JPH01110550A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition having improved strength and appearance, by blending a polymer blend consisting of a polyphenylene ether based resin with a graft monomer by macromonomer used as a compatibilizing agent. CONSTITUTION:100pts.wt. resin component consisting of (A) 10-90pts.wt. polyphenylene based resin [e.g., 2,6-dimethyl-1,4-phenylene)ether)] and (B) 90-10 pts.wt. polyfluorovinylidene based resin is blended with (C) 3-30pts.wt. graft polymer by macromonomer method having both of an unit compatible to A and unit compatible to B, functional group capable of carrying out vinyl addition polymerization at the one end of molecular chain and 1,000-50,000 number- average molecular weight. Polymer skeleton compatible to A includes, e.g., a polymer mainly containing styrene (derivative) and polymer skeleton compatible to B includes, e.g., a polymer mainly containing methyl methacrylate.

Description

Detailed Description of the Invention (a) Purpose of the Invention [Field of Industrial Application] The present invention relates to a resin composition that is used for a wide range of purposes, both for general consumption and industrial use, and among them, it has recently attracted particular attention as an engineering plastic. The present invention relates to a resin composition comprising a polyphenylene ether resin, which has been widely used in the industry, and a polyvinylidene fluoride resin, which is attracting attention as a fluororesin with excellent moldability.

[Prior art and its problems]

BACKGROUND OF THE INVENTION With the remarkable development of the polymer chemical industry in recent years, many polymer materials are being used in large quantities in daily life products, industrial products, vehicles, building materials, and the like.

Particularly after the oil crisis, the need for higher performance and higher functionality of products has increased, and even in the field of polymer materials, engineering plastics have shown remarkable growth potential. can be done. Under these circumstances, in the field of plastics, efforts are being made to improve and modify them in various ways in order to meet the diversifying demands of the market.

Polyphenylene ether has excellent mechanical properties, thermal properties, electrical properties, dimensional stability, and light weight, and is used as an engineering plastic that has attracted much attention in recent years, but when used alone, it has extremely poor moldability and is expensive. Because it is,
It is usually used as an alloy with polystyrene resin, which has good compatibility. This polymer alloy is commonly available under the trade name Noryl, a product of General Elm Kutric Co., Ltd., and Zylon, a product of Asahi Kasei. It stands out even when compared to other plastics, and is used in applications where general-purpose plastics cannot meet performance requirements, such as automobile interior materials and office equipment. However, there are drawbacks due to the inherent properties of polyphenylene ether, such as high melt viscosity, poor oil resistance,
Applications are often limited due to poor weather resistance.

On the other hand, polyvinylidene fluoride is a type of fluoropolymer that has unique properties such as chemical resistance, weather resistance, and non-adhesion.It also has excellent mechanical strength and moldability, so it can be used for general industrial use. Its application fields are expanding, including as a household molding material and as a paint/coating material. In addition, the copolymer of vinylidene fluoride and hexafluoropropene is
It is used as an elastomer with excellent heat resistance, chemical resistance, oil resistance, weather resistance, etc. In recent years, applications that utilize the unique piezoelectric and pyroelectric effects have also progressed. It is thought that demand for polyvinylidene fluoride resin, which has such unique characteristics, will continue to increase in the future as a highly functional material.

However, the use of this resin is often limited due to reasons such as relatively low heat distortion temperature, high mold shrinkage rate, high specific gravity, and high price.

As mentioned above, polyphenylene ether-based resins and polyvinylidene fluoride-based resins have different excellent properties and disadvantages due to the fact that the former is a non-grade resin and the latter is a crystalline resin. There is.

One method that has recently attracted attention as a method for improving and modifying existing resins to meet diversifying uses is a method using polymer blends. This method of mixing different polymers to take advantage of the characteristics of resins and compensate for their shortcomings can flexibly respond to the needs of resin users, avoid wasting resources due to excessive quality, and facilitate research into new resins.・It has the advantage of being able to reduce the investment burden that is inevitable for development.

Attempts to use polymer alloys or blends have been made for a long time, but for the reasons mentioned above, they have recently been actively used, particularly in the field of engineering plastics.

