JP2967358B2 - Polyarylene sulfide resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polyarylene sulfide resin composition, and more particularly, to a mechanical strength, particularly, without deteriorating the excellent heat resistance of a polyarylene sulfide resin. The present invention relates to a polyarylene sulfide resin composition having improved impact resistance, which can be suitably used, for example, in the electric and electronic fields and mechanical parts.

[Problems to be Solved by the Prior Art and the Invention] Polyarylene sulfide resin (PAS) such as polyphenylene sulfide (homo-PPS) has heat resistance, flame retardancy,
It is used in many fields as an engineering plastic with excellent properties such as high rigidity.

However, the polyarylene sulfide resin does not have sufficient impact resistance, and although a fibrous reinforcing material is generally compounded, it does not reach a satisfactory level depending on the application.

Therefore, in order to improve the impact resistance, an elastomer is also blended. However, even if the impact resistance is improved, other mechanical properties such as rigidity are reduced, and heat resistance and flame retardancy are also reduced. Will drop.

On the other hand, polyamide resin is a resin having excellent properties such as heat resistance and high rigidity, but has a problem of high water absorption.

Therefore, attempts have been made to improve the properties of both the polyarylene sulfide resin and the polyamide resin by making the polyarylene sulfide resin and the polyamide resin into a polymer alloy.

Japanese Patent Publication No. 59-1422 (JP-A-53-69255) discloses that 60-97% by weight of a polyphenylene sulfide resin and polyamide
A resin composition by a simple blend with 40 to 3% by weight is disclosed.

JP-A-63-69832 discloses that 10 to 90% by weight of polyphenylene sulfide, 90 to 10% by weight of a polyamide resin,
A fiber-reinforced thermoplastic resin composite material comprising reinforcing fibers of 3 mm or more is disclosed.

JP-A-61-126170 discloses a polyamide resin composition comprising 50 to 5% by weight of polyarylene sulfide and 95 to 50% by weight of nylon 46.

However, the resin compositions of these simple blends have insufficient compatibility, so that there is a problem that the mechanical strength is greatly reduced and the effect of improving the impact strength is small.

JP-A-1-174562 discloses a polyphenylene sulfide resin composition comprising 1 to 99% by weight of deionized polyphenylene sulfide and 1 to 99% by weight of a polyamide resin.

JP-A-59-155462 discloses a resin composition comprising a mixture of polyphenylene sulfide, polyamide and epoxy resin.

JP-A-63-146939 discloses a polyphenylene sulfide resin composition comprising a polyphenylene sulfide resin, a polyamide resin and an epoxy resin.

However, these resin compositions are considerably improved in physical properties by deionizing or improving the compatibility by adding an epoxy resin, but have no reactivity between the polyamide resin and the polyphenylene sulfide resin. Therefore, stability is not always sufficient.

JP-A-61-207462 discloses a resin composition in which a polyphenylene sulfide containing an amino group or an amide group is mixed with a thermoplastic elastomer and, if necessary, an inorganic filler.

However, since the elastomer is used, there is a problem that heat resistance is reduced.

 The present invention has been made based on the above circumstances.

That is, an object of the present invention is to use a reactive polyarylene sulfide and a polyfunctional compound to react a polyamide resin and a polyarylene sulfide resin to form an alloy, thereby improving mechanical properties, particularly impact strength and bending strength. Another object of the present invention is to provide a novel polyarylene sulfide resin composition having improved heat resistance and water absorption resistance.

