JPH0426345B2 - - Google Patents

Description

[Detailed description of the invention]

(1) Purpose of the invention [Field of industrial application] The present invention relates to resin compositions that are used in a wide range of applications for general consumption and industrial use, and among them, polyphenylene ether resin compositions that have recently attracted particular attention. It is related to. [Prior art and its problems] With the remarkable development of the polymer chemical industry in recent years, a large number of polymer materials are being used in a wide range of everyday products, industrial goods, vehicles, office machines, building materials, etc. 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, and we can feel the trends of the times in consumer trends. I can do it. Under these circumstances, even in the field of conventional general-purpose resins, efforts are being made to improve and modify them by various methods in order to respond to the diversifying needs of the market. Improvements and improvements made to meet the diversifying uses of existing resins
One of the methods of modification that has recently attracted attention is a method using polymer blends. This method of mixing different polymers in order to take advantage of the characteristics of resins and compensate for their shortcomings can flexibly respond to the diversifying needs of resin users, avoid wasting resources due to excessive quality, and create new It has the advantage of being able to reduce the inevitable investment burden for resin research and development. Polystyrene resin is a representative general-purpose plastic, along with polyolefin and polyvinyl chloride. Polystyrene resin has extremely excellent moldability. () Excellent transparency and easy coloring. () High dimensional accuracy. () It is lightweight. () Good water resistance. () It is cheap. Because it has such favorable properties, it is consumed in large quantities for everyday miscellaneous goods. On the other hand, it has a weakness in impact strength, so it cannot be used at all for applications that require mechanical strength, especially impact strength. High-impact polystyrene was developed to compensate for these drawbacks of polystyrene resin, and it absorbs impact stress and provides resistance to impact force by dispersing elastomer components in the resin matrix. be. Although this material has lost its transparency, it has 5 to 10 times the impact strength of general grade polystyrene.
Like general polystyrene, it is consumed in large quantities in fields where transparency is not particularly required. Polyphenylene ether is an engineering plastic that has received a lot of attention in recent years due to its excellent mechanical, thermal, and electrical properties, but it has a very high softening point and high melt viscosity, making it difficult to form. is extremely bad. Therefore, it is rarely used alone as a molded product, but rather by blending it with polystyrene or high-impact polystyrene with good compatibility. By blending polyphenylene ether with polystyrene, moldability is improved and the price is also advantageous. This polymer alloy is generally available under the trade name Noryl, a product of General Electric Company, USA, and Zylon, a product of Asahi Kasei Corporation, and is attracting attention as a resin with growth properties. In particular, the growth rate of consumption in recent years has been outstanding compared to other engineering plastics, and they are being used in applications where general-purpose plastics cannot meet performance requirements, such as automobile interior materials and office equipment. ing. ABS resin is acrylonitrile, butadiene,
It is a thermoplastic resin composed of three types of monomers, styrene, and has an excellent balance of mechanical properties, especially impact resistance, rigidity, and hardness, as well as excellent dimensional stability, moldability, and secondary processability, and a beautiful appearance. It is a resin that has The properties of ABS resin can be changed over a wide range by changing the combination or composition of the three types of monomers, and many grades are manufactured by various manufacturers. ABS resin's ability to change its physical properties continuously has resulted in it being often used as one component of polymer alloys. For example, polymer alloys with excellent moldability, flame retardancy, and impact resistance, obtained by blending ABS resin with polyvinyl chloride resin, are already in use in considerable quantities. Generally MBS, which replaces acrylonitrile in ABS resin with methyl methacrylate to increase transparency.
Resins known as resins are often used as impact modifiers for polyvinyl chloride resins. In addition, polymer blend products are now on the market that have improved moldability by blending polycarbonate resin with ABS resin, improved the notch dependence of impact strength, and reduced costs. Due to its excellent impact resistance, this polymer blend product has been used in some automobile bodies, where conventional plastic materials could not be used, and is praised for increasing the potential of thermoplastics. As a graft copolymer resin in which polybutadiene in ABS resin is replaced with other rubber components,
Known examples include AES resin (using EPDM rubber), AAS resin (using acrylic rubber), and ACS resin (using chlorinated polyethylene). Each of these resins has characteristics based on differences in rubber components, but the main objective was to solve the poor weather resistance of butadiene rubber in ABS resin by using other rubbers. Attempts to blend polystyrene, polyphenylene ether, or blends thereof with ABS resin, etc. are considered to be very interesting and of great practical value. As mentioned above, polystyrene and polyphenylene ether have the disadvantage of poor impact resistance, while high-impact polystyrene, which is blended with polyphenylene ether to solve this disadvantage, has a low surface gloss of molded products and a poor appearance. It has poor gasoline resistance, and physical properties such as surface hardness, mechanical strength, and heat resistance.