Regarding resin compositions consisting of polyphenylene ether-based resins and polyvinylidene fluoride-based resins, there are some reported examples, although the number is not large.

proposed a resin composition consisting of a polyphenylene oxide alloy and a polyvinylidene fluoride resin, to which 2% or 12% of a styrene-methyl methacrylate block polymer synthesized by an anionic polymerization method was added as a compatibilizer. There is (Journal of Poly
mer 5science: Pt, B: Polyme
r Ph1sics.

Nail, 973 (1986)).

Generally, block polymers and graft polymers having different types of polymer segments in the same molecule are said to be effective as compatibilizers for polymer blends.

Many attempts have been made to date to use block polymers synthesized by anionic polymerization as compatibilizers for incompatible polymer blends, with considerable success.

However, it cannot be said to be a universal compatibilizer because strict operations are required to produce block polymers, and the monomers that can be used are limited. For example, in order to produce the above-mentioned block polymer, in addition to strict purification operations, it is necessary to polymerize at a temperature as low as liquid nitrogen, which is extremely difficult to do industrially at low cost.

On the other hand, graft polymers are usually produced by chain transfer methods using peroxides, radiation grafting methods, polymer initiator methods, etc., but these methods generally have extremely low grafting efficiency and are difficult to control molecular weight and composition. Moreover, the types of graft polymers that can be synthesized are also limited.

Therefore, block polymers and graft polymers that can be used as compatibilizers when blending different types of polymers can be produced inexpensively and easily, and their molecular structure, composition, molecular weight, etc. can be controlled as desired. If it could be synthesized, its technical and economic value would be enormous.

(B) Structure of the Invention [Means for Solving the Problems] In consideration of the problems of the prior art as described above, the present inventors have worked diligently to obtain a blended molding material with excellent performance. As a result of investigation, the present invention was completed by discovering that the object can be achieved by blending a polymer blend of polyphenylene ether resin and polyvinylidene fluoride resin using a graft polymer produced by the macromonomer method as a compatibilizer.

That is, the present invention provides polyphenylene ether resin (A)
, polyvinylidene fluoride resin (B) and the above resin (A
This is a resin composition made of a graft polymer obtained by a macromonomer method and having both units compatible with (B) and units compatible with resin (B).

The present invention will be explained in more detail below.

[Macromonomer]

In the present invention, the macromonomer refers to a relatively low molecular weight polymer having a number average molecular weight of about 1,000 to 50,000, which has a functional group capable of vinyl addition polymerization at one end of its molecular chain.

Examples of the terminal structure of the macromonomer in the present invention include a methacryloyloxy group, an acryloyloxy group, a styryl group, an allyloxy group, and a vinyl group. A methacryloyloxy group is preferably used.

Further, the skeleton structure of the macromonomer in the present invention is a polymer skeleton of a vinyl polymerizable monomer, and is a polymer skeleton that is compatible with either a polyphenylene ether resin or a polyvinylidene fluoride resin.

Specifically, examples of polymer skeletons that are compatible with polyphenylene ether resins include polymer skeletons containing styrene or styrene derivative monomer units as a main component. Other monomers that can be copolymerized with styrene or styrene derivatives include (meth)acrylic acid esters, (meth)acrylonitrile, etc., and the content of these copolymerized components must be 20 to 0%. is preferred.

Examples of polymer skeletons compatible with polyvinylidene fluoride resins include polymer skeletons made of homopolymers or copolymers containing methyl methacrylate as a main component. Other monomers that can be copolymerized with methyl methacrylate include (meth)acrylic acid ester, (meth)
Examples include acrylonitrile, styrene, and styrene derivatives, and the content of these copolymer components is preferably 20 to 0%.

The molecular weight of the macromonomer in the present invention may be within a range that does not impair the polymerizability of the produced macromonomer, and preferably a number average molecular weight of 1000 to 5000.
0, more preferably 2,000 to 40,000. If the number average molecular weight is less than 1,000, the degree of polymerization as a polymer unit is too low, and the physical properties of the macromonomer used as a raw material are not reflected in the graft polymer, which is the reaction product, which is undesirable. On the other hand, if it exceeds 50,000, it is not preferable. This is not recommended since it tends to cause disadvantages such as a decrease in polymerizability and a tendency to cause phase separation in the reaction system.

