JP3217937B2 - Aromatic polycarbonate resin composition and molded article thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. 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 having a good surface appearance when formed into a molded product, and further having 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.

[0003] In order to improve the rigidity of the resin composition, a method of blending a fibrous filler such as glass fiber (Japanese Patent Laid-Open No.
JP-A-94556, JP-A-6-49344) and a method of blending scaly or plate-like inorganic fillers such as talc and mica (JP-A-55-129444, JP-A-5-222).
No. 283) is disclosed.

[0004] 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 comprises:
It is widely used as a material for automobile parts as a material having 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 lower), the molding is not performed. The appearance of the product is not so good that the fibrous filler such as glass fiber and carbon fiber is floating, and it is difficult to say that it is good.For example, if a good paint appearance is required, the coating film must be very thick There is a disadvantage that. Molding at a very high mold temperature (120 ° C. to 130 ° C.) makes it possible to obtain a molded article having a good appearance to some extent, but the molding cycle becomes longer and the productivity is significantly reduced. Has the problem that

[0005] 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 blended with a scaly or plate-like inorganic filler such as talc or mica is shown as glass fiber, carbon fiber or the like. The resin composition to which the fibrous filler is added is better than the appearance of a molded product, but has the disadvantage that the chemical resistance and mechanical properties are reduced due to its small reinforcing effect.

Accordingly, there is a need for a resin composition comprising an aromatic polycarbonate resin and a thermoplastic aromatic polyester resin reinforced with a filler having excellent mechanical properties such as surface appearance, chemical resistance, impact strength, and rigidity. I was

[0007]

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

The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, a specific wollastonite was blended with a resin composition comprising an aromatic polycarbonate resin and a thermoplastic aromatic polyester resin. And more preferably, an aromatic polycarbonate resin reinforced with an intended filler by compounding an olefin wax containing a carboxyl group and / or a carboxylic anhydride group and / or a rubbery polymer. And a resin composition comprising a thermoplastic aromatic polyester resin can be obtained, and the present invention has been achieved.

[0009]

The present invention relates to a resin composition comprising 90 to 50% by weight of an aromatic polycarbonate resin (component (a)) and 10 to 50% by weight of a thermoplastic aromatic polyester resin (component (b)). In contrast, wollastonite (c component) having an aspect ratio L / D = 3 to 50 (1 to 10)
0 parts by weight, 0 to 7 parts by weight of an olefin wax containing a carboxyl group and / or a carboxylic anhydride group (component (d)), and 1 to 70 parts by weight of a rubbery polymer (component (e)) The present invention relates to an aromatic polycarbonate resin composition and a molded article comprising the same.

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 dihydric phenol. It is usually produced by reacting a dihydric phenol with a carbonate precursor by a solution method or a melting method. Next, basic means of these manufacturing methods will be briefly described. In a reaction using, for example, phosgene as a 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, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. For promoting the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt may be used. 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 in which a predetermined ratio of an aromatic dihydroxy component is stirred with a carbonic acid diester while heating under an inert gas atmosphere to distill off the produced alcohol or phenol. It is performed 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. The reaction is completed under reduced pressure from the beginning while distilling off alcohol or phenols produced. Further, a catalyst usually used in a transesterification reaction to promote the reaction can be used. Examples of the carbonic acid diester used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like. Of these, diphenyl carbonate is particularly preferred.

The dihydric phenol used here includes:
The target is 2,2-bis (4-hydroxyphenyl) propane [commonly known as bisphenol A], but a part or the whole thereof 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) sulfone and the like. Examples of the carbonate precursor include carbonyl halide, carbonyl ester, and haloformate. 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 regulator, a branching agent, a catalyst for accelerating the reaction, and the like can be used. 2 of the aromatic polycarbonate resin thus obtained
Mixing more than seeds is acceptable.

