JPH05311075A - Polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To obtain a polycarbonate resin composition which can give a molding excellent in impact resistance, rigidity, appearance, etc., by mixing a polycarbonate/polyorganosiloxane copolymer with a polycarbonate and fine glass fibers in a specified ratio. CONSTITUTION:The composition is produced by mixing 10-90wt.% polycarbonate/polyorganosiloxane copolymer (A) with 0-80wt.% polycarbonate resin (B) and 10-60wt.% glass fibers (C) of a mean fiber diameter of 3mum or below in a Herschel mixter or the like in such a mixing ratio that the proportion of the polysiloxane part of component A is 0.5-40wt.% based on the total amount of components A and B. This composition can desirably be used as the material of various moldings used in, e.g. the fields of electrical and electronic equipments. Component A can be obtained, for example by reacting a polycarbonate oligomer with a polyorganosiloxane terminated with a reactive group (e.g. polydimethylsiloxane).

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, and more particularly to a polycarbonate resin composition which is excellent in impact resistance and rigidity and which is capable of obtaining a molded article excellent in surface appearance.

[0002]

2. Description of the Related Art Polycarbonate resins are excellent in mechanical strength, electrical characteristics, transparency and the like, and are widely used as engineering plastics in various fields such as electric / electronic equipment fields and automobile fields. ing. As a polycarbonate resin having such characteristics, a glass fiber reinforced polycarbonate resin to which glass fibers are added in order to improve rigidity and dimensional stability is known. However, the impact resistance is significantly lowered and the surface appearance tends to be deteriorated by adding the glass fiber. Various studies have been made on methods for improving the impact resistance, which is reduced by adding glass fibers to a polycarbonate resin. For example, JP-A-55-160052 and JP-A-2-17
Japanese Patent No. 3061 discloses a method of introducing a polycarbonate-polyorganosiloxane copolymer into a polycarbonate resin. The impact resistance is improved by introducing this polycarbonate-polyorganosiloxane copolymer. However, there is a problem that the surface appearance is inferior. Further, as a method of improving the surface appearance, for example, Japanese Patent Publication No. 2-60693 and Japanese Patent Laid-Open No. 2-20693.
Japanese Patent No. 18454 discloses a method of blending a glass fiber having an average fiber diameter of 2 μm or less with a polycarbonate resin. In the method of incorporating this glass fiber, the impact resistance is poor and the rigidity is not sufficient, and improvement is desired.

[0003]

Therefore, the present inventors have
In view of the above situation, the inventors have conducted earnest studies to solve the drawbacks of the conventional method and to develop a polycarbonate resin composition which is excellent in impact resistance and rigidity and can obtain a molded article excellent in surface appearance. As a result, the average fiber diameter of the polycarbonate-polyorganosiloxane copolymer was 3 μm.
The present inventors have found a polycarbonate resin composition capable of obtaining a molded product having desired properties by blending glass fibers of m or less. The present invention has been completed based on such findings. That is, the present invention relates to (A) polycarbonate-polyorganosiloxane copolymer 10 to
90% by weight, (B) 0 to 80% by weight of a polycarbonate resin, and (C) a glass fiber 10 having an average fiber diameter of 3 μm or less.
-60% by weight, and (A) Polycarbonate-
Provided is a polycarbonate resin composition characterized in that the proportion of polyorganosiloxane part in the polyorganosiloxane copolymer is 0.5 to 40% by weight based on the total amount of the components (A) and (B). To do.

The polycarbonate-polyorganosiloxane copolymer (PC-PDM) which is the component (A) of the present invention.
There are various S), but the general formula (I) is preferable.

