JPH0459872A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To provide the title composition excellent in resistance to heat, solvent and impact and mechanical strength, suitable for the industrial material field such as for automobiles, comprising each specific 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 modified polyphenylene sulfide prepared by modifying a polyphenylene sulfide with an organic compound having two or more amino or isocyanate groups in the molecule (e.g. ethylenediamine) and (B) 10-90wt.% of a modified polyphenylene ether prepared by modifying a polyphenylene ether with an organic compound having at least two kinds of functional groups selected from ethylenic double bond, carboxylic group, acid anhydride group etc., (e.g. maleic acid) with (C) 1-50 pts.wt. of a thermoplastic elastomer.

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.

<Prior art> Polyphenylene sulfide resin (hereinafter abbreviated as PPS) has properties suitable as a crystalline engineering plastic, such as excellent heat resistance, impact resistance, and rigidity, in a reinforced system reinforced with glass fiber, etc. It is used for various purposes, mainly injection molding. However, unreinforced PPS that is not reinforced with glass fiber or the like has no 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 that combining various polymers to form a polymer alloy is an effective way 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. ing. Polyphenylene ether is one of the non-grade thermoplastic resins suitable for such purposes. Many proposals have already been made regarding the modification of PPS with polyphenylene ether (hereinafter 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, Japanese Patent Application Laid-Open No. 58-157859 discloses PPE grafted with pps and styrene polymer.
A resin composition with improved compatibility consisting of
No. 164360 discloses a resin composition with improved compatibility consisting of pps, PPE, and epoxy resin, and JP-A-59-213758 discloses a resin composition with improved compatibility consisting of pps, PPE, polyamide resin, and epoxy resin. A resin composition with improved compatibility is proposed in Jikai Uta No. 6B-205358, which is composed of ppS, PPE, and a maleimide compound and has improved compatibility.

In addition, 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. Japanese Patent Laid-Open No. 1-259060 discloses a resin composition with improved compatibility and excellent heat resistance and solvent resistance. A resin composition with improved compatibility, excellent mechanical performance, heat resistance, and solvent resistance, which is composed of modified PPE modified with a modifier having a group and modified pps modified with the modifier,
JP-A-1-266160 discloses modified PP modified with a modifier having an ethylenic double bond and a functional group selected from a carboxyl group, an acid anhydride group, a hydroxyl group, and an epoxy group.
E and a modified PPS modified with the modifying agent and having at least two or more functional groups selected from a carboxyl group, an acid anhydride group, a hydroxyl group, an amino group, an epoxy group, a mercapto group, an oxazoline group, and an incyanate group in the molecule. A resin composition comprising a binder and having improved compatibility, mechanical performance, and excellent solvent resistance has been proposed.

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, β
Made of modified PPE modified with unsaturated carboxylic acids, it has improved compatibility in heat resistance, flame retardancy, solvent resistance, moldability,
A resin composition with excellent mechanical strength and impact resistance was published in JP-A-1
Publication No. 213361 describes a resin composition with improved compatibility, excellent heat resistance, flame retardance, solvent resistance, moldability, mechanical strength, and impact resistance, consisting of PPS, PPE, and glycidyl group-containing styrene resin. things are being 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
Although it does give a resin composition with better processability than when using E alone, it has poor impact resistance, insufficient compatibility, and significant delamination. PPE grafted with PPS and styrene polymer described in JP-A-58-157859
A resin composition consisting of pps described in JP-A-59-164360, a resin composition consisting of PPE and an epoxy resin, a pps described in JP-A-59-213758
and a resin composition consisting of PPE, a polyamide resin, and an epoxy resin, P described in JP-A No. 63-205358
Resin compositions consisting of PS, PPE, and maleimide compounds are PP grafted with styrenic polymers, respectively.
The purpose is to provide a resin composition in which the compatibility of PPS and PPE is improved by using E, using an epoxy resin, using an amide resin and an epoxy resin, and using a maleimide compound, Both are PPS and PPE described in Japanese Patent Publication No. 56-34032.
Although a slight improvement in compatibility is observed when compared to a composition consisting of the following compositions, the effect is still insufficient, and the lick impact resistance, especially 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.
A resin composition consisting of PE, a resin composition consisting of modified PPS, modified PPE, and a compound having two or more functional groups described in JP-A-1-266160 are both PPS.
and/or by modifying PPE with a compound that simultaneously has an ethylenic double bond and a functional group such as a carboxyl group or an acid anhydride group, and by adding a compound having a functional group to improve compatibility. , mechanical strength,
The purpose of this method is to provide resin compositions with improved solvent resistance, but even with these resin compositions, the effects are still far from satisfactory, and for this reason, impact resistance, especially notched Izo 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 of PPS, PPE, and glycidyl group-containing styrene resin described in the 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 By modifying with acids, we aim to improve compatibility,
The purpose of this method is to provide a resin composition with improved mechanical strength, solvent resistance, etc., but its effects are still far from being sufficient. 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 intensive 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, by combining PPS and PPH. A specific PPS resin composition consisting of modified pps and modified PPE, and P obtained by further adding a thermoplastic elastomer to the composition.
The present invention was achieved based on the discovery that a PS resin composition has excellent heat resistance, solvent resistance, mechanical strength, and impact resistance, particularly excellent notched isot impact strength, and can be used for molding applications. did.

