JPH01118569A - Polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition excellent in mechanical strengths, flow and flame retardancy, by using a specified polycarbonate and a polyamide resin as principal components. CONSTITUTION:This polycarbonate resin composition comprises a polycarbonate resin having repeating units (I) of formula I and repeating units (II) of formula II, terminated with pentahalogenophenoxy groups and having a viscosity-average MW>=5,000 and a polyamide resin (b). Although the molar fraction of said repeating units (I) and (II) may be suitably selected according to the purpose of use, etc., it is usually in the range of m/(m+n)=0.005-0.2 [wherein m is the molar fraction of repeating units (I), and n is that of repeating units (II)]. The degree of polymerization of the polycarbonate is suitably at least 5,000, preferably, in the range of 10,000-30,000, in terms of a viscosity-average MW. A polycarbonate of a viscosity-average MW<5,000 does not exhibit sufficient mechanical strengths such as impact resistance.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a polycarbonate resin composition, and more specifically, a polycarbonate resin composition having a novel structure and excellent mechanical strength, fluidity, and flame retardancy, which is mainly composed of polycarbonate and polyamide resin. The present invention relates to a polycarbonate resin composition.

[Prior art and problems to be solved by the invention] Conventionally, flame-retardant polycarbonates have, for example, halogen-substituted phenoxy groups (pentabromophenoxy groups, tetrachlorophenoxy groups, tribromophenoxy groups, etc.) at the terminals. polycarbonate with
Various methods are known, including JP-A-0715).

However, although these conventional polycarbonates have excellent flame retardancy, they do not have sufficient mechanical strength such as impact resistance or fluidity.

Therefore, the group of the present inventors has recently succeeded in developing a polycarbonate with a new structure that has significantly improved flame retardancy while maintaining the mechanical and optical properties of conventional polycarbonate. Gansho 62-L2967
3 specification).

However, this new polycarbonate has a high melt viscosity, so there are some problems with molding processability.
Stress cracks may occur depending on the organic solvent.

Under these circumstances, the inventors of the present invention have conducted intensive research to solve the problems while maintaining the advantages of the above-mentioned new polycarbonate.

[Means for solving the problem] As a result, by blending polyamide resin with this new polycarbonate, it is possible to
It has been found that fluidity and solvent resistance can be significantly improved, and flame retardancy can also be improved. The present invention was completed based on this knowledge. That is, the present invention has a repeating unit (1) represented by the formula (a) and a repeating unit (II) represented by the formula (a), a pentahalogenophenoxy group is bonded to the terminal position, and the viscosity average molecular weight is 5000 or more. The present invention provides a polycarbonate resin composition containing polycarbonate and (b) a polyamide resin as main components.

As mentioned above, the composition of the present invention has (a) a polycarbonate and (b) a polyamide resin as main components.
) has a repeating unit (1) represented by formula (B) and a repeating unit (II) represented by formula (B). The molar fraction of repeating units (1) and (IF) is not particularly limited (it is arbitrary and may be selected appropriately depending on the purpose of use, etc., but usually the molar fraction of repeating unit (1) is m, and when the mole fraction of repeating unit (II) is n, m/(m+ n
) = 0.005 to 0.2, preferably o, oi to 0,1
is within the range of

In addition, the polycarbonate that is component (a) has a pentahalogenophenoxy group at the terminal position of the molecule, especially at both ends, that is, the general formula (wherein, X1 to X5 each represent a halogen atom. A functional group represented by ), which can be different or different, is bonded to it.

Furthermore, regarding the degree of polymerization of the polycarbonate component (a), the viscosity average molecular weight is 5,000 or more, preferably 1
A range of 0,000 to 30,000 is suitable. If the viscosity average molecular weight is less than 5.000, mechanical strength such as impact resistance is insufficient.

This polycarbonate has the above repeating unit (■).

(II), and a pentahalogenophenoxy group of general formula (C) is bonded to the terminal position, and these random copolymers and block copolymers.

There are various types such as alternating copolymers.

Note that there is no problem even if a small amount of repeating units other than repeating units (I) and (II) are mixed into the molecular chain of this polycarbonate.

The polycarbonate component (a) can be produced by various methods, but a preferred method is the method described in Japanese Patent Application No. 62-29673.

On the other hand, the polyamide resin which is the component (b) of the composition of the present invention includes ring-opening polymers of lactams, polycondensates of diamines and dibasic acids, polycondensates of ω-amino acids, and the like. A mixture or copolymer of these may be used. Specifically, nylon-6, nylon-66, nylon-6/66, nylon-6/10. Nylon-6.1
2. Examples include nylon-11 and nylon-12.

The composition of the present invention has the above-mentioned (a) component and Φ) component as main components, and the blending ratio of these two components may be determined as appropriate depending on the type of each component, the use of the composition, etc. However, it is generally determined in the range of 30 to 99% by weight of polycarbonate as component (a), preferably 50 to 95% by weight, and 70 to 1% by weight, preferably 50 to 5% by weight of polyamide resin as component (b). .