[Means for Solving the Problems] To achieve the above object, the invention of claim 1 provides a polyarylene sulfide containing an amino group and / or an amide group, a polyamide resin, an acid, an acid anhydride, and It is selected from the group consisting of acid halides and contains, in one molecule, a compound having two or more functional groups capable of reacting with the amino group or amide group (however, it does not contain modified polyphenylene ether). It is a polyarylene sulfide resin composition characterized by the above, wherein the invention according to claim 2, wherein the total weight of the polyarylene sulfide and the polyamide resin is 1 to 99.
A total of 100 parts by weight of the amino group and / or amide group-containing polyarylene sulfide and 99 to 1% by weight of the polyamide resin based on the total weight; , Acid anhydrides, and acid halides, and within one molecule,
The polyarylene sulfide resin composition according to claim 1, comprising 0.01 to 5 parts by weight of a compound having two or more functional groups capable of reacting with the amino group or the amide group. The invention described in the above is selected from the group consisting of a polyarylene sulfide containing an amino group and / or an amide group, a polyamide resin, an acid, an acid anhydride and an acid halide. Or a polyarylene sulfide resin composition comprising a compound having two or more functional groups capable of reacting with an amide group and a filler (but not containing a modified polyphenylene ether). Item 4. The invention according to Item 4, wherein the total weight of the polyarylene sulfide and the polyamide resin is 1%.
A total of 100 parts by weight of the polyarylene sulfide containing the amino group and / or the amide group and the polyamide resin having a compounding amount of 99 to 1% by weight based on the total weight; The acid, an acid anhydride, and selected from the group consisting of acid hydride, and in one molecule, 0.01 to 5 parts by weight of a compound having two or more functional groups capable of reacting with the amino group or the amide group, 4. The composition according to claim 3, further comprising 5 to 400 parts by weight of a filler.
The polyarylene sulfide resin composition described in the above.
The modified polyphenylene ether is a modifying agent selected from polyphenylene ether having (a) an ethylenic double bond and (b) a compound having a carboxyl group or an acid anhydride group in a molecule at the same time, and a radical initiator. Refers to a modified polyphenylene ether obtained by modification in the presence or absence of

 Hereinafter, the present invention will be described in detail.

-Polyarylene sulfide- An important filling in the present invention is that the polyarylene sulfide is a polyarylene sulfide containing amino groups and / or amide groups.

The polyarylene sulfide used in the present invention is
It may be an uncrosslinked or partially crosslinked polyarylene sulfide and a mixture thereof, or may be a linear or branched polyarylene sulfide or a mixture thereof.

In addition, the polyarylene sulfide containing an amino group and / or an amide group used in the present invention may be a branched or straight-chain polyarylene sulfide homopolymer and a branched or linear polyarylene sulfide containing the amino group and / or an amide group. Alternatively, it may be a mixture with a linear polyarylene sulfide copolymer.

Regarding the content of the polymer in the mixture, the content of the amino group and / or amide group-containing component in the polyarylene sulfide copolymer containing the amino group and / or the amide group (the content of the unit having these groups) And the amount is not particularly limited. For example, the content of the polyarylene sulfide homopolymer is 0 to 99% by weight, preferably 20 to 60% by weight, and the amino group and / or Or the content of the polyarylene sulfide copolymer containing an amide group is from 1 to
It is 100% by weight, preferably 80 to 40% by weight. The content of the amino group and / or amide group-containing component (content of the monomer unit having an amino group and / or amide group) in the mixture is usually 0.1 to 50 mol%.

As the polyarylene sulfide homopolymer,
For example, linear or branched homo-polyphenylene sulfide (PPS) can be mentioned.

As the polyarylene sulfide homopolymer,
The melt index measured by ASTM method D 1238 74 (315.5 ° C, 5 kg load) is 10 to 1,000 g / 10 min, preferably 20
~ 3,000g / 10min, general formula The phenylene sulfide unit represented by 80 mol% or more,
Preferably, it is contained at 90 mol% or more.

 If this amount is less than 80 mol%, the heat resistance is insufficient.

The amino group and / or amide group contained in the polyarylene sulfide used in the present invention may be present in the polymer main chain or in the branched chain.

As the amino group, the following formula (I) Represented by the following formula (II): Is represented by

However, R ¹ , R ² , R ³ and R ⁴ are a hydrogen atom or an alkyl group, and may be the same or different.

As the alkyl group represented by R ^{1 to} R ⁴ , for example, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group is preferable.

In any case, in the present invention, usually, the amino group is -NH _2, the amide group is -CONH _2.

When the amino group and / or the amide group are bonded to the phenylene group constituting the polymer main chain, the content of the phenylene sulfide unit that bonds the amino group and / or the amide group is preferably 0.1 to 30 mol%, More preferably, it is 0.3 to 10 mol%.

