JPH01242663A - thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain the title resin composition improved in strength, heat resistance, moldability, etc., by adding a specified amount of a polycarbonate resin as a dispersibility improver to the system in the production of a thermoplastic resin composition by melt-mixing a polyphenylene ether resin with a polyester resin. CONSTITUTION:10-90 pts.wt. polyphenylene ether resin (A) comprising recurring units of formula I (wherein R1 and R2 are each a 1-8C hydrocarbon group, A hydrocarbonoxy, a hydrogen atom, a halogen atom or a halohydrocarbon group, and R3 and R4 are each a 1-8C hydrocarbon group) is mixed with 90-10 pts.wt. polyester resin (B) (e.g., polybutylene terephthalate resin). 5-100 pts.wt. polycarbonate resin comprising recurring units of formula II (wherein R1 and R2 are each H, a lower alkyl or a phenyl, and R3 is an alkyl) as a dispersibility improver is added to 100 pts.wt. obtained mixture and melt-mixed to produce a thermoplastic resin composition.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention provides a thermoplastic resin composition having excellent mechanical properties, heat resistance, and moldability, which is composed of a polyphenylene ether resin, a polyester resin, and a polycarbonate resin. Regarding.

[Prior art and problems to be solved by the invention] Although polyphenylene ether resin has excellent heat resistance, mechanical strength, dimensional stability, and electrical properties, it has poor solvent resistance and moldability. However, this resin was rarely used alone. On the other hand, polyester resin has excellent mechanical strength, electrical properties, and solvent resistance, and is used in various fields, but its applications have been limited due to its inferior heat resistance and impact strength. .

In the past, many attempts have been made to melt and mix polyphenylene ether resins and polyester resins in order to make resin compositions that take advantage of their advantages (Japanese Patent Laid-Open No. 49-7
5662, JP-A-59-159847, etc.).

However, although the moldability of a melt-mixed mixture of both resins is significantly improved compared to polyphenylene ether resin, the dispersibility of both resins is poor, so mechanical strength and heat resistance depend on the mixing ratio of both resins. The results are worse than expected.

Also, JP-A-60-260649, JP-A-62-
Publication No. 27457 and the like disclose a method of adding a styrene resin having an epoxy group when melt-mixing both resins in order to obtain a composition with improved dispersibility of both resins. The mechanical strength and heat resistance of the resin composition obtained by this method are not so high.

An object of the present invention is to provide a thermoplastic resin composition that takes advantage of the advantages of polyphenylene ether resin and polyester resin and has excellent mechanical strength, thermal properties, and moldability.

[Means for Solving the Problems] In order to solve the object of the present invention, as a result of intensive studies, it was found that by melt-kneading a polyphenylene ether resin, a polyester resin, and a polycarbonate resin, one thermoplastic resin, which is the object of the present invention, can be obtained. It has been found that a resin composition can be obtained.

That is, the object of the present invention can be achieved by adding 5 to 100 parts by weight of a polycarbonate resin to 100 parts by weight of a mixture consisting of 10 to 90 parts by weight of a polyphenylene ether resin and 10 to 90 parts by weight of a polyester resin.

It has not been known until now that when polyphenylene ether resin and polyester resin are melt-mixed, the dispersibility of the resins is improved by adding a polycarbonate resin. Although the conventional method of adding a styrene compatibilizer improves dispersibility, the mechanical properties and heat resistance of the resulting resin composition deteriorate. On the other hand, since polycarbonate resin has excellent mechanical properties and heat resistance, the resulting resin composition does not deteriorate the properties of polyphenylene ether resin or polyester resin, and this is a major feature of the present invention. .

The polyphenylene ether resin used in the present invention has the following general formula (1), where R and R2 are each a hydrocarbon group of carbon fi1 to B, a hydrocarbon oxy group, a halogenated hydrogen group, or a halogenated hydrocarbon group. R3 and R4 are each a monovalent group selected from hydrocarbon groups having 1 to 8 carbon atoms or a hydrogen atom.

Specific examples of the phenol compound which is the most preferable raw material are 2,6-dibutylphenol and 2,6-diethylphenol.

2-methyl-6-ethylphenol, 2-methyl-6-
Allylphenol, 2-methyl-6-phenylphenol, 2,8-cyfecholphenol.

