JPH0912847A - Aromatic polycarbonate resin composition and molded article thereof - Google Patents

Abstract

(57) [Summary] [Purpose] The surface appearance of molded products is good,
Further, the present invention provides an aromatic polycarbonate resin composition excellent in mechanical properties such as chemical resistance, fatigue properties, and rigidity, and molded articles made from the aromatic polycarbonate resin composition. [Structure] A resin composition comprising an aromatic polycarbonate resin (a component) and a thermoplastic aromatic polyester resin (b component) is used, and a specific wollastonite (c component), ethylene and / or a C3 or more An olefin-based copolymer (component d) of an α-olefin and an unsaturated carboxylic acid ester is blended, more preferably a carboxyl group and /
Or an olefinic wax containing an anhydride group thereof (e
Component) and / or a rubbery polymer (f component), and an aromatic polycarbonate resin composition reinforced with a filler,
And molded articles made from it.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a resin composition comprising a filler-reinforced aromatic polycarbonate resin and a thermoplastic aromatic polyester resin. More specifically, the present invention relates to a filler-reinforced aromatic polycarbonate resin composition which has a good surface appearance when formed into a molded product and further has excellent chemical resistance and mechanical properties such as impact strength and rigidity.

[0002]

2. Description of the Related Art A resin composition comprising an aromatic polycarbonate resin and a thermoplastic aromatic polyester resin is widely used in various industrial fields as a material having excellent mechanical properties, thermal properties, chemical resistance and the like.

In order to improve the rigidity of the resin composition, a method of incorporating a fibrous filler such as glass fiber (JP-A-54)
No. 94556, JP-A-6-49344), and a method of blending scale-like and plate-like inorganic fillers such as talc and mica (JP-A-55-129444 and JP-A-5-222).
No. 283) is disclosed.

A resin composition comprising an aromatic polycarbonate resin and a thermoplastic aromatic polyester resin reinforced with a fibrous filler such as glass fiber and carbon fiber is
It is widely used as a material for automobile parts as a material with excellent mechanical properties such as chemical resistance, fatigue properties, and rigidity. However, when a resin composition composed of an aromatic polycarbonate resin and a thermoplastic aromatic polyester resin reinforced with a fibrous filler such as glass fiber or carbon fiber is molded at a normal mold temperature (100 ° C. or less), The appearance of the product is conspicuous with the floating of fibrous fillers such as glass fiber and carbon fiber, but it is not good.For example, if a good coating appearance is required, the coating film must be made very thick. It has the drawback of Further, by molding at a very high mold temperature (120 ° C. to 130 ° C.), it is possible to obtain a molded product having a good appearance to some extent, but the molding cycle becomes long and the productivity remarkably decreases. There is a problem that

On the other hand, the appearance of a molded article of a resin composition comprising an aromatic polycarbonate resin and a thermoplastic aromatic polyester resin mixed with a scale-like or plate-like inorganic filler such as talc or mica is glass fiber, carbon fiber, etc. Although it is better than the appearance of a molded product of the resin composition containing the fibrous filler, it has a drawback that chemical resistance and mechanical properties are deteriorated due to its small reinforcing effect.

Therefore, there is a demand for a resin composition comprising an aromatic polycarbonate resin and a thermoplastic aromatic polyester resin, which are reinforced with a filler having excellent surface appearance, chemical resistance, and mechanical properties such as impact strength and rigidity. It had been.

[0007]

DISCLOSURE OF THE INVENTION The present invention provides a molded article which has a good surface appearance and is further excellent in chemical resistance and mechanical properties such as impact strength and rigidity. An object of the present invention is to provide a filler-reinforced aromatic polycarbonate resin composition comprising a polycarbonate resin and a thermoplastic aromatic polyester resin.

As a result of intensive studies to achieve the above object, the inventors of the present invention have found that a specific wollastonite in a resin composition comprising an aromatic polycarbonate resin and a thermoplastic aromatic polyester resin, and , Ethylene and / or an olefinic copolymer of an α-olefin having 3 or more carbon atoms and an unsaturated carboxylic acid ester, and more preferably an olefinic wax containing a carboxyl group and / or a carboxylic acid anhydride group. And / or by adding a rubbery polymer, it was found that a resin composition comprising an aromatic polycarbonate resin and a thermoplastic aromatic polyester resin reinforced with a desired filler can be obtained, and the present invention Arrived

[0009]

