JPH0459871A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To provide the title composition excellent in resistance to heat and solvents, mechanical strength etc., suitable for the industrial material field such as for automobiles, comprising a (modified) polyphenylene sulfide and (modified) polyphenylene ether at each specified amount. CONSTITUTION:The objective composition can be obtained by incorporating a total of 100 pts.wt. of (A) 90-10wt.% of a polyphenylene sulfide and/or modified one prepared by modifying the polyphenylene sulfide with an organic compound having two or more amino or isocyanate groups in the molecule and (B) 10-90wt.% of a polyphenylene ether and/or modified one prepared by modifying the polyphenylene ether with an organic compound having two or more amino or isocyanate groups in the molecule with (C) 1-50 pts.wt. of a thermoplastic elastomer. One or both of the components A and B is (are) modified polymer(s).

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a polyphenylene sulfide resin composition having excellent heat resistance, solvent resistance, mechanical strength and impact resistance.

<Conventional technology> Polyphenylene sulfide resin (hereinafter abbreviated as PPS)
In a reinforced system reinforced with glass fiber or the like, it has properties suitable as a crystalline engineering plastic, such as excellent heat resistance, impact resistance, and rigidity, and is used for various purposes, mainly injection molding. However, unreinforced PPS that is not reinforced with glass fiber or the like lacks toughness and is therefore extremely brittle. Furthermore, since the glass transition temperature is as low as 90° C., the heat resistance is insufficient, and it is currently difficult to use it for various molding applications.

In recent years, it has been found through various polymer combinations that it is an effective method to improve the lack of heat resistance of crystalline thermoplastic resins by combining them with non-grade thermoplastic resins that have a high glass transition temperature to form polymer alloys. ing. One of the non-grade thermoplastic resins suitable for such purposes is polyphenylene ether. Polyphenylene ether (hereinafter referred to as
Many proposals have already been made regarding the modification of PPS with PPE (abbreviated as PPE).

For example, in Japanese Patent Publication No. 56-34032, PPS and P
A resin composition made of PE and having excellent moldability and flame retardancy has been proposed. Furthermore, JP-A-58-157859 discloses PPS grafted with PPS and styrene polymer.
A resin composition composed of PE with improved compatibility was disclosed in Japanese Patent Application Laid-open No. 5
No. 9-164360 discloses a resin composition with improved compatibility consisting of PPS, PPE, and epoxy resin, and JP-A-59-213758 discloses a resin composition consisting of PPS, PPE, and epoxy resin.
A resin composition with improved compatibility consisting of PE, polyamide resin and epoxy resin has been disclosed in Japanese Patent Application Laid-Open No. 63-20535.
No. 8 proposes a resin composition with improved compatibility consisting of PPS, PPE, and a maleimide compound.

Furthermore, JP-A No. 64-31862 discloses a method comprising modified PPE and PPS modified with a modifying agent having an ethylenic double bond and a carboxyl group or an acid anhydride group, and an organic compound having at least two or more epoxy groups. JP-A-1-259060 discloses a resin composition with improved compatibility and excellent heat resistance and solvent resistance, which contains an ethylenic double bond and a functional group selected from a carboxyl group, an acid anhydride group, a hydroxyl group, and an epoxy group. Modified PP modified with a modifier having
JP-A-1-266160 discloses a resin composition with improved compatibility and excellent mechanical performance, heat resistance, and solvent resistance, which is composed of modified PPS modified with E and the modifier, and is disclosed in JP-A-1-266160. and carboxyl group, acid anhydride group, hydroxyl group,
Modified PPE modified with a modifier having a functional group selected from epoxy groups, modified PPS modified with the modifier, and carboxyl groups, acid anhydride groups, hydroxyl groups, amino groups, epoxy groups, mercapto groups, and oxazoline groups in the molecule. A resin composition has been proposed which is composed of a binder having a small number (or two or more) of functional groups selected from isocyanate groups, and has excellent compatibility, improved mechanical performance, and solvent resistance.