It is inferior to ABS resin. The physical properties of polyphenylene ether blend products, such as impact strength, gloss, and heat distortion temperature, are almost entirely due to the characteristics of the high-impact polystyrene that is blended with them. What kind of high-impact polystyrene is selected is extremely important. Polyphenylene ether polymer blend products blended with the aforementioned high-impact polystyrene are used as the final product for household items, electrical appliances, office equipment, automobile interiors, etc. in which this resin is used, due to the poor surface gloss derived from high-impact polystyrene. It is often not liked by consumers. In particular, the higher the quality of the product, the more important the aesthetic elements, such as the impression created by the product's appearance, become important issues. There have been surprisingly few attempts to blend polyphenylene ether resins, polystyrene resins, or mixtures thereof with ABS resins and the like. The reason for this is that even if the two resins, which are not compatible with each other, are simply mixed together, they will phase separate immediately, and these regions will not have sufficient mutual adhesion, resulting in a brittle molded product with low strength. Therefore, in order to obtain a molding material with physical properties that can withstand practical use by blending polyphenylene ether resin and ABS resin, some kind of ingenuity is required to achieve compatibility. Blends of styrenic resins into polyphenylene ethers are extensively described in US Pat. No. 3,383,435. Here, the styrenic resins include polystyrene, high impact polystyrene,
It mentions blended products using ABS resin. However, industrial interest has focused exclusively on high impact polystyrene. This is due to the compatibility limitations mentioned above. U.S. Patent No. 4,360,618 discloses a low nitrile content product with an acrylonitrile content of 2 to 8%.
It is reported that a blended product with both heat distortion temperature and impact strength was obtained using ABS resin. Examples of this patent show that the blended product has significantly superior impact strength and heat distortion temperature compared to blended products using general-purpose ABS resin, and also superior to those made using high-impact polystyrene. It has been shown that the thermal deformation temperature is comparable to the impact strength. In addition, in JP-A-59-49259, the content of acrylonitrile in ABS resin is limited to a lower level than usual to achieve a certain degree of compatibility improvement, and a thermoplastic resin composition with high impact strength and excellent gloss. getting things. However, these methods cannot be called essential solutions, and can be said to have achieved only a moderate degree of compatibility by using a resin with performance between high-impact polystyrene and ABS resin. In other words, it can be interpreted as an acceptance of a compromise in performance in order to obtain a certain degree of compatibility. In the above example, in order to mix resins that are essentially incompatible, one resin (ABS resin) is brought close to the other resin (polyphenylene ether resin), but this approach In order to obtain the desired polymer blend product, it is necessary to specify the resin that will be the raw material, which results in an increase in time, expense, and labor. Therefore, it is difficult to say that this is a wise method because it goes against the spirit of polymer blending, which is to freely combine various resins to obtain resins with excellent physical properties with easy operation and low cost. It would be of great practical value if a small amount of a compatibilizer could be added as a third component in addition to the resin to be blended to improve the miscibility of each component polymer. Generally, block polymers and graft polymers having different types of polymer segments in the same molecule are said to be effective as the third component for achieving such compatibilization. Block polymers can usually be synthesized by anionic polymerization, but it is difficult to maintain appropriate reaction conditions and the types of polymers that can be synthesized are extremely limited. Graft polymerization is usually carried out by peroxide chain transfer method, radiation grafting method, polymer initiator method, etc. However, these methods generally have extremely low grafting efficiency, difficult to control molecular weight and composition, and are difficult to synthesize. The types of polymers possible are also limited. Therefore, if block polymers and graft polymers that can be