JPS63227663A - Thermoplastic polymer composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic polymer composition having improved thermal characteristics and moldability, by compounding an aromatic polycarbonate oligomer free from halogen atom to a composition composed of an aromatic polycarbonate resin and a specific thermoplastic polymer. CONSTITUTION:The objective composition can be produced by compounding and uniformly mixing (A) 100pts.wt. of a resin composition composed of (A1) 20-90wt.% aromatic homo- or copolycarbonate resin having a viscosity-average molecular weight of >=15,000, preferably 20,000-35,000 and (A2) 80-10% aromatic polyester resin (e.g. polybutylene terephthalate) or aromatic vinyl compound polymer or copolymer (preferably ABS, MBS, etc.) with (B) 1-50pts., preferably 5-40pts. of an aromatic polycarbonate oligomer having a viscosity- average polymerization degree of 2-15, free from halogen atom and containing ordinary terminal group or long-chain alkyl group.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention is directed to adding an aromatic polycarbonate oligomer having a normal terminal group or a long-chain alkyl group to a composition of an aromatic polycarbonate resin and a specific thermoplastic resin. This is a thermoplastic resin composition with improved fluidity.

[Conventional technology]

Conventionally, as a method for improving the moldability of thermoplastic resins or compositions thereof, there has been known a method of adding a plasticizer to the resin. 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 the work environment due to the odor. This causes various harmful effects such as deterioration.

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 to be Solved by the Invention 3] As mentioned above, no method has been found for substantially maintaining the heat distortion temperature of a thermoplastic resin or its composition and improving the moldability (fluidity). attitude .

do not have.

[Means for solving problems]

The present inventors have developed a polycarbonate oligomer having 2 to 15 structural units having a normal or long-chain alkyl group at the terminal into a resin composition of an aromatic polycarbonate resin and a specific thermoplastic resin. The present inventors have discovered a thermoplastic resin composition with excellent thermal properties such as deformation temperature or excellent moldability, and have completed the present invention.

That is, the present invention provides aromatic polycarbonate resin 2
Resin composition (A) consisting of 0 to 90% by weight and 80 to 10% by weight of an aromatic polyester resin or an aromatic vinyl compound polymer or copolymer, and 100 parts by weight of a halogen having a viscosity average degree of polymerization of 2 to 15. This is a thermoplastic resin composition containing 1 to 50 parts by weight of an aromatic recarbonate oligomer (Fl) having no atoms.

The fairness of the present invention will be explained below.

First, the polycarbonate resin of the present invention is produced by the conventional polycarbonate resin manufacturing method, that is, by reacting an aromatic dihydric phenol compound, phosgene or carbonic diester, and a terminal capping agent. The aromatic homo- or copolycarbonate resin used in the present invention has a viscosity average molecular weight of 15,000 or more, preferably 20,000 to 20,000.
A range of 35,000 is preferred.

Here, the aromatic dihydric phenol compounds include bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, and bis(4-hydroxyphenyl)sulfoxide. (4-hydroxyphenyl) sulfide,
Bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4
-hydroxyphenyl)propane, 2,2-bis(4-
hydroxyphenyl)methane, l11-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-
Hydroxy-3,5-dichlorophenyl)propane, 2
．． 2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5
-dimethylphenyl)propane, 2,2-his(4-hydroxy-3,5-diethylphenyl'-3-)propane, 2,2-bis(4-hydroxy-3,5
-dipropylphenyl)propane, 1-phenyl-1,
1-bis(4-hydroxyphenyl)ethane, bis(4
-Hydroxyphenyl)-diphenylmethane is exemplified, and may be appropriately used alone or as a mixture of two or more, with 2,2-bis(4-hydroxyphenyl)propane being particularly preferred.

