JPH02272057A - Polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To provide a polycarbonate resin composition having excellent heat resistance, mechanical properties, improved flowability, etc., and suitable in the fields of OA.office equipments, etc., by compounding a specific ABS resin, a specified styrene-maleic anhydride copolymer and glass fibers in specific amounts, respectively. CONSTITUTION:A polycarbonate resin composition comprises (A) 20-80 pts.wt. of a polycarbonate resin having structural units of the formula (Z is 1-8C alkylene, etc.; R<1> and R<2> are H, chlorine, etc.; m and n are 1-4) and a viscosity- average mol.wt. of 10000-100000, (B) 5-80 pts.wt. of an ABS resin having a rubber component content of 10-30wt.% and a metal index of 10-60g/10min, (C) 5-60 pts.wt. of styrene-maleic anhydride copolymer having a maleic anhydride content of 3-20mol% and 5-100 pts.wt. of glass fibers, the sum of the components A, B and C being 100 pts.wt.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel polycarbonate resin composition. More specifically, the present invention is a glass fiber-reinforced polycarbonate alloy that has excellent heat resistance, mechanical properties, dimensional stability, etc., and has good fluidity, and is suitable for use in the OA/office equipment field, industrial materials field, etc. It is related to.

[Prior art] Aromatic polycarbonate resin has been used in many fields as an engineering plastic due to its excellent mechanical properties such as rigidity and impact resistance, heat resistance, electrical properties, and dimensional stability. Glass fiber-reinforced materials are used in applications that require particularly superior heat resistance, mechanical properties, and dimensional stability, such as chassis for electrical and electronic equipment. It is being

By the way, polycarbonate resins generally have a high melt viscosity and poor moldability, and those containing glass mm are particularly prone to this tendency. Therefore, in order to lower the melt viscosity and improve fluidity (moldability), it has been attempted to lower the molecular weight of the resin used,
One method is to increase the composition ratio of resins with low melt viscosity. However, although this method improves the fluidity of the resulting composition,
The drawback is that heat resistance is inevitably reduced significantly.

On the other hand, a composition containing polycarbonate, ABS resin, styrene-maleic anhydride copolymer, etc. is disclosed as a non-reinforced polycarbonate resin composition that improves fluidity without impairing heat resistance or mechanical properties. However, when this composition is strengthened with glass ma, the problem arises that the fluidity decreases and the moldability deteriorates.

[Problems to be Solved by the Invention] The present invention overcomes the drawbacks of conventional glass fiber-reinforced polycarbonate alloys, and has excellent heat resistance, mechanical properties, dimensional stability, etc., as well as fluidity. The purpose of this study was to provide a glass fiber reinforced polycarbonate alloy with a high standard.

[Means for Solving the Problems] As a result of intensive research to develop a glass fiber reinforced polycarbonate alloy having the above-mentioned preferable properties, the present inventors found that a specific ABS resin and styrene-maleic anhydride were added to the polycarbonate resin. It was discovered that the object could be achieved by a composition made by blending an acid copolymer in a predetermined ratio and further reinforcing this composition with a required amount of glass fiber, and based on this knowledge, the present invention was developed. I was able to complete it.

That is, the present invention provides (A) polycarbonate resin 20
~80 parts by weight, (B) ABS resin 5~80 with a rubber component content of 10~30% by weight and a melt index of lO~609/10 minutes (humidity 220°C, load 10 to 9)
Part by weight and (C) maleic anhydride unit content is 3 to 20
Contains 5 to 60 parts by weight of styrene-maleic anhydride copolymer in mol% such that the total amount thereof is 100 parts by weight, and CD) 5 to 50 parts by weight of glass fiber per 100 parts by weight of this total amount. The present invention, which provides a polycarbonate resin composition comprising parts by weight, will be described in detail below.

In the composition of the present invention, the polycarbonate resin used as component (A) is -Formula %Formula % (1) (where Z is an alkylene group having 1 to 8 carbon atoms, 2 to 8 carbon atoms,
8 alkylidene group, cycloalkylene group having 5 to 15 carbon atoms, cycloalkylene group having 5 to 15 carbon atoms, simple bond, -so, -5o--s--o--co- or child, chlorine atom, A bromine atom or an alkyl group having 1 to 8 carbon atoms, which may be the same or different, m and 1 each being an integer of 1 to 4,
When m is 2 to 4, R1 may be different from each other, and when n is 2 to 4, R3 may be different from each other) Polymers may be mentioned.

