JPS6369858A - Polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition having excellent physical properties, moldability and low water absorption, by compounding a polycarbonate resin having a specific molecular weight with a specific amount of an aromatic polycarbonate oligomer having long-chain alkyl at the terminal. CONSTITUTION:A polycarbonate resin having a viscosity-average molecular weight of >=20,000, preferably 24,000-35,000 is compounded with 1-60wt.%, preferably 5-40wt.% aromatic polycarbonate oligomer having an intrinsic viscosity of <=0.3 and an average polymerization degree of <=15, containing 2-15 constituent units of formula I (R is 1-10C straight, branched or cyclic alkylidene, etc.; R1-4 are H, halogen, etc.) on an average and produced by using a chain end terminator expressed by formula II or formula III (X is -COCl, etc.; Y is single bond, -COO-, etc.; n is 8-30).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is characterized by the physical properties of a polycarbonate resin having a viscosity average molecular weight of 20,000 or more mixed with an aromatic polycarbonate oligomer having a long chain alkyl group at the end. It is a polycarbonate resin composition with excellent moldability and low water absorption.

[Conventional technology]

Conventionally, as a method of improving the moldability of polycarbonate resin, a method of adding a plasticizer to the resin is known. Plasticizers include phthalate esters, aliphatic dibasic acid esters, glycol esters, fatty acid esters, phosphate esters, and others.Addition of these improves fluidity but lowers heat distortion temperature. other,
During molding, plasticizer vapor with a unique odor is generated, which aggregates and adheres to the mold surface, and is transferred to the surface of the molded product, causing poor appearance and deteriorating the working environment due to the odor. , causing various harmful effects.

Furthermore, in order to improve properties such as heat distortion temperature, a method of blending resins with good heat resistance is generally adopted, but in this case, although heat resistance is improved, fluidity is not improved. Furthermore, there is a method of blending a resin with low water absorption such as polystyrene in order to achieve low water absorption, but it is usually difficult to obtain a transparent composition due to poor compatibility between the components. be.

[Problem that the invention seeks to solve]

As described above, no method has been found so far to substantially maintain the heat distortion temperature of polycarbonate resin and improve it to have high fluidity and low water absorption.

[Means for Solving the Problems] The present inventors have improved thermal properties such as heat distortion temperature by blending a polycarbonate oligomer with 2 to 15 structural units having a long-chain alkyl group at the terminal into a polycarbonate resin. Alternatively, the inventors discovered a low water absorption polycarbonate resin composition with excellent moldability, and completed the present invention.

That is, the present invention provides a polycarbonate resin having a viscosity average molecular weight of 20,000 or more, which has an average of 2 to 15 structural units represented by the following general formula (1), and has a general formula (2) or (3).
This is a polycarbonate resin composition containing 1 to 60% by weight of an aromatic polycarbonate oligomer (B) using a terminal capping agent represented by:

(R in the formula is a linear, branched or cyclic alkylidene group having 1 to 10 carbon atoms, a aryl-substituted alkylene group, an aryl group, or -〇-, -CO-.

-s-, -5o-, -so□-, and R1-R4 represent hydrogen, a halogen atom, or an alkyl group) General formula (2) 20, 112h+1-X...
・(2) (X in the formula represents -COCI, -CODll, Y represents a simple bond - or -coo-, -o-, and n represents an integer from 8 to 30) The configuration will be explained.

First, the polycarbonate resin of the present invention is produced by a method similar to the method for producing conventional polycarbonate resins, that is, by reacting an aromatic dihydric phenol compound with phosgene or carbonic diester. The aromatic homo- or copolycarbonate resin used in the present invention has a viscosity average molecular weight of 20,000 or more, preferably 24,000 to 35
．． A range of 000 is preferred.