Examples of the terminal capping agent of the present invention include common terminal capping agents such as phenol, P-t-butylphenol, and tribromophenol; Aliphatic acid chlorides such as acid chloride, octylic acid chloride, lauric acid chloride, stearic acid chloride; acetic acid, propionic acid, acetic acid, caprylic acid, octylic acid, lauric acid,
Fatty acids such as stearic acid; methyl hydroxybenzoate, ethyl hydroxybenzoate, propinobe hydroquine benzoate, butyl hydroxybenzoate, octinope human[]xybenzoate, lauryl hydroxybenzoate, noryl hydroxybenzoate, stearyl hydroxybenzoate, etc. hydroxybenzoic acid alkyl esters; long chain alkyl-substituted phenols such as octylphenol, norylphenol, laurylphenol, palmitylphenol, stearylphenol;
Hydroxy, such as ethyl p-hydroxyphenylacetate,
Phenylic acid alkyl ester; examples include long-chain alkyloxyphenols such as octyl ether phenol (-octyloxyphenol), noryl ether phenol, lauryl ether phenol, palmityl ether phenol, occudecyloxyphenol, and dobusyloxyphenol. The amount used is 1 of the dihydric phenol used.
in the range of 0 to 1 mol%, preferably 7 to 2 mol%,
Two or more types of compounds may be used in combination.

It can also be used as a branched product, and examples of branching agents include phloroglycin, 2,6-dimethyl-2.4.6-)li(4-hydroxyphenyl)hebutene-3,4, 6-cymethyl-2.4.6-
) li (4-hydroxyphenyl)hebutene-2,1
,3,5-) U(2-hydroxyphenyl)penzole, L 1.1-)li(4-hydroxyaryl)ethane, 2.6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenyl Fennope α, Q”,
α”-)li (4-hydroxyphenyl)-1,3,5
-) polyhydroxy compounds exemplified by lyisopropylbenzene, and 3゜3-bis(4-hydroxyaryl)oxindole (-isatin bisphenol)
, 5-chloroisatin, 5.7-cycloisatin, 5
-Promyzatin is exemplified, and the amount used is in the range of 0.02 to 1.0 mol% of the dihydric phenol used.

The aromatic polyester resin to be combined with the above-mentioned aromatic polycarbonate includes polyethylene terephthalate, polybutylene lenticulate, a mixture of terephthalic acid and isophthalic acid as the dicarboxylic acid component, and 1,4-cyclohexane dimetatool as the diol component. Polyester resins obtained by polycondensation using terephthalic acid as a dicarboxylic acid component and 1,4-cyclohexanedimethanol and ethylene glycol as diol components, as well as polycaprolactone and others. Examples include polyesters with soft segments introduced into the chain.

Further, as aromatic vinyl compound polymers or copolymers, polystyrene (PS), high impact polystyrene (HIPS), acrylonitrile-styrene copolymer (AS), acrylonitrile-butadiene-styrene copolymer (ABS), Acrylic acid or meccrylic acid alkyl ester-butadiene-styrene copolymer (MBS
), acrylic acid or meccrylic acid alkyl ester-acrylonitrile-cyclodiene-styrene copolymer (M
ABS), acrylic acid or meccrylic acid alkyl ester-acrylic rubber-styrene copolymer (MAS),
Others include acrylonitrile-acrylic rubber-styrene copolymer disclosed in JP-A-48-48547, acrylonitrile-chlorinated polyolefin-styrene copolymer disclosed in JP-A-48-42452, and styrene-maleic anhydride. Examples of styrenic polymers include styrene-maleimide copolymer (SMA), styrene-maleimide copolymer (SMI), and styrene-maleic anhydride-maleimide copolymer.
, MBS, MABS, MAS, SMI, etc. are preferred.

The weight ratio of the aromatic polycarbonate resin and the aromatic vinyl compound polymer or copolymer is aromatic polycarbonate resin/aromatic vinyl compound polymer or copolymer - 20/80 to 90/10; Preferably 4
It is 0/60 to 80/20.

