JPH02222452A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition having improved compatibility in blending and impact resistance by comprising a resinous substance obtained by mixing polyarylene sulfide with other thermoplastic resin in organic solvent of high temperature and separating and a thermoplastic resin. CONSTITUTION:A1: 20-80wt.% polyarylene sulfide expressed by formula I (Ar is arylene group containing preferably >=70mol%, especially >=90mol% p- phenylene) is mixed with A2: 80-20wt.% thermoplastic resin except A1, preferably polysulfone or polyethersulfone, etc., having repeating unit expressed by formula II or formula III, etc., in an organic solvent (e.g., p-chloronaphthalene) at 100-400 deg.C and separated to obtain a resinous substance (A). Then, 1-99 pts.wt. The component A is mixed with 99-1 pts.wt. the component B: A1 and/or A2, and fibrous or granular reinforcing agent, as necessary, to afford the aimed resin composition.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention provides a resin-like material that is precipitated after mixing polyarylene sulfide (hereinafter referred to as PAS) and other thermoplastic resin in a high-temperature organic solvent. The present invention relates to a resin composition comprising improved blend compatibility and impact resistance.

Such compositions can be formed into various molded products by various molding methods such as injection molding, compression molding, extrusion molding, and pultrusion molding, and can be used in various fields.

(Prior art and problems to be solved by the invention) PAS represented by polyphenylene sulfide (hereinafter abbreviated as PPS) itself has excellent heat resistance, solvent resistance, and flame retardancy, and is used in the electronics field. It is used in various molding and processing fields, including

However, while PAS has excellent performance, the unreinforced version is very brittle and has insufficient mechanical properties such as impact resistance, so its application as a molding material is limited. is the current situation.

Attempts have been made to improve properties such as impact resistance and flexibility by blending PAS with other thermoplastic resins, but the compatibility between the two is often insufficient, and simple Blends have not been successful. Therefore, for example, JP-A-59-58052, JP-A-59-155461
, No. 59-155462, and No. 59-164360, attempts have been made to blend PPS and other thermoplastic resins by using a novolak epoxy resin as a blend compatibilizer, but the PPS used has a low degree of crosslinking. In addition, the heat resistance of the epoxy resin during molding was poor, and it also had the disadvantage that it easily gelled, causing problems in workability during molding.

In addition, a block copolymer consisting of a PPS moiety and a polyphenylene sulfide sulfone moiety (JP-A-62-205
157) or a block copolymer consisting of a PPS moiety and a polysulfone moiety (JP-A-61-24775)
5), but it cannot be said to be easy because it involves producing a block copolymer, and the resin suitable for blending must also be selected from the same resin as the block part in the block copolymer. It had drawbacks such as a narrow range.

(Means for Solving the Problems) The present inventors have developed PA, which has excellent heat resistance, chemical resistance, rigidity, etc.
As a result of intensive research to easily obtain a resin that can improve properties such as impact resistance and flexibility while taking advantage of the properties of S, and can be blended with PAS and other thermoplastic resins in a wide range of ways, we have developed a resin that can be blended with PAS and other thermoplastic resins as easily as possible. A resinous substance precipitated after mixing other thermoplastic resins in a high-temperature organic solvent is PA.
The present invention was achieved by discovering that it has excellent blend compatibility with S and other thermoplastic resins.

That is, the present invention provides a resin composition consisting of a resinous substance obtained by mixing PAS and other thermoplastic resins in a high-temperature organic solvent and precipitating the mixture, and PAS and/or other thermoplastic resins. be.

PAS, which is a component of the resinous material in the present invention and can be mixed with the resinous material, has the structural formula (-Ar-3
)a (Ar: arylene group). Here, the arylene group 1^r- is p-phenylene, m-phenylene, 0-phenylene, 2.6 naphthalene, 4.4' biphenylene, a divalent aromatic residue containing an aromatic ring having 6 carbon atoms. Furthermore, each aromatic ring has F
SC4! , Br5CHff, and other substituents may be introduced. These may be homopolymers, random copolymers, or block copolymers.

