JP2591837B2 - Polyphenylene sulfide resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polyphenylene sulfide resin composition having excellent heat resistance, flame retardancy, chemical resistance, impact resistance, mechanical strength, and moldability. It is.

[Prior Art] Polyphenylene sulfide is known as a high-performance engineering plastic having excellent heat resistance, chemical resistance and flame retardancy. However, polyphenylene sulfide has a serious drawback of poor impact strength.
Many attempts to improve such disadvantages have been proposed for blending or alloying with various resins and various elastomers. For example, JP-A-53-69255 and JP-A-1-174562 propose a resin composition comprising polyamide and polyphenylene sulfide, which is excellent in impact resistance and mechanical strength, and disclosed in JP-A-59-167040. JP-A-58-27740 and JP-A-61-161057 disclose a polyphenylene sulfide and styrene-hydrogenated conjugated diene block copolymer, or an acid-modified product thereof, a glycidyl methacrylate-modified product. A resin composition having excellent impact properties has been proposed. Japanese Unexamined Patent Publication (Kokai) No. 1-21359 discloses that polyphenylene sulfide, an amorphous thermoplastic resin having a glass transition point of 120 ° C. or higher, and a glycidyl group-containing thermoplastic polymer have excellent heat resistance, impact resistance, and solvent resistance. Resin compositions have been proposed. Japanese Patent Application Laid-Open No. 63-56559 proposes a polyamide resin composition comprising polyphenylene sulfide, nylon 46 and a modified rubbery polymer and having excellent impact resistance, chemical resistance and heat resistance.

[Problems to be Solved by the Invention] However, among these proposals, JP-A-53-69255, JP-A-1-174562 and the like disclose sufficient impact strength because the compatibility of both resins is still insufficient. In addition, JP-A-58-27740, JP-A-59-167040 and JP-A-61-161057 sacrifice heat resistance, which is an advantage of polyphenylene sulfide. However, a resin composition having a good balance of heat resistance and impact resistance has not yet been obtained. JP-A-63-56559 discloses a resin composition mainly composed of nylon 46, and no improvement has been made with respect to a resin composition mainly composed of polyphenylene sulfide.

Means for Solving the Problems In view of the above situation, the present inventors have conducted intensive studies to solve the problems of the conventional polyphenylene sulfide. It has been found that this problem can be solved by imparting reactivity with a group, and it is possible to provide a highly practical polyphenylene sulfide resin composition which maintains heat resistance and has excellent moldability and impact resistance. They have found the present invention and have come to the present invention.

That is, the present invention relates to (a) carboxyl group-containing polyphenylene sulfide 99
(B) hydrogenated block copolymer having at least one vinyl aromatic compound polymer block and at least one hydrogenated conjugated diene compound polymer block 1 to 50% by weight (c) polyamide (a) And (b) 1 to 63 parts by weight based on a total of 100 parts by weight of the polyphenylene sulfide resin composition.

 Hereinafter, the present invention will be described in detail.

The carboxyl group-containing polyphenylene sulfide used as the component (a) in the present invention is not particularly limited as long as it can be obtained by a known method. For example, a reaction between a halogen-substituted aromatic compound and an alkali sulfide (US Pat. No. 2513188)
JP-B-44-27671, JP-B-45-3368, JP-A-57-90014, etc.). Specifically, (a) alkali metal sulfide in an organic amide solvent is used. When reacting with dihalobenzene, the general formula (1) (X) _m Ar (COOH) _n (1) (where X is a halogen, Ar is an aromatic hydrocarbon group having 6 to 18 carbon atoms, and m is And n is an integer of 1 to 4.
4 is an integer. A) a method of polymerizing in the presence of a carboxyl group-containing aromatic halide represented by the formula (1).

(B) When reacting an alkali metal sulfide with dihalobenzene in an organic amide solvent, a general formula (2) (NO ₂ ) _x Ar (COOH) _y (2) (where Ar is a carbon number of 6 to 18) Aromatic hydrocarbon group, x is an integer of 1 to 4, and y is an integer of 1 to 4)
And a method of polymerizing in the presence of a carboxyl group-containing aromatic nitro compound.

