0.0001 to 5 parts by weight based on 100 parts by weight in total of (C).

As the ultraviolet absorber, a conventional ultraviolet absorber for a polycarbonate resin composition 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. Benzotriazole UV absorbers include:
For example, 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] and the like. The benzotriazole-based ultraviolet absorber is commercially available from, for example, American Cyanamid Co. as UV5411.

The benzophenone type ultraviolet 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 UV absorbers is not particularly limited, but is preferably a component.
0.000 for the total of 100 parts by weight of (A) + (B) + (C)
1 to 5 parts by weight.

Further, a compatibilizer can be added to the thermoplastic resin composition according to the present invention, if necessary. 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. Examples of the compatibilizer include Modiper CH430, L430D, and L150D manufactured by NOF Corporation. It is commercially available. Polymethyl methacrylate (PMMA) can also be used as a compatibilizer. The addition amount of these compatibilizers is not particularly limited, but preferably the components (A) + (B)
0.1 to 30 parts by weight based on 100 parts by weight of + (C).

The method for producing the resin composition according to the present invention is not particularly limited, and ordinary methods can be used satisfactorily. However, a melt mixing method is generally preferred. The use of small amounts of solvents is possible but generally not necessary. Equipment includes extruders, Banbury mixers, rollers,
A kneader or the like can be given as an example. These devices can be operated batchwise or continuously. Also,
The order of mixing the components is not particularly limited.

The polycarbonate-based resin composition according to the present invention is used in applications where sliding properties and abrasion resistance are required for movable parts such as electric equipment and OA equipment, for example, bearings for chassis and CD trays. It is suitable.

[0059]

According to the present invention, hydrolysis resistance is high,
A polycarbonate resin composition having excellent moisture resistance and good flame retardancy, excellent mechanical strength, and excellent sliding properties and abrasion resistance can be obtained. In particular,
In the present invention, the styrene-based resin, the slidability improving agent, and the phosphate ester-based compound having an acid value of 1 or less are contained together with the polycarbonate-based resin in a specific amount. Excellent in dynamics (coefficient of friction) and mechanical properties. In addition, those to which an epoxy-based stabilizer is added have improved long-term hydrolysis resistance, and those to which a silicon-based composite rubber is added have excellent impact resistance.

[0060]

EXAMPLES Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. The materials used in this example are as follows. Component (A): Polycarbonate (PC) As polycarbonate, polycarbonate LEXAN of bisphenol A (trade name; manufactured by Nippon GE Plastics Co., Ltd.) LEXAN141 was used. (In methylene chloride,
0.50 dl / g intrinsic viscosity measured at 20 ° C., Mv = about 23,000
(Calculated values)) For each of the other components, the following were used.

Component (B): Styrene-based resin ABS-1: ABS resin Santac AT-07 (trade name; manufactured by Mitsui Chemicals, Inc.) ABS-2: ABS resin UX050 (trade name; Ube Saikon Co., Ltd.)
SAN) SAN Resin SR05B (trade name; Ube Sycon Co., Ltd.)
For the determination of alkali metals in component (B), after incineration of the sample,
The solution was dissolved in pure water and subjected to an ICP method and an atomic absorption method.
The measured values are shown in Table 1.

[0062]

[Table 1]

Component (C) : Slidability improving agent Polytetrafluoroethylene: LUBRON L-5 (trade name;
Component (D): Phosphate ester FR-1: Bisphenol A-diphosphate CR741 (trade name, manufactured by Daihachi Chemical Co., Ltd.), Acid value 1.6 FR-2: Bisphenol A- Diphosphate CR741 (trade name, manufactured by Daihachi Chemical Co., Ltd.), acid value 0.64 FR-3: bisphenol A-diphosphate CR741S (trade name, manufactured by Daihachi Chemical Co., Ltd.), acid value 0.03 The acid value of the phosphoric acid ester of the component (C) was measured by the following method. (Method of evaluating phosphate ester acid value) A sample is dissolved in a mixed solution of ethyl alcohol and water, and then titrated 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 grade reagent) and ion-exchanged water 9: 1
Mix by volume ratio. Reagent (2): bromthymol blue solution To 0.10 g of bromthymol blue (special grade reagent), 20 ml of 95% by volume ethyl alcohol (special grade reagent) is added, and diluted with water to 100 ml. Reagent (3): N / 10 sodium hydroxide aqueous solution (N / 10 sodium hydroxide solution titer determination) Sulfamic acid (standard reagent) was dried in a vacuum sulfuric acid desiccator, and 0.2 to 0.3 g thereof was dried. Weigh correctly in a 200 ml Erlenmeyer flask, add about 25 ml of water to dissolve, and use bromthymol blue solution as an indicator in N / 10
Titrate with sodium hydroxide solution.

Titer = (S × P) / (0.9709 × A) S: Weight of sulfamic acid (g) P: Purity of sulfamic acid (%) A: Titration of N / 10 sodium hydroxide solution ( ml) Operation (1): Put 40 ml of a mixed solution of ethyl alcohol and water into a 200 ml Erlenmeyer flask with a measuring cylinder.

Operation (2): Bromthymol blue solution 1
Add 10 ml with a female pipette and titrate until the color of the aqueous solution of N / 10 sodium hydroxide is confirmed to be bluish green. Operation (3): An additional 10 g of the sample is weighed into this 200 ml Erlenmeyer flask using an electronic precision balance, and read to one decimal place. Operation (4): Titrate with N / 10 sodium hydroxide solution until the same blue-green color as in (2) is observed.

