JP3040142B2 - Reinforced resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to heat resistance, impact resistance, rigidity, dimensional stability, chemical resistance, moldability, useful for automobile parts, electric / electronic parts, etc. The present invention relates to a reinforced resin composition having excellent weather resistance and thermal stability, having a low coefficient of linear expansion, and giving a molded article having excellent surface gloss and appearance.

[Problems to be Solved by Conventional Techniques and Inventions] Conventionally, polycarbonate resins have the highest impact resistance among engineering plastics and are also known as resins having good heat resistance. Although it is used in various fields, it has drawbacks such as poor chemical resistance and moldability, and the thickness dependence of impact strength.

On the other hand, thermoplastic polyester is excellent in chemical resistance and moldability, but has drawbacks such as poor impact resistance and dimensional stability.

Various resin compositions have been developed for the purpose of making use of the characteristics of the respective materials and complementing the disadvantages, for example, JP-B-36-14035, JP-B-39-20434, and JP-B-55-94.
No. 35, Japanese Patent Publication No. 62-37671, Japanese Patent Publication No. 62-34792, Japanese Patent Publication No.
These are disclosed in JP-A-62-13378, JP-A-62-295951 and JP-A-63-83158.

However, these resin compositions require impact resistance, heat resistance, chemical resistance, weather resistance, and the like required for automobile parts and the like.
Rigidity and the like cannot be satisfied at the same time, and improvement is strongly desired.

Further, when used for automobile exterior parts and the like, it is desired to have a low linear expansion coefficient in order to reduce the gap between the parts.

Attempts have been made to mix glass fibers, etc., with the aim of lowering the coefficient of linear expansion, but this method causes a reduction in impact resistance, a reduction in molding workability, a defect on the molded product surface, etc., and is satisfactory. I can't get a molded product that can be made.

The present invention has been made to simultaneously satisfy a wide variety of required performances that cannot be satisfied by such a conventional resin composition.

Means for Solving the Problems The present inventors have conducted intensive studies in order to develop a resin composition having excellent characteristics that has solved the problems in the conventional resin composition as described above. By blending resin, thermoplastic polyester, mica and, if necessary, an impact modifier in a predetermined ratio,
The inventors have found that the object can be achieved, and have completed the present invention.

That is, the present invention relates to a polycarbonate resin of 5 to 95% (% by weight, the same applies hereinafter), a thermoplastic polyester of 5 to 95%, and an impact modifier.
A resin composition composed of 40% or less (hereinafter, also referred to as a resin composition used in the present invention) is mixed with 100 parts (parts by weight, hereinafter the same) of 0.5 to 100 parts of mica having an average particle size of 0.1 to 20 μm. The present invention relates to a reinforced resin composition.

[Examples] The polycarbonate resin used in the present invention is a polycarbonate resin derived from a compound having two phenolic hydroxyl groups (hereinafter referred to as dihydric phenol),
It is usually a resin obtained by reacting a dihydric phenol with phosgene or a dihydric phenol with a carbonic acid diester.

As the dihydric phenol, bisphenol A is particularly preferred, but is not limited thereto.

The molecular weight of the polycarbonate resin is preferably in the range of 10,000 to 60,000 in terms of viscosity average molecular weight. If the molecular weight is less than 10,000, impact resistance, chemical resistance and the like tend to decrease, and if it exceeds 60,000, moldability and the like tend to decrease.

The compounding amount of the polycarbonate resin is 5 to 95% in the resin composition used in the present invention, preferably 20 to 80%, and more preferably
40-80%. If the amount is less than 5%, the resulting molded article will have reduced impact resistance, heat resistance and dimensional stability, whereas if it exceeds 95%, the chemical resistance, moldability, etc. will be reduced. And is not preferred.

The thermoplastic polyester used in the present invention is a polymer or copolymer obtained from an aromatic dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof, and is usually an alternating polycondensate.

As the solution viscosity of the thermoplastic polyester, the logarithmic viscosity (IV) at a concentration of 0.5 g / dl at 25 ° C. in a phenol / tetrachloroethane = 1/1 (weight ratio) mixed solvent is 0.3 to 0.3.
2.0, more preferably in the range of 0.5 to 1.5. If the logarithmic viscosity (IV) is less than 0.3, the resulting molded article will have reduced impact resistance, chemical resistance and the like, while if it exceeds 2.0, the moldability will tend to be reduced.

Specific preferred examples of the thermoplastic polyester include, but are not limited to, polyethylene terephthalate and polytetramethylene terephthalate.