Examples of the carboxyl group-containing aromatic halogen compound represented by the general formula (1) include o-chlorobenzoic acid and m-chlorobenzoic acid.
-Chlorobenzoic acid, p-chlorobenzoic acid, o-bromobenzoic acid, m-bromobenzoic acid, p-bromobenzoic acid, o
-Iodobenzoic acid, m-iodobenzoic acid, p-iodobenzoic acid, 2,3-dichlorobenzoic acid, 2,4-dichlorobenzoic acid, 2,5-dichlorobenzoic acid, 2,6-dichlorobenzoic acid,
3,4-dichlorobenzoic acid, 3,5-dichlorobenzoic acid, 4,5
-Dichlorophthalic acid and mixtures thereof;
P-chlorobenzoic acid, o-chlorobenzoic acid and 2,4-dichlorobenzoic acid are preferably used.

Examples of the carboxyl group-containing aromatic nitro compound represented by the general formula (2) include o-nitrobenzoic acid, m-
Nitrobenzoic acid, p-nitrobenzoic acid, 3,4-dinitrobenzoic acid, 3,5-dinitrobenzoic acid, 3-nitrophthalic acid, 4-nitrophthalic acid and mixtures thereof.

The addition time of these carboxyl group-containing aromatic halides and carboxyl group-containing aromatic nitro compounds may be added together with dihalobenzene, or after the polymerization of alkali metal sulfide and dihalobenzene has started, the system May be added.

As the alkali metal sulfide used in the above production method,
Lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide and mixtures thereof may be used even in the form of a hydrate.
A preferred alkali metal sulfide is sodium sulfide. These alkali metal sulfides can be obtained by reacting an alkali metal hydrosulfide with an alkali metal base or hydrogen sulfide with an alkali metal base, but may be prepared in situ prior to the addition of dihalobenzene to the polymerization system. It is also possible to use one prepared outside the system.

Before the polymerization by adding dihalobenzene, the water in the system is preferably removed by distillation or the like so as to be about 4 mol or less per 1 mol of alkali metal sulfide. Can also be changed.

Examples of the dihalobenzene used in the above production method include p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene and 1-chloro-4. And p-dihalobenzene such as p-dichlorobenzene. If less than 30 mol% with respect to p-dihalobenzene, m
M-dihalobenzene such as dichlorobenzene, o-dihalobenzene such as o-dichlorobenzene and dichloronaphthalene, dibromonaphthalene, dichlorodiphenylsulfone, dichlorobenzophenone, dichlorodiphenylether, dichlorodiphenylsulfide, dichlorodiphenyl And dihalo aromatic compounds such as dibromodiphenyl and dichlorodiphenylsulfoxide. Further, it is also possible to copolymerize a polyhalo aromatic compound containing three or more halogens per molecule, for example, trichlorobenzene, tribromobenzene, triiodobenzene, tetrachlorobenzene, trichloronaphthalene, tetrachloronaphthalene and the like. .

As the polymerization solvent used in the above-mentioned production method, a polar solvent is preferable, and particularly, an aprotic organic amide which is stable to alkali at high temperature is preferable. Some examples of the organic amide used in the above production method include N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoramide, N-methyl-ε-caprolactam, N-ethyl-2-pyrrolidone, Examples include N-methyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, dimethyl sulfoxide, sulfolane, tetramethyl urea and the like, and mixtures thereof.

The polymerization is carried out at 200-300 ° C., preferably at
It is carried out with stirring for 0 hour, preferably 1 to 15 hours.

After the reaction, the amount of the carboxyl group in the carboxyl group-containing polyphenylene sulfide is determined by gas chromatograph of the unreacted carboxyl group-containing aromatic halide or the carboxyl group-containing aromatic nitro compound in the polymerization solvent, and the carboxyl group in the polymer is determined. Can be obtained by back-calculating the amount of

The content of the carboxyl group in the carboxyl group-containing polyphenylene sulfide used in the present invention is usually 0.01 to 20 mol%, preferably 0.05 to 5 mol%, more preferably 0.1 to 5 mol%.
It is in the range of 1 to 5 mol%. Carboxyl group content is 20
If it exceeds mol%, the heat resistance of polyphenylene sulfide is remarkably reduced, which is not preferable. If the amount is less than 0.01 mol%, the effects of the present invention are small and it is difficult to achieve the present invention.