used as compatibilizers when blending different types of polymers could be synthesized cheaply and easily, and in a way that allows the molecular structure and molecular weight of the composition to be controlled as desired, Its technical and economic value would be enormous. (2) 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 with the aim of obtaining a blend molding material with excellent performance. As a result of investigation, we discovered that the objective could be achieved by using a graft polymer produced by the macromonomer method as a compatibilizer in a polymer blend of polyphenylene ether resin and ABS resin, and by blending a specific amount of this, and completed the present invention. did. That is, the present invention involves copolymerizing an aromatic vinyl compound with a vinyl cyanide compound and/or methyl methacrylate in the presence of a polyphenylene ether resin and/or a polystyrene resin (A) and a rubbery polymer. The copolymer resin (B) consists of a copolymer resin (B) and the graft polymer shown below, and the proportion of the graft polymer is
The resin composition contains 3 to 20 parts by weight based on 100 parts by weight of the total amount of the resin (A) and resin (B). Graft polymer: A graft polymer synthesized by the macromonomer method (hereinafter referred to as a graft polymer by the macromonomer method), which is a polymer whose main component is a styrene monomer unit that is compatible with the resin (A) above. unit, and a polymethyl methacrylate or acrylonitrile/styrene copolymer unit that is compatible with the resin (B),
A graft polymer in which one of them is a branch component and the other is a trunk component. [Graft polymer obtained by macromonomer method] The graft polymer obtained by macromonomer method in the present invention is a graft polymer obtained using a macromonomer as a raw material. Moreover, the macromonomer in the present invention means a relatively low molecular weight (1000 to 20000 in number average molecular weight) polymer having a polymerizable functional group at one end of the molecular chain. Examples of the terminal polymerizable functional group of the macromonomer in the present invention include an acryloyloxy group, a methacryloyloxy group, an allyloxy group,
Examples include vinyl polymerizable groups such as styryl groups. The most preferred terminal functional group is a methacryloyloxy group. The polymer skeleton in the macromonomer needs to be a polymer mainly composed of styrene monomer units represented by polystyrene, polymethyl methacrylate, or an acrylonitrile/styrene copolymer. The number average molecular weight of the above macromonomer is determined by gel permeation chromatography (hereinafter referred to as GPC).
) is the polystyrene equivalent molecular weight,
The measurement conditions are as follows. Equipment: High performance liquid chromatography (e.g., Toyo Soda Kogyo Co., Ltd., product name HLC-802UR) Column: Polystyrene gel (e.g., Toyo Soda Kogyo Co., Ltd., product names G4000H8 and G3000H8) Elution solvent: Tetrahydrofuran Outflow rate: 1.0 ml/min Column temperature: 40°C Detector: RI detector The graft polymer used in the present invention can be easily synthesized by copolymerization of the radically polymerizable monomer described later and the macromonomer described above. In the method for producing a graft polymer using such a macromonomer, the content of the homopolymer () of the branch and trunk components is extremely small. () The molecular weight of the trunk component, the molecular weight of the entire graft polymer, and the weight ratio of branches and trunk can be easily controlled. () The combination of branch components and trunk components can be freely selected depending on the purpose. With these characteristics, it is possible to easily obtain a high-performance graft polymer that cannot be obtained with conventional graft polymers. An example of the method for producing a macromonomer in the present invention is to polymerize the radically polymerizable monomer to form the aforementioned polymer skeleton in the presence of a chain transfer agent having a carboxyl group in the molecule to form a carboxyl group at one end. An example of this method is to synthesize a polymer having a glycidyl group (hereinafter referred to as a prepolymer), and then react it with a radically polymerizable monomer having a glycidyl group in the molecule. As the chain transfer agent having a carboxyl group in the molecule used in this case, mercaptans such as mercaptoacetic acid, 3-mercaptopropionic acid, 2-mercaptopropionic acid, etc. are preferably used in the sense that they have an appropriate chain