Furthermore, in Japanese Patent Application Laid-open No. 1-213359, PPS
A resin composition comprising PPE and a glycidyl group-containing thermoplastic polymer with improved compatibility and excellent heat resistance, flame retardance, solvent resistance, moldability, mechanical strength, and impact resistance has been disclosed in JP-A-1999-1. -213360 publication describes acid-modified PPS and α
A resin composition with improved heat resistance, flame retardance, solvent resistance, moldability, mechanical strength, and impact resistance, consisting of a compatible agent made of modified PPE modified with β-unsaturated carboxylic acids, has a special property. Japanese Patent Publication No. 1-213361 discloses a product made of PPS, PPE, and a glycidyl group-containing styrene resin, which has improved compatibility and has excellent heat resistance, flame retardance, solvent resistance, moldability, mechanical strength, and impact resistance. Resin compositions have been proposed.

<Problem to be solved by the invention> However, among these proposals, the
The composition consisting of PPS and PPE described in Publication No. 32 is PP
Compared to the case of using E alone, although it does give a resin composition with excellent processability, the impact resistance is poor, the compatibility is insufficient, and delamination is significant. P grafted with PPS and styrene polymer described in JP-A-58-157859
A resin composition made of PE, a resin composition made of PPS, PPE, and an epoxy resin described in JP-A No. 59-164360, a resin composition made of P as described in JP-A No. 59-213758
Resin compositions consisting of PS, PPE1 polyamide resin and epoxy resin, and resin compositions consisting of PPS, PPE and maleimide compound described in JP-A No. 63-205358, use PPE grafted with a styrene polymer, and epoxy resin. The purpose is to provide a resin composition in which the compatibility of PPS and PPE is improved by using a resin, an amide resin and an epoxy resin, and a maleimide compound. PP5 (!:P
Although a slight improvement in compatibility is observed when compared to compositions made of PE, the effect is still insufficient, and therefore the impact resistance, particularly the notched Izo impact value, is low.

In addition, modified PPE described in JP-A No. 64-31862
and a resin composition consisting of PPS and an epoxy compound, modified PPS and modified P described in JP-A-1-259060.
The resin compositions made of PE, the resin compositions made of modified PPS, modified PPE, and a compound having two or more functional groups described in JP-A-1-266160 all contain PPS and/or PPE with ethylenic double bonds. By modifying with a compound that simultaneously has functional groups such as a carboxyl group and an acid anhydride group, and by adding a compound that also has a functional group, we aim to improve compatibility, resulting in a resin with improved mechanical strength and solvent resistance. However, the effects of these resin compositions are still not sufficient, and therefore the impact resistance, especially the notched Izot impact value, is low.

Furthermore, PPS and P described in JP-A-1-213359
A resin composition comprising PE and a glycidyl group-containing polymer, a resin composition comprising modified PPS and modified PPE described in JP-A-1-213360, JP-A-1-213361
Regarding the resin composition made of PPS, PPE, and glycidyl group-containing styrene resin described in the above publication, by adding a glycidyl group-containing polymer, or by converting PPS and/or PPE into an acid compound or an α,β-unsaturated carbon Improve compatibility by modifying with acids,
The purpose is to provide a resin composition with improved mechanical strength, solvent resistance, etc., but its effects cannot be said to be sufficient, so impact resistance, especially notched Izot impact value is low. For this reason, at present, a resin composition with sufficient performance as a molding material, particularly excellent notched Izot impact value, has not been obtained.

Therefore, the present inventors conducted extensive studies to obtain a resin material with excellent practical properties such as heat resistance, solvent resistance, mechanical strength, and impact resistance, especially notched isot impact strength, in a combination of PPS and PPE. , PPS and/or modified PPS, PPE and/or modified PPE, and the PPS resin composition obtained by further adding a thermoplastic elastomer to the composition have excellent heat resistance, solvent resistance, mechanical properties. The present inventors have discovered that the material has excellent physical strength and impact resistance, particularly notched isot impact strength, and can be used for molding purposes, and have thus arrived at the present invention.

<Means for Solving the Problems> That is, the present invention provides (1) (A) polyphenylene sulfide and/or a polyphenylene sulfide having two amino groups or isocyanate groups in the molecule;
(B) polyphenylene ether and/or modified polyphenylene ether modified with an organic compound having two or more amino groups or isocyanate groups in the molecule 1
(2) (A) polyphenylene sulfide and/or a polyphenylene sulfide resin composition containing 0 to 90% by weight of modified polyphenylene sulfide and/or modified polyphenylene ether; group or isocyanate group to 2
(B) polyphenylene ether and/or modified polyphenylene ether modified with an organic compound having two or more amino groups or isocyanate groups in the molecule 1
(C) 1 to 50 parts by weight of thermoplastic elastomer is blended with 100 parts by weight of a resin composition comprising 0 to 90% by weight and containing at least one of modified polyphenylene sulfide and modified polyphenylene ether. A polyphenylene sulfide resin composition is provided.

