JPH0485360A - Reinforced resin composition - Google Patents

Abstract

PURPOSE:To prepare the title compsn. excellent in impact strength, rigidity, heat resistance, dimensional stability, chemical resistance, weatherability, etc., by compounding a specified amt. of mica into a resin compsn. comprising a polycarbonate resin, a thermoplastic polyester, and an impact modifier each in a specified amt. CONSTITUTION:100 pts.wt. resin compsn. comprising 95-5wt.% polycarbonate resin (e.g. Panlite L-1250, a product of Teijin Kasei Co., Ltd.), 5-95wt.% thermoplastic polyester (e.g. a polyethylene terephthalate), and 40wt.% or lower impact modifier (e.g. a PP) is compounded with 0.5-100 pts.wt. mica.

Description

[Detailed Description of the Invention] [Industrial Field of Application] The present invention provides a method of applying
It has excellent heat resistance, impact resistance, rigidity, dimensional stability, chemical resistance, moldability, weather resistance, and thermal stability, and has a low coefficient of linear expansion, giving molded products excellent surface gloss and appearance. This invention relates to a reinforced resin composition that provides molded articles.

[Conventional technology/issues to be solved by the invention] Polycarbonate resin has traditionally been known as a resin with the highest impact resistance among engineering plastics and good heat resistance. Although it is used in various fields, it has drawbacks such as poor chemical resistance and moldability, and thickness dependence of impact strength.

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

In order to take advantage of the characteristics of each material and compensate for their shortcomings, various resin compositions have been developed, such as Japanese Patent Publication No. 3B-14035 and Japanese Patent Publication No. 39-20434.
, Special Publication No. Sho 55-9435, Special Publication No. Sho 82-37671, Special Publication No. Sho 62-34792, Special Publication No. Sho 62-13378
No., JP-A-82-295951, JP-A-63-831
It is disclosed in various publications such as No. 58.

However, these resin compositions do not simultaneously satisfy the impact resistance, heat resistance, chemical resistance, weather resistance, rigidity, etc. required for automobile parts. It is desired to have a low coefficient of linear expansion in order to reduce gaps between parts.

In order to lower the coefficient of linear expansion, attempts have been made to incorporate glass fiber, etc. This method results in a decrease in impact resistance, a decrease in moldability, and defects in the surface of the molded product, so it is not completely satisfactory. Molded products cannot be replaced.

The present invention was made in order to simultaneously satisfy a wide variety of required performances that cannot be satisfied with such conventional resin compositions.

[Means for Solving the Problems] The present inventors have conducted extensive studies in order to develop a resin composition having excellent characteristics that solves the problems of conventional resin compositions as described above, and have developed polycarbonate. The present inventors have discovered that the objective can be achieved by blending resin, thermoplastic polyester, mica, and, if necessary, an impact modifier in a predetermined ratio, and have completed the present invention.

That is, in the present invention, the polycarbonate resin is 5 to 95% (weight%, the same applies hereinafter).
, thermoplastic polyester 5-95%, impact modifier 4
Resin composition consisting of 0% or less (hereinafter also referred to as resin composition used in the present invention) 1 (10 parts (parts by weight, same hereinafter))
and 0.5 to 100 parts of mica.

[Example] 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), and is usually a combination of dihydric phenol and phosgene, or dihydric phenol and dihydric phenol. It is a resin obtained by reaction with carbonic acid diester.

As the dihydric phenol, especially bisphenol A
is 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, etc. tend to deteriorate, and if it exceeds 60,000, moldability, etc. tend to deteriorate.

The content of the polycarbonate resin in the resin composition used in the present invention is 5 to 95%, preferably 20 to 80%, and more preferably 40 to 80%. If the amount is less than 5%, the impact resistance, heat resistance, dimensional stability, etc. of the molded product obtained will decrease, while if it exceeds 95%, chemical resistance, moldability, etc. will decrease. And it's not desirable.

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.

The solution viscosity of the thermoplastic polyester is the logarithmic viscosity (1
v) is preferably in the range of 0.3 to 2.0, more preferably 0.5 to 1.5. If the logarithmic viscosity (IV) is less than 3, the impact resistance, chemical resistance, etc. of the resulting molded product will decrease, while if it exceeds 2.0, molding processability, etc. will tend to decrease. occurs.

