JP3201836B2 - Polycarbonate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin composition having excellent mechanical properties, appearance and impact resistance and having good melt heat stability.

[0002]

2. Description of the Related Art Conventionally, in order to make up for the lack of rigidity of polycarbonate resin, glass fiber is blended, and a molded article having excellent heat resistance and rigidity without decomposing polycarbonate resin has been obtained. Floating on the surface caused poor appearance and reduced surface impact.

In order to obtain excellent heat resistance, rigidity and appearance by blending an inorganic filler such as talc with the polycarbonate resin, the polycarbonate resin is decomposed due to the talc blending, and instead, a poor appearance such as silver is caused. (Japanese Patent Laid-Open No. 4-100829).

[0004]

SUMMARY OF THE INVENTION Under such circumstances, the present invention provides a polycarbonate resin molded article having excellent rigidity, appearance, and surface impact, and having good melting heat stability and mechanical strength in industrial scale production. It is an object of the present invention to provide a polycarbonate resin composition for obtaining a resin.

[0005]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, when blending talc with a polycarbonate resin, an aromatic polyester resin and a specific organic phosphate were mixed. It has been found that a polycarbonate resin molded product having excellent rigidity, appearance, and surface impact can be obtained by being used in combination and having good melt heat stability and mechanical strength in industrial-scale production, and the present invention has been achieved. It was done.

That is, the gist of the present invention is (A),
Based on the sum of (B), (C) and (D), aromatic polycarbonate resin (A) 50 to 97% by weight, talc (B) 1 to 35% by weight, aromatic polyester resin (C)
1 to 48% by weight, and the following formula: O = P (OR) _n (OH) _3-n (wherein R is an alkyl group having 10 to 30 carbon atoms, and n is 1 or 2). Organic polycarbonate (D) in an amount of 0.005 to 1% by weight.

Hereinafter, the present invention will be described specifically.

The aromatic polycarbonate resin used in the present invention can be obtained by a phosgene method of reacting various dihydroxydiaryl compounds with phosgene, a transesterification method of reacting a dihydroxydiaryl compound with a carbonate ester such as diphenyl carbonate, or the like. A typical example thereof is a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A).

As the dihydroxydiaryl compound as the raw material, in addition to bisphenol A, bis (4-
(Hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) ) Phenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-t-butylphenyl) propane, 2,2-bis (4-hydroxy- 3-bromophenyl) propane,
2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,
Bis (hydroxyaryl) alkanes such as 5-dichlorophenyl) propane, bis (hydroxyaryl) such as 1,1-bis (4-hydroxyphenyl) cyclopentane and 1,1-bis (4-hydroxyphenyl) cyclohexane Cycloalkanes, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-
Dihydroxydiaryl ethers such as 3,3'-dimethyldiphenylether, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxy-3,
Dihydroxydiaryl sulfides such as 3'-dimethyldiphenyl sulfide, 4,4'-dihydroxydiphenyl sulphoxide, 4,4'-dihydroxy-
Dihydroxydiarylsulfoxides such as 3,3'-dimethyldiphenylsulfoxide; and dihydroxydiarylsulfones such as 4,4'-dihydroxydiphenylsulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone. Can be

These may be used alone or in admixture of two or more. Alternatively, piperazine, dipiperidyl hydroquinone, resorcin, and 4,4'-dihydroxydiphenyls may be used in combination.

The talc (B) used in the present invention
Is a natural product composed of MgO and a silicate generally represented by the chemical composition formula Mg ₃ (Si ₄ O ₁₀ ) (OH) ₂ , and may be an iron-containing species or a nickel-containing species. The crystal shape of the talc particles is not particularly limited, and may be plate-like crystals or columnar crystals.

The average particle diameter of talc is 0.5 to
It is preferable to use a particle having a size of 6 μ and substantially not containing particles having a particle size of more than 30 μ.

Preferably, the talc surface may be treated with various silane coupling agents such as epoxy silane and amino silane.

The aromatic polyester resin used in the present invention is typically a polyalkylene terephthalate or a polyalkylene terephthalate obtained by a polycondensation reaction of an aromatic dicarboxylic acid such as terephthalic acid or a dialkyl ester thereof with an aliphatic glycol. There is a copolymer mainly composed of Preferable examples include polyethylene terephthalate, polybutylene terephthalate, and the like.