transfer constant. However, 3-mercaptopropionic acid and 2-mercaptopropionic acid are particularly preferred because they cause less coloration of the product. Further, as the radically polymerizable monomer having a glycidyl group in the molecule, glycidyl methacrylate (hereinafter abbreviated as GMA), glycidyl acrylate, allyl glycidyl ether, etc. are used, and among these, GMA is particularly preferred. Although the method for producing the macromonomer described above is based on a radical polymerization method using a chain transfer agent, methods other than the radical polymerization method may be used. For example, a method for producing macromonomers by anionic polymerization using an organometallic compound as an initiator is an excellent method for obtaining macromonomers with well-regulated molecular weights. The molecular weight of the prepolymer and macromonomer is
The produced macromonomer may have a number average molecular weight of 1,000 to 20,000, preferably 3,000 to 20,000, as long as it does not impair polymerizability. If the molecular weight is less than 1,000, the degree of polymerization as a polymer unit is too low and the compatibilizing effect of the graft polymer using this material as a raw material is unfavorable, and if it exceeds 20,000, the polymerizability during graft polymer production will decrease. This is not preferred because it tends to cause problems such as phase separation of the reaction system. The method for producing the graft polymer in the present invention is a method of copolymerizing a macromonomer and a radically polymerizable monomer. The radically polymerizable monomer is a monomer selected from the group of compounds consisting of methyl methacrylate, styrene, and a mixture of acrylonitrile and styrene. Such a radically polymerizable monomer forms the backbone component of the graft polymer by copolymerization with the macromonomer, but if the macromonomer used has a polymer skeleton that is compatible with the resin (A), When using a mixture of acrylonitrile and styrene that forms a backbone component that is compatible with resin (B), and when the macromonomer has a polymer skeleton that is compatible with resin (B), A)
Use methyl methacrylate or styrene to form a backbone component that is compatible with Furthermore, in the present invention, other vinyl monomers may be used in combination with the above radically polymerizable monomers, if desired, and such vinyl monomers include methyl acrylate, ethyl (meth)acrylate, butyl (meth)acrylate. and (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate, α-methylstyrene, parachlorostyrene, and vinyl acetate. As the polymerization method, any one of solution polymerization, bulk polymerization, emulsion polymerization, and dispersion polymerization may be used in the presence of a conventionally known radical polymerization initiator. In the graft polymer used in the present invention, units compatible with the resin (A) and units compatible with the resin (B) may be located in either the trunk component or the branch component in the graft polymer molecule. The weight composition of these two types of units in the graft polymer is preferably such that the minor component is 5% or more, more preferably 15% or more. If the minor component is less than 5%, it is not preferable because it becomes almost a single unit in fact, and a great effect as a compatibilizer cannot be expected. Furthermore, in the graft polymer of the present invention, the above-mentioned compatible units are contained in the graft polymer in an amount of 70% by weight.
It is preferably at least 80% by weight, and more preferably at least 80% by weight. Examples of the incompatible unit include units obtained by polymerizing monomers other than the monomers that produce the compatible units, such as vinyl acetate and acrylic ester. Also, regarding the molecular weight of the graft polymer,
Polystyrene equivalent number average molecular weight by GPC
5000 to 200000 is preferable, and 10000 to 100000 is more preferable. If the number average molecular weight is less than 5,000, the polymer unit is too short and a large compatibilizing effect cannot be expected, which is undesirable. If the number average molecular weight exceeds 200,000, the rate of dissolution into the resin to be blended is low, which is undesirable. [Polyphenylene ether resin and/or polystyrene resin (A)] The polyphenylene ether resin in the present invention is mainly composed of polyphenylene ether resin,
This refers to those containing other resins such as polystyrene resins, block copolymers, graft copolymers, etc., if necessary. Polyphenylene ether resin has U.S. patent no.