The number average molecular weight of the above macromonomer is determined by gel permeation chromatography (hereinafter referred to as GPC).
The measurement conditions are as follows.

Apparatus: High performance liquid chromatography (e.g. Toyo Soda Kogyo, product name: HLC-8021JR) Column: Polystyrene gel (e.g., Toyo Soda Kogyo, product name: G4000)
118 and G3000H8) Elution solvent: Tetrahydrofuran (hereinafter abbreviated as THF) Outflow rate: 1. Oml/min Column temperature = 40°C Detector: R■Detector Examples of the method for producing the macromonomer in the present invention include radical chain transfer method and anionic polymerization method.

An example of a method for producing a macromonomer by radical polymerization is to polymerize a radically polymerizable monomer in the presence of a chain transfer agent having a carboxyl group in the molecule to obtain a polymer having a carboxyl group at one end, and then A method of reacting the polymer with a radically polymerizable monomer containing a glycidyl group can be mentioned.

Chain transfer agents having a carboxyl group in the molecule to be used at this time include, for example, mercaptoacetic acid, 3-mercaptopropionic acid, 2-mercaptopropionic acid, and
-Mercaptan compounds such as mercaptopropionic acid are preferably used.

Examples of radically polymerizable monomers having a glycidyl group in the molecule include glycidyl methacrylate (hereinafter abbreviated as GMA), glycidyl acrylate, allyl glycidyl ether, and GMA is particularly preferred.

The macromonomer in the present invention can be produced by a method other than the above-mentioned radical polymerization method, and an anionic polymerization method using an organometallic compound as an initiator makes it possible to obtain a macromonomer with a well-regulated molecular weight. can.

[Graft polymer by macromonomer method] The graft polymer by macromonomer method in the present invention is
It refers to a graft polymer produced using a macromonomer as a raw material.

The method for producing a graft polymer using such a macromonomer method has the following features: i) The content of the polymer and the backbone component pomopolymer is small.

ii) The molecular weight of the branch component, the overall molecular weight of the graft polymer, and the ratio of the technique and the trunk can be easily controlled.

iii) Combinations of branch components and trunk components can be freely selected depending on the purpose.

It has been attracting a lot of attention recently because it can easily obtain high-performance graft polymers that cannot be obtained by conventional methods.

The graft polymer in the present invention is a graft polymer that has both a unit that is compatible with the polyphenylene ether resin (A) and a unit that is compatible with the polyvinylidene fluoride resin (B), and each unit is a graft polymer that is It forms the trunk component or branch component in the molecule. That is, the molecular structure is as follows: (a) The branch component is a vinyl polymer segment that is compatible with polyvinylidene fluoride resin derived from a macromonomer, and the trunk component is a vinyl polymer segment that is compatible with polyphenylene ether resin. (b) One branch component is a vinyl polymer segment that is compatible with polyphenylene ether resin derived from a macromonomer, and the backbone component is a vinyl polymer segment that is compatible with polyvinylidene fluoride resin. It is necessary that the polymer segment be either a polymer segment or a polymer segment.

The graft polymer of type (a) is a macromonomer having a skeleton of a polymer segment that is compatible with polyvinylidene fluoride resin, and a monomer that forms a polymer segment that is compatible with polyphenylene ether resin. It can be obtained by copolymerizing styrene or a styrene derivative, or a monomer mixture consisting of these monomers as main components and other monomers.

As other monomers, (meth)acrylic acid esters, (meth)acrylonitrile, etc. are suitably used, and it is preferable that 2 in the monomer mixture is 20 to 0%.

The graft polymer of type (b) is a macromonomer whose skeleton is a polymer segment that is compatible with a polyphenylene ether resin, and a monomer that forms a polymer segment that is compatible with a polyvinylidene fluoride resin. It can be obtained by copolymerizing methyl methacrylate or a monomer mixture consisting of methyl methacrylate as a main component and other monomers. Other monomers include (meth)acrylic ester, (
Meta)acrylonitrile, styrene or styrene derivatives are preferably used, and the amount thereof in the monomer mixture is preferably 20 to 0%.