The blending amount of the thermoplastic polyester is 5 to 95% in the resin composition used in the present invention, preferably 20 to 80%, and furthermore
20-60%. If the compounding amount is less than 5%, the resulting molded article will have reduced chemical resistance, moldability, etc., while 95%
If the amount exceeds the above range, impact resistance, heat resistance, etc. decrease, which is not preferable.

Preferred specific examples of the impact modifier used in the present invention include core / shell type graft polymers, polyolefin polymers, thermoplastic polyester elastomers and the like. These may be used alone or in combination of two or more.

The ratio of the impact modifier in the resin composition used in the present invention is 40% in terms of heat resistance, rigidity, moldability, and the like.
It is as follows.

The core / shell type graft polymer is obtained by graft-polymerizing a vinyl compound on a rubber-like elastic material.

The rubber-like elastic body preferably has a glass transition temperature of 0 ° C or lower, more preferably -40 ° C or lower.

Specific examples of such a rubber-like elastic material include, for example, polybutadiene, butadiene-styrene copolymer, diene rubber such as butadiene-butyl acrylate copolymer, polybutyl acrylate, and polyethyl acrylate 2-ethylhexyl. Acrylic rubber, ethylene-propylene copolymer, olefin rubber such as ethylene-propylene-diene copolymer may be exemplified, but from the viewpoint of weather resistance and impact resistance, butadiene-acrylate copolymer, for example, Butadiene-butyl acrylate copolymer is preferably used.

Among the butadiene-acrylate copolymers, acrylate 50-70% and butadiene 30-50
% Is particularly preferred. When the content of the acrylate in the copolymer is less than 50%, good weather resistance cannot be obtained. On the other hand, when the content exceeds 70%, the impact resistance, particularly the low-temperature impact resistance, tends to decrease. It is in.

There is no particular limitation on the average particle size of the rubber-like elastic body,
Those having a range of 0.05 to 2.0 μm are preferably used. Further, the gel content is not particularly limited, but 10 to 90
%, More preferably in the range of 40 to 90%.

Examples of the vinyl compound used for producing the core / shell type graft polymer include an aromatic vinyl compound, a vinyl cyanide compound, an acrylate, and a methacrylate. These may be used alone or in combination of two or more. Examples of the aromatic vinyl compound include styrene, examples of the vinyl cyanide compound include acrylonitrile, examples of the acrylate ester include butyl acrylate, and examples of the methacrylate ester include methyl methacrylate.

When the core-type / shell-type graft polymer is prepared, the ratio of the rubber-like elastic material to the vinyl-based compound is 10 to 90%, more preferably 30 to 85%, and the vinyl-based compound is 90 to 90%. %, More preferably 15 to 70%. If the proportion of the rubber-like elastic body is less than 10%, the impact resistance tends to decrease,
On the other hand, if it exceeds 90%, the heat resistance tends to decrease.

Specific examples of the polyolefin-based polymer include, for example, polyethylene, polypropylene and the like, which can be suitably used, but are not limited thereto. The polyolefin-based polymer may be a homopolymer or a copolymer, and the degree of polymerization of the polyolefin-based polymer is not particularly limited, and may be arbitrarily selected as long as the melt index is usually in the range of 0.05 to 50 g / 10 minutes.・ Can be used.

The thermoplastic polyester-based elastomer is a copolymer of an aromatic dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof and a polyether having a number average molecular weight of 700 to 3,000, and is derived from polyether. It is preferable that the proportion of the component is in the range of 5 to 80%, more preferably 10 to 70%. If the proportion of the component derived from polyether is less than 5%, impact resistance tends to decrease, and if it exceeds 80%, heat resistance tends to decrease.

The solution viscosity of the thermoplastic polyester elastomer is logarithmic viscosity (IV) at a concentration of 0.5 g / dl at 25 ° C. in a phenol / tetrachloroethane = 1/1 (weight ratio) mixed solvent.
Is preferably in the range of 0.3 to 2.0, more preferably 0.4 to 1.5. If the logarithmic viscosity is less than 0.3, impact resistance, chemical resistance and the like tend to decrease, while if it exceeds 2.0, moldability tends to decrease.

