JPS6144954A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:The titled composition having excellent physical chracteristics such as heat distortion temperature, and excellent moldability, consisting of a thermoplastic resin and a specified aromatic polycarbonate oligomer. CONSTITUTION:An aromatic dihydric phenolic compound such as 2,2-bis(4-hydroxyphenyl)propane is reacted with a polycarbonate precursor such as phosgene in the presence of a molecular weight modifier (e.g. phenol) to give an aromatic polycarbonate oligomer which has an intrinsic viscosity (in methylene chloride, at 25 deg.C) of 0.3 or lower and contains in average 2-15 constitutional units of the formula (where X is a 1-6C alkylidene, O, S or sulfonyl; R1-4 each are H or an alkyl). Then one or more thermoplastic resins selected from among PE, PS, polyamide resin, heat-resistant engineering plastic, etc., and 1-30wt% said oligomer are compounded.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention provides a thermoplastic resin composition with excellent physical properties such as heat distortion temperature or moldability, which is obtained by blending an aromatic polycarbonate oligomer with a thermoplastic resin. It is a thing.

[Conventional technology]

Conventionally, as a method for improving the moldability of thermoplastic resins, 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. In addition, 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 creating an odor-filled work environment. This causes various harmful effects, such as deterioration of

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.

[Problem that the invention seeks to solve]

As described above, no method has so far been found for substantially maintaining or increasing the heat distortion temperature of a thermoplastic resin and improving the moldability (fluidity).

[Means for solving problems]

The present inventors discovered a thermoplastic resin composition with excellent thermal properties such as heat distortion temperature or moldability by blending a polycarbonate oligomer having 2 to 15 structural units into a thermoplastic resin, and the present invention. was completed.

That is, in the present invention, 1 to 30 aromatic polycarbonate oligomers (B) having an average of 2 to 15 structural units represented by the following general formula +11 are added to the thermoplastic resin (A).
It is a thermoplastic resin composition formed by blending % by weight.

(X in the formula is an alkylidene group having 1 to 6 carbon atoms, an oxygen atom, a sulfur atom, or a sulfonyl group, and RI"" Ra
represents hydrogen or an alkyl group) The structure of the present invention will be described below.

First, as the thermoplastic resin of the present invention, olefin polymers such as polyethylene, polypropylene, polybutene, polyisobutylene, polymethylpentene-11 ethylene-propylene copolymer; polymethyl methacrylate, methyl methacrylate, etc. Copolymers with ethyl acrylate, n-butyl acrylate, etc. as main components, acrylate polymers such as polyethyl acrylate, polybutyl acrylate; polystyrene (PS), high impact polystyrene (HIPS), acrylonitrile-styrene Copolymer (As), ABS, MBS,
MABSSMAS, others are represented by the acrylonitrile-acrylic rubber-styrene copolymer disclosed in JP-A-48-48547, the acrylonitrile-chlorinated polyolefin-styrene copolymer disclosed in JP-A-48-42452, etc. Styrenic polymer; nylon-6, nylon-66, nylon-12, nylon-6
, 12, polyamide resins represented by nylon-11, MX polyamide, etc.; saturated polyester resins represented by polyethylene terephthalate, polybutylene terephthalate, etc.; polyvinyl acecool, polyvinyl acetate,
Vinyl alcohol-vinyl acetate copolymer, vinyl chloride-
Examples include thermoplastic resins that are one or a mixture of two or more selected from vinyl acetate copolymers, polyvinyl chloride, polysulfone, and the like.

Additionally, additives such as heat stabilizers, antioxidants, light stabilizers, colorants, inorganic fillers, glass fibers, carbon fibers, lubricants, and antistatic agents may be added to these thermoplastic resins as necessary. can be added naturally.

