JPH02235964A - Resin composition - Google Patents

Abstract

PURPOSE:To prepare a resin compsn. excellent in the impact resistance and blend compatibility by compounding a polyarylene sulfide and/or another thermoplastic resin into a resinous material precipitated from the mixture of a specific block copolymer with another thermoplastic resin in an org. solvent at a high temp. CONSTITUTION:A block copolymer comprising polyarylene sulfide parts (e.g. polyphenylene sulfide) and polyarylene sulfide sulfone parts is mixed with another thermoplastic resin (e.g. nylon 66) in an org. solvent (e.g. alpha- chloronaphthalene) at a high temp., and a resinous material is precipitated from the resulting mixture. Said resinous material is compounded with a polyarylene sulfide (e.g. polyphenylene sulfide) and/or another thermoplastic resin (e.g. nylon 66).

Description

Detailed Description of the Invention (Industrial Application Field) The present invention provides a block copolymer comprising a polyarylene sulfide (hereinafter abbreviated as PAS) part and a polyphenylene sulfide sulfone (hereinafter abbreviated as ppss) part. The present invention relates to a resin composition with improved mechanical properties such as blend compatibility and impact resistance, which comprises a resinous material precipitated after mixing another thermoplastic resin in a high-temperature solvent.

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, flame retardancy, and dimensional stability. It is used in various molding and processing fields including the electronics field.

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

Up until now, 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 Two-component blend systems have not been successful.

Therefore, for example, JP-A-59-58052, JP-A-59-1
55461, 59-155462, 59-1
6 4 3 6 0, attempts have been made to blend PPS and other thermoplastic resins using a novolac-based epoxy resin as a blend compatibilizer, but the PPS used has a low degree of crosslinking. In addition, the epoxy resin has poor heat resistance during molding, and has disadvantages such as easy calcification, which causes problems in workability during molding.

In addition, a block copolymer consisting of a PPS moiety and a ppss moiety (Japanese Patent Laid-Open No. 62-20515) or a block copolymer consisting of a PPS moiety and a polysulfone moiety (Japanese Patent Laid-open Publication No. 61-247755) is used as PAS.
(or pps), but the resin suitable for blending is the same resin as the zorosoku moiety in the block copolymer, and there are drawbacks such as a narrow range of resin selection.

(Means for Solving the Problems) The present inventors have discovered that P has excellent heat resistance, chemical resistance, rigidity, etc.
As a result of intensive research to obtain a resin that takes advantage of the properties of AS, improves properties such as impact resistance and flexibility, and can be blended extensively with other thermoplastic resins,
The resin-like material precipitated after mixing a Bronok copolymer consisting of a PAS portion and a ppss portion with other thermoplastic resins in a high-temperature organic solvent has excellent blend compatibility with PAS and other thermoplastic resins. This discovery led to the present invention.

That is, the present invention combines a block copolymer consisting of a PAS portion and a ppss portion with another thermoplastic resin and a resin-like substance precipitated after mixing in a high-temperature organic solvent, and PAS and/or another thermoplastic resin. The present invention provides a dry resin composition.

PAS, which is a constituent part of the block copolymer used for the resinous material and can be mixed with the resinous material, is a polymer represented by the structural formula (-Ar-S-)n[:Ar:arylene group]. It is. Here, -hr of the arylene group
-1d. , p-phenylene, m-phenylene, 0-phenylene, 2,6-naphthalene, 4,4-biphenylene,
Or ({彉o-@-), (one《shico=(column), (
At least 2 carbon atoms 6, such as tatami SO2-《ツ》 etc.
It is a divalent aromatic ring residue containing an aromatic ring, and furthermore, substituents such as F, Cl, Br, CH3, etc. may be introduced into each aromatic ring. These may be homopolymers, random copolymers, or block copolymers. Note that the PAS of the present invention includes PA
It does not contain a Zoronok copolymer consisting of an S portion and a ppss portion.

