JPH0433959A - Polyphenylene sulfide resin composition - Google Patents

Abstract

PURPOSE:To obtain a resin composition having heat resistance, solvent resistance, mechanical strength and impact resistance, comprising a specific (modified) polyphenylene sulfide, a specific (modified) maleimide-based copolymer and optionally a thermoplastic elastomer. CONSTITUTION:A composition comprising (A) 90-10wt.% A1: polyphenylene sulfide (PPS for short) and/or A2: PPS modified with an organic compound simultaneously containing an ethylenic double bond and a functional group selected from COOH, an acid anhydride group and epoxy group in the molecule, (B) 10-90wt.% B1: a maleimide-based polymer copolymer composed of 90-10wt.% N-arylmaleimide unit, 10-90wt.% vinyl-based unit and 0-10pts.wt. based on 100pts. wt. total amounts of these units of a maleic anhydride unit and/or B2: a modified polyphenylene sulfide prepared by modifying the component B1 with the component A2 with a proviso that a combination of the component A1 and a maleimide-based copolymer not containing a maleic anhydride unit is omitted and optionally a thermoplastic elastomer.

Description

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

<Conventional technology> Polyphenylene sulfide resin (hereinafter abbreviated as PPS resin) 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 resin that is not reinforced with glass fiber or the like lacks toughness and is extremely brittle. Furthermore, the glass transition temperature is 90℃
Due to its low heat resistance, it is currently difficult to use it for various molding applications.

In recent years, various polymer combinations have revealed that an effective way to improve the heat resistance of crystalline thermoplastic resins is to combine them with non-grade thermoplastic resins that have a high glass transition point to form polymer alloys. There is. One of the non-grade thermoplastic resins suitable for this purpose is styrene/
N-phenylmaleimide copolymers are mentioned, and it is known that useful resin compositions can be obtained especially by blending them with polyamide resins (for example, Plastic Swage 1).
January 990 issue).

Modification of PPS resin with maleimide resin has been proposed in JP-A-61-9452, but here mainly a cross-linked PPS resin is used, and the maleimide resin improves the fluidity of PPS resin. It is only added as an agent, and it increases the strength of the resulting resin composition.
Practical properties such as impact resistance are still insufficient.

<Problems to be Solved by the Invention> Therefore, the present inventors conducted extensive studies in order to obtain a resin composition with excellent practical properties such as heat resistance, impact resistance, and solvent resistance by combining PPS resin and maleimide resin. As a result, a specific PPS resin composition consisting of a PPS resin and/or a modified PPS resin, a maleimide copolymer and/or a modified maleimide copolymer, and a PPS obtained by further adding a thermoplastic elastomer to the composition. It was discovered that the resin composition has excellent impact resistance, heat resistance, and solvent resistance, and can be used for molding purposes, and the present invention was achieved.

Means for Solving the Problems> That is, the present invention provides (A) polyphenylene sulfide resin and/or polyphenylene sulfide resin having (a) an ethylenic double bond and (b) a carboxyl group or an acid anhydride group in the molecule. and (8) 90 to 10% by weight of a modified polyphenylene sulfide resin modified with an organic compound having a functional group selected from the group consisting of epoxy groups, 90 to 10% by weight of N-arylmaleimide structural units, and 10 to 10% of vinyl structural units. 90% by weight and a total of N-arylmaleimide structural units and vinyl structural units 10
A maleimide copolymer consisting of 0 to 10 parts by weight of maleic anhydride structural units based on 0 parts by weight, and/or the maleimide copolymer contains (a>ethylenic double bond and (b') carboxyl) in the molecule. Modified maleimide copolymers 10 to 90 modified with an organic compound simultaneously having a functional group selected from the group consisting of an acid anhydride group, an acid anhydride group, and an epoxy group
% by weight, excluding resin compositions consisting of a combination of a PPS resin and a maleimide copolymer containing no maleic anhydride structural unit.

The PPS resin (A) used in the present invention is a polymer containing a structure of 0 mol % or more, more preferably 90 mol % or more, and if the repeating unit is less than 70 mol %, heat resistance will be impaired, so it is not preferable.

