JP3212468B2 - Reinforced aromatic polycarbonate resin composition and molded article - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a reinforced aromatic polycarbonate resin composition and a molded article therefrom. More specifically, the present invention relates to a reinforced aromatic polycarbonate resin composition having high rigidity, excellent impact resistance, and low anisotropy of a molded article, and a molded article made therefrom.

[0002]

2. Description of the Related Art Aromatic polycarbonate resins have excellent mechanical properties, are widely used as engineering plastics, and are widely used in fields requiring dimensional accuracy and rigidity by blending glass fibers and carbon fibers. It is used. However, with the recent increase in the performance of information devices and the like, severe low warpage is required more than ever. A composition in which glass fiber, carbon fiber, or the like is blended with respect to such a demand is in a situation in which warpage is increased due to anisotropy accompanying fiber orientation, and it is not possible to cope with the situation. As a method for solving this problem, a method of filling glass powder has been conventionally known, but glass powder could not obtain sufficient performance in terms of strength and rigidity.
Instead, in recent years, a method of compounding a plate-like filler such as glass flake has been known and used in a wide range of fields. However, the slab filler alone is inferior in rigidity and impact resistance to the composition of the fibrous reinforcing material, and a desired and satisfactory product has not been obtained. Therefore, although a composition using a fibrous reinforcement and a platy filler in combination has been proposed, the addition of the fibrous reinforced material reduces the anisotropy improvement effect obtained by the platy filler, resulting in high rigidity. There has been no aromatic polycarbonate resin composition that simultaneously satisfies excellent impact resistance and reduced anisotropy.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a reinforced aromatic polycarbonate resin composition having high rigidity, excellent impact resistance, and low anisotropy of a molded article, and a molded article made therefrom. It is something you want to do. The present inventor has conducted intensive studies to achieve the above object, and as a result, a mixture comprising an aromatic polycarbonate resin or a polymer alloy of an aromatic polycarbonate resin and a thermoplastic graft copolymer and a specific ratio of a specific inorganic filler to a mixture. A reinforced aromatic polycarbonate having high rigidity and excellent impact resistance while maintaining a small anisotropy of a molded product by blending a specific amount of an olefin wax having a carboxyl group and / or a derivative group thereof. The present inventors have found that a resin composition and a molded article therefrom can be obtained, and have completed the present invention.

[0004]

The present invention provides (A-1) 45 to 97% by weight of an aromatic polycarbonate resin and (B) at least one inorganic filler selected from glass flakes, metal flakes, mica and talc. A carboxyl group and / or a derivative group thereof were added to a mixture consisting of 3 to 55% by weight and (C) 100 parts by weight of the mixture.
A reinforced aromatic polycarbonate resin composition (referred to as "composition I") consisting essentially of 0.02 to 3 parts by weight of an olefin wax having a range of 0.1 to 6 meq / g and a molded article thereof. And (A-1) aromatic polycarbonate resins 7 to 9
6% by weight, (A-2) 1 to 90% by weight of a thermoplastic graft copolymer obtained by grafting an aromatic vinyl compound and a vinyl cyanide compound to a diene rubber component, and (B) glass flakes, metal flakes, mica and talc. The carboxyl group and / or its derivative group is added to the mixture of 3-55% by weight of the at least one inorganic filler and (C) 100 parts by weight of the mixture .
Olefin wax having a range of 1 to 6 meq / g .
Reinforced aromatic polycarbonate resin composition consisting essentially of 02 to 3 parts by weight (referred to as "composition II")
And molded articles from it.

In compositions I and II of the present invention, (A
-1) The aromatic polycarbonate resin used as the component is a resin usually used as an engineering resin, and is an aromatic polycarbonate resin obtained by reacting a dihydric phenol with a carbonate precursor. Typical examples of the dihydric phenol used here are 2,2
2-bis (4-hydroxyphenyl) propane (commonly known as
Bisphenol A), bis (4-hydroxyphenyl)
Methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2 -Bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) ether, 4,4′-dihydroxydiphenyl, Bis (4-hydroxyphenyl)
And sulfide and bis (4-hydroxyphenyl) sulfone. Preferred dihydric phenols are bis (4-hydroxyphenyl) alkanes, of which bisphenol A is particularly preferred.