2.8-dibutylphenol, 2-methyl-6-propylphenol, 2,3.8-trimethylphenol, 2,3-dimethyl-6-ethylphenol.

2.3.8- Triethylphenol, 2,3.8
-) ribrovirphenol, 2,6-dimethyl-3-ethylphenol, 2,6-dimethyl-3-propylphenol, and the like.

The most preferred polyphenylene ether resin is
polyphenylene ether obtained from 2,8-dimethylphenol, and 2,6-dibutylphenol,
2,3. fl-) It is a polyphenylene ether obtained by copolymerization of dibutylphenol. The intrinsic viscosity [η] (0.5% chloroform solution, 30°C) of the polyphenylene ether resin used is preferably from 0.3 to 3.0, and polyphenylene ether copolymerized with a styrene monomer or , a mixture of styrenic polymers can also be used. Graft copolymerization of styrene monomers or addition of styrene polymers improves moldability, but heat resistance and mechanical strength decrease. The amount is preferably 30 parts by weight or less. The amount of polyphenylene ether resin used in the present invention is 10 to 90 parts by weight,
More preferably, it is 30 to 70 parts by weight. Use ψ is lQ
If the quantity i is less, the heat resistance will deteriorate, and the amount used will be 7 parts.
When the amount is more than 0 parts by weight, molding processability deteriorates and it is not suitable.

The polyester resin used in the present invention is a high molecular weight thermoplastic resin having an ester bond in the main chain of the molecule, and is a polycondensation resin obtained from a dicarboxylic acid or its derivative and a dihydric alcohol or a dihydric phenol compound. Examples include a polycondensation compound obtained from a dicarboxylic acid or a derivative thereof and a cyclic ether compound, a polycondensation compound obtained from a metal salt of a dicarboxylic acid and a dihalogen compound, and a ring-opening polymer of a cyclic ether compound.

Here, the dicarboxylic acid derivative refers to acid anhydride, esterified product, or acid trichloride. Dicarboxylic acid may be aliphatic or aromatic, and aromatic dicarboxylic acids include, for example, terephthal , isophthalic acid, phthalic acid, chlorphthalic acid.

Nitrophthalic acid, p-carboxylphenylacetic acid.

m-phenylene diglycolic acid, p-phenylene diglycolic acid, diphenyldiacetic acid, diphenyl-p, p'-
dicarboxylic acid, diphenyl-■, -°-dicarboxylic acid,
diphenyl-4,4°-diacetic acid, diphenylmethane-p
, p'-dicarboxylic acid, diphenylethane-m, m'-
Dicarboxylic acid, stilbenzylcarboxylic acid, diphenylbutane-p,p'-dicarboxylic acid.

Benzophenone-4,4'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-], 5-dicarboxylic acid, naphthalene-2,8-dicarboxylic acid.

Naphthalene-2,7-dicarboxylic acid, p-carboxyphenoxyacetic acid, p-carboxyphenoxybutyric acid, 1
．． 2-diphenoxypropane-p,p'-dicarboxylic acid, 1.4-diphenoxypropane-p,p'-dicarboxylic acid, 1.5-diphenoxypentane-p,p'-dicarboxylic acid, 1.8- Diphenoxyhexane-p, p'-
Dicarboxylic acid, p-(p-carboxyphenoxy)
benzoic acid,! , 2-2-2-methoxyphenoxy)-
Ethane-PIF'-dicarboxylic acid.

1.3-bis(2-methoxyphenoxy)propane-p
, p'-dicarboxylic acid, 1,4-bis(2-methoxyphenoxy)-butane-p,p'-dicarboxylic acid.

Examples of the aliphatic dicarboxylic acid include 1,5-bis(2-methoxyphenoxy)-3-oxypentane-p,p'-dicarboxylic acid.

For example, oxalic acid, succinic acid, adipic acid, corkic acid,
Magellain ugly, sebacic acid, dodecanedicarboxylic acid, undecanedicarboxylic acid, maleic acid.

Examples include fumaric acid. Examples of preferred dicarboxylic acids are aromatic dicarboxylic acids, and more preferably,
Mention may be made of terephthalic acid, isophthalic acid or phthalic acid.

Examples of dihydric alcohols include ethylene glycol, trimethylene glycol, butane-1,3-diol, and butane-1,4-diol.