PPS resins are generally made of a relatively low molecular weight polymer 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. In the case of the polymer obtained by the method described in the above-mentioned Japanese Patent Publication No. 45-3368, after polymerization, it can be heated in an oxygen atmosphere or treated with peroxide, etc. It is also possible to increase the degree of polymerization by adding a crosslinking agent and heating, and in the present invention, it is possible to use a PPS resin obtained by any method, but the effect of the present invention is remarkable. and because the toughness of the PPS resin itself is excellent,
An essentially linear polymer having a relatively high molecular weight obtained by the production method typified by Japanese Patent No. 2240 may be more preferably used.

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

Next, the maleimide copolymer used in the present invention (
B) is a copolymer consisting of an N-arylmaleimide constitutional unit represented by the following formula (1), a vinyl constitutional unit represented by the following formula (2), and a maleic anhydride constitutional unit represented by the following formula (3). It is. These may be random copolymers or block copolymers.

\N/...(1) As the PPS resin used in the present invention, any PPS resin can be used as described above, but for example,
The impact resistance of the resin composition is significantly improved by using a resin composition that has been deionized by treatment with an acid or an acid aqueous solution, hot water, or an organic solvent as proposed in Publication No. 174562. preferred.

(Xl and A phenyl group is generally used.) -CH2-C- (2) (Y represents an aryl group, a carboxyl group and its ester, a cyano group, etc.) R represents hydrogen or a methyl group ) The N-arylmaleimide monomer used in the method of copolymerizing an N-arylmaleimide monomer, a vinyl monomer, and maleic anhydride is represented by the following formula (4).

\N/ ...(4) As a synthesis method for the maleimide copolymer (B), for example, a method of copolymerizing an N-arylmaleimide monomer, a vinyl monomer and maleic anhydride, a method of copolymerizing an N-arylmaleimide monomer, a vinyl monomer and maleic anhydride, One possible method is to react a vinyl copolymer containing maleic acid with aniline, followed by dehydration and ring closure, but the method is not limited to these methods.

Here, X engineering and
Generally used are chlorine, methyl group, ethyl group, phenyl group, and substituted phenyl group.

Vinyl monomers include styrene, p-methylstyrene,
Aromatic vinyl monomers represented by vinyltoluene, t-butylstyrene, α-methylstyrene, monobromostyrene, dipromostyrene, tribromostyrene, monochlorostyrene, dichlorostyrene, trichlorostyrene, dimethylstyrene, etc., methacryl Examples include (meth)acrylic acid ester monomers represented by methyl acid and methyl acrylate, and vinyl cyanide monomers represented by acrylonitrile and methacrylonitrile. It can also be used as Among these vinyl monomers, preferred monomers are styrene, α-methylstyrene, methyl methacrylate, and acrylonitrile, and a particularly preferred monomer is styrene from the viewpoint of heat resistance.

The method for producing the maleimide copolymer (B) from the N-arylmaleimide monomer, vinyl monomer, and maleic anhydride is not particularly limited, and conventional emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, etc. It can be produced by polymerization, bulk-suspension polymerization.

The maleic anhydride-containing vinyl copolymer used in the synthesis method by reacting the vinyl copolymer containing maleic anhydride with aniline and then dehydrating and ring-closing the copolymer contains maleic anhydride and copolymerized with this. It is a copolymer obtained by copolymerizing other possible vinyl monomers, and contains the maleic anhydride fIim component of the formula (3).

Here, other vinyl monomers that can be copolymerized with maleic anhydride include styrene, p-methylstyrene,
Aromatic vinyl monomers represented by vinyltoluene, t-butylstyrene, α-methylstyrene, monobromostyrene, dipromostyrene, tribromostyrene, monochlorostyrene, dichlorostyrene, trichlorostyrene, dimethylstyrene, etc., methacryl Examples include (meth)acrylic acid ester monomers represented by methyl acid and methyl acrylate, and vinyl cyanide monomers represented by acrylonitrile and methacrylonitrile. It can also be used as

Among these vinyl monomers, preferred monomers are styrene, α-methylstyrene, methyl methacrylate, and acrylonitrile, and a particularly preferred monomer is styrene from the viewpoint of heat resistance.

These maleic anhydride-containing vinyl copolymers are produced by conventional solution polymerization or bulk polymerization.

The reaction for forming a maleimide copolymer by this method consists of the following two steps: a first reaction and a second reaction.

