JPH04202466A - Flame-retardant polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To obtain the title compsn. improved in flame-retardant properties and excellent esp. in low-temp. impact strength by compounding an arom. polycarbonate resin with a copolycarbonate resin having specific structural units. CONSTITUTION:1-99.8wt.% arom. polycarbonate resin is compounded with 99--0.2wt.% copolycarbonate resin having structural units of formulas 1 and II (wherein n is 1-200; R is 2-6C alkylene; B is a divalent group selected from the group consisting of 1-10C linear, branched, and cyclic alkylidene, aryl-substd. alkylene, aryl, O, S, CO, and SO2; and R<1> to R<4> are each H, halogen, or 1-4C alkyl). The obtd. compsn. has improved flame-retardant properties, is excellent in impact strength. esp. in its thickness dependence and in low-temp. impact strength, and hence is useful as a molding material for a precision part and a part to be used at a low temp.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention provides an improved flame retardant material that exhibits excellent mechanical properties, particularly impact resistance at low temperatures, good appearance and good moldability. It is a polycarbonate resin composition with excellent transparency, so it can be suitably used for various purposes.

[Conventional technology and issues]

Aromatic polycarbonate resins have excellent heat resistance, impact resistance, electrical properties, dimensional stability, etc., and are transparent, so they are used as useful engineering plastics for various purposes.

However, flame retardancy is not necessarily sufficient. To improve the flame retardancy of aromatic polycarbonate resins, conventional methods have been to use Br-containing polycarbonate copolymers or blend Br-containing polycarbonate oligomers to improve mechanical properties and heat resistance. However, the excellent impact resistance of polycarbonate resin has been degraded.

[Means to solve the problem]

The present inventors have discovered that flame retardancy can be improved by blending a copolycarbonate resin having a polysiloxane chain with an aromatic polycarbonate resin, and have arrived at the present invention.

That is, the present invention provides aromatic polycarbonate resins 1-
Copolycarbonate resin having 99.8% by weight and structural units represented by the following structural formulas (A) and (B) 99-
This is a flame-retardant polycarbonate resin composition containing 0.2% by weight.

(n in structural formula (A) represents a positive number of 1 to 200, and R represents an alkylene group having 2 to 6 carbon atoms.

In addition, B in structural formula (B) is a linear, branched, or cyclic alkylidene group having 1 to 10 carbon atoms, an aryol-substituted alkylene group, an aryol group, or -o-, -s-+ - co-+-
3o2-, and R1, R2R3 and R4 represent hydrogen, halogen or an alkyl group having 1 to 4 carbon atoms. ) Also, in the present invention, the copolycarbonate resin has 5
-50% by weight, and the copolycarbonate resin has 0.2 to 5 structural units represented by structural formula (A).
0% by weight, and furthermore, R in the structural formula (A) is -
This is a flame-retardant polycarbonate resin composition consisting of CHR5-CH2- (R5 in the formula is bonded to the carbon atom on the benzene ring side and represents hydrogen or a methyl group).

The configuration of the present invention will be explained below.

The aromatic polycarbonate resin of the present invention is produced by a conventional aromatic polycarbonate resin production method in which a dihydric phenol compound is reacted with phosgene, carbonate, or chloroformate.

Furthermore, the copolycarbonate resin of the present invention is characterized in that it has a structural unit of the above structural formula (A) consisting of bisphenol having a silicone chain and an aliphatic chain as a structural unit, and is different from conventional aromatic polycarbonate resins. In the manufacturing method, the same manufacturing method as the conventional interfacial polymerization method is suitably applied, except that a silicone compound of general formula (1) shown below and a dihydric phenol having a fatty chain are used in part. .

n and R in the formula are the same as in structural formula (A).

Structural formula (
The structural unit represented by A) is not particularly limited, but is preferably in the range of 0.2 to 50% by weight, particularly preferably in the range of 0.5 to 25% by weight. The repeating number (n) of units is in the range of 1 to 200, preferably in the range of 5 to 100. In addition, R in the structural formula (A)
Examples include ethylene, propylene, isopropylene, butylene, pentylene, hexylene, etc.
Particularly preferred is -CHR5-[1'H2- (R5 in the formula is bonded to the carbon atom on the benzene ring side and represents hydrogen or a methyl group). The structural unit of this structural formula (A) is introduced by using a dihydric phenol having phenolic hydroxyl groups represented by the following maximum (1) at both ends in the same manner as ordinary bisphenol.