Here, as the aromatic dihydric phenol compound, 2.
2-bis(4-hydroxyphenyl)furopane, 2,2
-bis(4-hydroxy-3,5-dimethylphenyl)
Propane, bis(4-hydroxyphenyl)methane, 1
．． 1-bis(4-hydroxyphenyl)ethane, 2.2
-bis(4-hydroxyphenyl)butane, 2゜2-his(4-hydroxy-3,5-diethylphenyl)propane, 2.2-bis(4-hydroxy-3,5-dipropylphenyl)furopane, 1 .1-bis(4-hydroxyphenyl)cyclohexane, 1-phenyl-1,1-
Examples include bis(4-hydroxyphenyl)ethane, which may be used alone or as a mixture of two or more.

In addition, as a molecular weight regulator, ordinary phenol, p-t
- Monohydric phenol compounds such as butylphenol and tribromophenol are exemplified, and the amount used is 1 to 10 mol%, preferably 2.0 to 3 mol% of the dihydric phenol used.
．． It is in the range of 5 mol%.

Furthermore, it can also be used as a branched product, and examples of branching agents include phloroglycin, 2.6-cymethyl-2.4.6-)(4-hydroxyphenyl)
Hebutene-3,4,6-dimethyl-2.4.6-)su(4-hydroxyphenyl)hebutene-2,1,3,5
-tri(2-hydroxyphenyl)penzole, 1,1
．． 1-)Su(4-hydroxyphenyl)ethane, 2.6
-bis(2-hydroxy-5-methylbenzyl)-4-
Methyl fluorenol, α, α1. αTLl, polyhydroxy compounds exemplified by 4-hydroxyphenyl L-1,3,5-triisopropylbenzene, and 3
．． Examples include 3-bis(4-hydroxyaryl)oxindole (-isatinbisphenol), 5-chloroisatin, 5,7-dichloroisatin, 5-promyzatin, and the amount used is 0.02 of the dihydric phenol used.
It is in the range of 1.0 mol%.

Next, the method for producing the long-terminated alkyl aromatic polycarbonate oligomer of the present invention is different from the conventional method for producing aromatic polycarbonate oligomers by simply changing the terminal capping agent. The above general formula (2) having an alkyl group
, (3) may be added.

Here, as the dihydric phenol, the same ones as those used in the production of the above-mentioned polycarbonate resin are exemplified, and they can be used alone or in combination.

The molecular weight regulators used in producing this oligomer include capric acid chloride, lauric acid chloride,
Aliphatic acid chlorides such as myristic acid chloride, palmitic acid chloride, stearic acid chloride, cerotic acid chloride; fatty acids such as capric acid, lauric acid, myristic acid, balmitic acid, stearic acid, cerotic acid, etc.; octylphenol, norylphenol, lauryl Long-chain alkyl-substituted phenols such as phenol, valmitylphenol, and stearylphenol; Long-chain alkyl esters of hydroxybenzoic acid such as octyl hydroxybenzoate, lauryl hydroxybenzoate, noryl hydroxybenzoate, and stearyl hydroxybenzoate; octyl ether phenol (- Examples include long-chain alkyloxyphenols such as octyloxyphenol), noryl etherphenol, lauryl etherphenol, palmityl etherphenol, octadecyloxyphenol, and dobusyloxyphenol.

The amount used is 13 to 100 mol% of the dihydric phenol used.
, preferably in the range of 16 to 50 mol%, and the aforementioned long-chain alkyl group-containing dihydric phenol is used in combination with a terminal capping agent such as ordinary phenol, pt-butylphenol, tribromophenol, etc. Naturally, this is also possible, and when used together, it is preferable to use a conventional terminal capping agent in an amount of 50 mol% or less.

If the intrinsic viscosity of the terminal long-chain alkyl aromatic polycarbonate oligomer as described above is greater than 0.3 or the average degree of polymerization is greater than 15, the effect of improving fluidity will be insufficient, which is undesirable.

Further, in the production of polycarbonate oligomers, a trifunctional or higher functional compound containing two or more phenolic groups can be used as part of the aromatic dihydric phenol compound.

The amount of the terminal long chain alkyl polycarbonate oligomer blended with the polycarbonate resin is 1 to 60% by weight, preferably 5 to 40% by weight of the composition with the polycarbonate resin.
Select from a range of weight %. If it is used in an amount exceeding 60% by weight, the physical properties will greatly deteriorate, which is undesirable, and if it is less than 1% by weight, the improvement in fluidity and water absorption will be insufficient, which is undesirable.