<Means for Solving the Problems> That is, the present invention provides: (1) (A) Modified polyphenylene sulfide 90-10 obtained by modifying polyphenylene sulfide with an organic compound having two or more amino groups or isocyanate groups in the molecule.
(B) Modified polyphenylene obtained by modifying polyphenylene ether with an organic compound that simultaneously has (a) an ethylenic double bond and (b) a functional group selected from the group consisting of a carboxyl group, an acid anhydride group, and an epoxy group. Ether 10~
90% by weight of a polyphenylene sulfide resin composition and (2) (A) a modified polyphenylene sulfide 90-10 obtained by modifying polyphenylene sulfide with an organic compound having two or more amino groups or isocyanate groups in the molecule.
(B) Modified polyphenylene obtained by modifying polyphenylene ether with an organic compound that simultaneously has (a) an ethylenic double bond and (b) a functional group selected from the group consisting of a carboxyl group, an acid anhydride group, and an epoxy group. Ether 10~
The present invention provides a polyphenylene sulfide resin composition in which 1 to 50 parts by weight of (C) thermoplastic elastomer is blended with 100 parts by weight of a resin composition comprising 90% by weight.

PPS (A) used in the present invention has a structural formula of % or more,
More preferably, it is a polymer containing 90 mol% or more, and if the content of the repeating unit is less than 70 mol%, heat resistance will be impaired, which is not preferable.

Generally, pps is a polymer with a relatively small molecular weight obtained by the production method typified by Japanese Patent Publication No. 45-3368, and an essentially linear polymer obtained by the production method typified by Japanese Patent Publication No. 52-12240. There are polymers with relatively high molecular weight, etc., and in the polymer obtained by the method described in Japanese Patent Publication No. 45-3368, after polymerization, by heating in an oxygen atmosphere or by adding peroxide etc. It is also possible to increase the degree of polymerization and use it by adding a crosslinking agent and heating it, and in the present invention, it is possible to use PPS obtained by any method, but the effects of the present invention are remarkable. In addition, because PPS itself has excellent toughness, essentially linear and relatively high molecular weight polymers obtained by the production method typified by the above-mentioned Japanese Patent Publication No. 52-12240 are more preferably used. obtain.

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

The PPS used in the present invention can be any PP as described above.
Although S can also be used, for example, JP-A-1-1745
The impact resistance of the resin composition is significantly improved by using one that has been deionized by treatment with an acid or acid aqueous solution, hot water, or an organic solvent as proposed in Publication No. 62. preferred.

Among these relatively high molecular weight PPS, the number average molecular weight (Fu) and weight average molecular weight (M
It has a molecular weight distribution with a ratio of Mw/Mn=10, and also meets ASTM D1238
-86 (315.5℃, 5000g load) Melt flow rate value (MF, ) is 200g/1
Particularly preferably used is PpS which is 0 m1n or less and has a retention rate of melt flow rate satisfying 50<MFs<MF 1sX 100<120.

