JPS63122757A - Polyphenylene ether resin composition - Google Patents

Abstract

PURPOSE:To obtain a polyphenylene ether resin composition having excellent resistance to organic solvent and mechanical strength, by using an epoxy group- containing polystyrene resin, etc., in combination with other compound as compatibilizing agent and introducing a large amount of polyolefin into the composition. CONSTITUTION:(A) 30-98wt%, preferably 50-70wt% component composed of (A1) 10-75wt% polyphenylene ether resin having an intrinsic viscosity of 0.15-0.70dl/g [e.g. poly(2,6-dimethyl-1,4-phenylene) ether] and (A2) 90-25wt% polyolefin resin having an MFR of 0.03-40 (e.g. polypropylene) is compounded with (B) 70-2wt%, preferably 50-30wt% component composed of (B1) a polystyrene resin containing epoxy group and (B2) a polyolefin resin containing functional group (preferably a polymer produced by the graft copolymerization of 0.3-10wt% maleic anhydride component to a polyolefin resin), wherein the amount of the functional group in the component (B2) is 0.2-5mol per 1mol of the epoxy group in the component (B1).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyphenylene ether resin composition having excellent organic solvent resistance and mechanical strength.

(Prior art) Polyphenylene ether resin has excellent thermal, mechanical, and electrical properties and is therefore useful as a resin for molding materials, but it has drawbacks in processability, oil resistance, and impact resistance. , its scope of use is limited.As a method to improve these drawbacks, a method of improving the bottom shape processability by mixing other resins, such as styrene polymers, is disclosed in U.S. Pat. No. 3,388.
3.435, but the oil resistance is not improved at all.

On the other hand, various blends with polyolefins that have excellent oil resistance have been studied, and a blend of polyolefins and polyphenylene ethyl has been proposed in Japanese Patent Publication No. 7069/1982, but it meets the high level of requirements required in the industrial field. Mechanical strength that sufficiently satisfies this cannot necessarily be achieved.

Furthermore, JP-A-53-71158, JP-A-54-889
No. 60 and JP-A No. 59-100159 disclose a method for improving the compatibility between polyphenylene ether and polyolefin,
It has been proposed to blend a block copolymer of styrene and butadiene or a hydrogenated product of these into the sidelight, but since the amount of polyolefin blended is small and polyphenylene ether is essentially the linking phase, the polyolefin The organic solvent resistance it possesses is not fully demonstrated. Also, JP-A-5
No. 8-103557, JP-A No. 60-76547 Each K120 weight 1 is blended with % or more polyolefin and used as a compatibilizer, for example, a diblock copolymer consisting of an alkenyl aromatic compound and a conjugated diene, etc. Compositions are disclosed that incorporate hydrogenated compounds of:

According to (2), the tensile properties and brittleness are improved, but the required levels of rigidity and heat resistance are not fully satisfied.

Furthermore, Japanese Patent Publication No. 60-260649 discloses blending polyolefin, polyester, and polyamide with polyphenylene ether to improve oil resistance.
There is no disclosure of mechanical properties, which are important properties of the composition, but polyphenylene ether and polyolefin have a relatively high level of mechanical strength balance, good moldability, and excellent oil resistance required in the field of industrial parts. At present, no resin composition has been obtained.

(Season for Invention) Therefore, based on the ideas described below, the inventors of the present invention
We have conducted extensive research into introducing a large amount of polyolefin into polyphenylene ether resin and completely improving its compatibility.

That is, in order to improve the compatibility of both chemically inert and incompatible polymers, that is, the polyphenylene ether resin <a> and the polyolefin resin (b), the base material is physically evenly mixed with component (a), Component (C) having an epoxy group, which is a highly chemically active functional group, physically mixes uniformly with component (b) and interacts with the epoxy group introduced into component (C). By sharing component (d) having a functional group, for example, a maleic anhydride group, it is attempted to make components (a) and (b), which are originally incompatible, compatible. Thanks to the action of the modified polymers (C) and (d), a composition having both the excellent properties inherent to polyphenylene ether and polyolefin was obtained, and the present invention was completed.

That is, the present invention provides a resin composition having excellent organic solvent resistance and mechanical strength and comprising the following components <1) and (2).