There are no particular limitations on the method for preparing the composition of the present invention, and a conventional method may be used, for example, by thoroughly mixing a polycarbonate resin and a polycarbonate oligomer in a blender, and then melting and pelletizing in a vented extruder or the like. The method of doing so is fine.

In addition, additives such as heat stabilizers, antioxidants, light stabilizers, colorants, inorganic fillers, glass fibers, carbon fibers, lubricants, and antistatic agents are naturally added to these polycarbonate resins as necessary. can be added.

〔Example〕

This will be explained below using synthesis examples, examples, and comparative examples. Note that "1%" and "parts" in Synthesis Examples and Examples are based on weight unless otherwise specified.

Synthesis Example-1 In a reaction tank with an internal capacity of 400β equipped with a stirrer, a phosgene blowing pipe, and a cooling jacket, 25 kg of a 48% caustic soda aqueous solution, 200 C of water, and 100 A of methylene chloride were placed.
, Hydrosulfide 100g, 2.2-bis(4-h hydroxyphenyl)propane (=BPA)2
7.5 kg were added one after another, and 16.6 kg of phosgene was blown in for 30 minutes while keeping the liquid temperature in the range of 15 to 20°C.
Made it react.

After that, 6 kg of 48% caustic soda aqueous solution was added to the reaction system.

A solution of 100 g of triethylamine 'J6 and 18.4 kg of lauryl para-oxybenzoate (-POllR) dissolved in methylene chloride 501 was added, and stirring was continued for an additional 60 minutes.

The precipitated methylene chloride layer was extracted from the reaction solution and transferred to a purification tank with an internal capacity of 300β equipped with a stirrer,
After neutralizing with 1% phosphoric acid aqueous solution of 1001 and water and washing with water, transfer to a solidification tank with an internal capacity of 5001, and
The mixture was heated under stirring with 1 and methylene chloride was distilled off. After cooling, the precipitate was separated and dried to obtain 45 kg of terminal long chain alkyl aromatic polycarbonate oligomer powder.

The melting point was 185 to 189°C, the number average molecular weight was 1.600 by end group analysis, and the number average degree of polymerization was about 4.

Synthesis example-2 In Synthesis Example-1, the amount of phosgene was 15.0 kg.

35 kg of aromatic polycarbonate oligomer powder was obtained in the same manner except that the amount of POBH was changed to 10.5 kg.

The melting point was 205 to 209°C, the number average molecular weight by end group analysis was 2.400, and the number average degree of polymerization was about 7.

Synthesis example-3 In Synthesis Example-1, the amount of phosgene was 14.6 kg.

Octadesyloxyphenol 8.7k instead of POBH
38 kg of aromatic polycarbonate oligomer powder was obtained in the same manner except that g was used.

The melting point was 206-209°C, the number average molecular weight was 3.300 by end group analysis, and the number average degree of polymerization was about 10.

Synthesis Example 4 45 kg of aromatic polycarbonate oligomer powder was obtained in the same manner as in Synthesis Example 1 except that 18.2 kg of stearic acid chloride was used instead of POr)R.

The melting point was 170 to 175°C, the number average molecular weight by end group analysis was 1.500, and the number average degree of polymerization was about 4.

Dissolve 3.7 kg of sodium hydroxide in 42 A of water,
7.3 kg of BPA, 25 g of 2.6-dimethyl-2.4.6-) IJ (4-hydroxyphenyl)hebutene=3 (T P H), and 8 g of hydrosulfide were dissolved while maintaining the temperature at °C.

To this, methylene chloride 28β was added and while stirring, para-tertiary-butylphenol (TBP) 1
68 g was added and 3.5 kg of phosgene was blown in over 60 minutes.

After the phosgene injection was completed, the reaction solution was vigorously stirred to emulsify it. After emulsification, 8 g of triethylamine and amine were added and stirred for about 1 hour to further polymerize.

The polymerization solution was separated into an aqueous phase and an organic phase, and the organic phase was neutralized with phosphoric acid. After repeating water washing until the pH of the washing solution became neutral, 35j2 of isopropanol was added and the polymerization was precipitated. By filtering the precipitate and then drying it,
A white powdery polycarbonate resin was obtained.