In addition, the organic compound that modifies pps is an organic compound having two or more amino groups or isocyanate groups in the molecule, such as ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1.7 -Diaminohebutane, 1.8-diaminooctane, 1,9-diaminononane, 1.10-diaminodecane, 1゜12-diaminododecane, 0-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2. 4-Toluenediamine, 2゜6-toluenediamine, m-xylylene diamine, p-xylylene diamine, 4.4-diaminodiphenylmethane, 3.3-1 diaminodiphenylmethane, 4.4-1 diaminodiphenylpropane, 4 , 4゛-diaminobiphenyl, 4.4゛-diaminodiphenyl ether, 4゜4-1diaminodiphenylsulfone, 4
．． 4-diaminodiphenyl sulfide, 4.4'diaminobenzophenone, 1.3-bis(3-aminophenoxy)benzene, 1.4-bis(4-aminophenoxy)
Polyamine compounds such as benzene, 3.3-1 dimethyl-4.4-diaminodiphenylmethane, 3.3°-dichloro-4,4-1 diaminodiphenylpropane, 9.9-bis(4-aminophenyl)fluorene, bis =(p
-aminocyclohexyl)methane, bis-(p-aminocyclohexyl)propane, m-phenylene diisocyanate, p-phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, diphenylsulfone diisocyanate, triphenylmethane diisocyanate, hexamethylene Diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 3-incyanate ethyl-3,5,5-trimethylcyclohexyl isocyanate, diphenylpropane diisocyanate, cyclohexylene diisocyanate, diphenylethyl-
Polyisocyanate compounds such as 4,4'-diisocyanate can be mentioned.

These organic compounds contain 0.0% per 5100 parts by weight of PP.
It is used in an amount of 0.01 to 20 parts by weight, preferably 0.1 to 10 parts by weight.

In addition, modified pps can be produced 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, the melt-kneading method is convenient. Moreover, it is preferable from the point of view of high efficiency, such as a method in which PPS and an organic compound used for modification are modified while being melt-kneaded at a temperature of 290 to 330° C. while applying a shear rate of 10 seconds or more. The modified PPS of the present invention is not limited by its manufacturing method as long as it has the above characteristics.

Next, P used as component (B) in the present invention
PE is a bonding unit (where Ro, R2, R3, and R4 are each selected from the group consisting of hydrogen, halogen, hydrocarbon, or substituted hydrocarbon group, and may be the same or different from each other) ) and has a reduced viscosity (0.5 g/cH!, 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, and /or copolymers are used. Specific examples include poly(2゜6-dimethyl-1,4-phenylene 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
-dichloro-1,4-phenylene ether), and 2,6-dimethylphenol and other phenols (e.g., 2,3,6-trimethylphenol).
Examples include polyenylene ether copolymers such as copolymers with Among them, poly(2,6-cymethyl-1
．． 4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2.3゜6-trimethylphenol is preferred, especially poly(2,6-dimethyl-l,4-)
unilene ether) is preferred.

The method for producing such PPE is not particularly limited as long as it can be obtained by a known method. For example, as described in US Pat. No. 3,306,874, a complex of a cuprous salt and an amine is produced. Used as a catalyst, for example 2.
It can be easily produced by oxidative polymerization of 6-xylenol.

The PPE used as component (B) has (a>
For this purpose, an organic compound having an ethylenic double bond and (b) a functional group selected from a carboxyl group, an acid anhydride group, and an epoxy group can be used after being modified in the presence or absence of a radical initiator. necessary to achieve. Specifically, the organic compounds used for this modification include maleic acid, fumaric acid, chloromaleic acid, citraconic acid, itaconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hymic acid, methylhymic acid, acrylic acid, and puranic acid. , unsaturated carboxylic acids exemplified by tetratonic acid, vinyl acetic acid, methacrylic acid, pentenoic acid, angelic acid, etc., maleic anhydride, chloromaleic anhydride, citraconic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, methyl Unsaturated acid anhydride compounds exemplified by tetrahydrophthalic anhydride, himic anhydride, methylhimic anhydride, etc., unsaturated epoxy compounds exemplified by glycidyl maleate, glycidyl acrylate, glycidyl methacrylate, etc. A mixture of two or more types can also be used.