It has been described in many publications including 3306874 and 3306875. That is, polyphenylene ethers are self-condensation products of monovalent mononuclear phenols made by reacting phenols with oxygen in the presence of copper complex catalysts. 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 50, and Q is hydrogen, halogen,
Indicates a monovalent substituent selected from the group consisting of a hydrocarbon group that does not contain a tertiary α-carbon atom, a halohydrocarbon group that has at least two carbon atoms between a halogen atom and a phenyl nucleus, and a hydrocarbon oxy group. . Preferred examples of polyphenylene ethers include those in which each Q has an alkyl group, preferably 1 to 4 alkyl groups, and the most preferred polyphenylene ether resin is poly(2,6-dimethyl-1, 4phenylene) ether. The polystyrene resin in the present invention is a resin used in general molding materials. When polyphenylene ether resin and polystyrene resin are used together, any mixing 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 adopted. In addition to polyphenylene ether resin and polystyrene resin, the polyphenylene ether resin in the present invention may also contain block copolymers such as styrene-butadiene block copolymer as an impact strength enhancer, and various rubber components such as ethylene-butadiene block copolymer. Vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-propylene-diene monomer 3
A small amount of the original copolymer, styrene-butadiene copolymer rubber, etc. may be contained. The allowable amount of these reinforcing agents added is 20% by weight or less based on the polyphenylene ether resin. In addition, the polyphenylene ether resin in the present invention includes flame retardants, ultraviolet absorbers, lubricants, stabilizers,
A small amount of resin additives such as antistatic agents may be included. The allowable addition amount of these additives is 20% by weight or less based on the polyphenylene ether resin. [Copolymer resin (B) formed by copolymerizing an aromatic vinyl compound with a vinyl cyanide compound and/or methyl methacrylate in the presence of a rubbery polymer] The copolymer resin (B) in the present invention is , means a copolymer resin obtained by polymerizing () an aromatic vinyl compound, () a vinyl cyanide compound, and/or methyl methacrylate in the presence of a rubbery polymer.
Specifically, (a) an ABS resin obtained by graft polymerizing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a butadiene rubber, and (b) an aromatic vinyl compound and methacrylic acid obtained in the presence of a butadiene rubber. Obtained by graft polymerization of methyl
MBS resin (c) AAS resin obtained by graft polymerization of an aromatic vinyl compound and a vinyl cyanide compound in the presence of acrylic rubber (d) A graft polymerization of an aromatic vinyl compound and a vinyl cyanide compound in the presence of chlorinated polyethylene ACS obtained by polymerization
Resin (d) Ethylene-propylene-diene monomer 3
Examples include AES resins obtained by graft polymerizing aromatic vinyl compounds and vinyl cyanide compounds in the presence of the original copolymer rubber.
ABS resin is preferably used. In addition to the above-mentioned aromatic vinyl compound, vinyl cyanide compound, and methyl methacrylate, the monomers to be grafted in these copolymer resins (B) may contain small amounts of other monomers. The content of other monomers in this case is 10% by weight or less in the copolymer resin (B). Examples of aromatic vinyl compounds include styrene, α-
Styrene monomers such as methylstyrene, chlorostyrene, p-methylstyrene, and vinylstyrene are used alone or in combination in any proportion. Generally, styrene is used alone or as a mixture consisting mainly of styrene and containing small amounts of other styrenic monomers. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and acrylonitrile is preferably used. The copolymer resin (B) in the present invention may also contain small amounts of resin additives such as flame retardants, ultraviolet absorbers, lubricants, stabilizers, and antistatic agents. The permissible addition amount of these additives is 20% by weight in the copolymer resin (B).
It is as follows. [Manufacture of resin composition] The resin composition of the present invention is composed of resin (A), resin (B), and a graft polymer produced by a macromonomer method, and the blending ratio of the graft polymer is that of resin (A) and resin. 3 to 20 parts per 100 parts by weight of the total amount of (B)
Parts by weight. The blending ratio of resin (A) and resin (B) is 10 to 90
Parts by weight, preferably 90 to 10 parts by weight of the resin (B). 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. If the amount of the graft polymer is less than 3 parts by weight, the compatibilizing effect will be insufficient, and if it exceeds 20 parts by weight, the physical properties of the resin composition will deteriorate and it will be disadvantageous in terms of cost, which is not preferred. The resin composition of the present invention can be prepared by blending the resin (A), the resin (B), and the graft polymer using a conventional blending method.