The blending ratio of component (a) polycarbonate is 99
If the amount exceeds % by weight, sufficient fluidity and solvent resistance cannot be imparted to the composition. Moreover, if it is less than 30% by weight, impact resistance decreases.

In addition, the composition of the present invention may contain various inorganic fillers, additives, other synthetic resins, elastomers, etc. in addition to the above-mentioned components (a) and (b), as long as they do not impede the purpose of the present invention. It can be blended according to the requirements. Furthermore, the flame retardancy of the composition can be further improved by adding various flame retardants. These various additive components are explained as follows.

First, the inorganic filler added for the purpose of increasing the mechanical strength, durability, or weight of the resin composition of the present invention includes:
For example, glass fiber, glass peas.

Glass flakes, carbon black, calcium sulfate,
Examples include calcium carbonate, silica, asbestos, talc, clay, mica, and quartz powder.

In addition, the additives include hindered phenol,
Phosphorous (sulfite ester, phosphate ester), amine-based antioxidants, benzotriazole-based, benzophenone-based ultraviolet absorbers, aliphatic carboxylic ester-based, paraffin-based external lubricants, and more. Examples include a mold release agent, an antistatic agent, a coloring agent, and the like. Here, the above-mentioned hindered phenolic antioxidants include BIT (2,6-di-tert-butyl-p-cresol), "Irganox 1076J (trade name)" and "Irganox 1010" manufactured by Ciba Geigy. (Product name), “Ethyl 330” manufactured by Ethyl
J (product name), “Sumilizer〇MJ” manufactured by Jumin Kagaku ■
(product name) etc. are preferably used. Examples of other synthetic resins include polyethylene, polypropylene, polystyrene, AS resin, ABS resin, and polymethyl methacrylate. In addition, as elastomers, isobutylene-isoprene rubber, styrene-
Examples include butadiene rubber, ethylene-propylene rubber, and acrylic elastomer.

In addition, tetrabromobisphenol A is used as a flame retardant.
(TBA), polycarbonate oligomers produced by the reaction of TBA and phosgene, flame retardants such as decabromobisphenol A, brominated epoxy, and even s b, o : I+
- Examples include flame retardant aids such as sodium antimonate.

The polycarbonate resin composition of the present invention can be obtained by blending and kneading the above-mentioned components. combination,
Conventional methods can be used for kneading, such as a pump blender, Henschel mixer, or Banbury mixer.
, drum tumbler-9 single screw extruder, two-wheel screw extruder.

This can be carried out using a co-kneader, multi-screw extruder, or the like. The heating temperature during kneading is usually 250 to 300°.
C is appropriate.

The thus obtained polycarbonate resin composition can be molded by various known molding methods, such as injection molding, extrusion molding, compression molding, two-turn calendar molding, etc., to molded products in the automotive field such as automobile bumpers, and in the home appliance field. Molded products can be manufactured.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples.

Synthesis Example (Synthesis of polycarbonate oligomer of bisphenol A) In a flask with an internal volume of 2j2 and equipped with a stirrer, 91 g of bisphenol A, 330 n+f of methylene chloride, and 1.
560 mf of a 7N aqueous sodium hydroxide solution was added and stirred, and phosgene was blown therein for 70 minutes while cooling in a water bath. When the resulting reaction solution was allowed to stand at room temperature, a methylene chloride solution of the oligomer was separated and produced in the lower layer. This oligomer solution has an oligomer concentration of 300 g/f, a number average molecular weight of 550, and a chloroformate group concentration of 1.0.
It was mol/2.

Production Example 1 (Production of polycarbonate) In a container with an internal volume of 501 cm and equipped with a stirrer, the polycarbonate oligomer synthesized in the above synthesis example 82° Aqueous sodium hydroxide solution of bisphenol sulfone [123 g (0.49 mol) of bisphenol sulfone, sodium hydroxide] 6
9 g, water 520 mff1) 640 ctrl and triethylamine 4.4 g (0,043 mol) were added, and 500
Stir by rotating.

After 10 minutes, an aqueous sodium hydroxide solution of pentabromophenol [230 g (0.47 mol) of pentabromophenol, 37.6 g of sodium hydroxide, and 2.84 mol of water] was added and stirred. After 50 minutes, an aqueous sodium hydroxide solution of bisphenol A [bisphenol A 510 g (2.24 mol), sodium hydroxide 260 g, water 4.41]
4.91 and methylene chloride 62 were added and stirred.

After stirring for 60 minutes, the resulting reaction product was separated into an aqueous phase and a methylene chloride phase containing the produced copolymer (polycarbonate consisting of repeating unit (1') and repeating unit (n)).

This methylene chloride phase was mixed with water and acid (0.1N hydrochloric acid).

Washed with water. Methylene chloride was removed from this methylene chloride sum at 40°C under reduced pressure to obtain a white powder.

