JPH0354256A - Resin composition comprising polyphenylene sulfide - Google Patents

Abstract

PURPOSE:To obtain a polyphenylene sulfide resin composition improved in an interfacial adhesion between resin and rubber and impact resistance by melt-kneading a polyphenylene sulfide resin with a specified crosslinking agent and blending the obtained mixture with an elastic ionomer resin component. CONSTITUTION:A composition obtained by melt-kneading (at 280-340 deg.C) 95-99.9wt.%, desirably 97-99wt.% polyphenylene sulfide resin (A) (desirably of a melt viscosity of 1,000-5,000P) with 0.1-5wt.%, desirably 1-3wt.% nonblocked polyisocyanate compound (e.g. 4,4'-diphenylmethane diisocyanate) is mixed with an ionomer (B) (desirably of a mol.wt. of 30,000-500,000, e.g. a combination of an ethylene/acrylic acid copolymer with a metallic ion such as Na<+> or Zn<2+>) in an A to B ratio of (70-97):(30-3), desirably (80-90):(20-10) to obtain an impact- resistant polyphenylene sulfide resin composition.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a polyphenylene sulfide resin composition with improved impact resistance. This invention relates to a polyphenylene sulfide resin composition which has improved impact resistance by incorporating an ionomer into the polyphenylene sulfide resin obtained by melt-kneading the compound. (Prior Art) Conventionally, as a polyphenylene sulfide resin with improved impact resistance, JP 59-207921A discloses a polyphenylene sulfide resin containing an unsaturated carboxylic acid or its anhydride,
A composition comprising an α-olefin copolymer elastomer obtained by graft copolymerizing or a derivative thereof and an epoxy resin is disclosed. Also, JP-A-58-1547 and JP-A-59-
Publication No. 152953 discloses a set 7i! in which a polyphenylene sulfide resin contains an ethylene-glycidyl methacrylate copolymer! Disclosing things. Also, JP-A-63
Japanese Patent No. 95265 discloses a composition in which polyphenylene sulfide resin contains polyisoptylene. (Problems to be Solved by the Invention) However, even in the composition described in the above publication, the effect of improving impact resistance is insufficient. More specifically, as is known in the art, the molecular chains of polyphenylene sulfide resins have poor reactivity, so rubbers rich in reactivity such as the copolymers described in the above-mentioned publication, or similar Even if a highly reactive epoxy resin is blended, the adhesion at the interface with the polyphenylene sulfide resin is insufficient, so it is currently not possible to achieve a sufficient impact resistance improvement effect. ．． Therefore, the inventor of the present invention has conducted intensive studies to improve the adhesion at the interface between Borif-X nylene sulfide resin and rubber, and by blending a certain amount of a specific elastic resin into polyphenylene sulfide resin that has undergone specific treatment. this! The inventors have discovered that the problem can be solved, and have arrived at the present invention. (Means for Solving the Problems) That is, the present invention provides polyphenylene sulfide resin,
As an essential precept, the present invention provides a resin composition comprising an ionomer contained in a resin obtained by melt-kneading a non-blocked polyfunctional isocyanate compound. The polyphenylene sulfide used in the present invention contains 70 mol% or more of repeating units, more preferably 90 mol% or more of repeating units represented by
It is a polymer containing mol% or more, and the above repeating unit is 7
If it is less than 0 mol%, heat resistance will be impaired, which is not preferable. PPS generally includes a polymer with a relatively small molecular weight obtained by a manufacturing method typified by Japanese Patent Publication No. 45-3368, and a polymer obtained by a manufacturing method typified by Japanese Patent Publication No. 52-12240. There are essentially linear and relatively high molecular weight polymers obtained, and in the polymer obtained by the method described in Japanese Patent Publication No. 45-3368, by heating in an oxygen atmosphere after polymerization, Alternatively, it is possible to increase the degree of polymerization by adding a crosslinking agent such as peroxide and heating, and it is also possible to use PPS obtained by any method in the present invention. Furthermore, less than 30 mol% of the repeating units of PPS can be composed of repeating units having the following ill structure. The melt viscosity of PPS used in the present invention is not particularly limited as long as it is possible to obtain a shaped product, but in terms of the toughness of PPS itself, it is 100 poise or more, and in terms of shapeability, it is 100 poise or more. ,000 boads or less is more preferably used. Among them, a particularly preferable range is 1,000 to s,
ooo It's Boaz.