P P S (A) used in the present invention is a polymer containing 70 mol% or more, more preferably 90 mol% or more of repeating units represented by the structural formula: If it is less than 70 mol%, heat resistance will be impaired, which is not preferable. Generally, PPS is
A polymer with a relatively low molecular weight obtained by the production method typified by Japanese Patent Publication No. 68, and an essentially linear polymer with a relatively high molecular weight obtained by the production method typified by Japanese Patent Publication No. 52-12240. There are bodies, etc., and the above-mentioned
In the polymer obtained by the method described in No. 368,
After polymerization, it is possible to increase the degree of polymerization and use it by heating in an oxygen atmosphere or by adding a crosslinking agent such as peroxide and heating. It is also possible to use PPS, but because the effect of the present invention is remarkable and the toughness of PPS itself is excellent, the essential A linear polymer having a relatively high molecular weight can be more preferably used.

Furthermore, less than 30 mol% of the repeating units of PPS can be composed of repeating units having the following structural formula.

The PPS used in the present invention can be any PP as described above.
Although S can also be used, for example, JP-A-1-17456
An acid or an acid aqueous solution as proposed in Publication No. 2,
It is preferable to use a resin composition that has been deionized by treatment with hot water or an organic solvent, since this will significantly improve the impact resistance of the resin composition.

Among these relatively high molecular weight PPS, the number average molecular weight (Mn) and weight average molecular weight (M
w) has a molecular weight distribution that satisfies the ratio Mw/Mn<10, and also meets ASTM D1238.
-86 (315.5℃, 5,000g load) melt flow rate value (MF5) is 200g/
Particularly preferably used is PPS which is 10 m1n or less, has a melt flow rate retention rate of 50 < MF s /MF, and satisfies TeX100 < 120.

(Here, MF5 and MF15 represent melt flow rate values at residence times of 5 minutes and 15 minutes, respectively.) Next, PP used as component (B) in the present invention
E is a bonding unit (where R□, R2, R3, and R4 are each selected from the group consisting of hydrogen, halogen, hydrocarbon, or substituted hydrocarbon group, and are the same or different); ) and has a reduced viscosity (0.5 g/J chloroform solution, measured at 30°C) in the range of 0.15 to 0.70, more preferably in the range of 0.20 to 0.60. Copolymers and/or copolymers are used.

A specific example is poly(2,6-cymethyl-1.4
-) unilene ether), poly(2-methyl-6-nityl-1,4-)unilene ether), poly(2,6-diphenyl-1,4-phenylene ether), poly(2-
methyl-6-phenyl-1,4-phenylene ether)
, poly(2,6-dipolyrolow-1,4-)unilene ether), and 2,6-dimethylphenol and other phenols (e.g., 2,3,6-trimethylphenol). Examples include polyphenylene ether copolymers such as copolymers of Among them, poly(2,6-
Copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferred, particularly poly(2,6-dimethyl-1,4-), enylene ether) is preferred.

The method for producing such PPE is not particularly limited, and those obtained by known methods can be used. For example, Ha described in U.S. Pat. No. 3,306.874
It can be easily produced by, for example, oxidative polymerization of 2,6-xylenol using a complex of cuprous salt and amine according to y as a catalyst.