Preferred specific examples of the thermoplastic polyester include:
In particular, polyethylene terephthalate and polytetramethylene terephthalate may be mentioned, but the present invention is not limited thereto.

The content of the thermoplastic polyester in the resin composition used in the present invention is 5 to 95%, preferably 20 to 80%, and more preferably 20 to 60%. If the blending amount is less than 5%, the chemical resistance and molding processability of the resulting molded product will decrease, while if it exceeds 95%, the impact resistance, heat resistance, etc. will decrease,
Undesirable.

Preferred specific examples of the impact modifier used if necessary 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 proportion of the impact modifier in the resin composition used in the present invention is 40% from the viewpoint of heat resistance, rigidity, moldability, etc.
It is as follows.

The core/shell type graft polymer is one in which a vinyl compound is graft-polymerized onto a rubber-like elastic body.

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 rubber-like elastic bodies include diene rubbers such as polybutadiene, butadiene-styrene copolymers, butadiene-butyl acrylate copolymers,
Examples include acrylic rubbers such as polybutyl acrylate and 2-ethylhexyl polyacrylate, and olefin rubbers such as ethylene-propylene copolymers and ethylene-propylene-diene copolymers. From the above, butadiene-acrylic acid ester copolymers, such as butadiene-butyl acrylate copolymers, are preferably used.

Among the butadiene-acrylic ester copolymers, 50 to 70% of acrylic ester and 30% butadiene
Particularly preferred are copolymers with ~50%. If the content of acrylic ester in the copolymer is less than 50%, good weather resistance cannot be achieved, whereas if it exceeds 70%, impact resistance, especially low-temperature impact resistance, tends to decrease. .

There is no particular limitation on the average particle diameter of the rubber-like elastic body, but 0
．． Those in the range of 0.05 to 2.0 are preferably used.

In addition, there is no particular limitation on the gel content, but 10
-90%, more preferably 40-90%.

Examples of the vinyl compounds used in the production of the core/shell type graft polymer include aromatic vinyl compounds, vinyl cyanide compounds, acrylic esters, and methacrylic esters. These may be used alone or in combination of two or more. Particularly preferred examples of the aromatic vinyl compound include styrene, an example of the vinyl cyanide compound is acrylonitrile, an example of the acrylic ester is butyl acrylate, and an example of the methacrylic ester is methyl methacrylate.

When preparing the core/shell type graft polymer, the ratio of the rubbery elastic material to the vinyl compound is 1
The vinyl compound is preferably 90-10%, more preferably 15-70%, compared to 0-90%, more preferably 30-85%. If the proportion of the rubber-like elastic body is less than 10%, impact resistance tends to decrease, while if it exceeds 90%, heat resistance tends to decrease.

Specific examples of the polyolefin polymer include polyethylene, polypropylene, etc., which may be suitably used, but are not limited thereto.

The polyolefin polymer may be a homopolymer or a copolymer, and there is no particular restriction on the degree of polymerization of the polyolefin polymer, and it can be arbitrarily selected as long as it has a melt index of usually 0.05 to 50 g and 710 min.・Used vines.

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

The solution viscosity of the thermoplastic polyester elastomer is 0.5 g/d at 25°C in a phenol/tetrachloroethane-1/1 (weight ratio) mixed solvent, and the logarithmic viscosity (1■) at 9 is 0.3 to 2. .0, even 0.4-1,
A value in the range of 5 is preferred. If the logarithmic viscosity is less than 0.3, impact resistance, chemical resistance, etc. tend to decrease;
If it exceeds 2.0, molding processability etc. tend to deteriorate.

Specific examples of aromatic dicarboxylic acids or ester-forming derivatives thereof used in the production include terephthalic acid, isophthalic acid, and ester-forming derivatives thereof. These may be used alone or in combination of two or more. On the other hand, specific examples of diols or ester-forming derivatives thereof include ethylene glycol, propylene glycol, tetramethylene glycol, and ester-forming derivatives thereof.