As the carbonate precursor, carbonyl halide, carbonate ester or haloformate is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol and the like.

In producing an aromatic polycarbonate resin by reacting the above-mentioned dihydric phenol with a carbonate precursor, the dihydric phenol may be used alone or in combination of two or more. If necessary, a catalyst and a molecular weight regulator may be used. , An antioxidant and the like may be used. The aromatic polycarbonate resin may be a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a mixture of two or more aromatic polycarbonate resins.

The molecular weight of the aromatic polycarbonate resin is 12,000 to 30,000 in terms of viscosity average molecular weight (M).
0 is preferable, and 13,000 to 25,000 is particularly preferable. With an aromatic polycarbonate resin having a viscosity average molecular weight of less than 12,000, even if a specific inorganic filler is blended, the mechanical strength cannot be sufficiently improved, and an aromatic polycarbonate resin having a viscosity average molecular weight of more than 30,000 Since the resin is inferior in fluidity during molding, extrusion and molding are difficult, and it is difficult to obtain a good molded product. The viscosity average molecular weight in the present invention is determined by inserting the specific viscosity (η _sp ) obtained from a solution obtained by dissolving 0.7 g of an aromatic polycarbonate resin in 100 ml of methylene chloride at 20 ° C. into the following equation.

Η _sp /c=[η]+0.45×[η] ² c
(Where [η] is the intrinsic viscosity) [η] = 1.23 × 10 ^-4 M ^0.83 c = 0.7

The inorganic filler used as the component (B) in the compositions I and II of the present invention is at least one selected from glass flakes, metal flakes, mica and talc. The glass flakes and metal flakes in the present invention are preferably plate-shaped. Further, the average particle size is preferably 10 to 1000 μm, and the average particle size is (a) and the thickness is (c).
When the ratio is (a) / (c), the ratio is preferably from 5 to 500, more preferably from 6 to 450, and even more preferably from 7 to 400. If the average particle size is less than 10 μm or the (a) / (c) ratio is less than 5, the rigidity is not sufficient, and the average particle size exceeds 1000 μm or (a)
If the / (c) ratio exceeds 500, the appearance of the molded article deteriorates, which is not preferable. The average particle size of the glass flakes and metal flakes here is calculated as the median size of the weight distribution of the particle sizes determined by the standard sieving method. The mica in the present invention is preferably a powder having an average particle diameter of 1 to 80 μm from the viewpoint of securing rigidity. The talc in the present invention is preferably a powder having an average particle diameter of 0.01 to 20 μm from the viewpoint of securing rigidity. Here, the average particle diameter of mica and talc refers to a value measured by a laser diffraction method. In the case of mica and talc, if the average particle size is smaller than this range, the rigidity becomes insufficient, and if the average particle size exceeds this range, the appearance of the molded product is unfavorably deteriorated.

The inorganic filler preferably has been surface-treated with a silane coupling agent or the like. By this surface treatment, decomposition of the aromatic polycarbonate resin is suppressed. The silane coupling agent referred to here is the following formula

[0012]

Embedded image

[Where Y is a group having reactivity or affinity with the resin matrix such as an amino group, an epoxy group, a carboxylic acid group, a vinyl group, a mercapto group, and a halogen atom;
Represents a single bond or an alkylene group having 1 to 7 carbon atoms,
An amide bond, an ester bond, an ether bond or an imino bond may be interposed in the alkylene molecular chain, and X represents an alkoxy group, preferably an alkoxy group having 1 to 4 carbon atoms or a halogen atom]. Specifically, vinyl trichlorosilane, vinyl triethoxy silane, vinyl trimethoxy silane, γ-
Methacryloxypropyltrimethoxysilane, β-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl- γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane and the like. Further, such an inorganic filler is preferably used in the form of a granulated granule with a binder because it is easy to handle. However, the above average particle size range does not apply to such granules.

