JP2000086847A - Oil-resistant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which has excellent flowability and can give a product excellent in oil resistance, impact resistance, and heat resistance by compounding an aromatic polycarbonate with a syndiotactic styrene resin and a compatibilizer comprising a specified copolymer. SOLUTION: This composition comprises 100 pts.wt. component comprising 1-99 pts.wt. aromatic polycarbonate and 1-99 pts.wt. syndiotactic styrene resin and 0.1-100 pts.wt. compatibilizer. The compatibilizer is at least one member selected among a copolymer comprising an aromatic vinyl monomer and a monomer copolymerizable therewith, a rubbery polymer having a glass transition temperature (Tg) of -30 deg.C and a graft copolymer prepared by grafting thereonto an aromatic vinyl monomer A and a monomer B copolymerizable with monomer A, wherein monomers A and B are in the form of their respective homopolymers and/or a copolymer thereof. The copolymer as the compatibilizer has a nonuniform distribution in relation to the ratio between the monomer components constituting it.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a resin composition having excellent oil resistance. More specifically, the present invention relates to a resin composition having excellent oil resistance, impact resistance, heat resistance, and fluidity.

[0002]

2. Description of the Related Art Polycarbonate resin compositions have excellent heat resistance and impact resistance, and are therefore used in a wide variety of fields, including automobile parts, home electric parts, and OA equipment parts. Has been reached. However, the polycarbonate resin composition having excellent impact resistance has a disadvantage of being inferior in oil resistance, and has a problem that it is not possible to simultaneously obtain both high impact resistance and oil resistance.

On the other hand, in recent years, higher impact resistance has been required for polycarbonate resin compositions used in such fields. For example, an ABS resin (acrylonitrile / butadiene /
A composition to which a styrene copolymer resin) or MBS resin (methyl methacrylate / butadiene / styrene copolymer resin) is added (Japanese Patent Publication No. 38-15225); a composition to which polystyrene or rubber-modified polystyrene is added (Japanese Patent Publication No. 43-43) No. 6295), a resin composition composed of polycarbonate, polystyrene and MBS resin (methyl methacrylate / butadiene / styrene copolymer resin) (WO
80/00027), an elastomeric core-shell type compatibilizer for improving the compatibility between an impact-resistant styrene copolymer comprising an ethylenically unsaturated nitrile, an olefinic elastomer and styrene, and an aromatic polycarbonate. Resin composition [JP-A-2-228]
No. 353 (corresponding to EP-379039)]. However, although the resin composition disclosed in the above publication has a certain degree of impact strength, it has many problems in practical use because of its extremely low oil resistance.

As described above, a resin composition containing polycarbonate having both high oil resistance and high impact strength has not been known so far, and development of such a composition is strongly desired.

[0005]

SUMMARY OF THE INVENTION In view of such circumstances, an object of the present invention is to provide a resin composition which does not have the above-mentioned problems, that is, has excellent oil resistance, impact strength and heat resistance. Is what you do.

[0006]

Means for Solving the Problems The present inventors have proposed oil resistance,
As a result of intensive studies on improving impact strength and flame retardancy, surprisingly, by blending a syndiotactic styrenic resin and a specific compatibilizer with aromatic polycarbonate, fluidity, heat resistance It has been found that it is possible to dramatically improve oil resistance and impact strength while maintaining the above, and arrived at the present invention.

That is, the present invention relates to (A) 1 to 99 parts by weight of an aromatic polycarbonate, (B) 100 parts by weight of a component comprising 1 to 99 parts by weight of a syndiotactic styrene resin, and (C) a compatibilizer. A composition comprising 0.1 to 100 parts by weight, wherein (C) is a copolymer comprising (a) an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer; And (b) the glass transition temperature (Tg) is-
A rubber-like polymer having a temperature of 30 ° C. or lower, an aromatic vinyl monomer (M1) and an aromatic vinyl monomer (M
At least one compatibilizer selected from graft copolymers comprising 1) and a copolymerizable monomer (M2), wherein the monomers (M1) and (M2) are homopolymers, respectively. And / or may be copolymerized with each other, wherein the copolymer as the component (C) is non-uniform with respect to the ratio of the monomer components constituting the copolymer. Distribution, whereby the copolymer consists of copolymer molecules with different solubility parameter (SP) values, with the copolymer molecule having the largest SP value and the copolymer molecule having the smallest SP value SP value difference between 0.3 and 1.0
[(Cal / cm ³ ) ^1/2 ], and the copolymer has an average SP value of 10.6-11.2 [(cal / c 3
m ³ ) ^1/2 ].

Hereinafter, the present invention will be described in detail.

The resin composition of the present invention comprises (A) an aromatic polycarbonate, (B) a syndiotactic styrene resin, (C) a compatibilizer, and if necessary, (D) polyphenylene ether, and (E) Amorphous styrenic resin,
(F) It contains a thermoplastic elastomer.

The above component (A) is a component that forms the main component of the resin composition of the present invention together with the component (B) and plays a role in maintaining the strength of a molded product. The component (B) is a component for imparting oil resistance to the component (A). The component (C)
It is a component for compatibilizing the component (A) and the component (B). The component (D) is a component for imparting heat resistance. The components (E) and (F) are components for imparting fluidity and further impact strength.

In the resin composition of the present invention, (A)
It is important that (B) and (B) are used together, and excellent oil resistance and impact strength are exhibited.

Next, the impact strength is further improved by using the above-mentioned specific compatibilizer (C).

One example of the copolymer useful as the compatibilizer (C) is a non-uniform distribution with respect to the ratio of specific monomer components constituting the copolymer (hereinafter referred to as “copolymer composition”). Acrylonitrile-styrene copolymer (AS resin) having "distribution"). However, the conventional AS resin has a uniform copolymer composition and does not have a copolymer composition distribution. According to JP-A-51-119789, the reason for this is that "unevenness in the polymerization composition not only impairs the mechanical properties and stability of the obtained polymer, but also causes the resin to be colored." It is mentioned that. As described above, the commercially available AS resin has a uniform copolymer composition and is different from the component (C) defined in the present invention. Even when such a commercially available AS resin is used as the compatibilizer (C) for the aromatic polycarbonate and the styrene-based thermoplastic elastomer used in the present invention, both high impact strength and excellent melt fluidity are achieved at the same time. Can not do.

Further, in the present invention, the copolymer as the component (C) has a non-uniform distribution with respect to the ratio of the monomer components constituting the copolymer, whereby the copolymer is dissolved. SP value difference between the copolymer molecule having the largest SP value and the copolymer molecule having the smallest SP value (ΔS
P value) is 0.3 to 1.0 [(cal / cm ³ ) ^1/2 ], and the average SP value of the copolymer is 10.6 to 11.2.
[(Cal / cm ³ ) ^1/2 ] is essential, preferably 10.6 to 10.9, more preferably 10.7.
１10.8.