In particular, PAS preferably used in the present invention is a PAS that is measured at 300°C using a parallel plate type viscoelasticity measuring device.
, the real part [η] of the complex viscosity at 100 rad/see is 102 to 105 poise, preferably 500 to 5
The above-mentioned PA has a melt viscosity within the range of 000 poise.
70 mol% of the arylene group in the structural formula of S
Particularly preferably PPS is composed of 90 mol% or more of the -7-enylene (-'D) moiety. It takes p
The shape of the molecular chain of ps is linear, branched, partially crosslinked, or a mixture thereof. In addition, p- contained in PPS
Structural components other than the phenylene sulfide moiety (-@-S-) include, in addition to the above, those formed during the synthesis process or post-treatment of the polymer, such as (.-@-so-), (-
Some of them include 《filtration s-s-), ({叉-SO2-S-), etc.

Commercially available PPS products include, for example, Ryton PPS manufactured by Philips Trollium Co., Ltd. and Toray PPS manufactured by Toray Industries.

A block copolymer consisting of a PAS part and a PPSS part used in a resinous substance mainly consists of a part of the polymer whose repeating unit is ( s- ) and a part of the polymer whose repeating unit is (
--@rs-> according to the manufacturing method shown in JP-A-62-115030 and JP-A-63-278935 regarding block copolymers having repeating units, or various other methods. Obtained by manufacturing method.

As an example of the production method, for example, sodium sulfide and bis(p
Aromatic sulfide sulfone polymer with terminal chlorphenyl group obtained by reacting chlorphenyl) sulfontho in N-methylpyrrolidone and terminal obtained by reacting sodium sulfide and P-dichlorobenzene in N-methylpyrrolidone. Examples include a method of producing a block copolymer by heating sodium sulfide group type polyphenylene sulfide in N-methylpyrrolidone.

The block copolymer may contain PAS from the time of manufacture.
A homopolymer of PPSS and a random copolymer of PAS and ppss may also be included as long as they do not impair the effects of the present invention.

Further, the melt viscosity of the block copolymer is preferably 10 to 20,000 poise at 300°C.

The proportion of ppss moiety in the block copolymer is 1 to
It is selected in the range of 80% by weight, preferably in the range of 5 to 60% by weight. If it exceeds 80% by weight, heat resistance etc. will deteriorate, which is not preferable. Further, if it is less than 1% by weight, the desired effect of the present invention will not be exhibited.

The thermoplastic resin, which is another component of the resinous material of the present invention and is also a resin that can be mixed with the resinous material, can be any of the various thermoplastic resins described in the known literature regarding PAS. Possible, for example, polyethersulfone, polysulfone, polyarylsulfone, polyarylate, polyetheretherketone, polyetherketone, polyetherimide, thermoplastic polyester, polyamide, phenoxy resin, polyamideimide, polyphenylene Oxide, polycarbonate, polyacetal, fluororesin, ethylene, propylene,
Homopolymers or copolymers of monomers such as butylene, pentene, phtadiene, isogrene, styrene, (meth)acrylic esters, (meth)acrylonitrile, etc.
Block and graft copolymers, as well as modified (co)polymers such as maleic acid-grafted ethylene-butene copolymers and polyolefins modified with sulfuric acid, oxidizing agents, etc.
Examples include polymers. Among them, the most preferable monoha is (-
Polysulfone, polyethersulfone, polyarylsulfone having @-so2-), (-@B t{kunso2-); (-《γco-4佉0-), c Polyetherketones and polyetheretherketones with repeating units such as o->; bisphenol visiting conductors such as bisphenol A and inphthalic acid;
Polyarylates preferably synthesized from dibasic acids such as terephthalic acid or derivatives thereof; polymers of 2,6-disubstituted phenols or polymers of 2,6-monosubstituted phenols and polyhydric phenols; Certain polyphenylene oxides;
Thermoplastic polyesters represented by polyethylene terephthalate, polybutylene derephthalate, and poly(cyclohexane dimethylene terephthalate); nylon-6,
Nylon-66, Nylon-64, Nylon MX:D
Polyamide represented by 6 (copolymer obtained from meta-xylene diamine and azonic acid); bisphenol A
Phenoxy resin, a thermoplastic polyether whose main raw material is shrimp chlorohydrin; bisphenols as a pace, this and diphenyl car? Polycarbonate obtained by reaction with ester or phosgun; general group group, R is a divalent aromatic group and/or a divalent aliphatic group,
R' is hydrogen, an aliphatic group, or a phenyl group), such as polyamideimide. (Unexamined Japanese Patent Publication No. 59-64
667, 59-155461, 59-155
462, 59-164360) The resinous substance used in the composition of the present invention is the above-mentioned PAS
It is obtained by mixing a block copolymer consisting of a polypropylene and a ppss moiety and another thermoplastic substance in an organic solvent at high temperature, in some cases under high temperature and pressure, and then precipitating the mixture.