Among these organic compounds, preferred are maleic acid,
These include maleic anhydride, methylhimic anhydride, and glycidyl methacrylate, and particularly preferred are maleic anhydride and glycidyl methacrylate. These organic compounds are used in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 8 parts by weight, based on 100 parts by weight of PPE.

It is also possible to use a radical initiator if necessary. The radical initiator used here is not limited in any way as long as it is a known one; for example,
dicumyl peroxide, di-tert-butyl peroxide, tert-butyl cumyl peroxide, 2
．． Examples include 5-dimethyl-2,5-di(tert-butylperoxy)hexane.

In addition, the method for producing 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, the melt-kneading method is convenient. Moreover, it is preferable because it is highly efficient.

Further, the resin composition of the present invention can be obtained by blending modified PPS (A) and modified PPE (B), and the blending ratio of these is modified PP5 (A> is 90 to 10% by weight, especially 80-20% by weight, modified PPE (B) 1
It is selected from the range consisting of 0 to 90% by weight, especially 20 to 80% by weight. Here, modified PPS (A> is 10% by weight)
If the modified PPE (B) exceeds 90% by weight, only a PPS resin composition with extremely poor solvent resistance will be obtained; conversely, if the modified PPS (A) exceeds 90% by weight, the modified PPE ( 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) A polymer alloy consisting of a 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, for example, a polyolefin elastomer, a polystyrene elastomer, a polyamide elastomer,
Known elastomers such as polyester elastomers, polyurethane elastomers, and fluorine elastomers can be used, among which polyolefin elastomers and polystyrene elastomers are preferably selected.

Examples of the polyolefin elastomer include ethylene-(meth)acrylic acid copolymer, ethylene-glycidyl (meth)acrylate copolymer, ethylene-propylene-diene copolymer, ethylene-propylene copolymer,
Examples include ethylene-butene copolymers, ethylene-propylene copolymers, ethylene-butene copolymers, and maleic anhydride-modified products thereof.

Next, examples of polystyrene elastomers include:
A block copolymer of a vinyl aromatic compound and a conjugated diene compound or a hydrogenated product of this block copolymer (hereinafter referred to as
hydrogenated block copolymers), and furthermore, these block copolymers, hydrogenated block copolymers and α,
Examples include modified products (modified polystyrene elastomers) obtained by reactions of β-unsaturated carbonic acids or derivatives thereof. Examples of these polystyrene-based elastomers include styrene-butadiene-styrene block copolymers, styrene-isoprene-styrene block copolymers, and hydrogenated products of these block copolymers (hydrogenated block copolymers). Furthermore, examples thereof include block copolymers and hydrogenated block copolymers modified with maleic acid.

Specific examples of these polystyrene elastomers include the "Califlex TR" and "Krayton G" series manufactured and sold by Shell Chemical Co., Ltd.

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

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 them, maleic anhydride is preferably used.

The α,β-unsaturated carboxylic acid or its derivative is in the range of 0.01 to 20 parts by weight, preferably 0.1 to 1 part by weight, based on 100 parts by weight of the block copolymer or hydrogenated block copolymer.
It is used in a range of 0 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 1 to 50 parts by weight based on 100 parts by weight of a resin composition composed of modified PPS (A>) and modified PPE (B),
Preferably, it is blended in an amount of 3 to 40 parts by weight. If the thermoplastic elastomer (C) exceeds 50 parts by weight, the heat resistance of the resulting resin composition will decrease, which is not preferable.

