JPH07258528A - Polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To obtain a molded product having substantially the same specific gravity as a general-purpose polycarbonate and excellent mechanical properties such as rigidity and weld strength by incorporating hollow glass bodies treated with an epoxysilane as a filler into a polycarbonate resin compsn. CONSTITUTION:(A) 50-98wt.% polycarbonate resin having a viscosity-average mol.wt. of 10,000 to 50,000 is blended with (B) 50-2wt.% hollow glass bodies having an average particle size of 3 to 80mum and treated with an epoxysilane. There can be mentioned various kinds of hollow glass bodies, one kind of which is fine granular bodies (glass balloons) formed using low alkali glass as a glass species and each having a cavity. Such glass balloons can usually be easily obtd. by expanding glass grains with a blowing agent. A bifunctional epoxysilane is pref. used as the epoxysilane. Blending and kneading are effected according to a customary method using e.g. a ribbon blender. The heating temp. during kneading is usually selected within the range of 240 to 300 deg.C.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a polycarbonate resin composition. More specifically, the present invention relates to a polycarbonate resin composition capable of obtaining a molded article having a specific gravity equivalent to that of a general polycarbonate and excellent mechanical properties such as rigidity and weld strength by selecting a filler to be blended with a polycarbonate resin. Is.

[0002]

2. Description of the Related Art Generally, various kinds of synthetic resins are blended with various inorganic fillers for the purpose of improving or increasing the mechanical strength and durability. Among them, it is known that the glass hollow body has a low specific gravity and an improved strength such as rigidity by blending it. For example, Reinf. Plast, Vol.
No. 12, p. 12 to 13, (1990) describe a material in which a polyurethane-based thermoplastic resin is mixed with a hollow glass body having a particle size of about 70 μm. Further, as synthetic resin, polyethylene and polystyrene have a particle size of about 20 to 120 μm.
Studies have been conducted on the viscous behavior of resin compositions filled with glass balloons in the above range [Research Report of Institute of Textile and Polymer Materials, Institute of Industrial Technology, No. 126, p.9-15, (1981)]. Further, JP-A-4-23851 discloses a resin composition in which a glass balloon is added to a styrene resin. In addition, in Japanese Patent Laid-Open No. 61-236859,
A crystalline resin such as a polybutylene terephthalate resin or a polyacetal resin is disclosed.

On the other hand, polycarbonate resin is excellent in mechanical strength (particularly impact resistance), electrical characteristics, transparency and the like, and is widely used as an engineering plastic in various fields such as electric and electronic equipment fields, home electric appliances fields, and automobile fields. It's being used. As a polycarbonate resin having such characteristics, a resin composition containing glass fiber, talc, mica, potassium titanate whiskers, or the like has come to be used as a material having an improved appearance and improved rigidity. However, when these effective inorganic fillers are blended with the polycarbonate resin, there is a problem that the molecular weight of the polycarbonate resin is significantly reduced due to hydrolysis or the like when it stays in the molding machine during molding. As a result, there is a problem that the mechanical strength is remarkably lowered and the original characteristics of the polycarbonate resin are largely impaired. Further, in the case of spherical or plate-like inorganic fillers, there is a problem that the weld strength is significantly reduced.

[0004]

Therefore, the present inventors have
In view of the above situation, by eliminating the drawbacks of the conventional method, by selecting a filler to be blended with the polycarbonate resin,
The inventors have conducted intensive studies to develop a polycarbonate resin composition having a specific gravity equivalent to that of a general polycarbonate (PC) and excellent in mechanical properties such as rigidity and weld strength. As a result, they have found that the object of the present invention can be achieved by selecting an epoxysilane-treated hollow glass body as the filler. The present invention has been completed based on such findings. That is, the present invention provides a polycarbonate resin composition comprising (A) a polycarbonate resin of 50 to 98% by weight and (B) an epoxysilane-treated glass hollow body of 50 to 2% by weight. .