[0005]

[Chemical 1]

[In the formula, R ¹ and R ² are each a hydrogen atom, a halogen atom (for example, chlorine, bromine, fluorine, iodine) or an alkyl group having 1 to 8 carbon atoms, and they may be the same. And may be different, m and n
Are each an integer of 1 to 4, and when m is 2 to 4, R ¹ may be the same or different, and when n is 2 to 4, they are the same. Or it may be different. Z is an alkylene group having 1 to 8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, and 5 carbon atoms.
15 cycloalkylene groups, cycloalkylidene group or -SO ₂ of 5 to 15 carbon atoms -, - SO -, - S -, -
O-, -CO- bond, single bond or general formula (II)

[0007]

[Chemical 2]

The bond represented by ] A polycarbonate part having a repeating unit having a structure represented by the general formula (III)

[0009]

[Chemical 3]

[In the formula, R ³ , R ⁴ and R ⁵ are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group, and may be the same or different. Further, p and q are each an integer of 0 or 1 or more. ] A polyorganosiloxane part having a repeating unit represented by The degree of polymerization of the polyorganosiloxane part is preferably 5 or more, more preferably 100 or more. The above polycarbonate-polyorganosiloxane copolymer is a block composed of a polycarbonate part having a repeating unit represented by the general formula (I) and a polyorganosiloxane part having a repeating unit represented by the general formula (III). Copolymer having a viscosity average molecular weight of 10,000 to 50,000
0, preferably 15,000 to 35,000.
The n-hexane soluble content of the polycarbonate-polyorganosiloxane copolymer is preferably 1.0% by weight or less.

This polycarbonate-polyorganosiloxane copolymer is, for example, a polycarbonate oligomer (PC
An oligomer) and a polyorganosiloxane having a reactive group at the end (eg, a polydialkylsiloxane such as polydimethylsiloxane (PDMS) or polydiethylsiloxane or polymethylphenylsiloxane) constituting the polyorganosiloxane part, Dissolve in a solvent such as methylene, chlorobenzene, chloroform, add an aqueous solution of bisphenol sodium hydroxide,
It can be produced by carrying out an interfacial reaction using triethylamine, trimethylbenzylammonium chloride or the like as a catalyst. In addition, Japanese Patent Publication No. 44-30105
It is also possible to use a polycarbonate-polyorganosiloxane copolymer produced by the method described in JP-B No. 45-20510. Here, the polycarbonate oligomer having a repeating unit represented by the general formula (I) is prepared by a solvent method, that is, in the presence of a known acid acceptor and a molecular weight modifier in a solvent such as methylene chloride.
General formula (IV)

[0012]

[Chemical 4]

(Wherein R ¹ , R ² , Z, m and n are
Same as above. ) And a carbonate precursor such as phosgene, or a transesterification reaction between the dihydric phenol and a carbonate precursor such as diphenyl carbonate. There are various dihydric phenols represented by the above general formula (IV), and particularly 2,2-bis (4
-Hydroxyphenyl) propane [so-called bisphenol A] is preferred. Further, a part or all of bisphenol A may be replaced with another dihydric phenol. As dihydric phenols other than bisphenol A,
Bis (4-hydroxyphenyl) alkanes other than bisphenol A, 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; such as bis (3,5-dichloro-4-hydroxyphenyl) propane Examples thereof include halogenated bisphenols.

In the present invention, the polycarbonate oligomer used for producing the polycarbonate-polyorganosiloxane copolymer may be a homopolymer using one of these dihydric phenols, or two or more thereof may be used. It may be a copolymer. Further, it may be a thermoplastic random branched polycarbonate obtained by using a polyfunctional aromatic compound in combination with the dihydric phenol. In order to produce a polycarbonate-polyorganosiloxane copolymer having an n-hexane soluble content of 1.0% by weight or less, for example, the polyorganosiloxane content in the copolymer is set to 10% by weight or less, When the number of repeating units represented by the general formula (III) is 100 or more and the catalyst such as a tertiary amine is 5.3 × 10 ^-3 mol / (kg / oligomer) or more, the above copolymerization is carried out. It is preferable to carry out.
The ratio of the polyorganosiloxane part to the total amount of the above components (A) and (B) is 0.5 to 40% by weight, preferably 1.0 to 35% by weight. Here, when the content is less than 0.5% by weight, impact resistance is not improved, while on the other hand, 40% by weight
If it exceeds, a copolymer having a sufficient molecular weight cannot be obtained.