Further, the structure of the carboxyl group-containing polyphenylene sulfide used in the present invention may be any of a straight-chain structure, a branched structure obtained by heat treatment, and a mixture thereof.

Then, the melt viscosity of the carboxyl group-containing polyphenylene sulfide (by a Koka type flow tester (die:
(φ = 0.5mm, L = 2mm) Measured at 300 ° C under a load of 10Kg) For the branched one, before heating, it is 10 to 10,000 poise, preferably 100 to 5,000 poise, and more preferably 400 to 2,000 poise. The melt viscosity after the treatment is 100 to 100,000 poise, preferably 1,000 to 50,000 poise, more preferably 3,000 poise.
Those having a poise of up to 30,000 poise are preferably used.

In addition, the melt viscosity of a linear product is 100 to 100,000 poise,
Preferably 300-50,000 poise, more preferably 500-
30,000 poises can be suitably used.

If the melt viscosity exceeds 100,000 poise, moldability deteriorates, which is not preferable. If the melt viscosity is less than 100 poise, the mechanical strength decreases, which is not preferable.

Recovery of polyphenylene sulfide from the reaction mixture obtained in this manner may be performed by using a conventional technique.For example, after recovering the solvent by distillation, flushing, etc., the polymer is washed with water, hot water, organic acid and And / or a method of recovering the solvent by filtering the reaction mixture and then washing the polymer with water, washing with hot water, and washing and recovering the acid with an organic acid and / or an inorganic acid. No.

The hydrogenated block copolymer having at least one vinyl aromatic compound polymer block and at least one hydrogenated conjugated diene compound polymer block used as the component (b) in the present invention includes vinyl aromatic compound-conjugated A hydrogenated block copolymer which is a hydrogenated product of a diene block copolymer (hereinafter, referred to as an unhydrogenated block copolymer) is exemplified. Here, the unhydrogenated block copolymer is a block copolymer composed of at least one vinyl aromatic compound polymer block A and at least one conjugated diene compound polymer block B. B, AB-
A, BABA, (AB-) _4- Si, ABAB-
It has a structure such as A.

The unhydrogenated block copolymer contains 5 to 50% by weight, preferably 10 to 50% by weight of a vinyl aromatic compound in the whole block copolymer.
-40% by weight.

Further, referring to the block structure, a vinyl aromatic compound polymer block A is a homopolymer block of a vinyl aromatic compound or a vinyl aromatic compound.
It is a copolymer block of a vinyl aromatic compound and a conjugated diene compound containing more than 70% by weight, preferably more than 70% by weight.

The conjugated diene compound polymer block B is a conjugated diene homopolymer block or a copolymer block of a conjugated diene and a vinyl aromatic compound containing more than 50%, preferably 70% by weight or more of a conjugated diene compound.

The distribution of the conjugated diene compound or vinyl aromatic compound in the polymer blocks A and B may be random, tapered (one in which the monomer component increases or decreases along the molecular chain), partially block-like or any of these. Any combination may be used, and further, a vinyl aromatic compound polymer block A and a conjugated diene compound polymer block B
In the case where there are two or more, each of the polymer blocks may have the same structure or different structures.

Examples of the vinyl aromatic compound constituting the block copolymer include styrene, p-methylstyrene, vinyltoluene, 4-t-butylstyrene, 1,1-diphenylethylene and the like. The above compounds can be used. The preferred vinyl aromatic compound is styrene.

As the conjugated diene compound, for example, butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-
1,3-butadiene and the like;
More than one compound can be used. Preferred conjugated diene compounds are butadiene and / or isoprene.

Further, the conjugated diene compound polymer block B can arbitrarily select a microstructure in the block.

The number average molecular weight of the unhydrogenated block copolymer is 5,000 to 1,0
The molecular weight distribution (the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / M) is preferably from 10,000 to 800,000, and more preferably from 30,000 to 500,000.
n)) is preferably 10 or less.