The polycarbonate oligomer of the present invention includes 2.2=bis(4-hydroxyphenyl)propane, 2.2-bis(
4-hydroxy-3,5-dimethylphenyl)propane, bis(4-hydroxyphenyl)methane, 1゜l-bis(4-hydroxyphenyl)ethane, 2,2-bis(
4-hydroxyphenyl)butane, 2,2-bis(4-
Hydroxy-3,5-diethylphenyl)propane, 2
．． Aromatic dihydric phenol compounds represented by 2-bis(4-hydroxy-3,5-dipropylphenyl)propane, ■,■-bis(4-hydroxyphenyl)cyclohexane, etc. and carbonate precursors represented by phosgene. Aromatic dihydric phenols are obtained by reaction with
The oligomers may be used alone or in combination, and are generally low molecular weight substances having an intrinsic viscosity of 0.3 or less at 25° C. in methylene chloride. The molecular weight regulator used in producing this oligomer may be, for example, in an interfacial polymerization method using phosgene, by adding, for example, phenol, alkyl-substituted phenol, etc. to the polymerization system to block the terminals. If the intrinsic viscosity of the polycarbonate oligomer 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.

In addition, in the production of polycarbonate oligomers, trifunctional or higher functional compounds containing two or more phenolic OH groups, such as low molecular weight phenol novolak, etc. may be used as part of the above aromatic dihydric phenol compound. I can do it.

The amount of polycarbonate oligomer mixed with the above thermoplastic resin (including the composition thereof) is selected from the range of 1 to 30% by weight, preferably 5 to 20% by weight of the composition with the thermoplastic resin. If it is used in an amount exceeding 30% by weight, the physical properties will deteriorate significantly, which is not preferable, and if it is less than 1% by weight, the improvement in fluidity will be insufficient, which is not preferable.

The composition of the present invention can be prepared by any conventional method, for example, by thoroughly mixing a thermoplastic resin and a polycarbonate oligomer in a blender, and then melting the mixture in a vented extruder or the like to pelletize the composition. The method of doing so is fine.

〔Example〕

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

Synthesis Example-1 25 kg of 48% caustic soda aqueous solution, 250 β of water, and 60 kg of methylene chloride were placed in a reaction tank equipped with a stirrer, a phosgene blowing pipe, and a cooling jacket with an internal capacity of 400 β.
β, hydrosulfide 100g, 2.2-bis(4-hydroxyphenyl)propane (=BPA)2
7.5 kg of phosgene were added one after another, and 16.6 kg of phosgene was blown in over 30 minutes while maintaining the liquid temperature in the range of 15 to 20°C to cause a reaction.

Thereafter, 6 kg of 48% caustic soda aqueous solution, 100 g of triethylamine, and 9.0 kg of paratertiary butylphenol (=TBP) were added to the reaction system, and methylene chloride 507! A solution dissolved in 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 3001 cm equipped with a stirrer.
After neutralizing with 1% phosphoric acid aqueous solution of 100β and water and washing with water, transfer to a solidification tank with an internal capacity of 500β,
The mixture was stirred and heated together with 1, and methylene chloride was distilled off. After cooling, the precipitate was filtered and dried to obtain 35 kg of aromatic polycarbonate oligomer powder.

The melting point of the polycarbonate oligomer prepared by 14° is 2
The temperature was 05 to 209° C., the viscosity average molecular weight was 3×10°, the number average molecular weight was 1.3×10′ 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, T
33.6 kg of aromatic polycarbonate oligomer powder was obtained in the same manner except that the amount of BP was changed to 5.2 kg.

The melting point of the obtained polycarbonate oligomer is 229
~232°C1 viscosity average molecular weight 5 x Io', number average molecular weight by end group analysis 2. lXl0', 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.

+r was obtained for the aromatic polycarbonate oligomer powder 33' in the same manner except that the TBP amount was 3.6 kg.

The melting point of the obtained polycarbonate oligomer is 235
The viscosity average molecular weight was ~238° C1 7×10′, the number average molecular weight was 2.9×1 G′ by end group analysis, and the number average degree of polymerization was about 10.

Examples 1 to 3 and Comparative Example 1 Polyethylene (Mitsubishi Kasei ■, trade name: Novate Tsuku) and the polycarbonate oligomer obtained in Synthesis Example 1 were mixed in a tumbler with the composition shown in Table 1. , respectively −
It was extruded into pellets using a Hendt type extruder.