In addition, the organic compound that modifies PPS and PPE is an organic compound having two or more amino groups or isocyanate groups in the molecule, such as ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, .7-Diaminohebutane, 1,8-diaminooctane, 1.9-
Diaminononane, 1.10-diaminodecane, 1°12
-diaminododecane, 0-funylenediamine, m-fuynylenediamine, p-fuynylenediamine, 2.4-
1-toluene diamine, 2.6-toluene diamine, m-xylylene diamine, p-xylylene diamine, 4.4'
-diaminodiphenylmethane, 3.3'-diaminodiphenylmethane, 4.4'-diaminodiphenylpropane, 4.4'-diaminobiphenyl, 4.4'-
Diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfide, 4,4'-diaminobenzophenone, 1.
3-bis(3-aminophenoxy)benzene, 1.4-
Bis(4-aminophenoxy)benzene, 3.3' -
Dimethyl-4,4'-diaminodiphenylmethane, 3
．． Polyamine compounds such as 3'-dichloro-4,4'-diaminodiphenylpropane, 9,9-bis(4-aminophenyl)fluorene, bis-(p-aminocyclohexyl)methane, bis-(p-aminocyclohexyl)propane , m-phenylene diisocyanate, p-
Funidine diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, diphenylsulfone diisocyanate, triphenylmethane diisocyanate, hexamethylene diisocyanate, 3
-Isocyanate methyl-3,5,5-1-limethylcyclohexyl isocyanate, 3-isocyanatoethyl 3,5.5-)limethylcyclohexyl isocyanate, diphenylpropane diisocyanate, cyclohexylene diisocyanate, diphenylethyl-4,4'
- Polyisocyanate compounds such as diisocyanates may be mentioned.

These organic compounds are usually PPS or PPE100
0.01 to 20 parts by weight, preferably 0.01 to 20 parts by weight.
It is used in an amount of 1 to 10 parts by weight.

In addition, the method for producing modified PPS or modified PPE is obtained by reacting it in a molten state, a dissolved state, or a slurry state at a temperature of 80 to 350°C, and among these known methods, a melt-kneading method is used. For example, PPS or PPE and the organic compound used for modification are heated at 290 to 330°C.
Examples include a method in which the modified PPS or modified PPE of the present invention is modified by melt-kneading while applying a shear rate of 10 sec-" or more at a temperature of It is not limited by.

The PPS resin composition of the present invention comprises the above component (A) and (
It is based on a resin composition composed of component B) and contains at least one of modified PPS and modified PPE.

Specifically, it is a resin composition composed of each combination exemplified by modified PPS and PPE, PPS and modified PPE, modified PPS and modified PPE, and this combination has excellent compatibility (layer delamination prevention property), Improves mechanical strength, heat resistance, solvent resistance, impact resistance, especially notched Izo impact value.

On the other hand, a resin composition composed of a combination of PPS and PPE containing neither modified PPS nor modified PPE has poor compatibility, and therefore no improvement in impact resistance, particularly notched Izot impact value, is observed.

Furthermore, the resin composition of the present invention is composed of PPS and/or modified PPS (A) and PPE and/or modified PPS (A).
E can be obtained by combining the two components of (B), but
These compounding ratios are PPS and/or modified pp
S (A) is 90-10% by weight, preferably 80-20%
% by weight of PPE and/or modified PPE from 10 to 90
% by weight, preferably from 20 to 80% by weight. where PPS and/or modified P P
If S (A) is less than 10% by weight and PPE and/or modified PPE (B) is more than 90% by weight, only a PPS resin composition with extremely poor solvent resistance will be obtained; or modified PPS (^) if it exceeds 90% by weight, PPE and/or modified PPS
If (B) is less than 10% by weight, it is not preferable because heat resistance decreases.

Furthermore, the PPS resin composition of the present invention has the above-mentioned (A),
(B) is a polymer alloy consisting of each combination of components,
Furthermore, in order to further improve the impact resistance of the resulting resin composition, a thermoplastic elastomer can be added as component (C) in the present invention.

The thermoplastic elastomer used as component (C) of the present invention includes known ones such as polyolefin elastomer, polystyrene elastomer, polyamide elastomer, polyester elastomer, polyurethane elastomer, and fluorine elastomer, among others, Polyolefin elastomers and polystyrene elastomers can be suitably selected.

Examples of polyolefin elastomers include ethylene-(meth)acrylic acid copolymer, ethylene-propylene-diene copolymer, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-propylene copolymer, and ethylene. -Maleic anhydride modified products of butene copolymers and the like.

Next, examples of polystyrene-based elastomers include block copolymers of vinyl aromatic compounds and conjugated diene compounds, or hydrogenated products of these block copolymers (hereinafter abbreviated as hydrogenated block copolymers), and further, Modified products (
(modified polystyrene elastomer).