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
) with ethylene oxide added to bisphenol A
Examples include modified polyethylene glycol. Furthermore, as a specific example of polyether that can be used,
Examples include those exemplified in Japanese Patent No. -92953. These may be used alone or in combination of two or more. The number average molecular weight of the polyether is preferably in the range <700 to 3000 as described above. When the molecular weight is less than 700, heat resistance tends to decrease, while when it exceeds 3000, thermal stability tends to decrease.

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

The mica preferably has an average diameter of 0.1 to 20J.
IOI is more preferably 0.5 to IOI. If the average diameter is less than 0.1 mm, there will be little improvement in linear expansion coefficient and rigidity, and the surface gloss of molded products exceeding 20 um may decrease, become uneven, and impact resistance may decrease. becomes larger or more likely to occur.

Examples of the mica include muscovite, phlogovite, and biotite.

In addition, mica as described above can be used as a silane coupling agent,
It may be surface-treated with a coupling agent such as a titanate coupling agent.

Examples of the silane coupling agent include epoxysilane, aminosilane, and vinylsilane. Examples of titanate coupling agents include monoalkoxy type, chelate type, and coordinate type.

There are no particular limitations on the method of surface treating mica with a coupling agent, and any conventional method may be used. For example, this can be done by adding 0.1-10% of a coupling agent to mica and mixing at high speed while heating.

The blending amount of mica is in the range of 0.5 to 100 parts, preferably 2 to 100 parts of the resin composition used in the present invention.
-40 parts, more preferably 5-10 parts. If the amount of mica added is less than 0.5 parts, the effect on rigidity and linear expansion coefficient will not be sufficient, and if it exceeds 100 parts, the gloss of the molded product will decrease or the surface will become uneven, which is not preferable.

The reinforced resin composition of the present invention contains stabilizers such as phosphite and phenol stabilizers, light stabilizers, flame retardants, plasticizers, lubricants, mold release agents, ultraviolet absorbers, antistatic agents, pigments and dyes, etc. Can be mixed. Further, if necessary, it is also possible to use a small amount of reinforcing agent other than mica.

The reinforced resin composition of the present invention can be produced by any method. For example, it is produced by mixing using a blender super mixer or the like, or by kneading using a single or multi-screw extruder. Mixing and kneading may be carried out by mixing the polycarbonate resin, thermoplastic polyester, mica, and impact modifier used if necessary, or by first mixing and kneading some of the components.
It may be mixed and kneaded with the remainder.

The thus obtained reinforced resin composition is molded into automobile parts, electric/electronic parts, miscellaneous goods, etc. by various known methods such as injection molding and extrusion molding.
The molded product has excellent heat resistance, impact resistance, rigidity, dimensional stability, chemical resistance, moldability, weather resistance, and thermal stability, as well as a low coefficient of linear expansion, and the surface gloss of the molded product It has an excellent appearance.

Hereinafter, the reinforced resin composition of the present invention will be specifically explained based on Examples.

Examples 1 to IO and Comparative Examples 1 to 5 The following dry polycarbonate resin, thermoplastic polyester (polyethylene terephthalate resin), impact modifier, reinforcing agent, and phosphite stabilizer were added in the proportions shown in Table 1. The mixtures were premixed and melt-kneaded at 270° C. using a twin-screw press ratio machine to produce pellets. Test pieces were prepared by injection molding using the obtained pellets, and evaluated by the following method. The results are shown in Table 1.