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

The dicarboxylic acids 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, anthracenedicarboxylic acid, 4,4-diphenyletherdicarboxylic acid, 4,4-diphenoxyethanedicarboxylic acid, adipic acid, sebacine Acid, azelaic acid,
Dodecane diacid, 1,3-cyclohexanedicarboxylic acid,
Even with 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, -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-xylene diol, bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A-bis (2-hydroxyethyl ether), etc. may be used alone or in combination of two or more. 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 decadioate) polyester ether copolymer,
Polyarylate and the like can be mentioned. These thermoplastic aromatic polyester resins may be used alone or as a mixture. 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 component) used in the present invention is used.
Minute) is a natural white mineral with needle-like crystals (calcium
), With the chemical formula CaSiO_ThreeUsually represented by
SiO _Two 50% by weight, 47% by weight of CaO, other F
e_TwoO_Three, Al_TwoO_ThreeEtc., the specific gravity is about
2.9. In the present invention, the wollastonite is
Aspect ratio L / D = 3-50, preferably 5-50
Must be in range. In the present invention, the aspect ratio L
/ D means scanning wollastonite with scanning electron microscope
Shaded, average fiber of 100 wollastonite fibers in the photo
It is expressed by the ratio between the length (L) and the average fiber diameter (D).
is there.

If the aspect ratio is less than 3, the reinforcing effect is insufficient, and the chemical resistance and the like are lowered. If the aspect ratio is more than 50, the appearance of the obtained molded article is deteriorated, which is not preferable. . In addition, the wollastonite may be used after being subjected to a surface treatment with an ordinary surface treatment agent, for example, a coupling agent such as a silane coupling agent or a titanate coupling agent.

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

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

Commercially available olefin waxes include, for example, Diacarna-PA30 (Mitsubishi Chemical Corporation)
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 (e))
Examples thereof include diene-based elastic polymers such as butadiene-alkyl (meth) acrylate-styrene copolymer, acrylic-based elastic polymers such as butadiene-alkyl acrylate-alkyl (meth) acrylate copolymer, and polyorganosiloxane rubber. And a polyalkyl (meth) acrylate rubber component having a structure in which they are intertwined with each other.
A mixture of more than one species can be used.

The aromatic polycarbonate resin composition of the present invention comprises 9 parts of the above aromatic polycarbonate resin (a component).
Resin composition 1 comprising 0 to 50% by weight, preferably 80 to 60% by weight, and 10 to 50% by weight, preferably 20 to 40% by weight of a thermoplastic aromatic polyester resin (component (b)).
1 to 100 parts by weight, preferably 5 to 70 parts by weight, of wollastonite (component (c)) having an aspect ratio L / D of 3 to 50 with respect to 00 parts by weight, containing a carboxyl group and / or a carboxylic anhydride group. 0 to 7 parts by weight, preferably 0.02 to 5 parts by weight, more preferably 0.05 to 3 parts by weight of an olefin-based wax (d component), and a rubbery polymer (e component)
In an amount of 1 to 70 parts by weight, more preferably 5 to 50 parts by weight.

When the blending ratio of the aromatic polycarbonate resin (component (a)) exceeds 90% by weight, the chemical resistance decreases, and when it is less than 50% by weight, the mechanical strength such as impact strength decreases. Absent.

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

In the present invention, the desired resin composition can be obtained from the resin composition comprising the component a, the component b, and the component c. In order to further improve rigidity and impact resistance, a carboxyl group is used. It is possible to compound an olefin-based wax (component (d)) containing a group and / or a carboxylic anhydride group.

If the compounding ratio of the olefin wax containing a carboxyl group and / or a carboxylic anhydride group (component (d)) exceeds 7 parts by weight, the appearance and mechanical strength are undesirably reduced.

In order to further improve the impact resistance, particularly in a low-temperature atmosphere, a rubbery polymer (component (e)) can be blended.

The compounding ratio of the rubbery polymer (component (e)) is 1
If the amount exceeds 00 parts by weight, the rigidity and chemical resistance 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 auxiliary (for example, antimony trioxide) as long as the object of the present invention is not impaired. , Sodium antimonate, etc.), nucleating agents (eg, sodium stearate, ethylene-sodium acrylate, etc.), stabilizers (eg, phosphate esters, phosphite esters, etc.), antioxidants (eg, hindered phenol 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.