Next, the aromatic polycarbonate oligomer (B) without halogen atoms and having a viscosity average degree of polymerization of 2 to 15, which is blended into the above thermoplastic resin composition, is prepared under the above conditions except that the molecular weight is prepared to be low. It is manufactured by the same manufacturing method as aromatic polycarbonate resin, and 2
, 2-bis(4-hydroxyphenyl)propane, 2.
2-bis(4-hydroxy-3,5-dimethylphenyl)propane, bis(4-hydroquinphenyl)methane,
1.1-bis(4-hydroxyphenyl)ethane, 2,
2-bis(4-hydroxyphenyl)butane, 2,2-
Bis(4-hydroxy-3,5-diethylphenyl)propane, 2.2-bis(4-hydroxy-3,5-dipropylphenyl)propane, 1.1-bis(4-hydroxyphenyl)cyclohexane, 1~phenyl-1,1
- Obtained by the reaction of an aromatic dihydric phenol compound such as bis(4-hydroxyphenyl)ethane with a carbonate precursor such as phosgene, and aromatic dihydric phenols can be used alone or in combination. Generally speaking, the oligomer is a low molecular weight substance having an intrinsic viscosity of 0.3 or less at 25° C. in methylene chloride. The same molecular weight regulator is used when producing this oligomer, and the amount used is 100 to 10 mol%, preferably 50 to 20 mol%, based on the dihydric phenol compound. Two or more types of terminators may be used in combination. In addition, in the production of polycarbonate oligomers, trifunctional or higher-functional compounds containing two or more phenolic groups, such as low molecular weight phenol novolaks, etc., may be used as part of the above-mentioned aromatic dihydric phenol compounds. Can be done.

A resin composition of the above aromatic polycarbonate resin and an aromatic polyester resin or an aromatic vinyl compound polymer or copolymer (A>100 parts by weight, 1 to 50 parts by weight of the aromatic polycarbonate oligomer of the present invention) parts, preferably 5 to 40 parts by weight, to produce the thermoplastic resin composition of the present invention.If the blending amount exceeds 50 parts by weight, the physical properties will deteriorate unfavorably, and if it is less than 1 part by weight, This is not preferable because the improvement in fluidity is insufficient.

There are no particular limitations on the method for preparing the composition of the present invention, and conventional methods may be used, for example, aromatic polycarbonate resins, aromatic polyester resins, aromatic vinyl compound polymers or copolymers, thermoplastic resins, and polycarbonate oligomers. A method may be used in which the components are sufficiently mixed in a blender, and then melted in a vent-type extruder or the like to form pellets.

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 to.

〔Example〕

This will be explained below using synthesis examples, examples, and comparative examples. In addition, "%" and "part" in the synthesis examples and examples are based on weight unless otherwise specified.

Synthesis Example 1 In a reaction tank with an internal capacity of 400 p equipped with a stirrer, a phosgene blowing pipe, and a cooling jacket, 25 kg of a 48% caustic soda aqueous solution, 250 β of water, and 601 methylene chloride were added.
1 Hydrosulfide 100g, 2.2-bis(
4-hydroxyphenyl)propane (= BPA) 27
．． 5 kg of phosgene were added one after another, and 15 kg of phosgene was blown in over 10 minutes to cause a reaction while maintaining the liquid temperature in the range of 15 to 20°C.

Then, a solution of 6 kg of 48% aqueous sodium hydroxide solution, 100 g of triethylamine, and 5.2 kg of para-tert-butyl-phenol (-TBP) dissolved in 50 l' of methylene chloride was added to the reaction system,
Stirring was continued for a minute.

=11- Extract the precipitated methylene chloride layer from the reaction solution, transfer it to a purification tank with an internal capacity of 300β 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 500p, and
The mixture was heated with A while stirring, and methylene chloride was distilled off. After cooling, the precipitate was filtered and dried to obtain long chain alkyl aromatic polycarbonate oligomer powder 33.6k.
I got g.

The melting point of the obtained polycarbonate oligomer is 229~
At 232°C, the viscosity average molecular weight is 5.0×103, and the number average molecular weight by end group analysis is approximately 2. lx10', and the number average degree of polymerization was 7.

Synthesis Example 2 In Synthesis Example 1, the amount of phosgene was 14.6 kg, TB
33 kg of aromatic polycarbonate oligomer powder was obtained in the same manner except that the amount of P was changed to 3.6 kg.