The present invention is based on 100 parts by weight of a resin composition comprising 90 to 50% by weight of an aromatic polycarbonate resin (a component) and 10 to 50% by weight of a thermoplastic aromatic polyester resin (b component). In contrast, wollastonite (c component) 1 to 10 having an aspect ratio L / D = 3 to 50
0 parts by weight, 0.1 to 30 parts by weight of an olefin copolymer (d component) of ethylene and / or an α-olefin having 3 or more carbon atoms and an unsaturated carboxylic acid ester, a carboxyl group and / or a carboxylic anhydride. The present invention relates to an aromatic polycarbonate resin composition containing 0 to 5 parts by weight of a group-containing olefin wax (e component) and 0 to 100 parts by weight of a rubbery polymer (f component), and a molded article made of the same. It is a thing.

The aromatic polycarbonate resin (component a) used in the present invention is an aromatic polycarbonate resin having a viscosity average molecular weight of 10,000 to 100,000, preferably 15,000 to 60,000, derived from a dihydric phenol. It is usually produced by reacting a dihydric phenol with a carbonate precursor by a solution method or a melting method. Next, the basic means of these manufacturing methods will be briefly described. In the reaction using, for example, phosgene as the carbonate precursor, the reaction is usually performed in the presence of an acid binder and a solvent. Examples of the acid binder include sodium hydroxide,
An alkali metal hydroxide such as potassium hydroxide or an amine compound such as pyridine is used. As the solvent, for example, a halogenated hydrocarbon such as methylene chloride or chlorobenzene is used. A catalyst such as a tertiary amine or a quaternary ammonium salt may be used to accelerate the reaction. At that time, the reaction temperature is usually 0 to 40 ° C., and the reaction time is several minutes to 5 hours.

The transesterification reaction using a carbonic acid diester as a carbonate precursor is a method of distilling off the alcohol or phenol to be formed by stirring a predetermined proportion of an aromatic dihydroxy component with a carbonic acid diester in an inert gas atmosphere while heating. Done by. The reaction temperature varies depending on the boiling point of the produced alcohol or phenol, and is usually in the range of 120 to 300 ° C. From the initial stage of the reaction, the reaction is completed while reducing the pressure to distill off the produced alcohol or phenols. Further, a catalyst usually used in transesterification reaction may be used to accelerate the reaction. Examples of the carbonic acid diester used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate and dibutyl carbonate. Of these, diphenyl carbonate is particularly preferred. The dihydric phenol used here is 2,2-bis (4-hydroxyphenyl) propane [commonly called bisphenol A], but part or all of it may be replaced with another dihydric phenol. Other dihydric phenols include, for example, bis (4-hydroxyphenyl) methane,
1,1-bis (4-hydroxyphenyl) ethane, 2,2
-Bis (4-hydroxy-3,5-dimethylphenyl)
Propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl)
Examples include sulfone. Examples of the carbonate precursor include carbonyl halide, carbonyl ester, haloformate and the like, and specific examples thereof include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol and a mixture thereof. In producing the aromatic polycarbonate resin, an appropriate molecular weight modifier, branching agent, catalyst for accelerating the reaction and the like can be used. Two or more kinds of the aromatic polycarbonate resins thus obtained may be mixed.

The thermoplastic aromatic polyester resin (component b) used in the present invention is a resin obtained by polycondensation reaction of dicarboxylic acid or its derivative and glycol or its derivative, and either dicarboxylic acid or glycol is aromatic. It has a group group.

Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbenedicarboxylic acid, 4,4-biphenyldicarboxylic acid, Orthophthalic acid, 2,6-naphthalenedicarboxylic acid, bisbenzoic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4-diphenyl ether dicarboxylic acid, 4,4-diphenoxyethane dicarboxylic acid, adipine Acid, sebacic acid, azelaic acid,
Dodecane diacid, 1,3-cyclohexanedicarboxylic acid,
1,4-cyclohexanedicarboxylic acid alone,
Two or more types can be mixed and used. Among these compounds, terephthalic acid and isophthalic acid alone or a mixture thereof are particularly preferred.

As the glycol, ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, trans- or cis-2,2,4,4,4. -Tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexane Dimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A-bis (2-hydroxyethyl ether), etc. may be used alone or in combination of two or more. I can do things. Among these, ethylene glycol and 1,4-butanediol are particularly preferred.