The polycarbonate resin can be prepared by reacting a dihydric phenol with a carbonate precursor such as phosgene or by reacting a dihydric phenol with a carbonate precursor such as phosgene in a solvent such as methylene chloride in the presence of a known acid acceptor or molecular weight modifier. It can be produced by a transesterification reaction with a carbonate precursor such as.

As the dihydric phenol, for example, 1,2-bis(4
-Hydroxyphenyl)propane (bisphenol A)
, 2.2-bis(3-methyl-4-hydroxyphenyl)propane, 2.2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 1.2-bis(4-hydroxyphenyl)ethane, 3.3-bis(4-hydroxyphenyl)pentane, 1.1-(4-hydroxyphenyl)cyclohexane, 4.4'-dihydroxydi2
enyl, his(4-hydroxyphenyl) sulfite,
his(4-hydroxyphenyl)sulfone, bis(4-
hydroxyphenyl) sulfoxide, bis(4-hydroxyphenyl) ether, 4,4'-dihydroxybenzophenone, etc., or 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 2,2-bis(3 , 5-dichloro-4-hydroxyphenyl)propane, 32-bis(3-chloro-4-hydroxyphenyl)propane, 2.2-bis(3-bromo-4-hydroxyphenyl)propane halogenated bisphenols, etc. Among these dihydric phenols, bisphenol A is particularly suitable. Further, these dihydric phenols may be used alone or in combination of two or more types. moreover,
The polycarbonate resin used in the present invention may be a thermoplastic random branched polycarbonate made by reacting a polyfunctional aromatic compound with two phenols and/or a carbonate precursor, or a blend of polycarbonate resins of 2Q or more. It may be.

The polycarbonate resin has a viscosity average molecular weight of 10.000-100, from the viewpoint of mechanical strength and moldability.
000 is preferable, especially is, ooo~40,
000 is preferred.

In the composition of the present invention, A used as component (B)
BSalt fat is usually a conjugated diene rubber-aromatic vinyl compound-vinyl cyanide graft copolymer 100-15
It is a mixture of % by weight and % by weight of aromatic vinyl compound-vinyl cyanide copolymer O~851i. The conjugated diene rubber-aromatic vinyl compound-vinyl cyanide graft copolymer is obtained by graft polymerizing an aromatic vinyl compound or vinyl cyanide onto a conjugated diene rubber, and the graft copolymer The content of the conjugated diene rubber component in the coalescence is usually selected within the range of 5 to 70% by weight, and although there are no particular restrictions on the content ratio of aromatic vinyl compound units and vinyl cyanide units, it is usually within the range of 5 to 70% by weight. The ratio is selected in the range of 50:5Q to 80,820.

On the other hand, there is no particular restriction on the content ratio of aromatic vinyl compound units and cyanide vinyl units in the aromatic vinyl compound-vinyl cyanide copolymer, but the weight ratio is usually 5.
Selected in the range of 5:45 to 85:15.

Preferred examples of the conjugated diene rubber include butadiene rubber-like polymers such as polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, and butadiene-acrylic acid ester copolymer. In addition, examples of aromatic vinyl compounds include styrene, halogenated styrene, vinyltoluene, a-
Examples include methylstyrene and vinylnaphthalene, and among these, styrene is particularly preferred. Furthermore, examples of vinyl cyanide include acrylonitrile, methachloronitrile, and σ-halogenated acrylonitrile, among which acrylonitrile is preferred. Note that a part of the aromatic vinyl compound and vinyl cyanide may be replaced with other vinyl compounds, such as acrylic ester, methacrylic ester, vinyl acetate, vinyl chloride, etc. Among these, acrylic ester or methacrylic acid ester is preferable.

In the composition of the present invention, the ABS resin as the component (B) has a rubber component content in the range of 10 to 30% by weight, and has a melt index measured at a temperature of 220°C and a load of 10 to 9. (M x ) is 10~601F/10
It needs to be within minutes. If the content of the rubber component is less than 10% by weight, the effect of improving impact resistance will not be sufficiently exhibited, and if it exceeds 30% by weight, the fluidity and heat resistance of the resulting composition will tend to decrease. On the other hand, M! If so9. Heat resistance exceeding 'lo' decreases.

