JPS6154337B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides an improved resin composition, particularly a polyphenylene ether resin, which is characterized by incorporating a specific hydrocarbon resin derived from petroleum or coal and a relatively large amount of inorganic filler, which impairs moldability. The present invention relates to a polyphenylene ether resin composition that can be molded into molded articles having high rigidity and high dimensional stability without any problems. Polyphenylene ether resin is well known as a thermoplastic resin with excellent physical properties such as mechanical properties, electrical properties, chemical resistance, and heat resistance. If higher rigidity and dimensional stability are sought, the screw torque during extrusion becomes excessive, and even if the resin temperature is raised to near the decomposition temperature of the resin, the torque will be excessive. Further, even if the torque capacity of the screw is increased, resin decomposition due to shear heat generation and a surging phenomenon in the strands occur, resulting in extremely poor productivity. In addition, such compositions have poor fluidity during injection molding, so they are rarely used for large-sized molded products. Furthermore, it has been evaluated that the surface appearance of molded products is poorer than that of other resins blended with inorganic fillers due to the lifting of fillers such as glass.
For the reasons mentioned above, at present, polyphenylene ether resin compositions containing an inorganic filler of 15 parts by weight or more, particularly 20 to 30 parts by weight, have only low marketability. Furthermore, because of its extremely poor extrusion processability, there is currently no commercially available great polyphenylene ether resin composition having an inorganic filler content of 30 parts by weight or more. The present invention solves the drawbacks of these inorganic filler-containing polyphenylene ether resins by adding a hydrocarbon resin derived from petroleum or coal. The object of the present invention is to provide a new and improved polyphenylene ether resin composition that can exhibit a molded product appearance, good flowability, and high rigidity. The polyphenylene ether resin contains 1 to 60 parts by weight of a highly unsaturated hydrocarbon resin in cracked naphtha obtained by cracking petroleum to substantially maintain the various properties of the polyphenylene ether resin, especially for injection. A resin composition intended to provide a material suitable for molding is disclosed in Japanese Patent Publication No. 57-13584, but it has been confirmed that the impact strength of this resin composition is greatly reduced, making it difficult to use in practical applications. It cannot be denied that there are restrictions. Furthermore, the resin composition disclosed in JP-A No. 47-3136 also causes a decrease in impact strength. In contrast, the present invention contains (a) 20 to 100 parts by weight of polyphenylene ether resin, (b) 0 parts by weight of vinyl aromatic polymer.
~80 parts by weight, (c) one or more of aromatic hydrocarbon resin obtained from petroleum naphtha, tenpen phenolic resin, and coumaron indene resin derived from coal tar of (a) and ( b) total
5 to 60 parts by weight, preferably 10 parts by weight per 100 parts by weight
~40 parts by weight, and (d) an inorganic filler was blended at a ratio of 51 to 200 parts by weight, preferably 51 to 150 parts by weight, based on a total of 100 parts by weight of (a), (b) and (c). It is something. The resin composition thus obtained maintains the physical properties of polyphenylene ether resin, including impact strength, while improving fluidity during molding, and has a high content of inorganic filler, which was previously considered impossible. For example, a content of 80 to 150 parts by weight (45 to 60%) can be made possible, and thus a molded product with excellent rigidity, dimensional stability, surface appearance, etc. can be molded with satisfactory molding performance. It is a suitable resin composition. In the composition of the present invention, the polyphenylene ether used as component (a) has the general formula (In the formula, the ether type oxygen atom of one unit is connected to the benzene nucleus of the next adjacent unit, and n is at least
is an integer of 50, and each Q is a hydrogen, a halogen, a hydrocarbon group having no tertiary α-carbon atom,
a monovalent substituent selected from a hydrocarbonoxy group and a halohydrocarbonoxy group having at least two carbon atoms between the halogen atom and the phenyl group. Particularly preferred polyphenylene ethers for the purposes of the present invention are those having alkyl substituents in two positions ortho to the ether type oxygen atom, i.e., where Q is
Each is an alkyl group, particularly preferably a methyl group, a typical example of which is poly(2,6-dimethyl-1,
4-phenylene) ether. Preferably, the polymer has an intrinsic viscosity of about 0.5 as measured in chloroform at 25°C. The vinyl aromatic polymer which is component (b) in the composition of the present invention contains at least 25 parts by weight of repeating units derived from a vinyl aromatic compound represented by the following formula. Here, R is hydrogen, a lower alkyl group or a halogen, Z is a vinyl group, hydrogen, a halogen or a lower alkyl group, and P is 0 or an integer from 1 to 5. The term "lower alkyl group" as used herein means an alkyl group having 1 to 6 carbon atoms. Such polystyrene resins include not only homopolymers represented by polystyrene or polystyrene chloride, but also natural or synthetic rubbers such as polybutadiene polyisoprene, butyl rubber,
EPDM rubber, ethylene propylene copolymer,