Specific examples of the thermoplastic aromatic polyester used in the present invention include polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane dimethylene terephthalate, poly (ethylene terephthalate / Cyclohexane dimethylene terephthalate) copolymer, poly (ethylene terephthalate / emolein isophthalate) copolymer, poly (butylene terephthalate / butylene dodecadioate) polyester ether copolymer,
Polyarylate and the like can be mentioned. These thermoplastic aromatic polyester resins may be used alone or in combination. Among these thermoplastic polyester resins, it is preferable to use polybutylene terephthalate, polyethylene terephthalate, or a mixture of polybutylene terephthalate and polyethylene terephthalate.

The wollastonite (c composition used in the present invention
Min) is a natural white mineral (calcium methacylate) with needle-shaped crystals.
Is a chemical formula, and has the chemical formula CaSiO._ThreeRepresented by
SiO _Two 50 wt%, CaO 47 wt%, other F
e_TwoO_Three, Al_TwoO_ThreeIt has a specific gravity of approx.
2.9. In the present invention, the wollastonite is
Aspect ratio L / D = 3 to 50, preferably 5 to 50
Must be in range. In the present invention, the aspect ratio L
/ D is a scanning electron micrograph of wollastonite
Average fiber of 100 wollastonite fibers in the photo
It is expressed by the ratio of the fiber length (L) and the average fiber diameter (D).
is there.

The wollastonite may be surface-treated with an ordinary surface treatment agent such as a coupling agent such as a silane coupling agent or a titanate coupling agent. Aspect ratio is 3
When the ratio is less than the above range, the reinforcing effect is insufficient, the chemical resistance and the rigidity are deteriorated, and when the aspect ratio exceeds 50, the appearance of the obtained molded product is deteriorated, which is not preferable.

The olefin copolymer (d component) used in the present invention is obtained by polymerizing ethylene and / or α-olefin having 3 or more carbon atoms and unsaturated carboxylic acid ester. Examples of the α-olefin having 3 or more carbon atoms constituting the olefin-based copolymer include propylene, butene-1, hexene-1, decene-1, 4,
-Methylbutene-1, 4-methylpentene-1 and the like can be mentioned, but propylene or butene-1 is preferable. The unsaturated carboxylic acid ester is an unsaturated carboxylic acid having 3 to 8 carbon atoms, for example, an alkyl ester such as acrylic acid and methacrylic acid, and specific examples thereof include methyl acrylate, ethyl acrylate, and acrylic acid n. -Propyl, isopropyl acrylate, n-butyl acrylate,
Examples thereof include isobutyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, and the like, with ethyl acrylate or methyl methacrylate being preferred.

The olefin copolymer of the present invention contains ethylene and / or α-olefin having 3 or more carbon atoms in an amount of 50 to 9
It is preferable to use a copolymerized product in the range of 9% by weight and 1 to 50% by weight of the unsaturated carboxylic acid ester.

The olefin wax (component (e)) containing a carboxyl group and / or a carboxylic acid anhydride group used in the present invention means a carboxyl group and / or a carboxylic acid anhydride obtained by specially treating the olefin wax. It is a wax with a base.

The carboxyl group and the carboxylic acid anhydride group may be bonded to any part of the olefin wax, and the concentration thereof may be 1 g of the olefin wax.
The range of 0.1 to 6 meq / g is preferable. 0.1m
When it is less than eq / g, the effect of improving rigidity and impact resistance becomes insufficient, and when it is more than 6 meq / g, the thermal stability of the olefin wax itself is deteriorated, which is not preferable.

Examples of commercially available products of such an olefin wax include Diacarna-PA30 (Mitsubishi Kasei Co., Ltd.).
Manufacture: trade name), 2203 of high wax acid treatment type
A, 1105A (trade name, manufactured by Mitsui Petrochemical Co., Ltd.), oxidized paraffin (trade name, manufactured by Nippon Seiro Co., Ltd.) and the like, and these are used alone or as a mixture of two or more.

Rubbery polymer used in the present invention (component f)
Examples thereof include diene-based elastic polymers such as butadiene-alkyl (meth) acrylate-styrene copolymers, acrylic elastic polymers such as butadiene-alkyl acrylate-alkyl (meth) acrylate copolymers, and polyorganosiloxane rubbers. Examples thereof include a composite elastic polymer having a structure in which a polyalkyl (meth) acrylate rubber component is intertwined with each other.
A mixture of more than one species can be used.