In this case, the content is determined based on amino groups and / or
Alternatively, it means the mole% of the phenylene sulfide unit in the entire mixture of the polyarylene sulfide copolymer containing a phenylene sulfide unit and a polyarylene sulfide homopolymer which binds to an amide group.

If this content exceeds 30 mol%, the crystallinity of the polyphenylene sulfide resin itself decreases, and the physical properties such as heat resistance decrease. Further, when the content is less than 0.1 mol%,
In some cases, the reaction with the bifunctional compound in the present invention does not sufficiently occur, and the physical properties are not so much improved.

The polyarylene sulfide copolymer having an amino group and / or an amide group as described above is obtained from ASTM D-1238.
(316.5 ° C., load 5 kg), the melt index is usually 10 to 10,000 g / 10 minutes, preferably 20 to 3,
000 g / 10 minutes, and polyarylene sulfide copolymers of various molecular weights are employed depending on the application.

The amino group and / or amide group-containing polyarylene sulfide can be obtained by employing various methods for copolymerizing an amino group and / or a comonomer containing an amino group.

Examples of the comonomer include chloro-substituted anilines, such as monochloroaniline, dichloroaniline, N-alkylmonochloroanilyl, and N-alkyldichloroaniline, chlorosubstituted acetanilides such as chloroacetanilide, and dichlorobenzamide. By copolymerizing chloro-substituted benzamides of the formula

Examples of the polymerization method using the comonomer include a method of polymerizing p-dichlorobenzene and the comonomer containing the amino group and / or the amide group in the presence of sulfur and sodium carbonate, p-dichlorobenzene A method of polymerizing an amino group and / or an amide group-containing comonomer in a polar solvent in the presence of sodium sulfide or sodium hydrosulfide and sodium hydroxide or hydrogen sulfide and sodium hydrosulfide, N-methylpyrrolidone, dimethyl Examples thereof include a method of reacting sodium sulfide with p-dichlorobenzene and the comonomer containing the amino group and / or amide group in an amide solvent such as acetamide or a sulfone solvent such as sulfolane. At this time, in order to adjust the degree of polymerization, a polymerization aid such as an alkali metal salt of a carboxylic acid or a sulfonic acid, an alkali metal halide such as lithium chloride, or an alkali hydrosulfide may be added.

By such a method, a polyarylene sulfide having an amino group and / or an amide group can be converted into an amino-substituted phenylene sulfide-bonded copolymer component containing an amino group and / or an amide group. [However, R ¹ and R ² represent the same meaning as described above. ], Amide group-substituted phenylene sulfide bond [However, R ³ and R ⁴ represent the same meaning as described above.] In addition, the polymer has various amino-substituted arylene sulfide bonds, amide-substituted arylene sulfide bonds, amino-substituted alkylene sulfide bonds, amide-substituted alkylene sulfide bonds, and the like.

Incidentally, the polyarylene sulfide in the present invention,
In addition to a copolymer component derived from a comonomer having an amino group and / or an amide group, (However, R ⁵ represents an alkyl group, a nitro group, a phenyl group, an alkoxy group, a carboxylic acid group or a metal base of a carboxylic acid.) Trifunctional phenyl sulfide bond And the like.

Furthermore, the polyarylene sulfide used in the present invention can be used after being treated with an acid such as acetic acid for the purpose of improving the compatibility with the polyamide resin.

-Polyamide resin- The polyylene sulfide resin composition of the present invention contains a polyamide resin.

The polyamide resin used in the present invention is a polyamide containing amino acids, lactams, or diamines and dicarboxylic acids as main components.

Lactams such as ε-caprolactam, enantholactam, ω-laurolactam, to name specific examples of the constituent components;
ε-aminocaproic acid, 11-aminoundecanoic acid, 12-
Amino acids such as aminododecanoic acid, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,2,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, m -Xylylenediamine, p-xylylenediamine, 1,3-bisaminomethylcyclohexane, 1,4
Diamines such as -bisaminomethylcyclohexane, bis-p-aminocyclohexylmethane, bis-p-aminocyclohexylpropane, and isophoronediamine, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecandioic acid, and 1,4-cyclohexanedicarboxylic acid There are dicarboxylic acids such as acid, 1,3-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and dimer acid.