Natural rubber, polysulfide rubber, polyurethane rubber, etc. modified, styrene acrylonitrile copolymer, styrene butadiene copolymer, styrene maleic anhydride copolymer, styrene acrylonitrile butadiene terpolymer,
Poly-α-methylstyrene, ethylvinylbenzene and divinylbenzene copolymers, A-B-A and A-B type copolymers (where A is polystyrene and B is a diene elastomer such as polybutadiene or polyisoprene), grafts of polystyrene and polybutadiene, and Examples include radial block copolymers and styrene-butadiene-modified acrylic resins. The aromatic hydrocarbon resin obtained from petroleum naphtha, which is the component (c) of the composition of the present invention, contains highly unsaturated hydrocarbon components in cracked naphtha obtained by cracking petroleum, and its main component is is an aromatic hydrocarbon oligomer obtained by polymerizing an unsaturated hydrocarbon mixture, which is an unsaturated aromatic hydrocarbon represented by mixed vinyl toluene and mixed vinyl xylene, and has a polymerization degree of 5 to 20, preferably 10 to 15
The ball-and-softening point defined by ASTM is 70°C to 160°C, and it is commonly called ``coumaron'', which is derived from a mixture of unsaturated polycyclic aromatic hydrocarbons contained in the light fraction produced by carbonization of resin and coal. A resin called "indene resin" and a terpene phenolic resin derived from petroleum naphtha have a ball and softening point of 70.
One or more types of resins having a temperature of 150°C to 150°C can be used. The inorganic filler that is the component (d) of the composition of the present invention may be one or more of inorganic fillers such as glass fiber, glass beads, glass flakes, clay mica, carbon fiber, metal fiber, metal flakes, and talc. Includes combinations. These ingredients include 20 to 100 parts by weight of (a) and 0 to 100 parts by weight of (b).
80 parts by weight, (c) 5 to 60 parts by weight, preferably 10 to 40 parts by weight, based on the total of 100 parts by weight of (a) and (b), (d)
51 to 100 parts by weight of (a), (b) and (c)
It is blended in a proportion of 200 parts by weight, preferably 51 to 150 parts by weight. If desired, the above-mentioned components (a) and (b) may be used in a form in which a part or all of them are graft copolymerized with each other. The compositions of the invention may further contain flame retardants, flame retardant aids, processing aids, pigments, dyes, stabilizers, plasticizers, etc. for their customary purposes. The compositions of the invention may be prepared in any conventional manner. For example, a preferred method involves mixing powdered or pelleted materials, extruding the mixture into strands, and chopping the strands into pellets. The pellets can be molded into the desired shape by conventional methods, such as injection molding. The present invention will be explained in more detail with reference to Examples below. In the following examples, all resin compositions were prepared in the following manner. First, the ingredients were thoroughly mixed in a Henschel mixer. In this way, the cylinder temperature is
The mixture was passed through a twin-screw extruder set at 280-300°C to form pellets in a melt-kneader. The pellets were injection molded at a mold temperature of 70°C using an injection molding machine set at a cylinder temperature of 250-300°C. Physical testing of the compositions was conducted in the following manner. That is, the heat distortion temperature was measured under a stress of 18.6 kg/ ^cm2 , the notched Izo impact strength was measured using a 1/8 x 1/2 x 2 1/2 inch test piece, and the tensile strength was measured using an ASTM No. 5 dumbbell. . Melt index shows the measured value at 300℃ and 10kg. Poly(2,6-dimethyl-) used as component (a)
1,4-phenylene) oxide resin (hereinafter referred to as PPO)
) is in powder form with an intrinsic viscosity of 0.45~
It was 0.5d/g. As other composition components, products having respective characteristics were arbitrarily selected as shown below and used in the following Comparative Examples and Examples. Therefore, each component used in these comparative examples and examples is only used as a representative example, and any component can be used within the scope of the present invention as long as it has the same or similar characteristics. be able to. The components used in the following comparative examples and examples are diene-modified polystyrene resin (hereinafter referred to as component (b)).
Mitsubishi Monsanto Chemical Industries, Ltd. (referred to as HIPS)
The product name is Dialex HT-644 manufactured by Co., Ltd., the component (c) is Picco 6146 manufactured by Rika Hercules Co., Ltd. as an aromatic hydrocarbon resin, and the Picofin D- manufactured by Rika Hercules Co., Ltd. as a terpene phenolic resin. 125 (Piccophyn D-125) was used. As the component (d), chopped grass (trade name: CS-471S) manufactured by Nittobo Co., Ltd. was used. Furthermore, Pico
6146 is an oligomer mixture of vinyltoluene and vinylxylene (molecular weight 1370), Picofin D-125 is a terpene-phenol resin (weight average molecular weight
1750). As a comparative example for component (c), α-pinene resin (weight average molecular weight 800) manufactured by Rika Hercules was used. In addition, Zylon H is a commercially available product (manufactured by Asahi Kasei) that is mainly composed of a graft copolymer of polyphenylene ether and styrene, and according to the analysis of the present inventors,
Approximately 60% by weight of PPO and approximately 40% polystyrene component
It is estimated to be % by weight. The results of tests using resin compositions prepared by appropriately combining these various components (additives if necessary) are shown in the table below.