As described above, the PPS resin composition of the present invention has (A), (B
) and (C), but if necessary, glass fibers, alumina fibers, silicon carbide fibers, ceramic fibers may be added to the extent that the properties of the PPS resin composition of the present invention are not impaired. , asbestos fiber, gypsum fiber,
Fibrous reinforcing agents such as metal fibers and carbon fibers, silicates such as wollastenite, sericite, kaolin, mica, clay, bentonite, asbestos, talc, alumina silicate, alumina, silicon chloride, magnesium oxide, zirconium oxide, oxidation Metal compounds such as titanium, carbonates such as calcium carbonate, magnesium carbonate, and dolomite, sulfates such as calcium sulfate and barium sulfate, non-fibrous reinforcing agents such as glass peas, boron nitride, silicon carbide, and silica, various flame retardants, A crystallization accelerator (nucleating agent), a silane coupling agent such as mercaptosilane, vinylsilane, aminosilane, or epoxysilane, 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 kneading method using a single-screw extruder, a twin-screw extruder, a Nigu, a Brabender, etc. is used. Among these, a melt-kneading method using an axle or twin-screw extruder is preferred.

The melt-kneading 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 retardance, and moldability in industrial materials fields such as automobiles, electricity, electronics, and machinery.

<Examples> Hereinafter, the present invention will be further described in detail using examples. Unless otherwise specified, percentages, parts and ratios used in the examples represent percentages by weight, parts by weight and ratios by weight, respectively.

In addition, the Izot impact strength, tensile strength, heat distortion temperature, melt flow rate, molecular weight 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-(315.5°C, 5000g load) Measurement of molecular weight and molecular weight distribution: Manufactured by WaterS,
Using a gel permeation chromatography device, Polymer Papers 44
It was carried out according to the method disclosed in Vol. (1987), February issue, pages 139-141.

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 mol, containing 40% water of crystallization), 4 g of sodium hydroxide, 1.36 kg of sodium acetate trihydrate (approximately 10 mol), and N-methyl -2-pyrrolidone (hereinafter abbreviated as NMP)
7.9 kg of distilled water containing 1.36 kg of water was gradually heated to 205°C while stirring. l! was removed. Add 1,4-dichlorobenzene to the residual mixture3.
Add 75 kg (25,5 mol) and NMP2-,
Heated at 65°C for 4 hours. The reaction product was washed 5 times with warm water at 70°C, then put into 20μ of a pH 4 acetic acid aqueous solution heated to 90°C, kept stirring for about 30 minutes, filtered, and the pH of the tear fluid reached 7. Wash with deionized water at about 90°C until dry and dry under reduced pressure at 120°C for 24 hours to obtain powdered P.
PS I got about 2 dazzles. 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 PPS was obtained. This is designated as PP5-2.

Molecular weight distribution of PPS 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.

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-phenylene diisocyanate was used for PP5-2. This is designated as PP5-5.

In addition, 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-phenylene diisocyanate for 100 parts by weight of PP5-2. A pellet of modified PPS was obtained.

This is designated as PP5-6.

Reference Example 4 (Preparation of PPH) After sufficiently purging the inside of a stainless steel reactor having an oxygen inlet at the bottom of the reactor, a cooling coil, and a stirring blade inside with nitrogen, 53.6 g of cupric bromine was added. , di-n-butylamine 1110 g, toluene 18. Q, n-butanol 15.11, methanol 4.1! 2. to the mixed solvent of
8.75 kg of 6-xylenol was dissolved and charged into the reactor.

Continuing to blow oxygen into the reactor while stirring, the temperature was increased to 210
Polymerization was carried out for 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 from P and methanol/
Add a hydrochloric acid mixture to decompose the remaining catalyst in the polymer,
Furthermore, it was thoroughly washed with methanol and then dried to obtain PPE in the form of a pale yellowish white powder (reduced viscosity 0.59>. This is referred to as PPE-1.

Reference Example 5 (Preparation of modified PPH) 1.5 parts by weight of maleic anhydride and 0.1 parts by weight of dicumyl peroxide based on 1100 parts by weight of PPE obtained in Reference Example 4
Parts by weight were triblended and melt-kneaded using a twin-screw extruder set at 1.290 to 310°C to obtain pellets of maleic anhydride-modified PPH. This will be referred to as PPE-2.