When the ΔSP value is 0.3 to 1.0 [(cal /
cm ^{3) 1/2} When it is out of range], no high impact strength. The ΔSP value is preferably from 0.3 to 0.8 [(c
al / cm ^{3) 1/2],} more preferably 0.4 to 0.6
[(Cal / cm ³ ) ^1/2 ]. (C) Average component S
If the P value is less than 10.6, the compatibility with the component (A) decreases, while if the average SP value exceeds 11.2,
The compatibility with the component (B) decreases. The SP value of the component (A) is higher than the SP value of the component (B). If the SP values of the component (A) and the component (B) are different from each other, the compatibility between the components decreases, but the SP value of the compatibilizer (C) has a distribution. The copolymer molecule having the maximum SP value of (A) is compatible with the component (A), while the copolymer molecule having the minimum SP value is compatible with the component (B), and as a result, the component (A) And component (B) were found to be compatible with each other, and the present invention was completed.

In the present invention, the aromatic polycarbonate used as the component (A) can be selected from aromatic homopolycarbonates and aromatic copolycarbonates. The production method includes a phosgene method in which phosgene is blown into a bifunctional phenolic compound in the presence of a caustic alkali and a solvent, or a transesterification method in which a bifunctional phenolic compound is transesterified with diethyl carbonate in the presence of a catalyst. Can be mentioned. The aromatic polycarbonate preferably has a viscosity average molecular weight of 10,000 to 100,000. Here, the bifunctional phenolic compound is
2,2′-bis (4-hydroxyphenyl) propane,
2,2′-bis (4-hydroxy-3,5-dimethylphenyl) propane, bis (4-hydroxyphenyl) methane, 1,1′-bis (4-hydroxyphenyl) ethane, 2,2′-bis ( 4-hydroxyphenyl) butane, 2,2′-bis (4-hydroxy-3,5-diphenyl) butane, 2,2′-bis (4-hydroxy-3,
5-dipropylphenyl) propane, 1,1′-bis (4-hydroxyphenyl) cyclohexane, 1-phenyl-1,1′-bis (4-hydroxyphenyl) ethane, and especially 2,2′-bis (4-Hydroxyphenyl) propane [bisphenol A] is preferred. In the present invention, the bifunctional phenolic compounds may be used alone or in combination.

The syndiotactic styrene resin used as the component (B) in the present invention is a crystalline styrene polymer, and has excellent heat resistance and chemical resistance as compared with ordinary amorphous atactic polystyrene. Although it has features, it is brittle and has a disadvantage of poor impact resistance. Syndiotactic structure means that the stereochemical structure has a syndiotactic structure, that is, a steric structure in which phenyl groups, which are side chains with respect to a polymer main chain formed from carbon-carbon bonds, are alternately located in opposite directions. Meaning, the tacticity is quantified by nuclear magnetic resonance (13C-NMR) using isotope carbon. Tacticity measured by this method can be represented by the existence ratio of a plurality of continuous structural units, for example, a dyad for two, a triad for three, and a pentad for five.

In the present invention, (B) is generally a polystyrene or poly (alkylstyrene) having a syndiotacticity of 75% or more, preferably 85% or more in dyad, or 30% or more, preferably 50% or more in pentad. , Poly (halogenated styrene), poly (alkoxystyrene), poly (vinylbenzoic acid), and mixtures thereof, or copolymers containing these as the main components. Examples of poly (alkylstyrene) include poly (methylstyrene), poly (ethylstyrene), poly (isopropylstyrene), poly (tertiary butylstyrene), and poly (halogenated styrene) include poly (chlorostyrene). ), Poly (bromostyrene), poly (fluorostyrene) and the like. Examples of poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene). Of these, polystyrene and poly (p-
Methylstyrene), poly (m-methylstyrene), poly (p-tert-butylstyrene), poly (p-chlorostyrene), poly (m-chlorostyrene), poly (p
-Fluorostyrene), and a copolymer of styrene and p-methylstyrene.

The weight average molecular weight of (B) in the present invention is 5,000 or more, preferably 10,000 to 2,000.
The number average molecular weight is 2,500 or more, preferably 5,000 to 1,000,000.

The above (B) can be produced by a known production method. For example, in the presence of a catalyst comprising a titanium compound and an alkylaluminoxane in an inert hydrocarbon solvent or in the absence of a solvent, a styrene monomer and / or It can be produced by polymerizing a substituted styrene monomer.

[0021] There are various as titanium compound used as the catalyst, but is preferably general formula _{TiR1 a R2 b R3 c X1 4-} (a + b + c) or _{TiR1 d R2 e X1 3- (d} + e) (Wherein R1, R2 and R3 are each hydrogen and have 1 to 1 carbon atoms
It represents an alkyl group of 20, an alkoxy group having 1 to 20 carbon atoms, a cyclopentadienyl group, a substituted cyclopentadienyl group or an indenyl group, and X1 represents a halogen.
a, b, and c each represent an integer of 0 to 4, and d and e each represent an integer of 0 to 3. ) Is at least one compound selected from the group consisting of titanium compounds and titanium chelate compounds. As the above compound, a compound which forms a complex with an ester or an ether may be used.

On the other hand, the alkylaluminoxane constituting the main component of the catalyst together with the titanium compound is obtained by contacting various organic aluminum compounds with a condensing agent. As the organoaluminum compound, various compounds can be used, but usually, a trialkylaluminum is used. Examples of the trialkylaluminum include trimethylaluminum, triethylaluminum, tri-i-butylaluminum and the like. One or more of these organoaluminum compounds may be used together with the condensing agent. As the condensing agent, water is typically mentioned, but any other agent that causes a condensation reaction of the organoaluminum compound may be used. Further, another organometallic compound may be mixed, or an alkylaluminoxane may be adsorbed or carried on an inorganic substance.

The mixing ratio of the titanium compound and the alkylaluminoxane varies depending on the type of each component, the type of the raw material styrene, the type of the styrene derivative, and other conditions, and cannot be uniquely defined. Ratio of aluminum to titanium in the titanium compound, ie, aluminum / titanium (molar ratio) is 1
10 to 10 ^6, preferably 10 to 10 ⁶ .

In the present invention, styrene or a derivative of styrene is polymerized in the presence of the main component catalyst.
The polymerization may be performed in a bulk form, or may be performed in an alicyclic hydrocarbon such as cyclohexane or an aliphatic hydrocarbon such as pentane, hexane or heptane, or in an aromatic hydrocarbon solvent such as benzene, toluene or xylene. Although the polymerization temperature is not particularly limited, it is usually carried out at 0 to 120 ° C.

After the polymerization, if necessary, a styrene-based polymer having extremely high syndiotacticity can be obtained by deashing with an acid or alkali washing solution, followed by washing and drying.

In the present invention, 1 comprising (A) and (B)
The amount of (A) in 00 parts by weight is from 1 to 99 parts by weight,
Preferably 10 to 80 parts by weight, more preferably 20 to 80 parts by weight.
70 parts by weight, most preferably 30 to 60 parts by weight.