In addition, the PPS used in the present invention may contain antioxidants, heat stabilizers, lubricants, crystal nucleating agents, etc., to the extent that the effects of the present invention are not impaired.
Customary additives such as UV inhibitors, colorants and small amounts of other resinous or rubbery polymers can be added. Furthermore, for the purpose of controlling the degree of crosslinking of PPS, an ordinary peroxide-based crosslinking agent and a crosslinking accelerator such as a thiophosphinate metal salt described in JP-A-59-131650, or Publication No. 58-204045, Japanese Unexamined Patent Publication No. 1973
It is also possible to blend crosslinking inhibitors such as dialkyltin dicarboxylate and aminotriazole described in JP 8-204046 and the like.

Methods for blending polyfunctional isocyanates into PPS are already known. For example, JP-A-57-1689
In the lower right column of page 3 of the specification of Publication No. 45, it is disclosed that 0.1 to 10% by weight of isocyanate is added to PPS. However, there is no suggestion whatsoever about impact-resistant PPS compounded with a special elastomer. A preferred embodiment of the present invention is to incorporate an ionomer into a resin obtained by melt-kneading 95 to 99.9 weight 2 of a polyphenylene sulfide resin and 0.1 to 5 weight 2 of a non-blocked polyfunctional isocyanate compound. The unblocked polyfunctional isocyanate compound in the present invention includes an isocyanate compound having two or more unblocked incyanates in one molecule, and has the general formula: R- (N=C-0)n or R- (N=C=S)n (wherein, R is an organic group dominated by elements such as carbon, hydrogen, sulfur, phosphorus, nitrogen, oxygen, etc., and n is an integer of 2 or more.) unblocked polyfunctional isocyanate compound,
Alternatively, there are isothiocyanate compounds. The general types are roughly divided into aliphatic type and aromatic type, and modified types include dimeric type, 3t type (isocyanurate type), multimeric type, carbodiimide modified type, etc.
Any isocyanate compound can be used in the present invention. However, blocked isocyanates (
Block-type isocyanate compounds (also known as masked isocyanates), in which isocyanates are reacted in advance with acidic sodium sulfite, phenol, cresol, lactams, heterocyclic compounds, hydrocyanic acid, sulfites, etc., and then regenerated at high temperatures, are It is not included because it has little effect on the purpose. As a specific compound, for example, 4
．． 4゜-diphenylmethane diisocyanate}, 4.4'
-Diphenylpropane diisocyanate, carbodiimide modified diphenylmethane diisocyanate, naphthylene 1,5-diisocyanate, toluene diisocyanate, dimerized toluene diisocyanate, hexamethylene diisocyanate, 3fi hexamethylene diisocyanate, pentamerized hexamethylene diisocyanate, heptamerized hexamethylene Diisocyanate, polymethylene polyphenyl polyisocyanate, phenylene diisocyanate, 3,3°-dimethyldiphenylmethane-4.4”-
Diisocyanate, 3,3゜-dimethyl-4,4゜-diphenylene diisocyanate, 3,3゛- and toluene-
4,4'-diisocyanate, xylene diisocyanate, isophorone diisocyanate, triphenylmethane triisocyanate, lysine diisocyanate, dicyclohexyldimethylmethane diisocyanate, diethyl fumarate diisocyanate, triisocyanatebenzene, triisocyanatenaphthalene, bis(4-incyanate phenyl) Ether, bis(4-isocyanate phenyl) thioether, bis(4-isocyanate phenyl) sulfone, tris(4-isocyanate phenyl) phosphite, tris(4-isocyanate phenyl) phosphate, and corresponding isothiocyanates. There are also non-bronch type polyfunctional isocyanate compounds such as the above-mentioned aromatic isocyanate compounds to which water is added. The melt-kneading in the present invention can be carried out using a known device, such as a kneader, roll mill, or extruder, which is normally used for kneading resin melts. Types of extruders include single-screw, twin-screw, co-kneader, etc., and the composition of the present invention can be obtained using any of these extruders. The kneading temperature is higher than the melting point of the polyphenylene sulfide resin, and sufficient kneading is possible within the commonly used range of 280°C to 340'C. In addition, it is preferable that the polyphenylene sulfide resin is pre-dried as a pretreatment, and the a-kneading is preferably carried out in an inert gas atmosphere. The unblocked polyfunctional isocyanate compound is used at a ratio of 0.1 to 5 weight χ, preferably 1 to 3 weight χ. The isocyanate compound is considered to function effectively as a crosslinking agent for crosslinking the polyphenylene sulfide resins together, but if the mixing ratio is 0.1 times IX or less, the modification effect in the present invention decreases. On the other hand, if the weight χ is more than 5, the degree of cross-linking increases too much, and it tends to become brittle. Ionomers have been discovered as particularly excellent alloy-type elastomers. The method for producing the ionomer used in the present invention is already well known (Japanese Patent Publication No. 39-6810), and is produced by reacting a base copolymer with a metal compound capable of ionizing the copolymer. .