First reaction The second reaction, or first reaction, is a ring-opening reaction in which aniline is added to the maleic anhydride unit of the maleic anhydride-containing vinyl copolymer, and a copolymer with adjacent carboxyl groups and amide groups is formed. Ru.

The second reaction is a ring-closing reaction in which the carboxyl group and the amide group of the copolymer in which the carboxyl group and the amide group are adjacent are imidized by dehydration, thereby forming an N-arylmaleimide structural unit. Examples of the dehydration means in the second reaction include a physical dehydration method using heating and a chemical dehydration method using a dehydrating agent.

In addition, in the present invention, it is preferable to leave maleic anhydride units by adjusting the reaction conditions of the first reaction and the second reaction and the amount of aniline added, from the viewpoint of fully realizing the effects of the present invention.

In addition, the organic compound that modifies the PPS resin and maleimide copolymer has (a) an ethylenic double bond in the molecule and (b) a functional group selected from the group consisting of a carboxyl group, an acid anhydride group, and an epoxy group. It is an organic compound having simultaneously maleic acid, fumaric acid, chloromaleic acid, citraconic acid, itaconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hymic acid,
Unsaturated carboxylic acids exemplified by methylhimic acid, acrylic acid, puranic acid, crotonic acid, vinyl acetic acid, methacrylic acid, pentenoic acid, angelic acid, etc., maleic anhydride, chloromaleic anhydride, citraconic anhydride, itaconic anhydride acids, unsaturated acid anhydride compounds exemplified by tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, himic anhydride, methylhimic anhydride, etc., unsaturated compounds exemplified by glycidyl maleate, glycidyl acrylate, glycidyl methacrylate, etc. Examples include epoxy compounds, and two or more of these can also be used in combination.

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 generally used in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 8 parts by weight, per 100 parts by weight of the PPS resin or maleimide copolymer.

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, such as dicumyl peroxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, 2.5
-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane,
-butylperoxy)hexyne-3, n-butyl-4,
4-bis(tert-butylperoxy)valerate,
1.1-bis(tert-butylperoxy)3,3.
Examples include 5-trimethylcyclohexane, tert-butylperoxytriphenylsilane, and tert-butylperoxytrimethylsilane, and one or more types can be suitably selected from these. In addition to these organic peroxides, as radical initiators, 2,3-dimethyl-2,3-diphenylbutane, 2,3-diethyl-2
, 3-diphenylbutane, 2゜3-dimethyl-2,3-
Di(p-methylphenylbutane), 2,3-dimethyl-
Compounds such as 2,3-di(bromophenyl)butane may also be used. The amount of this radical initiator used is 0.0 parts by weight per 100 parts by weight of PPS resin or maleimide copolymer.
It is 1 to 10 parts by weight.

In addition, the method for producing a modified PPS resin or a modified maleimide copolymer can be carried out at 80 to 350°C in a molten state, dissolved state, or slurry state in the presence or absence of a radical initiator.
Among these known methods, the melt-kneading method is preferable because it is simple and highly efficient.
The S resin or maleimide copolymer and the organic compound used for modification are heated at 250 to 330°C in the presence of a radical initiator.
Examples include a method of denaturing while melt-kneading while applying a shear rate of 105 eC-1 or more at a temperature of . but,
The modified PPS resin or modified maleimide copolymer of the present invention is not limited by its manufacturing method as long as it has the above characteristics.

The N-arylmaleimide structural unit in the maleimide copolymer and/or modified maleimide copolymer (B) is preferably 10 to 90% by weight, particularly 30 to 70% by weight. If it is less than 10% by weight, the heat resistance of the resulting maleimide copolymer (B) and thus the PPS resin composition of the present invention will decrease, and if it exceeds 90% by weight, the impact resistance and resistance of the PPS resin composition will decrease. This is not preferable because it reduces drug properties.

Furthermore, the maleic anhydride structural unit contained in the maleimide copolymer and/or modified maleimide copolymer is 10 parts by weight or less per 100 parts by weight of the total amount of the N-arylmaleimide structural unit and the vinyl structural unit. , preferably 8 parts by weight or less. If the maleic anhydride structural unit exceeds 10 parts by weight, it is not preferable because the thermal stability of the maleimide copolymer decreases, and as a result, the heat resistance of the PPS resin composition decreases.