The compatibilizer used as the component (C) in the present invention includes (a) a copolymer comprising an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer; A) a rubbery polymer having a glass transition temperature (Tg) of -30 ° C. or lower, and an aromatic vinyl monomer (M1) grafted thereon;
And a graft copolymer comprising an aromatic vinyl monomer (M1) and a copolymerizable monomer (M2). Examples of the monomer copolymerizable with the aromatic vinyl monomer include, for example, an unsaturated nitrile monomer, an acrylate monomer, a methacrylate ester monomer, an acrylate monomer, and a methacrylic acid monomer. body,
One or two or more monomers selected from α, β-unsaturated carboxylic anhydride monomers and maleimide monomers can be mentioned.

The copolymer (a) of the compatibilizer (C) is
Preferably 98 to 50% by weight, more preferably 97 to 7% by weight.
5% by weight, most preferably 97-88% by weight of aromatic vinyl monomer, preferably 2-50% by weight, more preferably 3-25% by weight, most preferably 3-12% by weight
Is a copolymer comprising the aromatic vinyl monomer and a copolymerizable monomer.

The aromatic vinyl monomer includes styrene, α-methylstyrene, p-methylstyrene, p-methylstyrene,
Chlorostyrene, p-bromostyrene, 2,4,5-tribromostyrene and the like can be mentioned. Styrene is most preferred, but styrene and other aromatic vinyl monomers described above may be combined. Specific examples of the unsaturated nitrile monomer which is a monomer copolymerizable with the aromatic vinyl monomer include acrylonitrile and methacrylonitrile, and specific examples of the acrylate monomer Examples are acrylates having an alkyl group having 1 to 8 carbon atoms, such as methyl acrylate and butyl acrylate, and specific examples of methacrylate monomers include those having carbon atoms such as methyl methacrylate. Methacrylic acid esters having 1 to 8 alkyl groups,
Specific examples of the α, β-unsaturated carboxylic acid anhydride monomer include maleic anhydride and itaconic anhydride. Specific examples of the maleimide monomer include maleimide and N-methylmaleimide. , N-phenylmaleimide and the like. Among them, acrylonitrile is most preferable as the monomer copolymerizable with the aromatic vinyl monomer.

The solution viscosity (a 10% by weight copolymer solution in methyl ethyl ketone at a measurement temperature of 25 ° C.) as an index of the molecular weight of the copolymers (a) and (b) used as the compatibilizer (C) in the present invention is as follows: It is preferably 2 to 10 cP (centipoise). If the solution viscosity is less than 2 cP, the impact strength decreases, while if it exceeds 10 cP, the melt fluidity decreases.

The copolymer (a) used as the compatibilizer (C) in the present invention may be prepared by a conventional solution polymerization, bulk polymerization, suspension polymerization,
It can be produced by a method such as emulsion polymerization. The solution viscosity of the copolymer can be controlled by the polymerization temperature, the type and amount of the initiator, and the amount of the chain transfer agent. Further, the control of the copolymer composition can be performed by the charged monomer composition. The control of the copolymer composition distribution can be performed by selecting a reactor. That is, a complete mixing type reactor is used to narrow the composition distribution, and a plug flow type reactor is used to widen the composition distribution. It is also possible to control the composition distribution by combining a plurality of copolymers having a narrow composition distribution.

The graft copolymer (b) used as the compatibilizer (C) in the present invention is preferably 5 to 80% by weight of a rubbery polymer having a glass transition temperature (Tg) of -30 ° C. or lower.
And the monomer 9 shown in the description of the copolymer (a)
5 to 20% by weight of a graft copolymer. This graft copolymer is composed of a matrix resin in which a rubber-like polymer is dispersed in a particle form, and has a rubber particle diameter of 0.5 to 4.0 μm.
m is preferable, and 0.8 to 1.5 μm is particularly preferable.

Examples of the rubbery polymer include diene rubbers such as polybutadiene, poly (styrene-butadiene), and poly (acrylonitrile-butadiene); saturated rubber obtained by hydrogenating the diene rubber; isoprene rubber; chloroprene rubber; and polyacrylic acid. Acrylic rubber such as butyl and ethylene-propylene-diene monomer terpolymer (EPDM) can be exemplified. Particularly, a diene rubber is preferable. The rubbery polymer in the component (C) needs to have a glass transition temperature (Tg) of −30 ° C. or lower, and if it is higher than −30 ° C., the impact resistance decreases.

The graft copolymer (b) used as the compatibilizer (C) in the present invention can be produced by a usual method such as solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, etc. A bulk polymerization method is preferred in which a uniform polymerization stock solution comprising a polymer, a monomer mixture, and a polymerization solvent is supplied to a continuous multistage bulk polymerization reactor equipped with a stirrer, and the polymerization and devolatilization are continuously performed. Graft copolymer (b) by bulk polymerization
In the case of preparing a compound, the control of the solution viscosity, which is an index of the molecular weight, can be performed by the polymerization temperature, the type and amount of the initiator, and the amount of the chain transfer agent. The control of the copolymer composition is performed by the charged monomer composition, and the control of the copolymer composition distribution is
It can be carried out by the method described in the description of the copolymer (a). The rubber particle diameter is controlled by the number of rotations under stirring, and the size of the rubber particles is increased by increasing the number of rotations, while the size of the particles is increased by decreasing the number of rotations.

The compatibilizer (C) used in the present invention
In both the copolymer (a) and the graft copolymer (b), the aromatic vinyl monomer and the monomer copolymerizable with the aromatic vinyl monomer form a random copolymer. May be formed, a block copolymer may be formed, or a graft copolymer may be formed.

In the present invention, the amount of (C) is (A)
0.1 to 100 parts by weight per 100 parts by weight of (B)
Parts by weight, preferably 0.1 to 50 parts by weight, more preferably 1 to 30 parts by weight, most preferably 2 to 30 parts by weight.
-20 parts by weight.

In the present invention, (D) a polyphenylene ether can be blended if necessary, and is a homopolymer and / or a copolymer comprising a bonding unit represented by the following formula.

[0038]

Embedded image

However, R ¹ , R ² , R ³ and R ⁴ are each selected from the group consisting of hydrogen, hydrocarbon and substituted hydrocarbon groups, and may be the same or different.

Specific examples of the polyphenylene ether include poly (2,6-dimethyl-1,4-phenylene ether), 2,6-dimethylphenol and 2,3,3-dimethylphenol.
A copolymer with 6-trimethylphenol is preferred,
Among them, poly (2,6-dimethyl-1,4-phenylene ether) is preferred. The method for producing the polyphenylene ether is not particularly limited. For example, a complex of a cuprous salt and an amine according to the method described in US Pat. No. 3,306,874 is used as a catalyst, and for example, 2,6-xylenol Can be easily produced by oxidative polymerization, and in addition, US Pat. No. 3,306,87
No. 5, U.S. Pat. No. 3,257,357,
U.S. Pat. No. 3,257,358 and JP-B-52
It can be easily produced by the methods described in JP-A-17880 and JP-A-50-51197. Reduced viscosity ηsp / c of the polyphenylene ether used in the present invention
(0.5 g / dl, chloroform solution, measured at 30 ° C.)
Is preferably in the range of 0.20 to 0.70 dl / g, and more preferably in the range of 0.30 to 0.60 dl / g. Reduced viscosity η of polyphenylene ether
Means for satisfying the above requirements regarding sp / c include adjustment of the amount of a catalyst in the production of the polyphenylene ether.