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

The test results are shown in Table 1.

In addition, the melt index (Ml) is based on ASTM D 1
23B (190℃0.325kg), heat distortion temperature (
HDT) according to ASTM D 648, load 18
．． Measured at 6 kg/cd.

Table 1 Examples-4 to 12 and Comparative Examples-2 to 4 Polystyrene (Mitsubishi Monsando ■, product name: Diamond
2x), ABS (Mitsubishi Monsanto ■, trade name: Dialex), PMMA (Asahi Kasei ■, trade name: Delpet) and the polycarbonate oligomer obtained in Synthesis Example 2 were tumbled with the composition shown in Table 2. Mix at
Pellet 7) and heat distortion temperature test pieces were obtained in the same manner as in Examples 1 to 3.

The test results are shown in Table 2.

In addition, MI is 8 STM D 1238 (PS: 20
0℃ 5kg, ABS: 230℃ 3.8kg, PMM
A: 190°C, 1.2 kg).

Table 2 Examples-13 to 18 and Comparative Examples-5,6 Polybutylene terephthalate (Mitsubishi Kasei ■, trade name: Tubadol), glass-filled polybutylene terephthalate (Mitsubishi Kasei ■, trade name: Tubadol) and Synthesis Example-2 The polycarbonate oligomers obtained in Table 3 were mixed in a tumbler with the composition shown in Table 3, and pellets and test pieces for heat distortion temperature were obtained in the same manner as in Examples 1 to 3.

The test results are shown in Table 3.

In addition, Ml is ASTM D 1238 (PB'r:
230℃ 2.16kg, PBT (glass tls): 2
3S°C 2.16 kg).

Table 3 Examples-19 to 21 and Comparative Example-7 Holisulfone (Union Carbide@) and Synthesis Example-3
The polycarbonate oligomers obtained in Table 4 were mixed in a tumbler with the composition shown in Table 4, and pellets and test pieces for heat distortion temperature were obtained in the same manner as in Examples 1 to 3.

The test results are shown in Table 4.

Regarding fluidity, by measuring the flow value "Q value",
These are 11 mmφX under a pressure of 160 kg/c+a.
The unit is the amount of molten resin flowing out from a 10inL nozzle.
It is expressed in 10'cc/sec. [Operations and Effects of the Invention] As described above, the thermoplastic resin composition of the present invention is effective in improving physical properties such as heat distortion temperature and molding processability. It is.

That is, when a polycarbonate oligomer is added to polyethylene, polypropylene, etc. whose processing temperature is usually about 170 to 190°C, the fluidity is almost the same but the heat distortion temperature is improved, and A where the processing temperature is 200 to 240°C is obtained.
In the case of BS, polystyrene, and methyl methacrylate, both fluidity and heat distortion temperature are improved. Furthermore, for PBT processed at a processing temperature of 230 to 260°C, there is almost no decrease in heat deformation temperature, fluidity is improved, and processing temperature is 320 to 35°C.
With polyarylates and polysulfones that are as high as 0°C, the heat distortion temperature tends to remain the same or slightly lower, but the fluidity is greatly improved, resulting in extremely excellent performance that can greatly improve moldability. It is clear that it is a thing.

Patent Applicant Mitsubishi Gas Chemical Co., Ltd. Agent (9070) Pediatric Sadafumi Proceedings (Hoshosho (spontaneous) October 17, 1980)

Claims (1)

[Claims] A thermoplastic resin (A) is blended with 1 to 30% by weight of an aromatic polycarbonate oligomer (B) having an average of 2 to 15 structural units represented by the following general formula (1). A thermoplastic resin composition. General formula (1): ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・(1) (X in the formula is an alkylidene group having 1 to 6 carbon atoms, an oxygen atom, a sulfur atom, or a sulfonyl group. , R_1 to R_4 represent hydrogen or an alkyl group)