As a method for producing the unhydrogenated block copolymer, any method may be used as long as it has the above-mentioned structure. For example, Japanese Patent Publication No. 40-2379
The vinyl aromatic compound-conjugated diene compound block copolymer can be synthesized in an inert solvent using a lithium catalyst by the method described in Japanese Patent Publication No. 8 (1994) -89.

Further, the hydrogenated block copolymer is the above-mentioned unhydrogenated block copolymer, for example, JP-B-42-8704 and JP-B-43-870.
No. 6636, JP-A-59-133203, JP-A-60-7900
Hydrogenation may be performed by the method described in JP-A No. 5 (1993) -205.

At this time, at least 80% of the aliphatic double bond based on the conjugated diene compound of the unhydrogenated block copolymer is hydrogenated, and the polymer block mainly composed of the conjugated diene compound is morphologically converted into an olefinic compound polymer block. Needs to be converted to

The hydrogenation rate of the aromatic double bond based on the vinyl aromatic compound copolymerized with the vinyl aromatic compound polymer block A and the conjugated diene compound polymer block B is not particularly limited.

The amount of the non-hydrogenated aliphatic double bond contained in the hydrogenated block copolymer can be easily known by an infrared spectrophotometer, a nuclear magnetic resonance apparatus or the like.

Further, in order to have reactivity with the carboxyl group in polyphenylene sulfide and the amino group at the terminal of the polyamide, a carboxyl group and / or a carboxyl group derivative (hereinafter abbreviated as carboxyl group) is added to the hydrogenated block copolymer of the component (b). And / or may contain an epoxy group.

The hydrogenated block copolymer containing a carboxyl group or the like is produced by a known method such as graft-copolymerizing an unsaturated carboxylic acid and / or an unsaturated carboxylic acid derivative onto the above-mentioned hydrogenated block copolymer.

Examples of the unsaturated carboxylic acid and / or unsaturated carboxylic acid derivative used herein include acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, butenedicarboxylic acid, and the above carboxylic acids. And derivatives thereof such as alkyl esters, acid anhydrides and imides, and one or more of them can be used.

Preferred specific examples of the unsaturated carboxylic acid and / or the unsaturated carboxylic acid derivative include maleic anhydride, itaconic anhydride, maleic acid, fumaric acid, maleic imide, itaconic imide, citraconic imide, and the like.
Particularly, maleic anhydride, itaconic anhydride and maleic imide can be preferably used.

In addition, the epoxy group-containing hydrogenated block copolymer is obtained by graft copolymerization of the above-mentioned hydrogenated block copolymer with a glycidyl group-containing unsaturated compound. Although all compounds having a glycidyl group and a glycidyl group can be used, examples of the unsaturated compound containing a glycidyl group include the following general formulas (3) and (4) (In the formula, R represents hydrogen, a lower alkyl group or a lower alkyl group substituted with a glycidyl ester group.) In the formula, R represents hydrogen, a lower alkyl group or a lower alkyl group substituted with a glycidyl ester group. ), Specifically, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, allyl glycidyl ether and the like.

In addition to these glycidyl group-containing unsaturated compounds, for example, diglycidyl maleate, methyl glycidyl maleate, ethyl glycidyl maleate, isopropyl glycidyl maleate, t-butyl glycidyl maleate, diglycidyl fumarate Methyl glycidyl fumarate, isopropyl glycidyl fumarate, diglycidyl itaconate, methyl glycidyl itaconate, isopropyl glycidyl itaconate, diglycidyl 2-methylene glutarate, 2
Glycidyl group-containing unsaturated compounds such as glycidyl esters such as methyl glycidyl methylene glutarate;

One or more of the above-mentioned glycidyl group-containing unsaturated compounds can be used.

Preferred specific examples include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, allyl glycidyl ether, and the like, with glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether being particularly preferred.

