JPH01138262A - Polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in mechanical strengths, abrasion resistance, sliding properties and flame retardancy and useful for large injection moldings, by mixing a specified polycarbonate with a fluorocarbon resin as main components. CONSTITUTION:60-99wt.% polycarbonate (A) having m mol of repeating units of formula I and n mol of repeating units of formula II at m to m+n ratio of 0.005-0.2, terminated with pentahalogenophenoxy groups of formula III (wherein X<1-5> are each a halogen) and having a viscosity-average MW >=5000, and 1-40wt.% fluorocarbon resin (B) such as polytetrafluoroethylene of, preferably, an m.p. of 300-350 deg.C are mixed together as main components, and 1-40 pts.wt., per 100 pts.wt. total of A and B, glass fiber (C) surface-treated with a silane coupling agent and having a fiber length of 1-8mm and a fiber diameter <=20mum, an inorganic filler (D) such as carbon black, clay or calcium carbonate, additives (E) such as an anti-oxidant and an ultraviolet absorber and other synthetic resins such as PE and PP, etc., are optionally added to the mixture and the obtained mixture is melt-kneaded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polycarbonate resin composition, and more specifically, the present invention relates to a polycarbonate resin composition that has mechanical strength, flame retardance, abrasion resistance, and This invention relates to a polycarbonate resin composition with excellent sliding properties.

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

However, although these conventional polycarbonates have excellent flame retardancy, they have problems in mechanical strength such as impact resistance, abrasion resistance, and sliding properties.

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 62-29673
No. Specification).

However, this new polycarbonate has some problems in wear resistance and sliding properties.

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 problems]

As a result, they found that by blending a fluororesin into this new polycarbonate, it was possible to significantly improve abrasion resistance and sliding properties, as well as flame retardance, without impairing mechanical properties. The present invention was completed based on this knowledge. That is, the present invention provides a polycarbonate having a repeating unit (n) represented by formula (a), a pentahalogenophenoxy group bonded to the terminal position, and a viscosity average molecular weight of 5000 or more;
b) A polycarbonate resin composition containing a fluororesin as a main component is provided.

The composition of the present invention is mainly composed of (a) a polycarbonate and (b) a fluororesin as described above, where the polycarbonate as the component (a) is a repeating compound represented by the formula (A). It has a unit (1) and a repeating unit (II) represented by formula (B). The molar fraction of this repeating unit (IL(n) is not particularly limited and may be selected as appropriate depending on the purpose of use, etc., but usually the molar fraction of the repeating unit (1) is m, and the molar fraction of the repeating unit (IL(n) is Unit (II
), m/(m+n)=0.
It ranges from OO5 to 0.2, preferably from 0.01 to 0.1.

In addition, the polycarbonate that is component (a) has a pentahalogenophenoxy group at the terminal position of the molecule, particularly at both ends, that is, the general formula (wherein, X l and X S each represent a halogen atom. They may be the same or different.) The functional groups represented by these are bonded to each other.

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 (■).

(I[), 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 (1) 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 fluororesin which is the component (b) of the composition of the present invention may be any resin as long as it has a fluorine atom in its molecule, and in particular, a resin having a carbon-fluorine bond in its molecule, e.g. Polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyhynylidene fluoride, hexafluoropropylene-tetrafluoroethylene copolymer, chlorotrifluoroethylene-vinylidene fluoride copolymer, etc. are preferred, and among these, particularly those with a melting point Polytetrafluoroethylene of 300-350°C is preferred.

The composition of the present invention has the above-mentioned (a)) component and (1)) component as main components, and the blending ratio of these two components can be adjusted as appropriate depending on the type of each component and the intended use of the composition. Generally, component (a) polycarbonate 60~
99% by weight, preferably 70-95% by weight, 1-40% by weight of fluororesin as component (b), preferably 30-5% by weight
Defined in weight% range. If the blending ratio of the polycarbonate component (a) exceeds 99% by weight, sufficient wear resistance and sliding properties cannot be imparted to the composition. In addition, if it is less than 60% by weight, impact resistance decreases, and
Flow marks are more likely to occur on molded products.

