JPH05156162A - Resin composition - Google Patents

Abstract

PURPOSE:To prepare a polyphenylene sulfide resin compsn. excellent in the resistances to heat, chemicals, and impact by compounding a polyphenylene sulfide resin with a specified amt. of a specific modified olefinic polymer. CONSTITUTION:50-99.5 pts.wt. polyphenylene sulfide resin is compounded with 50-0.5 pt.wt. modified olefinic polymer which has a structural unit of formula I (wherein R is H or CH3; and Ar is a 6-33C hydrocarbon group having at least one glycidyloxy group), pref. a structural unit of formula II, based on 2-1,000 olefinic (e.g. ethylenic) repeating units.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyphenylene sulfide resin composition having excellent impact resistance.

[0002]

2. Description of the Related Art Polyphenylene sulfide resin is a resin having extremely high heat resistance and excellent chemical resistance, and is used in a wide range of fields such as electric / electronic products, automobile parts, office equipment parts, aviation and space equipment parts. Is expected as a heat resistant molded product. However, since polyphenylene sulfide is rigid and brittle, it does not function as a molding material as a single resin. Various investigations have been made to solve the above problems, but at present, it is difficult to say that they are sufficient. Thus, there is a demand for a polyphenylene sulfide resin having excellent impact resistance while maintaining other physical properties (heat resistance, chemical resistance, etc.).

[0003]

In view of such a background, the present invention provides a polyphenylene sulfide resin composition having excellent impact resistance while maintaining excellent properties such as heat resistance and chemical resistance. That is the purpose.

[0004]

That is, the present invention is represented by the following general formula (I) per 50 to 99.5 parts by weight of a polyphenylene sulfide resin (A) and 2-1000 repeating units of olefin. Modified polyolefin-based polymer (B) having one structural unit having a glycidyl group
The content of the composition is 50 to 0.5 parts by weight.

[0005]

[Chemical 3]

(In the formula, R represents a hydrogen atom or a methyl group. Ar represents a C _{6 to} C ₂₃ aromatic hydrocarbon group having at least one glycidyloxy group.)

The present invention will be described in detail below. The polyphenylene sulfide resin (A) of the present invention has, for example, a structural formula obtained by reacting a halogen-substituted aromatic compound with an alkali sulfide.

[0008]

[Chemical 4]

Those shown in (for example, US Pat.
No. 13,188, Japanese Patent Publication No. 44-27671). The glycidyl group-containing substance contained in the modified polyolefin polymer (B) is represented by the above general formula (I). For example, the compound represented by the following general formula (III), which is a starting material of the general formula (I), has at least 1 phenolic hydroxyl group.
After condensing one or more aromatic hydrocarbons with N-methylol acrylamide or N-methylol methacrylamide or an alkyl ether derivative of N-methylol acrylamide or N-methylol methacrylamide with an acid catalyst, the phenolic hydroxyl group is glycidylated. Can be easily obtained. When 2,6-xylenol and N-methylol acrylamide are combined, a compound represented by the following formula (IV) having the following structure is obtained, and when modified with a polyolefin polymer, represented by the above formula (II). Be in shape. Regarding the production method of these glycidyl group-containing products, the present inventors have already disclosed in JP-A-60-1.
It is disclosed in No. 30580.

[0010]

[Chemical 5]

(In the formula, R represents a hydrogen atom or a methyl group. Ar represents a C _{6 to} C ₂₃ aromatic hydrocarbon group having at least one glycidyloxy group.)

[0012]

[Chemical 6]

The modified polyolefin polymer (B)
As the polyolefin or olefin monomer contained in, homopolymers of ethylene, propylene, 1-butene, 1-pentene, isobutene, etc .: Conjugated dienes such as butadiene, isoprene, chloroprene, phenylpropadiene: Conjugated dienes of these Homopolymer: cyclopentadiene, 1,5-norbonanodiene, 1,3-
Cyclohexadiene, 1,4-cyclohexadiene,
Examples include cyclic dienes such as 1,5-cyclohexadiene and 1,3-cyclooctadiene: homopolymers of these cyclic dienes: α, ω-non-conjugated dienes and the like. Also,
Not only these olefins but also random copolymers and block copolymers with other unsaturated monomers copolymerizable with vinyl ether, vinyl acetate, vinyl propionate, methyl acrylate, acrylonitrile, styrene and the like can be used. it can.