Examples of the above-mentioned aliphatic glycols include ethylene glycol, propylene glycol, tetramethylene glycol, hexamethylene glycol and the like, and a small amount of other diols or polyhydric alcohols such as fatty acids together with these aliphatic glycols. 20% by weight or less of cyclohexanediol based on aliphatic glycols,
Cyclohexane dimethanol, xylylene glycol,
Bisphenol A, 2,2-bis (4-hydroxy-
3,5-dibromophenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane, 2,2
-Bis (4-hydroxyethoxy-3,5-dibromophenyl) propane, glycerin, pentaerythritol, or the like may be used as a mixture.

Also, when terephthalic acid or its dialkyl ester is used as the aromatic dicarboxylic acid or its dialkyl ester, a small amount of another dibasic acid or polybasic acid or its alkyl ester, together with terephthalic acid or its dialkyl ester, For example, 20% by weight based on terephthalic acid or its dialkyl ester
The following phthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenylcarboxylic acid, adipic acid, sebacic acid,
Trimesic acid, trimellitic acid or an alkyl ester thereof may be used as a mixture.

The organic phosphate (D) used in the present invention is represented by the following formula.

O = P (OR) _n (OH) _{3-n In the} formula, R is a linear or branched alkyl group having 10 to 30 carbon atoms. If the alkyl group has a small number of carbon atoms, the boiling point of the compound will be low. Thus, when the resin composition is melted and kneaded at a high temperature, the resin composition is liable to evaporate and scatter, so that it is preferably a higher alkyl group. Particularly preferred is O = P (OC ₁₈
H ₃₇ ) _n (OH) _{3 -n} .

The above components used in the present invention are as follows:
It is blended in the following ratio.

The aromatic polycarbonate resin (A) is used in an amount of 50 to 50% based on the total weight of (A), (B), (C) and (D).
97% by weight, talc (B) of 1 to 35% by weight, aromatic polyester resin (C) of 1 to 48% by weight, and the following formula: O = P (OR) _n (OH) _3-n R is an alkyl group having 10 to 30 carbon atoms, and n is 1 or 2.) 0.005 to 1% by weight of the same organic phosphate ester (D) represented by the formula: %.

Here, the aromatic polycarbonate resin (A)
Is 50 to 97% by weight, preferably 55 to 90% by weight.
% By weight. When the amount is 50% by weight or less, the heat resistance, mechanical properties,
Properties such as dimensional characteristics are impaired, and if it is 97% by weight or more, the effect of improving rigidity and melting heat stability is small.

The amount of talc (B) is in the range of 1 to 35% by weight, preferably 5 to 30% by weight. If the amount is less than 1% by weight, the effect of improving rigidity is small, and if it exceeds 35% by weight, the effect of improving surface impact resistance is small.

The blending amount of the aromatic polyester resin (B) is in the range of 1 to 48% by weight, preferably 9 to 44% by weight. If the amount is less than 1% by weight, the effect of improving the melting heat stability is small, and if it exceeds 48% by weight, properties such as mechanical properties and dimensional properties are impaired, and the effect of improving surface impact properties is small.

The content of the organic phosphate (E) is 0.005 to 1% by weight, preferably 0.01 to 0.5% by weight.
% By weight. If the amount is less than 0.005% by weight, the effect of improving the melt heat stability is small, and if it exceeds 1% by weight, the melt heat stability is reduced due to the decomposition of the organic phosphate (E) itself.

The composition of the present invention is used by mixing these four components with a tumbler, a blender, a Banbury mixer, an extruder, etc., and it is most preferable to melt-knead the mixture with an extruder.

Further, in addition to the above-mentioned compounds, the composition of the present invention may contain various known additives such as lubricants such as paraffin wax, polyethylene wax, fatty acid ester, glass fiber, carbon fiber, mineral fiber, Fillers such as stainless steel fiber, glass flakes, glass beads, silica, calcium carbonate, nucleating agents, antioxidants such as hindered phenols and phosphites, ultraviolet absorbers, flame retardants,
It may contain a foaming agent, an antistatic agent, a pigment, a dye, and the like. In the composition of the present invention, other resins such as polyethylene, polystyrene, ethylene-α-olefin copolymer, MBS, acrylic rubber and the like as ABS or an elastomer are mixed within a range not impairing the effects of the present invention. Can be used.

Further, the resin composition of the present invention can be obtained by injection molding,
Molding can be performed by various methods known to those skilled in the art, such as extrusion molding and compression molding.

[0028]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the invention.