Component (1) 30-98 weight ratio (a)
Polyphenylene ether resin (b) Polyolefin resin However, the proportion of component (a) and component (b) is based on the total amount of both components (a)'! JS 1 o~75 weight ratio component (2) 70~2% by weight (C)
Epoxy group-containing polystyrene resin (d) Functional group-containing polyolefin resin However, component (C) and component (d)
) is the amount in which the functional groups in component (dJ) are in a ratio of 0.2 to 5 with respect to the epoxy group emole in component (C). Therefore, in the present invention, component (C), component ( It is thought that d) functions as a compatibilizer for component (a) and component (b+) due to chemical interaction between the components.

(Specific tax BA of the invention) (1) Polyphenylene ether resin (a) The polyphenylene ether used in the present invention has a cyclic structural unit represented by the general formula, in which the chytyl oxygen atoms in the two units are as follows: connected to the benzene nucleus of an adjacent unit, n is at least 30, and Q is each independently hydrogen, halogen, a hydrocarbon group not containing a tertiary α-carbon atom, or between the halogen atom and the phenyl nucleus. selected from the group consisting of a halohydrocarbon violet group having at least 2 carbon atoms, a hydrocarbon oxy group, and a halohydrocarbon oxy group having at least 2 carbon atoms between the norogen atom and the phenyl nucleus represents a monovalent substituent. Typical examples of 0poIJ phenylene ethers include poly(2,6-dimethyl-1,4-phenylene)ether, holJ(296-dinityl-1.Q), which may be the same or different. 4-) Unilene ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, Bo! j (2-methyl-6-furopyru-1,4-phenylene) ether, poly(2,6-diprobyl-1,4-phenylene) ether, poly(2-
Ethyl-6-brobyl-1,4-)unilene) ether, poly(2,6-sif'thyl-1゜4-phenylene)ether % Poly(2+6 77"Lopenyl-1,4-phenylene) ether, poly(2゜ty-sila r;
-Simethoxy1,4-phenylene)ether, poly(
2,6-jethoxy-1,4-phenylene ether,
Poly(2-methoxy-6-nitoxy-1,4-]diunine) ether, poly(2-ethyl-6-methialyloxy-1,4-phenylene) ether, BoIJ (2,6
-cyc ao -1,4-phenylene) ether, poly(
2-Meh? 6-phenyl-1,4-)unilene) ether, 1J(2,6-dipenzyl-1,4-)unilene) ether, poly(2-ethoxy-1,4-phenylene) ether, poly(2-chloro) -1,4-phenylene ether, poly(2,5-dibromo-1,4-7 enylene) ether and the like; also 2,6-dimethylphenol and 2,3,6-trimethylphenol. copolymers, copolymers of 2,6-dimethylphenol and 2.3.5.6-titramethylphenol, copolymers of 2,6-dinitylphenol and 2.3.6-trimethylphenol, etc. Mention may also be made of copolymers.

A particularly preferred polyphenylene ether resin (a) is poly(2,6-dimethyl-1,4-phenylene) nityl.

Furthermore, the polyphenylene ether used in the present invention is
It also includes polyphenylene ethers modified by grafting styrenic monomers (eg, styrene, p-methylstyrene, α-methylstyrene, etc.) onto the polyphenylene ether defined by the above general formula.

In addition, the preferred molecular weight range is 30°C as a scale.
The value of intrinsic viscosity in chloroform is 0.1
It is in the range of 5 to 0.70 dl/f, more preferably 0.25 to 0.60 dl/f, particularly preferably 0
．． If the value is smaller than this, the mechanical strength of the composition will be low, and if it is larger than this, the molding processability of the composition will be reduced, which is undesirable. 2) Polyolefin resin (b
) The polyolefin resin used in the present invention includes propylene, butene-1, pentene-11, hexene-1,3 methylbutene-1,4 methylpentene=1, heptene-1,
These include homopolymers of ethylene-free α-olefins such as octene-1, copolymers containing these α-olefins as the main constituents and copolymers with ethylene-containing α-olefins, and mixtures thereof. In the case of copolymerization, several types may be used in combination.