The PPS resin composition of the present invention comprises the above component (A) and (
This is based on a resin composition composed of component B), but excludes a resin composition composed of a combination of PPS and a maleimide copolymer that does not contain maleic anhydride structural units. . Specifically, a maleimide copolymer containing PPS and maleic anhydride structural units,
PPS and modified maleimide copolymers, modified PPS and maleimide copolymers not containing maleic anhydride structural units, modified PPS and maleimide copolymers containing maleic anhydride structural units, modified PPS and modified maleimide copolymers It is a resin composition composed of each combination exemplified by combination, and has excellent compatibility (layer releasability) and improved impact resistance, heat resistance, and solvent resistance.

On the other hand, a resin composition composed of a combination of PPS and a maleimide copolymer containing no maleic anhydride structural unit has poor compatibility, and therefore no improvement in impact resistance 1 or heat resistance is observed.

Moreover, the PPS of the present invention and/or modified PPS (A
) and the maleimide copolymer and/or modified maleimide copolymer (B), PPS and/or modified PPS (A) is 90 to 10% by weight, preferably 90 to 20% by weight, 10 to 90% by weight of maleimide copolymer and/or modified maleimide copolymer (B)
, preferably 10 to 80% by weight. Pps and/
Or modified PP5(A) is less than 10% by weight, maleimide copolymer and/or modified maleimide copolymer (
If B) exceeds 90% by weight, only a PPS resin composition with extremely poor solvent resistance will be obtained; on the contrary, PPS and/or
Or when modified PPS (A) exceeds 90% by weight,
If the amount of the maleimide copolymer and/or modified maleimide copolymer is less than 10% by weight, it is not preferable because the heat resistance decreases.

In addition, the PPS resin composition of the present invention has the above-mentioned (A), (
B) 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, 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 polyolefin elastomers include ethylene-(meth)acrylic acid copolymer, ethylene-glycidyl methacrylate copolymer, and ethylene-propylene-
Examples include diene copolymers, ethylene-propylene copolymers, ethylene-butene copolymers, ethylene-propylene copolymers, and ethylene-butene copolymers modified with maleic anhydride or glycidyl methacrylate.

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
These block copolymers, hydrogenated block copolymers and α, β
- Examples include modified products (modified polystyrene elastomers) resulting from reactions of unsaturated carboxylic acids or derivatives thereof.

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. , modified glycidyl methacrylate, and the like.

As a specific example of these polystyrene elastomers, for example, "
Examples include the "Califlex TR" and "Clayton G" series.

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, maleimide compound, glycidyl Examples include methacrylate, among which maleic anhydride and glycidyl methacrylate are preferably used. The amount of α,β-unsaturated carboxylic acid or derivative thereof is in the range of 0.01 to 20 parts by weight, preferably 0.1 parts by weight, based on 100 parts by weight of the block copolymer or hydrogenated block copolymer.
It is used in a range of 10 parts by weight.

Further, the radical initiator used as necessary is not limited as long as it is a known one, for example,
dicumyl peroxide, di-tert-butyl peroxide, tert-butyl cumyl peroxide, 2
．． 5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(te
rt-butylperoxy)hexyne-3, n-butyl-
4,4-bis(tert-butylperoxy)valerate, tert-butylperoxytriphenylsilane,
Examples include tert-butylperoxytrimethylsilane and benzoyl peroxide, and one or more types can be selected from these.

The amount of the radical initiator used is 0.01 to 10 parts by weight based on 100 parts by weight of the block copolymer or hydrogenated block copolymer.

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.

Furthermore, these exemplified thermoplastic elastomers may be used not only alone, but also in combination of two or more.

Furthermore, the thermoplastic elastomer (C) used in the present invention is PPS and/or modified PPS (A)
1 to 50 parts by weight, preferably 3 to 40 parts by weight, per 100 parts by weight of the resin composition composed of (B) and the maleimide copolymer and/or modified maleimide copolymer (B). If the thermoplastic elastomer (C) is less than 1 part by weight, no improvement in impact resistance will be observed, and if it exceeds 50 parts by weight, the heat resistance of the resulting PPS resin composition will decrease, so this is not recommended. .