These components are subjected to polymerization alone or in the form of a mixture of two or more, and any of the polyamide homopolymers and copolymers thus obtained can be used in the present invention.

Particularly useful polyamides useful in the present invention are polycaproamide (nylon 6), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (nylon 66), and polyhexamethylene sebacamide (nylon 610). ), Polyundecaneamide (nylon 11), polydodecaneamide (nylon 12), and copolymers and mixtures of these polyamides. Preferred among these are one of nylon 6, nylon 66, nylon 46, or a mixture thereof.

The degree of polymerization of the polyamide used here is not particularly limited, and the relative viscosity at 25 ° C. of a 1% concentrated sulfuric acid solution is 1.5.
Those within the range of ~ 5.0 can be used arbitrarily.

-Acid, acid anhydride, acid halide-In the polyarylene sulfide resin composition of the present invention,
In addition to the polyarylene sulfide having the amino group and / or the amide group and the polyamide resin, it is selected from an acid, an acid anhydride, and an acid halide, and in one molecule, two or more that can react with the amino group or the amide group. (Hereinafter, may be simply referred to as a specific compound) is used.

The functional group of these specific compounds is not particularly limited as long as it reacts with an amino group or an amide group of polyarylene sulfide.
OH, -COX (where X represents a halogen atom),-
C (= O) OC (= O)-(anhydride group) can be mentioned.

It is important that the specific compound has at least two functional groups in its molecule. One of the at least two functional groups reacts with an amino group and / or an amide group in the polyarylene sulfide;
The remaining one functional group greatly contributes to the development of wettability or adhesiveness.

The specific compound having a functional group as described above can be represented by the following general formula.

AR ⁶ -B In this general formula, A and B are -COOH, -COX or Wherein A and B may be the same or different from each other, and R ⁶ represents an alkylene group or an aromatic hydrocarbon group. X represents a halogen atom.

As a typical example of the specific compound represented by the general formula,
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonamethylenedicarboxylic acid, 1,10-decamethylenedicarboxylic acid, 1,11-un General formula HOOC-R such as decamethylenedicarboxylic acid, 1,12-dodecamethylenedicarboxylic acid, 1,13-tridecamethylenedicarboxylic acid, 1,14-tetradecamethylenedicarboxylic acid, phthalic acid, isophthalic acid, and terephthalic acid ⁷ -COOH (provided that, R ⁷ represents an alkylene group or an aromatic hydrocarbon group.) a dicarboxylic acid represented by, phthaloyl chloride, formula XC (= O) -R ⁸
—C (＝ O) X (where R ⁸ represents an alkylene group or an aromatic hydrocarbon group), a dicarboxylic acid halide, ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cycloalkyl Pentanecarboxylic dianhydride, pyromellitic anhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3 '
-Benzophenonetetracarboxylic dianhydride, 3,3 ', 4,
4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,
3'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2
-Bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1- Bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 4,4′- (P-phenylenedioxy) diphthalic dianhydride, 4,4 '-(m-phenylenedioxy)
Diphthalic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic acid Dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2,
3,6,7-anthracenetetracarboxylic dianhydride, 1,2,
7,8-phenanthrenetetracarboxylic dianhydride and the like,
Next formula (However, R ⁹ represents an alkylene group or a divalent aromatic hydrocarbon group.).

Among the above specific compounds, dicarboxylic dianhydride is preferred, and pyromellitic anhydride is particularly preferred.

One of these specific compounds may be used alone, or two or more of them may be used in combination.

-Filler-The polyarylene sulfide resin composition of the present invention may contain a filler.

Examples of the filler include an inorganic filler and an organic filler.

Examples of the inorganic filler include glass fibers (chopped strands and milled fibers), carbon fibers, metal fibers, fibrous potassium titanate, asbestos, and various kinds of fibrous inorganic materials such as whiskers such as silicon carbide and silicon nitride. Filler, graphite, charcoal, talc, mica, silica, boron nitride, barium sulfate, calcium sulfate, kaolin, clay, pyrophyllite,
Bentonite, sericite, zeolite, ferrite,
Attapulgite, wollastonite, calcium silicate, magnesium carbonate, dolomite, antimony trioxide, magnesium oxide, zinc oxide, titanium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass powder, glass beads, quartz, quartz glass, Metal powders such as iron, zinc, copper, aluminum and nickel can be used.

