JP2981572B2 - Polycarbonate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention has improved mechanical properties, in particular, improved flame resistance, which has excellent impact resistance at low temperatures, good appearance and good moldability. It is a polycarbonate resin composition which has excellent transparency and can be suitably used for various applications.

[Conventional technology and issues]

Aromatic polycarbonate resins are used for various applications as useful engineering plastics because they are excellent in heat resistance, impact resistance, electrical properties, dimensional stability and the like and are transparent.

However, the flame retardancy is not always sufficient. As this improvement method, conventionally, for the purpose of improving the flame retardancy of an aromatic polycarbonate resin, a method of forming a polycarbonate copolymer containing Br or blending a polycarbonate oligomer containing Br has been known for its mechanical properties and heat resistance. However, the polycarbonate resin has a poor impact resistance.

[Means for solving the problem]

The present inventors have studied to obtain a polycarbonate resin composition having excellent flame resistance and impact resistance, and found that both are improved by blending a copolycarbonate resin having a polysiloxane chain, The present invention has been reached.

That is, the present invention provides a copolycarbonate resin (1) having the structural units represented by the following structural formulas (A) and (B), or the copolycarbonate resin (1) and a halogen-free aromatic polycarbonate resin (2) Is a flame-retardant polycarbonate resin composition obtained by blending a halogen-containing aromatic polycarbonate (3) with the above composition.

(N in the structural formula (A) represents a positive number of 1 to 200, R represents an alkylene group having 2 to 6 carbon atoms, and B in the structural formula (B) represents a straight chain having 1 to 10 carbon atoms; A branched or cyclic alkylidene group, an aryl-substituted alkylene group, an aryl group or-
O -, - S -, - CO -, - SO 2 - shows ^{a, R 1, R 2, R} 3 and R ⁴ is hydrogen, halogen or an alkyl group having 1 to 4 carbon atoms. In the present invention, the blending amount of the halogen-containing polycarbonate (3) is 100% by weight of the copolycarbonate resin (1) or the composition of the copolycarbonate resin (1) and the aromatic polycarbonate resin (2). On the other hand, it is in the range of 1 to 50% by weight, and the structural unit represented by the structural formula (A) of the copolycarbonate resin (1) is 0.2% based on 100% by weight of the copolycarbonate resin (1). And R in the structural formula (A) of the copolycarbonate resin (1) is -CH
R ⁵ —CH ₂ — (wherein R ⁵ is bonded to the carbon atom on the benzene ring side and represents hydrogen or a methyl group).

 Hereinafter, the configuration of the present invention will be described.

The copolycarbonate resin (1) of the present invention has a structural unit of the structural formula (A) composed of bisphenol having a silicone chain and a fatty chain as a structural unit, and is a conventional aromatic polycarbonate resin. In the above method, a production method similar to the conventional interfacial polymerization method is suitably applied except that a dihydric phenol having a silicone chain and a fatty chain represented by the following general formula (1) is partially used. is there.

General formula (1); N and R in the formula are the same as those in the structural formula (A).

The structural unit represented by the structural formula (A) in the copolycarbonate resin is not particularly limited, but is preferably not more than 0.1.
The range of 2 to 50% by weight, particularly the range of 0.5 to 25% by weight is suitable, and the number of repeating siloxane units (n) in the structural formula (A) is in the range of 1 to 200, preferably in the range of 5 to 100. It is. Further, R in the structural formula (A) is ethylene,
Propylene, isopropylene, butylene, pentylene,
Hexylene and the like are exemplified, and CHR ⁵ —CH ₂ — (wherein R ⁵ is a bond to a carbon atom on the benzene ring side and represents hydrogen or a methyl group) is particularly preferable. The structural unit of the structural formula (A) is introduced by using a dihydric phenol represented by the general formula (1) and having a phenolic hydroxyl group at both terminals in the same manner as ordinary bisphenol. The compound represented by the general formula (1) is obtained by converting a phenol having an olefinic unsaturated carbon-carbon bond, preferably vinylphenol or isopropenylphenol, to a polysiloxane chain having a predetermined polymerization degree (n). It is easily produced by subjecting the terminal to a hydrosilation reaction.

The aromatic polycarbonate resin (2) of the present invention is produced by a conventional method for producing an aromatic polycarbonate resin in which a halogen-free dihydric phenol compound is reacted with phosgene, carbonate ester, or chloroformate. Things.

Further, the aromatic polycarbonate (3) of the present invention is:
It is a halogenated polycarbonate oligomer produced by a conventional method for producing an aromatic polycarbonate resin or oligomer by reacting a halogen-containing dihydric phenol compound with phosgene, carbonate or chloroformate.