In this way, the PPS resin composition of the present invention has (A) and (B)
and component (C), but if necessary, glass fibers, alumina fibers, silicon carbide fibers, ceramic fibers, Fibrous reinforcing agents such as asbestos fibers, gypsum fibers, metal fibers, carbon fibers, silicates such as wollastenite, sericite, kaolin, mica, clay, bentonite, asbestos, talc, alumina silicate, alumina, silicon chloride, Metal compounds such as magnesium oxide, zirconium oxide, and titanium oxide, carbonates such as calcium carbonate, magnesium carbonate, and dolomite, sulfates such as calcium sulfate and barium sulfate, non-fibrous materials such as glass peas, boron nitride, silicon carbide, and silica. Strengthening agents, various flame retardants, crystallization accelerators (nucleating agents), silane coupling agents such as mercaptosilane, vinylsilane, aminosilane, epoxysilane, antioxidants, heat stabilizers,
Ultraviolet absorbers, colorants, 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, twin screw extruder, kneader, 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 Izod impact strength, heat distortion temperature and solvent resistance in this example were each measured by the following measuring methods.

Izot impact strength: ASTM D256 heat distortion temperature: ASTM D648 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 In an autoclave, 3.26 m of sodium sulfide (25 mol, containing 40% water of crystallization), 4 g of sodium hydroxide, 1.36 m of sodium acetate trihydrate (about 10 mol) and N
-Methyl-2-pyrrolidone (hereinafter abbreviated as NMP) 7
．． 9- was charged, and the temperature was gradually raised to 205° C. while stirring, and about 1.51 hours of distilled water containing 1.36 hours of water was removed.

3.75 b of 1,4-dichlorobenzene (2
5.5 mol) and NMP2 were added and heated at 265°C for 4 hours. The reaction product was washed 5 times with 70°C warm water,
Dry under reduced pressure at 80°C for 24 hours to obtain a melt viscosity of approximately 2.500.
About 2 kg of powdered PPS of poise (320°C, shear rate 1.000 sec-1) was obtained. This is designated as PP5-1.

Reference Example 2 (Deionization treatment of PPS) Approximately 2 kg of the PPS powder obtained in Reference Example 1 was added to 20 Jl of a pH 4 acetic acid aqueous solution heated to 90°C! Put it inside, about 3
After continuing to stir for 0 minutes, it was filtered, washed with deionized water at about 90°C until the pH of the r-liquid reached 7, and dried under reduced pressure at 120°C for 24 hours to form a powder. This is designated as PP5-2.

Reference Example 3 (Preparation of modified PPS) PP5-1 obtained in Reference Example 1 and PP5 obtained in Reference Example 2
-2 Tri-blend 2.0 parts by weight of maleic anhydride to 100 parts by weight, and melt-knead the mixture using a twin-screw extruder set at 290 to 310°C to obtain maleic anhydride-modified PP.
Obtained S beret. These are PP5-3 and P
It is set as P5-4. Further, modification was carried out under the same conditions and method except that 5.0 parts by weight of maleic anhydride was used for 100 parts by weight of PP5-2.

This is designated as PP5-5.

Further, 100 parts by weight of PP5-2 was modified under the same conditions and method except that 1.5 parts by weight of glycidyl methacrylate was used instead of maleic anhydride to obtain pellets of glycidyl methacrylate-modified PPS. These are designated as PP5-6.

Reference Example 4 (Preparation of maleimide copolymers) Maleimide copolymers synthesized from N-arylmaleimide monomers, vinyl monomers, and maleic anhydride (B-1 to B-6)
) is shown below.

Among the raw material monomers shown in Table 2, 100 parts of a vinyl monomer mixture was dissolved in 100 parts of methyl ethyl ketone along with 0.3 parts of benzoyl peroxide initiator, and the mixture was charged into a reaction tank, and the hot water temperature in the tank was adjusted. Sufficient stirring was performed while maintaining the temperature at 75°C. Polymerization was carried out by dropping a predetermined amount of N-arylmaleimide and maleic anhydride dissolved in 100 parts of methyl ethyl ketone at a predetermined rate into the solution, resulting in maleimide copolymers (B-1 to B-6) having various compositions. ) was obtained.

Reference Example 5 (Preparation of maleimide copolymer) A method for preparing a maleimide copolymer (B-7>) synthesized by reacting a maleic anhydride-containing vinyl copolymer with aniline and then subjecting it to dehydration and ring closure. It is shown below.

