JPH02251567A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic resin composition having excellent blending compatibility and excellent mechanical characteristics such as heat resistance, impact resistance, etc., by blending a mixture of a polyarylene sulfide resin and another thermoplastic resin with a phenoxy resin. CONSTITUTION:100 pts.wt. mixture consisting of (A) 95 to 10 pts.wt. polyarylene sulfide resin, preferably polyphenylene sulfide resin having 10<2> to 10<5> poise (300 deg.C) dynamic viscosity and (B) 5 to 90 pts.wt.. another thermoplastic resin, preferably nylon 66 or polybutylene terephthalate is blended with (C) 1 to 30 pts.wt.. phenoxy resin which is a high molecular weight thermoplastic polyether resin obtained by reacting bisphenol A with epichlorohydrin, containing no epoxy group at both ends and having 5X10<2>-10<5>cps solution viscosity of 40% solid content in methyl ethyl ketone to give a composition.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention 8A is a polyarylene sulfide resin (hereinafter referred to as P
It is abbreviated as AS. ) and other thermoplastic resins, the phenoxy resin is used as an essential third component in the blend, and mechanical properties such as blend compatibility and impact resistance are particularly improved. The present invention relates to a resin composition.

Such compositions can be molded into various electrical/electronic parts,
Molded products with shapes suitable for machine parts, automobile parts, sports equipment, miscellaneous goods, etc. can be provided, and can be used in various fields.

(Prior Art and its Problems) Many compositions of PAS and other thermoplastic resins are known. However, most of these compositions have insufficient compatibility, resulting in problems such as a significant decrease in mechanical properties such as bending strength and impact resistance, and poor surface condition of molded products. However, it is difficult to say that Plain P has achieved its original purpose.

For this reason, Japanese Patent Application Publications No. 59-58052 and No. 59-1554
61, 59-155462, 59-164360,
As seen in Publications No. 59-207921 and No. 59-213758, when blending polyphenylene sulfide resin (hereinafter abbreviated as PPS) with various thermoplastic resins, lac-based epoxy resin is Attempts have been made to add it as a ternary substance. However, the pps used in this case is limited to those with low viscosity and low degree of crosslinking, and also tends to form during molding, and the melt viscosity becomes extremely high, making molding impossible. There are also problems such as the molding conditions being limited to a very narrow range.

A block copolymer consisting of a PPS moiety and a polyphenylene sulfide sulfone moiety (Japanese Patent Application Laid-Open No. 62-2051
5) or a block copolymer consisting of a PPS moiety and a polysulfone moiety (JP-A-61-247755), but these methods were not convenient because a block copolymer was produced.

(Means for Solving the Problems) As a result of intensive studies, the present inventors have found that in order to solve the above problem,
The inventors have discovered that the above-mentioned problems can be solved by using a phenoxy resin as an essential third component in blending PAS and other thermoplastic resins, and have arrived at the present invention.

The resin composition obtained by the present invention can use PAS with high viscosity and high degree of crosslinking, does not become dull during molding, has excellent compatibility between resins, and improves the hard but brittle properties of PAS. Furthermore, it is a highly practical molding material that fully achieves the original purpose of blending, as it also improves the disadvantages of other thermoplastic resins used with PAS, such as moldability, heat resistance, water resistance, and chemical resistance. .

In other words, the original F! A contains (95 to 10 parts by weight of N polyarylene sulfide resin and (B) 5 to 9 parts by weight of other thermoplastic resin)
For 100 parts by weight of a mixture consisting of 0 parts by weight, (C)
A thermoplastic resin composition characterized by containing 1 to 30 parts by weight of a phenoxy resin.

The pAs Fi used in the present invention has the structural formula (-Ar-8-
) n [Ar: arylene group].

Here, -Ar- of the arylene group is p-phenylene, o
-phenylene, m-phenylene, 2,6-naphthalene A divalent aromatic ring residue containing an aromatic ring with a prime number of 6, and each aromatic ring has a substituent such as F, CL-Br, CH3, etc. Sometimes it is introduced. These may be homopolymers or block copolymers.