After further drying at 120°C for 1 day and night, the mixture was melted in an extruder and made into pellets. Glass transition temperature (Tg) of this pellet
When measured, it was 154°2°C. The viscosity average molecular weight was 18.800, and when the molecular weight distribution was measured by gel permeation chromatography, it showed a distribution with a single peak at the above value.

Furthermore, the molar ratio of the repeating unit (I) in this copolymer was determined to be 0.024.

The bromine content of the obtained pellets was measured and was 6.2.
wt% (sample was alkali decomposed and analyzed by Polhard method). Hereinafter, the polycarbonate obtained here will be referred to as PC-1.

Production Example 2 (Production of Polycarbonate) Polycarbonate oligomer 8f synthesized in the above synthesis example was placed in a container equipped with a stirrer having an internal volume of &Oj2.

Aqueous sodium hydroxide solution of bisphenol sulfone [123 g (0.49 mol) of bisphenol sulfone.

69g of sodium hydroxide, 520g of water + 640m of water!
and 4.4 g (0,043 mol) of triethylamine were added thereto and stirred at 500 rpm.

After 10 minutes, an aqueous sodium hydroxide solution of pentabromophenol [215 g (0.44 mol) of pentabromophenol, 35.1 g of sodium hydroxide].

2.8 f) of water was added and stirred. After 50 minutes, a sodium hydroxide aqueous solution of bisphenol A [bisphenol A51
0 g (2.24 mol), 260 g of sodium hydroxide,
4.41) 4.9 f of water and 61 g of methylene chloride were added and stirred.

After stirring for 60 minutes, the resulting reaction product was separated into an aqueous phase and a methylene chloride phase containing the formed copolymer (polycarbonate consisting of repeating unit (1) and repeating unit (II)).

This methylene chloride phase was mixed with water and acid (0.1N hydrochloric acid).

Washed with water. Methylene chloride was removed from this methylene chloride sum at 40° C. under reduced pressure to obtain a white powder. After drying 120"C1 day and night, it was melted in an extruder and made into pellets. The glass transition temperature (Tg) of this pellet was measured and was 153.8°C. The viscosity average molecular weight was 17.600. When the molecular weight distribution was measured by gel permeation chromatography, it showed a distribution with a single peak at the above value.

Furthermore, the molar ratio of the repeating unit (I) in this copolymer was determined to be 0.02.

The bromine content of the obtained pellets was measured and was found to be 5.8.
It was wt%. (The sample was subjected to alkali decomposition and analyzed using the Polhardt method). Hereinafter, the polycarbonate obtained here will be referred to as PC-2.

Examples 1 to 8 and Comparative Examples 1 to 4 After drying each of the various polycarbonate and polyamide resins shown in Table 1 in predetermined amounts, they were chip-blended and fed to an extruder, and kneaded at a temperature of 270°C. The composition was pelletized.

Further, the obtained pellets were dried at 120°C for 112 hours, and then injection molded at a molding temperature of 270°C and a mold temperature of 80'C to obtain test pieces. The tensile strength, flame retardance, and solvent resistance of the obtained test piece were measured. The flow value of the pellets was also measured. The results are shown in Table 1.

(Left below) *1 Idemitsu Petrochemical ■ Taflon A-2200 (polycarbonate from bisphenol A and phosgene) *2 Manufactured by Ube Industries ■, tlBE Nyl:! N101
3B*3 Made by Ube Industries ■, IRE nylon 2020B
*4 Made by Asahi fiberglass, l'1A409c,
Glass fiber with a diameter of 13 μm and a length of 3 mm *5 Stearic acid monoglyceride (manufactured by Riken Vitamin, Rikemar 5100A > *5 Polycarbonate oligomer from TBA and phosgene (manufactured by Great Lakes).

BC-58) *7 Shown in parts by weight based on 100 parts by weight of the total of polycarbonate and polyamide.

*8 Based on JIS K-7113 *91/4 ellipse method (Shinta et al., “Color Materials”, Vol. 39, 455
(1966)), Solvent: Mixed solvent of toluene (40% by volume) and isooctane (60% by volume) *10 Based on JIS K-7210 Measurement temperature: 280
°C*ll tlL94 compliant (3,2re thickness) [Effects of the invention] As shown above, the resin composition of the present invention has significantly improved fluidity and solvent resistance while retaining the mechanical strength inherent to polycarbonate. It also has excellent flame retardancy.

Therefore, the resin composition of the present invention can be used in various industrial materials such as home appliances, office automation equipment, and automobiles.

It is widely and effectively used as a building material.

Claims (1)

[Claims] (1) (a) It has a repeating unit (I) represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ and a repeating unit (II) represented by the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and the terminal A polycarbonate having a pentahalogenophenoxy group bonded to the position and having a viscosity average molecular weight of 5000 or more and (
2) A polycarbonate resin composition containing polyamide resin as a main component.