When block copolymers and other thermoplastic resins are mixed in a high-temperature organic solvent, modifiers such as sulfur and organic peroxides may be added as necessary to enhance the effectiveness of the resulting resinous material. It is possible to mix them.

The proportion of the block copolymer consisting of the PAS part and the ppss part in the resinous material is 20 to 80% by weight, preferably 30 to 70% by weight.

The solvent used for mixing is a solvent in which the block copolymer and other thermoplastic resin substantially dissolve or swell;
For example, α-chloronaphthalene, α-methylnaphthalene, n-methyl-2-pyrrolidone, diphenyl ether,
Diphenyl natoka is used. These may be used alone or in combination of two or more. In addition, the mixing temperature is
Although it cannot be absolutely defined because it varies depending on the type of solvent used, the type of thermoplastic resin, the mixing ratio with the block copolymer, etc., it is usually in the range of 100°C to 400°C. If it is less than 100°C, a resinous substance that improves blend compatibility cannot be obtained, and if it exceeds 400°C, the block copolymer and thermoplastic resin will decompose significantly, which is not preferable.

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

Precipitation of the resinous substance can be carried out 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.

The resinous substance of the present invention is preferably 99 to 1 part by weight, preferably 97 to 5 parts by weight when PAS is used in combination with 1 to 99 parts by weight, preferably 3 to 95 parts by weight, of the resinous substance described above.
If other thermoplastic resins are used together, the thermoplastic resin is contained in an amount of 99 to 1 part by weight, preferably 95 to 5 parts by weight.

(However, the total shall be 100 parts by weight.) In addition, when PAS and other thermoplastic resins are used together in the resinous substance,
(Resin-like substance) / (PAS) / (other thermoplastic resin) = 1-6 0/9 9-10/1-90, preferably 2-4 0/9 5-70/5-70 (total 100
Part by weight. ).

Note that the thermoplastic resin in the resinous material 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 the blend compatibility is not inhibited.

If necessary, a fibrous or granular reinforcing agent can be added to the composition of the present invention, and by adding it in an amount of usually 5 to 300% by weight based on the resin composition, the strength can be improved. Rigidity, heat resistance, and dimensional stability can be improved. Examples of the fibrous reinforcing agent include carbon fiber, glass fiber, silane lath fiber, ceramic fiber, asbestos fiber, and metal fiber. In addition, granular reinforcing agents include silicates, carbonates, sulfates, etc.
Examples include 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 in which the resin composition is melt-kneaded using an ordinary melt extruder and then pelletized. The melting temperature is preferably 280 to 400°C, and if it exceeds 400°C, the resin will decompose, which is not preferable.