First, as the polycarbonate resin (PC) as the component (A) which constitutes the resin composition of the present invention,
There are various ones, but preferably the general formula (I)

[0006]

[Chemical 1]

[Wherein, X is a hydrogen atom, a halogen atom (for example, chlorine, bromine, fluorine, iodine) or an alkyl group having 1 to 8 carbon atoms, and when there are a plurality of X, they are the same. May or may not be a
And b are integers of 1 to 4, respectively. And Y
Is a single bond, an alkylene group having 1 to 8 carbon atoms, or 2 to carbon atoms.
8 alkylidene group, C5-C15 cycloalkylene group, C5-C15 cycloalkylidene group or -S
-, - SO -, - SO 2 -, - O -, - CO- bond or general formula (II) or (II ')

[0008]

[Chemical 2]

The bond represented by ] It can be easily produced by reacting a dihydric phenol represented by the formula with phosgene or a carbonate compound. That is, for example, in a solvent such as methylene chloride, in the presence of a known acid acceptor or molecular weight regulator,
It is produced by a reaction between a dihydric phenol and a carbonate precursor such as phosgene, or by a transesterification reaction between a dihydric phenol and a carbonate precursor such as diphenyl carbonate.

Here, there are various dihydric phenols represented by the above general formula (I).
2-bis (4-hydroxyphenyl) propane [bisphenol A] is preferred. Examples of dihydric phenols other than bisphenol A include bis (4
-Hydroxyphenyl) alkane as 1,1- (4-
Hydroxyphenyl) methane; 1,1- (4-hydroxyphenyl) ethane; hydroquinone; 4,4′-dihydroxydiphenyl; bis (4-hydroxyphenyl)
Cycloalkane; Bis (4-hydroxyphenyl) sulfide; Bis (4-hydroxyphenyl) sulfone; Bis (4-hydroxyphenyl) sulfoxide; Bis (4
-Hydroxyphenyl) ether; compounds such as bis (4-hydroxyphenyl) ketone or bis (3,5-
Dibromo-4-hydroxyphenyl) propane; halogenated bisphenols such as bis (3,5-dichloro-4-hydroxyphenyl) propane and the like can be mentioned. These dihydric phenols may be used alone or in combination of two or more. Examples of the carbonic acid ester compound include diaryl carbonate such as diphenyl carbonate and dialkyl carbonate such as dimethyl carbonate and diethyl carbonate.

The polycarbonate resin used in the present invention is
A homopolymer using one of these dihydric phenols may be used, or a copolymer using two or more types may be used, and further, a polyfunctional aromatic compound may be obtained in combination with the dihydric phenol. It may be a thermoplastic randomly branched polycarbonate resin. Also, the number average degree of polymerization n
A copolymer resin such as a polycarbonate-polyorganosiloxane copolymer having an organosiloxane block of 5 or more may be used. The polycarbonate resin used in the present invention may have an appropriate molecular weight depending on the application, etc., but has a viscosity average molecular weight of 10000 to 50000, preferably from the viewpoint of mechanical strength and moldability. 12,000-30,000, more preferably 15,000
It is from 00 to 25,000. Viscosity average molecular weight is 10,000
If the amount is less than the above, the specific gravity may be low and the desired effect of improving the mechanical properties may not be recognized. Further, if it exceeds 50,000, the moldability is deteriorated, which is not preferable.

Next, there are various kinds of epoxysilane-treated glass hollow bodies as the component (B) constituting the resin composition of the present invention. For example, as a method for producing the same, first, a glassy fine granular material (glass balloon) having cavities is prepared by using alkali-containing glass, low-alkali glass, non-alkali glass or the like as a glass species. This glass balloon is usually easily obtained by expanding glass particles with a foaming agent. As the glass species, low-alkali glass or non-alkali glass is preferably used because of its effect on the polycarbonate resin. The glass balloon thus obtained usually has a specific gravity of 0.20 to 1.5 and a particle size of 3
˜80 μm, preferably 5-70 μm. And
Those having a pressure resistance of 400 (kg / cm ² ) or more are preferably used. If the particle diameter of the glass balloon is less than 3 μm, the effect of sufficiently improving mechanical properties such as rigidity is not recognized, and if it exceeds 80 μm, the glass balloon may be broken, and as a result, the resin composition It is not preferable because the specific gravity becomes large and the desired effect of improving mechanical properties is not recognized.