The aromatic polycarbonate resin composition of the present invention contains 9 parts of the above-mentioned aromatic polycarbonate resin (component a).
Resin composition 1 comprising 0 to 50% by weight, preferably 80 to 60% by weight, thermoplastic aromatic polyester resin (component b) 10 to 50% by weight, preferably 20 to 40% by weight
1 to 100 parts by weight of wollastonite (component c) having an aspect ratio L / D = 3 to 50, preferably 5 to 70 parts by weight, and ethylene and / or α having 3 or more carbon atoms.
An olefin containing 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight of an olefin copolymer (component d) of an olefin and an unsaturated carboxylic acid ester, and a carboxyl group and / or a carboxylic acid anhydride group. 0 to 7 parts by weight of the wax (e component), preferably 0.02 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, and 0 to 100 parts by weight of the rubbery polymer (f component), It is preferably 1 to 70 parts by weight, more preferably 5 to 50 parts by weight.

If the blending ratio of the aromatic polycarbonate resin (a component) exceeds 90% by weight, the chemical resistance will decrease, and if it is less than 50% by weight, the mechanical strength such as impact strength will decrease, which is preferable. Absent.

When the mixing ratio of wollastonite (component c) having an aspect ratio L / D = 3 to 50 is less than 1 part by weight, the reinforcing effect is small and the rigidity becomes insufficient. This is not preferable because the appearance of the product deteriorates.

If the blending ratio of the olefinic copolymer (d component) of ethylene and / or α-olefin having 3 or more carbon atoms and unsaturated carboxylic acid ester is less than 0.1, chemical resistance and impact resistance are improved. The effect is small, and if it exceeds 30 parts by weight, the rigidity is lowered, which is not preferable.

In the present invention, a component, b component, c component,
It is possible to obtain a desired resin composition with a resin composition comprising the component d, but in order to further improve rigidity and impact resistance, an olefin containing a carboxyl group and / or a carboxylic acid anhydride group. It is possible to add a system wax (component e).

When the blending ratio of the olefin wax (component e) containing a carboxyl group and / or a carboxylic acid anhydride group exceeds 7 parts by weight, the appearance and mechanical strength are deteriorated, which is not preferable.

Further, in order to further improve impact resistance, particularly impact resistance at low temperature, it is possible to add a rubbery polymer (component f). If the compounding ratio of the rubbery polymer (component f) exceeds 100 parts by weight, the rigidity and chemical resistance will decrease, which is not preferable.

The composition of the present invention contains a flame retardant (for example, brominated bisphenol, brominated polystyrene, brominated polycarbonate, etc.) and a flame retardant aid (for example, antimony trioxide) within a range not impairing the object of the present invention. , Sodium antimonate, etc.), nucleating agents (eg sodium stearate, ethylene-sodium acrylate etc.), stabilizers (eg phosphoric acid ester, phosphorous acid ester etc.), antioxidants (eg hindered phenolic compounds) etc),
Light stabilizers, coloring agents, foaming agents, lubricants, release agents, antistatic agents, and the like may be added. Also, a small amount of another thermoplastic resin may be added.

The resin composition of the present invention can be uniformly mixed with a V-type blender, a ribbon mixer, a tumbler or the like, and then melt-kneaded with an ordinary extruder or the like to form pellets. The resin composition thus obtained can be easily molded by any method such as injection molding, extrusion molding, compression molding or rotational molding.

[0033]

The present invention will be described in more detail with reference to the following examples. The evaluation was based on the following method. (1) Surface appearance: R manufactured by Nippon Bee Chemical Co., Ltd.
After applying -230 Dover White and drying at 80 ° C for 1 hour, a universal surface profilometer (SURFCOM3B.
E-MD-S10A: manufactured by Tokyo Seimitsu Co., Ltd., with a stylus diameter of 2
Average surface roughness (R
a) was measured. It can be judged that the smaller the average surface roughness (Ra) value, the better the surface appearance. The coating thickness was 30 μm. (2) Impact strength; according to ASTM D256, [1 /
8 ″] test pieces were used to measure notched Izod impact strength in an atmosphere of 23 ° C. and −30 ° C. (3) Rigidity: A bending test was performed in accordance with ASTM D790, and a bending elastic modulus was measured. Chemical property: A strain of 1% was applied to the tensile test piece used in ASTM D638, and the sample was immersed in Esso-regular gasoline at 30 ° C. for 3 minutes, and then the tensile strength was measured to calculate the retention rate. Retention rate (%) = (strength of treated sample / strength of untreated sample) × 100

[Examples 1 to 14 and Comparative Examples 1 to 10] The amounts of the components shown in Tables 1 and 2 and the phosphorus stabilizer (cyclic neopentane tetrayl bis (octadecyl phosphite): Asahi) Denka Kogyo Co., Ltd. PEP-
0.1 part by weight of 8) was mixed and pelletized at a cylinder temperature of 270 ° C. by a vent type extruder having a diameter of 30 mm [VSK-30 manufactured by Nakatani Co., Ltd.]. 120 this pellet
After drying at ℃ for 5 hours, injection molding machine [Japan Steel Works, Ltd.]
Manufactured by J-120SA], a test piece was prepared at a cylinder temperature of 270 ° C. and a mold temperature of 70 ° C.
It was shown to.