Particularly, PAS preferred for use in the present invention was measured using a parallel plate viscometer at 300°C, 10°C.
The real part [η'] of the complex viscosity at 0 rad/sec is 1
0" to 10' potse, preferably 500 to 5
PPS has a melt viscosity within the range of 000 poise, and is 70 mol % or more, particularly preferably 90 mol % or more of the -Ar portion in the general structural formula of the PAS. The shape of the molecular chain of PPS used is linear, branched, partially crosslinked, or a mixture thereof. In addition, PPS included in PPS or formed by the synthesis process or post-processing process
Commercially available PS products include Frilaps Vetroleum's Rydon PPS and Higashishino Higashi PPS.

On the other hand, other thermoplastic resins that are components of the resinous material in the present invention and can be mixed with the resinous material include PA
Any of the various thermoplastic resins described in the known literature regarding S can be used, such as polysulfone, polyethersulfone, polyarylsulfone, polyetherketone, polyetheretherketone, polyarylate, phenylene oxide, thermoplastic resin, etc. Plastic polyester, polyamide, polycarbonate, polyacetal, polyamideimide, polyetherimide, polyimide, fluororesin and monomers such as ethylene, propylene, butylene, pentene, butadiene, isoprene, styrene, (meth)acrylic acid ester, (meth)acrylonitrile, etc. homopolymers or copolymers of polymers, block and graft copolymers, and modified (co)polymers such as maleic acid-grafted ethylene-butene copolymers, polyolefins modified with sulfuric acid, oxidizing agents, etc. Examples include polymers.

Among these, preferred are polysulfone, polyethersulfone, polyarylsulfone having a repeating unit; polyetherketone, polyetheretherketone having a repeating unit; bisphenol derivatives such as bisphenol A and isophthalic acid, terephthalic acid, or these. Polyarylates preferably synthesized from dibasic acids such as derivatives of phenols; polymers of 2,6-disubstituted phenols or 2,6-
Polyphenylene oxide, which is a polymer of substituted phenol and polyhydric phenol; polyethylene terephthalate;
Thermoplastic polyesters represented by polybutylene terephthalate and poly(cyclohexane dimethylene terephthalate); nylon-6, nylon-66, nylon-6
4. Polyamide represented by nylon-MXD 6 (copolymer of m-xylene diamine and adipic acid); Polycarbonate (based on bisphenols, obtained by reaction of this with diphenyl carbonate or phosgene) In the formula, the total is a trivalent aromatic group, R is 2
a valent aromatic group and/or a divalent aliphatic group, R' is hydrogen,
aliphatic group or phenyl group), etc. (Unexamined Japanese Patent Publication No. 59-64667, No. 59-1
55461, 59-155462, 59-1643
(See Publication No. 60) The resinous substance used in the composition of the present invention is the above-mentioned P
It is obtained by mixing AS and other thermoplastic resins in an organic solvent at high temperature, in some cases under high temperature and pressure, and then precipitating the mixture.

In order to enhance the effect of the resulting resinous material, modifiers such as sulfur and organic peroxides may be added as necessary when PAS and other thermoplastic resins are mixed in a high-temperature organic solvent. It is possible.

The proportion of PAS in the resinous substance is 20-80% by weight
and preferably 30 to 70% by weight.

The organic solvent used for mixing is a solvent that substantially dissolves or swells PAS and other thermoplastic resins, such as α-chloronaphthalene, α-methylnaphthalene, n-methyl-2-
Pyrrolidone, diphenyl ether, diphenyl, etc. are used. These may be used alone or in combination of two or more. The mixing temperature cannot be unconditionally defined as it varies depending on conditions such as the type of solvent used, the type of thermoplastic resin, and the mixing ratio with PAS, but it is usually 10
It is in the range of 0 to 400°C. If the temperature is less than 100''C, a resinous material that improves blend compatibility cannot be obtained, and if it exceeds 400''C, the decomposition of PAS and other thermoplastic resins will be significant, which is not preferable.