The content of the inorganic filler (component B) is as follows:
For the composition I, the composition (A-1) and the component (B) per 100% by weight in total, and for the composition II, the composition (A-1)
It is 3 to 55% by weight, preferably 5 to 50% by weight, per 100% by weight of the total of the component, the component (A-2) and the component (B). If it is less than 3% by weight, the effect of improving rigidity is not sufficient, and if it is more than 55% by weight, the fluidity at the time of molding is inferior.

In the compositions I and II of the present invention, an olefin wax having a carboxyl group and / or a derivative group thereof is used as the component (C).
As the carboxyl group derivative, a carboxylic anhydride group,
Examples thereof include metal salts of carboxylic acids, alkyl esters and aryl esters of carboxylic acids. The carboxyl group and / or its derivative group may be attached to any part of the olefin-based wax, and the concentration thereof
Is 0.1 to 6 meq / g per gram of the olefin wax.
Range. If it is less than 0.1 meq / g, the rigidity and impact resistance are not sufficiently improved, and if it is more than 6 meq / g, the thermal stability of the olefin wax itself deteriorates, which is not preferable.

Commercially available olefin waxes include, for example, Diacarna-PA30 (Mitsubishi Chemical Corporation)
Manufacture), 2203A, 110 of high wax acid treatment type
5A (manufactured by Mitsui Petrochemical Industries, Ltd.) and paraffin oxide (manufactured by Nippon Seiro Co., Ltd.). In the present invention, the olefin wax can be used alone or as a mixture of two or more. The amount of these olefinic waxes (component (C)) is about (A-1)
With respect to 100 parts by weight of the mixture consisting of the component and the component (B), the composition (A-1) and the component (A-
The amount is 0.02 to 3 parts by weight, preferably 0.03 to 1 part by weight, per 100 parts by weight of the mixture comprising the component (2) and the component (B). If it is less than 0.02 parts by weight, the rigidity and impact resistance are not sufficiently improved, and if it is more than 3 parts by weight, the tensile strength is greatly reduced, and the rigidity is also undesirably reduced.

A composition obtained by blending such an olefinic wax with an aromatic polycarbonate resin composition containing glass fibers has been known (Japanese Patent Application Laid-Open No. 56-1981).
No. 45944). However, the effect obtained by blending the olefin wax according to the fiber reinforcement represented by glass fiber is only an improvement in impact resistance, and the effect obtained by mixing the aromatic polycarbonate resin of the present invention and a specific inorganic filler is obtained. It was surprising that the addition of such an olefin wax improved not only the impact resistance but also the rigidity. This is because such an olefin-based wax has an affinity for the inorganic filler, thereby reducing the adhesiveness between the inorganic filler and the aromatic polycarbonate resin. It is considered that the stiffness is also improved by the relaxation and the suppression of the breakage and breakage of the inorganic filler. As a result, the reinforced aromatic polycarbonate resin composition of the present invention has good properties such as high rigidity, excellent impact resistance, and low anisotropy. Further, as another advantage, when mica and talc are used as the inorganic filler, the olefin wax covers the mica and talc surfaces, thereby suppressing decomposition of the aromatic polycarbonate resin and improving thermal stability. Also, it has the effect of enabling high filling of these fillers.

The thermoplastic graft copolymer used as the component (A-2) in the composition II of the present invention comprises a diene rubber component as a base, and an aromatic vinyl compound component and a vinyl cyanide compound capable of graft copolymerization with the diene rubber component. It is a copolymer obtained by graft polymerization of components. Examples of the diene rubber component include polybutadiene, polyisoprene, and a styrene-butadiene copolymer, and polybutadiene is preferably used. Examples of the aromatic vinyl compound component grafted to these diene rubber components include styrene, α-methylstyrene, p-methylstyrene, alkoxystyrene, and halogenated styrene, and styrene is preferably used. Examples of the vinyl cyanide compound component include acrylonitrile, methacrylonitrile, and chloroacrylonitrile, and acrylonitrile is preferably used. Further, methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate and the like can be used. Among these thermoplastic graft copolymers, an ABS resin is preferably used.