Then, the obtained glass balloon is surface-treated with an epoxysilane-based surface treatment agent,
It serves as a hollow glass body of the component (B). The epoxy silane-based surface treatment agent, there are various things,
A difunctional silane represented by the general formula (III) (D) _m -Si- (E) _n ... (III) is preferably used. Here, in the above general formula (III), D represents a reactive group with the filler, and examples thereof include alkoxy groups such as methoxy group, ethoxy group and propoxy group, and halide groups such as chlorine and bromine. E represents an epoxy group, m and n are integers of 1 to 3, and m + n = 4. General formula (I
Examples of the epoxysilane-based surface treatment agent represented by II) include 3-glycidoxypropylmethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, epoxyethyltriethoxysilane, and γ-glycidoxypropyltrisilane. Methoxysilane, glycidoxyethyltriethoxysilane, 1,2-epoxybutyltriethoxysilane, 1,2-epoxybutoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be mentioned. . Various methods can be adopted as a method for surface-treating a glass balloon using the above-mentioned epoxysilane-based surface treatment agent. For example, any of a dry method which is a direct treatment method for a glass balloon, a slurry method, a spray method, a direct method which is an integral blending method, and a masterbatch method may be used. The treatment amount is usually 0.1 to 5% by weight, preferably 0.5 to 2% by weight, based on the glass balloon.
Is.

The resin composition of the present invention comprises the above-mentioned component (A).
And (B), but the blending ratio thereof is 50 to 98 of the polycarbonate resin as the component (A).
% By weight and 50 to 2% by weight, and preferably 30 to 4% by weight of the epoxysilane-based surface-treated glass hollow body as the component (B).
It is compounded in a weight percentage. Where (B)
When the content of the component is less than 2% by weight, mechanical properties such as rigidity are not sufficient, and the improvement effect cannot be recognized. Also, 50% by weight
If it exceeds, the crack ratio in the molded product obtained using the resin composition of the present invention becomes high, and at the same time, the specific gravity becomes large, which is not preferable.

The resin composition of the present invention contains the above-mentioned components (A) and (B) as essential components, and, if necessary, as the component (C), various additive components, for example, inorganic fillers. Various additives such as agents, other synthetic resins, elastomers and the like can be blended within a range that does not impair the object of the present invention. The inorganic filler is added for the purpose of improving or increasing the mechanical strength and durability of the resin composition, and examples thereof include glass fiber (GF), carbon fiber (CF), potassium titanate whiskers, and boro. Examples thereof include aluminum acid whiskers, boron fibers, silicon nitride fibers, glass flakes, carbon black, calcium sulfate, calcium carbonate, calcium silicate, titanium oxide, alumina, silica, asbestos, talc, clay, mica and quartz powder. Further, as the various additives,
For example, hindered phenol-based, phosphite-based, and phosphate-based antioxidants, benzotriazole- and benzophenone-based UV absorbers, hindered amine-based light stabilizers, aliphatic carboxylic acid ester-based antioxidants, and the like. Examples include paraffin-based external lubricants, commonly used flame retardants, release agents, antistatic agents, coloring agents, and the like.

Other synthetic resins include, for example, polyester [eg, polyethylene terephthalate (PET), polybutylene terephthalate (PBT)].
Etc.], polyamide, polyethylene, polypropylene,
Polystyrene, acrylonitrile-styrene (AS) resin, acrylonitrile-butadiene-styrene (ABS)
Resin), polymethylmethacrylate, etc. can be mentioned. Further, as the elastomer, isobutylene-
MBS which is isoprene rubber, styrene-butadiene rubber and hydrogenated products thereof, ethylene-propylene rubber, acrylic elastomer and core-shell type elastomer
(Methyl methacrylate-butadiene-styrene) rubber, MAS (methyl methacrylate-butyl acrylate-styrene) rubber, etc. may be mentioned. Among them, core-shell type elastomer MAS rubber and the like are preferable.

The resin composition of the present invention comprises the above-mentioned component (A).
And the component (B) and, if necessary, various additive components used as the component (C) are mixed and kneaded. The compounding and kneading are methods commonly used, for example, ribbon blender, Henschel mixer,
It can be carried out by a method using a Banbury mixer, a drum tumbler, a single-screw extruder, a twin-screw extruder, a co-kneader, a multi-screw extruder or the like. The heating temperature during kneading is usually 240 to
It is selected in the range of 300 ° C. The polycarbonate resin composition thus obtained is applied to various known molding methods such as injection molding, blow molding, extrusion molding, compression molding, calender molding, rotational molding, etc., for molding products in the field of OA and household appliances. Molded articles can be manufactured.

[0018]

The present invention will be further described in detail with reference to production examples, examples and comparative examples. Examples 1 to 3 Polycarbonate (P
C) After dry-blending the epoxysilane-treated glass balloon, it was kneaded at 260 ° C. and a screw rotation speed of 60 rpm using a vented single-screw extruder [NVC-50, manufactured by Nakatani Machinery Co., Ltd.] to form pellets. The obtained pellets were dried at 120 ° C. for 12 hours, and then injection-molded at a molding temperature of 260 ° C. and a mold temperature of 80 ° C. to prepare a predetermined test piece.