The compound represented by maximum (1) is a phenol having an olefinic unsaturated carbon-carbon bond, preferably vinylphenol or isopropenylphenol, and a polysiloxane chain having a predetermined degree of polymerization (n). It is easily produced by subjecting the terminal to a hydrosilation reaction.

Here, as dihydric phenol compounds that can be used for producing the above-mentioned aromatic polycarbonate resin or as a comonomer of a copolycarbonate resin, bis(4-hydroxyphenyl)methane, bis(
4-hydroxyphenyl) ether, bis(4-hydroxyphenyl) sulfone, bis(4-hydroxyphenyl) sulfoxide, bis(4-hydroxyphenyl) sulfide, bis(4-hydroxyphenyl) ketone, 1
, 1-bis(4-hydroxyphenyl)ethane, 2.2
-bis(4-hydroxyphenyl)propane, 2,2-
Bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2
-bis(4-hydroxy-3,5-dibromophenyl)
Propane, 2゜2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(
4-hydroxy-3-chlorophenyl)propane, 2.
2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 1,1-bis(4-hydroxyphenyl)
-1-phenylethane and bis(4-hydroxyphenyl)diphenylmethane are exemplified. Among these 2.2
-bis(4-hydroxyphenyl)propane, 1,1-
Bis(4-hydroxyphenyl)cyclohexane is preferred from the viewpoint of thermal stability. In addition, terminal capping agents or molecular weight regulators are usually used, and these include compounds having a -valent phenolic hydroxyl group, such as ordinary phenol, p-tert-butylphenol, tribromophenol, etc. , long-chain alkylphenol, aliphatic carboxylic acid chloride, aliphatic carboxylic acid, hydroxybenzoic acid alkyl ester, hydroxy phenyl acid alkyl ester, alkyl ether phenol, and the like.

The machine is capable of handling all dihydric phenol compounds used.
100 to 0.5 mol, preferably 50 to 0 mol
The amount is in the range of 2 moles, and it is naturally possible to use two or more kinds of compounds in combination. Further, a branching agent is added in an amount of 0.1 to 3 mol%, particularly 0.01 to 3 mol%, based on the above dihydric phenol compound.
A branched polycarbonate can be obtained by using them together in a range of 1 to 1.0 mol%, and the branching agents include phloroglycin, 2.
6-dimethyl-2.4.6-tri(4-hydroxyphenyl)hebutene-3,4,6-dimethyl-2.4.6
- tri(4-hydroxyphenyl)hebutene-2,
1,3,5-)li(2-hydroxyphenyl)penzole, 1.1.1-tri(4-hydroxyphenyl)ethane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methyl Phenol, α, α′, α′−
Polyhydroxy compounds exemplified by tri(4-hydroxyphenyl)-1,3,5-triisoflobilbenzene, and 3,3-bis(4-hydroxyaryl)oxindole (=isatin bisphenol), 5
-Chlorisatin, 5.7-dichlorisatin, 5-bromiisatin, etc. are exemplified.

The blending ratio of aromatic polycarbonate and copolycarbonate resin in the flame-retardant polycarbonate resin composition comprising the above components of the present invention is not particularly limited, but usually aromatic polycarbonate/copolycarbonate resin = 1/99. -99,810.2, preferably from the range of 50,150-9,515. If the blending amount of the copolycarbonate resin of the present invention is too small, the improvement in flame retardance will be insufficient and is generally undesirable.Also, even if the blending amount is too large, it is preferable from the viewpoint of flame retardancy, but the price and From other points of view, it is preferable to use it as a subcomponent.

The flame-retardant polycarbonate resin composition of the present invention as described above can be blended with various additives conventionally known to polycarbonate resins, such as reinforcing materials and fillers. , stabilizers, ultraviolet absorbers, antistatic agents, lubricants, mold release agents, dyes, pigments, etc. For example, phosphorous acid or phosphite is particularly suitable as a stabilizer. In addition, examples of mold release agents include esters of mono- or polyhydric alcohols of saturated fatty acids, and preferred examples include stearyl stearate, behenyl behenate, pentaerythritol tetrastearate, and dipentaerythritol hexaoctoate. Ru. Organic or inorganic fillers such as glass powder, glass peas, synthetic mica or fluorinated mica, zinc oxide, carbon fibers, especially glass fibers including those with a fiber diameter of 2 or less, zinc oxide whiskers, stainless steel fibers, Kevlar fibers, etc. Naturally, resins such as polycarbonate oligomers derived from bisphenol A, polyester carbonates, and polyarylates can be suitably used depending on the purpose.