In the present invention, the amount of (D) is (A)
1 to 500 parts by weight, preferably 1 to 300 parts by weight, more preferably 5 to 200 parts by weight, and most preferably 10 to 100 parts by weight with respect to 100 parts by weight of (B).
100 parts by weight.

In the present invention, (E) an amorphous styrene resin can be blended if necessary, and examples thereof include a rubber-modified styrene resin and / or a non-rubber-modified styrene resin. The amorphous rubber-modified styrenic resin refers to a polymer in which a rubbery polymer is dispersed in a matrix in a matrix made of a vinyl aromatic polymer, and an aromatic polymer is present in the presence of the rubbery polymer. A vinyl monomer and, if necessary, a vinyl monomer copolymerizable therewith are added to obtain a monomer mixture by a known polymerization method such as bulk polymerization, emulsion polymerization and suspension polymerization.

Examples of such resins include impact-resistant polystyrene, ABS resin (acrylonitrile-butadiene-styrene copolymer), AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), and AES resin (acrylonitrile-ethylene copolymer). Propylene rubber-styrene copolymer).

Here, the rubber-like polymer preferably has a glass transition temperature (Tg) of -30 ° C. or lower.
If it exceeds 30 ° C., the impact resistance tends to decrease.

Examples of such rubbery polymers include diene rubbers such as polybutadiene, poly (styrene-butadiene) and poly (acrylonitrile-butadiene), and saturated rubbers obtained by hydrogenating the diene rubbers, isoprene rubbers, chloroprene rubbers. , An acrylic rubber such as polybutyl acrylate, and an ethylene-propylene-diene monomer terpolymer (EPDM). A diene rubber is particularly preferred.

The aromatic vinyl monomer as an essential component in the graft-polymerizable monomer mixture to be polymerized in the presence of the rubbery polymer is, for example, styrene, α-methylstyrene, paramethylstyrene, or the like. Yes, styrene is most preferred, but other aromatic vinyl monomers described above may be copolymerized mainly with styrene.

Further, if necessary as the component (E),
One or more monomer components copolymerizable with the aromatic vinyl monomer can be introduced. When it is necessary to increase oil resistance, unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile can be used.

When it is necessary to lower the melt viscosity during blending, an acrylate comprising an alkyl group having 1 to 8 carbon atoms can be used. Further, when it is necessary to further increase the heat resistance of the resin composition, α-methylstyrene, acrylic acid, methacrylic acid,
Monomers such as maleic anhydride and N-substituted maleimide may be copolymerized. The content of the vinyl monomer copolymerizable with the vinyl aromatic monomer in the monomer mixture is from 0 to 40.
% By weight.

The rubbery polymer in the rubber-modified styrenic resin is preferably 5 to 80% by weight, particularly preferably 1 to 80% by weight.
0 to 50% by weight, a graft-polymerizable monomer mixture,
Preferably 95 to 20% by weight, more preferably 90 to 5% by weight.
It is in the range of 0% by weight. Within this range, the balance between impact resistance and rigidity of the target resin composition is improved. Further, the rubber particle diameter of the styrene-based polymer is 0.1 to 5.0.
μm is preferred, and 0.2 to 3.0 μm is particularly preferred. Within the above range, impact resistance is particularly improved.

The reduced viscosity ηsp / c of the resin portion, which is a measure of the molecular weight of the rubber-modified styrenic resin (0.5 g / dl,
30 ° C. measurement: toluene solution when the matrix resin is polystyrene, methyl ethyl ketone when the matrix resin is an unsaturated nitrile-aromatic vinyl copolymer)
It is preferably in the range of 0.30 to 0.80 dl / g, and more preferably in the range of 0.40 to 0.60 dl / g. Reduced viscosity ηsp of rubber-modified styrenic resin
Means for satisfying the above requirement regarding / c include adjustment of the amount of polymerization initiator, polymerization temperature, and amount of chain transfer agent.

In the present invention, the amount of (E) is (A)
1 to 500 parts by weight, preferably 1 to 300 parts by weight, more preferably 5 to 200 parts by weight, and most preferably 10 to 100 parts by weight with respect to 100 parts by weight of (B).
100 parts by weight.

In the present invention, if necessary, (F) a styrene-based thermoplastic elastomer can be blended, and the block copolymer comprising an aromatic vinyl unit and a conjugated diene unit, or the conjugated diene unit portion is partially Is a hydrogenated styrene-based thermoplastic elastomer, particularly from the viewpoint of thermal stability.

The aromatic vinyl monomer constituting the block copolymer is, for example, styrene, α-methylstyrene, paramethylstyrene, p-chlorostyrene, p-bromostyrene, 2,4,5-tribromobenzene. Styrene is the most preferable, and styrene is most preferable. However, other aromatic vinyl monomers described above may be copolymerized mainly with styrene.

Further, examples of the conjugated diene monomer constituting the block copolymer include 1,3-butadiene and isoprene.

In the block structure of the block copolymer, a polymer block composed of an aromatic vinyl unit is represented by S, and a polymer block composed of a conjugated diene and / or a partially hydrogenated unit thereof is represented by B. When displaying with,
SB, S (BS) n (where n is an integer of 1 to 3), S
(BSB) n, where n is an integer of 1 to 2
A block copolymer or (SB) nX (where n is 3 to 6)
Integer. X is a residue of a coupling agent such as silicon tetrachloride, tin tetrachloride, and a polyepoxy compound. It is preferable to use a star-shaped (star) block copolymer having a B-part as a bonding center. Above all, SB type 2 and SBS 3
And SBSB type 4 linear block copolymers are preferred.

The proportion of the aromatic vinyl monomer in the above block copolymer is 1 to 99% by weight, preferably 10 to 99% by weight.
It is from 90 to 90% by weight, more preferably from 20 to 80%, and most preferably from 30 to 70%. Within the above range, excellent impact strength is exhibited.

In the present invention, the most preferred hydrogenated styrene-based thermoplastic elastomer in (F) is obtained by hydrogenating the above-mentioned block copolymer comprising an aromatic vinyl unit and a conjugated diene unit by a known method. can get. For example, FLRamp, etal, J.Amer.Chem.Soc., 83,4672
(1961) A method for hydrogenation using a triisobutylborane catalyst described in Hung Yu Chen, J. Polym. Sci. Polym. Lette
r Ed., 15,271 (1977), a method of hydrogenation using toluenesulfonyl hydrazide, or Japanese Patent Publication No. Sho 42
No. -8704, a method of hydrogenating using an organic cobalt-organoaluminum-based catalyst or an organic nickel-organoaluminum-based catalyst, selectively hydrogenating a 1,2-vinyl bond prior to a 1,4-bond JP-A-52-41890 using a catalyst that can be used, or JP-A-59-133203 and JP-A-60-220147 using a catalyst that can be hydrogenated under mild conditions of low temperature and low pressure. This is a method disclosed in Japanese Patent Publication No.

In the present invention, the amount of (F) is (A)
1 to 500 parts by weight, preferably 1 to 300 parts by weight, more preferably 5 to 200 parts by weight, and most preferably 10 to 100 parts by weight with respect to 100 parts by weight of (B).
100 parts by weight.