(Effects of the Invention) The resin composition of the present invention can be applied to, for example, electrical and electronic parts such as connectors, printed circuit boards, and molded products for sealing, automotive parts such as Lang reflectors, various electrical components, various buildings, automobiles, and aircrafts. Injection molding/compression molding of interior materials such as tennis rackets, skis, golf clubs, fishing rods, etc., precision parts such as OA equipment parts, watch parts, camera parts, etc., or composite sheets. It is used as a molding material with excellent impact resistance in extrusion molding and pultrusion molding of noquibs and sheets, as well as in various molding power industries such as fibers.

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

Synthesis example (synthesis of block copolymer consisting of pps and ppss moieties) 107 N-methylpyrrolidone 198 (
1. Sodium hydrosulfide 1.2 Aquarium 388y, Sodium hydroxide 200g, Bis(p-chlorophenyl)sulfone 1. 4 3 6,! 7, under nitrogen atmosphere,
The reaction was carried out at 200°C for about 6 hours. Furthermore, bis(p-chlorophenyl)sulfone 72F. ! : 200 liters of N-methylpyrrolidone was added and reacted at 200° C. for 1 hour to obtain a ppss polymer with terminal chlor7enyl groups.

Next, N-methylpyrrolidone 3 was added to the 107 autoclave.
100F, sodium hydrosulfide hemihydrate 5 9 7.
5. P and sodium hydroxide 3.08. P-dichlorobenzene 102. l and N-methylpyrrolidone 700y
was added and reacted at 260° C. for 2 hours to obtain PPS with a terminal sodium sulfide group.

The ppss reactant and the pps reactant were charged into an autoclave and reacted at 220° C. for 3 hours, and purified by a known method to obtain a block copolymer containing about 50% by weight of the ppss portion. The melt viscosity of this block copolymer measured using a Koka type flow tester was approximately 600 poise at 300°C. Subsequently, heat crosslinking was performed in air at 260°C for a predetermined time,
ASTM D-1238-74 (315.6℃, 5kg
The melt flow rate measured at 170 (
g/10 min) was obtained. This block copolymer is used in the Examples and Comparative Examples shown below.

Example 1/Comparative Example 1 Nylon-66 (BA
(manufactured by SF) was used. First, a resinous material was prepared as follows using the above block copolymer and nylon-66.

In α-chloronaphthalene at 220℃, 50/5
Block copolymer and nylon with a blending ratio of 0 (wt%)
66 at a concentration of 10% by weight for about 1 hour while stirring, and after cooling and precipitating while stirring, methanol was further added to separate the precipitate, and the precipitate was vacuum dried at 120°C for about 5 hours to form a resin. Obtained substance.

pps (Ryton PRO-6, made by Filinnos Petroleum, [η'] = 800 to 1000 poise)
A mixture of , resinous substance and nylon-66 in the blending ratio shown in Table 1 (the resinous substance was added in an amount of 5% by weight based on the total weight of pps and nylon-66) was heated to 290% by weight using an extruder.
After melt-kneading at ~310°C and forming into pellets, an injection molding machine was used to produce 20 rod-shaped specimens with a cross-sectional area of 3.15 x 3.15 m. It was possible to eject smoothly without clumping. Moreover, the appearance of the molded product was uniform and the compatibility was good. An Izod impact test (without notch) was conducted to examine impact resistance. The results are shown in Table 1.

For comparison, rod-shaped specimens were also prepared without containing resinous substances. When no resinous substance was used, the appearance of the molded product was non-uniform or had a noyal shape, and the compatibility was poor.

Furthermore, from the results shown in Table 1, it can be seen that the impact resistance is improved by adding a resinous substance.

/ / / / / / / / / / Example 2-11 / Comparative Example 2-11 Prosoc copolymer-polyethersulfone system (Example 2
), Brosoc copolymer-polycar? Neto type (Example 3)
, block copolymer-polybutylene terephthalate (
Example 4), block copolymer-polyarylate system (
Example 5), block copolymer-nylon W6 system (Example 6), block copolymer monomodified polyphenylene oxide system (Example 7), block copolymer-phenoxy resin system (Example 8), Block copolymer-ABS resin system (Example 9), block copolymer-polyethylene system (Example 10), and Bronok copolymer-polysulfone system (Example 11) were treated in the same manner as in Example 1. A resin-like substance was prepared.