There is no limit to the amount of organic solvent used as long as it is within a range that can substantially dissolve and mix the resin, but in order to increase productivity, it is desirable to increase the concentration as much as possible.

The resin-like substance can be precipitated by one or a combination of various methods for separating a polymeric substance from a polymeric solution, such as a cooling precipitation method, a precipitation method by adding a non-solvent, and a solvent distillation method.

In the resin composition of the present invention, when PPS is used in combination with 1 to 99 parts by weight, preferably 3 to 95 parts by weight, of the resinous substance described above, 99 to 1 part by weight, preferably 97 parts by weight, of PPS is used.
-5 parts by weight, and when used in combination with other thermoplastic resins, it contains 99 to 1 parts by weight, preferably 95 to 5 parts by weight. (However, the total shall be 100 parts by weight.) When PPS and other thermoplastic resins are used together in the resinous substance, (resinous substance) / (PPS) /
(Other thermoplastic resins) = 1-60/99-20/1-8
0, preferably 2 to 40/95 to 7015 to 70 (the total is 100 parts by weight).

Note that the thermoplastic resin in the resinous substance and the thermoplastic resin to be blended later do not necessarily have to be the same, and different resins can be used as long as blend compatibility is not inhibited. be.

It is possible to blend a fibrous or granular reinforcing agent into the composition of the present invention as needed, and by blending it in a range of usually 5 to 300% by weight based on the resin composition, strength and rigidity can be improved. , heat resistance and dimensional stability can be improved. Examples of fibrous reinforcing agents include carbon fiber, glass fiber,
Silane glass fiber, ceramic fiber, asbestos fiber,
Examples include metal fibers. Further, examples of the granular reinforcing agent include silicates such as mica and talc, carbonates, sulfates, metal oxides, glass beads, and silica.

Two or more of these may be used in combination, and if necessary, they may be treated with a coupling agent such as a silane type.

The method for preparing the resin composition of the present invention is not particularly limited, and may be, for example, a method of melt-kneading with a conventional melt extruder and pelletizing. The melting temperature is preferably 280 to 400°C, and temperatures exceeding 400°C are not preferred because the resin will decompose.

(Effects of the Invention) The resin composition of the present invention can be used, for example, in electrical/electronic parts such as connectors, printed circuit boards, and molded products for sealing, in automobile parts such as lamp reflector 1 and various electrical components, in various buildings, automobiles, etc. Injection molding and compression molding of interior materials for aircraft, leisure and sports equipment such as tennis rackets, golf clubs, fishing rods, precision parts such as OA equipment parts and camera parts, composite sheets, pipes, etc.
It is used as a molding material with excellent impact resistance in various molding fields such as extrusion molding and pultrusion molding of sheets, and fibers.

(Example) The present invention will be explained by giving examples, but the present invention is not limited thereto.

Examples 1 to 5, Comparative Examples 1 to 5 PPS (Rydon PRO-6, manufactured by Philips Petroli, Am Co., Ltd. (η') = 800 to 1000 pois
As shown in Table 1, polyamide (two types), polyether sulfone, polyphenylene oxide, and polycarbonate were used as other thermoplastic resins to be blended in e).

First, a resinous material was prepared using the above PPS and thermoplastic resin as follows.

PPS and each thermoplastic resin in α-chloronaphthalene at 220°C at a blending ratio of 50150 and a total resin concentration of 10% by weight.
The solution was blended with stirring for about 1 hour, and the precipitate was cooled and precipitated while stirring. Methanol was further added to separate the precipitate, and the resinous substance was vacuum-dried at 120'C for about 5 hours. Obtained.

A blend of PPS, thermoplastic resin, and resinous material in the proportions shown in Table 1 was heated at 290 to 340° in an extruder.
After melt-kneading with C, it was made into pellets.