Among the various inorganic fillers, fibrous inorganic fillers are preferred, and glass fibers are particularly preferred.

When using glass fibers, the average fiber diameter is usually 20 μm or less, particularly preferably 5 to 14 μm, the aspect ratio is usually 5 to 500,
In particular, it is preferably from 10 to 300.

In addition, glass fiber is glass fiber without surface treatment,
Alternatively, any glass fiber treated with a surface treatment agent can be used, but glass fiber treated with a surface treatment agent is preferred.

The surface treatment agent may be a commonly used surface treatment agent, but is preferably an aminosilane-based surface treatment agent, a blocked isocyanate-based treatment agent, or an epoxysilane-based treatment agent.

The various inorganic fillers may be used alone or in combination of two or more.

When two or more inorganic fillers are used, it is preferable to use the fibrous inorganic filler in combination with another inorganic filler. When such a combination is used, it is desirable to use a fibrous inorganic filler, preferably glass fiber, in an amount of at least 5% by weight, preferably 10% by weight or more based on the total amount of the inorganic filler.

Other inorganic fillers when glass fibers are used in combination may not necessarily be treated with a surface treatment agent.

In order to surface-treat the inorganic filler with the surface treatment agent, the inorganic filler is immersed in the surface treatment agent or a solution containing the same, or the surface treatment agent or a solution containing the same is applied to the surface of the inorganic filler. The surface treatment agent may be attached to the surface of the inorganic filler by spraying.

In addition, examples of the organic filler include aramid fiber, ultrahigh molecular weight polyethylene powder and fiber.

Further, in the composition of the present invention, another resin can be added as necessary. These resins include, for example, ethylene, butylene, pentene, butadiene, isoprene, chloroprene, styrene, α-methylstyrene,
Homopolymer or copolymer such as vinyl acetate, vinyl chloride, acrylate, (meth) acrylonitrile, polyurethane, polyacetal, polycarbonate, polysulfone, polyallylsulfone, polyethersulfone, polyarylate, polyphenylene oxide,
Examples thereof include homopolymers such as polyetheretherketone, polyimide, silicone resin, phenoxy resin, fluororesin, and polyarylether, random copolymers, block copolymers, and graft copolymers. In addition, a polyolefin resin modified with an unsaturated carboxylic acid or a derivative thereof can also be used.

These can be used alone or in combination of two or more.

-Compounding amount of each component-The polyarylene sulfide resin composition of the present invention comprises the above-described components, that is, a mixture of the polyarylene sulfide and the polyamide resin, the acid,
Acid anhydrides and acid halides, each containing, in one molecule, a compound having two or more functional groups capable of reacting with the amino group or the amide group, and containing the filler compounded as necessary I do.

The mixing ratio of the polyarylene sulfide and the polyamide resin varies depending on the desired properties, but the polyarylene sulfide is 1 to 99% by weight, preferably 5 to 80% by weight.
To 99% by weight of polyamide resin, preferably 95%
~ 20% by weight.

When the addition ratio of each of the polyarylene sulfide and the polyamide resin is less than 1% by weight, the effects intended by the present invention are small.

Acids, acid anhydrides, and acid halides, and in one molecule, the compounding amount of the compound having two or more functional groups capable of reacting with the amino group or the amide group is the above-described polyarylene sulfide homopolymer. And 0.01 to 5 parts by weight with respect to 100 parts by weight of the total weight of the polyarylene sulfide and the polyamide resin, which is composed of a mixture of a polyarylene sulfide copolymer containing an amino group and / or an amide group. Preferably 0.05 to 3
Parts by weight.

If the amount is less than 0.01 part by weight, the adhesion or wettability of a polyarylene sulfide resin composition containing a polyarylene sulfide having an amino group and / or an amide group and this specific compound is not sufficient. In some cases, polyarylene sulfide having an amino group and / or an amide group and a polyarylene sulfide resin composition containing this specific compound do not show any improvement in mechanical properties. is there. If the amount exceeds 5 parts by weight, the effect corresponding to the increase in the amount may not be obtained.