As a method for obtaining the modified polyolefin-based polymer (B), a compound represented by the general formula (III) and at least one monomer selected from the above-mentioned combinations are used by using a radical polymerization initiator. It is synthesized by a method such as bulk polymerization, emulsion polymerization, solution polymerization, or suspension polymerization. As the radical polymerization initiator, for example, a cumene hydroperoxide, a tertiary butyl hydroperoxide, a benzoyl peroxide, a lauroyl peroxide, a decanoyl peroxide, an azo compound such as acetyl peroxide or an azo compound such as azobisisobutyronitrile is used alone. Alternatively, they may be used in combination of two or more. As a simpler method, a compound represented by the general formula (III), the above polyolefin-based (co) polymer, and a radical initiator are sufficiently mixed under a solvent-free condition at a temperature at which they do not previously react, and then an extruder or a Banbury mixer. It can be produced by using a kneading device such as a kneader, a kneader and a roll which is used in a general synthetic resin field. In particular, the latter method is preferably adopted from the viewpoint of operability and economy.

The amount of the modified polyolefin resin grafted is preferably in the range of 0.5 to 50%, more preferably 2 to 50%.
It is in the range of 20%.

The weight ratio of the composition of the polyphenylene sulfide resin (A) and the modified polyolefin polymer (B) can be variously selected according to the purpose, but from a practical point of view, each component is polyphenylene sulfide. Resin (A) is 50 to 99.5 parts by weight, preferably 80 to 98.
Parts by weight, and the modified polyolefin-based polymer (B) is 5
It is used in the range of 0 to 0.5 part, preferably 20 to 2 parts.

Polyphenylene sulfide resin (A) and glycidyl group-containing modified polyolefin polymer (B)
The method for producing the composition consisting of is carried out using a known method. For example, a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, a roll, etc. are used. Further, in kneading, a known glycidyl group reaction initiator may be added at the time of molding in order to improve the impact resistance effect. For example, a known initiator such as an amine type or an acid anhydride type may be used. The molding process of the resin composition of the present invention can be performed by a usual method such as injection molding or extrusion molding. The melt-kneading temperature, from the viewpoint of sufficiently melting the composition, from the viewpoint of thermal deterioration and gelation prevention of the modified polyolefin-based polymer,
The range of 280 to 340 ° C is preferable. When kneading,
If necessary, additives such as an ultraviolet absorber, a release agent, a heat stabilizer, a plasticizer, a lubricant, an antistatic agent, a foaming agent, a dispersant, a coloring agent, and a flame retardant may be added. Furthermore, an inorganic filler such as talc, aluminum hydroxide, magnesium hydroxide, silica, glass fiber or glass powder, powdered metal, or an inorganic reinforcing material such as carbon black can be added.

The polyphenylene sulfide-based resin composition according to the present invention exhibits particularly excellent impact resistance, but other properties (heat resistance, chemical resistance, etc.) are almost the same as those of polyphenylene sulfide. Moreover, it is characterized in that it can be processed without any particular problem in terms of moldability.

[0019]