These thermoplastic graft copolymers may be produced by any one of bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization. The grafting method may be a single-stage graft or a multi-stage graft. Good. Further, the thermoplastic graft copolymer may be used alone or in combination of two or more.

These thermoplastic graft copolymers are preferably used for improving the fluidity of the mixture. The content of the thermoplastic graft copolymer is (A-1)
It is 1 to 90% by weight, preferably 5 to 60% by weight, per 100% by weight of the total of the component, the component (A-2) and the component (B).

The reinforced aromatic polycarbonate resin composition of the present invention may contain any additives such as brominated bisphenol, brominated epoxy resin, brominated polystyrene, brominated polycarbonate, and the like, as long as the objects and effects of the present invention are not impaired. Flame retardants such as triphenyl phosphate, phosphonamide and red phosphorus; flame retardant aids such as antimony trioxide and sodium antimonate; heat stabilizers such as phosphates and phosphites; hindered phenols An antioxidant, a light stabilizer, a release agent, a flow modifier, a colorant, a lubricant, a foaming agent, and the like, as described above, may be incorporated in an effective expression amount as necessary. Further, other reinforcing materials and fillers, for example, glass powder, glass beads, polytetrafluoroethylene, calcium carbonate, carbon black, metal powder and the like may be blended as long as the objects and effects of the present invention are not impaired. Further, for example, a thermoplastic resin such as polyethylene, polypropylene, polystyrene, polyethylene terephthalate, polybutylene terephthalate, polyamide, acrylic resin, aromatic polyester, phenoxy resin, and epoxy resin, and an elastic material may be blended.

The reinforced aromatic polycarbonate resin composition of the present invention can be produced by any method. For example, a method of mixing with a tumbler, a V-type blender, a Nauter mixer, a Banbury mixer, a kneading roll, and an extruder is appropriately used. The resin composition thus obtained is molded by various known methods such as injection molding, extrusion molding and compression molding.

[0023]

The present invention will be described below with reference to examples. The evaluation was performed by the following methods (1) to (4). (1) Flexural modulus [kgf / cm ² ]: ASTM D-
790. (2) Impact value [kgf · cm / cm]: ASTM D-
It was measured by 256 (with Izod notch, thickness 3.2 mm). (3) Tensile strength [kgf / cm ² ]: ASTM D-6
38. (4) Mold shrinkage [%]: width 50 mm x length 100 mm
× A square plate having a thickness of 4 mm is formed by injection molding under the same conditions and left at 23 ° C. in a 50% RH atmosphere for 24 hours.
The square plate dimensions were measured with a three-dimensional measuring machine (manufactured by Mitutoyo Corporation), and the molding shrinkage was calculated. Further, as a measure of anisotropy, a value was calculated by dividing the value of the molding shrinkage in the perpendicular direction by the value in the flow direction.

Examples 1 to 11 and Comparative Examples 1 to 16 After the resins, inorganic fillers and waxes shown in Tables 1, 2 and 3 were dry-blended in the proportions shown in Tables 1, 2 and 3. Using a vented single-screw extruder with a screw diameter of 30 mm [VSK-30, manufactured by Nakatani Machinery Co., Ltd.], the mixture was melt-kneaded at a cylinder temperature of 290 ° C, pellets were obtained by strand cutting, and the obtained pellets were heated at 120 ° C. After drying with a hot air circulating drier for 5 hours, a bending test piece was formed at a cylinder temperature of 300 ° C. and a mold temperature of 100 ° C. by an injection molding machine [SG150U manufactured by Sumitomo Heavy Industries, Ltd.]
An impact test piece and a tensile test piece were obtained. Further, the square plate for measuring the molding shrinkage is subjected to a cylinder temperature of 300 by the same injection molding machine.
At a mold temperature of 100 ° C. and under the same injection conditions.