The content ratio of these two types of segments in the graft polymer is such that the amount of the segment present in a small amount is preferably 5% by weight or more, and more preferably 10% by weight or more. If the amount of the component present in a small amount is less than 5% by weight, it is not preferable because it becomes almost a single unit in fact, so that no great effect as a compatibilizer can be expected.

Radical polymerization is generally employed as the polymerization method for producing the graft polymer in the present invention, including solution polymerization in the presence of a conventionally known radical initiator, bulk polymerization, suspension polymerization, and emulsification. Any polymerization method may be used.

Regarding the molecular weight of the graft polymer, the number average molecular weight determined by GPC is preferably 5,000 to 300,000, more preferably 10,000 to 200,000. If the number average molecular weight is less than 5,000, the polymer unit is too short and no significant compatibilizing effect can be expected, which is undesirable. If the number average molecular weight exceeds 30,000'0, the rate of dissolution into the resin to be blended will be slow, which is undesirable.

[Polyphenylene ether resin] The polyphenylene ether resin used in the present invention includes polyphenylene ether itself, a resin composition consisting of polyphenylene ether and polystyrene resin, and if necessary, other resins such as elastomer components. , a block copolymer, a graft copolymer, etc. are added in small amounts.

For polyphenylene ether, U.S. Patent No. 330
It has been described in many publications including 6874 and 3306875. That is, polyphenylene ether resin is a self-condensation product of monovalent mononuclear phenol synthesized by reacting phenol with oxygen in the presence of a copper complex catalyst. Preferred polyphenylene ethers are those represented by the following general formula.

where the oxygen ether atom of one unit is connected to the benzene nucleus of the next adjacent unit, n is a positive integer of at least 5
0, and Q consists of hydrogen, halogen, a hydrocarbon group not containing a tertiary α-carbon atom, a halohydrocarbon group having at least two carbon atoms between the halogen atom and the phenyl nucleus, and a hydrocarbonoxy group. Indicates a monovalent substituent selected from the group.

More preferred polyphenylene ether resins are those in which each Q has an alkyl group, more preferably 1 to 4 alkyl groups, and the most preferred polyphenylene ether resin is poly(2,6-dimethyl-1,4 phenylene) ether. .

The polystyrene resin contained in the polyphenylene ether resin in the present invention includes polystyrene resins used for general molding materials and so-called high-impact polystyrene modified with butadiene rubber to improve impact strength.

As a mixing method to obtain a resin composition consisting of polyphenylene ether and polystyrene resin, any method may be used as long as it enables sufficient dispersion and mixing of these two resins, and generally an extruder, A melt kneading method using a kneader, open rolls, etc. is employed.

In addition to polyphenylene ether and polystyrene resin, the polyphenylene ether resin in the present invention includes block copolymers such as styrene-butadiene block copolymer as an impact strength enhancer, and various rubber components such as ethylene-vinyl acetate copolymer. It may contain a small amount of rubber, ethylene-propylene-diene monomer terpolymer, ethylene-ethyl acrylate copolymer, styrene-butadiene copolymer rubber, etc. Its content is 20% by weight or less based on the polyphenylene ether resin.

In addition, the polyphenylene ether resin in the present invention is
A small amount of resin additives such as flame retardants, ultraviolet absorbers, lubricants, stabilizers, and antistatic agents may be included, and the content thereof is 20% by weight or less based on the polyphenylene ether resin.

[Polyfluorinated vinylidene resin]

As the polyvinylidene fluoride resin in the present invention,
Homopolymers of vinylidene fluoride or copolymers containing vinylidene fluoride as a main component with other vinyl monomers may be mentioned, and other vinyl monomers used for copolymerization with vinylidene fluoride include hex-4)-fluoro Examples include fluorine-based monomers such as propene, pentafluoropropene, chlorotrifluoroethylene, and other vinyl monomers.

The amount of other vinyl monomers used is preferably 20% by weight or less, more preferably 10% by weight or less.