[Table] In Table 1, Comparative Example 1 (81.8 parts of inorganic filler per 100 parts of resin) and Comparative Examples 1 and 2 (81.8 parts and 1500 parts of inorganic filler per 100 parts of resin, respectively) In Example 1, it was "impossible to extrude", whereas in Example 1, the chopped glass
“Easy” despite being filled with 45% by weight.
It may be noted that in Example 2, the extrudability was significantly improved to "fair" even though the amount of chopped glass filled reached 60% by weight. Furthermore, the glass filling amount of Examples 1 and 2 was 45 and 60.
The weight percent was previously thought to be impossible for a modified polyphenylene ether resin, and the bending elastic modulus of 155,800 kg/cm ² when filled with 60 weight percent glass is close to the elastic modulus of metal even though it is a thermoplastic resin. It deserves to be evaluated as such. What is further noteworthy is that the reduction in Izot impact strength due to glass filling seen in the Comparative Examples is not observed in the Examples, but on the contrary, it tends to increase.

[Table] Table 2 shows that it is possible to fill as much as 45% by weight chopped glass only when a specific hydrocarbon resin is added. That is, comparative example 2
In this case, extrusion was impossible due to torque over, strand surging, and resin decomposition. Further, in Comparative Example 3, the glass in the strand appeared to be repelled from the resin, and although the torque was sufficiently low, extrusion was not possible. This seems to be because the added resin did not have sufficient affinity for the PPO resin. On the other hand, in Examples 3 and 4, good extrusion was achieved. This indicates that the resin additive effective in the present invention is a specific hydrocarbon resin.

【table】

[Table] As is clear from Table 3, in Comparative Example 4 which does not contain Pico 6140 (aromatic hydrocarbon resin),
Although extrusion was impossible due to occurrence of torque over and strand surging, in Example 5 of the present invention, high rigidity and easy extrusion were achieved.

Claims (1)

[Scope of Claims] 1 (a) 20 to 100 parts by weight of polyphenylene ether resin, (b) 0 to 80 parts by weight of vinyl aromatic polymer, (c) aromatic hydrocarbon resin obtained from petroleum naphtha, terpene (a) and (b) a total of 100 phenolic resins and one or more coumaron indene resins derived from coal tar.
5 to 60 parts by weight per part by weight, and (d) 51 to 200 parts by weight per 100 parts by weight of (a), (b) and (c) inorganic filler in total. A novel polyphenylene ether resin composition.