The hydrogenated block copolymer containing a carboxyl group or the like and / or an epoxy group can be obtained by adding an unsaturated carboxylic acid and / or an unsaturated carboxylic acid derivative and / or an unsaturated compound containing a glycidyl group to the hydrogenated block copolymer. It is obtained by a graft reaction in the presence or absence of an oxide, and the reaction can be carried out in any of a molten state and a solution state. For example, while performing a graft reaction of the hydrogenated block copolymer using a vent extruder, the remaining unreacted unsaturated carboxylic acid and / or unsaturated carboxylic acid derivative and / or glycidyl group-containing unsaturated compound are forcibly vented. And a method of grafting an unsaturated carboxylic acid and / or an unsaturated carboxylic acid derivative and / or a glycidyl group-containing unsaturated compound in a state in which the hydrogenated block copolymer is dissolved in a solvent or in a suspension state. Can be mentioned.

Organic peroxides that can be provided as needed during this reaction include, for example, dicumyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2. , 5-Di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-
(Butyl peroxy) hexyne-3, n-butyl-4,4-
Bis (t-butylperoxy) valerate, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane and the like can be mentioned, and one or more can be suitably selected from these. Further, in addition to these organic peroxides, as a radical initiator, 2,3-dimethyl-2,3-diphenylbutane, 2,3-diethyl-2,3-diphenylbutane, 2,3
-Dimethyl-2,3-di (p-methylphenyl) butane,
The graft reaction may be performed using a compound such as 2,3-dimethyl-2,3-di (bromophenyl) butane.

The above-mentioned organic peroxides and radical initiators that can be used in the graft reaction can be suitably used usually in the range of 0.01 to 5 parts by weight per 100 parts by weight of the hydrogenated block copolymer.

Further, the hydrogenated block copolymer containing a carboxyl group or the like and / or an epoxy group can be obtained by completely removing unreacted unsaturated carboxylic acids and / or unsaturated carboxylic acid derivatives and / or glycidyl group-containing unsaturated compounds. Or it may be left as it is.

The amount of the unsaturated carboxylic acid and / or the unsaturated carboxylic acid derivative and / or the glycidyl group-containing unsaturated compound grafted in the block copolymer can be easily known by a known method. You can know by performing instrumental analysis such as photometer and NMR, and titration analysis. Further, the remaining amount of unreacted unsaturated carboxylic acid and / or unsaturated carboxylic acid derivative and / or glycidyl group-containing unsaturated compound can be easily measured by, for example, gas chromatography.

The content of such a grafted unsaturated carboxylic acid and / or unsaturated carboxylic acid derivative and / or glycidyl group-containing unsaturated compound is usually 0.01 to 20% by weight, preferably 0.05 to 10% by weight, more preferably 0.1 to 10% by weight. It is in the range of 5.0% by weight.

The polyamide used as the component (c) in the present invention is ε
Polyamides obtained by ring-opening polymerization of lactams such as caprolactam, ω-dodecalactam, polyamides derived from amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, ethylenediamine, tetramethylenediamine , Hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 1,3- and 1,4-bis (aminomethyl) cyclohexane, bis ( Aliphatics such as 4,4'-aminocyclohexyl) methane, meta and paraxylylenediamine,
Alicyclic and aromatic diamines and adipic acid, sebacic acid, dodecane diacid, 1,3- and 1,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, dimer acid, and acid derivatives of these acid chlorides, etc. And polyamides, copolymerized polyamides, and mixed polyamides derived from the above-mentioned aliphatic, alicyclic, aromatic dicarboxylic acids or acid derivatives such as acid halides.

Of these, polycaproamide (nylon 6), polyundecaneamide (nylon 11), polydodecaneamide (nylon 12), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46) And copolymerized polyamides containing these as main components are useful, preferably nylon 66, nylon
46, more preferably nylon 46 is useful.

As the polymerization method of the polyamide, generally known melt polymerization, solid phase polymerization, solution polymerization and a method combining these can be adopted. The degree of polymerization of the polyamide is not particularly limited, and any polyamide having a relative viscosity (1 g of the polymer dissolved in 100 ml of 98% concentrated sulfuric acid and measured at 25 ° C.) in the range of 2.0 to 5.0 can be arbitrarily selected according to the purpose. .