Specific examples of the aromatic dicarboxylic acid or its ester-forming derivative used in the production of the thermoplastic polyester elastomer include, for example, terephthalic acid, isophthalic acid, and their ester-forming derivatives. These may be used alone or in combination of two or more. On the other hand, specific examples of the diol or its ester-forming derivative include, for example, ethylene glycol, propylene glycol, tetramethylene glycol, and their ester-forming derivatives. These may be used alone or in combination of two or more. Further, specific examples of the polyether include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, a copolymer of ethylene oxide and propylene oxide, and 2,2-bis (p-hydroxyphenyl) propane (bisphenol A). And bisphenol A-modified polyethylene glycol in which ethylene oxide is added. Further, specific examples of polyethers that can be used include JP-A-2-92953.
Japanese Unexamined Patent Application Publication No. H10-26095. These may be used alone or in combination of two or more. The number average molecular weight of the polyether is 700 to 3 as described above.
A range of 000 is preferred. If the molecular weight is less than 700, the heat resistance tends to decrease, while if it exceeds 3000, the thermal stability tends to decrease.

In the present invention, as a reinforcing agent (filler), mica which is an aluminum silicate-based mineral is preferably used.

The mica has an average diameter of 0.1 to 20 μm, more preferably 0.5 to 10 μm. If the average diameter is less than 0.1 μm, the effect of improving the coefficient of linear expansion and rigidity is small, and if the average diameter exceeds 20 μm, the surface of the molded product may have reduced gloss, unevenness, or a large decrease in impact resistance. Easier to do.

Examples of the mica include, for example, those of the type such as muscobite, phlogopite, and biotite.

Further, the mica may be subjected to a surface treatment with a coupling agent such as a silane coupling agent or a titanate coupling agent.

Examples of the silane coupling agent include epoxy silane, amino silane, and vinyl silane. Examples of titanate-based coupling agents include monoalkoxy type, chelate type, and coordinate type.

The method of surface-treating the mica with a coupling agent is not particularly limited, and can be carried out by a usual method. For example, it can be performed by adding 0.1 to 10% of a coupling agent to the mica and mixing at high speed while heating.

The amount of the mica is the resin composition 100 used in the present invention.
To 0.5 part to 100 parts, preferably 2 to 100 parts.
It is 40 parts, more preferably 5 to 10 parts. If the amount of the mica is less than 0.5 part, the effect on the rigidity and the coefficient of linear expansion is not sufficient, and if it exceeds 100 parts, the gloss of the molded article is lowered or the surface becomes uneven, which is not preferable.

The reinforced resin composition of the present invention includes phosphite-based, phenol-based stabilizers, light stabilizers, flame retardants, plasticizers, lubricants, mold release agents, ultraviolet absorbers, antistatic agents, pigments / dye, etc. Can be blended. If necessary, a small amount of a reinforcing agent other than the mica may be used.

The production of the reinforced resin composition of the present invention can be performed by any method. For example, it is manufactured by mixing using a blender, a super mixer, or the like, or kneading with a single-screw or multi-screw extruder. For mixing and kneading, polycarbonate resin, thermoplastic polyester, average particle system
The mica of 0.1 to 20 μm and the impact modifier used if necessary may be mixed at once, and some of the components may be mixed and kneaded first, followed by mixing and kneading with the rest. Is also good.

The reinforced resin composition thus obtained is molded into automobile parts, electric / electronic parts, miscellaneous goods, etc. by various known methods, for example, injection molding, extrusion molding, etc., and the molded article has heat resistance. , Impact resistance, rigidity, dimensional stability,
Excellent in chemical resistance, molding processability, weather resistance and thermal stability, and has low coefficient of linear expansion, surface gloss of molded products,
The appearance is excellent.

Hereinafter, the reinforced resin composition of the present invention will be specifically described based on examples.

Examples 1 to 9 and Comparative Examples 1 to 6 The following dried polycarbonate resin, thermoplastic polyester (polyethylene terephthalate resin), impact modifier, reinforcing agent and phosphite-based stabilizer
The mixture was premixed in the proportions shown in the table and melt-kneaded at 270 ° C. using a twin screw extruder to produce pellets. A test piece was prepared from the obtained pellet by an injection molding method and evaluated by the following method. The results are shown in Table 1.