A polymerization tank equipped with a reflux condenser, a stirrer, and a dropping funnel was charged with 60 parts of styrene and 50 parts of methyl ethyl ketone, and after purging the inside of the system with nitrogen gas, the temperature was raised to 85°C.

On the other hand, separately 40 parts of maleic anhydride and 0 parts of benzoyl peroxide
．． A solution of 15 parts dissolved in 180 parts of methyl ethyl ketone was prepared and charged into a dropping funnel. While maintaining the bath temperature at 85° C. and stirring, a maleic anhydride-benzoyl peroxide-methyl ethyl ketone solution was continuously added from the dropping funnel over a period of 8 hours. After the addition, the temperature was kept at 85°C for an additional hour. A colorless and transparent liquid was obtained. When we sampled a portion and measured the polymerization rate by gas chromatography, we found that styrene was 98%, maleic anhydride was 99%
%Met.

To the copolymer solution obtained here, 38.4 parts of aniline and 0.3 parts of triethylamine, which are 0.97 times equivalent to maleic anhydride, were added and reacted at 160°C for 5 hours to form a maleimide copolymer ( B-7) was obtained. According to 13C-NMR analysis, the addition rate of acid anhydride groups to imide groups was 95%.

Reference Example 6 (Preparation of modified maleimide copolymer) Reference Example 4
Maleimide copolymers B-1 and B-3100 obtained in
Tri-blending 2.0 parts by weight of maleic anhydride with respect to parts by weight was melt-kneaded using a twin-screw extruder set at 250 to 270°C to obtain pellets of a maleic anhydride-modified maleimide copolymer. . These are B-8 and B-, respectively.
9. Further, modification was carried out under the same conditions and method except that 5.0 parts by weight of maleic anhydride was used for 100 parts by weight of B-3.

This is designated as B-10.

In addition, modification was carried out under the same conditions and method except that 1.5 parts by weight of glycidyl methacrylate was used instead of maleic anhydride for 100 parts by weight of B-3 to obtain pellets of a glycidyl methacrylate-modified maleimide copolymer. Ta. This is designated as B-11.

Reference Example 7 The thermoplastic elastomer used in this example and comparative example is shown below.

C-1: Ethylene-glycidyl methacrylate (88/
12 weight ratio) Copolymer C-2: Styrene-butadiene-styrene copolymer (“Califlex TRKX65S” manufactured by Shell Chemical ■) C-3: Styrene-ethylene/butylene-styrene copolymer (“Califlex TRKX65S” manufactured by Shell Chemical ■) C-4: M-modified styrene-ethylene/butylene-styrene copolymer (“Krayton FG1901X” manufactured by Shell Chemical ■) C-5 = Epoxy-modified styrene-ethylene/butylene-
1 part by weight of styrene copolymer C-3, 1 part by weight of glycidyl methacrylate, and 0.1 part by weight of di-tert-butyl peroxide were triblended using a Henschel mixer, and a vented twin-screw extruder set at 210 to 230°C. The extrudable strands were cut using a pelletizer to obtain an epoxy-modified styrene-ethylene/butylene-styrene copolymer.

C-6: Ethylene-butene copolymer (“Tafmer A-4085” manufactured by Mitsui Petrochemical ■) Examples 1 to 12 PPS and/or modified PPS and maleimide copolymer and/or modified maleimide copolymer were triblended in the composition ratios shown in Table 2, and melt-kneaded and pelletized using a co-rotating twin-screw extruder set at 290 to 310°C at a screw rotation speed of 10 orpm.

Using this pellet, injection molding was performed using an in-line screw molding machine to form a test piece.

(Temperature condition setting: 290-310℃, mold temperature: 140℃
Table 2 shows the Izot impact strength, heat distortion temperature, and solvent resistance test results measured on the obtained test pieces.

Comparative Examples 1 to 6 PPS-2, PP5-4 and maleimide copolymer B-1
, B-3, B-4, B-5, and B-6 were triblended in the composition shown in Table 2, but kneading, molding, and measurement were carried out in exactly the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 1 is a resin composition composed of an unmodified PPS resin and a maleimide copolymer that does not contain maleic anhydride structural units, and delamination was observed, resulting in low impact resistance and a low heat distortion temperature. The value of is also unstable at 172-185°C. Comparative Example 2 has a low heat distortion temperature because the maleic anhydride structural unit in the maleimide copolymer exceeds 10% by weight. Comparative Example 3 shows that N in the maleimide copolymer
- Since the arylmaleimide structural unit is less than 10% by weight and the vinyl structural unit is more than 90% by weight, the heat distortion temperature is low.