In the present invention, (A), (B) and (C)
(D) For the resin components other than (E) and (F), for example, a thermoplastic resin such as a polyamide-based, polyester-based, polyphenylene sulfide-based, or polymethacrylate-based resin alone or a mixture of two or more kinds thereof can be used. .

The resin composition of the present invention may contain, if necessary, one or more selected from saturated higher aliphatic carboxylic acids or metal salts thereof, carboxylic acid ester waxes, organosiloxane waxes, polyolefin waxes, and polycaprolactone. Two or more release agents (G) can be blended.

The amount of (G) is 10 (A) and (B).
With respect to 0 parts by weight, preferably 0.01 to 5 parts by weight, more preferably 0.1 to 5 parts by weight, most preferably,
0.3 to 1 part by weight.

Among the above (G), one or more compounds selected from saturated higher aliphatic carboxylic acids and metal salts thereof are preferred.

The carboxylic acid of the saturated higher fatty acid is preferably a straight-chain saturated monocarboxylic acid having 12 to 42 carbon atoms. For example, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, montanic acid and the like can be mentioned. Examples of the metal of these metal salts include lithium, sodium, potassium, magnesium, calcium, aluminum, zinc and the like, and particularly preferred are zinc stearate, magnesium stearate, calcium stearate, and aluminum stearate.

In the present invention, if necessary, a copolymer resin comprising an aromatic vinyl unit and an acrylate unit, an aliphatic hydrocarbon, a higher fatty acid, a higher fatty acid ester, a higher fatty acid amide, a higher aliphatic alcohol, or a metal One or two or more fluidity improvers (H) selected from soaps can be blended.

The amount of (H) is determined by dividing (A) and (B) by 10
0 parts by weight, preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, most preferably,
1 to 5 parts by weight.

The aromatic vinyl unit of the copolymer resin as (H) is, for example, styrene, α-methylstyrene, paramethylstyrene, p-chlorostyrene, p-bromostyrene, 2,4,5-tribromostyrene And the like, and styrene is most preferred, but the above-mentioned other aromatic vinyl monomer may be copolymerized mainly with styrene. The acrylate unit is an acrylate ester having an alkyl group having 1 to 8 carbon atoms, such as methyl acrylate and butyl acrylate.

Here, the content of the acrylate unit in the copolymer resin is preferably 3 to 40% by weight.
5-20% by weight is preferred. Also, the solution viscosity (MEK of 10% by weight of resin) which is an index of the molecular weight of the copolymer resin is used.
(Solution, measurement temperature 25 ° C.) is preferably 2 to 10 cP (centipoise). If the solution viscosity is less than 2 cP, the impact strength decreases, while if it exceeds 10 cP, the effect of improving the fluidity decreases.

The aliphatic hydrocarbon-based processing aid as (H) includes liquid paraffin, natural paraffin, microwax, polyolefin wax, synthetic paraffin, and partial oxides thereof, or fluorides and chlorides.

The higher fatty acids as (H) include saturated fatty acids other than those described in the section of the release agent (G), and unsaturated fatty acids such as ricinoleic acid, ricinberidic acid and 9-oxy-12-octadecenoic acid. It is.

The higher fatty acid ester as (H) may be a monohydric alcohol ester of a fatty acid such as methyl phenylstearate or butyl phenylstearate, or a monohydric alcohol ester of a polybasic acid such as a diester stearate of diphenylstearyl phthalate. And sorbitan monolaurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquiolate, sorbitan triolate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate , Sorbitan esters such as polyoxyethylene sorbitan monooleate, monoglyceride stearate,
Fatty acid esters of glycerin monomers such as oleic acid monoglyceride, capric acid monoglyceride, behenic acid monoglyceride, polyglycerin fatty acid esters such as polyglycerin stearate, polyglycerin oleate, polyglycerin laurate, and polyoxyethylene mono Fatty acid esters having a polyalkylene ether unit such as laurate, polyoxyethylene monostearate and polyoxyethylene monooleate; and neopentyl polyol fatty acid esters such as neopentyl polyol distearate.

Higher fatty acid amides as (H) include monoamides of saturated fatty acids such as phenylstearic acid amide, methylol stearic acid amide, methylol behenic acid amide, coconut oil fatty acid diethanolamide, lauric acid diethanolamide, and coconut oil fatty acid diethanolamide. And N, N′-substituted monoamides such as oleic acid diethanolamide and the like.
Saturated fatty acid bisamides such as (hydroxyphenyl) stearamide, ethylenebis (stearic acid amide), ethylenebis (12-hydroxyphenyl) stearic acid amide, hexamethylenebis (12-hydroxyphenyl) stearic acid amide, and m-xylylenebis (12
-Hydroxyphenyl) stearic acid amide and the like.

The higher aliphatic alcohol as (H) is
Monohydric alcohols such as stearyl alcohol and cetyl alcohol; polyhydric alcohols such as sorbitol and mannitol; and polyoxyethylene dodecylamine and polyoxyethylene bactadecylamine. Allylated ethers having an alkylene ether unit, polyoxyethylene lauryl ether, polyoxyethylene tridodecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene alkyl ether such as polyoxyethylene oleyl ether, polyoxyethylene Polyoxyethylene alkyl phenyl ether such as ethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether;
Polyepichlorohydrin ether, polyoxyethylene bisphenol A ether, polyoxyethylene ethylene glycol, polyoxypropylene bisphenol A
It is a dihydric alcohol having a polyalkylene ether unit such as ether or polyoxyethylene polyoxypropylene glycol ether.

The metal soap as (H) is a metal salt of a higher fatty acid such as stearic acid described above, such as barium, calcium, zinc, aluminum or magnesium.

In the present invention, if necessary, a thermoplastic elastomer (I) other than a styrene-based thermoplastic elastomer (I) can be blended. For example, polyolefin-based, polyester-based, polyurethane-based, 1,2-polybutadiene-based, polyvinyl chloride System.

The amount of (I) is 10 (A) and (B).
0 parts by weight, preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight, most preferably 2 to 10 parts by weight.
Parts by weight.

In the present invention, when light resistance is required, if necessary, an ultraviolet absorber, a hindered amine light stabilizer, an antioxidant, an active species scavenger, a light shielding agent, a metal deactivator, or One or more light resistance improvers (J) selected from quenchers can be blended.

The amount of (J) is calculated by dividing (A) and (B) by 10
0 to 100 parts by weight, preferably 0.05 to 20 parts by weight,
More preferably, it is 0.1 to 10 parts by weight, most preferably 0.1 to 5 parts by weight.