Examples of these polystyrene elastomers include styrene-butadiene-styrene block copolymers,
Examples include styrene-isoprene-styrene block copolymers and hydrogenated products of these block copolymers (hydrogenated block copolymers), as well as maleic anhydride-modified products of these block copolymers and hydrogenated block copolymers. Examples include.

Specific examples of these polystyrene-based elastomers include 1'Califlex TR'' and ``Krayton G'' series manufactured and sold by Shell Chemical Company.

Furthermore, these block copolymers, hydrogenated block copolymers and α,β-unsaturated carboxylic acids or derivatives thereof are melted in the presence or absence of a radical generator, and heated at 80 to 350°C in the dissolved state. It is also possible to denature by reacting at temperature.

Examples of α,β-unsaturated carboxylic acids or derivatives thereof used in this modification include maleic acid, maleic anhydride, fumaric acid, itaconic acid, acrylic acid, acrylic acid ester, crotonic acid, and maleimide compounds. Among these, maleic anhydride is preferably used. α
, β-unsaturated carboxylic acid or its derivative is in the range of 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the block copolymer or hydrogenated block copolymer.
Used in parts by weight.

The method for producing the modified polystyrene elastomer can be carried out in any of the known melt mixing state or solution mixing state, and is not limited thereto. moreover,
These exemplified thermoplastic elastomers may be used alone or in combination of two or more.

Thermoplastic elastomer (C) used in the present invention
is PPS and/or modified PPS (A) and PP
1 to 50 parts by weight, preferably 3 to 40 parts by weight, per 100 parts by weight of the resin composition composed of E and/or modified P PE (B). If the thermoplastic elastomer (C) exceeds 50 parts by weight, the heat resistance of the resulting resin composition will decrease, which is not preferable.

In this way, the PPS resin composition of the present invention has (A) and (B)
It is composed of each component (C), and if necessary, glass fibers, alumina fibers, silicon carbide fibers, ceramic fibers, and asbestos may be added to an extent that does not impair the properties of the PPS resin composition of the present invention. fibers, gypsum fibers, metal fibers, carbon fibers and other fibrous reinforcements, wollastenite,
Silicates such as sericite, kaolin, mica, clay, bentonite, asbestos, talc, alumina silicate, metal compounds such as alumina, silicon chloride, magnesium oxide, zirconium oxide, titanium oxide, carbonates such as calcium carbonate, magnesium carbonate, and dolomite. salts, sulfates such as calcium sulfate and barium sulfate, glass peas, non-fibrous reinforcing agents such as boron nitride, silicon carbide, and silica, various flame retardants, crystallization promoters (nucleating agents), mercaptosilane, vinylsilane, and acinosilane. , a silane coupling agent such as epoxy silane, an antioxidant, a heat stabilizer, an ultraviolet absorber, a coloring agent, etc. can also be added.

The means for preparing the PPS resin composition of the present invention is not particularly limited, and
For example, a heating melt mixing method using a single screw extruder, twin screw extruder, kneader, Brabender, etc. is used. Among these, a melt mixing method using a single-screw or twin-screw extruder is preferred.

The melting crosstalk temperature is preferably 280° C. or higher in order to sufficiently melt the PPS, and 340° C. or lower in order to prevent thermal decomposition.

The PPS resin composition of the present invention obtained in this way is
Various conventionally known processing methods such as injection molding, extrusion molding, and foam molding are possible. In addition, it can be widely used as a molding material with excellent heat resistance, impact resistance, flame retardant, and moldability in industrial materials fields such as automobiles, electricity, electronics, and machinery.

<Example> Hereinafter, the present invention will be further explained in detail using Examples.

The % parts and ratios used in the examples represent weight %, parts by weight, and weight ratios, respectively, unless otherwise specified.

In addition, the Izot impact strength, tensile strength, heat distortion temperature, melt flow rate, molecular sac and molecular weight distribution, and solvent resistance in this example were each measured by the following measuring methods.

Izotsu impact strength: ASTM D256 tensile strength
: ASTM D638 Heat distortion temperature : ASTM D648 Melt flow rate: ASTM D1238-86 (
Measurement of molecular weight and molecular weight distribution: using a gel permeation chromatography device manufactured by Waters, as disclosed in Kobunshi Ronshu Vol. 44 (1987) February issue, pages 139-141. It was carried out according to the method.