In Comparative Example 4, the N-arylmaleimide structural unit was more than 90% by weight and the vinyl structural unit was less than 10% by weight, so the Izot impact value was low, and furthermore, cracking was observed in the solvent resistance test. It will be done. Comparative example 5 is P
In the composition ratio of PS resin and maleimide copolymer,
Since the PPS resin exceeds 90% by weight, the heat distortion temperature is low. In Comparative Example 6, since the P and PS citrus content was less than 10% by weight, cracks were observed in the solvent resistance test.

Examples 13 to 18 Same as Example 1 except that PPS resin and/or modified PPS resin, maleimide copolymer and/or modified maleimide copolymer, and thermoplastic elastomer were triblended with the composition shown in Table 3. Kneading, molding and measurement were carried out in exactly the same manner. The results are shown in Table 2.

As is clear from the Examples in Tables 2 and 3, the resin compositions of the present invention (Examples 1 to 18) have excellent compatibility, and have excellent Izot impact value, heat distortion temperature, and solvent resistance. Excellent in balance.

Comparative Example 7.8 Example 1 except that the PPS resin and/or modified PPS resin, maleimide copolymer and/or modified maleimide copolymer, and thermoplastic elastomer were triblended with the composition shown in Table 3. Knead in exactly the same way as
Molding and measurement were performed. The results are shown in Table 2.

Comparative Example 7 is a resin composition composed of an unmodified PPS resin, a maleimide copolymer containing no maleic anhydride structural unit, and a thermoplastic elastomer (C-6), and delamination was observed. The impact resistance is low, and the heat deformation temperature is unstable at 155 to 170°C. In Comparative Example 8, the thermoplastic elastomer was present in an amount of 50 parts by weight or more based on 100 parts by weight of the PPS resin and maleimide copolymer, so the heat resistance was low.

<Effects of the Invention> The polyphenylene sulfide resin composition of the present invention has excellent compatibility and is excellent in impact resistance, heat resistance, and solvent resistance in a balanced manner.

Patent application Daitoshi Co., Ltd.

Claims (2)

[Claims] (1) (A) polyphenylene sulfide and/or 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 in the molecule. 90-10% by weight of modified polyphenylene sulfide modified with (B) 90-10% by weight of N-arylmaleimide structural units, 10-90% by weight of vinyl-based structural units, and the total of N-arylmaleimide structural units and vinyl-based structural units. A maleimide copolymer containing 0 to 10 parts by weight of maleic anhydride structural units per 100 parts by weight, and/or a maleimide copolymer containing (a) an ethylenic double bond, (b) a carboxyl group, an acid anhydride group, and Consists of 10 to 90% by weight of a modified maleimide copolymer obtained by modifying the maleimide copolymer with an organic compound simultaneously having a functional group selected from the group consisting of epoxy groups, and consists essentially of polyphenylene sulfide and maleic anhydride structural units. A polyphenylene sulfide resin composition excluding a resin composition composed of a combination of a maleimide copolymer that does not contain. (2) (A) polyphenylene sulfide and/or 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 in the molecule. 90-10% by weight of modified polyphenylene sulfide, (B) 90-10% by weight of N-arylmaleimide structural units, 10-90% by weight of vinyl-based structural units, and a total of 100% of N-arylmaleimide structural units and vinyl-based structural units. A maleimide copolymer consisting of 0 to 10 parts by weight of maleic anhydride structural units and/or a molecule containing (a) an ethylenic double bond, (b) a carboxyl group, an acid anhydride group, and an epoxy 10 to 90% by weight of a modified maleimide copolymer obtained by modifying the maleimide copolymer with an organic compound simultaneously having a functional group selected from the group consisting of polyphenylene sulfide and maleic anhydride constituent units. (C) A polyphenylene sulfide resin composition in which 1 to 50 parts by weight of a thermoplastic elastomer is blended to 100 parts by weight of the resin composition excluding the resin composition composed of a combination of maleimide copolymers that do not contain it. thing.