Next, the polycarbonate resin (PC) which is the component (B) of the present invention can be easily produced by reacting a dihydric phenol with phosgene or a carbonate compound. That is, for example, 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 a molecular weight regulator, or by reacting dihydric phenol with diphenyl carbonate. It is produced by a transesterification reaction with another carbonate precursor. Here, the dihydric phenol may be the same as or different from the compound represented by the general formula (IV). Examples of the carbonic acid ester compound include diaryl carbonate such as diphenyl carbonate and dialkyl carbonate such as dimethyl carbonate and diethyl carbonate.

On the other hand, the glass fiber of the component (C) used together with the polycarbonate-polyorganosiloxane copolymer of the component (A) and the polycarbonate resin of the component (B) has an average fiber diameter of 3 μm or less, preferably 2 μm.
m or less, more preferably 1 μm or less. When the average fiber diameter exceeds 3 μm, the surface appearance is poor and the rigidity is insufficient, which is not preferable. Its fiber length is 0.1-8mm,
It is preferably 0.3 to 6 mm, and the glass fiber may be any of alkali-containing glass, low-alkali glass and non-alkali glass. The form of the glass fiber is not particularly limited, and examples thereof include various types such as roving, milled fiber, chopped strand and the like. These glass fibers may be used alone or in combination of two or more kinds. It can also be used in combination with glass materials such as glass beads, glass flakes, and glass powder. Furthermore, in order to improve the affinity with resins, these glass materials contain aminosilane-based,
It may be surface-treated with a silane coupling agent such as an epoxy silane type, a vinyl silane type, an acryl silane type, a chromium complex compound or a boron compound.
As a suitable example of such a glass, as a commercially available product, E-FMW-800 (average fiber diameter of 0.
8 μm).

The resin composition of the present invention comprises the above-mentioned respective components (A), (B) and (C), and the mixing ratio of them is the polycarbonate (A) component.
Polyorganosiloxane copolymer 10 to 90% by weight, preferably 15 to 85% by weight, component (B) component polycarbonate resin 0 to 80% by weight, preferably 0 to 70% by weight and component (C) average fiber 10 to 60% by weight, preferably 15 to 55% by weight of glass fiber having a diameter of 3 μm or less
Is. (C) Component glass fiber content of 10% by weight
If it is less than the above range, the improvement in rigidity is insufficient and the desired mechanical strength cannot be obtained. On the other hand, if it exceeds 60% by weight, it is difficult or impossible to knead the resin, which is not preferable.

If desired, the resin composition of the present invention may contain various additives as the component (D) within a range not impairing the object of the present invention. For example,
Plate-like filler, granular filler, carbon fiber, metal fiber, inorganic filler, metal powder, and various additives,
Antioxidants such as hindered phenol type, phosphite type, phosphoric acid type, amine type, UV absorbers such as benzotriazole type and benzophenone type, light stabilizers such as hindered amine type, aliphatic carboxylic acid ester type And external lubricants such as paraffin and the like, commonly used flame retardants, flame retardant aids, release agents, antistatic agents, colorants and the like.

The resin composition of the present invention is prepared by blending the above-mentioned components (A), (B) and (C) with (D) if necessary, and kneading. A resin composition can be obtained. And, a method usually used for the compounding and kneading, for example, a ribbon blender, a Henschel mixer, a Banbury mixer, a drum tumbler, a single screw extruder, a twin screw extruder, a co-kneader, a multi-screw extruder, etc. Can be done using. The heating temperature for kneading is usually selected in the range of 250 to 300 ° C. The polycarbonate resin composition thus obtained can be applied to various known molding methods, for example, injection molding, blow molding, extrusion molding, compression molding, calender molding, rotational molding, and the like. It can be used to manufacture molded articles in various fields such as the automobile field.

[0020]

[Nippon Mineral Co., Ltd., average fiber diameter 0.8 μm]

II: A is surface-treated with aminosilane coupling agent. III: Glass fiber, MA-409C [Asahi Fiber Glass Co., Ltd., average fiber diameter 13 μm] IV: Glass beads, EGB-731A [Toshiba Parodyni Co., Ltd.] , Average particle size 30-40μ
m]