Examples 1 to 7 and Comparative Examples 1 to 9 As the aromatic polycarbonate resin (A), a bisphenol A type polycarbonate resin (A1) having a viscosity average molecular weight of 22,000 (manufactured by Mitsubishi Kasei Corporation, trade name: NOVAREX) 7022A) as talc (B) by Hayashi Kasei Co., Ltd.
Manufactured and trade name: Micron White 5000S (B1) and Micron White 5000S, epoxy silane 1%, talc (B2) surface-treated as an aromatic polyester resin (C), polyethylene terephthalate resin having an intrinsic viscosity of 0.77 ( C1) (manufactured by Nippon Unipet Co., Ltd., trade name: RT-543F) and polybutylene terephthalate resin (C2) having an intrinsic viscosity of 1.10 (Mitsubishi Kasei Corporation)
(Trade name: Novadur 5010) as an organic phosphate (D) represented by the following formula: O = P (OC ₁₈ H ₃₇ ) _n (OH) _3-n (a mixture of n = 1 and 2) MBS (manufactured by Mitsubishi Rayon Co., Ltd., trade name: Metablen C223S (E1)) using compound (D1) and an elastomer component
And E901 (E2) and a composite rubber-based graft copolymer obtained by graft-polymerizing one or more vinyl monomers onto a composite gum of a polyorganosiloxane rubber and a polyalkyl (meth) acrylate rubber, or the composite rubber Core-shell elastomer (Metablen S2001 (E3), trade name, manufactured by Mitsubishi Rayon Co., Ltd.) comprising a mixture of a vinyl-based graft copolymer and a vinyl-based polymer;
1) (03MA409 manufactured by Asahi Fiberglass Co., Ltd.)
After mixing using C) with the composition shown in Tables 1 and 2,
Using a single screw extruder with a screw diameter of 40 mm, resin temperature 2
The mixture was melt-kneaded at 70 to 280 ° C and pelletized.

[0030]

[Table 1]

[0031]

[Table 2]

Further, the pellets were placed in an atmosphere at 120 ° C. for 5 minutes.
After drying for an hour, using an injection molding machine with a mold clamping force of 75 tons (trade name: IS75PNII manufactured by Toshiba Machine Co., Ltd.), the cylinder temperature is 260 to 270 ° C, the mold temperature is 90 to 100 ° C, the injection time is 15 seconds, and the cooling is performed. At a time of 15 seconds, various test pieces required for the following plant value measurement were injection molded.

Using the obtained test pieces, tensile strength, tensile elongation, flexural modulus and surface impact energy were measured.

Further, in order to compare the heat stability of the composition, the cylinder temperature was set to 280 using the same injection molding machine.
The same test piece was molded at a temperature of 180 ° C. and a residence time of 180 seconds, and the appearance of the obtained molded article was observed.

The results are shown in Tables 3 and 4.

[0036]

[Table 3]

[0037]

[Table 4]

In the examples and comparative examples, methods for measuring various physical properties are as follows. The measurement was performed at a standard temperature of 23 ° C.

Tensile strength: Performed according to ASTM D-638.

Tensile elongation: Measured in accordance with ASTM D-638.

Flexural modulus: Performed in accordance with ASTM D-790.

Impact energy test conditions: Tester: High Rate Impact Te
ster RIT8000 (Rheometric.I)
nc.・ Test speed: 4.43 m / sec (assuming a drop from a height of 1 m) ・ Test piece: 100 mm × 2 mmt sheet ・ 100 mm × 2 mmt sheet was subjected to an impact test by the method shown in FIG. Impact energy was measured.

[0043]

The resin composition of the present invention has improved rigidity and melt heat stability while maintaining excellent appearance, heat resistance and mechanical strength having an aromatic polycarbonate resin.

Therefore, it has become possible to obtain a polycarbonate resin composition from which a molded article having good appearance and mechanical strength can be produced stably in production on an industrial scale.

The polycarbonate resin composition can be used for many purposes, but is particularly suitable for automobile parts and mechanical parts.

[Brief description of the drawings]

FIG. 1 is a schematic explanatory view of a method for measuring surface impact energy.

Claims (1)

(57) [Claims] 1. An aromatic polycarbonate resin (A) 5 based on the sum of (A), (B), (C) and (D).
0 to 97% by weight, talc (B) 1 to 35% by weight, aromatic polyester resin (C) 1 to 48% by weight, and the following formula O = P (OR) _n (OH) _3-n (where R is A polycarbonate resin composition comprising 0.005 to 1% by weight of an organic phosphate (D) represented by the following formula (1): an alkyl group having 10 to 30 carbon atoms, and n is 1 or 2.