Solvent resistance test: After immersing an ASTM No. 1 dumbbell test piece in heptane at 25°C for 60 minutes, the presence or absence of cracks was observed.

Reference Example 1 (PPS Preparation 1) In an autoclave, 3.26 kg of sodium sulfide (25 moles, containing 40% water of crystallization), 4 g of sodium hydroxide, 1.36 kg of sodium acetate trihydrate (approximately 10 moles), and N-methyl - 7.9 kg of 2-pyrrolidone (hereinafter abbreviated as NMP) was charged, and the temperature was gradually raised to 205°C while stirring.
About 1.51 kg of distilled water containing 1.36 kg of water was removed.

3.75 kg of 1,4-dichlorobenzene (
25.5 mol) and 2 kg of NMP were added and heated at 265° C. for 4 hours. The reaction product was washed 5 times with warm water at 70°C, and then added to 2OA of acetic acid aqueous solution (p) (4) heated to 90°C. After stirring for about 30 minutes, it was filtered and the pH of the solution was adjusted. 7 with deionized water at about 90°C, and dried under reduced pressure at 120°C for 24 hours to obtain powdered PF3.
Approximately 2 kg was obtained. This is designated as PP5-1.

Reference Example 2 (PPS Preparation 2) The heating performed at 265°C for 4 hours in Reference Example 1 was heated to 275°C.
PPS was prepared in exactly the same manner as in Reference Example 1, except that the temperature was changed to 8 hours at °C, and about 2 kg of powdered PF3 was obtained. This is designated as PP5-2.

Molecular weight distribution of PPS bulk powder obtained in Reference Examples 1 and 2,
Table 1 shows the melt flow rate value and the retention rate of the melt flow rate value.

Table 1 Reference Example 3 (Preparation of modified PPS) PP5-1 obtained in Reference Example 1 and PP5 obtained in Reference Example 2
-2 Tri-blend 1.0 parts by weight of p-phenylene diisocyanate to 100 parts by weight, and
Melt-knead using a twin-screw extruder set at 10°C to obtain p-
Pellets of phenylene diisocyanate-modified PPS were obtained.

These are designated as PP5-3 and PP5-4, respectively. Furthermore, modification was carried out under the same conditions except that 3.0 parts by weight of p-fuynylene diisocyanate was used for PP5-2. This is designated as PP5-5.

Further, modification was carried out under the same conditions and method except that 1.5 parts by weight of 2,4-toluenediamine was used instead of p-fuynylene diisocyanate with respect to 100 parts by weight of PP5-2. ) Pellets of luenediamine-modified PPS were obtained. This is designated as PP5-6.

Reference Example 4 (Preparation of PPE) Inside the stainless steel reactor, which has an oxygen inlet at the bottom of the reactor and a cooling coil and stirring blade inside, the air was sufficiently replaced with nitrogen, and then the bromide 2 copper 53.6g, G-n-
8.75 kg of 2,6-xylenol was dissolved in a mixed solvent of 1.110 g of butylamine, 18 L of toluene, 15 L of n-butanol, and 42 L of methanol, and charged into a reactor.

Oxygen was continuously blown into the reactor while stirring, and polymerization was carried out for 210 minutes. Water was circulated through the cooling coil during polymerization to maintain the internal temperature at 30°C. After the polymerization is completed, the precipitated polymer is separated, a methanol/hydrochloric acid mixture is added to decompose the remaining catalyst in the polymer, and the polymer is sufficiently washed with methanol and dried to form a pale yellowish white powder of PPE (reduced). A viscosity of 0.59) was obtained.

Reference Example 5 (Preparation of modified PPE) For 1100 parts by weight of PPE obtained in Reference Example 4, p-
Tri-blending 0.8 parts by weight of phenylene diisocyanate was melt-kneaded using a twin-screw extruder set at 290 to 310°C to obtain p-phenylene diisocyanate-modified P.
PE pellets were obtained. This will be referred to as PPE-2.

In addition, modification was carried out under the same conditions and method except that 1.0 parts by weight of 2,4-toluenediamine was used instead of p-phenylene diisocyanate for 1100 parts by weight of PPE-1, and 2.4-1 toluenediamine A pellet of modified PPE was obtained. This will be referred to as PPE-3.

Reference Example 6 The thermoplastic elastomer used in this example and comparative example is shown below.