In addition to the above components (a) and (b), the composition of the present invention may contain glass fibers, various inorganic fillers, additives, other synthetic resins, and elastomers, as long as they do not impede the purpose of the present invention. etc. can be blended as necessary. 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, various kinds of glass fibers can be used for the purpose of increasing the mechanical strength, durability, or weight of the resin composition of the present invention, and there are no particular restrictions. Glass fibers such as alkali-containing glass fibers, low-alkali glass fibers, alkali-free glass fibers, etc., which are currently available, can be used as appropriate. Further, the form of the glass fiber is not particularly limited, and may be any form such as roving, chopped strand, strand, or milled fiber, but if the fiber diameter becomes too large, the strength of the composition will deteriorate. There is a risk that the appearance will deteriorate. On the other hand, if the fiber diameter is too small, the fibers may break during kneading or molding, which may reduce the strength of the composition. In addition, in order to further increase the flame retardancy and mechanical strength of the composition, the glass fibers may be optionally mixed with a coupling agent such as aminosilane, epoxysilane, borane, vinylsilane, methacrylsilane, etc.
Alternatively, the surface may be treated with a chromium complex, a boron compound, or the like. Among these glass fibers, especially fiber length 1
-8ffII11, especially those having 2 to 7 cylinders, having a fiber diameter of 20 μm or less, especially 3 to 15 μm, and having been surface-treated with a silane coupling agent are preferred.

In the composition of the present invention, the blending ratio of the above-mentioned glass fibers is not particularly limited and may be appropriately selected depending on the purpose of use and desired properties, but usually (A) polycarbonate and (
B) The amount of glass fiber is in the range of 1 to 40 parts by weight, preferably 5 to 30 parts by weight, based on a total of 100 parts by weight of the fluororesin.

By adding an appropriate amount of this glass fiber, it becomes flame retardant and rigid.

Improved dimensional stability. However, if too large a quantity is blended, the fluidity will decrease, which is not preferable.

Examples of the inorganic filler include carbon black, calcium sulfate, calcium carbonate, silica, asbestos, talc, clay, mica, and quartz powder.

In addition, the additives include hindered phenol,
Phosphorus-based (sulfurous acid ester, phosphate ester), amine-based antioxidants, benzotriazole-based, benzophenone-based ultraviolet absorbers, aliphatic carboxylic acid ester-based.

Examples include a paraffin-based external lubricant, a mold release agent, an antistatic agent, a coloring agent, and the like. Here, the above-mentioned hindered phenolic antioxidants include BHT (2,6-di-tert-butyl-p-cresol), Irganox 1076J (trade name) manufactured by Ciba Geigy, and Irganox 10IOJ (trade name) manufactured by Ciba Geigy. Product name), manufactured by Ethyl Co., Ltd. “Ethyl 330J (
(product name), Sumilizer GMJ (product name) manufactured by Juju Chemical Co., Ltd. are preferably used.Other synthetic resins include polyethylene, polypropylene, polystyrene,
Various resins such as AS resin, ABS resin, and polymethyl methacrylate can be mentioned. Also, as the elastomer, isobutylene-isoprene rubber.

Examples include styrene-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, and brominated epoxy, and flame retardant aids such as Sb2O2 and sodium antimonate.

The polycarbonate resin composition of the present invention can be obtained by blending and kneading the above-mentioned components. combination,
The kneading can be done using a conventional method, such as a ribbon blender, Henschel mixer, or Banbury mixer.
, drum tumbler-two single screw extruder, twin screw extruder.

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

The polycarbonate resin composition thus obtained can be molded into parts for electrical and electronic equipment, OA equipment, automobiles, etc., especially rotating parts, by applying various known molding methods, such as injection molding, extrusion molding, compression molding, two-turn calendar molding, etc. Molded products such as members, moving members, driving members, etc. can be manufactured.

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

Synthesis Example (Synthesis of polycarbonate oligomer to bisphenol) In a flask with an internal volume of 21 and equipped with a stirrer, 91 g of bisphenol A, 330 n/2 of methylene chloride, and 1.7 g of methylene chloride were added.
560 mff1 of normal sodium hydroxide aqueous 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/l,
The number average molecular weight is 550, and the concentration of chloroformate groups is 1.
It was 0 mol/l.

Production Example 1 (Production of Polycarbonate) 8ffi of the polycarbonate oligomer synthesized in the above synthesis example was placed in a container with an internal volume of 502 mm and equipped with a stirrer.