Production Example 1 (Production of PC Oligomer) 60 kg of bisphenol A was dissolved in 400 liters of a 5% sodium hydroxide aqueous solution to prepare an aqueous solution of bisphenol A sodium hydroxide. Then, a sodium hydroxide aqueous solution of bisphenol A kept at room temperature was introduced at a flow rate of 138 liters / hour and methylene chloride was introduced at a flow rate of 69 liters / hour into a tubular reactor having an inner diameter of 10 mm and a pipe length of 10 m through an orifice plate, Flow phosgene in parallel to this, 10.7 kg /
It was blown in at a flow rate of time and reacted continuously for 3 hours. The tubular reactor used here was a double tube, and cooling water was passed through the jacket to keep the reaction solution discharge temperature at 25 ° C. Further, the pH of the discharged liquid was adjusted so as to show 10 to 11. The reaction solution thus obtained is allowed to stand, whereby the aqueous phase is separated and removed, and the methylene chloride phase (220
Liter) was collected. Methylene chloride was removed by evaporation to obtain a flake-shaped polycarbonate oligomer. The degree of polymerization of the polycarbonate oligomer obtained here is 3 to
It was 4.

Production Example 2-1 (Synthesis of Reactive PDMS) 1483 g of octamethylcyclotetrasiloxane, 18.1 g of 1,1,3,3-tetramethyldisiloxane and 35 g of 86% sulfuric acid were mixed,
The mixture was stirred at room temperature for 17 hours. After that, the oil phase is separated,
25 g of sodium hydrogen carbonate was added and stirred for 1 hour. After filtration, vacuum distillation was performed at 150 ° C. and 3 torr to remove low-boiling substances. To a mixture of 60 g of 2-allylphenol and 0.0014 g of platinum as platinum chloride-alcoholate complex was added 294 g of the oil obtained above at a temperature of 90 ° C. The mixture was stirred for 3 hours while maintaining the temperature of 90 to 115 ° C. Extract the product with methylene chloride,
Excess 2-allylphenol was removed by washing 3 times with 80% aqueous methanol. The product was dried over anhydrous sodium sulphate and evaporated in vacuo to a temperature of 115 ° C. The obtained terminal phenol PDMS has a number of repeating dimethylsilanooxy units of 150 by NMR measurement.
Met.

Production Example 2-2 (Synthesis of Reactive PDMS) In Production Example 2-1,
The amount of 1,3,3-tetramethyldisiloxane is 7.72 g.
The same operation as in Production Example 2-1 was performed except that the above procedure was changed to. The terminal phenol PDMS thus obtained had a repeating number of dimethylsilanooxy units of 350 as measured by NMR. Production Example 2-3 (Synthesis of Reactive PDMS) In Production Example 2-1, 1,
137 g of 1,3,3-tetramethyldisiloxane
The same operation as in Production Example 2-1 was performed except that the above procedure was changed to. The number of repeating dimethylsilanooxy units in the obtained terminal phenol PDMS was 20 as determined by NMR. Production Example 2-4 (Synthesis of Reactive PDMS) In Production Example 2-1,
The amount of 1,3,3-tetramethyldisiloxane was 33.5 g
The same operation as in Production Example 2-1 was performed except that the above procedure was changed to. The terminal phenol PDMS thus obtained was found to have 80 repeating dimethylsilanooxy units by NMR measurement.

Production Examples 3-1 to 13 The reactive PDMSag obtained in Production Examples 2-1 to 4 was dissolved in 2 liters of methylene chloride and mixed with 10 liters of the PC oligomer obtained in Production Example 1. A solution prepared by dissolving 26 g of sodium hydroxide in 1 liter of water and triethylamine dcc were added thereto, and the mixture was stirred at 500 rpm for 1 hour at room temperature. Then, a 5 wt% sodium hydroxide aqueous solution 5
A solution prepared by dissolving 600 g of bisphenol A in liter, 8 liter of methylene chloride and bg of p-tert-butylphenol were added and stirred at 500 rpm for 2 hours at room temperature. Then add 5 liters of methylene chloride,
Further, washing with 5 liters of water, washing with 5 liters of 0.01N aqueous sodium hydroxide solution with alkali, washing with 5 liters of 0.1N hydrochloric acid and washing with 5 liters of water,
Finally, methylene chloride was removed, and chip-shaped PC-PDM
An S copolymer was obtained. Table 1 shows the amounts of a, b, and d used in Production Examples 3-1 to 13.