C-1: Styrene-butadiene-styrene copolymer (11Califlex TRKX65S" manufactured by Shell Chemical ■) C-2: Styrene-ethylene/butylene-styrene copolymer (Krayton G 1650" manufactured by Shell Chemical ■) C- 3 = Acid-modified styrene-ethylene/butylene-styrene copolymer (“Krayton FG1901X” manufactured by Shell Chemical Company Ltd.) C-4 = Ethylene-butene copolymer (“Tafmer A-4085” manufactured by Mitsui Petrochemical Company Ltd.) Example 1 ~7 PPS and/or modified PPS and PPE and/or modified PPE were triblended at the composition ratio shown in Table 2, and the screw rotation speed was The mixture was melt-kneaded and pelletized at 1100 tp. Using this pellet, injection molding was performed using an in-line screw molding machine to form a test piece (temperature condition setting: 290-310°C, mold temperature:
140-150°C). Table 2 shows the Izot impact strength, tensile strength, heat distortion temperature, and solvent resistance test results of the obtained test pieces.

Comparative Examples 1 to 3 PPS-1, PP5-4, PP5-5 and PPE-1, P
Crosstalk, molding, and measurement were carried out in exactly the same manner as in Example 1, except that PE-2 and PPE-3 were triblended with the composition shown in Table 2. The results are shown in Table 2.

Comparative Example 1 is a resin composition composed of unmodified PPS and unmodified PPE, and due to insufficient compatibility, the impact resistance (both notched Izot impact value and unnotched Izot impact value) is low. Comparative example 2 contains 90% PPS by weight.
, the heat distortion temperature is low. In Comparative Example 3, since the PPS content was less than 10% by weight, cracks were observed in the solvent resistance test.

Examples 8 to 11 Kneading, molding and measurement in the same manner as in Example 1 except that PPS and/or modified PPS, PPE and/or modified PPE, and thermoplastic elastomer were triblended with the composition shown in Table 2. I did it. The results are shown in Table 2.

As is clear from the Examples in Table 2, the resin compositions of the present invention (Examples 1 to 11) are excellent in Izo impact strength, especially notched Izo impact strength, and furthermore have excellent tensile strength, heat distortion temperature, The three solvent resistance properties are also excellent in balance.

Comparative Example 4.5 Completely the same as Example 1 except that PPS-1, PP5-4, PPE-1, PPE-2, and thermoplastic elastomers C-2 and C-4 were triblended with the composition shown in Table 2. Crosstalk, molding, and measurement were performed using the following methods. The results are shown in Table 2.

Comparative Example 4 is a resin composition composed of unmodified PPS, unmodified PPE, and a thermoplastic elastomer, and due to insufficient compatibility, the impact resistance, particularly the notched Izo impact value, is low. Comparative Example 5 has low heat resistance because the thermoplastic elastomer is present in an amount of 50 parts or more relative to 100 parts by weight of modified PPS and modified PPE.

<Effects of the Invention> The PPS resin composition of the present invention has excellent impact resistance, particularly notched Izot impact strength, and is also excellent in heat resistance, mechanical strength, and solvent resistance in a balanced manner.

Patent application Daitoshi Co., Ltd.

Claims (2)

[Claims] (1) (A) polyphenylene sulfide and/or 90 to 10% by weight of modified polyphenylene sulfide modified with an organic compound having two or more amino groups or isocyanate groups in the molecule, and (B) polyphenylene ether and/or the same. Modified polyphenylene ether 1 modified with an organic compound having two or more amino groups or isocyanate groups in the molecule
A polyphenylene sulfide resin composition comprising 0 to 90% by weight and containing at least one of modified polyphenylene sulfide and modified polyphenylene ether. (2) (A) polyphenylene sulfide and/or 90 to 10% by weight of modified polyphenylene sulfide modified with an organic compound having two or more amino groups or isocyanate groups in the molecule, and (B) polyphenylene ether and/or the same. Modified polyphenylene ether 1 modified with an organic compound having two or more amino groups or isocyanate groups in the molecule
(C) 1 to 50 parts by weight of thermoplastic elastomer is blended with 100 parts by weight of a resin composition comprising 0 to 90% by weight and containing at least one of modified polyphenylene sulfide and modified polyphenylene ether. Polyphenylene sulfide resin composition.