JPH0477552A - thermoplastic resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to the use of terminal-modified polyphenylene ether and polyamide produced by reacting polyphenylene ether with an alkoxysilane compound to obtain a resin composition of polyphenylene ether and polyamide. The present invention relates to a high-performance thermoplastic resin composition that has the heat resistance, mechanical strength, and dimensional accuracy characteristic of polyphenylene ether, as well as the solvent resistance and moldability of polyamide. The present resin composition is useful as a material for applications in the automobile, electrical and electronic fields, which are becoming increasingly diverse and sophisticated.

(Prior art) Polyphenylene ether having an unsubstituted or substituent group on the phenylene ring, particularly poly(2,6-dimethyl-1,4-phenylene ether), has excellent heat resistance and mechanical strength, and is useful as a so-called engineering plastic. However, it is well known that it has an undesirable property of being difficult to mold by injection molding or the like due to its high melt viscosity. Furthermore, the impact strength and solvent resistance of the same resin are insufficient in many fields of use as engineering plastics. As an attempt in cases where desired properties cannot be fully satisfied with a single resin material,
The concept of compensating for insufficient properties by mixing other resin materials is well known. Materials in which the moldability of polyphenylene ether is improved by blending polystyrene, which has good compatibility with polyphenylene nityl and has good moldability, are widely used. However, in this case, both components do not have good solvent resistance, and the mixed composition also does not have sufficient solvent resistance.

Polyamide is widely used as one of the typical engineering plastics with excellent heat resistance, solvent resistance, moldability, etc. However, this resin has disadvantages such as poor dimensional stability, hygroscopicity, heat deformation resistance under high loads, and impact resistance, so its uses are limited to:
Limited. Therefore, if a composition that has both the good properties of polyphenylene ether and polyamide and compensates for the undesirable effects can be obtained, it will be possible to provide a resin material that can be used in a wide range of fields, and its industrial significance is extremely large. It can be said to be a thing. Therefore, in order to provide a molding material that compensates for the drawbacks without sacrificing the advantages of both, a composition obtained by simply melting and mixing the same resins, for example, is disclosed in US Pat. No. 33,797.
No. 92, Specifications of No. 4338421, Special Publication No. 1973-
No. 997 and No. 59-41663. However, in such a simple blend system, polyphenylene ether and polyamide have essentially poor compatibility, so the adhesion at the interface of this two-phase structure is not good, and this two-phase structure has a uniform and finely dispersed form. When subjected to shear stress during molding processes such as injection molding,
Layer peeling (delamination) is likely to occur, the appearance of the obtained molded product is deteriorated, the two-phase interface becomes a defective part, and a composition with excellent mechanical strength and impact resistance cannot be obtained.

One possible way to solve the above problems in generally incompatible polymer blends is to modify polyphenylene ether with functional groups to improve the mutual affinity of the two components, and to There is a method of melt-kneading it with polyamide. From this point of view, many functionalized polyphenylene ethers have been proposed for the purpose of increasing the reactivity of polyphenylene ethers. For example, an example of the functionalization is a method using carboxyl group- or carboxylic anhydride-functionalized polyphenylene ether (Japanese Patent Publication No. 62-500
No. 456, JP-A-63-10656, JP-A No. 63-544
27, etc.), a method using an epoxy group-functionalized polyphenylene ether (Japanese Patent Application Laid-Open No. 62-257957, Japanese Patent Publication No. 63-503388, etc.), a method using an amide group- or imide group-functionalized polyphenylene ether ( (Japanese Patent Publication No. 1983-500803, etc.), a method using alkoxysilyl group-functionalized polyphenylene ether (Japanese Patent Publication No. 63-500803, etc.);
No. 3-503392, etc.), and resin compositions with various polyamides have been proposed. However, even if these methods are used, it is often insufficient to improve the phase properties of both bophenylene ether and polyamide, and the mechanical strength of the resulting composition is still not sufficient. , further improvements are desired.

(Problems to be Solved by the Invention) The present invention provides a thermoplastic resin composition containing polyphenylene ether and polyamide, which has particularly excellent heat-resistant rigidity, dimensional accuracy, moldability, solvent resistance, impact strength, and dispersion structure. The purpose is to provide

(Means for Solving the Problems) As a result of intensive studies to solve the above problems, the present inventors have developed a heat-resistant polyphenylene ether blended with polyamide and functionalized polyphenylene ether that is extremely easily modified using a specific method. The inventors have discovered that a plastic resin composition can achieve the above object, and have arrived at the present invention.

That is, the present invention is a thermoplastic resin composition characterized by comprising the following components (A) and (B).

(A)-9 formula (wherein each Q' represents a halogen atom, a secondary or secondary alkyl group, a phenyl group, an aminoalkyl group, a hydrocarbonoxy group, or a halohydrocarbonoxy group, and each Q2 represents a Represents a hydrogen atom, a halogen atom, a primary or secondary alkyl group, a phenyl group, a haloalkyl group, a hydrocarbonoxy group, or a halohydrocarbonoxy group, n represents a number of 10 or more, and X is an oxygen atom or nitrogen R1 represents an alkylene group having 1 to 12 carbon atoms, and R2 and R3 each represent a hydrocarbon group having 1 to 6 carbon atoms.

S is 1 when X is an oxygen atom, and 2 when X is a nitrogen atom.
and t is an integer of 1 to 3).
10-90% by weight (B) Polyamide 90-1
0% by weight The composition of the present invention of functionalized polyphenylene ether (hereinafter referred to as functionalized polyphenylene ether) (A) having the above structure and polyamide (B) has a mechanical property that combines the characteristics of polyphenylene ether and the characteristics of polyamide. It is extremely useful as a molding material with good properties, moldability, dimensional accuracy, and solvent resistance.

Hereinafter, the structure of the thermoplastic resin composition of the present invention will be explained.

Functionalized Polyphenylene Ether The functionalized polyphenylene ether used in the present invention is produced by the following method. The details are described below.

A compound having an alkoxysilyl group and a glycidyl group represented by the -AU formula (III) in the same molecule in a polyphenylene ether represented by the general formula (II) (wherein Q', Q2 and n are the same as above) ( m) (in the formula, X, R', R2, R'', s and t are the same as above) to obtain a functionalized polyphenylene ether (A) represented by the general formula (2).

Polyphenylene ether is a homopolymer or copolymer having the structure of formula (II).

Suitable examples of primary alkyl groups for Q' and Q2 are methyl, ethyl, n-propyl, n-butyl, n-amyl, isoamyl, 2-methylbutyl, n-hexyl, 2,3-
Dimethylbutyl, 2-13- or 4-methylpentyl or heptyl. Examples of secondary alkyl groups are isopropyl, 5ec-butyl or l-ethylpropyl. In many cases, each Q1 is an alkyl group or a phenyl group,
In particular, it is an alkyl group having 1 to 4 carbon atoms, and each 02 is a hydrogen atom.

Suitable polyphenylene ether homopolymers include:
For example, it is composed of a 2,6-dimethyl-1,4=phenylene ether unit. Suitable copolymers include:
It is a random copolymer consisting of a combination of the above units and 2.3.6 trimethyl-1.4-phenylene ether units. Many suitable homopolymers and random copolymers include
Described in patents and literature. Also suitable are polyphenylene ethers containing molecular moieties that improve properties such as, for example, molecular weight, melt viscosity and/or impact strength. For example, polyphenylene ether is obtained by graft polymerizing a vinyl monomer such as a vinyl aromatic compound such as acrylonitrile or styrene, or a polymer such as polystyrene or an elastomer thereof onto polyphenylene ether.

The molecular weight of polyphenylene ether is usually such that the intrinsic viscosity at 30°C in chloroform is about 0.2 to 0.8 a/g.

Polyphenylene ethers are usually produced by oxidative coupling of the monomers described above. Regarding the oxidative coupling polymerization of polyphenylene ether, a large number of catalyst systems are known. There are no particular restrictions on the selection of the catalyst, and any known catalyst can be used. For example,
6 containing at least one heavy metal compound such as copper, manganese, cobalt, etc., usually in combination with various other substances.
) have a glycidyl group and an alkoxysilyl group in the same molecule, N-glycidyl-N,
N-bis[3-(methyldimethoxysilyl)propyl]
Amine, N-glycidyl-N, N-bis[3-(trimethoxysilyl)propyl]amine, 3-glycidyloxypropyl(methyl)dimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyl Examples include pyru(methyl)jethoxysilane. Particularly preferred are 3-glycidyloxypropyltrimethoxysilane or 3-glycidyloxypropyl(methyl)jethoxysilane.

-119 The functionalized polyphenylene ether (A) represented by the formula (I) has an alkoxysilyl group and a glycidyl group represented by the general formula (IJI) in the same molecule as the polyphenylene ether represented by the -9 formula (II). It can be easily produced by reacting a compound in an organic solvent in the presence of a basic catalyst.

The organic solvent used here is desirably capable of dissolving polyphenylene ether. Specifically, aromatic solvents such as benzene, toluene, and xylene; chlorobenzene,
Halogenated aromatic solvents such as dichlorobenzene, halogenated hydrocarbon solvents such as chloroform, trichloroethylene, carbon tetrachloride, N-methyl-2-pyrrolidone, 1.
Examples include aprotic polar solvents such as 3-dimethyl-2-imidazolidinone. Examples of the basic catalyst include alcoholades such as sodium methoxide and sodium ethoxide; tertiary amines such as benzyldimethylamine and tributylamine; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; .

In this reaction, 2 to 50 mol, preferably 5 to 20 mol, of the functionalizing agent represented by the -9 formula (III) is used per 1 mol of the terminal phenolic hydroxyl group of polyphenylene ether. The organic solvent is used in an amount of 500 to 1000 parts by weight per 100 parts by weight of polyphenylene ether. The basic catalyst is 1 per 100 parts by weight of polyphenylene ether used.
~3 parts by weight is used.

The shooting procedure for producing functionalized polyphenylene ether (A) is to heat and dissolve polyphenylene ether (II) in an organic solvent, then add a basic catalyst dissolved in a small amount of ethanol or methanol, The functionalizing agent (III) is added at a temperature of 0.degree. C. and further heated until the reaction is complete.

Warm opening=Polyamide The polyamide of component (B) used in the present invention has a -CONH- bond in the polymer main chain and can be melted by heating. Typical examples include nylon-4, nylon-6, nylon-6,6, nylon-4,6, nylon-12, nylon-6,10, etc. In addition, aromatic diamine, aromatic Low crystallinity or non-quality polyamides or transparent nylons containing monomer components such as dicarboxylic acids, or mixtures thereof may also be used.

Preferred polyamides (B) used in the present invention are nylon-6,6, nylon-6 or non-grade polyamides.

The polyamide used in the present invention has a relative viscosity of 20 to 8.
0 (measured in 198% concentrated sulfuric acid at 25°C, JIS K
6810 test method) is preferred.

Distribution A of components A and B The selection of the blending ratio of components (A) and (B) of the thermoplastic resin composition of the present invention is determined by the required performance of the intended use of the final molded product.

That is, although properties such as moldability, mechanical strength, solvent resistance, dimensional accuracy, and high-temperature rigidity can often be adjusted by the characteristics of each component and their blending ratio, for example, rigidity and impact strength, etc. The contradictory properties of expression mechanisms are often difficult to reconcile. For practical purposes, usually
This is done from the perspective of achieving an appropriate balance of various properties such as formability, mechanical strength, and high-temperature rigidity. Therefore, although there is essentially no limit to the blending ratio of each component in the composition of the present invention, it can be said that the following ranges are practically useful.

Component (A): Functionalized polyphenylene ether 90-10
Weight% Component (B) - Polyamide 10 to 90% by weight In addition, component (A) used in the present invention may be used alone, or may be a mixture of functionalized polyphenylene ether and unfunctionalized polyphenylene ether. .

Other additional components can be added to the resin composition according to the invention. For example, well-known antioxidants, weather resistance improvers, nucleating agents, flame retardants, etc. for polyamides, well-known antioxidants, weather resistance improvers, plasticizers, etc. for polyphenylene ether,
Styrenic resins, flow improvers, etc. can be used as additional ingredients. Furthermore, addition of organic/inorganic fillers and reinforcing agents, particularly glass fiber, mica, talc, wollastonite, potassium titanate, calcium carbonate, silica, etc., is effective in improving rigidity, heat resistance, dimensional accuracy, etc. For practical purposes, various known colorants and dispersants thereof can be used.

Furthermore, impact strength improvers are added, especially styrene-butadiene copolymer rubber and its hydride, nytylene-brobylene-(diene) copolymer rubber, and their α and β-
Unsaturated carboxylic anhydride modified product, unsaturated glycidyl ester or unsaturated glycidyl ether modified product, copolymer consisting of unsaturated epoxy compound and ethylene, unsaturated epoxy compound, ethylene and ethylenically unsaturated compound Addition of a copolymer or the like is effective in improving the impact strength of the composition. The above impact strength improvers may be used alone or in combination of two or more. The blending amount of the impact strength improver varies depending on the target physical property value, but for example, in the case of improving the balance between rigidity and impact strength of the composition, it is 5 to 3 parts by weight per 100 parts by weight of the resin component of the composition.
It is 0 parts by weight.

The method for mixing the thermoplastic resin composition of the present invention is to mix the above-mentioned components in various mixing machines, such as a screw extruder, a twin-screw extruder, and a twin-screw extruder.
A method of cross-mixing using a machine, a Banbury mixer, etc., a method of removing the solvent after mixing solutions or suspensions of various components,
Any method can be used, such as adding a common non-solvent to precipitate, separating and recovering. Further, the mixing order may be any possible order, but when mixing by the melt mixing method, it is preferable to sequentially mix the ingredients starting from the one with the highest viscosity.

(Examples) Hereinafter, the present invention will be explained in detail with reference to Examples, but the scope of the present invention is not particularly limited thereby.

Preparation Example of Functionalized Polyphenylene Ether Polyphenylene ether and toluene were charged into a reactor in the amounts shown in Table 1, and the polyphenylene ether was dissolved by heating and stirring. After heating to the reaction temperature described in the same table, sodium ethoxide was dissolved in ethanol and added, followed by a predetermined amount of the functionalizing agent described in the same table, and the mixture was heated and stirred to react. After the reaction was completed, the reaction mixture was poured into 2512 acetonitrile to precipitate the functionalized polyphenylene ether formed. After separation, it was washed again with acetonitrile 25I2 and dried under reduced pressure at 80°C to obtain a functionalized polyphenylene ether. These obtained resins were designated as functionalized polyphenylene ethers (a) and (b), and the results are shown in Table 1.

Example 1.2 and Comparative Examples Functionalized polyphenylene ether (a) (b), polyamide (polyamide-6 manufactured by BASF, trade name Ultramid KR4411) and unfunctionalized polyphenylene ether (manufactured by Nippon Polyether Co., Ltd., in chloroform at 30°C) Using a blast mill manufactured by Toyo Seiki Co., Ltd. with an internal volume of 60 cc and the composition shown in Table 2, under the conditions of 280 ° C. and a rotation speed of 6 Orpm.
The mixture was melt-kneaded for 6 minutes. The obtained resin composition was press-molded at 280°C to create a sheet with a thickness of 2 mm. Various test pieces were cut out from this sheet and their physical properties were evaluated.

The results are shown in Table 2. As is clear from these results, when functionalized polyphenylene ether and polyamide are blended, uniform dispersion of very fine, almost spherical polyphenylene ether is observed, and a composition with high impact strength and high high temperature elastic modulus is obtained. Obtained.

The measurement and evaluation methods are as follows.

(1) Cut a test piece with a bending modulus width of 25 mm x length of 80 mm, and JIS
It was measured using an Instron testing machine in accordance with K7203. In addition, the value of the bending elastic modulus at 80°C is
A constant temperature chamber was installed so that the test piece, the support stand used for measurement, and the pressurizing wedge part were placed in the hot air constant temperature chamber, and the temperature was kept at 80℃±1℃.
Measurements were carried out after conditioning the sample in an atmosphere for 20 minutes or more.

(2) Izot impact strength According to JIS K7110, the unnotched Izot impact strength at 23°C was measured using three 2 mm thick test pieces stacked one on top of the other.

(3) Dispersion Form In order to examine the two-phase dispersion state of the obtained resin composition, the cross section was observed using a scanning electron microscope model S-2400 manufactured by Hitachi, Ltd.

Claims (1)

[Scope of Claims] A thermoplastic resin composition comprising the following components (A) and (B). (A) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (In the formula, Q^1 is each a halogen atom, a primary or secondary alkyl group, a phenyl group, an aminoalkyl group, a hydrocarbon oxy group or halohydrocarbonoxy group, Q^2
each represents a hydrogen atom, a halogen atom, a primary or secondary alkyl group, a phenyl group, a haloalkyl group, a hydrocarbonoxy group, or a halohydrocarbonoxy group, n represents a number of 10 or more, and X is an oxygen atom Or represents a nitrogen atom, R^1
represents an alkylene group having 1 to 12 carbon atoms, R^2 and R
^3 each represents a hydrocarbon group having 1 to 6 carbon atoms. s is 1 when X is an oxygen atom and 2 when X is a nitrogen atom
and t is an integer of 1 to 3) End group-modified polyphenylene ether 1
0-90% by weight (B) Polyamide 90-10% by weight