A sodium hydroxide aqueous solution of bisphenolsulfone [123 g (0.49 mol) of bisphenol sulfone, 69 g of sodium hydroxide, 640 cal/520 mL of water, and 4.4 g (0,043 mol) of triethylamine were added and stirred at 500 rpm.

After 10 minutes, an aqueous sodium hydroxide solution of pentabromophenol [230 g (0.47 mol) of pentabromophenol, 37.6 g of sodium hydroxide, and 2.81'J of water] was added and stirred. After 50 minutes, add sodium hydroxide aqueous solution to bisphenol [bisphenol A 510 g (2,24
mol), sodium hydroxide 260g, water 4.4E)4.
942 and 6i 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 phase at 40°C under reduced pressure to obtain a white powder.

Further, after drying for 120'C1 day and night, melt it in an extruder,
Made into pellets. The glass transition temperature (Tg
) was measured and found to be 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 subjected to alkaline decomposition and analyzed by Holhardt method). Hereinafter, the polycarbonate obtained here will be referred to as PC-1.

Production Example 2 (Production of Polycarbonate) In a container with an internal volume of 501 mm and equipped with a stirrer, the polycarbonate oligomer synthesized in the above synthesis example was placed in an aqueous sodium hydroxide solution of 82° bisphenol sulfone [123 g (0.49 mol) of bisphenol sulfone].

Sodium hydroxide 69g, water 520n + J2) 640m
1 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].

2.8ff of water was added and stirred. After 50 minutes, a sodium hydroxide aqueous solution of bisphenol A [bisphenol A5
10 g (2.24 mol), 260 g of sodium hydroxide
, 4.4f]4.9f of water and 6°C 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 units (I) and repeating units (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 further drying at 120°C for 1 day and night, the mixture was melted in an extruder and made into pellets. The glass transition temperature (T g
) was measured and found to be 153.8°C. The viscosity average molecular weight was 17,600, and when the molecular weight distribution was measured by Kölper 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 Holhardt method). Hereinafter, the polycarbonate obtained here will be referred to as PC-2.

Examples 1 to 7 and Comparative Examples 1 to 4 Predetermined amounts of various polycarbonate, fluororesin, and other additives such as glass fiber shown in Table 1 were added to a drum tumbler.
After preliminary kneading, the mixture was supplied to an extruder and kneaded at a temperature of 300°C to obtain a polycarbonate resin composition, which was pelletized.

Further, the obtained pellets were injection molded at a molding temperature of 300°C and a mold temperature of 80°C to obtain test pieces. The flexural modulus, flame retardance, and coefficient of dynamic friction of the obtained test piece were measured.

The results are shown in Table 1.

(Space below) *1 Taflon A-2200 (polycarbonate made from bisphenol A and phosgene) manufactured by Idemitsu Petrochemical ■2 TLP~IOF~1 (manufactured by Mitsui Fluorochemical ■)
Polytetrafluoroethylene, melting point 327°C) *3
Made of Asahi fiberglass, MA409C, diameter 13μ
, 3 mm long aminosilane-treated glass fiber *4 Riken Vitamin Co., Ltd. Rikemar 5100A (stearic acid monoglyceride) *5 Great Lake Co., Ltd. BC-58 (polycarbonate oligomer from TBA and phosgene) *6
It is expressed in parts by weight based on the total of 100 parts by weight of polycarbonate and fluororesin.

*7 Conforms to UL standard 94 (thickness 3.2 mm) *8
Based on ASTM D 1894, load 2.0kg*9
Conforms to ASTM D 1790*10 Thickness 3
Cabinet 2 width 121. A square plate having a length of 12 cm was injection molded (resin temperature: 300°C), and its appearance was visually judged.

(Effects of the Invention) As stated above, the resin composition of the present invention has significantly improved abrasion resistance and sliding properties while retaining the mechanical strength inherent to polycarbonate, and has excellent flame retardancy. It is.

Therefore, the resin composition of the present invention can be used in various industrial materials 9 such as home appliances, OA equipment, and precision equipment.

Widely and effectively used in automobiles, building materials, etc.

In particular, the resin composition of the present invention is suitable for large-scale injection molding.

J-11--

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 (
b) A polycarbonate resin composition containing a fluororesin as a main component.