Particularly preferable PAS for use in the present invention is a PAS measured using a parallel grade viscoelastic device at 300°C.
The real part of the complex viscosity at 0 rad/sea, that is, the dynamic viscosity [η] has a melt viscosity in the range of 102 to 105 poise, preferably SOO to 5000 poise, and has a melt viscosity in the range of SOO to 5000 poise, and in the general structural formula of the above PAS resin. -Ar
- mole of 70 moles or more, particularly preferably 90 moles of Vi. The shape of the molecular chain of such PPS is linear, branched, partially crosslinked, or a mixture thereof.

In addition to the above-mentioned structural components other than the p-phenylene sulfide moiety contained in pps, there are also components formed by, for example, the polymer synthesis process or post-treatment.

Examples of commercially available PPS include Rydon PP5 (Philips Petroleum Corporation) and Toshi PP5 (Toshisha).

Further, as the other thermoplastic resins used in the present invention, any of the various thermoplastic resins described in known literature regarding PAS can be used, such as polyethersulfone, polysulfone, polyarylsulfone, polyarylate, polyetheretherketone, polyetherketone, polyetherimide, thermoplastic polyester, polyamide, polyamide Pimide, polyphenylene oxy)
', yje liquor? Homopolymers or copolymers of monomers such as esters, polyacetals, fluororesins, polyimides, ethylene, propylene, butylene, pentene, butadiene, imprene, styrene, (meth)acrylic acid esters, (meth)acrylonitrile, Also included are block and graft copolymers, and modified (co)polymers such as maleic acid-grafted ethylene-butene copolymers and polyolefins modified with sulfuric acid, oxidizing agents, and the like.

polysulfone, polyethersulfone, polyarylsulfone with which repeating unit, I-lyetherketone with which repeating unit, polyetherketone, poly(1) x, -f-lyetherketone; 2. Combine or 2
, polyphenylene oxide, which is a polymer of 6-substituted phenol and polyhydric phenol; thermoplastic polyesters represented by polyethylene terephthalate, polybutylene terephthalate, and poly(cyclohexane dimethine/terephthalate); nylon-6, nylon-66, nylon- 64, nylon MXD 6 (meta-xylene diamine and a divalent aliphatic group, R' is hydrogen, an aliphatic group, or a phenyl group), and the like.

(Refer to Publication Nos. 59-64667, 59-155461, 59-155462, and 59-164360) In the present invention, the phenoxy resin used as the essential third component of the blend is bisphenol A like the epoxy resin. The major difference from epoxy resin is that it is a high molecular weight thermoplastic polyether resin that does not have epoxy groups at either end.

Preferred phenoxy resins for use in the present invention have a solution viscosity of 40 solids in methyl ethyl ketone (MEK) solution ranging from 5 x 102 to IQ" cps, preferably from 103 to 5 x 10' cps.

Such phenoxy resin has a thermal decomposition temperature of about 420°C (TGA measurement, 1O weight loss in air).
The molding temperature is higher than the upper limit of 400°C for UCAR phenoxy P (KH)l grade) and PAS, and has excellent heat resistance.

Commercially available phenoxy resins include Union Carbide's UCAR phenoxy (grade PfG (H).

PKI'IJ%PKHC%PKHM30, etc.) are used.

The ratio of each component in the resin composition of the present invention varies depending on the type and purpose of the thermoplastic resin used, so it cannot be unconditionally defined, or it may be difficult to determine the ratio between (A) PAS and (B) other thermoplastic resins. The ratio is (A) 95 to 103 parts by weight, B) 5 to 90 parts by weight, preferably #1 (A) 90 to 20 parts by weight, and B) 10 to 80 parts by weight. (However, the total amount is 10,031 parts) and the phenoxy resin is
The total amount of PAS and other thermoplastic resins is 1 to 30 parts by weight, preferably 3 to 20 parts by weight per 100 parts of cod. If the phenoxy resin is less than 1 part by weight, no effect will be exhibited.
30] If the amount exceeds i part, the heat resistance will deteriorate, which is not preferable.