[0032]

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 made by Nippon Bee Chemical Co., Ltd.
After applying -230 Dover White and drying at 80 ° C for 1 hour, a universal surface profiler (SURFCOM3B.
E-MD-S10A: manufactured by Tokyo Seimitsu Co., Ltd.)
μm, stylus pressure 0.07 g, average surface roughness (R
a) was measured. The smaller the value of the average surface roughness (Ra), the better the appearance. The coating thickness is 30
μm. (2) Impact strength: Notched Izod impact strength was measured on a [1/8 "] test piece in an atmosphere of 23 ° C and -30 ° C in accordance with ASTM D256. (3) Rigidity: Bending test was performed in accordance with ASTM D790. (4) Chemical resistance: A tensile test piece used in accordance with ASTM D638 was subjected to 1% strain, immersed in 30 ° C. esso regular gasoline for 3 minutes, and then subjected to a tensile strength test. The retention was calculated by the following formula: retention (%) = (strength of treated sample / strength of untreated sample) × 100.

Examples 1 to 8 and Comparative Examples 1 to 9 The components shown in Tables 1 and 2 were added in the amounts shown in the table and a phosphorus-based stabilizer (cyclic neopentanetetraylbis (octadecylphosphite): Asahi PEP- manufactured by Denka Kogyo Co., Ltd.
8) was mixed in 0.1 part by weight, and pelletized at a cylinder temperature of 270 ° C. with a vent-type extruder [VSK-30 manufactured by Nakatani Corporation] having a diameter of 30 mm. This pellet is
After drying at ℃ for 5 hours, injection molding machine [Nippon Steel Works, Ltd.
J-120SA], a test piece was prepared at a cylinder temperature of 270 ° C. and a mold temperature of 70 ° C. The evaluation results are shown in Tables 1 and 2.

The symbols for the components shown in Tables 1 and 2 are as follows. (A) Aromatic polycarbonate resin Bisphenol A type polycarbonate: Panlite L-
1250; manufactured by Teijin Chemicals Limited, viscosity average molecular weight 25,
(B) thermoplastic aromatic polyester resin polyethylene terephthalate resin: TR-8580;
Teijin Limited, intrinsic viscosity 0.8 (hereinafter referred to as PET) Polybutylene terephthalate resin: TRB-H; Teijin Limited, intrinsic viscosity 1.07 (hereinafter referred to as PBT) (C) Inorganic filler Lastnite: WIC10; Kinsei Matech 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 W-)
(D) Olefin-based wax Olefin-based wax obtained by copolymerization of α-olefin and maleic anhydride: Diacarna-PA30; manufactured by Mitsubishi Kasei Corporation (maleic anhydride content = 10% by weight) (E) Rubbery polymer Butadiene-alkyl acrylate-alkyl methacrylate copolymer: EXL-2602; manufactured by Kureha Chemical Industry Co., Ltd. (hereinafter referred to as E-1) Polyorganosiloxane component and polyalkyl ( Composite rubber in which a meth) acrylate rubber component has an interpenetrating network structure: 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 Nitto Boseki Co., Ltd., average diameter (D) = 13 μm aspect ratio L / D = 230 (hereinafter referred to as GF) Talc: -3; Nippon Talc Co. (hereinafter referred to as T)

[0035]

[Table 1]

[0036]

[Table 2]

[0037]

The resin composition of the present invention has a good surface appearance when formed into a molded product, and more specifically, is excellent in chemical resistance and mechanical properties such as impact strength and rigidity.
Useful for various industrial applications such as the automotive field.

Continuation of front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 67/00-67/04 C08L 69/00

Claims (3)

(57) [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 to 100 parts by weight of wollastonite (c component) having an aspect ratio L / D of 3 to 50, and an olefin wax containing a carboxyl group and / or a carboxylic anhydride group (d component) based on 0 part by weight. , And an aromatic polycarbonate resin composition comprising 1 to 70 parts by weight of a rubbery polymer (component (e)). 2. The aromatic polycarbonate resin composition according to claim 1, wherein the compounding ratio of the olefin wax containing a carboxyl group and / or a carboxylic anhydride group (component (d)) is 0.02 to 5 parts by weight. 3. A molded article obtained by molding the aromatic polycarbonate resin composition according to claim 1 or 2 .