The base copolymer contains an α-olefin represented by the general formula RCH-CHt (where R is selected from the group consisting of hydrogen and an alkyl group having 1 to 8 carbon atoms) and an α,β monoethylenically unsaturated group. Among these, α-olefin-monocarboxylic acid copolymers are particularly suitable. Examples of base copolymers that can be suitably used include ethylene/acrylic acid copolymer, ethylene/methacrylic acid copolymer, ethylene/itaconic acid copolymer, and ethylene/acrylic acid copolymer.
Maleic acid copolymer, ethylene/acrylic acid/methyl methacrylate copolymer, ethylene/methacrylic acid/vinyl acetate copolymer, ethylene/acrylic acid/vinyl alcohol copolymer, ethylene/propylene/acrylic acid copolymer, Ethylene/styrene/acrylic acid copolymer, ethylene/methacrylic@/acrylonitrile copolymer, ethylene/vinyl chloride/acrylic acid copolymer, ethylene/chlorotrifluoroethylene/methacrylic acid copolymer, polyethylene/acrylic acid graft copolymer Examples include polymers, polypropylene/acrylic acid graft copolymers, and the like. In addition, when the base copolymer is an α-olefinino-monocarboxylic acid copolymer, metal ions having a valence of 1 to 3 (for example, Na'', K', L
i', Cu", Be", Mgt'Zn", AI
", etc.) are suitable, and in the case of α-olefin-dicarboxylic acid copolymers, those having a monovalent valence (for example, Na", K', L1°, etc.) are suitable.

An example of an ionomer used is a combination of ethylene-acrylic acid copolymer and metal ions such as Na or Zn''.

formates, acetates, hydroxides, methoxides of the above metals;
Ionomers can be produced by reacting carbonates etc. with the above base copolymers. The molecular weight of the ionomer is 10,000 to 1,000,0
00, preferably from 20,000 to 800,000, more preferably from 30,000 to soo,ooo. In the present invention, there is no particular restriction on the ratio of PPS and ionomer to be blended, but if the ionomer is less than 3 parts by weight, it will be difficult to obtain the desired effect, and if it exceeds 30 parts by weight, the strength, rigidity, and heat resistance of PPS will deteriorate. Therefore, the ionomer is preferably 30 to 3 parts by weight, more preferably 30 to 3 parts by weight based on 70 to 97 parts by weight of PPS.
P375-95 parts by weight, ionomer-25-5
A range of 20 to 10 parts by weight of ionomer can be preferably selected for 80 to 90 parts by weight of PPS. In the method of melt-kneading PPS, isocyanate compound, and ionomer, the mixing order does not matter, but the most preferable method is to melt-knead PPS and isocyanate compound in advance, and then knead the ionomer. To simplify the process, a method of mixing pps, an isocyanate compound, and an ionomer at the same time may be adopted. In the present invention, it is possible to mix mm-shaped and/or granular reinforcing agents in an amount not exceeding 300 parts by weight based on a total of 100 parts by weight of PPS and ionomer, and usually 10 to 10 parts by weight. By blending within the range of 300 parts by weight, it is possible to improve strength, rigidity, heat resistance, dimensional stability, etc. Examples of such fibrous reinforcing agents include inorganic fibers such as glass fibers, glass fibers, alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers, gypsum fibers, and metal fibers, and carbon fibers. In addition, granular reinforcing agents include silicates such as wollastenite sericite, kaolin, mica, clay, bentonite, asbestos, talc, and alumina silicate; alumina, silicon oxide, magnesium oxide, zirconium oxide,
Metal oxides such as titanium oxide; carbonates such as calcium carbonate, magnesium carbonate, and dolomite; silicates such as calcium sulfate and barium sulfate; glass beads, boron nitride, silicon carbide, Saroyan, and silica. may be hollow (porous). Two or more of these reinforcing agents can be used in combination, and if necessary, they can be pretreated with a coupling agent such as a silane type or titanium type before use. There are no particular limitations on the means for preparing the Mt2 product of the present invention, but PP
A typical method is to melt-knead S and isocyanate, then add an ionomer and melt-knead, and then melt-knead the reinforcing agent in an extruder at a temperature higher than the melting point of PPS, followed by pelletizing. The melt-kneading temperature is 280°C.
~340'C is preferable, and below 280°C, PP
The melting of S may become insufficient, and if the temperature exceeds 340"C, the ionomer may undergo thermal deterioration and gelation, so care must be taken. The present invention will be explained in more detail with reference to Examples below. Reference Example 1 (Production of isocyanate-treated PPS) After drying pps powder (Tovren T-4) at 150'C for 3 hours, the temperature was lowered to 50'C, and 4,4'-diphenylmethane diisocyanate was added to the PPSIOO section. against 2
After mixing in a Henshil mixer in a nitrogen atmosphere for 30 seconds, the mixture was pelletized in a nitrogen atmosphere at a cylinder temperature of 290 to 300°C using a "PCM-30" twin screw extruder manufactured by Ikegai Steel. Example 1 Beresit obtained in Reference Example 1 and ionomer [Hyōran 1706 (manufactured by Mitsui Polychemicals ■) Znh is used as a metal ion] Beret were dry blended at a weight ratio of 90:10, and this was mixed using a biaxial machine. 310 after feeding to the kneading extruder
Melt and knead at ℃, extrude into strands, cut,
I got that &lI awesome pellet. Regarding the pellet, 290~3
Test pieces for measuring physical properties were obtained by injection molding at 20°C. The Izod impact strength of the obtained test piece was measured according to ASTM D-256 method to evaluate the impact resistance. Example 2 Beleft and ionomer of Reference Example 1 [Himilan 170
6 (manufactured by Mitsui Polyke Kamekal ■)) Perent and 80:2
The same operation as in Example 1 was performed except that dry blending was carried out at a weight ratio of 0. The obtained results are also shown in Table 1. Example 3 Bereft obtained in Example 1 and glass fiber [ECSO3
-↑717DI! (manufactured by Nippon Electric Glass Co., Ltd.)] and 60:
They were dry blended at a weight ratio of 40%, melt-kneaded at 310°C, extruded into strands, and cut to obtain pellets. Thereafter, injection molding and physical property evaluation were performed in the same manner as in Example 1. The obtained results are also shown in Table 1. Example 4 Beret and 7 ionomer of Reference Example 1 [High ξ Run 170
6 (manufactured by Mitsui Polychemicals)] and glass fiber (EC
303-T717DE (manufactured by Nippon Electric Glass Co., Ltd.)] and 8
The same operation as in Example 1 was performed except that dry blending was performed at a weight ratio of 0:20:67. The obtained results are also shown in Table 1. Examples 5 to 8 The same operations as in Example were carried out except that the type of ionomer was changed. The results are also shown in Table 1.