The resin composition of the present invention includes fibrous reinforcing materials such as glass fiber, carbon fiber, potassium titanate, asbestos, silicon carbide, and aramid fiber; barium sulfate, calcium sulfate, kaolin, clay, pyrophyllite, bentonite, zeolite, mica, Mica, Merck, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, dolomite, antimony trioxide, zinc oxide, titanium oxide, magnesium ferment, iron oxide, molybdenum disulfide, graphite, gypsum, glass peas, glass balloon, Inorganic fillers such as quartz powder can be included in the composition in amounts up to 80JI. When adding these reinforcing agents or fillers, known silane coupling agents can be used in combination.

In addition, the composition of the present invention may contain small amounts of a mold release agent, a coloring agent, a heat stabilizer, an ultraviolet stabilizer, a blowing agent, a flame retardant, a flame retardant aid, and a rust preventive agent within a range that does not depart from the purpose of the present invention. It can be made to contain.

The ptg method for the composition of the present invention can be carried out by various known methods. For example, the raw materials are mixed in advance in a mixer such as a tumbler or a Henschel mixer, then fed to a nine-shaft, two-screw extruder, and melt-kneaded at 230 to 400°C.
There are methods for preparing it as pellets.

(Effects) The resin composition of the present invention can be used, for example, in electrical/electronic parts such as connectors, printed circuit boards, and soil molded products, automotive parts such as lamp reflector 1 and various electrical components, various buildings, aircraft, and automobiles. interior materials, leisure and sports equipment such as tennis rackets, ski golf clubs, fishing rods, acoustic materials such as enclosures for speakers, back decks for stringed instruments, etc., precision parts such as OA equipment parts, camera parts, and clock parts, etc. It is used as a molding material with excellent mechanical properties such as heat resistance and impact resistance in various molding fields such as injection molding and compression molding, and extrusion molding and pultrusion molding of composites, sheets, etc.

(Examples) The present invention will be specifically explained below with reference to Examples, but the present invention is not limited only to these Examples.

Example 1, Comparative Example I PAS was pps (Rydon PR06, manufactured by Phillips Petroleum), and phenoxy resin was UCAR.
Phenoxy resin, grade PKHH (Union Carbide), thermoplastic resin, polyamide nylon 6
6 (BA8F Company Tai) was used. In addition, pps 300℃,
The real part of the complex viscosity at 100 rad/see [η is 700 to 1000 (pois@), the viscosity at 40 rad/see is 4500 to 7000, while the phenoxy resin is
(cps).

The blending weight ratio of (PPS/nylon-66) is (5015
0), and the phenoxy resin is PPS and nylon 6
Added 5X4jk4 for total weight of 6. After melt-kneading these mixtures at 290 to 310 DEG C., sample pieces were prepared and subjected to a bending test, an isot (no notch) impact test, and a tensile impact test. Further, after being left in hot water at 70°C for 24 hours, a bending test and a weight increase measurement were performed to evaluate water resistance. For the bending test, a test piece with a thickness of 2 mm, a width of 1018 cm, and a length of 301 N1 is used. For the Izotsu impact test, a rod-shaped test piece with a cross section of 3.15 x 3.15 mm is used for the tensile impact test. In case, diameter 1.5 mm, length 81
1s was used.

In all cases, injection molding could be carried out smoothly without any formation of molds. Moreover, the appearance of the molded products was uniform, and the compatibility was good. As Comparative Example 1, a test was carried out in the same manner as in Example 1 except that it did not contain phenoxy resin. The results are summarized in Table 1.

The appearance of the product without adding phenoxy resin is /4'-
The compatibility was poor as it had a round shape and was non-uniform. Due to insufficient compatibility in the comparative example,
Impact resistance has not been sufficiently improved.

In addition, poor water resistance and a decrease in p1 strength were also observed.

The inclusion of phenoxy resin as the third component of the blend increases compatibility and improves impact value.
It can be seen that water resistance is also improved.