Here, the above-mentioned copolycarbonate resin (1),
As the dihydric phenolic compound used for producing the aromatic polycarbonate resin (2) and the halogen-containing polycarbonate (3), 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-dimethylphenyl) propane, 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, 1,1-
Bis (4-hydroxyphenyl) -1-phenylethane and bis (4-hydroxyphenyl) diphenylmethane are exemplified. For the production of halogen-free polycarbonate and copolycarbonate resin, 2,2-bis (4-hydroxyphenyl) propane and 1,1-bis (4
-Hydroxyphenyl) cyclohexane is preferred from the viewpoint of thermal stability. In addition, a terminating agent or a molecular weight regulator is usually used, and examples thereof include compounds having a monovalent phenolic hydroxyl group, and other than ordinary phenol, p-tert-butylphenol, tribromophenol and the like. And long-chain alkyl phenols, aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, hydroxybenzoic acid alkyl esters, hydroxy phenyl acid alkyl esters, and alkyl ether phenols. The amount used is the amount of all dihydric phenol compounds used.
The amount is in the range of 100 to 0.5 mol, preferably 50 to 2 mol, per 100 mol, and it is naturally possible to use two or more compounds in combination. Further, a branching agent may be used in combination with the above dihydric phenol compound in an amount of 0.01 to 3 mol, particularly 0.1 to 1.0 mol%, to form a branched polycarbonate. Examples of the branching agent include phloroglysin, 2,6 -Dimethyl-2,4,6-
Tri (4-hydroxyphenyl) heptene-3,4,6-
Dimethyl-2,4,6-tri (4-hydroxyphenyl) heptene-2,1,3,5-tri (2-hydroxyphenyl)
Benzol, 1,1,1-tri (4-hydroxyphenyl)
With ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol, α, α ′, α ″ -tri (4-hydroxyphenyl) -1,3,5-triisopropylbenzene Examples thereof include polyhydroxy compounds, and 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chlorisatin, 5,7-dichlorisatin, 5-bromoisatin, and the like.

In the flame-retardant polycarbonate resin composition of the present invention, the blending amount of the halogen-containing polycarbonate (3) with respect to the above-mentioned copolycarbonate resin (1) or the composition of the copolycarbonate resin (1) and the aromatic polycarbonate resin (2) is as follows. , Although there is no particular limitation,
1-50 of the resin component in the composition from the viewpoint of maintaining impact resistance
% By weight, more preferably in the range of 5 to 30% by weight. The ratio of the copolycarbonate (1) to the aromatic polycarbonate resin (2) is not particularly limited, and a wide range of copolycarbonate resin (1) / aromatic polycarbonate resin (2) = 1/99 to 99/1. But is more preferably selected from the range of 50/50 to 10/95.

When the amount of the copolycarbonate resin (1) in the composition is too small, the improvement in impact resistance is insufficient, and when the amount of the halogen-containing polycarbonate (3) is too small, the improvement in flame retardancy is insufficient. It is. On the other hand, a large amount of the halogen-containing polycarbonate (3) is not preferable because impact resistance is reduced.

As described above, the flame-retardant polycarbonate resin composition of the present invention may contain, if desired, various additives conventionally known to polycarbonate resins, such as reinforcing materials and fillers. , Stabilizer, UV absorber,
Monophosphoric acid esters described in JP-A-61-55145, or JP-A-59-45351 and JP-A-2-11526 as antistatic agents, lubricants, release agents, dyes, pigments and other flame retardants.
2, the condensed phosphate described in 2, or JP-A-52-5
And metal salts of aromatic sulfonic acids described in No. 4742. Further, an elastomer or the like for improving impact resistance can be added. For example, phosphorous acid or phosphite is particularly suitable as a stabilizer. Examples of the release agent include esters of mono- or polyhydric alcohols of saturated fatty acids, and preferred examples thereof include steeryl stearate, behenyl behenate, pentaerythritol tetrastearate, and dipentaerythritol hexaoctoate. You. Glass powder, glass beads, synthetic mica or fluorinated mica, zinc oxide, carbon fiber, especially glass fiber including those having a fiber diameter of 2 μm or less;
Organic or inorganic fillers and reinforcing agents such as zinc oxide whiskers, stainless steel fibers and Kevlar fibers, as well as resins such as polyester carbonate and polyarylate can be suitably suitably used according to the purpose.

〔Example〕

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

Reference Example 1 3.7 kg of sodium hydroxide was dissolved in water 42 and 6,735 g of 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as “BPA”) was shown at page 7 while maintaining at 20 ° C. In the general formula (1), 356 g of n = 50 (hereinafter referred to as “BY16-752”) and 15 g of hydrosulfite were dissolved.