The present invention is a resin composition comprising the above specific components, wherein component (a) is 99 to 50% by weight, preferably 90 to 50% by weight, and component (b) is 1 to 50% by weight, preferably 10 to 50% by weight. weight%
(C) components 1 to 6 with respect to 100 parts by weight of the resin composition comprising
3 parts by weight, preferably 5 to 60 parts by weight, more preferably 5 parts by weight
Consists of ~ 55 parts by weight.

If the content of the component (a) is less than 50% by weight, a resin composition excellent in both processability and heat resistance cannot be expected, which is not preferable. Also,
If the amount of the component (c) is less than 1 part by weight based on 100 parts by weight of the total of the components (a) and (b), the heat resistance is lowered.

As described above, the polyphenylene sulfide resin composition of the present invention is composed of each component of (a), (b) and (c), but a thermoplastic elastomer such as ethylene-ethylene may be used as long as the object of the present invention is not impaired. Propylene-ethylidene norbornene copolymer (EPDM rubber), ethylene-propylene copolymer (EP rubber), and ethylene-butene 1 copolymer, styrene-butadiene block copolymer,
It is also possible to add a styrene-based block copolymer elastomer such as a styrene-isoprene block copolymer, an amide-based elastomer, an ester-based elastomer, a urethane-based elastomer, or the like, or a rubbery polymer such as a conjugated diene rubber or an acrylic rubber. It is. Furthermore, polyesters such as polyethylene, polystyrene, polybutene, poly-methylstyrene, polyvinyl acetate, polyvinyl chloride, polyacrylate, polymethacrylate, polyacrylonitrile, polyethylene terephthalate, polybutylene terephthalate, and polyarylate,
Polyurethane, polyacetal, polycarbonate, polyphenylene ether, polysulfone, polyether sulfone, polyallyl sulfone, polyphenylene sulfide sulfone, polyether ketone, polyether ether ketone, polyphenylene sulfide ketone, polyimide, polyamide imide, silicone resin, phenoxy resin, fluorine It is also possible to add a thermoplastic resin or a thermosetting resin such as a homopolymer such as a resin or an epoxy resin, a random polymer or a block, a graft copolymer and a mixture thereof.

In addition, as necessary, reinforcing fibers such as glass fibers, carbon fibers, ceramic fibers such as alumina fibers, aramid fibers, wholly aromatic polyester fibers, metal fibers, potassium titanate whiskers and silicon carbide whiskers, calcium carbonate, mica, etc. , Talc, silica, barium sulfate, calcium sulfate, kaolin, clay, pyroferrite, bentonite, sericite, zeolite, nepheline sinite, attapulgite, wollastonite, ferrite, calcium silicate, magnesium carbonate, dolomite, antimony trioxide, Zinc oxide, titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite, gypsum,
Inorganic fillers such as glass beads, glass powder, glass balloons, quartz and quartz glass, and organic and inorganic pigments can also be blended. As glass fiber, for example, fiber length
1.5-12mm, chopped strand with fiber diameter 3-20μ,
Milled fiber having a fiber length of 30 to 500 µm and a fiber diameter of 3 to 20 µm, glass flakes and glass powder of 325 mesh or less can be mentioned.

In addition, plasticizers and release agents such as aromatic hydroxy derivatives, silane-based, titanate-based coupling agents, lubricants,
Heat stabilizer, weather resistance stabilizer, crystal nucleating agent, foaming agent, rust inhibitor, ion trapping agent, flame retardant, flame retardant auxiliary, antioxidant, ultraviolet absorber, hindered amine light stabilizer, coloring agent For the purpose of controlling the degree of crosslinking of polyphenylene sulfide, a metal salt of thiophosphinic acid or a crosslinking inhibitor such as dialkyltin dicarboxylate or aminotriazole may be added as necessary.

The polyphenylene sulfide resin composition of the present invention can be produced by various methods using the above-mentioned components. For example, a heat-melt kneading method using a single-screw extruder, a twin-screw extruder, a kneader, a Brabender or the like can be mentioned, and among them, a melt-kneading method using a twin-screw extruder is most preferable.
The maximum kneading temperature is not particularly limited, but is usually
It can be arbitrarily selected from 280 to 400 ° C.