Example 4 According to the blending amount shown in Table 1, polycarbonate (P
Example 1 except that C), the epoxysilane-treated glass balloon and the glass fiber (GF) were dry blended.
It carried out similarly to. Example 5 According to the blending amount shown in Table 1, polycarbonate (P
C), epoxy silane treated glass balloon and polyethylene terephthalate were dry blended,
It carried out like Example 1. Examples 6 and 7 According to the compounding amounts shown in Table 1, polycarbonate (P
Example 1 except that the epoxysilane-treated glass balloons different from C) and Example 1 were dry blended.
It carried out similarly to.

Comparative Example 1 Example 1 was repeated except that the polycarbonate (PC) was used alone. Comparative Examples 2 to 7 According to the blending amount shown in Table 1, polycarbonate (P
Example 1 was repeated except that C) and other components were dry blended.

With respect to the test pieces obtained in Examples and Comparative Examples, the weld high speed tensile strength, the density and the flexural modulus were measured as the quality evaluation. The results are shown in Table 2.

[0022]

[Table 1]

[0023]

[Table 2]

The raw materials used in the examples and comparative examples are as follows. (A) PC: TAFRON FN2200 (Mv = 2,200
0) [Polycarbonate manufactured by Idemitsu Petrochemical Co., Ltd.] (B) Glass hollow body 1) Glass balloon (G balloon) A: HSC110B (average particle diameter 12 μm, specific gravity 1.1, epoxysilane treatment) [Toshiba Ballotini Co., Ltd. ), Pressure resistance strength of about 1,000 kg / cm ² ] B: HSC110 (average particle diameter 12 μm, specific gravity 1.1, untreated) [Toshiba Ballotini Co., pressure resistance strength of about 1.0
00 kg / cm ² ] C: HSC110A (average particle size 12 μm, specific gravity 1.1, aminosilane treatment) [Toshiba Ballotini Co., Ltd., pressure resistance strength of about 1,000 kg / cm ² ] D: HSC110C (average particle size 12 μm, Specific gravity 1.1, acrylic silane treatment) [manufactured by Toshiba Ballotini Co., Ltd., compressive strength about 1,000 kg / cm ² ] E: PZ-6000PE (average particle size 40 μm, specific gravity 0.7)
5. Epoxysilane treatment) [Asahi Glass Co., Ltd.] F: Average particle size 100 μm, specific gravity 1.26, epoxysilane treatment (however, the pressure resistance indicates the pressure resistance when 13% is broken) 2) Glass beads (G beads) G: EMB-20 (average particle size 9 μm, specific gravity 2.6, untreated) [Toshiba Ballotini Co., Ltd.] (C) Others 1) Glass fiber H: 03MA409C (length 3 mm, Diameter 13 μm, urethane, aminosilane treatment) [Asahi Fiber Glass Co., Ltd.
2) Polyethylene terephthalate I: MA-523 [Mitsubishi Rayon Co., Ltd.]

The measurement of each item in the quality evaluation is
I followed (1) Weld high-speed tensile strength Tensile tester: TENSILON / UTM-5 (ORIE
Test condition: Test speed: 1.0 m / s (2) Density according to JIS-K7112 (3) Bending elastic modulus according to JIS-K7203

[0026]

As described above, according to the polycarbonate resin composition of the present invention, by selecting and blending the epoxysilane-treated hollow glass body as the filler, the general P
It is possible to obtain a molded product having a specific gravity equivalent to that of C and excellent in mechanical properties such as rigidity and weld strength. Therefore,
INDUSTRIAL APPLICABILITY The polycarbonate resin composition of the present invention is effectively used as a raw material for various molded products, particularly molded products in the OA field and the field of home appliances.

Claims (3)

[Claims] 1. (A) Polycarbonate resin 50 to 98
%, And (B) 50 to 2% by weight of epoxysilane-treated hollow glass body, a polycarbonate resin composition. 2. The polycarbonate resin composition according to claim 1, wherein the polycarbonate resin as the component (A) has a viscosity average molecular weight of 10,000 to 50,000. 3. The polycarbonate resin composition according to claim 1, wherein the epoxy silane-treated glass hollow body as the component (B) has an average particle diameter of 3 to 80 μm.