The ultraviolet absorber as (J) absorbs light energy and undergoes intramolecular proton transfer to become a keto-type molecule (benzophenone or benzotriazole) or cis-trans isomerization. (Cyanoacrylate-based) is a component for releasing and rendering harmless as thermal energy. Specific examples are 2,
4-dihydroxybenzophenone, 2-hydroxy-4
-Methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5'-methylenebis (2-
2-hydroxybenzophenones such as hydroxy-4-methoxybenzophenone) and 2- (2′-hydroxy-
5′-methylphenyl) benzotriazole, 2-
(2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′,
5′-di-t-butylphenyl) benzotriazole,
2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2-
(2′-hydroxy-3′-t-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) benzotriazole, 2,2′- 2- (2 ′) such as methylenebis (4-t-octyl-6-benzotriazolyl) phenol
-Hydroxyphenyl) benzotriazoles, phenyl salicylate, resorcinol monobenzoate,
2,4-di-t-butylphenyl-3 ′, 5′-di-t
Benzoates such as -butyl-4'-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2-ethyl-2'-ethoxyoxanilide, 2-ethoxy-4'-dodecyl Substituted oxanilides such as oxanilide; and cyanoacrylates such as ethyl-α-cyano-β, β-diphenylacrylate and methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate.

The hindered amine light stabilizer as (J) decomposes hydroperoxide generated by light energy to form stable NO—radicals, N—OR,
A component for generating and stabilizing -OH. Specific examples thereof include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-
4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis (2,2,
6,6-tetramethyl-4-piperidyl sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6
-Pentamethyl-4-piperidyl) -1,2,3,4-
Butanetetracarboxylate, bis (1,2,2,
6,6-pentamethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl -2- (3 ', 5'-di-t-
Butyl-4-hydroxybenzyl) malonate, 1-
(2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4
-Piperidylamino) hexane / dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4)
-Piperidylamino) hexane / 2,4-dichloro-6
-T-octylamino-s-triazine polycondensate, 1,
6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate and the like.

The antioxidant as the component (J) stabilizes peroxide radicals such as hydroperoxy radicals generated during thermoforming or light exposure, and decomposes the generated peroxides such as hydroperoxides. It is a component for performing. Examples are hindered phenolic antioxidants and peroxide decomposers. The former is a radical chain inhibitor, and the latter decomposes the peroxide generated in the system into more stable alcohols to prevent autoxidation.

Specific examples of the hindered phenolic antioxidant as the antioxidant include 2,6-di-t-butyl-4-methylphenol, stylated phenol, n-octadecyl-3- (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionate, 2,2 '
-Methylenebis (4-methyl-6-t-butylphenol), 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-
Di-t-pentylphenyl) ethyl] -4,6-di-t
-Pentylphenyl acrylate, 4,4'-butylidenebis (3-methyl-6-t-butylphenol),
4,4'-thiobis (3-methyl-6-t-butylphenol), alkylated bisphenol, tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 3 , 9-
Bis [2- [3- (3-t-butyl-4-hydroxy-
5-methylphenyl) -propionyloxy] -1,1-
Dimethylethyl] -2,4,8,10-tetraoxyspiro [5.5] undecane.

Specific examples of the peroxide decomposer as the antioxidant include trisnonylphenyl phosphite,
Triphenyl phosphite, tris (2,4-di-t-
Organic phosphorus peroxide decomposers such as butylphenyl) phosphite or dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipro Pionate,
It is an organic sulfur peroxide decomposer such as pentaerythrityltetrakis (3-laurylthiopropionate), ditridecyl-3,3'-thiodipropionate, 2-mercaptobenzimidazole and the like.

The active species scavenger as (J) is a component for scavenging free halogen generated during thermoforming or light exposure. Specific examples thereof include basic metal salts such as calcium stearate and zinc stearate, hydrotalcite, zeolite, magnesium oxide, organotin compounds, and organic epoxy compounds.

The hydrotalcite as the active species trapping agent is a hydrated basic carbonate or an anhydrous basic carbonate such as magnesium, calcium, zinc, aluminum and bismuth, and includes natural products and synthetic products. As a natural product,
One having a structure of Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O is mentioned. In addition, as a synthetic product, Mg _0.7 Al _0.3 (O
H) ₂ (CO ₃ ) _0.15 · 0.54 H ₂ O, Mg _4.5 Al
₂ (OH) ₁₃ CO ₃ · 3.5 H ₂ O, Mg _4.2 Al ₂ (O
_{H) 12.4 CO 3, Zn 6} Al 2 (OH) 16 CO 3 · 4H
₂ O, Ca ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O, Mg ₁₄ B
i ₂ (OH) _29.6 · 4.2H ₂ O and the like.

As the zeolite, Na ₂ O.Al ₂
A-type zeolite represented by O ₃ · 2SiO ₂ · XH ₂ O,
Alternatively, zeolite substituted with a metal containing at least one metal selected from Group II and Group IV metals of the periodic table can be used. And as a substitution metal, it is Mg, Ca, Zn, Sr, Ba, Zr, Sn, etc., and especially Ca, Zn, Ba is preferred.

The organic epoxy compound as the active species-capturing agent includes epoxidized soybean oil, tris (epoxypropyl) isocyanurate, hydroquinone diglycidyl ether, terephthalic acid diglycidyl ester, 4,4 ′
-Sulfobisphenol / polyglycidyl ether, N
-Glycidyl phthalimide or hydrogenated bisphenol A glycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexylspiro [5,5] -3,4-epoxy ) Cyclohexane-m-
Dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, 4-vinylepoxycyclohexane, bis (3,4
-Epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-
3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene epoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,4- Epoxy cyclohexane carboxylate), dioctyl epoxy hexahydrophthalate, di-epoxy hexahydrophthalate
Alicyclic epoxy compounds such as 2-ethylhexyl;

The light-shielding agent (J) is a component for preventing light from reaching the inside of the polymer. Specific examples thereof include rutile-type titanium oxide (TiO ₂ ), zinc oxide (ZnO), chromium oxide (Cr ₂ O ₃ ), and cerium oxide (CeO ₂ ).

The metal deactivator (J) is a component for forming a chelate compound and inactivating heavy metal ions in the resin in the chelate compound. Specific examples thereof include an acid amine derivative, benzotriazole, and derivatives thereof.

The quencher as (J) is a component for inactivating functional groups such as photo-excited hydroperoxide and carbonyl group in the polymer by energy transfer, and organic nickel and the like are known. .

Further, the composition of the present invention may contain an inorganic filler and a plasticizer to such an extent that its characteristics are not impaired. Examples of the inorganic filler used here include calcium carbonate, magnesium carbonate, silica, carbon black, glass fiber, titanium oxide, clay, mica, talc, magnesium hydroxide, and aluminum hydroxide. As the plasticizer, for example, polyethylene glycol, dioctyl phthalate (DO)
And phthalic acid esters such as P). In addition, other additives such as a flame retardant, an organic / inorganic pigment, a heat stabilizer, an antioxidant, an antiblocking agent, a foaming agent, an antistatic agent, and an antibacterial agent are also preferably used.

In the present invention, particularly preferred examples of the resin composition include the following.

(A) Aromatic polycarbonates 1 to 9
9 parts by weight, (B) syndiotactic styrene resin
100 parts by weight of a component comprising 1 to 99 parts by weight, (C) 0.1 to 100 parts by weight of a copolymer comprising an aromatic vinyl monomer and an unsaturated nitrile monomer, which satisfies the requirements of the present invention; (D) 1 to 500 parts by weight of polyphenylene ether, (E) 1 to 500 parts by weight of rubber-modified styrene resin, (F) hydrogenated styrene thermoplastic elastomer
1 to 500 parts by weight.