EXAMPLES The present invention will now be specifically described with reference to Examples, but the present invention is not limited to these.
In the following description, "part" and "%" mean "part by weight" and "% by weight", respectively, unless otherwise specified. Reference Example 1: Synthesis of modified polyethylene JIS K6760
Melt flow rate measured by the method of 7 g / 10 min Low density polyethylene (manufactured by Showa Denko KK: Sho
lex-M171) 100 parts, N- {4-
5 parts of (2,3-epoxypropoxy) -3,5-dimethylphenylmethyl} acrylamide [abbreviated as modifier (IV) hereinafter], and α, α'-bis (t-butylperoxy-m-isopropyl) A mixture of 0.1 parts of benzene (Nippon Oil and Fats Co., Ltd .: Perbutyl-P) at room temperature was mixed with a twin-screw extruder (Ikegai Iron and Steel Co., Ltd .: PCM-30) set at 220 ° C. at a speed of 4 kg / hour. Supplied.
After the extruded reaction product is cooled with water and pelletized, the temperature is 80 ° C.
And dried under reduced pressure for 3 hours. The resulting dried pellets are 120
After dissolving in xylene heated to ℃, the xylene solution was added dropwise to acetone to reprecipitate the modified polyethylene resin, whereby unreacted modifier (IV) and modifier (I
After removing the homopolymer of V), elemental analysis of nitrogen atoms contained in the modified polyethylene resin after reprecipitation and FT-I
The grafting amount of the modifier (IV) was calculated from the analysis value of the epoxy group by the R method to be 3.9%, and the grafting reaction rate was 82%.
Met. The modified olefin polymer had one structural unit derived from the modifier (IV) per 146 repeating units of olefin. Here, the graft amount means% of the modifier contained in the modified polyethylene, and the graft reaction rate means the ratio (%) of the modifier reacted with the polyethylene in the modifier used for modifying the polyethylene. To do.

Reference Examples 2 to 4: Synthesis of Modified Polyolefin Resin Modified polyethylene resin (Reference Example 2) was prepared in the same manner as in Reference Example 1 except that only the number of parts of the modifier (IV) relative to polyethylene was changed. 3) and modified ethylene-propylene rubber (Reference Example 4) were synthesized, and the graft amount and graft reaction rate of the modifier were measured. The results are shown in Table 1.

[0021]

[Table 1]

Examples 1 to 9 Polyphenylene sulfide resin (P-made by Phillip Corporation)
4) 100 parts, 80 parts of glass fiber as a filler, and the modified polyolefin-based polymers a- obtained in Reference Examples 1 to 4 above.
d was added at a ratio shown in Table 1 at room temperature and mixed, and
Twin screw extruder set at 0 ° C (PC made by Ikegai Iron & Steel Co., Ltd .: PC
M-30) was fed at a rate of 8 kg / hr, the extrusion reaction product was cooled with water to be pelletized, and then dried under reduced pressure at 120 ° C. for 15 hours to produce a pelletized resin composition. Next, the pellets were supplied to an injection molding machine set at 310 ° C., and a test piece for mechanical property evaluation was molded under a mold temperature of 150 ° C. Izod impact strength (AS) measured on the obtained test piece
TM D-256), heat distortion temperature (ASTM D-64
8) and the results of the immersion in toluene at room temperature for 24 hours are shown in Table 2, which shows that the impact resistance is extremely large, the heat distortion temperature is smaller than that of polyphenylene sulfide alone, and the appearance is not changed by immersion in toluene.

[0023]

[Table 2]

[0024]

INDUSTRIAL APPLICABILITY As described above, the present invention can provide a polyphenylene sulfide resin composition having improved impact resistance while maintaining heat resistance and chemical resistance.

Claims (3)

[Claims] 1. A polyphenylene sulfide resin (A)
50 to 99.5 parts by weight, and a modified polyolefin-based polymer (B) 50 to 50 having 1 structural unit having a glycidyl group represented by the following general formula (I) per 2-1000 repeating units of olefin. A polyphenylene sulfide resin composition comprising 0.5 part by weight. [Chemical 1] (In the formula, R represents a hydrogen atom or a methyl group. Ar represents a C _{6 to} C ₂₃ aromatic hydrocarbon group having at least one glycidyloxy group.) 2. The resin composition according to claim 1, wherein the structural unit having a glycidyl group contained in the modified polyolefin polymer (B) is represented by the following formula (II). [Chemical 2] 3. The repeating unit of the olefin contained in the modified polyolefin polymer (B) is ethylene, propylene, 1-butene, 1-pentene, isobutene, butadiene, isoprene, chloroprene, phenylpropadiene, cyclopentadiene, 1 , 5-norbornanodiene,
From a homopolymer of a monomer selected from 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,5-cyclohexadiene and 1,3-cyclooctadiene or a mixture thereof, or from two or more kinds of the monomers described above. The resin composition according to claim 1, which comprises the following copolymer or a mixture thereof, and a mixture of the homopolymer and the copolymer.