(Polycarbonate resin) Panlite L-1250 manufactured by Teijin Chemicals Ltd. (viscosity average molecular weight 25,000) (Thermoplastic polyester) EFG-85A (polyethylene terephthalate resin, logarithmic viscosity (IV) 0.85) manufactured by Kuraray Co., Ltd. C-1: WP-547 (polypropylene) manufactured by Sumitomo Noblen Co., Ltd. C-2: FW-20G (linear low density polyethylene) manufactured by Mitsubishi Kasei Co., Ltd. C-3: Emulsion polymerization method A core obtained by graft-copolymerizing 60 parts of a mixture of 20% of acrylonitrile, 30% of methyl methacrylate and 50% of styrene on 40 parts of a rubbery elastic body having an average particle size of 0.15 μm composed of 67% of butyl acrylate and 33% of butadiene. / Shell-type graft polymer C-4: butyl acrylate 6
0.15μm average particle system consisting of 4% and 36% butadiene
A mixture of 60 parts of rubber-like elastic material made of acrylonitrile 15%, methyl methacrylate 30% and styrene 55%
Core / shell type graft polymer obtained by graft copolymerization of 40 parts C-5: The proportion of components derived from dimethylene terephthalate and ethylene glycol prepared by the method described in JP-A-2-92953 is 40%. , Number average molecular weight 1000
The dimethylene terephthalate and 1 were prepared by the same method as the thermoplastic polyester elastomer C-6: C-5 having a ratio of a component derived from bisphenol A-modified polyethylene glycol of 60% and an intrinsic viscosity (IV) of 0.70. 85% of the component derived from 4,4-butanediol, and 15% of the component derived from bisphenol A-modified polyethylene glycol having a number average molecular weight of 1,000,
Thermoplastic polyester-based elastomer having a logarithmic viscosity (IV) of 0.80 (Reinforcing agent) E-1: Mascobite mica having an average diameter of 6.2 μm E-2: Muscobite mica having an average diameter of 2.5 μm E-3: Average 2.5 μm diameter mascotite mica is γ-
Surface treated with methacryloxypropyl-trimethoxysilane E-4: Muscovite-type mica with an average system of 70 μm E-5: Calcium carbonate with an average system of 4.0 μm (phosphite-based stabilizer) ADEKA ARGUS CHEMICAL CO., LTD. (Izod impact value) ASTM D-256, 1/4 inch, notched, measured at 23 ° C.

(Falling ball strength) A 150 mm x 150 mm x 3 mm flat plate was used as a test piece and measured at a measurement temperature of -30 ° C.
m).

(Flexural modulus) ASTM D-790, measured at 23 ° C.

(Heat resistance) Measured with ASTM D-648, 4.6 kg / cm ² load.

(Spiral flow value) Using a 3.5 oz injection molding machine, cylinder temperature 280 ° C,
At an injection pressure of 100 kg / cm ² (gauge pressure) and a mold temperature of 70 ° C, the flow length was measured using a spiral wound mold with a gate of 3 mm x 3 mm, width of 4 mm and thickness of 3 mm.

(Linear expansion coefficient) Measured by ASTM D-696.

(Surface gloss) Measured JIS K-7105, 60 degree reflectance.

(Appearance of molded product) Using a 5-ounce injection molding machine, cylinder temperature 280 ° C,
The appearance of a box-shaped molded product having a weight of about 100 g molded at a mold temperature of 70 ° C. was visually observed and evaluated according to the following criteria.

：: Surface unevenness and unevenness are hardly observed △: Surface unevenness and unevenness are recognized ×: Surface unevenness and unevenness are remarkable [Effects of the Invention] When the reinforced resin composition of the present invention is used, it is excellent in impact resistance, rigidity, heat resistance, dimensional stability, moldability, chemical resistance, weather resistance, heat stability, and low wire. A molded article having an expansion coefficient and excellent in surface gloss and appearance of the molded article can be obtained. This molded product satisfies a wide variety of performance requirements.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C08L 67/00 C08L 67/00 (56) References JP-A-1-70554 (JP, A) JP-A-62-295953 (JP) , A) JP-A-59-131646 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 67/00-67/04 C08L 69/00

Claims (4)

(57) [Claims] (1) 95 to 5% by weight of a polycarbonate resin, 5 to 95% by weight of a thermoplastic polyester, and an impact modifier 40
100% by weight of the resin composition consisting of
A reinforced resin composition containing 0.5 to 100 parts by weight of mica of 0.1 to 20 μm. 2. The reinforced resin composition according to claim 1, wherein the thermoplastic polyester is polyethylene terephthalate. 3. The reinforced resin composition according to claim 1, wherein the mica is surface-treated with a silane coupling agent or a titanate coupling agent. 4. An impact modifier comprising an acrylic ester 50
Copolymer of 70 to 70% by weight and butadiene 30 to 50% by weight
A core / shell type graft polymer obtained by graft-polymerizing 10 to 90% by weight of at least one of an aromatic vinyl compound, a vinyl cyanide compound, an acrylate ester and a methacrylate compound in the presence of 90% by weight; The reinforced resin composition according to claim 1, wherein the composition is at least one member selected from the group consisting of a polyolefin-based polymer and a thermoplastic polyester-based elastomer.