The symbols showing the components in Tables 1 and 2 are as follows. (A) Aromatic polycarbonate resin Bisphenol A type polycarbonate: Panlite L-
1250; Teijin Kasei Co., Ltd., viscosity average molecular weight 25,
000 (hereinafter referred to as PC) (B) thermoplastic aromatic polyester resin polyethylene terephthalate resin: TR-8580;
Teijin Ltd., intrinsic viscosity 0.8 (hereinafter referred to as PET) Polybutylene terephthalate resin: TRB-H; Teijin Ltd., intrinsic viscosity 1.07 (hereinafter referred to as PBT) (C) Inorganic filler Wa Last night: WIC10; manufactured by Kinsei Matec Co., Ltd., average diameter (D) = 4.5 μm, aspect ratio L
/ D = 8 (hereinafter referred to as W-1) Wollastonite: 30A; manufactured by Sumitomo Corporation, average diameter (D) = 3 μm, aspect ratio L / D = 17 (hereinafter referred to as W-
2) (D) Olefin-based copolymer EEA resin: NUC-6220; manufactured by Nippon Yunika Co., Ltd. (EA content = 7% by weight) (hereinafter referred to as EEA) (E) Olefin-based wax α-olefin Olefin wax by copolymerization with maleic anhydride: Diakarna-PA30; manufactured by Mitsubishi Kasei Co., Ltd. (maleic anhydride content = 10% by weight) (hereinafter referred to as WAX) (F) Rubbery polymer butadiene-alkyl Acrylate-alkyl methacrylate copolymer: EXL-2602; manufactured by Kureha Chemical Industry Co., Ltd. (hereinafter referred to as E-1) A polyorganosiloxane component and a polyalkyl (meth) acrylate rubber component have an interpenetrating network structure. Composite rubber: S-2001; manufactured by Mitsubishi Rayon Co., Ltd. (hereinafter referred to as E-2) (X) Inorganic filler other than wollastonite Glass fiber: 3PE-941; manufactured by Nittobo Co., Ltd., average diameter (D) = 13 μm aspect ratio L / D = 230 (hereinafter referred to as GF) Talc: P-3; Nippon Talc Co., Ltd. (hereinafter referred to as T) )

[0036]

[Table 1]

[0037]

[Table 2]

[0038]

INDUSTRIAL APPLICABILITY The resin composition of the present invention has a good surface appearance when formed into a molded product, and further has excellent chemical resistance and mechanical properties such as impact strength and rigidity. It is useful for various industrial applications such as.

Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C08L 69/00 LPR C08L 69/00 LPR LPT LPT // (C08L 67/02 69:00 23:02 91:06 21:00)

Claims (4)

[Claims] 1. An aromatic polycarbonate resin (a component)
Resin composition 10 comprising 90 to 50% by weight and 10 to 50% by weight of a thermoplastic aromatic polyester resin (component b).
1 part by weight to 100 parts by weight of wollastonite (component c) having an aspect ratio L / D of 3 to 50, ethylene and / or an α-olefin having 3 or more carbon atoms and an unsaturated carboxylic acid ester relative to 0 parts by weight. 0.1 to 30 parts by weight of an olefinic copolymer (d component), 0 to 7 parts by weight of an olefinic wax containing a carboxyl group and / or a carboxylic acid anhydride group (e component), and a rubbery weight. An aromatic polycarbonate resin composition containing 0 to 100 parts by weight of the coalescence (component f). 2. The aromatic polycarbonate resin composition according to claim 1, wherein the compounding ratio of the olefin wax (component e) containing a carboxyl group and / or a carboxylic acid anhydride group is 0.02 to 5 parts by weight. 3. The compounding ratio of the rubbery polymer (component f) is 1.
The aromatic polycarbonate resin composition according to claim 1 or 2, which is ˜70 parts by weight. 4. A molded product obtained by molding the aromatic polycarbonate resin composition according to claim 1.