For example, it can be easily obtained by melt-kneading using an extruder, kneader, open roll, or the like. A preferred method for obtaining the resin composition is to mix using a Henschel mixer or the like, heat and melt the mixture using an extruder, extrude it, and cut it into pellets. The resin composition of the present invention can also be obtained by adding a graft polymer to a resin that is a mixture of resin (A) and resin (B), for example, a resin generally called high impact polystyrene. The pellet-like composition thus obtained is molded into a desired shape by, for example, extrusion molding, thermoforming, injection molding, or the like. The resin composition of the present invention may contain well-known additives such as plasticizers, pigments, flame retardants, reinforcing agents such as glass filaments or fibers, stabilizers, and the like. [Function] The graft polymer used in the present invention serves as a compatibilizer to firmly adhere the interface between different polymers of resin (A) and resin (B), and achieves fine dispersion, thereby creating a resin composition with excellent performance. give something. This is possible because the graft polymer used in the present invention simultaneously has in its molecule a polymer unit that is compatible with the resin (A) and a polymer unit that is compatible with the resin (B). According to the present invention, polyphenylene ether resin has excellent heat resistance, dimensional stability, electrical properties,
Resin (B) without compromising mechanical strength, water resistance, etc.
It can exhibit impact resistance, surface gloss, and oil resistance. The present invention will be explained in more detail by reference examples, examples, and comparative examples below. In addition, the % stated in each example
All mean percentages by weight and all parts mean parts by weight. Reference Example 1 (Production of methyl methacrylate macromonomer) In a glass flask equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen gas inlet,
350 parts of methyl isobutyl ketone, 100 parts of methyl methacrylate, 0.5 parts of azobisisobutyronitrile,
Charge 1.06 parts of 3-mercaptopropionic acid, heat after introducing nitrogen, and maintain the liquid temperature at 80°C, and add 400 parts of methyl methacrylate, 2.0 parts of azobisisobutyronitrile, and 4.24 parts of 3-mercaptopropionic acid. 1 part of the mixed solution was continuously added dropwise over 3 hours.
After that, when the reaction was continued for another 5 hours, the conversion rate of methyl methacrylate was determined by gas chromatography.
It was 96.8%. After converting from nitrogen bubbling to air bubbling,
Hydroquinone monomethyl ether 0.17 in the reaction solution
1 part, 9.25 parts of glycidyl methacrylate, and 4.25 parts of tetrabutylammonium bromide were added, and the mixture was heated and reacted at 90°C for 10 hours. The reaction conversion rate determined from the acid value of the reaction solution was 95.9%. The reaction solution was poured into 10 times the volume of n-hexane to precipitate it, and then dried under reduced pressure at 80°C to obtain 482 parts of methyl methacrylate macromonomer. Polystyrene equivalent molecular weight by GPC is 10500
(number average) and 20,000 (weight average). Reference Example 2 (Production method of styrene macromonomer) In a glass flask equipped with a stirrer, a reflux condenser, two dropping funnels, a thermometer and a gas inlet,
Charge 500 parts of styrene and 300 parts of butyl acetate, 500 parts of styrene in one dropping funnel (referred to as dropping funnel A), and 12.5 parts of azobisisobutyronitrile in the other funnel (referred to as dropping funnel B).
-21.2 parts of mercaptopropionic acid, butyl acetate
250 parts of the mixture was added. After introducing nitrogen gas, the reaction solution was heated and kept at 90° C., and then added dropwise through dropping funnel A over 4 hours and dropping funnel B over 10 hours.
After heating for another 2 hours, the polymerization conversion rate of styrene is
It became 92.5%. After converting from nitrogen bubbling to air bubbling,
0.3 parts of hydroquinone monomethyl ether, 27.0 parts of glycidyl methacrylate, and 7.5 parts of tetrabutylammonium bromide were added and reacted at 90°C for 9 hours. The reaction addition rate calculated from the acid value is 91.0
It was %. Precipitate the reaction solution in 10 times the volume of methanol and heat at 80°C.
Dry under reduced pressure to obtain solid styrene macromonomer.