Among these, propylene, a homopolymer of butene-1,3-methylbutene-1,4-methylpentene-1, and a copolymer containing these α-olefins as the main constituent are preferred, and especially a homopolymer of propylene is preferred. It is preferable to use a copolymer or a copolymer mainly composed of propylene, which exhibits crystallinity at least partially derived from polypropylene.

There are no particular restrictions on the molecular weight of these polyolefin resins, but from the viewpoint of mechanical strength and moldability, the MFR (230°C, load 2.16 mm) is generally used as a guideline.
A range of 0.03 to 40 is preferred, a range of O,OS to 15 is more preferred, and a range of 0.10 to 8 is particularly preferred.

(3) Epoxy group-containing polystyrene resin (C) In the epoxy group-containing polystyrene resin of the present invention, a copolymer of a styrene monomer and an unsaturated monomer having an epoxy group, or a copolymer of a polystyrene resin and an unsaturated monomer Any graft polymer having an epoxy group introduced therein may be used.

Here, examples of the unsaturated monomer having an epoxy group include glycidyl methacrylate, butyl glycidyl arate, butyl glycidyl fumarate, propyl glycidyl maleate, glycidyl acrylate, and the like.

In addition, during this copolymerization, other monomers other than the above-mentioned unsaturated monomer having an epoxy group, such as methyl acrylate, methyl methacrylate, vinyl acetate, etc., may be copolymerized in an amount not exceeding a majority amount. It is possible.

In addition, polystyrene resins, which are the basic structure of epoxy group-containing polystyrene resins, include homopolymers such as polystyrene, polychlorostyrene, and polyα-methylstyrene, and copolymers thereof, such as styrene-acrylonitrile copolymers. and styrene-divinylbenzene copolymer.

Furthermore, as the epoxy group-containing polystyrene resin in the present invention, in addition to copolymerization with the above-mentioned epoxy group-containing unsaturated monomer, for example, unsaturated bonds present in the polystyrene resin can be prepared using known methods such as It also includes those into which epoxy groups are introduced by oxidation using hydrogen peroxide or organic peracids.

Among these epoxy group-containing polystyrene resins, preferred are those obtained by graft copolymerizing polystyrene resins with an unsaturated monomer component having an epoxy group in an amount of 0.1 to 20% by weight; It is copolymerized with a styrene monomer in a range of 15% by weight, especially glycidyl methacrylate component! 1.0~1
Copolymerization with styrene and monomers in a range of 0% by weight is preferred.

(4) Functional group-containing polyolefin resin (d) The functional group-containing polyolefin resin used in the present invention has a functional group that can react with an epoxy group, and the functional group includes, for example, a carboxyl group and its Examples include polar groups such as salts, carboxylic anhydride groups, hydroxyl groups, mercapto groups, amino groups, amide groups, and ester groups. Of course, these can be used in combination.

In addition, the olefin resin part which is the basic structure of the resin is ethylene, propylene, butene-1, pentene-15hexene-1. 3 Methylbutene 1. 4 methylpentene 1
, homopolymers of alpha olefins such as heptene 1 and octene 1, copolymers with different kinds of alpha olefins, copolymers with alpha olefins as the main constituent and other heptamers, and composites thereof. .

Preferred examples of these functional group-containing polyolefin resins (d) include those obtained by graft copolymerizing an unsaturated carboxylic acid or an unsaturated carboxylic acid derivative component in a range of 0.1 to 20% by weight to a polyolefin resin; Or,
A product copolymerized with an olefin monomer in a range of 0.1 to 15 weight percent, particularly preferably a maleic anhydride component graft copolymerized to a polyolefin resin in a range of 0.3 to 10 weight percent. It is.

Below this range, chemical activity is poor and the compatibilizing ability is insufficient; above this range, physical compatibility with fraction (b) may be impaired, and This is not preferable because it causes difficulties in molding processability.

On the other hand, the type of polyolefin part of this functional group-containing polyolefin resin is determined by the type of polyolefin resin in fraction (b), and generally, the polyolefin resin in fraction (1)) is determined by the type of polyolefin resin in fraction (b). The same type as the main constituent component is preferable from the viewpoint of physical compatibility.