In the case of the above composition, the balance characteristics of oil resistance, moldability (flowability), impact resistance and heat resistance are excellent.

The composition thus obtained is, for example,
It is possible to perform continuous molding for a long time using an injection molding machine or an extrusion molding machine, and the obtained molded product has oil resistance,
Excellent fluidity, heat resistance and impact resistance.

[0095]

The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited thereto.

In Examples and Comparative Examples, various measurements were performed using the following measuring methods or measuring machines.

(1) Analysis of Resin Composition 5 g of the resin composition was dissolved in 100 ml of methyl ethyl ketone and separated using an ultracentrifuge (20,000 rpm).
m, 1 hour). Then, the supernatant obtained by separation was added with 2
A double amount of methanol was added to precipitate a resin component, and the solution portion and the resin portion were separated using an ultracentrifuge. For the solution part, GPC (gel permeation chromatography) [manufactured by Tosoh Corporation, main unit (with RI refractive index detector) HLC-8020; column manufactured by Tosoh Corporation, two G1000HXL; mobile phase tetrahydrofuran; flow rate 0.8 ml / min; pressure 60 kgf
/ Cm ² ; temperature INLET 35 ° C, OVEN 40
° C, RI 35 ° C; sample loop 100 ml; injection sample amount 0.08 g / 20 ml], and assuming the area ratio of each component on the chromatogram to be the weight fraction of each component, The composition and amount were determined.
On the other hand, for the above resin part, the ratio of integral values of aromatic protons or aliphatic protons was determined using a Fourier transform nuclear magnetic resonance apparatus (proton-FT-NMR), and the rubber-modified styrene resin and aromatic polycarbonate were determined. And the amount of a thermoplastic resin such as polyphenylene ether.

(2) SP value (δ) [Solubility Parameter] and average SP value The SP value was determined by Polymer Engineering and Science, 14,
(2), 147 (1974), and were calculated from the Δe1 and Δv1 data summarized in the literature.

Δ = √ [Σ (Δe1) / Σ (Δv1)] (where Δe1 is the aggregation energy per unit functional group, Δv1 is the molecular volume per unit functional group, and the unit of δ is ( cal / cm ³ ) ^1/2 .) The copolymer,
The SP value of the blend of the copolymer and the copolymer assumes that the addition rule is satisfied.In the case of a copolymer, a monomer unit or in the case of a blend, the SP value of each component copolymer is expressed by the weight ratio of the SP ratio. It was calculated by proportional distribution and this was taken as the average SP value. For example, the average SP value of the acrylonitrile-styrene copolymer was calculated from the proportional distribution of the weight ratio of the polyacrylonitrile SP value of 14.39 and the polystyrene SP value of 10.52.

(3) Distribution of Ratio of Monomer Component of Compatibilizer (Maximum SP Value and Minimum SP Value) For example, when the compatibilizer is an acrylonitrile-styrene copolymer, liquid chromatography is used. The analysis was performed by developing CN groups in the compatibilizer with a filler having nitrile (CN) bonds.

More specifically, using LC-6A manufactured by Shimadzu Corporation as liquid chromatography and ZorbaxCN manufactured by DuPont USA as a column, a sample dissolved in tetrahydrofuran was used as a mobile phase using a mixed solvent of tetrahydrofuran and n-heptane as a mobile phase. C., and the nitrile distribution was measured from the absorption value at a wavelength of 254 nm with a UV detector. The SP value corresponding to the right end portion of the obtained peak was defined as “maximum SP value”, and the SP value corresponding to the left end portion of the peak was defined as “minimum SP value”. For example, in the peak shown in FIG. 1, the SP value 11.0 is the maximum SP value, and the SP value 10.5 is the minimum SP value. The nitrile content and distribution in the sample were determined by, for example, preparing a calibration curve using an AS resin (acrylonitrile-styrene copolymer) having a known nitrile content in advance, and calculating based on the curve.

In the case where monomers such as acrylates, methacrylates, and unsaturated carboxylic anhydrides are used in place of acrylonitrile, the distribution of the ratio of the monomer components is similarly determined by chromatography. be able to.

(4) Izod Impact Strength Measured at 23 ° C. by a method according to ASTM-D256. (V notch, 1/4 inch test piece) (5) Heat deformation temperature Measured by a method in accordance with ASTM-D648 and used as a measure of heat resistance. (1/8 inch thickness of test piece, load 18.
(6 kg / cm ² ) (6) Melt flow rate (MFR) The melt flow rate was measured by a method based on ASTM-D1238 as an index of melt fluidity. It was determined from the extruded amount per 10 minutes (g / 10 minutes) under the conditions of a load of 2.16 kg and a melting temperature of 280 ° C.

(7) Oil Resistance The molded article was immersed in kerosene at 23 ° C. for 24 hours to evaluate the surface appearance.

[0105] The following components were used for each component used in Examples and Comparative Examples.

(A) Aromatic polycarbonate (PC) A commercially available bisphenol A type polycarbonate [Calibur 3 manufactured by Sumitomo Dow Co., Ltd.] (hereinafter referred to as PC) was used. The SP value of the PC is 11.3.

(B) Syndiotactic styrene resin Syndiotactic polystyrene (manufactured by Idemitsu Petrochemical Co., Ltd.) (referred to as SPS) shown in Table 1 was used. Melting point 27
0 ° C, weight average molecular weight 320,000.

(C) Compatibilizer 3.4 parts by weight of copolymers AS-1 to AS-2, AS-4 to AS-5 acrylonitrile, 81.6 of styrene
Parts by weight, 15 parts by weight of ethylbenzene, and 1,1-bis (t-butylperoxy) -3,3,3 as an initiator.
A mixture of 0.03 parts by weight of 5-trimethylcyclohexane was mixed at a rate of 0.7 liter / hour with a stirrer in series 3.
The liquid is continuously fed to a step-type plug flow type reactor, the first stage is a stirring speed of 100 rpm, 126 ° C., the second stage is 20 rpm
Polymerization was performed at 135 ° C., 10 rpm and 147 ° C. in the third stage. Subsequently, the polymerization liquid was led to a devolatilizer at 230 ° C. to remove unreacted monomers and a solvent to obtain a random copolymer (hereinafter, referred to as AS-1). As a result of analyzing the obtained copolymer, the ratio of the monomer components of the copolymer was 6% by weight of an acrylonitrile unit, 94% by weight of a styrene unit, and the average SP value was 10.75 (single amount) The ratio of body components is determined by infrared absorption spectroscopy). When the distribution of the ratio of the monomer components of the copolymer was measured by liquid chromatography analysis, the acrylonitrile unit was 0%.
-12% by weight, and the maximum SP value of the copolymer molecule is 1
1.0, the minimum SP value was 10.5, and the ΔSP value was 0.5.

In the production of the copolymer AS-1, as shown in Table 2, monomers (acrylonitrile and styrene)
Was changed to prepare copolymers having different ratios and distributions of the monomer components of the copolymer (PS, AS).
-2, AS-4 to AS-5).

