JPH0245559A - Polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having excellent fluidity, impact resistance, etc., and suitable for household appliance, etc., without deteriorating the rigidity and heat-deformation resistance by compounding a novel polycarbonate having specific structure with specific amounts of a rubber elastomer and an inorganic filler. CONSTITUTION:The objective composition is produced by compounding (A) 100 pts.wt. of a polycarbonate resin containing the recurring unit of formula I and the recurring unit of formula II at a molar ratio [m/(m+n)] of 0.005-0.2, preferably 0.01-0.1 wherein m and n are molar fractions of the former and the latter unit, respectively, having a pentahalogenophenoxy group bonded to the terminal and having a viscosity-average molecular weight of >=5,000, preferably 10,000-30,000 with (B) 1-50 pts.wt. (preferably 2-40 pts.wt.) of a rubber elastomer (e.g., MAS resin) and (C) 1-50 pts.wt. (preferably 2-40 pts.wt.) of an inorganic filler (e.g., glass fiber or aluminum fiber).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a polycarbonate resin composition, and more specifically, it is made by blending polycarbonate with a new structure with an inorganic filler together with a rubber-like elastic material, and has high rigidity and heat deformation resistance. Fluidity and impact resistance while maintaining properties.

This invention relates to a polycarbonate resin composition with excellent flame retardancy.

[Prior art and problems to be solved by the invention] Conventionally,
Examples of flame-retardant polycarbonates include polycarbonates having a halogen-substituted phenoxy group (pentabromophenoxy group, tetrachlorophenoxy group, tribromophenoxy group, etc.) at the end (Japanese Patent Publication No. 46-40
Various types are known, including Japanese Patent Publication No. 715).

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 62-29673
No. Specification).

However, this new polycarbonate has the disadvantage that when a rubber-like elastic body is blended in order to further improve its fluidity and impact resistance, the resulting composition has a decrease in heat deformation resistance and rigidity.

Under these circumstances, the inventors of the present invention have conducted extensive research in order to eliminate the above-mentioned drawbacks while maintaining the advantages of the new polycarbonate.

[Means for Solving the Problems] As a result, it has been found that the above problems can be solved by blending an inorganic filler with a rubber-like elastic body into this new polycarbonate. 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 (It) represented by the formula, a pentahalogenophenoxy group is bonded to the terminal position, and a viscosity average molecular weight of 5000 or more. certain polycarbonate 10
0 parts by weight.

The present invention provides a resin composition comprising (b) 1 to 50 parts by weight of a rubber-like elastic material and (C) 1 to 50 parts by weight of an inorganic filler.

The composition of the present invention is mainly composed of (a) a polycarbonate, (b) a rubbery elastic material, and (C) a rubbery elastic material and/or an inorganic filler, as described above. a
The polycarbonate component () has a repeating unit (1) represented by formula (A) and a repeating unit (n) represented by formula (B).

The molar fraction of the repeating units (I) and (II) is not particularly limited and may be selected as appropriate depending on the purpose of use, but usually the molar fraction of the repeating unit (I) is m , when the molar fraction of repeating unit (II) is n, m/(m
+ n)~0.005~0.2, preferably 0.01~
It is in the range of 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 I and X S each represent a halogen atom. X 5 may be the same or different.) A functional group represented by the following is bonded.

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 for this polycarbonate, which is the repeating unit (I).

(II) and a pentahalogenophenoxy group of general formula (C) is bonded to the terminal position, and there are various types such as random copolymers, alternating block copolymers, etc. of these.

Note that there is no problem even if a small amount of repeating units other than repeating units (1) and (n) are mixed in 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, various kinds of rubber-like elastic bodies can be used as the component (b) of the composition of the present invention, but the following (1) and (2) are particularly preferred. For example, there is a resin polymer obtained by polymerizing one or more vinyl monomers into the presence of (1) a rubbery polymer mainly composed of alkyl acrylate and/or alkyl methacrylate. As the alkyl acrylate and alkyl methacrylate, those having an alkyl group having 2 to 10 carbon atoms are suitable, and specific examples thereof include ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, n-octyl methacrylate, etc. It will be done. These rubber-like polymers mainly composed of alkyl acrylates contain 70% by weight or more of the alkyl acrylates and other vinyl monomers copolymerizable therewith, such as methyl methacrylate,
30% by weight of acrylonitrile, vinyl acetate, styrene, etc.
It means a polymer obtained by reacting the following: In addition,
In this case, polymers obtained by appropriately adding and reacting polyfunctional monomers such as divinylbenzene, ethylene dimethacrylate triallyl cyanurate, and triallyl isocyanurate as a crosslinking agent are also included.