Obtained 912 copies. The polystyrene equivalent molecular weight by GPC was 4700 (number average) and 9400 (weight average). Reference Example 3 (Production of styrene-methyl methacrylate graft polymer) In a glass flask equipped with a stirrer, reflux condenser, dropping funnel, thermometer and gas inlet,
800 parts of styrene, 200 parts of toluene, and 200 parts of the methyl methacrylate macromonomer produced in Reference Example 1 were charged, and a solution of 5 parts of azobiscyclohexanecarbonitrile and 100 parts of toluene was placed in the dropping funnel. After nitrogen was introduced into the flask, the initiator solution from the dropping funnel was added dropwise over 1 hour while heating and raising the temperature and keeping the reaction solution at 100°C. After aging for 3 hours, 5 parts of azobiscyclohexanecarbonitrile and 200 parts of toluene were added, and the mixture was reacted for an additional 2 hours. This solution was poured into a metal vat and dried under reduced pressure at 80°C to obtain 937 parts of a solid styrene-methyl methacrylate graft polymer. Polystyrene equivalent molecular weight by GPC is 32,000 (number average) and 141,000
(weight average). The composition of the obtained graft polymer was 79% by weight of the trunk component consisting of styrene units and 21% by weight of the branch components consisting of methyl methacrylate units. Reference Example 4 (Production of styrene-methyl methacrylate graft polymer) In a glass flask equipped with a stirrer, reflux condenser, dropping funnel, thermometer and gas inlet,
A solution containing 200 parts of toluene, 5 parts of azobisisobutyronitrile, 300 parts of toluene, 666 parts of methyl methacrylate, and 333 parts of the styrene macromonomer produced in Reference Example 2 were placed in a dropping funnel. After introducing nitrogen into the flask, the solution in the dropping funnel was added dropwise over 4 hours while heating and raising the temperature and keeping the reaction solution at 90°C. After aging for 2 hours, 5 parts of azobisisobutyronitrile and 200 parts of toluene were added, and the mixture was reacted for an additional 2 hours. This solution was poured into a metal vat and dried under reduced pressure at 80°C to obtain 982 parts of a solid styrene-methyl methacrylate graft polymer. The polystyrene equivalent molecular weight of this graft polymer by GPC was 25,000 (number average) and 131,000 (weight average). The composition of the obtained graft polymer was 66% by weight of the trunk component consisting of methyl methacrylate units and 34% by weight of the branch component consisting of styrene units. Reference Example 5 (Production of styrene-acrylonitrile graft polymer) In a glass flask equipped with a stirrer, reflux condenser, dropping funnel, thermometer and gas inlet,
Charge 500 parts of toluene and 30 parts of the styrene macromonomer produced in Reference Example 2, and add 37.5 parts of styrene, 12.5 parts of acrylonitrile, and 30 parts of toluene to the dropping funnel.
part, azobiscyclohexanecarbonitrile 0.8
Add the mixture of 1 part to 1 part. After nitrogen was introduced, the temperature was raised, and the solution in the dropping funnel was added dropwise over 2 hours while the reaction solution was kept at 100°C. After reacting for an additional 2 hours, 0.8 part of azobiscyclohexanecarbonitrile was added and the mixture was aged for 2 hours. The polymerization conversion rate of styrene determined by gas chromatography was 97.8%. The reaction solution was poured into 10 times the volume of n-hexane to cause precipitation. Dry under reduced pressure at 80℃ to form solid styrene.
74.3 parts of acrylonitrile graft polymer were obtained. The polystyrene equivalent molecular weight of this polymer by GPC is 22,000 (number average) and 105,000 (weight average)
It was hot. In addition, the composition of the obtained graft polymer was 62% by weight of the trunk component consisting of styrene units and acrylonitrile units, and 38% by weight of the branch components consisting of styrene units, and the styrene units and acrylonitrile units accounted for 62% by weight of the above-mentioned trunk component. The proportions were 46% by weight of styrene units and 16% by weight of acronitrile units. Comparative Reference Example 1 A solution consisting of 50 parts of polystyrene, 100 parts of benzene and benzoyl peroxide was maintained at 80°C and stirred for 2 hours, and then methyl ethyl ketone was added.
Added 300 copies. The resulting solution was poured into methanol to obtain polystyrene containing active oxygen as a precipitate. A graft polymer was synthesized by dissolving 20 parts of the above active oxygen-containing polystyrene in a solution consisting of 45 parts of styrene and 15 parts of acrylonitrile, and maintaining the resulting solution at 130°C for 6 hours. Comparative Reference Example 2 A solution consisting of 50 parts of ABS resin, 100 parts of benzene and 2 parts of benzoyl peroxide was maintained at 80°C and stirred for 2 hours, and then methyl ethyl ketone was added.