In addition, anhydrous maleic M1 was added to PPE-1100 parts by weight.
．． Modification was carried out under the same conditions and method except that 0.8 parts by weight of glycidyl methacrylate was used instead of 5 parts by weight to obtain pellets of glycidyl methacrylate-modified PPH. 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 (“Califlex TRKX65S” manufactured by Shell Chemical) C-2: Styrene-ethylene/butylene-styrene copolymer (“Clayton G1650” manufactured by Shell Chemical) C-3 : M-modified styrene-ethylene/butylene-styrene copolymer (“Crayton FG1901X” manufactured by Shell Chemical ■) C-4: Ethylene-butene copolymer (“Tafmer A-4085” manufactured by Mitsui Petrochemical ■) Example 1 ~4 Modified PPS prepared in Reference Example 3 (PPS-3 to PP5
-6> and modified PPE prepared in Reference Example 5 (PPE-2,
PPE-3> in the composition ratio shown in Table 2, and melt-kneaded using a co-rotating twin-screw extruder set at 290 to 310°C at a screw rotation speed of 100 rl)m to form pellets. It became. Using this pellet, injection molding was performed using an in-line screw molding machine to form a test piece (temperature condition setting: 290 to 310°C, mold temperature: 140 to 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 4 PPS-1, PP5-3, PP5-4 and PPE-1, P
Cross-wire, molding, and measurement were performed in exactly the same manner as in Example 1, except that PE-2 was triblended with the composition shown in Table 2. The results are shown in Table 2.

Comparative Example 1.2 is a combination of unmodified pps and modified PPE,
It is a combination of modified PPS and unmodified PPH, and due to insufficient compatibility, the impact resistance, especially the notched Izot impact value, is low. Comparative Example 3 has 90% PPS by weight
The heat deformation temperature is low because it exceeds . Comparative example 4 is PPS
is less than 10% by weight, cracks are observed in the solvent resistance test.

Examples 5 to 8 Modified PPS (PPS-4 to PP5-6> and modified PPE
(PPE-1, PPE-3> and the thermoplastic elastomer were tri-blended with the composition shown in Table 2, but the crosstalk, molding, and measurement were carried out in the same manner as in Example 1. The results are shown in Table 2. Shown below.

As is clear from the Examples in Table 2, the resin compositions of the present invention (Examples 1 to 8) are excellent in Izot impact strength, especially notched Izot impact strength, and also have excellent tensile strength, heat distortion temperature, The three solvent resistance properties are also excellent in balance.

Comparative Example 5.6 Completely the same as Example 1 except that PPS-3, PP5-4, PPE-1, PPE-2, and thermoplastic elastomers C-2 and C-4 were triblended with the composition shown in Table 2. The mixture was kneaded, molded and measured. The results are shown in Table 2.

Comparative Example 5 is a resin composition composed of modified PPS, unmodified P P'E, and a thermoplastic elastomer, and due to insufficient compatibility, the impact resistance, especially the notched Izo impact value, is low. .

In Comparative Example 6, the thermoplastic elastomers were modified PPS and modified P.
Since the amount is 50 parts by weight or more based on 100 parts by weight of PE, the heat resistance is low.

<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) Modified polyphenylene sulfide 90-10 obtained by modifying polyphenylene sulfide with an organic compound having two or more amino groups or isocyanate groups in the molecule
(B) Modified polyphenylene obtained by modifying polyphenylene ether with an organic compound that simultaneously has (a) an ethylenic double bond and (b) a functional group selected from the group consisting of a carboxyl group, an acid anhydride group, and an epoxy group. Ether 10~
A polyphenylene sulfide resin composition consisting of 90% by weight. (2) (A) Modified polyphenylene sulfide 90-10 obtained by modifying polyphenylene sulfide with an organic compound having two or more amino groups or isocyanate groups in the molecule
(B) Modified polyphenylene obtained by modifying polyphenylene ether with an organic compound that simultaneously has (a) an ethylenic double bond and (b) a functional group selected from the group consisting of a carboxyl group, an acid anhydride group, and an epoxy group. Ether 10~
A polyphenylene sulfide resin composition in which 1 to 50 parts by weight of (C) thermoplastic elastomer is blended with 100 parts by weight of a resin composition comprising 90% by weight.