[0025]

[Table 1]

Table 2 shows Mv (viscosity average molecular weight), PDMS chain length (n: dimethylsilanooxy units), PDMS content and n-hexane soluble content of the obtained PC-PDMS copolymer. ..

[0027]

[Table 2]

The PDMS chain length (n: dimethylsilanooxy unit), PDMS content and n-hexane soluble content were measured by the following methods. [PDMS chain length (n: dimethylsilanooxy unit), P
Measurement of DMS Content] PDMS chain length was measured by ¹ H-NMR.
It was determined by the intensity ratio of the peak of the methyl group of dimethylsiloxane seen at 0.2 ppm and the peak of the methylene group of the PC-PDMS bond portion seen at 2.6 ppm. Also, PDMS
The content is 0.2 ppm by comparison with the peak of the isopropyl methyl group of bisphenol A seen at 1.7 ppm in ¹ H-NMR.
It was determined by the intensity ratio of the peak of the methyl group of dimethylsiloxane seen in m.

(Measurement of n-hexane soluble content) Soxhlet extracted component using n-hexane as a solvent. That is, 15 g of a chip-shaped copolymer, which is a sample, is used as a cylindrical filter paper N
It was collected at 0.84 (28 x 100 mm) and extracted with 300 ml of n-hexane by refluxing once every 3 to 4 minutes (20 ml / cycle) for 8 hours. Then, after evaporating 300 ml of n-hexane, the residue was weighed and used as an n-hexane-soluble component.

Examples 1 to 18 and Comparative Examples 1 to 25 P obtained as a base polymer in Production Examples 3-1 to 13
As C-PDMS copolymer and polycarbonate resin,
(E) Tafflon A-2200 [trade name: Mv = 21,00
0; manufactured by Idemitsu Petrochemical Co., Ltd.] and (G) Iupilon H
4000 (trade name: Mv = 15,000; manufactured by Mitsubishi Gas Chemical Co., Inc.) and the glass materials (I to IV) described above,
Blended in the proportions shown in Table 3, pellets were prepared by an extruder with a 30 mm vent, and injection molded at a molding temperature of 300 ° C. to obtain a molded product. The glass fiber was supplied from the downstream side of the hopper supply position of the raw material resin of the extruder.

[0031]

[Table 3]

[0032]

[Table 4]

[0033]

[Table 5]

For the molded articles obtained in the examples and comparative examples, Izod impact strength, flexural modulus and tensile breaking strength were measured as performance evaluation. Also, the surface appearance was checked. The results are shown in Table 4.

[0035]

[Table 6]

[0036]

[Table 7]

[0037]

[Table 8]

Further, the pellets obtained in Example 13 and Comparative Example 18 were press-molded at 300 ° C. and the haze was measured. The results are shown in Table 5.

[0039]

[Table 9]

Each measuring method and test method was as follows. Izod impact strength: Based on JIS K-7110. Flexural modulus: Based on JIS K-7103. Tensile breaking strength: Based on JIS K-7113. Surface appearance: ◯: Surface smoothness Δ: Surface is slightly rough. X: The surface is rough. Haze: Based on JIS K-7105. 3mm thick test piece is used

[0041]

INDUSTRIAL APPLICABILITY As described above, according to the present invention, a polycarbonate resin for a molded product having the original mechanical properties of polycarbonate, excellent impact resistance and rigidity, and excellent surface appearance. A composition can be obtained. Therefore, the polycarbonate resin composition of the present invention can be effectively used as a raw material for various molded products that are widely used in the fields of electric / electronic devices and automobiles.

Claims (1)

[Claims] 1. A polycarbonate-polyorganosiloxane copolymer (A) of 10 to 90% by weight, (B) a polycarbonate resin of 0 to 80% by weight, and (C) an average fiber diameter of 3
The proportion of the polyorganosiloxane part in the polycarbonate-polyorganosiloxane copolymer (A) is 10% to 60% by weight, and the proportion of the polyorganosiloxane part is 0 relative to the total amount of the components (A) and (B). A polycarbonate resin composition, characterized in that it is 0.5 to 40% by weight.