In the composition of the present invention, styrene-maleic anhydride copolymer (SMAIt resin) used as component (C)
, can be obtained by copolymerizing styrene and maleic anhydride according to a conventionally known method. As the polymerization method, either bulk polymerization method or solution polymerization method may be used,
Further, although the polymerization may be carried out in a single polymerization tank, it is preferable to carry out the polymerization in a continuous multi-stage system in which a plurality of stages of polymerization tanks are arranged in series.

In this continuous multi-stage polymerization method, a fixed amount of a reaction solution containing styrene and a copolymer produced by a certain degree of reaction in the previous stage is sequentially flowed through each stage, and a predetermined amount of maleic anhydride is added at each stage. is used.

In the composition of the present invention, the content of maleic anhydride M units in the styrene-maleic anhydride copolymer is 3 to 2.
It is necessary that the amount is 0 mol %, preferably in the range of 5 to 15 mol %. If the content is less than 3 mol%, the resulting composition will have insufficient heat resistance, and if it exceeds 20 mol%, the impact resistance will tend to decrease. In addition, the styrene-maleic anhydride copolymer has an f-Ml of 0.5 to 109/1 when measured at a temperature of 230°C and a load of 2.16 at 9.
It is desirable to use one within the range of 0 minutes.

Regarding the content ratios of the polycarbonate resin as the component (A), the ABS resin as the component (B), and the styrene-maleic anhydride copolymer as the component (C) in the composition of the present invention,
The total content of the components (A), (B) and (C) is 100
! ! The amount of component (A) is 20 to 80 parts by weight, preferably 30 to 70 parts by weight. ! 5 to 5 parts of component (B)
o21 parts by weight, preferably 10 to 70 parts by weight, and (C)
5 to 60 parts by weight of the ingredients, preferably lO to 50! ! It is necessary to contain it in the proportion of parts by weight. The content of the polycarbonate resin of the component (A) is 20! Below it is a! It has poor mechanical properties, and if it exceeds the somji portion, fluidity decreases and moldability deteriorates. In addition, (B) component ABS
5 resins! ! If it is less than 8 parts, the notch sensitivity will be high.
If it exceeds 0 parts by weight, heat resistance will decrease. On the other hand, if the content of the styrene-maleic anhydride copolymer (C) component is less than 5 parts by weight, the effect of improving heat resistance is small, and if it exceeds 60 parts by weight, impact resistance tends to decrease.

In the composition of the present invention, the above (A), CB) and (C
Glass fiber is blended as component (D) in an amount of 5 to 100 parts by weight with respect to 100 parts by weight of the total amount of components (). If the amount of glass fiber blended is less than 5 parts by weight, the stiffness improvement effect will not be sufficiently exhibited, and if it exceeds 100 parts by weight, fluidity will decrease and moldability will deteriorate.

The glass fiber may be any of alkali-containing glass, low-alkali glass, and alkali-free glass.
Further, there is no particular restriction on its form, and any form such as roving, chopped strand, or milled fiber can be used.

In addition, in the present invention, glass fibers having a diameter of 5 to 15 pm that have been previously treated with a surface treatment agent are treated with a suitable binding agent to be bundled into 100 to 1000 fibers, and the resulting strands are It is advantageous to use chopped strands cut to about 0.1 to 6 strands. Examples of the surface treatment agent include silane-based, titanate-based,
Examples include aluminum-based, chromium-based, zirconium-based, and borane-based coupling agents, among which silane-based coupling agents and titanate-based coupling agents are preferred, with silane-based coupling agents being particularly preferred.

There are no particular limitations on the method of treating the glass fibers with the surface treatment agent, and any conventional method can be used, such as an aqueous solution method, an organic solvent method, a spray method, and the like.

Further, as the sizing agent, there are, for example, urethane type, acrylic type, acrylonitrile-styrene type copolymer type, epoxy type, etc., and any of them can be used.

There are no particular restrictions on the method of convergence treatment of glass fibers using this convergence agent, and any conventional methods such as dip coating, roller coating, spray coating, flow coating, and tin coating may be used. A method can be used.

For the purpose of imparting flame retardancy to the composition of the present invention, various halogen-based flame retardants (bromine-containing flame retardants) can be used as desired. Examples of the flame retardant include decabromodiphenyl oxide, tetrabromobisphenol A epoxy, octabromodiphenyloxide, tetrabromobisphenol A1 and tetrabromobisphenol S.
Examples include. These flame retardants may be used alone or in combination of two or more, or it is also advantageous to use them in combination with antimony trioxide to further increase the flame retardant effect. .