The melting point of the obtained polycarbonate oligomer is 235~
At 238℃, what is the viscosity average molecular weight? , 0X103, the number average molecular weight was approximately 2.9X10', and the number average degree of polymerization was 10 by end group analysis.

Synthesis Example 3 25 kg of 48% caustic soda aqueous solution, 2501 water, and 60 methylene chloride were placed in a reaction tank with an internal capacity of 400 p equipped with a stirrer, a phosgene blowing tube, and a cooling jacket.
p11 hydrosulfide 100, BPA27
．． 5 kg of phosgene were added one after another, and 15 kg of phosgene was blown in for 30 minutes to cause a reaction while maintaining the liquid temperature in the range of 15 to 20°C.

Thereafter, a solution of 6 kg of a 48% aqueous sodium hydroxide solution, 100 g of triethylamine, and 10.5 kg of lauryl para-oxybenzoate (-POBR) dissolved in methylene chloride 5H was then added to the reaction system, 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 1001 and water and washing with water, transfer to a solidification tank with an internal capacity of 500β, and
The mixture was heated with stirring along with β, and methylene chloride was distilled off. After cooling, the precipitate was filtered and dried to obtain 35 kg of terminal long chain alkyl aromatic polycarbonate oligomer powder.

The melting point of the obtained polycarbonate oligomer is 205~
The temperature was 209°C, the viscosity average molecular weight was 2.4×103, and the average degree of polymerization was 7.

Synthesis Example 4 In Synthesis Example 3, the amount of phosgene was 14.6 kg, PO
38 kg of aromatic polycarbonate oligomer powder was obtained in the same manner except that 8.7 kg of octadecyloxyphenol was used in place of BH.

The melting point of the obtained polycarbonate oligomer is 206~
At 209℃, the number average molecular weight according to end group analysis is approximately 3.0×
103, and the average degree of polymerization was 10.

Synthesis Example 5 45 kg of aromatic polycarbonate oligomer powder was obtained in the same manner as in Synthesis Example 3, except that 18.2 kg of stearic acid chloride was used instead of POBH.

The melting point of the obtained polycarbonate oligomer is 170~
175℃, number average molecular weight by end group analysis is approximately 1.5X
103, and the average degree of polymerization was 4.

Examples 1 to 10 and Comparative Examples 1 to 5 Aromatic polycarbonate resin (manufactured by Mitsubishi Gas Chemical Company, trade name: Kneepilon S-2000, hereinafter referred to as PC),
ABS (Mitsubishi Monzanto ■, trade name: Dialex), polybutylene terephthalate (Mitsubishi Kasei ■, trade name: Tubadol, hereinafter referred to as PBT), or Synthesis Example 1
The aromatic polycarbonate oligomers produced in Steps 1 to 5 (hereinafter referred to as 1 to 5) were mixed in a tumbler at the ratios listed in Table 1, and then extruded into pellets using a vented extruder with a shaft. .

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.

Regarding fluidity, by measuring the flow value "Q value",
These are the amounts of molten resin flowing out from a nozzle of 1 mmφ x 10 mmL at 240° C. or 280° C. under a pressure of 160 kg/cd, expressed in units of ×lOgcc/sec.

Also, the heat distortion temperature rHDTJ is 18.6 kg/cn according to 8STM D 648! It was measured with

[Operation and effects of the invention]

As described above, the thermoplastic resin composition of the present invention is a molding material that substantially maintains physical properties such as heat distortion temperature, and has significantly improved Q value, which represents fluidity, and has extremely excellent moldability. It is clear that this is of great industrial significance.

Claims (1)

[Claims] Resin composition (A) consisting of 20 to 90% by weight of aromatic polycarbonate resin and 80 to 10% by weight of aromatic polyester resin or aromatic vinyl compound polymer or copolymer.
To 100 parts by weight, a halogen-free aromatic polycarbonate oligomer (B
) is blended in an amount of 1 to 50 parts by weight.