The resin composition of the present invention obtained as described above can be obtained by various known methods, such as a printed wiring board, an electronic component sealing material, various connector components, a heat-resistant paint, a thin molded product, a fiber, a sheet, and a film. , Tubes, etc. can be molded into molded products of various shapes, and processing methods such as injection molding, extrusion molding, foam molding, etc. are possible. Specific application fields include automobiles, electricity, electronics, machinery, etc. In the field of industrial materials, it can be widely used as a molding material having excellent heat resistance, flame retardancy, moldability and impact resistance.

For sealing electronic components, for example, electronic components such as
ICs, transistors, diodes, coils, capacitors, resistors, varistors, connectors, various sensors,
Transformers, switches, etc. or parts that are hybridized of these are mechanically protected with a resin composition, maintaining electrical insulation,
It is provided for sealing for the purpose of preventing the property change due to the external atmosphere, etc.When the polyphenylene sulfide resin composition of the present invention is used for sealing these electronic components, the melt viscosity at 320 ° C. is 1,500 poise or less, Preferably, 1,200 poise or less can be suitably used.

[Effect of the Invention] The polyphenylene sulfide resin composition of the present invention provides a resin composition having excellent heat resistance, flame retardancy, molding processability, and impact resistance, and can be used as various large-sized molding materials. Also, it can be used as a material having toughness even in applications of electronic component sealing materials requiring high fluidity.

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

The melt viscosity of the polyphenylene sulfide produced in the following Reference Examples was measured at 300 ° C. under a 10 kg load using a Koka flow tester (die; φ = 0.5 mm, L = 2 mm).

In addition, analysis of the carboxyl group introduced into the polyphenylene sulfide was carried out by quantifying unreacted carboxyl group-containing aromatic halides and carboxyl group-containing aromatic nitro compounds in the polymerization solvent after the reaction was completed by gas chromatography, and analyzing the carboxyl groups in the polymer. The amount was determined by back calculation.

Reference Example 1 (Polyphenylene sulfide) Internal volume equipped with stirrer, dehydration tower, and jacket
N-methylpyrrolidone (NMP) 11 in a 530 liter reactor
0 l and sodium sulfide (purity: Na ₂ S60.2 wt%) 6
1.1 kg was charged, and the mixture was heated with a jacket under agitation and passed through a dehydration column until the internal temperature reached about 200 ° C. Next, 68.7 kg of p-dichlorobenzene and 48 liters of N-methylpyrrolidone were added, the temperature was raised to 225 ° C. over 2 hours, reacted at 225 ° C. for 2 hours, and then raised to 250 ° C. over 30 minutes. Then, the reaction was further performed at 250 ° C. for 3 hours.

After completion of the reaction, the reaction mixture was transferred to a solvent recovery device equipped with a stirrer, jacket and a reduced pressure line. At this time, N
30 liters of methylpyrrolidone were added. Subsequently, the mixture was heated under reduced pressure to distill off 210 liters of a distillate mainly composed of N-methylpyrrolidone.

Subsequently, 200 liters of water was added to form a water slurry, which was heated and stirred at 80 ° C. for 15 minutes, and then centrifuged to collect a polymer.

Further, the polymer was returned to the solvent recovery device, 200 liters of water was added, and the mixture was heated and stirred at 100 ° C. for 30 minutes. After cooling, the polymer powder was recovered by a centrifuge.

 This operation was repeated twice.

The obtained polymer was transferred to a jacketed ribbon blender and dried. The polyphenylene sulfide thus produced was introduced into a ribbon blender having an internal volume of 150 liters, and the temperature was raised to 250 ° C. in the air with stirring to cure for 2 hours. The melt viscosity at the end of curing was 2000 poise.
The polyphenylene sulfide thus obtained is converted to PP
S.