Vinyl monomers reacted in the presence of this rubbery polymer include aromatic vinyl compounds such as styrene and α-methylstyrene; acrylic esters such as methyl acrylate and ethyl acrylate; methyl methacrylate and methacrylic acid. It refers to monomers such as methacrylic esters such as ethyl, and one or more of these monomers are polymerized.

Further, this monomer is polymerized with other vinyl monomers, such as vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; vinyl esters such as vinyl acetate and vinyl propionate. The polymerization reaction can be carried out by various methods such as bulk polymerization, suspension polymerization, and emulsion polymerization, and those produced by emulsion polymerization are particularly preferred.

The resin polymer thus obtained contains 2 of the rubber components.
It is preferable that the content is 0% by weight or more. Specifically, such a resin polymer has an n content of 60 to 80% by weight.
Examples include MAS resin elastomers such as graft copolymers of -butyl acrylate, styrene, and methyl methacrylate, and MAS resin elastomers that are copolymers of styrene and methyl methacrylate.

Examples of the above-mentioned MAS resin elastic body include the product name rKM-330J manufactured by Rohm & Haas, and the product name "Metaprene W 529J" manufactured by Mitsubishi Rayon ■.

In addition, a copolymer obtained by copolymerizing an alkyl acrylate and/or alkyl methacrylate with a polyfunctional polymerizable monomer having a conjugated diene type double bond may contain one or two vinyl monomers. There are resin polymers obtained by polymerizing more than one species.

As the alkyl acrylate and alkyl methacrylate, those mentioned above are used. In addition, examples of polyfunctional polymerizable monomers having conjugated diene type double bonds include conjugated diene compounds such as isoprene and butadiene, and nonconjugated double bonds in addition to conjugated diene type double bonds in one molecule. Examples include compounds that have

Examples of such compounds include 1-methyl-2-vinyl-4,6-hebutadien-1-ol; 7-methyl-3-methylene-1,6-octadiene, 1,3.7-
There are octatrienes, etc.

When copolymerizing the above alkyl acrylate and/or alkyl methacrylate with a polyfunctional polymerizable monomer having a conjugated diene type double bond, an aromatic vinyl compound such as styrene or α-methylstyrene is used as necessary;
Acrylonitrile.

Vinyl monomers such as vinyl cyanide compounds such as methacrylonitrile; vinyl ester compounds such as vinyl acetate and vinyl propionate; vinyl ether compounds such as methyl vinyl ether; and vinyl halide compounds such as vinyl chloride can also be added. .

Furthermore, a crosslinking agent such as ethylene dimethacrylate or divinylbenzene may be added.

In addition, when producing a copolymer by copolymerizing an alkyl acrylate and/or an alkyl methacrylate and a polyfunctional polymerizable monomer having a conjugated diene type double bond,
A polyfunctional polymerizable monomer with a conjugated diene type double bond is
It should be used in a proportion of 0.1 to 20% by weight, preferably 1 to 10% by weight in the copolymer.

The vinyl monomers to be polymerized with the copolymer thus obtained include those listed above, and one or more of these may be used.

The polymerization reaction can be carried out by various methods such as bulk polymerization, suspension polymerization, and emulsion polymerization, and those produced by emulsion polymerization are particularly preferred.

The resin polymer obtained as described above can be used as the rubber-like elastic body which is the component (b) of the present invention.

Preferred examples of such resin polymers are shown below. The first are alkyl (meth)acrylates such as n-butyl acrylate, 2-ethylhexyl acrylate, and methyl methacrylate, butadiene, ethylene dimethacrylate, divinylbenzene, etc. A small amount of a crosslinking agent is copolymerized using a conventional method, and a vinyl monomer such as styrene, acrylonitrile, or vinyl chloride is added to the resulting latex as a graft component monomer, and the resulting latex is graft-polymerized using a conventional method. It is a graft copolymer.

The second is the above alkyl (meth)acrylate,
A non-conjugated double bond in addition to a conjugated diene type double bond is copolymerized with a compound in one molecule by a conventional method, and a vinyl monomer as described above is added to the obtained latex as a graft component monomer. This is a graft copolymer obtained by graft polymerization using a conventional method. Incidentally, the graft copolymerization may be carried out in one stage, or may be carried out in multiple stages by changing the components of the graft component monomer in multiple stages.