Furthermore, the composition of the present invention may optionally include calcium carbon, calcium sulfate, barium sulfate, aluminum hydroxide, talc, clay, mica, silica, diatomaceous earth, montmorillonite, etc., as long as the object of the present invention is not impaired. Inorganic fillers such as bentonite, zinc borate, and barium metaborate, or additives such as antioxidants, light stabilizers, lubricants, antistatic agents, and colorants can be blended.

There are no particular limitations on the w4!1 method for preparing the polycarbonate resin composition of the present invention, and methods conventionally used for preparing glass fiber-reinforced polycarbonate resin compositions can be used. )component,
The required amounts of component (C), component (D), and various additive components used as necessary, for example,
Mix with a ribbon blender, Henschel mixer, tumbler blender, etc., or further mix after mixing.
A method of melting and kneading using a f/<< mixer, Nigoo, open roll, single screw extruder, two-wheel screw extruder, single screw reciprocating screw kneader, etc. can be used. At this time, the supply of glass fiber is
Either the top or side feeding method may be used; the melting crosstalk temperature is usually selected within the range of 240 to 280°C.

The composition of the present invention thus obtained can be molded into a desired molded article by a molding method such as injection molding, extrusion molding, or compression molding.

[Example] Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited in any way by these examples.

In addition, each physical property was determined by the following method.

(1) Bending strength, bending modulus It was determined in accordance with JISK-7203.

(2) Izotsu impact strength (with notch) JISK-71
10.

(3) Heat distortion temperature (HDT) Determined according to JIS K-7207 t; (load m l
8.6 kg/cra.

(4) Spiral 70-length (SFL) forming temperature 2
Under the conditions of 60℃ and injection pressure 80 kg/cl'-G,
Find the length when injection molded inside a metal plate with a thickness of 3 mm.
;.

In addition, the symbols for each component have the following meanings.

PC: Polycarbonate resin manufactured by Idemitsu Petrochemical Co., Ltd., Taflon FN2200ABS (A
BS resin, rubber component polybutadiene) ABS-1: Rubber component content 18% by weight Acrylonitrile unit content 20% by weight Styrene unit content 62% by weight Ml (220°C, tokg) 35g/10 min ABS-2i Rubber component content 5% by weight Ml 359/10 minutes ABS-3: Rubber component content 70% by weight Ml 359/10 minutes ABS-4: Rubber component content 1.8% by weight MI 59/
10 minutes ABS-5: Rubber component content 18Fi amount%M! 70g
/10 min SMA: Styrene-maleic anhydride copolymer, maleic anhydride unit content 14 mol%, Ml (230°C, 2.1 skg) 29/10 min 6F After treatment with glass fiber aminosilane coupling agent, urethane-based bundle Examples 1 to 6, Comparative Examples 1 to 9 The components shown in Table 1 were blended in the proportions shown in the table. Knead and pelletize at 240°C using a twin-screw extruder (TEM-35B).

Next, the pellet thus obtained was dried at 80° C. for 6 hours or more, and then molded products for physical property tests were produced using an injection molding machine and various evaluations were performed. The results are shown in Table 1.

(The following is a blank space) [Effect of the invention J The polycarbonate resin composition of the present invention has excellent heat resistance, mechanical properties, dimensional stability, etc., as well as fluidity (moldability).
It is a glass fiber reinforced polycarbonate alloy with improved properties, and is suitably used as a material for various parts in the fields of OA-office equipment and industrial materials, particularly chassis for electrical and electronic equipment.

Patent applicant: Idemitsu Petrochemical Co., Ltd. Representative Patent Attorney Fujibe Kubota

Claims (1)

[Claims] 1 (A) 20 to 80 parts by weight of polycarbonate resin, (
B) The rubber component content is 10 to 30% by weight, and the melt index is 10 to 60 g/10 minutes (temperature 220 ° C.,
5 to 80 parts by weight of ABS resin (load 10 kg) and (C)
Contains 5 to 60 parts by weight of a styrene-maleic anhydride copolymer having a maleic anhydride unit content of 3 to 20 mol% so that the total amount thereof is 100 parts by weight, and this total amount is 100 parts by weight. In contrast, (D) glass fiber 5-100
A polycarbonate resin composition comprising parts by weight.