Furthermore, the polyvinylidene fluoride resin in the present invention may contain a small amount of other resin components (the content thereof is as follows:
The content in the polyvinylidene fluoride resin is preferably 20% by weight or less, more preferably 10% by weight or less.

Furthermore, the polyvinylidene fluoride resin in the present invention may contain a small amount of resin additives such as flame retardants, ultraviolet absorbers, lubricants, stabilizers, and antistatic agents, and the amount added is 20% of the polyvinylidene fluoride resin. % by weight or less.

As the polyvinylidene fluoride resin, commercially available polyvinylidene fluoride resins such as KF Polymer manufactured by Kureha Kagaku ■, Dulite manufactured by DuPont, Dyflor' manufactured by Dynamite Nobel, etc. can also be used.

[Production method of resin composition]

The resin composition of the present invention is composed of a polyphenylene ether resin (A), a polyvinylidene fluoride resin (B), and a graft polymer produced by a macromonomer method, and the blending ratio of the resin (A) and the resin (B) is is resin (A
) is preferably 10 to 90 parts by weight, and 90 to 10 parts by weight of resin (B), and the blending ratio of the graft polymer is 3 to 30 parts by weight per 100 parts by weight of the total amount of resin (A) and resin (B). Preferably.

If the amount of resin (A) or resin (B) is less than 10 parts by weight, the properties of the resin will not be reflected in the physical properties of the resin composition, which is not preferable. Furthermore, if the amount of the graft polymer is less than 3 parts by weight, the compatibilizing effect will be insufficient, and if it exceeds 30 parts by weight, the physical properties of the resin composition will deteriorate and it will be disadvantageous in terms of cost, which is not preferable.

The resin composition of the present invention can be produced by melt-kneading the three components of resin (A), resin (B), and graft polymer using a conventional blending method, such as an extruder, kneader, open roll, etc. easily obtained. A preferred method for obtaining a resin composition for pellets is a method of mixing using a Henschel mixer or the like, followed by heating, melting, kneading, and extrusion using an extruder or the like, and cutting the resultant into pellets.

The pellet-like composition thus obtained can be processed into a molded article of a desired shape by, for example, injection molding, press molding, extrusion molding, blow molding, or the like.

The resin composition of the present invention contains well-known additives such as plasticizers, pigments, flame retardants, reinforcing fibers such as glass fibers and carbon fibers, inorganic/organic fillers, stabilizers, and impact strength improvers. An appropriate amount of an elastomer or the like as an agent can be contained.

[Effect]

The graft polymer used in the present invention acts as a compatibilizer to firmly adhere the interface of different polymers of polyphenylene ether resin (A)/polyvinylidene fluoride resin (B),
Achieving fine dispersion provides a resin composition with excellent performance. q indicates that the graft polymer used in the present invention has polymer units compatible with the resin (A) and resin (B).
) is made possible by having polymer units that are compatible with each other in the molecule at the same time. According to the present invention, polyphenylene ether resin has excellent heat resistance, dimensional stability,
It is possible to obtain a resin composition that has electrical properties, mechanical strength, water resistance, etc., and the excellent weather resistance, oil resistance, chemical resistance, toughness, non-adhesion, etc. of polyvinylidene fluoride resin.

The present invention will be described in more detail below with reference to Reference Examples, Examples, and Comparative Examples. All percentages listed on each side are by weight.
and parts mean parts by weight.

Reference Example 1 Production of styrene-methyl methacrylate graft polymer I In a glass flask equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer, 400 parts of distilled water and 5 parts of polyvinyl alcohol (Kuraray Ql% Hover/1z420) were added. % aqueous solution, 10 parts of calcium phosphate suspension (Super Thai manufactured by Nihon Kagaku Kogyo ■), 5 parts of sodium dodecylbenzenesulfonate (Emar 2F manufactured by Kao ■)
% aqueous solution was charged. A solution prepared by dissolving 20 parts of a polymethyl methacrylate macromonomer (macromonomer AA-6 manufactured by Toagosei Chemical Industry Co., Ltd.) with a terminal methacrylate type and 2 parts of azobisisobutyronitrile in 80 parts of a styrene monomer was placed in a dropping funnel. After heating the flask to set the temperature of the internal liquid at 80°C, the monomer mixture was added dropwise from the dropping funnel over 1 minute. 8 at 80°C
The polymerization was completed after a period of time. During this time, the rotation speed of the stirrer was 3.
It was kept at 40 rpm. No problems such as bronking occurred during the reaction. After the reaction, the mixture was filtered, pickled, washed with water, and dried under reduced pressure to obtain 91 parts of a solid styrene-methyl methacrylate graft polymer. The styrene equivalent molecular weight by GPC was Mn=42,000 and Mw=150,000, and no peak of residual macromonomer was observed in the GPC chart.