Diameter 2mmφ, length 15II+I11 using an injection molding machine
Dumbbell-shaped (dull-shaped) specimen, 2m thick, 10m
A sheet-like specimen with a width of m was prepared and heated at a temperature of about 1
A heat treatment was performed for a period of time. Then, a high-speed tensile fracture test (dumbbell-shaped specimen) and a bending test (
The elongation at break and the energy at break were determined, and the impact resistance was compared. The test speed is 500 mm/min for the high-speed tensile fracture test.

The bending test is 2 mm/win. The results are shown in Table 1.

In addition, as a comparative example, Example 6 does not contain a resinous substance.
-8, Comparative Examples 6-8 PPS-nylon 66-based (Example 6), PP5-polyethersulfone-based (Example 7), and PP5-polycarbonate-based (Example 8) were treated in the same manner as in the above examples. Each resinous material was prepared. Resin-like material for each prefecture of PP5-thermoplastic resin with the blending ratio as shown in Tables 2 to 4! Izot impact strength (without notches) and tensile impact strength were tested with and without addition of 5% by weight. In addition, as a comparative example, a sample containing no resinous material was similarly tested.

In addition, the shape of the sample has a cross-sectional area of 3 in terms of Izotsu impact strength.
．． 15 x 3.15 mm", and a diameter of 1.5 mmφ was used for tensile impact strength.

From the results in Tables 2 to 4, it can be seen that those containing resinous substances have improved strength.

Examples 9 to 13, Comparative Examples 9 to 13 PPS-polybutylene terephthalate system (Example 919)
, PP5-polyphenylene oxide system (Example 10)
, PP5-polyarylate system (Example 11L PP5
Regarding the -ABS resin system (Example 12) and the PP5-polyethylene (Example 13), respective resinous substances were prepared in the same manner as in the previous example.

PP5-thermoplastic resin having the compounding ratio as shown in Tables 5 to 9 contains 8% by weight of resinous substances (Examples 9 to 13) and cases without additives (comparison). Examples 9-1
Regarding 3), an Izot impact test (no notch) was conducted.

From the results in Tables 5 to 9, it can be seen that those containing resinous substances have improved strength.

The resin used was PPS (Rydon PRO-6),
Polybutylene terephthalate (Planac BT-120
, manufactured by Dainippon Ink & Chemicals Co., Ltd.), polyphenylene oxide (Ubiece AV60), polyethylene) (U
Polymer 11-100, manufactured by Unitika), ABS resin (
Stylac, manufactured by Asahi Kasei Kogyo Co., Ltd.), and polyethylene (Shorex F5010, manufactured by Showa Denko Co., Ltd.).

Examples 14 to 17 Regarding PPS-nylon 66 (Example 14), PP5-polyethersulfone (Example 15), pps-polybutylene terephthalate (Example 16), PP5-polyphenylene oxide (Example 17), Each resinous material was prepared in the same manner as in the previous example.

Melt blending was performed on PPS and each resinous substance,
An Izot impact test (without notches) was conducted. The results are shown in Table 10.

The resin used was the same as in the previous example.

Comparative Examples 14 to 16 Nylon-66 (used in the above examples) was used as a thermoplastic resin to be blended with PPS (Rydon PRO-6).
Comparative Example 14), polycarbonate (Comparative Example 15), polybutylene terephthalate (Comparative Example 16), and further P
A sample for an impact test was prepared using a resin composition using a novolac epoxy resin (Evicron N695, manufactured by Dainippon Ink & Chemicals) as a blend compatibilizer for PS and the thermoplastic resin.

The blending weight ratio of PPS/each thermoplastic resin/novolak epoxy resin is (50/4 B/2) and (80/1 B/2).
), but in each case, gelation occurred during molding and the melt viscosity increased, making it impossible to create sample pieces.

Agent: Patent Attorney Katsutoshi Takahashi

Claims (1)

[Claims] 1. A resin composition consisting of a resinous substance obtained by mixing polyarylene sulfide and other thermoplastic resin in a high-temperature organic solvent and precipitating the same, and polyarylene sulfide and/or other thermoplastic resin.