2.2-Dimethylpropane-1,4-diol.

Examples include cia-2-butene-1,4-diol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene glycol, and cyclohexane dimetatool. Examples of preferred dihydric alcohols are ethylene glycol, butane-1,4-diol, or cyclohexane dimetatool. Examples of dihydric phenol compounds include hydroquinone and resorcinol.

Bisphenol A and the like can be mentioned. Examples of the cyclic ether compound include ethylene oxide and propylene oxide.

Further, examples of the cyclic ester compound include δ-valerolactone and ε-caprolactone. The dihalogen compound to be reacted with the dicarboxylic acid metal salt is a compound obtained by replacing two hydroxyl groups of the dihydric alcohol or dihydric phenol compound with halogen atoms such as chlorine or bromine. Intrinsic viscosity of the polyester resin used (m-cresol 1% solution, 2
5° C.) is preferably 0.8 to 3.0.

The amount of polyester resin used in the present invention is 10 to 90 parts by weight. If the amount used is less than 10 parts by weight, moldability will deteriorate, and if it exceeds 90 parts by weight, heat resistance will deteriorate, which is not preferable.

The polycarbonate resin used in Suekanko has the following general formula (
2) In the formula, R1 and R2 are hydrogen, a lower alkyl group or a phenyl group, and R3 is an alkyl group.

It is produced by a melt method or a solution method using dihydric phenol and a carbonate precursor.

Examples of dihydric phenols include bisphenol A (2,2-bis(4-hydroxyphenyl)propane), bis(4-hydroxydiphenyl)methane)
, 1.1-bis(4-hydroxyphenyl)ethane), 2.2-bis(4-hydroxy-3-methylphenyl)propane), etc.
Preferred dihydric phenols are bis(4-hydroxyphenyl)alkane compounds, particularly bisphenol A.

Dihydric phenols can be used alone or in combination. Examples of carbonate precursors include haloformates. Representative examples include phosgene, diphenyl carbonate, di/\roformates of dihydric phenols, and mixtures thereof.

When producing aromatic polycarbonate, a suitable molecular weight regulator, branching agent, catalyst, etc. can also be used.

Intrinsic viscosity (0.5% methylene chloride solution, 20°C) is 0
．． The amount of polycarbonate resin used in the present invention is preferably 1 to 1.3. The amount of polycarbonate resin used in the present invention is 10
5 to 100 parts by weight, more preferably 10 parts by weight
~70 parts by weight. When the amount used is less than 5 parts by weight, dispersibility deteriorates, resulting in a decrease in mechanical strength, #Ii, and properties, and when it exceeds 100 parts by weight, moldability deteriorates, which is not preferable.

The thermoplastic resin composition of the present invention has good moldability.

Various reinforcing materials and fillers can be added as long as the physical properties are not impaired. Examples of 1 reinforcing material and 2 filling materials include glass fiber,
Asbestos A fiber, carbon fiber, silica fiber, silica
Alumina fiber, alumina lam.

Zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, stainless steel, aluminum, titanium, copper,
Metal fibers such as brass and magnesium, organic ta fibers such as polyamide, fluororesin, polyester, and acrylic resin, copper, and iron.

Metal powders such as nickel, zinc, soot, lead, stainless steel, aluminum, gold, silver, etc., silicic acid 7
Examples include luminium, glass peas, carbon black, quartz powder, talc, titanium oxide, iron oxide, calcium carbonate, diatomaceous material, etc.

! a There are no particular restrictions on the male substance, but the average fiber diameter is 5 lm.
From 50u, m, la fiber length is 50Jj, m from 30mm
These reinforcing materials and fillers are preferably surface-treated with a known silane coupling agent or titanate coupling agent.

These reinforcing materials and fillers can be used alone or in combination of two or more.

The thermoplastic resin composition of the present invention contains hindered phenol within a range that does not impair the purpose of wood IJI.

hydroquinone, phosphites, and their substituted products; anti-fouling agents and heat stabilizers such as copper compounds such as copper iodide; ultraviolet absorbers such as resorcinol, salicylate, benzotriazole, and benzophenone; stearic acid and its derivatives; Salt, mold release agents such as stearyl alcohol, and halogen-based agents.

It is also possible to add one or more additives such as melamine or cyanuric acid flame retardants, flame retardant aids, sodium dodecylbenzenesulfonate, antistatic agents such as polyalkylene glycol, crystallization accelerators, dyes, and pigments. It is.