Added 300 copies. The resulting solution was poured into methanol to obtain an ABS resin containing active oxygen as a precipitate. Next, 20 parts of ABS resin containing active oxygen was dissolved in 80 parts of styrene, maintained at 110°C for 5 hours, and then further maintained at 140°C for 2 hours.
A graft polymer was synthesized. Examples 1 and 2 (Polystyrene/ABS resin composition) 100 parts of commercially available general polystyrene resin and 100 parts of ABS resin were blended together with 20 parts of the graft polymer produced in Reference Example 3 or Reference Example 5 using a twin-screw extruder. did. The extruder jacket temperature was 170°C. Test pieces prepared from this blend were subjected to a tensile test and a Charpy impact test. However, tensile test: According to JIS K7113, tensile speed 5
It was done in mm/min. Sharpie impact test: Conducted without notches according to JIS K7111. Comparative Examples 1 to 3 Resin compositions were prepared in the same manner as in Example 1 with no graft polymer added and those with 2 times and 60 parts of the graft polymer added, and were subjected to each test. The test results are shown in Table 1. Examples 3 to 5 (Polyphenylene ether resin/ABS resin composition) 100 parts of commercially available polyphenylene ether resin (polyphenylene ether content of 30%...hereinafter referred to as resin a) and 100 parts of ABS resin was blended with 20 parts of the graft polymer of Reference Example 3, Reference Example 4, or Reference Example 5 in a twin screw extruder. The extruder jacket temperature was 200°C. A test piece prepared from this blend was subjected to a tensile test and a Charpy impact test in the same manner as in Example 1. The test results are shown in Table 2. Comparative Example 4 A resin composition was prepared in the same manner as in Example 3, except that no graft polymer was added, and was subjected to each test. The test results are shown in Table 2. Examples 6 and 7 (Polyphenylene ether resin/ABS resin composition) 100 parts of commercially available polyphenylene ether resin (polyphenylene ether content of 70%...hereinafter referred to as resin a') and 100 parts of ABS resin 1 part were blended with 10 parts of the graft polymer of Reference Example 4 or Reference Example 5 in a twin screw extruder. The extruder jacket temperature was 200°C. A test piece prepared from this blend was subjected to a tensile test and a Charpy impact test in the same manner as in Example 1. The test results are shown in Table 3. Comparative Example 5 A resin composition was prepared in the same manner as in Example 6 except that no graft polymer was added, and was subjected to each test. The test results are shown in Table 3. Example 8 and Comparative Examples 6 to 8 100 parts of polyphenylene ether [manufactured by Japan GE Plastics Co., Ltd., trade name Noryl 534J] and ABS
From a resin composition obtained by mixing each component using 100 parts of resin [manufactured by Japan Synthetic Rubber Co., Ltd., trade name ABS12] and 16 parts of the following graft polymer or without using the graft polymer. Physical properties of the molded test pieces were measured in the same manner as in each of the above examples. Γ Example 8 Graft polymer consisting of 25 parts of polymethyl methacrylate type macromonomer and 7 parts of styrene (manufactured by Toagosei Kagaku Kogyo Co., Ltd., trade name: Rezada GP)
−200). Γ Comparative Example 6 Graft polymer of Comparative Reference Example 1. Γ Comparative Example 7 Graft polymer of Comparative Reference Example 2. Γ Comparative Example 8 No graft polymer was used. The measurement results are as follows.

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[Table] (3) Effects of the invention The resin composition of the present invention uses an excellent graft polymer as a compatibilizer, so that the resin (A)
It has improved miscibility with (B) and has excellent tensile strength, elongation, and impact strength, as well as surface gloss and oil resistance, making it particularly useful industrially as a molding material.

Claims (1)

[Claims] 1. Copolymerization of an aromatic vinyl compound with a polyphenylene ether resin and/or a polystyrene resin (A), a vinyl cyanide compound and/or methyl methacrylate in the presence of a rubbery polymer. A resin consisting of a copolymer resin (B) made of Composition. Graft polymer: A graft polymer synthesized by the macromonomer method, which is a graft polymer synthesized by the above resin.
Polymer units mainly composed of styrene monomer units that are compatible with (A) and polymethyl methacrylate or acrylonitrile that are compatible with resin (B) /
A graft polymer consisting of styrene copolymer units, one of which is a branch component and the other is a trunk component.