(Polycarbonate resin) L-1250 (Viscosity average molecular weight 25.000) (Thermoplastic polyester) EFG-85A manufactured by Kuraray (Polyethylene terephthalate resin, logarithmic viscosity (no, 85)) (Impact resistance Modifier) C-1: CyP-547 manufactured by Sumitomo Noblen (polypropylene) C-2 FW-20G manufactured by Mitsubishi Kasei ■ (linear low-density polyethylene) C-3: Butyl acrylate by emulsion polymerization method 67%
A core/shell type graft in which 60 parts of a mixture of 20% acrylonitrile, 30% methyl methacrylate, and 50% styrene was graft copolymerized onto 40 parts of the left rubber-like elastic body with an average particle diameter of 0.15 and 33% butadiene. Polymer C-4: By the same method as C-3, 15% acrylonitrile, 30% methyl methacrylate and 5 styrene were added to 60 parts of the rubber-like elastic body on the left with an average particle diameter of 0.15 consisting of 64% butyl acrylate and butadiene 3696.
Core/shell type graft polymer C-5 obtained by graft copolymerization of 40 parts of a mixture consisting of 5% = component derived from dimethylene terephthalate and ethylene glycol, produced by the method described in JP-A-2-92953. The proportion of components derived from bisphenol A-modified polyethylene glycol with a number average molecular weight of 1000 is 60%, and the thermoplastic polyester elastomer C-6 with a logarithmic viscosity (m) of 0.70: similar to C-5. The proportion of components derived from dimethylene terephthalate and 1,4-butanediol produced by the method was 85%, the proportion of components derived from bisphenol A-modified polyethylene glycol with a number average molecular weight of 1000 was 15%, and the logarithmic viscosity ( Thermoplastic polyester elastomer (reinforcing agent) with IV) of 0.80 E-1: Muscovite-type mica with an average diameter of 6.2 am E-2: Muscovite-type mica with an average diameter of 2.5 tan Mica E-3: Muscovite-type mica with an average diameter of 2.5
- Surface treated with methacryloxypropyltrimethoxysilane E-4: Muscovite-type mica with an average diameter of 70 mm E-5 = average diameter of 4. Ota's calcium carbonate (phosphite stabilizer) PPP-36 (Izod impact value) manufactured by Adeka Argus Chemical ■ ASTM D-256, 1 inch, 4 inches, with notch, 23
Measured in °C.

(Falling ball strength) 150 vrra x 150 + m+i as a test piece
Measurement is performed using a flat plate of X 3 +am at a measurement temperature of -30°C, and the half height of failure x the weight of the ball (kg-m) is calculated.

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

(Heat-resistant) Measured with ASTM D-648, 4.6kg/c-load.

(Spiral flow value) Using a 3.5 oz injection molding machine, cylinder temperature 280
°C, injection pressure 100 ) cg/cd (gauge pressure),
Mold temperature 70℃, gate 3, mm x 3 mm
, width 4mm.

A thinly wound mold with a thickness of 3 mm was used to measure the flow length.

(linear expansion coefficient) Measured according to ASTM D-698.

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

(Molding/product appearance) Using a 5-ounce injection molding machine, the cylinder temperature was 280°C.
The appearance of a box-shaped molded product weighing approximately 100 g that was molded at a mold temperature of 70°C was observed with the naked eye and evaluated according to the following criteria.

○: Almost no surface unevenness and unevenness Δ: Back surface unevenness and unevenness ×: Significant surface unevenness and unevenness [hereinafter referred to as margins] [Effects of the invention] Book When the reinforced resin composition of the invention is used, impact resistance, rigidity,
Heat resistance, dimensional stability, moldability, chemical resistance, weather resistance,
It is possible to obtain molded products that have excellent thermal stability and a low coefficient of linear expansion, and have excellent surface gloss and appearance.

This molded product satisfies a wide variety of performance requirements.

Special permission Out wish Man Kanebuchi Chemical Industry Co., Ltd.

Claims (1)

[Scope of Claims] 1. 100 parts by weight of a resin composition consisting of 95 to 5% by weight of polycarbonate resin, 5 to 95% by weight of thermoplastic polyester, and 40% by weight or less of an impact modifier, and 0% mica.
．． A reinforced resin composition containing 5 to 100 parts by weight. 2. The reinforced resin composition according to claim 1, wherein the thermoplastic polyester is polyethylene terephthalate. 3. Claim 1, wherein the mica has an average diameter of 0.1 to 20 μm.
The reinforced resin composition described. 4. Claim 3, wherein the mica is surface-treated with a silane coupling agent or a titanate coupling agent.
The reinforced resin composition described. 5 Impact resistance modifier is acrylic ester 50-70
Copolymer of 10% by weight and 30-50% by weight of butadiene
A core/shell type graft polymer obtained by graft polymerizing 10 to 90% by weight of at least one of aromatic vinyl compounds, vinyl cyanide compounds, acrylic esters, and methacrylic ester compounds in the presence of 90% by weight. 2. The reinforced resin composition according to claim 1, wherein the reinforced resin composition is one or more selected from the group consisting of , polyolefin polymers, and thermoplastic polyester elastomers.