Also small amounts of polyethylene and polypropylene.

Thermoplastic resins such as ethylene, vinyl acetate copolymers, ethylene-propylene copolymers, polyester elastomers, polyacetals, polysulfones, and modified products thereof;
For example acids and their derivatives.

Graft materials such as glycidyl methacrylate.

Phenolic resin, melamine resin, silicone resin.

A thermosetting resin such as an epoxy resin may also be added. The method for producing the thermoplastic resin composition of the present invention includes an extruder,
It can be carried out using a conventional melt mixing processing device such as a Banbury mixer or a kneader, and furthermore, it can be processed into molded products for various uses by injection molding, extrusion molding, etc.

[Example of the present invention] Hereinafter, the wood emitting j will be explained in more detail using examples.

Polyphenylene ether horizontal 1 used in Examples and Comparative Examples was produced as follows.

32.2 g of cupric bromide, di-n
-666 g of butylamine and 24 g of toluene with 2,6-
5.25 kg of xylenol was mixed and added, and after uniformly dissolving, polymerization was carried out for 90 minutes while keeping the inside of the reaction vessel at 30° C. while rapidly blowing oxygen.

After the polymerization was completed, 181 g of toluene was added, and then a 20% aqueous solution of ethylenediaminetetraacetic acid was added to stop the reaction. The resulting product mixture was centrifuged, the polymer melt phase was taken out, methanol was gradually added while stirring, the mixture was separated, and then dried to give polyphenylene ether m tll.
It's e 17.

Polyphenylene ether resin, polybutylene terephthalate resin, and polycarbonate resin in the proportions shown in Table 1 were melt-kneaded in a twin-screw extruder rotating in opposite directions with a screw diameter of 30 mm and set at 300° C. to obtain pellets. This pellet was injection molded at a molding temperature of 300°C and a mold temperature of 80°C to prepare a test piece for measuring physical properties, and measured tensile strength, tensile elongation, and flexural modulus according to the method described in ASTM.

Izot impact strength and heat distortion temperature were measured. Further, as a measure of the moldability of the obtained thermoplastic resin composition, the melt crosstalk torque was measured using a Brabender mixer under the conditions of a set temperature of 300° C. and a rotor rotation speed of 6 Orpm.

Furthermore, using a scanning electron m-microscope as a measure of monodispersity,
The dispersed particle diameter of the polyphenylene ether resin in the molded article was measured.

The results are shown in Table 1.

Pellets were prepared in the same manner as in Example 1, except that the polycarbonate resin was not used, and the physical properties, crosstalk torque, and dispersed particle size in the molded product were measured. The results are shown in Table 1.

Comparative Example Pellets were prepared in the same manner as in Example 1, except that the amount of polycarbonate resin used was changed to 150 parts by weight, and the physical properties and crosstalk torque were measured. The results are shown in Table 1.

Pellets were prepared in the same manner as in Example 1, except that the amount of polycarbonate resin used was changed, and the physical properties were determined.

The kneading torque was measured. The results are shown in Table 2.

Pellets were prepared in the same manner as in Example 1, except that acrylonitrile-styrene-glycidyl methacrylate copolymer was used in place of the polycarbonate resin in Example 2, and the physical properties and kneading torque were kept constant at 31. The results are shown in Table 2.

(Left space below) Pellets were prepared in the same manner as in Example 1, except that the polybutylene terephthalate resin in Example 3 was replaced with polyethylene terephthalate resin or PCTG10179, and the physical properties and crosstalk torque were measured. . The results are shown in Table 3.

(The following is a blank space) [Effects of the invention] By blending a specific amount of polycarbonate resin when melt-mixing polyphenylene ether resin and polyester resin, dispersibility is improved, and mechanical strength, heat resistance, and molding process are improved. A thermoplastic resin composition with excellent properties can be obtained.

Patent applicant: Ube Industries Co., Ltd.

Claims (1)

Scope of Claims: Contains 5 to 100 parts by weight of (c) polycarbonate resin per 100 parts by weight of a mixture consisting of (a) 10 to 90 parts by weight of polyphenylene ether resin and (b) 10 to 90 parts by weight of polyester resin. A thermoplastic resin composition characterized by: