JPS63183954A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition having excellent balance of heat resistance and impact resistance, extremely improved impact resistance and high molding properties, consisting of a dispersed phase of a specific polyphenylene ether, a thermoplastic resin matrix phase and a compatibilizing agent. CONSTITUTION:A composition consisting of (A) a dispersed phase obtained by subjecting one or more phenolic compounds shown by the formula (R1, R2, R3, R4 and R5 are H, halogen or polymer and at least one of R1-R5 is necessarily H), (B) a crystalline thermoplastic resin matrix phase and (C) a compatibilizing agent capable of compatibilizing the components A and B and having 0.01-10mu average particle diameter of the dispersed phase. The component A used has 0.45-0.55 reduced viscosity in a chloroform solution at 25 deg.C, polyethylene, polypropylene, etc., are used as the component B and an epoxy compound, etc., are used as the component C.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel thermoplastic resin composition that can be used as a molded article, sheet, film, etc. by injection molding, extrusion molding, or the like.

More specifically, it consists of a dispersed phase consisting of polyphenylene ether, a crystalline thermoplastic resin, an IJ plastic phase, and a compatibilizer. Heat Resistance 1 This relates to a novel thermoplastic resin composition with excellent mechanical properties and processability.

<Prior art> In general, polyphenylene ether has 1 mechanical properties, heat resistance, electrical properties, chemical resistance, and hot water resistance.

Although thermoplastic resins have excellent properties such as flame resistance and dimensional stability, they have the drawbacks of poor processability due to their high melt viscosity and relatively poor impact resistance.

Composites of polyphenylene ether and polystyrene are known as a method of reducing melt viscosity and improving molding processability while retaining the excellent properties of polyphenylene ether, but it is difficult to provide practical processability. Because of this, polyphenylene ether tends to lose its original excellent properties such as heat resistance, flame resistance, and chemical resistance. or.

The impact resistance of polyphenylene ether is still not sufficient even in combination with polystyrene.

On the other hand, crystalline thermoplastic resins are generally heat resistant.

It has features such as rigidity, strength, and oil resistance, but often has poor impact resistance. In order to improve impact strength, blending and copolymerization of rubber components have been carried out, but there is a problem that heat resistance and surface hardness are significantly reduced. Furthermore, when crystalline thermoplastic resins are melted, their viscosity decreases, making them easier to mold, but during molding, they rapidly solidify under conditions that are even slightly below the crystal solidification temperature, resulting in a problem that the molding conditions are narrow. Furthermore, in actual use, physical property changes and dimensional changes are significant, and further improvements are strongly desired. In addition, heat-resistant crystalline thermoplastic resins often have high water absorption, which causes problems such as not only dimensional stability in changes in physical properties but also appearance defects.

<Problems to be Solved by the Invention> From this point of view, it is possible to obtain a resin composition by blending polyphenylene ether and a crystalline thermoplastic resin, which has the features of both materials and has improved moldability and impact resistance. If you are
Kerosene properties are expected to have a wide range of new uses.

However, conventionally, polyphenylene ether and crystalline thermoplastic resin have significantly different melt viscosities and have been considered to be a combination with extremely poor customer dispersibility.

In fact, just by mixing it.

■ Stable take-off of extruded strands is nearly impossible due to the significant difference in viscosity between molten polymers.

Molding workability is also extremely poor.

■Also, the mechanical properties of the molded product, especially the impact resistance.

They often show values lower than expected from the additive properties of the impact strength of each individual product.

There were problems such as:

In order to solve these problems, for example, for polyphenylene ether and polyamide systems, Japanese Patent Publication No. 11966/1983,
It is described in publications such as JP-A-56-47432, JP-A-57-10642, and JP-A-60-58463 (
・Improvement methods using additives with reactivity or compatibility have been proposed. Especially the special public service 1966-11966.
Although the methods described in JP-A-56-47432 show effective effects, they are insufficient in improving impact strength.

This poses a limit to practical use.

Furthermore, JP-A-56-49753, JP-A-57-10
642 No. 1 JP-A-57-165448 and JP-A-5
No. 9-66452 etc. contain modified polystyrene.

Although there is a description of using polyphenylene ether or rubber in combination with a reactive additive, the definition of two dispersed phases is not clear, and even if polyphenylene ether becomes a dispersed phase, there is no description of its particle size, and such a composition However, there are problems with this product, such as an imbalance between impact resistance and heat resistance, and a lack of improvement in impact resistance, which limits its practical use.

Means for Solving the Problems> From this perspective, the present inventors conducted extensive and detailed research in order to develop a technique that is effective for improving resin compositions consisting of polyphenylene ether and crystalline thermoplastic resin. As a result of our research, we combined a dispersed phase consisting of borifunirenoether with a crystalline thermoplastic resin matrix phase and a compatibilizer.

By specifying the particle size of the dispersed phase, a resin composition with good balance between heat resistance and impact resistance, which also has significantly improved impact resistance and good moldability, was discovered, and the present invention was achieved.

In other words, one aspect of the present invention is.

(2) General formula (in the formula, I R11 R2+ R5I R41R5 is hydrogen.

It is a halogen atom, a hydrocarbon or a substituted hydrocarbon group, and at least one is necessarily hydrogen. ) One kind of thunol compound represented by or.

A dispersed phase consisting of polyphenylene ether obtained by oxidative polymerization of two or more types.

0 crystalline thermoplastic resin matrix phase and.

0 (A) and/or 2, and the average particle diameter of the dispersed phase is 0.01 to 1.
The present invention relates to a thermoplastic resin composition characterized in that it has a particle diameter of 0μ.

In the present invention. (g) What is polyphenylene ether?
General formula (wherein R,, R2, R5, R, and R5 are hydrogen,
It is selected from a halogen atom, a hydrocarbon group, or a substituted hydrocarbon group.

At least one of them is a hydrogen atom. ) is a polymer obtained by oxidative polymerization with oxygen or an oxygen-containing gas using one or more of the phenol compounds represented by the following formulas and an oxidative coupling catalyst.

R+, R2, Rs, R in the above general formula
Specific examples of 4 and R5 are hydrogen, chlorine, and bromine.

Fluorine, iodine, methyl, ethyl, n- or 1so-
propyl, pri-, 5eC- or t-butyl, chloroethyl, hydroxyethyl, phenylethyl,
Benozyl, hydroxymethyl, carboxyethyl, methoxycarbonylethyl.

Examples include cyanoethyl, phenyl, chlorophenyl, methylphenyl, dimethylphenyl, ethylphenyl, allyl, and the like.

A specific example of the above general formula is zunor.

o-, m-, or p-cresol, 2.6-.

2.5-, 2.4-, or 3.5-dimethylphenol, 2-methyl-6-phenylphenol.

2,6-'; phenylphenol, 2,6-dimethylphenyl, 2-methyl-6-ethylphenol,
Examples include 2,3.5-, 2,3.6- or 2,4.6-dolimethylphenol, 3-methyl-6-t-butylphenol, thymol, 2-methy)v-6-allylphenol, etc. . Furthermore, phenol compounds other than the above general formula, such as bisphenol-A, tetrabromobisphenol-A, resorcinol, hydroquinone,
With polyvalent hydroquine aromatic compounds such as novola resin.

Copolymerization with the above general formula is also possible.

Preferred among these compounds are:

A homopolymer of 2,6-dimethylphenol or 2,6-diphenyltunol and a large amount of 2゜6-xylenol and a small amount of 3-methy)v-5-tert-butylphenol or 2,3,6- )' J methylphenol copolymer.

The oxidative coupling catalyst used for oxidative polymerization of a phenol compound is not particularly limited, and 1
Any catalyst capable of polymerization can be used. For example, a typical example is cuprous chloride-triethylamine.

A catalyst consisting of a cuprous salt and a tertiary amine such as cuprous chloride-pyridine, a catalyst consisting of a cupric salt such as cupric chloride-pyridine-potassium hydroxide-amine-alkali metal hydroxide, Catalysts consisting of manganese salts and primary amines such as manganese chloride-ethanolamine, manganese acetate-ethylenediamine, etc. Catalysts consisting of manganese salts and phenolates or phenolates such as manganese chloride-sodium methylate and manganese chloride-sodium phenolate. , catalysts made of a combination of cobalt salts and tertiary amines, and the like.

The reaction temperature of oxidative polymerization to obtain polyphenylene ether is
When carrying out at a temperature higher than 40℃ (high temperature polymerization) and 40℃
It is known that there are differences in physical properties and the like between the following (low-temperature polymerization), but in the present invention, either high-temperature polymerization or low-temperature polymerization can be employed.

Furthermore, the hebophenylene/ether in the present invention is a styrene-based polymer (* also includes those in which other polymers are grafted to the above-mentioned polyphenylene ether). -47862, Special Publication No. 48-12197, Special Publication No. 5623-1973, Special Publication No. 38596-1972.

Special Publication No. 52-30991 (as shown).

A method of graft polymerizing styrene monomer and/or other polymerizable monomers with organic peroxide in the presence of polyphenylene ether, or JP-A-52-14
Examples include a method of melt-kneading the above-mentioned polyphenylene ether, a polystyrene polymer, and a radical generator, as shown in No. 2799.

In the present invention, (A) 25 of polyphenylene ether
The reduced viscosity measured with a chloroform solution at 10.5 °C/11100 is preferably 0.40 to 0.60. More preferably, it is 0.45 to 0.55. If the reduced viscosity is less than 0.40 or more than 0.60, the impact strength will decrease, which is not preferable.

In the present invention, (1) the scarlet crystalline thermoplastic resin matrix phase is polyethylene or polypropylene.

polyamide, thermoplastic polyester, polyacetal,
It is formed from at least one resin selected from polyphenylene sulfide and hypholyether ether glue.

Polyethylene in the present invention refers to crystalline polyethylene, including low density polyethylene, medium density polyethylene,
Refers to high-density polyethylene, linear low-density polyethylene, etc.

The polypropylene in this invention G is crystalline polypropylene, and in addition to propylene homopolymers, propylene and α-
Includes block or random copolymers copolymerized with olefins.

The polypropylene has a melt index of 01 to 10.
0 y/10 minutes, and a special number in the range of 0.5 to 40 minutes/10 minutes is suitable.

Homopolymers, block or random copolymers of propylene can be obtained, for example, by reaction in the presence of a combined catalyst with titanium trichloride and an alkyl aluminum compound, usually referred to as a Ziegler-Natsuta type catalyst.

As the polyamide in the present invention, a polyamide obtained by polycondensation of a lactam having three or more membered rings, a polymerizable ω-amino acid, a dibasic acid, and a diamine can be used. in particular.

Polymers such as ε-caprolactam, aminocaproic acid, enantholactam, 7-amitzhebutanoic acid, 11-aminoundecanoic acid, hexamethylene diamine, nonamethylene diamine, undecamethylene diamine, dodecamethylene diamine.

Polymers obtained by polycondensing diamines such as metaxylylene diamine with dicarboxylic acids such as teL/7thalic acid, isophthalic acid, adipic acid, cepatic acid, dodecane dibasic acid, and geltaric acid, or copolymers thereof One example is merging.

Specific examples include polyamide 6, polyamide 6.6. Polyamide 6.10. Polyamide 11. Polyamide 12. Examples include aliphatic polyamides such as polyamide 6.12, aromatic polyamides such as polyhexamethylene diamine terephthalamide, polyhexamethylene diamine isophthalamide, and xylene group-containing polyamides, and these may be used as a mixture or copolymer of two or more types. It can also be used as a combination.

What is thermoplastic polyester in the present invention?

It consists of a dicarboxylic acid component in which at least 40 mol% of the dicarboxylic acid component is terephthalic acid and a diol component, and the dicarboxylic acid component other than the above-mentioned terephthalic acid includes:
C2-20 aliphatic dicarboxylic acids such as adipic acid, sebacic acid, dodecanedicarboxylic acid, isophthalic acid,
Aromatic dicarboxylic acids such as naphthalene and dicarboxylic acids.

Alternatively, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid may be used alone or as a mixture, and the diol components include ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,6-hexane. Diol, 1.10-decanediol, l, 4
-Cyclohexanediol 0: Examples include aliphatic glycols such as 4.4'-dihydroxydiphenyl, alicyclic glycols, and aromatic glycols alone or in mixtures.

Among these thermoplastic polyesters, polybutylene terephthalate or polyethylene terephthalate can exhibit the effects of the present invention more desirably. In addition, in these cases, 2
The intrinsic viscosity measured at 5° C. is preferably in the range of 0.5 to 3.0, and it is difficult to obtain the desired mechanical strength even if an intrinsic viscosity outside this range is used.

The compatibilizer (C) in the present invention refers to an agent that can be compatibilized with the dispersed phase consisting of polyphenylene ether and/or the crystalline thermoplastic resin matrix phase, and stabilizes each phase. This term refers to a substance that has the function of allowing the phase to become unstable during actual use, and does not cause poor appearance or deterioration of physical properties.

Low molecular weight surfactants and soaps can also be used, but high molecular weight ones are preferable in terms of phase stability. More preferably.

In order to strengthen the stability of the phase, whether it is low molecular weight or high molecular weight, it is not a simple affinity.

It is preferable to use one that reacts with either or both of the phases, even if only partially. More desirably, the compatibilizer itself is (
It is preferable that the material has an affinity with or reacts with the components A) and/or (2) and has shock absorbing ability.

As a low molecular weight compatibilizing agent, one molecule contains a carboxylic acid group,
Acid anhydride group, acid amide group, imide group.

Carboxylic acid ester group, epoxy group, amino group.

At least one compound selected from compounds containing at least one incyanate group, a group containing an oxazoline ring, and a hydroxyl group.

Specifically, aliphatic carboxylic acids, aromatic carboxylic acids, esters, acid anhydrides, acid amides of these acids, imides of these carboxylic acids and/or acid anhydrides, or fatty acids. family glycols and phenols, or toluene diisocyanate and methylene bis(
4-phenylisocyanate), oxazolines such as 2-vinyl-2-oxazoline, epoxy compounds such as epichlorohydrin and glycidyl methacrylate, or aliphatic amines, aliphatic diamines, and fatty acids. Family triamine.

Aliphatic tetramine, etc. and m-phenyl diamine.

These include aromatic amines such as 4.4'-methylene dianiline and benzyschiff. Furthermore, the unsaturated compounds shown below are preferred.

Specific examples include maleic anhydride, maleic acid, fumaric acid, maleimide, maleic acid hydrazide, and a reaction product of maleic anhydride and diamine (wherein R represents an aliphatic or aromatic group). Structure: methylnadic anhydride, dichloromaleic anhydride, maleic acid amide, soybean oil, tung oil,
Natural oils and fats such as castor oil, linseed oil, hempseed oil, cottonseed oil, sesame oil, rapeseed oil, peanut oil, camellia oil, olive oil, coconut oil, sardine oil, acrylic acid, butenoic acid, crotonic acid, vinylacetic acid, methacrylic acid, pentene acid, angelic acid,
Typric acid, 2-pentenoic acid, 3-hen-5-dioic acid.

α-Ethyl acrylic acid.

β-Methylcrotonic acid, 4-pentenoic acid, 2-'hexenoic acid, 2-methyl-2-pentenoic acid, 3-methyl-2-pentene M, a-ethylcrotonic acid, 2.2
-dimethyl-3-butenoic acid, 2-heptenoic acid, 2-octenoic acid, 4-decenoic acid, 9-undecenoic acid, 10-undecenoic acid, 4-dodecenoic acid, 5-dodecenoic acid, 4-tetradecenoic acid.

9-tetradecenoic acid, 9-hexadenoic acid, 2-octadecenoic acid, 9-octadecenoic acid, icosenoic acid, tocosenoic acid, erucic acid, tetracosenoic acid, mycolipenic acid, 2
．． 4-Pentadiene acid.

2.4-hexadienoic acid, diallylacetic acid, geranic acid, 2.4-decadienoic acid, 2,4-dodecadienoic acid, 9
．． 12-hexadecadienoic acid, 9.12-octadecadienoic acid, hexadecatrienoic acid, linoleic acid, linuric acid, octadecatrienoic acid.

Icosadienoic acid, icosatrienoic acid, icosatetraenoic acid, linoleic acid, eleostearic acid, oleic acid, icosadinic acid enoic acid.

Erucic acid, docosadienoic acid, docosatrienoic acid, docosatetraenoic acid, docosapene citric acid.

Tetracosenoic acid, hexacosenoic acid, hexacosenoic acid,
Unsaturated carboxylic acids such as oftacosenoic acid and traacontenoic acid, or esters, acid amides, anhydrides, unsaturated oxazolines, or allyl alcohols of these unsaturated carboxylic acids.

Crotyl alcohol, methylvinylcarbinol, allylcarbinol, methylpropenylcarbinol, 4-
Penten-1-ol, 10-undecen-1-ol, flopargyl alcohol 21.4-pentadiene-
3-ol, l,4-hexadien-3-ol, 3.
5-hexadien-2-ol, 2.4-hexadien-1-ol, general formula CnHz oL sOH, C1H
21-tOH.

CnH21-e Alcohol represented by OH (where n is a positive integer), 3-butene-1,2-diol.

2,5-dimethyl-3-hexene-2,5-diol,
l,5-hexadiene-3,4-diol.

Unsaturated alcohols such as 2,6-octacyene-4,5-diol or OH of such unsaturated alcohols
Examples include unsaturated amines in which the group is replaced with an NH2 group.

Also included are incyanates such as toluenodiisocyanate and methylene diphenyl diisocyanate.

Furthermore, these compatibilizers were introduced. Also included are various polymers and rubbers of low molecular weight (eg, 500-10,000). In addition, as a high molecular weight compatibilizer, a high molecular weight compatibilizer (for example, 10,0
00 or more), but more preferably polyethylene, polypropylene, and polyolefin copolymers such as ethylene-propylene copolymers and ethylene-buone copolymers, polystyrene, or the aforementioned polyamides,
Thermoplastic polyester.

Alternatively, polyphenylene sulfide, polyacetal, or polyether ether ketone with a low molecular weight compatibilizer introduced therein may be used. These polymers also include those copolymerized with other components.

Even more preferred is at least one selected from modified rubber-like substances and epoxy compounds.

In the present invention, a modified rubber-like substance refers to a substance obtained by modifying a rubber-like substance.

Rubber-like materials in the present invention refer to natural and synthetic polymeric materials that are elastic at room temperature.

Specific examples include natural rubber, butadiene polymers, butadiene-styrene copolymers (including random copolymers, block copolymers, graft copolymers, etc.)
, isoprene polymer, chlorobutadiene polymer, butadiene-acrylonitrile copolymer, inbutylene polymer.

Inbutylene-butadiene copolymer, isobutylene-isoprene copolymer, acrylic acid ester copolymer, ethylene-propylene copolymer.

Ethylenoptene copolymer, ethylene-propylene-nonconjugated diene ternary copolymer, thiol rubber, polysulfide rubber, polyurethane rubber, polyether rubber (eg, polypropylene oxide, etc.).

epichlorohydrin rubber, polyester elastomer,
Examples include polyamide elastomer.

These rubber-like substances may be produced by any production method (eg, emulsion polymerization, solution polymerization) or with any catalyst (eg, peroxide, trialkyl aluminum, lithium halide, nickel-based catalyst).

Furthermore, those with various degrees of crosslinking and microstructures with various ratios (e.g., cis structure, trans structure,
(vinyl group, etc.), or those having various average rubber particle sizes are also used.

Various copolymers such as random copolymers, block copolymers, and graft copolymers can all be used as the rubber-like material of the present invention.

In the present invention, the rubber-like substance may be modified by introducing at least one of the above-mentioned low molecular weight compatibilizers by any method, and generally by copolymerization (random copolymerization, block copolymerization, etc.). Copolymerization, graft copolymerization, etc. are all included).

Examples include reactions to the main chain, side chains, and terminals of molecules.

Furthermore, in the present invention, the epoxy compound includes polypolymer resin, its precursor, and an epoxy group-containing copolymer.

For example, epoxy resins and epoxy resin precursors include bisphenol A epoxy resins, ortho-cresol novolak epoxy resins, glyc/dylamino epoxy resins, trifunctional epoxy/resins, tetrafunctional epoxy resins, and precursors thereof. be. It also includes epoxy resin compositions containing two-reactive diluents.

Further, the evoquino group-containing copolymer includes a copolymer of an unsaturated epoxy compound and an ethylenically unsaturated compound, an epoxidized polyester, an epoxidized polyamide, and the like.

Regarding copolymers consisting of unsaturated epoxy compounds and ethylenically unsaturated compounds, unsaturated epoxy compounds include compounds that each have an unsaturated group that can be copolymerized with an ethylenically unsaturated compound and an epoxy group in the molecule. It is.

Examples include unsaturated glycine esters and unsaturated glycine/dyl ethers represented by the following general formulas (1) and (2).

(R is a hydrocarbon group having 2 to 18 carbon atoms and having an ethylenically unsaturated bond.) (R is a hydrocarbon group having 2 to 18 carbon atoms having an ethylenically unsaturated bond, and X is -CH2- ○-1 Specific examples include glycidyl acrylate, glycidyl methacrylate, itaconic acid glycidyl ethers, allyl glycidyl ether, 2-methylallyl glycidyl ether, and styrene-p-glycidyl ether.

Ethylenically unsaturated compounds are olefins.

Vinyl esters of saturated carboxylic acids having 2 to 6 carbon atoms, esters of saturated alcohol components having 1 to 8 carbon atoms and acrylic acid or methacrylic acid, maleic esters, methacrylic esters, and fumaric esters, halogens Examples include vinyl compounds, styrenes, nitriles, vinyl ethers, and acrylamides.

Specifically, ethylene, propylene, butene-1, vinyl acetate, methyl acrylate, ethyl acrylate, methyl methacrylate, diethyl maleate, diethyl fumarate,
Examples include vinyl chloride, vinylidene chloride, styrene, acrylonitrile, isobutyl vinyl ether, and acrylamide. These may be used alone or as a mixture of two or more thereof. Among these, ethylene is particularly preferred.

There is no particular restriction on the composition ratio of the epoxy group-containing copolymer, but
A copolymer with an unsaturated epoxy compound of 0.1 to 50% by weight, preferably 1 to 30% by weight is desirable.

Epoxy group-containing copolymers can be made in various ways. Both a random copolymerization method in which the unsaturated epoxy compound is introduced into the main chain of the copolymer and a graft copolymerization method in which the unsaturated epoxy compound is introduced in the side chain of the copolymer can be adopted. Specifically, the production method involves combining an unsaturated epoxy compound and ethylene in the presence of a radical generator, at 500 to 4,000 atmospheres, at 100 to 300°C, in the presence or absence of an appropriate solvent or chain transfer agent. A copolymerization method, a method in which polypropylene is mixed with an unsaturated epoxy compound and a radical generator, and melt-ground copolymerized in an extruder, or an unsaturated epoxy compound and an ethylenically unsaturated compound are mixed in water or an organic solvent, etc. Examples include a method of copolymerizing in an inert solvent in the presence of a radical generator.

Among these epoxy compounds, a copolymer consisting of an unsaturated epoxy compound and an ethylenically unsaturated compound is particularly preferable, and in particular, a copolymer consisting of ethylene and an unsaturated epoxy compound and/or a copolymer consisting of ethylene and an unsaturated epoxy compound are preferred. A eutectic consisting of an ethylenically unsaturated compound and an unsaturated epoxy compound is more preferred.

In the present invention, (1) a dispersed phase consisting of polyphenylene ether, (3) a crystalline thermoplastic matrix phase, and (C)
In a resin composition comprising a compatibilizer that can be compatible with (9) and/or (2), the composition ratio of these Ω is preferably 1 to 65% by weight.

(3) is 35 to 98.9% by weight, (C) is 0.1 to 50% by weight, and more preferably (G) is 1 to 60% by weight.
, ■ is 40-98.9% by weight, 0 is 0.1-30% by weight
Yes.

Most preferably, (A) is 1-60% by weight and (B) is 4% by weight.
0 to 98.9% by weight, 0 being 0.1 to 20% by weight.

When (g) is less than 1% by weight, heat resistance and 1-dimensional stability.

If the moldability becomes poor and the amount exceeds 65% by weight,
(A) does not form a dispersed phase, resulting in poor impact strength and moldability. ■ is less than 35% by weight.

M) It is not possible to form an IJ plastic phase, resulting in lower impact strength and poor workability. Moreover, if it exceeds 98.9% by weight, heat resistance, two-dimensional stability, hygroscopicity, and moldability will not be improved. Furthermore, if (C) is less than 0.1% by weight, the phase becomes unstable and the impact strength decreases. If it exceeds 50% by weight, gelation will progress and moldability will be poor. In addition, (B) becomes difficult to form a matrix phase, making the phase unstable and reducing impact strength.

In addition, the average particle size of the dispersed phase composed of polyphenylene ether in the present invention is suitably 0.01 to 10μ. Preferably it is 0.05-5μ, more preferably 0.05-3μ. Even more preferably 0.1~
2μ, and both are preferably 0.1 to 168μ. If the particle size is outside the above range, the impact strength will decrease, which is not preferable.

In addition to the above formulation, the resin composition of the present invention also has an aspect ratio (ratio of major axis to minor axis) in a molded product of 10.
The above fibrous reinforced composite materials such as glass fiber, carbon fiber, polyamide fiber and metal whiskers, or
(E) Silica, alumina, calcium/umium carbonate, talc, mica, carbogluc, T with an average particle size of less than IOμ
Inorganic photonic agents (excluding fibrous materials) such as i0z and ZnO can be blended.

When blending the fibrous reinforced composite material or (E) an inorganic photonic agent, the blending amount is (A) a dispersed phase consisting of polyphenylene ether, (B) a crystalline thermoplastic resin matrix phase, and a zero phase. Resin composition 10 consisting of a tonerizing agent
The amount is 1 to 50 parts by weight relative to 0 parts by weight.

Furthermore, in the present invention, flame retardants such as Sb20g, flame retardant aids, other lubricants, and nucleating agents are used.

Plasticizers, dyes, pigments, antistatic agents, antioxidants.

One preferable embodiment may be to use it as a composite material to which a weather resistance imparting agent or the like is added.

There are no particular limitations on the method for producing the resin composition of the present invention9.
Commonly known methods can be used.

Methods of mixing in a solution state and evaporating the solvent or precipitating in a non-solvent are also effective, but from an industrial standpoint, a method of kneading in a molten state is actually used. For melt-kneading, commonly used kneading devices such as single-screw or twin-screw extruders and various types of kneaders can be used. Particularly preferred is twin-screw high kneading.

When kneading, it is preferable to uniformly mix each resin component in powder or pellet form in advance using a device such as a tumbler module or a Henschel mixer, but if necessary, mixing can be omitted and the resin components can be mixed in the kneading device. It is also possible to use a method of supplying a fixed amount of each separately.

The kneaded resin composition can be molded by various molding methods such as injection molding, extrusion molding, etc., but the present invention is also applicable to the present invention. It also includes a method in which a molded product is obtained by tri-blending during injection molding or extrusion molding and directly kneading during the melt processing operation without going through a kneading process in advance.

In the present invention, there is no particular restriction on the kneading order.

You may also knead 0, ■, and 0 all at once, or mix (
You may knead (g) and (2), then knead 0, or you may knead (g) and 0 in advance, then knead (1). Other kneading orders are also possible. However, (B)
The method of first kneading and then kneading (g) should be avoided because gelation occurs and a desirable final resin composition cannot be obtained.

The resin composition of the present invention can be made into molded products, sheets, chips, and films by injection molding or extrusion molding.

It is used as fibers, laminates, and coating materials. In particular, automotive parts 1, such as bumpers, springs, fenders, trims, door panels, wheel covers, side protectors, car wraps, trunk lids, trunk lids, roofs, etc., interior and exterior materials, as well as heat resistance requirements. Used for machine parts that are manufactured by It is also used as parts for motorcycles, such as covering materials, muffler covers, leg shields, etc.

Furthermore, housings are used as electrical and electronic components.

Yarn, connector, printed circuit board, boo I no,
Other 2 Used for parts that require strength and heat resistance.

<Examples> The present invention will be explained below with reference to Examples, but these are merely illustrative and the present invention is not limited thereto.
. In addition, the load deflection temperature test (H, D, T,
) was carried out according to JIS K7207. Eye lift impact strength (thickness 3.2-s) is JIS K7110
These are the test results. Also, M, I.

was measured according to JIS K7210.

Polyphenylene ether used in the present examples and comparative examples,
Epoxy compounds, modified rubber-like substances.

Obtained using the following recipe. Among the crystalline thermoplastic resin and epoxy compound, a commercially available epoxy resin was used.

■ Polyphenylene ether 2.6-dimethylphenol was dissolved in toluene and methanol, and manganese chloride-ethylenediamine was added under an oxygen atmosphere.

A car number was obtained by oxidative polymerization at a reaction temperature of 30°C.

■ Modified rubber-like substance ethylene propylene rubber, maleic anhydride and ternary butyl peroxene laurate were mixed in advance. Set the extruder with L/D = 28 at a barrel temperature of 2300C, and set the extruder with a barrel temperature of 2300C, and make a rotation speed of 6 Orpm.
An extruder reaction was carried out, and the modified rubber strands discharged from the die were cooled with water and pelletized.

■ The epoxy compound glycidyl methacrylate-ethylene-vinyl acetate copolymer was disclosed in JP-A-47-23490 and JP-A-4
It was produced with reference to the method described in Japanese Patent No. 8-11388. Namely.

Equipped with a supply port, a discharge port, and an agitator.

Glycidyl methacrylate using a 40 ton stainless steel reactor with temperature control.

While stirring while continuously feeding ethylene, vinyl acetate, a radical initiator, and a chain transfer agent, 1,400 to 1
, 600 atm, and 180 to 200°C.

■ Polyamide Polyamide 6.6: UBE nylon @2020B (manufactured by Ube Industries ■) Polyamide: UBE nylon @l013B
(Made by Ube Industries ■) ■ Polyester polyptyre/Telefuclad Toughpet PBT'N-1
000 (made by Mitsubishi Rayon ■) Polyethylene terephthalate: Unitika Polyester M
A 2101 [F] (manufactured by Unitika ■) ■・Epoxy resin Sumi Epoxy @ELM -434 Manufactured by Susumu Chemical Industry ■, 4
Functional epoxy resin, epoxy equivalent weight 110-13Of/
eq ■ Oleic acid amide "Denon SL-1'J Marubishi Yukaki Example 1 Polyphenylene ether (ηsp/c=0.47dl/
9° (reduced viscosity measured at 25°C in chloroform at a concentration of 0.5t/dt) 40wt% and polyamide 66rU
BE Nylo/2020B J 50wt% and maleic anhydride grafted ethylene propylene rubber (maleic anhydride graft amount 0.7wt% to ethidiethylene propylene rubber t%) were mixed at resin temperature using a continuous twin-screw kneader (TEX-4N manufactured by Japan Steel Works). 310℃, Suff'J - One rotation speed 50O
After melting and mixing at rpm, granulation was carried out using an injection molding machine (manufactured by Toshiba,
After molding a test piece using IS-150), physical properties were measured.

The physical property measurement results are shown in Table 1. In addition, the cross-section of the Izotsu impact test piece before the test was finished with a microtome and placed in carbon tetrachloride, which is a good solvent for polyphenylene ether, for 30 minutes (at room temperature).

The test piece was immersed and the polyphenylene ether was etched. This test piece was observed with a scanning electron microscope, and the dispersed particle size of polyphenylene ether was measured. The particle diameter was calculated by measuring the maximum diameter of each dispersed particle and averaging the two weights. The results are shown in Table 1.

Comparative Example 1 In Example 1, polyphenylene ether was
The experiment was carried out in the same manner except that c = 0.25. The results are shown in Table 1.

Example 2 Polyphenylene ether (ηsp/c=0.51)
Composition 1 consisting of 50 wt% and 50 wt% of polybutylene terephthalate "Toughpet PBT@N-1006J"
00 parts by weight, 1 part by weight of epoxy resin "Sumi Epoxy ELM 434 J" was added as a compatibilizer.

Using a small batch type two-shaft mixer "Laboplast Mill 0" (manufactured by Toyo Seiki), the temperature was 260℃ and the rotor rotation speed was 9Or.
pm, and melt-kneaded for 5 minutes. The obtained composition is
Press molding was performed at 70°C to prepare Izotsu impact test pieces and load deflection temperature test pieces.

Table 2 shows the physical property measurement results and the average dispersed particle diameter of polyphenylene ether measured by the method of Example 1.

Comparative Example 2 Instead of the epoxy resin as the compatibilizer in Example 2, oleic acid amide "Denone 5L-1'Jl" was used.

The same procedure was followed except that 1 part by weight of oil immersion (manufactured by 1) was added. The results are shown in Table 2.

Example 3 Polyphenylene ether (ηsp/c = 0.55
), 30wt% of polyethylene terephthalate "Unitika Polyester MA2101'J 5eNJt%, and grindyl methacrylate-ethylene-vinyl acetate (GM
A-E-VA) copolymer (14 wt%) was prepared in the same manner as in Example 2. Table 3 shows the physical property measurement results and the dispersed average particle diameter of Borif Nylene ether.

Comparative Example 3 A product having the same composition as Example 3 was first treated with polyethylene terephthalate "Unitika Polyester MA21" in the first stage.
80wt% of 01@J and 20wt% of GMA-E-VA copolymer were melt-kneaded in Labo Plastomill 0, then 70wt% of this composition and 30w of polyphenylene ether were mixed.
t% was mixed and molded again using Laboplasto Mill 0 in the same manner as in Example 3, and the physical properties were measured. The results are shown in Table 3.

Example 4 Polyphenylene ether (ηs'l)/c=0.52
) with 40wt% polyamide doro rUBE nylon@l
The same method as in Example 2 was carried out using 50 wt% o13BJ and low wt% maleic anhydride grafted ethylene propylene rubber. The results are shown in Table 4.

Example 5 Polyamide 66rU was used instead of polyamide 6 in Example 4.
It was carried out in the same manner as in Example 4 except that BE Nylon' 2020 B J was used. The results are shown in Table 4.

These Examples and Comparative Examples show that the smaller the average particle diameter of the dispersed phase made of polyphenylene ether, the higher the Izod impact value, and when it exceeds 10 μ, the Izod impact value becomes low, which is considered to be a practical problem. It can be seen that the particle size of the dispersed phase consisting of polyphenylene and ether is an important factor.

It was also discovered that the dispersed particle size can be changed by changing the molecular weight of polyphenylene ether, the compatibilizer, and the method of cross-talk. These facts are surprising and cannot be easily estimated using conventional polyphenylene ether composition techniques.

Example 6 In Example IG, polyphenylene ether was
The same procedure as in Example 1 was carried out except that /c=0.55 was used. The results are shown in Table 1.

Example 7 In Example 1, polyphenylene ether was
The same procedure as in Example 1 was carried out except that c=0.57 was used. The results are shown in Table 1.

Surprisingly, it can be seen from Table 1 that there is an appropriate range for the reduced viscosity of polyphenylene ether, and that when it is less than 0.40, the dispersed particle size becomes large and the Izod impact value decreases, which is not preferable. Furthermore, when the reduced viscosity approaches 0.6 mm, the 1-dispersion particle size tends to increase.

Example 8 Polyphenylene ether (ηsp/c=o, 47dg/
r) with 40wt% polyamide 66rUBE nylon ■
2020B J 50wt% and maleic anhydride grafted ethylene propylene rubber (maleic anhydride grafted 31
0.7wt% to ethidiethylene-propylene rubber wt%
were kneaded in a small batch-type twin-screw kneader "Laboplast Mill 0" at 260°C for 5 minutes at a rotor rotation speed of 90 rpm, and test pieces were prepared by press molding (270°C) and their physical properties were measured.Results are shown in Table 5.

Example 9 A test was carried out under the cross-wire conditions of Example 8, with the temperature changed to 280°C. The results are shown in Table 5.

From Examples 8 and 9, even if the composition is the same, the crosstalk conditions are different.
It can be seen that the particle size of the dispersed phase made of polyphenylene ether changes and the impact strength changes significantly. In other words, it is thought that the importance of the monodisperse particle size is clearly demonstrated.

Example 10 In Example 6, the composition of polyamide 66 was changed to 45 wt%.
The same method was used except that the glycidyl methacrylate-ethylene-vinyl acetate copolymer (glycidyl methacrylate content 10 wt% to copolymer) was changed to 5 wt%. The results are shown in Table 1.

Example 11 Polyphenylene ether (rr sp/c = 0.4
7 c///f) 50 wt% and maleic anhydride grafted ethylene propylene rubber (maleic anhydride graft amount 0)
．． 7wt% to ethidiethylene propylene rubber t% and o:
Continuously add 0.6 parts by weight of maleic anhydride (based on the total composition)
i111 fi is (person X -44■8 pieces'l1l
Al) Ol 1 *Polyamide 6r UBE nylon 01013B J 40wt% is charged from the tube and from the second hopper provided between the first hopper and the vent hole.
, resin temperature from 310℃ to 340℃, Screw IJ,
- After melt-kneading at a rotational speed of 38 or βm, granulation was performed.

Thereafter, a test piece was molded using an injection molding machine (Model 15-150E, manufactured by Toshiba Machinery Co., Ltd.), and the physical properties were measured.

The results are shown in Table 6.

Example 12 The same method as in Example 11 was carried out except that ethylene propylene rubber was used instead of the maleic anhydride grafted ethylene propylene rubber.

The results are shown in Table 6.

Example 13 In Example 12, 10 wt% of polystyrene (Dow rRPsJ) grafted with 2-vinyl-2-oxazoline was used instead of 0.6 parts by weight of maleic anhydride,
The same method as in Example 12 was carried out except that the polyphenylene ether was changed to 40% by weight.

The results are shown in Table 6.

From these Examples and Comparative Examples, in the composition of polynylene ether, crystalline thermoplastic resin, and compatibility agent,
The particle diameter of the dispersed phase made of polyphenylene ether has a surprising effect on impact strength, and is preferably 0.01 to 10 microns.

Preferably 0.05-5μ, more preferably 0.05-5μ
It has been found that the thickness is 3μ, more preferably 0.1 to 2μ, and most preferably 0.1 to 1.8μ.

<Effects of the Invention> As explained above, the resin composition according to the present invention comprises a dispersed phase composed of polyphenylene ether, a crystalline thermoplastic resin matrix phase, and a compatibilizer that can be compatibilized with either or both of them. By specifying the particle size of the dispersed phase made of polyphenylene ether, we were able to improve impact strength, something that could not be easily achieved with conventional technology.

This has been made possible with almost no decrease in heat resistance.

In particular, in compositions using polyphenylene ether, it has not been previously noted that the dispersed particle size has a large effect on impact strength.

In order to improve impact strength, it is necessary to use a large amount of rubber components, which leads to a corresponding decrease in heat resistance.

The present invention specifies the particle size of the dispersed phase made of polyphenylene ether, and specifies the compatibilizer and molecular weight of the polyphenylene ether to help obtain the specific particle size, thereby making it easier to achieve excellent high impact properties. This led to the invention of a new composition that has a balance between heat resistance and heat resistance.

2. The novel composition provided by the present invention can be processed by molding methods used for thermoplastic resins, such as injection molding, extrusion molding, etc.

It is processed into molded products, sheets, films, chives, neat materials, etc., and has heat resistance, impact resistance, and processability.

Provides a product with extremely good balance of physical properties such as dimensional stability.

Claims (16)

[Claims] (1) (A) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. is always hydrogen.) A dispersed phase consisting of polyphenylene ether obtained by oxidative polymerization of one or more phenolic compounds represented by (B) a crystalline thermoplastic resin matrix phase; ) and/or (B), and the average particle diameter of the dispersed phase is 0.01 to 1.
A thermoplastic resin composition characterized by having a particle size of 0μ. (2) (A) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. is always hydrogen.) A dispersed phase consisting of polyphenylene ether obtained by oxidative polymerization of one or more phenolic compounds represented by (B) a crystalline thermoplastic resin matrix phase; ) and/or a compatibilizing agent compatible with (B), wherein the composition has previously been
) and (C), and then (B), and the average particle size of the dispersed phase is 0.01 to 1.
A thermoplastic resin composition characterized by having a particle size of 0μ. (3) The resin composition according to claim 1 or 2, wherein the polyphenylene ether (A) has a reduced viscosity of 0.40 to 0.60 as measured in a chloroform solution at 25°C. (4) The resin composition according to claim 1 or 2, wherein the polyphenylene ether (A) has a reduced viscosity of 0.45 to 0.55 as measured in a chloroform solution at 25°C. (5) (B) At least one thermoplastic resin matrix phase selected from polyethylene, polypropylene, polyamide, thermoplastic polyester, polyacetal, polyphenylene sulfide, and polyether ether ketone.
Claim 1 or 2 formed of seed resin
The resin composition described in . (6) (C) The compatibilizer contains a carboxylic acid group, an acid anhydride group, an acid amide group, an imide group, a carboxylic acid ester group, an epoxy group, an amino group, an isocyanate group, or an oxazoline ring in the molecule. The resin composition according to claim 1 or 2, which is at least one selected from a compound containing at least one group and a hydroxyl group, a modified rubber-like substance, and an epoxy compound. (7) (C) The modified rubber-like substance as a compatibilizer has a carboxylic acid group, an acid anhydride group, an acid amide group, an imide group, a carboxylic acid ester group, an amino group, an isocyanate group, and a hydroxyl group in the molecule. The resin composition according to claim 6, which is a rubber-like substance modified with at least one compound selected from the group consisting of at least one compound. (8) A compound containing at least one carboxylic acid group, acid anhydride group, acid amide group, imide group, or amino group in the molecule is acrylic acid, maleic acid, fumaric acid, maleic anhydride, maleic hydrazide, or maleimide. The resin composition according to claim 6 or 7. (9) The resin composition according to claim 6, wherein the epoxy compound as the compatibilizer (C) is an epoxy resin and/or a precursor thereof. (10) (C) The epoxy compound as a compatibilizer is a copolymer of ethylene and an unsaturated epoxy compound and/or a copolymer of ethylene, an ethylenically unsaturated compound (excluding ethylene) and an unsaturated epoxy compound. The resin composition according to claim 6, which is a polymer. (11) The resin composition according to claim 1 or 2, wherein the average particle diameter of the dispersed phase is 0.05 to 5 μm. (12) The resin composition according to claim 1 or 2, wherein the dispersed phase has an average particle diameter of 0.05 to 3 μm. (13) The resin composition according to claim 1 or 2, wherein the dispersed phase has an average particle size of 0.1 to 2 μm. (14) The resin composition according to claim 1 or 2, wherein the average particle diameter of the dispersed phase is 0.1 to 1.8 μ. (15) (A) The dispersed phase consisting of polyphenylene ether is 1 to 65% by weight, (B) The crystalline thermoplastic resin matrix phase is 35 to 98% by weight.
．． 9% by weight, and (C) the compatibilizing agent is 0.1 to 50% by weight. (16) (A) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. is always hydrogen.) A dispersed phase consisting of polyphenylene ether obtained by oxidative polymerization of one or more phenolic compounds represented by (B) a crystalline thermoplastic resin matrix phase; ) and/or (B), and the average particle diameter of the dispersed phase is 0.01 to 1.
For 100 parts by weight of the resin composition having a particle diameter of 0 μ, (D) a fibrous reinforced composite material having an aspect ratio (ratio of major axis to minor axis) of 10 or more in the molded product, or (E) an average particle size of 1. A thermoplastic resin composition comprising 1 to 50 parts by weight of an inorganic filler (excluding fibrous materials) having a size of 10 μm or less.