Comparative Example 1 The same operation as in Example 1 was performed except that the ionomer was not mixed. The results are also shown in Table 1. Comparative Example 2 Beleft obtained in Comparative Example 1 and glass fiber [EC SO
3-T717DE (manufactured by Nippon Electric Glass Co., Ltd.)] and 60:4
The same evaluation as in Example 2 was performed except that dry blending was performed at a weight ratio of 0. The obtained results are also shown in Table 1. Comparative Example 3 Bereft of Reference Example 1 and glass fiber (ECSO3-T71
7IIE (manufactured by Nippon Electric Glass Co., Ltd.)] and 100:67 (D
The same operation as in Example 3 was performed except that dry blending was carried out at the weight ratio. The obtained results are also shown in Table 1. Comparative Example 4 Toubren T4 and ionomer [Himilan 1706 (
Mitsui Polyquet Cal @ J) [Bereno] and 90 = 10
The same operation as in Example 1 was performed except that dry blending was performed at a weight ratio of . The results are also shown in Table 3. Comparative Example 5 The pellet and glass fiber obtained in Comparative Example 4 [EC SO
3-T717ROE (manufactured by Nippon Electric Glass Co., Ltd.)] and 60 = 4
The same evaluation as in Comparative Example 2 was performed except that dry blending was performed at a weight ratio of 0. The obtained results are also shown in Table 3. Table 3 [Effects of the Invention] In the present invention, an elastic resin called an ionomer (n) is blended with a polyphenylene sulfide resin that has been pretreated with a specific non-Bronok type polyfunctional isocyanate compound ([). This has the effect that a polyphenylene sulfide resin composite having particularly excellent 81 impact resistance can be obtained compared to those that are not pre-treated with () or blended with the specific elastic resin (■).

Claims (1)

[Claims] A polyphenylene sulfide resin composition comprising an ionomer contained in a polyphenylene sulfide resin obtained by melt-kneading a polyphenylene sulfide resin and a non-blocked polyfunctional isocyanate compound.