More specifically, as such a resin polymer, styrene and methyl methacrylate are added to a rubber latex obtained by copolymerizing octyl acrylate and butadiene in a ratio of 7:3 for the former and the latter for grafting. There are MABS resin elastomers such as graft copolymers obtained by polymerization.

Examples of the above-mentioned MABS resin elastomer include rHIA 15J and rHIA 28J manufactured by Kureha Chemical Industry ■.

rHIA 30J (all product names are shown) and the like are preferably used.

There are also MBS resin elastomers such as graft copolymers obtained by adding styrene to rubber latex obtained by copolymerizing methyl methacrylate and butadiene and graft polymerizing the mixture.

As the above-mentioned MBS resin elastic body, Metaprene C-223J (trade name) manufactured by Mitsubishi Rayon ■ is preferably used.

Furthermore, other rubber-like elastic bodies, such as ABS resin elastic bodies,
Natural rubber (NR) or styrene-butadiene rubber (
SBR), polybutadiene rubber (BR), imprene rubber (IR), acrylonitrile-butadiene rubber (
NBR), acrylonitrile-isoprene rubber (NI
R), diene rubber such as chloroprene rubber (CR), and isobutylene-isopropylene rubber (IIR)
, ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), chlorosulfonated polyethylene rubber (C3M), ethylene vinyl acetate rubber (EVM), and other olefin rubbers, as well as various acrylic rubbers and other organosilicon rubbers. Compound rubber, organic fluorine compound rubber.

Examples include urethane rubber and ether rubber.

In the composition of the present invention, the rubber-like elastic body as the component (b) is blended at a ratio of 1 to 50 parts by weight, preferably 2 to 40 parts by weight, to 100 parts by weight of the polycarbonate as the component (a). do. Here, if the rubber-like elastic body is less than 1 part by weight, the effect of improving fluidity and impact resistance will not be sufficient, and if it exceeds 50 parts by weight, the rigidity will be significantly lowered.

Furthermore, in the composition of the present invention, it is necessary to add an inorganic filler as component (C). Various types of inorganic fillers can be used depending on the purpose of use of the composition, required properties, etc., such as glass fiber.

7 /L/ Minilam fiber, carbon fiber, calcium carbonate.

Magnesium carbonate, dolomite, silica, diatomaceous earth.

Alumina, titanium oxide, iron oxide, zinc oxide, magnesium oxide, calcium sulfate, magnesium sulfate, calcium sulfite, talc, clay, mica asbestos glass balloon, glass beads, calcium silicate, glass powder, montmorillonite, bentonite, carbon black, graphite, iron Powder, lead powder, aluminum powder, etc. can be used.

In the composition of the present invention, the inorganic filler as the component (C) is contained in an amount of 1 to 50 parts by weight, preferably 2 to 40 parts by weight, based on 100 parts by weight of the polycarbonate as the component (a). Blend. Here, if the inorganic filler is less than 1 part by weight, the effect of improving rigidity and heat deformation resistance is insufficient, and if it exceeds 50 parts by weight, the impact resistance and fluidity are significantly reduced.

The composition of the present invention comprises the above-mentioned (a), (b) and (C
) are essential components, but various additives may be added as necessary. Examples of additives include antioxidants such as hindered phenols, phosphorus (sulfurous acid esters, phosphate esters), amine-based antioxidants, benzotriazole-based and benzophenone-based ultraviolet absorbers, and aliphatic Carboxylic acid ester type 2 Paraffin type external lubricant, as well as mold release agent and antistatic agent 9
Coloring agents and the like can be mentioned. Here, as the above-mentioned hindered phenolic antioxidant, BIT (2,6-di-tert-butyl-P-cresol), Irganox 1076J (trade name) manufactured by Ciba Geigy.

"Irganox l0IOJ (product name)", manufactured by Ethyl "Ethyl 330J (product name)", manufactured by Jumin Chemical ■
Sumilizer GMJ (trade name) and the like are preferably used.