The amount of the filler is 5 to 400 parts by weight, preferably 20 to 300 parts by weight, based on 100 parts by weight of the mixture of the above-mentioned amino group and / or amide group-containing polyarylene sulfide and polyamide resin. .

When the amount of the filler is within the above range, it is possible to improve mechanical properties such as impact resistance and bending strength without lowering the heat resistance and rigidity of the polyarylene sulfide resin composition. If it exceeds 400 parts by weight, the content of the resin component is insufficient, and the kneading property and the moldability are reduced, and
When the compounding amount of the filler is less than 5 parts by weight, the heat resistance and the reinforcing effect due to the compounding of the filler may not be obtained in some cases.

—Preparation of Resin Composition— The preparation of the polyarylene sulfide resin composition of the present invention can be performed by various known methods.

When preparing a polyarylene sulfide resin composition,
There is no particular limitation on the order of mixing the components.

In preparing and mixing the polyarylene sulfide resin composition of the present invention, a polyarylene sulfide containing an amino group and / or an amide group, a polyamide resin, an acid, an acid anhydride, and an acid halide are selected. The compound having two or more functional groups capable of reacting with the amino group or the amide group can be mixed therein by various means. In the mixing, the amino group and / or the amide group in the polyarylene sulfide are mixed with the compound. It is not required to react with the functional group in the specific compound.

The polyarylene sulfide resin composition according to claim 1, wherein, when it is combined with a predetermined object, an amino group and / or an amide group in the polyarylene sulfide and a functional group in the specific compound are used. React to exhibit the adhesiveness or wettability of the polyarylene sulfide resin composition. In the polyarylene sulfide resin composition according to claims 3 and 4, the specific compound having a functional group, the polyarylene sulfide containing an amino group and / or an amide group, and a polyamide are first reacted. Polyarylene sulfide resin composition by a method of kneading with a filler, a method of simultaneously kneading each compounding component, a method of first reacting a specific compound having a functional group with a filler and then kneading the remaining components. Can be prepared.

The mixing means used for preparing the polyarylene sulfide resin composition of the present invention is not particularly limited as long as a uniform mixture can be obtained, and various mixing methods can be used.

Specific examples include ribbon blenders,
It can be performed by a tumble mixer, Henschel mixer, oven roll, Banbury mixer, Henschel mixer, single screw extruder, twin screw extruder, single screw reciprocating screw kneader, or the like.

The polyarylene sulfide resin composition thus obtained can be formed into various molded products by various molding methods such as injection molding, compression molding, extrusion molding, and used as various sealants and coating agents. You can also. For example, the polyarylene sulfide resin composition of the present invention can be formed into a flat plate, a film, a sheet, or the like, and a plywood or a laminate can be formed with such a plate and another plate, or A multilayer film or sheet can be formed by coextrusion.

Further, by the above-mentioned various molding methods, the polyarylene sulfide resin composition of the present invention can be used as a fiber, a pipe, a rod,
It can be formed into a molded product in various fields such as a mechanical field, an electric field, an electronic field and other fields such as a film, a sheet and a bearing.

[Examples] Next, the present invention will be described more specifically based on examples and comparative examples.

Example 1 Production of Amino Group-Containing Polyphenylene Sulfide Hydrous sodium sulfide (Na ₂ S •) was placed in a reaction vessel equipped with a stirrer.
833 mol and N-methyl-2-pyrrolidone (NMP)
510 was charged and dehydrated for 1 hour while maintaining the temperature at 145 ° C. under reduced pressure. Then, after cooling the reaction system to 45 ° C,
833 moles of p-dichlorobenzene and dichloroaniline (DC
A) 41.85 mol (5 mol%) was added, and the reaction was carried out at 240 ° C. for 5 hours. Thereafter, the reaction vessel was cooled and the contents were filtered off. Then, the cake was washed three times with hot water and then washed.
After washing once with NMP at 0 ° C. and three times with water, further washing once with acetone, and then drying at 185 ° C., a white granular amino group-containing polyphenylene sulfide (hereinafter referred to as DCA-P
Abbreviated as PS. ) 78 kg was obtained.