(Composition ratio of constituent fractions) By using together the epoxy group-containing polystyrene resin (c) and the functional group-containing polyolefin resin (d) shown in the claims, the ratio of the polyphenylene ether resin and the polyolefin resin can be adjusted to It shows good compatibility and mechanical strength with any range of materials, but it also has high heat resistance and rigidity.
From the viewpoint of organic solvent resistance, the ratio of polyphenylene ether resin to the total amount of polyphenylene ether resin and polyolefin resin is preferably in the range of 10 to 75% by weight, particularly preferably in the range of 25 to 65% by weight, especially 35% by weight. A range of 60% by weight is preferred. If the proportion of the polyphenylene ether resin is less than 100% by weight, the heat resistance rigidity will not be sufficient, and if it is more than 75% by weight, the organic solvent resistance will be poor, which is not preferable.

The total amount of component (2) in the resin composition according to the present invention, that is, the epoxy group-containing polystyrene resin (C) and the functional group-containing polyolefin resin (d) is 70 to 2
The percentage of heavy food intake is particularly preferably 60 to 10% by weight, particularly preferably 50 to 30% by weight. Component (2) is 2
In the range below % by weight, polyphenylene ether Ca)
There is a problem in the compatibility between the polyolefin (b) and the polyolefin (b), and in a range of 70% by weight or more, problems arise in terms of heat resistance rigidity and economy, which is not preferable.

In addition, the epoxy group-containing polystyrene resin (C) and the functional group-containing polyolefin resin (d
) is the amount of epoxy groups in component (C), ta
) Depending on the type and amount of the functional group in the component, it can vary widely, but the amount of chemically reactive functional group per mole of epoxy group is 0.2 to 5 moles, preferably 0.7 to 1 mole. ．．
The amount is preferably 5 mol, particularly preferably 0.8 to 1.2 mol.

The resin composition of the present invention may contain impact modifiers such as thermoplastics, thermosetting resins, rubbers, etc. other than the polyphenylene ethers, polyolefins, and polystyrene resins mentioned above, as necessary, within a range that does not impair the purpose of the present invention. May be blended. In addition, auxiliary ingredients such as antioxidants, weather resistance improvers, nucleating agents, slip agents, inorganic or organic fillers and reinforcing agents, flame retardants, various colorants, antistatic agents, and mold release agents may be added. is also possible. In particular, fillers such as glass fiber, mica, Merck, and calcium carbonate are effective in improving the balance of physical properties such as rigidity, and improving moldability, dimensional accuracy, and dimensional stability.

(Manufacturing method) As a blending method for obtaining the resin composition according to the present invention, generally, various methods of blending resins together, resins and stabilizers or colorants, or even resins and fillers can be applied. I can do it. For example, powder or granular components are uniformly dispersed in a Henschel mixer, a super mixer, a ribbon blender, a blender, etc., and then a twin-screw coaxial extruder, a two-screw coaxial extruder, a roll, A Banbury mixer, Plastomill, Prabender Plastograph melt mixer may be used. The melt-kneading temperature is usually in the range of 200°C to 350°C.

The resin composition thus obtained can be melted and mixed and then extruded to form a pellet.

The melt mixing method is common, but other methods, such as using a solvent (e.g. hot xylene) for each component, are possible. 'You may use and mix.

4. Example 1) Measurement and Evaluation Method The physical property values and properties in the Examples and Comparative Examples shown below were measured and evaluated under the following conditions.

(1) Dispersion form A part was cut out from the test piece evaluated for each physical property value in the Examples and Comparative Examples, and after ion etching, the dispersed particles were analyzed using a scanning electron microscope*M (Hitachi Urasaku Shin HH8-2R). The diameter was observed.

(2) Flexural modulus I S OR178-1974r'tocedure
12 (JIS K7203) using an Instron testing machine.

(3) Izot impact strength 180 R18O-1969 (JIS K7110
] Measured using Izot impact tester Y manufactured by Toyo Seiki Seisakusho in accordance with notched Izot impact strength.

3) Organic solvent resistance Bergen's 7m circle method (spE Jal 667 (1962)
)). Specifically, the minimum strain at which a crack occurs is determined by fixing a 2m thick test piece in a quarter-ellipse jig with a major axis of 24crn and a minor axis of 8crR, and immersing it in commercially available gasoline for 5 minutes. It was determined as the critical strain.