The symbols for resins, inorganic fillers and waxes in Tables 1, 2 and 3 are as follows. PC-1: aromatic polycarbonate resin [Panlite L-1225L manufactured by Teijin Chemicals Ltd .; viscosity average molecular weight 1]
9500] PC-2: aromatic polycarbonate resin [Panelite L-1225 manufactured by Teijin Chemicals Ltd .; viscosity average molecular weight 22]
500] PC-3: aromatic polycarbonate resin [Panlite L-1250 manufactured by Teijin Chemicals Ltd .; viscosity average molecular weight 24]
500] ABS: ABS resin [Santak UT-61 manufactured by Mitsui Toatsu Chemicals, Inc.] GFL: glass flakes [REFG manufactured by Nippon Sheet Glass Co., Ltd.]
-101, thickness 2-6 μm, average particle size 600 μm] Mica: Mica powder [A-41, manufactured by Mika Yamaguchi Mfg. Co., Ltd.]
Average particle size: 40 μm] Talc: talc [P-3 manufactured by Nippon Talc Co., Ltd., average particle size: 3 μm] CS: glass fiber [3PE-455 manufactured by Nitto Boseki Co., Ltd.]
MF: glass powder [PFE301 manufactured by Nitto Boseki Co., Ltd., fiber diameter 9 μm, average fiber length: 40 μm] W-1: olefin-based wax obtained by copolymerization of α-olefin and maleic anhydride [Mitsubishi Chemical Corporation ) Diamond Carna-PA30] W-2: Olefinic wax having carboxylic anhydride group [Wax acid treatment type 2203A manufactured by Mitsui Petrochemical Industry Co., Ltd.] W-3: Olefin having no carboxyl group and its derivative group Wax [HW manufactured by Mitsui Petrochemical Industries, Ltd.]
405MP]

[0026]

[Table 1]

[0027]

[Table 2]

[0028]

[Table 3]

As is clear from this table, for example, when Example 1 and Comparative Example 1 are compared, when the olefin wax is blended, the tensile strength is slightly lowered, but the rigidity is exhibited while maintaining the anisotropy. The flexural modulus is improved by about 10%, and the impact value is also increased. Also in Example 2 and Comparative Example 2, and Example 3 and Comparative Example 3, although the tensile strength was lowered, the molded product was in a sufficiently satisfactory range. On the other hand, the flexural modulus was 15 while maintaining the anisotropy. Up to about 25%, the impact value is also high.

[0030]

Industrial Applicability The reinforced aromatic polycarbonate resin composition of the present invention has improved rigidity and improved impact resistance while maintaining the excellent low anisotropy of an aromatic polycarbonate resin reinforced with a specific inorganic filler. Since it is excellent, it is suitable for a wide range of industrial fields including electric parts that require high dimensional accuracy and high rigidity, and the industrial effects achieved are outstanding.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08L 55/02 C08L 55/02 // (C08L 69/00 (C08L 69/00 55:02 55:02 91:06) 91: 06) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 69/00 C08K 3/00-13/08

Claims (4)

(57) [Claims] 1. A composition comprising (A-1) 45 to 97% by weight of an aromatic polycarbonate resin and (B) 3 to 55% by weight of at least one inorganic filler selected from glass flakes, metal flakes, mica and talc. For 100 parts by weight of the mixture and (C) the mixture, a carboxyl group and / or a derivative group thereof was added in an amount of 0.1 to 6 meq / g.
A reinforced aromatic polycarbonate resin composition substantially consisting of 0.02 to 3 parts by weight of the olefin wax contained in the box. 2. A molded article formed from the reinforced aromatic polycarbonate resin composition according to claim 1. (A-1) 7 to 96% by weight of an aromatic polycarbonate resin, and (A-2) 1 to 90% by weight of a thermoplastic graft copolymer obtained by grafting an aromatic vinyl compound and a vinyl cyanide compound to a diene rubber component. % And (B)
A carboxyl group and / or a derivative group thereof is added to 100 parts by weight of a mixture consisting of 3 to 55% by weight of at least one inorganic filler selected from glass flakes, metal flakes, mica and talc and (C) the mixture. A reinforced aromatic polycarbonate resin composition consisting essentially of 0.02 to 3 parts by weight of an olefin wax having a range of 0.1 to 6 meq / g . 4. A molded article formed from the reinforced aromatic polycarbonate resin composition according to claim 3.