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-axle 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 is molded by various known molding methods, such as injection molding, extrusion molding, compression molding, calendar molding, and 9-rotation molding, to produce parts for electrical and electronic equipment, OA equipment, automobiles, etc., especially rotary molding. 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 inner volume of 21 cm and equipped with a stirrer, put 91 g of bisphenol A + 33 methylene chloride salts and 560 ml of 1.7 N sodium hydroxide aqueous solution and stir. Then, phosgene was blown therein for 70 minutes while cooling in a water bath. When the resulting reaction solution was left 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 and the concentration of chloroformate groups with a number average molecular weight of 5501 is 1.0 mol/I! ．． It was later.

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

Aqueous sodium hydroxide solution of bisphenol sulfone [123 g (0.49 mol) of bisphenol sulfone, 69 g of sodium hydroxide. Add 520 ml of water: 1640 d and 4.4 g (0.043 mol) of triethylamine,
The mixture was stirred at 500 rpm.

After 10 minutes, pentabromophenol sodium hydroxide solution? Solution H (pentabromophenol 230g (0.47
mole), sodium hydroxide, 37.6 g. water 2,8f)
and stirred. After 50 minutes, a sodium hydroxide aqueous solution of bisphenol A [bisphenol A 510 g (2.2
4 mol), sodium hydroxide 260 g. water 4.4
14.9ff and 62 methylene chloride were added and stirred.

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

This methylenated chloride is converted into water and acid (0.1N hydrochloric acid).

Washed with water. Methylene chloride was removed from this chlorinated methylene 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 l 5 4.2°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 (1) 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) In a container with an internal volume of 50 ffi and equipped with a stirrer, a solution of polycarbonate oligomer 782 bisphenolsulfone synthesized in the above synthesis example in sthorium hydroxide was added. Night [Bisphenol sulfone sodium hydroxide 69g. Water 5 2 0d) 6 4
0mR.

and triethylamine 4.4 g (0.0 4 3
mol) 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 I of water! ．． ) and stirred. After 50 minutes, a sodium hydroxide aqueous solution of bisphenol A [bisphenol A 510 g (2.24
mol), sodium hydroxide 260g, water 4.4f)4.
9j2 and methylene chloride 6! 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 (I[)).

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 at 120"C day and night, it was melted in an extruder and made into pellets. The glass transition temperature (Tg) of the pellets was measured to be 153.8°C. The average molecular weight was 17,600, 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 (1) 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 11 and Comparative Examples 1 to 4 Predetermined amounts of various polycarbonates, rubber-like elastic bodies, and inorganic fillers shown in Table 1 were pre-kneaded in a drum tumbler, and then fed to an extruder at a temperature of 280°C. The mixture was kneaded to obtain a polycarbonate resin composition, which was pelletized.

Furthermore, the obtained pellets were molded at a temperature of 280°C.

Test pieces were obtained by injection molding at a mold temperature of 80°C. The bending rigidity, thermal deformation temperature, and Izot impact value of the obtained test pieces were measured. The results are shown in Table 1.

(Left below) *I Acrylic rubber: MAS rubber; Paraloid KM330 manufactured by Rohm & Haas *2 SBS: Styrene/butadiene/styrene rubber; Kaliflex TR manufactured by Shell Chemical *3 IIR
...Butyl rubber; JSR Butyl 26 manufactured by Japan Synthetic Rubber ■
8 *4 EPDM...Ethylene propylene diene rubber; EP 57P *5 C manufactured by Japan Synthetic Rubber Illiki
F...Glass fiber: Asahi fiberglass (1,13 MA409C diameter 13μ, length 3 +n+n glass fiber *6 Talc...average diameter 0.9μm *7 Calcium carbonate...calcium carbonate; Shiraishi Kogyo ■ Vi
got-10 *8 CF...Carbon fiber; Besphite made by Toho Rayon HTA-C6-3*9 JIS
Based on K-7203 *10 JIS K-7110
Compliant with (1/8 inch thickness, notched, measurement temperature 23
°C) *11 JIS K-6871 semi-1 (load 4.6 kg/cI11) *12 JIS K-7210 compliant (temperature 280
°C2 load 160 kg) *13 Conforms to UL standard 94 (1/16 inch thickness) [Effects of the invention] As mentioned above, the resin composition of the present invention does not cause a decrease in rigidity, heat distortion temperature, etc. , fluidity and impact resistance are significantly improved, and it also has excellent flame retardancy.

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

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 Polycarbonate 100 with a pentahalogenophenoxy group bonded to the position and a viscosity average molecular weight of 5000 or more
(b) 1 to 50 parts by weight of a rubber-like elastic material; and (c) 1 to 50 parts by weight of an inorganic filler.