Reference Example 2 Production of styrene-methyl meccrylate graft polymer (Exactly the same method as Reference Example I except for using 1 part of abbisisobutyronitrile) Suspension polymerization and post-treatment to produce solid styrene -Methyl methacrylate 94 parts of graft polymer were obtained. The styrene equivalent molecular weight by CP'C is Mn=52000 Mw=180000, and GP
No residual macromonomer peak was observed in the C chart.

Reference Example 3 Production of styrene-methyl methacrylate graft polymer■ 70 parts of styrene, 30 parts of macromonomer2. Suspension polymerization and post-treatment were carried out in exactly the same manner as in Reference Example (1) except that 2 parts of azobisisobutyronitrile were used to obtain 93 parts of a solid styrene-methyl methacrylate graft polymer. The styrene equivalent molecular weight by GPC is Mn=34
000 Mw=180000, and no peak of residual macromonomer was observed in the GPC chart.

Example 1 Commercially available polyphenylene ether resin (manufactured by Engineering Plastics Q@, trade name Noryl 534J) 16
0 parts and 290 parts of vinylidene polyfluoride resin were combined with 50 parts of the styrene-methyl methacrylate graft polymer produced in Reference Example 1 using a twin-screw extruder (vent type, rotating in the same direction).

29 mm in diameter, L/D=25). The resin temperature was 250°C. Melt flow index of the resulting blend composition (275°C, 2,1
(under a load of 6 kg), tensile strength (dumbbell-shaped test pieces were prepared from sheets obtained by press-molding pellets of the blend composition at 250°C, and the test was conducted at a tensile speed of 10 mm/min according to JIS K7113), and Impact strength (unnotched and notched impact test specimens were prepared from sheets obtained by press-molding pellets of the blend composition at 250°C, and conducted using a Charpy impact tester according to JTS K7111), load Deflection heat deformation temperature (a test piece was prepared from a sheet obtained by press-molding pellets of the blend composition at 250°C, and the test was carried out under a load of 18.5 kg according to JIS K7207). The results are shown in Table-1.

Example 2 50% of the graft polymer produced in Reference Example 2
Example 1 was carried out in exactly the same manner as in Example 1, except for using The results are shown in Table-1.

Example 3 The same method as in Example 1 was carried out, except that 165 parts of polyphenylene ether resin, 285 parts of polyvinylidene fluoride resin, and 50 parts of the graft polymer produced in Reference Example 3 were used as the graft polymer. The results are shown in Table-1.

Comparative Example A process was carried out in exactly the same manner as in Example 1, except that 200 parts of polyphenylene ether resin and 300 parts of polyvinylidene fluoride resin were used, and no graft polymer was used. The results are shown in Table-1.

In Table 1, PP01PVDF and CP represent polyphenylene ether resin, polyvinylidene fluoride resin, and graft polymer, respectively.

Table 1 (c) Effects of the Invention As specifically shown in the Examples, the resin composition of the present invention has a polyphenylene ether resin and a polyvinylidene fluoride resin that are densely mixed together by the action of the graft polymer. This makes it possible to produce molded products with improved strength and appearance that combine the excellent properties of both resins.
Industrially useful.

Claims (1)

[Claims] 1. A polyphenylene ether resin (A), a polyvinylidene fluoride resin (B), and a macromonomer method containing both a unit compatible with the resin (A) and a unit compatible with the resin (B). A resin composition consisting of a graft polymer.