〔Example〕

Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples.

Reference example 1 Dissolve 3.7 kg of sodium hydroxide in 421 parts of water,
2,2-bis(4-hydroxyphenyl)propane (hereinafter referred to as rBPA J) while keeping at ℃ 6,73
5g, general formula (1) shown on page 7 with n=50 (
Hereinafter, it will be referred to as rBY16-752J. ) 356 g and 15 g of hydrosulfide were dissolved.

To this, methylene chloride (hereinafter referred to as rMcJ) 30
While adding and stirring A, 148 g of pt-butylphenol (hereinafter referred to as rPTBP) was added, and then 3.5 kg of phosgene was blown in over 60 minutes.

After the phosgene injection was completed, the reaction mixture was vigorously stirred to emulsify it, and after the emulsification, 8-triethylamine was added and the mixture was stirred for about 1 hour, followed by polymerization.

The polymerization solution was separated into an aqueous phase and an organic phase, and the organic phase was neutralized with phosphoric acid. After repeating washing with water until the pH of the washing solution became neutral, 351% of isopropanol was added to the polymerization solution. was precipitated. By filtering the precipitate and then drying it, a white powdery copolycarbonate resin (r C-P
(denoted as CO5J) was obtained.

Reference example 2 In reference example 1, BPA 6,690g, 165B
A white powder copolycarbonate resin (hereinafter referred to as rc-PC15J) was prepared in the same manner except that the amount was 1,186 g.
I got it.

Examples 1 to 5 and Comparative Examples 1 to 3 As shown in Table 1 below, copolycarbonate and aromatic polycarbonate resin produced by the production method shown in Reference Example 1.2 (manufactured by Mitsubishi Gas Chemical Co., Ltd., Nipilon S- 2
000, molecular weight 25.000), each alone or in combination in the amount ratio listed in Table 1 at a cylinder temperature of 2.
The mixture was melt-kneaded using an extruder at 50 to 270°C to form pellets.

After drying this pellet in a hot air dryer at 120°C for 5 hours or more, a test piece for measuring physical properties was produced and tested at a cylinder temperature of 270°C. For comparison, a copolymerized polycarbonate resin (molecular weight 25.000,
r' Br-CPC) was also tested. The results are shown in Table 1.

The physical properties were measured as follows.

-Flammability: According to UL-94. Test piece thickness 1.6m
m.

-1,Z, :Izod impact value, unit kg cm
/cm, ・H, D, T, : Heat deformation temperature, load 1
8.6kg/crd.

・Total light transmittance: Made by Suga Test Machine ■, Direct reading Heath computer, thickness 3mm.

[Operation and effects of the invention]

The flame-retardant polycarbonate resin composition of the present invention not only has improved flame retardancy, but also has extremely excellent impact resistance, particularly its thickness dependence and impact resistance at low temperatures. Therefore, it is understood that general molded products are useful as molding materials suitable for annual rings, precision molded products, and molded products for low-temperature applications.

Claims (1)

[Scope of Claims] 1. 1 to 99.8% by weight of an aromatic polycarbonate resin5 and 99 to 0.2% by weight of a copolycarbonate resin having structural units represented by the following structural formulas (A) and (B). A flame-retardant polycarbonate resin composition. Structural formula (A): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Structural formula (B); ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (n in structural formula (A) represents an integer from 1 to 200, and R represents an alkylene group having 2 to 6 carbon atoms. In addition, B in structural formula (B) represents a linear, branched, or cyclic alkylidene group having 1 to 10 carbon atoms, an aryl-substituted alkylene group, an aryl group, or -O- ,−
Indicates S-, -CO-, -SO_2-, R^1, R^2
, R^3 and R^4 are hydrogen, halogen or carbon number 1-4
represents an alkyl group. 2. The flame-retardant polycarbonate resin composition according to claim 1, wherein the copolycarbonate resin is in a range of 5 to 50% by weight. 3. The flame-retardant polycarbonate resin composition according to claim 1, wherein the copolycarbonate resin contains 0.2 to 50% by weight of the structural unit represented by the structural formula (A). 4. R in the structural formula (A) of the copolycarbonate resin
The flame-retardant polycarbonate resin according to claim 1, wherein is -CHR^5-CH_2- (R^5 in the formula is bonded to a carbon atom on the benzene ring side and represents hydrogen or a methyl group). Composition.