The viscosity average molecular weight of this powder determined from the intrinsic viscosity in a methylene chloride solution was 25.000.

Reference Example 2 A branched aromatic polycarbonate resin was obtained in the same manner as Reference Example 1 except that the amount of TBP was changed to 134 g.

The viscosity average molecular weight of this branched aromatic polycarbonate resin was 32.000.

Dissolve 3.7 kg of sodium hydroxide in 421 parts of water,
While maintaining the temperature at °C, 7.3 kg of BPA and 8 g of hydrosulfide were dissolved.

Methylene chloride 28A was added to this, 160 g of TBP was added while stirring, and 3.5 kg of phosgene was blown in over 60 minutes.

After the phosgene injection was completed, the reaction solution was vigorously stirred to emulsify it. After emulsification, 8 g of triethylamine was added and the mixture was stirred for about 1 hour to allow 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 water washing until P I-1 in the washing solution became neutral, 351% of Impropatool was added. , the polymer was precipitated. A white powdery polycarbonate resin was obtained by filtering the precipitate and then softening it.

The viscosity average molecular weight of this powder determined from the intrinsic viscosity in a methylene chloride solution was 24.000.

Reference Example-4 A branched aromatic polycarbonate resin was obtained in the same manner as in Reference Example-3 except that the amount of TBP was changed to 120 g.

The viscosity average molecular weight of this branched aromatic polycarbonate resin was 33.000.

Examples-1 to 8 and Comparative Examples-1 to 4 Polycarbonate resins obtained in Reference Examples-1 to 4 and synthesis examples-
Polycarbonate obtained in steps 1 to 4;
The compositions shown in the table were mixed in a tumbler and extruded into pellets using a vented extruder with a shaft.

The obtained pellets were molded into test pieces for heat distortion temperature measurement and water absorption measurement test pieces using an injection molding machine.

The test results are shown in Table 1.

The description in Table 1 is as follows.

- HDT: The heat distortion temperature was measured at a load of 18.6 kg/c according to 8STM 0648.

・Water absorption rate: 120 5cm square molded pieces with a thickness of 3.2mm
The weight was measured after drying at °C for 12 hours and after immersing in pure water for 24 hours and removing surface moisture.

・Q value: Flow tester, 280℃, 160kg/c
n? The amount of molten resin flowing out from a nozzle of 1 mmφ×10 m+nL under the pressure of is expressed in units of (x 1j' cc/5ec).

[Operation and effects of the invention]

As mentioned above, the polycarbonate resin composition of the present invention is
The decrease in physical properties such as heat distortion temperature is small, the moldability is greatly improved, and the water absorption rate is also significantly reduced.

Therefore, it is possible to maintain the extremely excellent performance of high-molecular weight aromatic polycarbonate resins used for ordinary injection molding and extrusion molding, and also to obtain compositions with low water absorption, which is normally difficult to achieve. It is suitably used for various purposes by taking advantage of its high efficiency.

Claims (1)

[Scope of Claims] A polycarbonate resin having a viscosity average molecular weight of 20,000 or more, containing an average value of 2 to 20% of the structural units represented by the following general formula (1).
A polycarbonate resin composition containing 1 to 60% by weight of an aromatic polycarbonate oligomer (B) having 15 terminal terminators represented by general formula (2) or (3). General formula (1) ▲There are numerical formulas, chemical formulas, tables, etc.▼... (1) (R in the formula is a straight chain, branched or cyclic alkylidene group having 1 to 10 carbon atoms, an aryl-substituted alkylene group, Aryl group, or -O-, -CO-, -S-, -SO-,
-SO_2-, and R_1 to R_4 represent hydrogen, halogen, or an alkyl group) General formula (2): CnH_2_n_+_1-X...(2
) General formula (3): ▲There are mathematical formulas, chemical formulas, tables, etc.▼・
...(3) (X in the formula represents -COCl, -COOH, Y represents a simple bond - or -COO-, -O-, and n is 8
~ represents an integer of 30)