This DCA-PPS had a content of the amino group-containing unit of 5 mol%, a logarithmic viscosity number [ηinh] of 0.26, and a melt index of 59 g / 10 min.

Production of Polyphenylene Sulfide Resin Composition Next, according to the composition ratio (parts by weight) of each component shown in Table 1, that is, the above DCA-PPS was used as a polyarylene sulfide containing amino group and / or amide group in 50 parts.
Parts by weight, 50 parts by weight of nylon 66 (UBE Nylon 66, manufactured by Ube Industries, Ltd.) as polyamide resin and 0.5 parts by weight of pyromellitic anhydride are mixed and melt-mixed with a twin-screw extruder to produce pellets. did.

Subsequently, the pellets were injection molded under the conditions of a cylinder temperature of 320 ° C. and a mold temperature of 135 ° C. to produce a test piece. The Izod impact strength, bending strength, and heat distortion temperature (HD
T) and water absorption were measured.

Izod impact strength: Conforms to ASTM D 256 Flexural strength: Conforms to ASTM D 790 1-8 inches, span 50 mm Speed 2.0 mm / min Heat distortion temperature (HDT): Conforms to ASTM D 648 18.5 kg / cm ² Water absorption: ASTM D Table 1 shows the results according to 0570.

(Comparative Example 1) In Example 1, instead of DCA-PPS, linear homopolyphenylene sulfide (hereinafter referred to as homo-PPS) is abbreviated. The logarithmic viscosity number [ηinh] is 0.26, and ASTM method D 1238
Only｝ whose melt index measured at 74 (315 ° C., 5 kg load) was 59 g / 10 minutes was used.

Pellets of this homo-PPS resin alone were produced, and the physical properties were measured in the same manner as in Example 1.

 The results are shown in Table 1.

(Comparative Example 2) The procedure of Example 1 was repeated, except that pyromellitic anhydride was not added.

 The results are shown in Table 1.

(Example 2) According to the composition ratio shown in Table 1, a mixture of homo-PPS and DCA-PPS was used as polyphenylene sulfide, nylon 66 was used as a polyamide resin, and pyromellitic anhydride was compounded. Performed similarly to 1.

 The results are shown in Table 1.

(Examples 3 and 4) The procedure of Example 2 was repeated except that glass fibers were added.

According to the composition ratio shown in Table 1, nylon 66 or nylon 46 was used as the polyamide resin.

 The results are shown in Table 1.

(Example 5) Production of amide group-containing polyphenylene sulfide In the method for producing amino group-containing polyphenylene sulfide of Example 1, 2,5-diphenylaniline was used instead of dichloroaniline.
The reaction was carried out in the same manner as in the above-mentioned production method of amino group-containing polyphenylene sulfide except that 41.85 mol of dichlorobenzamide was used and reacted at 230 ° C. for 5 hours.

The obtained amide group-containing polyphenylene sulfide (hereinafter abbreviated as DCBA-PPS) has an amide group-containing unit content of 5 mol%, a logarithmic viscosity [ηinh] of 0.28, and a melt index of 80 g / 10 min. there were.

In Example 4, it carried out similarly to Example 4 except having used DCBA-PPS instead of DCA-PPS.

 The results are shown in Table 1.

(Comparative Examples 2 and 3) Homo-PPS was used as polyphenylene sulfide, and pyromellitic anhydride was not added, and the same operation as in Example 1 was performed according to the composition ratio shown in Table 1.

 The results are shown in Table 1.

(Comparative Example 5) The procedure of Comparative Example 4 was repeated, except that pyromellitic anhydride was added.

 The results are shown in Table 1.