Methylene chloride (hereinafter referred to as “MC”) 30
While stirring, 148 g of pt-butylphenol (hereinafter referred to as “PTBP”) was added, and 3.5 kg of phosgene was added.
I blew it in 0 minutes.

After the phosgene blowing was completed, the reaction solution was vigorously stirred to emulsify the reaction solution, and an emulsifier and 8 ml of triethylamine were added, followed by stirring for about 1 hour to carry out polymerization.

The polymerization liquid was separated into an aqueous phase and an organic phase, the organic phase was neutralized with phosphoric acid, and the water was washed repeatedly until the pH of the wash became neutral.After that, 35 isopropanol was added to precipitate the polymer. I let it. The precipitate is filtered and then dried to obtain a white powdery copolycarbonate resin (hereinafter referred to as “C-PC05”).
To be described).

Examples 1 to 3 and Comparative Examples 1 to 3 As shown in Table 1 below, a copolycarbonate resin and an aromatic polycarbonate resin produced by the production method shown in Reference Example 1 (Iupilon S, manufactured by Mitsubishi Gas Chemical Co., Ltd.) -2000, molecular weight 25,000) and a polycarbonate oligomer from tetrabromobisphenol A (manufactured by Mitsubishi Gas Chemical Company, Inc., FR-34), blended at the ratios shown in Table 1 and having a cylinder temperature of 250 to 270 ° C. The mixture was melt-kneaded using an extruder to form pellets.

The pellets were dried in a hot air drier at 120 ° C. for 5 hours or more, and then a test piece for measuring physical properties was produced at a cylinder temperature of 270 ° C. and tested.

 The results are shown in Table 1.

 The measurement of physical properties was as follows.

・ UL-94: Combustibility according to UL-94. Specimen thickness 1.6mm & 0.8mm ・ IZ: Izod impact value. Unit: kg cm / cm. Specimen thickness 1/4 "&1/8" ・ HDT: Thermal deformation temperature. Load 18.6 kg / cm ² · Transmittance: Total light transmittance (%). Suga Test Machine Co., Ltd., direct reading haze computer, test piece thickness 3mm. [Functions and Effects of the Invention] The flame-retardant polycarbonate resin composition of the present invention not only has improved flame retardancy, but also has excellent impact resistance, particularly its thickness dependency and low-temperature impact resistance. It is. Therefore, it is understood that ordinary molded articles are useful as molding materials suitable as precision molded articles and molded articles for low-temperature use as a matter of course.

────────────────────────────────────────────────── ─── Continuing from the front page (72) Inventor Makoto Mizutani 5-6-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Pref. Inspector, Plastic Center, Mitsubishi Gas Chemical Co., Ltd. Yumiko Isshiki (56) References JP-A-2-36258 ( JP, A) JP-A-2-240656 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 69/00

Claims (4)

(57) [Claims] 1. A copolycarbonate resin (1) having structural units represented by the following structural formulas (A) and (B), or a copolycarbonate resin (1) and a halogen-free aromatic polycarbonate resin (2): A flame-retardant polycarbonate resin composition obtained by blending the halogen-containing aromatic polycarbonate (3) with the composition of (1). (N in Structural Formula (A) represents an integer of 1 to 200, R represents an alkylene group having 2 to 6 carbon atoms, and B in Structural Formula (B) represents a linear or branched chain having 1 to 10 carbon atoms. A chain or cyclic alkylidene group, an aryl-substituted alkylene group, an aryl group or-
O -, - S -, - CO -, - SO 2 - shows ^{a, R 1, R 2, R} 3 and R ⁴ is hydrogen, halogen or an alkyl group having 1 to 4 carbon atoms. ) 2. The compounding amount of the halogen-containing polycarbonate (3) is 100% by weight of a copolycarbonate resin (1) or a composition of the copolycarbonate resin (1) and a halogen-free aromatic polycarbonate resin (2). The flame-retardant polycarbonate resin composition according to claim 1, wherein the content is in the range of 5 to 30% by weight. 3. The copolycarbonate resin (1) has a structural unit represented by the structural formula (A) of 0.2 to 50% by weight based on 100% by weight of the copolycarbonate resin (1). The flame-retardant polycarbonate resin composition according to the above. 4. The copolycarbonate resin (1) wherein R in the structural formula (A) is —CHR ⁵ —CH ₂ — (in the formula, R ⁵ is bonded to a carbon atom on the benzene ring side, and hydrogen or The flame-retardant polycarbonate resin composition according to claim 1, which represents a methyl group.