The acid value is calculated as follows. 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) Component (E): Composite rubber-based graft copolymer: Metablen S-200
1 (trade name; manufactured by Mitsubishi Rayon Co., Ltd.) Acrylic rubber: Paraloid EXL2315 (trade name; manufactured by Kureha Chemical Industry Co., Ltd.) (used for comparative example) Component (F): 3,4-epoxy epoxy stabilizer Cyclohexylmethyl-3'-4'-epoxycyclohexanecarboxylate (Celloxide 2021
P, trade name; manufactured by Daicel Chemical Industries) Component (G): anti-dripping agent polytetrafluoroethylene (Teflon (R) 30J,
(Product name: Mitsui Dupont Fluorochemical Co., Ltd.)

[0067]

Example 1 and Comparative Example 1 Using the above-mentioned materials and the composition shown in Table 2, the twin-screw extruder was used to adjust the extrusion conditions such that the screw rotation speed was 200 rpm and the barrel set temperature was 270 to 280.
The mixture was extruded at a temperature of ° C. and cut to produce pellets. Using the pellets thus produced, a test piece was molded by an 80 t injection molding machine manufactured by Toyo Machine Metal Co., Ltd. The molding conditions were a barrel temperature of 260 ° C and a mold temperature of 60 ° C.
Set to.

Mechanical properties such as Izod impact strength and tensile strength were evaluated in accordance with standard ASTM. Flame retardancy test is U
Tests were conducted in accordance with L94 / V0, VI, VII. 5
Of these specimens were used as a bulletin 94 “combustion test for material classification” of Underwriters Laboratories Inc.
(Referred to as UL-94) at a thickness of 1/16 inch. According to this test method, the test material was UL-94V-based on the results of five materials.
It was rated in any of 0, VI and V-II.

The humidity resistance was evaluated at 100 ° C./100
% RH was evaluated by tensile strength after leaving the test piece in a high temperature and high humidity oven. In addition, slidability was evaluated according to JIS K 7125
The evaluation was performed by measuring the dynamic friction coefficient according to. The measurement of the coefficient of kinetic friction is carried out on metals and on glass fibers 20
The test was carried out in two ways for the modified PPO resin molded article with% addition.

Table 2 shows the results.

[0071]

[Table 2]

As shown in Table 2, the system using ABS having a low alkali metal content has a higher tensile strength and a higher coefficient of friction after aging under humidity, and has remarkably improved moisture resistance.

[0073]

Examples 2 and 3, Comparative Example 2
In the same manner as in Example 1, pellets were produced with the composition shown in Table 1 and evaluated. Table 3 shows the results.

[0074]

[Table 3]

As shown in Table 3, when the acid value of the phosphoric acid ester is lower than 1 and lower than 0.1, the moisture resistance can be remarkably improved.

[0076]

Example 4, Comparative Example 3 Pellets were produced using the above-described materials and having the compositions shown in Table 4 in the same manner as in Example 1, and evaluated. Table 4 shows the results.

[0077]

[Table 4]

As shown in Table 4, the addition of an epoxy stabilizer can significantly improve the moisture resistance even under severe high temperature and high humidity aging.

[0079]

Example 5 and Comparative Examples 4 and 5
In the same manner as in Example 1, pellets were produced with the composition shown in Table 1 and evaluated. Table 5 shows the results.

[0080]

[Table 5]

As shown in Table 5, the addition of the composite rubber was carried out while maintaining excellent flame retardancy, moisture resistance, slidability and mechanical strength.
This indicates that the impact resistance can be significantly improved. In each of the examples, the coefficient of kinetic friction hardly changed before and after aging, and the sample was excellent in moisture resistance.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C08L 63/00 C08L 63/00 A 101/00 101/00 F term (reference) 4J002 BB003 BC02X BC11X BD123 BD153 BN14X BN15X BN174 CD175 CD185 CG00W CG01W CG03W CP033 EL027 EW046 FD030 FD035 FD037 FD050 FD136 FD200 FD203 GM05 GQ00

Claims (5)

[Claims] (A) a polycarbonate resin having a viscosity average molecular weight in the range of 10,000 to 100,000
90 parts by weight (B) 1 to 50 parts by weight of a styrene resin, (C) 0.5 to 30 parts by weight of a slidability improver, (D) a phosphate compound having an acid value of 1 or less,
(A) A polycarbonate resin composition containing (A), (B) and (C) in an amount of 1 to 30 parts by weight based on 100 parts by weight in total. 2. A composite rubber-based graft copolymer obtained by grafting a vinyl-based monomer onto (E) a composite rubber containing a polyorganosiloxane and a polyalkyl (meth) acrylate, comprising: And (C) a total of 100 parts by weight of the polycarbonate resin composition according to claim 1 in an amount of 20 parts by weight or less. 3. The polycarbonate resin composition according to claim 1, wherein the content of the alkali metal contained in the styrene resin (B) is 1 ppm or less. 4. The polycarbonate resin composition according to claim 3, wherein the alkali metal contained in (B) the styrene resin is sodium and / or potassium. 5. The composition according to claim 1, further comprising 0.01 to 10 parts by weight of the epoxy stabilizer (F) based on 100 parts by weight of the total of (A), (B) and (C). 5. The polycarbonate resin composition according to any one of items 1 to 4.