At this time, make sure that no cracks occur ◎ (extremely good)
, those with a critical strain value of 1.5% or more are rated O (good), and 1.
It was judged as 0 to 1.5% Δ (fair) and less than 1.0% Δ (poor).

2) Mixing of resin composition A predetermined amount of each component shown in Table 1 was melt-kneaded at 280°C using a Toyo Seiki Urasakusho Enlaboplasto Mill kneader,
After preparing the composition, it was made into powder using a pulverizer.

3) Preparation of test pieces for measuring and evaluating physical properties A sheet was used that was pressure-molded at 280°C using a Toryo Seiki-type Seisho Ishi hydraulic compression molding machine.

4) Separation (1) Polyphenylene ether tree AW (a) Mitsubishi Yuka ■
The prototype poly(2,6-dimethyl-1゜4-phenylene phether) (intrinsic viscosity in chloroform at 25℃ is 0.4
7 dt/fl (abbreviated as PPE in Table 1) (2) Polyolefin resin (b) Propylene-ethylene block copolymer sold by Mitsubishi Yuka (trade name: Mitsubishi Polypro BC8D%MFR)
(abbreviated as PP in Table 1) (3) Epoxy-containing polystyrene resin (C) Ethylbenzene and glycidyl methacrylate (abbreviated as PP in Table 1) using total solvent and benzoyl peroxide as an initiator. GM below
Steel 7-G obtained by copolymerizing AJ at 80°C for 6 hours
MA copolymer (Mitsubishi Yuka ■prototype, styrene content 95
%, GMA content 5%, weight average molecular weight 14 (1
,000) was used. (abbreviated as P S GMA in Table 1) (4) Functional group-containing polyolefin resin (d) 100 parts of propylene-ethylene block copolymer (trade name Mitsubishi Polypro BC8D), 4277910 parts of anhydrous male and 300 parts of chlorobenzene were mixed. , after heating and dissolving at 110°C, 10 parts of benzoyl peroxide was added over 6 hours,
After the addition, maleic anhydride graft copolymerized polypropylene (maleic anhydride content: 8.2 parts) obtained by further reaction at the same temperature for 3 hours was used. (abbreviated as M-PP in Table 1)
5) Impact strength modifier A partially hydrogenated styrene-butadiene block copolymer (trade name: Kraton Q1652) sold by Shell Kagaku (■) was used.

(abbreviated as 5EBS in Table 1) 6) Each component was melted and mixed in the proportions shown in Example Table 1, and the physical properties of the composition were evaluated! It was measured. The results were as shown in Table-1.

As shown in Table 1, by using a compatibilizer for the epoxy group-containing polystyrene resin (C) and the functional group-containing polyolefin resin (d) in combination, the dispersion of the borifuenylene ether resin (a) becomes compatible. Compared to Comparative Examples 1 to 3 in which no agent was blended, the compatibility between (a) and polyolefin resin (b), which were originally incompatible with each other, was improved.
It is clear that a resin composition having high rigidity, excellent organic solvent resistance, and mechanical strength can be obtained, which combines the characteristics originally possessed by each of the following.

(Margin below)

Claims (1)

[Scope of Claims] 1) A polyphenylene ether resin composition having excellent organic solvent resistance and mechanical strength and comprising the following components (1) and (2). Component (1) 30 to 98% by weight (a) Polyphenylene ether resin (b) Polyolefin resin However, the ratio of component (a) to component (b) is such that component (a) is 10 to 98% by weight relative to the total amount of both. This amount is 75% by weight. Component (2) 70-2% by weight (c) Epoxy group-containing polystyrene resin (d) Functional group-containing polyolefin resin However, the ratio of component (c) to component (d) is based on the epoxy group in component (c). 0 functional groups in component (d) per mole
．． The amount is a ratio of 2 to 5. 2) The polyphenylene ether resin composition according to claim 1, wherein the functional group-containing polyolefin resin is obtained by graft copolymerizing a maleic anhydride component to a polyolefin resin in a range of 0.3 to 10% by weight. thing