Example 2.3 Using the same resin as in Example 1, (PPS/Nylon 66
/ phenoxy resin) blending ratio is (80/2015) and (
30/7015) was investigated. The preparation and evaluation of the test piece were the same as in Example 1. The results are in Table 1
are summarized in

′! Example 4-9. Comparative Example 2-7 pps-nylon 6 system (Example 4), pps-nylon MXDS system (Example 5), pps-polyethylene terephthalate system (Example 6), PP5-/rif-5-lenterephthalate system (Example 7) For the PPS-ABS resin system (Example 8) and the PP5-polyethylene system (Example 9), sample pieces were prepared in the same manner as in Example 1 using the formulations shown in Tables 2 to 7, respectively. (The phenoxy resin was added at the weight ratio shown in each table to the total weight of PPS and thermoplastic resin.)

In both cases, injection molding was able to be carried out smoothly without any formation of molds. An Izot impact test (without notches) was conducted in the same manner as in Example 1.

For comparison, a case where no phenoxy resin was added was investigated. The results are summarized in Tables 2 to 7.

It can be seen from Table 6 that impact resistance is improved by adding phenoxy resin.

The thermoplastic resins used were nylon 6 series (manufactured by Unitika), nylon MXD 6 (RENY 6301, manufactured by Mitsubishi Gas Chemical Co., Ltd.), and polyethylene terephthalate (Mitsui PIT J 125, manufactured by Mitsui Pet Resin Co., Ltd.).
Liptylene terephthalate (Planac BT-120
, manufactured by Dainippon Ink & Chemicals Co., Ltd.), ABS resin (Stylac, manufactured by Asahi Kasei Industries, Ltd.), and polyethylene (Silux F5010, manufactured by Showa Denko Co., Ltd.).

Not/Example 10-12. Comparative Example 8-10 PPS-polyethersulfone system (Example 10), pp
For the s-polysulfone system (Example 11) and the pps-modified polyphenylene oxide system (Example 12), sample pieces were prepared using the same method as in Example 1 using the formulations shown in Tables 8 to 10, respectively. (The phenoxy resin was added at the weight ratio shown in each table to the total weight of PPS and thermoplastic resin). However, the melt mixing was performed at 320 to 340°C.

In all cases, the melt viscosity was suitable, the fluidity was good, and injection molding could be carried out smoothly without ruching. Izot impact test M similar to Example 1 (without notch)
I did this. The results are shown in Tables 8 to 10.

For comparison, the case where no phenoxy resin was added was investigated, and the results are summarized in Tables 8 to 10.

From the results in Table 6, it can be seen that the impact resistance is improved by adding phenoxy resin.

The resin used was PPs (Rydon PRO-6
), phenoxy resin (PKHH), polyethersulfone (PFXB 3600, manufactured by ICI), polysulfone (UDELP-3500, manufactured by Union Carbide), modified polyphenylene oxide (Niepilon AV)
-60, manufactured by Mitsubishi Gas Chemical Co., Ltd.).

)' / Comparative Example 11-12 As Comparative Example 11 / Riethersulfone (PE5360
Using modified polyphenylene oxide (AV-60) as Comparative Example 0) and Comparative Example 12, injection molding was attempted at 320 to 340°C in the same manner as in the above example. It was not possible to perform a proper ejection.

Comparative Example 13-16 As the third component of the blend, a lac-based epoxy resin (Ebikukun N 69) was used instead of phenoxy resin.
5/manufactured by Dainippon Ink & Chemicals Co., Ltd.] to carry out melt blending. PAS is PPS (Rydon PR06), and thermoplastic resin is nylon 66 (BASF; Comparative Example 1)
3) Polybutylene terephthalate (Planac BT-
120; Comparative Example 14), preethersulfone (PES
3600; Comparative Example 15) and modified polyphenylene oxide (Iupiace AV-eo: Comparative Example 16). In each comparative example, the blending weight ratio of (PPS/thermoplastic resin/epoxy resin) was (5o/4872) and (80/18
/2) We investigated the case.

Injection molding was attempted using the same method as in the above example, but in each case, ruching occurred and the melt viscosity of the resin composition also became very high, so the injection molding did not proceed smoothly and the sample specimen could not be created.

Claims (1)

[Claims] (A) 95 to 10 parts by weight of polyarylene sulfide resin and (B) 5 to 90 parts by weight of other thermoplastic resin, to 100 parts by weight of the mixture, 1 to 3 parts by weight of phenoxy resin.
A thermoplastic resin composition containing 0 parts by weight.