Copolymer AS-3 The same experiment was repeated except that the reactor was changed to a completely mixed reactor in the production of AS-1. As a result of analyzing the obtained copolymer, the ratio of the monomer component of the copolymer was 11% by weight of acrylonitrile unit and 8% of styrene unit.
It was 9% by weight (by infrared absorption spectroscopy). When the distribution of the ratio of the monomer components of the copolymer was measured by liquid chromatography analysis, the acrylonitrile unit was 7 to 12% by weight, and the maximum SP value of the copolymer molecule was 11.0. , The minimum SP value was 10.8, and the ΔSP value was 0.2.

(D) Polyphenylene ether (PPE) Commercially available powdered polyphenylene ether [produced by Asahi Kasei Corporation (hereinafter referred to as PPE)] was used. The reduced viscosity ηsp / c is 0.55 dl / g.

(E) Rubber-modified styrenic resin (HIP
S) Commercially available rubber-modified styrene resin of high cis polybutadiene [manufactured by Asahi Kasei Corporation (hereinafter referred to as HIPS)]
Was used. The rubber content is 12.1% by weight, the weight average particle diameter of the rubber is 1.5 μm, and the reduced viscosity ηsp / c is 0.53 d.
1 / g.

(F) Styrene thermoplastic elastomer Styrene-butadiene block copolymer Styrene-butadiene copolymer [manufactured by Asahi Kasei Corporation
Styrene / butadiene block = 60/40 (hereinafter T
PE-1)] was used. Hydrogenated styrene-butadiene block copolymer A styrene-butadiene copolymer (TPE-1) obtained by hydrogenating the butadiene portion by the hydrogenation method described above (hereinafter referred to as TPE-2) is used. Was.

Examples 1 to 16 Comparative Examples 1 to 8 Mixing was carried out at the weight ratios shown in Tables 1 and 2 and a twin screw extruder (Wer
ZSK-40mm manufactured by ner Pfleiderer
Φ), the number of rotations is 295 rpm, and the discharge amount is 80 kg /
h and melt kneading at 280 ° C.

A test piece was prepared from the pellet thus obtained using an injection molding machine (Model IS80A, manufactured by Toshiba Machine Co., Ltd.) under the conditions of a cylinder temperature of 230 ° C. and a mold temperature of 60 ° C., and the MFR and IZOD impact strength were measured. The heat deformation temperature and the oil resistance were evaluated. Tables 1 and 2 show the results.

[0116]

[Table 1]

[0117]

[Table 2]

According to FIG. 1 and Tables 1 and 2, when (B) a syndiotactic styrene resin is blended with (A) an aromatic polycarbonate, oil resistance is improved, but impact strength is reduced. However, a copolymer having a specific monomer ratio and a specific distribution of the monomer ratio (a copolymer having a specific average SP value and a SP value distribution) is used as a compatibilizer in (A) and (B). ) Improves the impact strength. Further (D)
When a component selected from polyphenylene ether, (E) a rubber-modified styrene-based resin, and (F) a styrene-based thermoplastic elastomer is blended, the impact strength is further improved, and particularly when three components are present simultaneously, an extremely excellent impact strength is developed. You can see that.

[0119]

The resin composition of the present invention is excellent in oil resistance, impact resistance, heat resistance, and fluidity, so that the VTR,
Distribution boards, TVs, audio players, capacitors,
Household outlet, boombox, video cassette, video disc player, air conditioner, humidifier,
Household appliances such as electric warm air machines, chassis or parts, CD-ROM main frame (mechanical chassis),
OA for printers, faxes, PPCs, CRTs, word processing copiers, electronic cash registers, office computer systems, floppy disk drives, keyboards, types, ECRs, calculators, toner cartridges, telephones, etc.
Equipment housing, chassis or parts, connector, coil bobbin, switch, relay, relay socket, LE
D, variable condenser, AC adapter, FBT high pressure bobbin,
Electronic and electrical materials such as FBT case, IFT coil bobbin, jack, volume shaft, motor parts, instrument panel, radiator grill, cluster, speaker grill, louver, console box, defroster garnish, ornament, fuse box, relay case It is suitable for automotive materials such as connector shift tape, etc., and plays a large role in these industries.

[Brief description of the drawings]

FIG. 1 is a liquid chromatography measurement result showing the acrylonitrile composition distribution of the compatibilizer [acrylonitrile-styrene copolymer (AS resin)] used in Examples 11, 16 and Comparative Example 6. In the figure, the minimum S
P value, maximum SP value, SP of the largest amount of copolymer molecule
Value, the SP value difference between the maximum SP value and the minimum SP value (Δ
SP value) and the average SP value were calculated using the Izod impact strength (kg
· Cm / cm).

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 11, 1998 (1998.9.1)
1)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

[0116]

[Table 1]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI theme coat ゛ (reference) C08L 69/00 C08L 69/00 71/12 71/12 F term (reference) 4J002 BC03X BC043 BC07X BC074 BC084 BC094 BC11X BC114 BC12X BH014 BH024 BN063 BN123 BN143 BN153 BP013 CG01W CH073 FD010 FD020 FD040 FD050 FD070 FD160 FD200

Claims (4)

[Claims] 1. An aromatic polycarbonate (A)
A composition comprising 99 parts by weight, (B) 100 parts by weight of a component comprising 1 to 99 parts by weight of a syndiotactic styrene resin, and (C) 0.1 to 100 parts by weight of a compatibilizer. ) Is (a) a copolymer comprising an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer, and (b) a rubbery material having a glass transition temperature (Tg) of -30 ° C or lower. At least one selected from a graft copolymer comprising a polymer, an aromatic vinyl monomer (M1) grafted thereon, and a monomer (M2) copolymerizable with the aromatic vinyl monomer (M1) Wherein the monomers (M1) and (M2) may be homopolymers thereof and / or may be copolymerized with each other. The copolymer as the component (C) is a monomer component constituting the copolymer. Has a non-uniform distribution with respect to rate, whereby the copolymer solubility parameter (S
P). The SP value difference between the copolymer molecule having the maximum SP value and the copolymer molecule having the minimum SP value is 0.3 to 1.0 [( cal / cm
³ ) ^1/2 ], and the average SP value of the copolymer is 10.
6 to 11.2 [(cal / cm ³ ) ^1/2 ]. 2. A polyphenylene ether (D) based on 100 parts by weight of (A) and (B), and (E)
The resin composition according to claim 1, comprising one or more components selected from an amorphous styrene resin and (F) a thermoplastic elastomer. 3. The resin composition according to claim 2, wherein (F) is a hydrogenated thermoplastic elastomer. 4. The monomer copolymerizable with the aromatic vinyl monomer in the compatibilizer (C) is an unsaturated nitrile monomer,
Acrylic acid ester monomer, methacrylic acid ester monomer, acrylic acid monomer, methacrylic acid monomer, α, β-
The resin composition according to any one of claims 1 to 3, wherein the resin composition is at least one monomer selected from the group consisting of unsaturated carboxylic anhydride monomers and maleimide monomers.