Note) Homo-PPS; Homo-polyphenylene sulfide, MI = 59
g / 10 min DCA-PPS; amino group-containing polyphenylene sulfide,
Amino group-containing phenylene sulfide unit content is 5
Mol%, MI = 29 g / 10 min DCBA-PPS; amide group-containing polyphenylene sulfide,
An amide group-containing phenylene sulfide content of 5 mol%,
MI = 80g / 10min Nylon 66; Ube Industries, Ltd., UBE Nylon 66 Nylon 46; Japan Synthetic Rubber Co., Ltd., JSR TS300 GF; Glass fiber, 13φμm × 3mm, Asahi Fiberglass Co., Ltd., FT525 Pyromellitic anhydride; commercial reagent (Evaluation) As seen in Examples 2 and 3, Example 2
Polyarylene sulfide, which is a mixture of polyphenylene sulfide and amino group-containing polyphenylene sulfide, and a polyamide resin, and a combination of pyromellitic dianhydride and Example 3, wherein glass fiber is further blended. , Izod strength and bending strength are improved. It can be seen that HDT also increased and heat resistance improved.

Comparing Example 3 with Comparative Example 3 (homo-PPS mixed with glass fiber), the impact strength was 45 kg · cm / c.
increased from m ² 80kg · cm / cm ² and by a large margin, the bending strength 2,300k
g / cm ² to 3,100 kg / cm ² . Moreover, it can be seen that the heat distortion temperature HDT increased from 259 to 271 ° C., and the heat resistance also improved.

Further, as shown in Comparative Example 5, when only homo-PPS was used as the polyarylene sulfide and pyromellitic dianhydride was added in the same manner as in the present invention, the effect obtained was:
Small compared to the present invention.

[Effect of the Invention] The polyarylene sulfide resin composition of the present invention is selected from a polyarylene sulfide containing an amino group and / or an amide group, a polyamide resin, an acid, an acid anhydride, and an acid halide. In the molecule, a compound having two or more functional groups capable of reacting with the amino group or the amide group, and a filler, without impairing the excellent heat resistance of the polyarylene sulfide, rather, the heat resistance. By improving and toughening with a polyamide resin, the obtained polyarylene sulfide resin composition has significantly improved mechanical properties, particularly impact resistance, and also improved water absorption resistance.

Therefore, a molded article obtained from the polyarylene sulfide resin composition by injection molding or other molding methods makes an important contribution to industrial fields such as mechanical, electric and electronic fields.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ identification code FI C08K 3:00) (58) Investigation field (Int.Cl. ⁶ , DB name) C08L 77/00-77/12 C08L 81 / 02 C08K 5/09-5/098

Claims (4)

(57) [Claims] 1. A polyarylene sulfide having an amino group and / or an amide group, a polyamide resin,
Selected from the group consisting of acids, acid anhydrides, and acid halides, and containing, in one molecule, a compound having two or more functional groups capable of reacting with the amino group or amide group (provided that modified polyphenylene ether Is not included.)
A polyarylene sulfide resin composition, characterized in that: 2. A polyarylene sulfide containing an amino group and / or an amide group in an amount of 1 to 99% by weight based on the total weight of the polyarylene sulfide and the polyamide resin. 99-1
100% by weight of the polyamide resin having a blending amount of 100% by weight, and selected from the group consisting of the acid, acid anhydride and acid halide, and capable of reacting with the amino group or amide group in one molecule. Compound having two or more functional groups 0.
2. The polyarylene sulfide resin composition according to claim 1, wherein the composition comprises 01 to 5 parts by weight. 3. 3. A polyarylene sulfide containing an amino group and / or an amide group, a polyamide resin,
It contains a compound selected from the group consisting of acids, acid anhydrides, and acid halides and having, in one molecule, two or more functional groups capable of reacting with the amino group or amide group, and a filler. And a modified polyphenylene ether are not contained.) 4. An amino group and / or amide group-containing polyarylene sulfide in an amount of 1 to 99% by weight based on the total weight of the polyarylene sulfide and the polyamide resin. 99-1
100% by weight of the polyamide resin having a blending amount of 100% by weight, and selected from the group consisting of the acid, acid anhydride and acid halide, and capable of reacting with the amino group or amide group in one molecule. Compound having two or more functional groups 0.
4. The polyarylene sulfide resin composition according to claim 3, wherein the composition comprises 01 to 5 parts by weight and 5 to 400 parts by weight of the filler. 5.