(Block copolymer/thermoplastic resin-5 075 0% by weight) pps (Ryton PRO-6), the above resinous substance and each thermoplastic resin were prepared in the same manner as in Example 1 to prepare each test piece. Created. (Resin-like substances are added at the weight ratio shown in each table to the total of pps and thermoplastic resin)
In either case, injection molding could be carried out smoothly without caking. In addition, all molded products had a uniform appearance and were excellent in compatibility. An Izonot impact test (without notch) was conducted in the same manner as in Example 1. The results are shown in Tables 2 to 11.

For comparison, the case where no resinous substance was added was investigated, and the results are summarized in Tables 2 to 11. It can be seen that the impact resistance is improved by adding the resinous substance.

The thermoplastic resin used was polyethersulfone (P
E8 3600, manufactured by ICI), polycarbonate (Ubilon S-2000, manufactured by Mitsubishi Gas Chemical Co., Ltd.), polybutylene terephthalate (Planac BT-120, manufactured by Dainippon Ink and Chemicals), polyarylate (U, le rimer U- 100, manufactured by Unitika), nylon ■■6 (R
ENY6301, Mitsubishi Gas Chemical Co., Ltd.), modified polyphenylene oxide (Iupilon AV-60, Mitsubishi Gas Chemical Co., Ltd.), phenoxy resin (Grade PKI{H, Union Carbide Co., Ltd.), ABS resin (Stylac, Asahi Kasei Corporation) ), polyethylene (Shorenox F501
0, manufactured by Showa Denko), polysulfone (UDEL P-
3 5 0 0. (manufactured by Union Carbide).

/ / / / / / / / Example 12-15 Block copolymer-nylon 66 (BASFIIJ
I, Example 12), block copolymer-7j9 1J ethersulfone (PES 3600, Example 13)
), Prosoc copolymer monomodified polyphenylene ogicide (Ubiece AV-60, Example 14), block copolymer-polybutylene terephthalate (Pranasoc BT-
120, Example 15), a resinous material was produced in the same manner as in Example 1. (Block copolymer/thermoplastic resin - 50/50) Melt blending was performed using only pps and a resinous substance. The weight ratios of the blends are shown in Table 12.

All of the obtained molded products had a uniform appearance and good compatibility. An Izod impact test similar to that in Example 1 (without a punch) was conducted to measure impact resistance. The results are shown in Table 12.

/ q' / Comparative Example 12-15 Melt blending was performed using a novolac epoxy resin (Epicron N695, manufactured by Dainippon Ink & Chemicals) instead of the resinous material. PPS is Ryton PRO
- 6, thermoplastic resin is nylon - 6 6 (
Manufactured by BASF, Comparative Example 12), Polycar? Neto (Iupilon S-2000, Comparative Example 13), polybutylene terephthalate (Plananoc BT-120, Comparative Example 14),
Polyether sulfone (PES3600, Comparative Example 15)
was used.

The blending weight ratio of PPS/thermoplastic resin/epoxy resin is (
Sample molding was attempted in the same manner as in Example 1 for the cases of (50/4 8/2) and (80/18/2), but
Celification occurred and the melt viscosity increased, making it impossible to prepare a sample piece.

Agent: Patent attorney Katsutoshi Takahashi

Claims (1)

[Claims] A resin-like substance precipitated after mixing a block copolymer consisting of a polyarylene sulfide part and a polyphenylene sulfide sulfone part and another thermoplastic resin in a high-temperature organic solvent, and a polyarylene sulfide and/or
A resin composition consisting of other thermoplastic resins.