Reference Example 2 (Carboxyl-containing polyphenylene sulfide) Internal volume equipped with a stirrer, dehydration tower, and jacket
N-methylpyrrolidone (NMP) 11 in a 530 liter reactor
0 l and sodium sulfide (purity: Na ₂ S60.2 wt%) 6
1.1 kg was charged, and the mixture was heated with a jacket under agitation and passed through a dehydration column until the internal temperature reached about 200 ° C. Next, 68.0 kg of p-dichlorobenzene, 0.684 kg of 2,4-dichlorobenzoic acid and 48 l of N-methylpyrrolidone were added, the temperature was raised to 225 ° C. over 2 hours, and the reaction was carried out at 225 ° C. for 2 hours. Thereafter, the temperature was raised to 250 ° C. over 30 minutes, and further reacted at 250 ° C. for 3 hours.

After the completion of the reaction, the mixture was cooled, and the polymer obtained by filtering the reaction mixture was transferred to a collector equipped with a stirrer and a jacket.

Subsequently, 200 liters of water was added to form a water slurry, which was heated and stirred at 80 ° C. for 30 minutes, cooled, and then filtered to collect a polymer.

Further, the polymer is returned to the recovery device, and a 1% NH ₄ Cl aqueous solution 200
One liter was added, and the mixture was heated and stirred at 175 ° C. for 60 minutes. After cooling, the mixture was filtered to recover a polymer powder.

Subsequently, 200 liters of water was added to form a water slurry, which was heated and stirred at 80 ° C. for 30 minutes, cooled, and then filtered to collect a polymer.

The obtained polymer was transferred to a jacketed ribbon blender and dried. The polyphenylene sulfide thus produced was introduced into a ribbon blender having an internal volume of 150 liters, and the temperature was raised to 250 ° C. in the air with stirring to cure for 10 hours. The polyphenylene sulfide thus obtained is designated as PPS I.

The melt viscosity of the obtained polymer is 4,000 poise,
The carboxyl group content was 0.98 mol%.

Reference Example 3 (Carboxyl-containing polyphenylene sulfide) A polyphenylene sulfide obtained in the same manner as in Reference Example 2 except that 0.684 kg of p-chlorobenzoic acid was used instead of 0.684 kg of 2,4-dichlorobenzoic acid in Reference Example 2. Is PPS II.

The melt viscosity of the obtained polymer is 3,500 poise,
The carboxyl group content was 0.42 mol.

Reference Example 4 (Hydrogenated block copolymer) As a hydrogenated block copolymer, a styrene-hydrogenated butadiene-styrene ternary block copolymer (Toughtec H1041 manufactured by Asahi Kasei Corporation) was used. This polymer is referred to as SEBS.

Reference Example 5 (Carboxyl group-containing hydrogenated block copolymer) As a carboxyl group-containing block copolymer, a maleic acid-modified styrene-hydrogenated butadiene-styrene ternary block copolymer (manufactured by Asahi Kasei Corporation, Tuftec M1913) was used. This polymer is referred to as SEBS-AN.

Reference Example 6 (Epoxy Group-Containing Hydrogenated Block Copolymer) 5 parts by weight per 100 parts by weight of styrene-hydrogenated butadiene-styrene ternary block copolymer (Tuftec H1041 manufactured by Asahi Kasei Corporation) which is a hydrogenated block copolymer Of glycidyl methacrylate and 0.3 parts by weight of Pehexa 25B (manufactured by NOF CORPORATION) and uniformly mixed by dry blending.
The denaturation reaction was carried out with a 40 mmφ vented twin-screw extruder set to 0 ° C. while performing forced bend (decompression degree: 750 mmHg gauge pressure) using a vacuum pump. The obtained epoxy group-containing hydrogenated block copolymer was subjected to a reflux treatment for 20 hours with a Soxhlet extractor using acetone, and titration analysis of the epoxy value revealed that 1.8% by weight of glycidyl methacrylate was grafted. . The polymer obtained here is
SEBS-GMA.

Reference Example 7 (Nylon 66) As nylon 66, Amilan CM3001-N (manufactured by Toray Industries, Inc.) was used. This polymer is referred to as PA66.

Reference Example 8 (Nylon 46) As nylon 46, Unitika nylon 46 resin F5000 (manufactured by Unitika) was used. This polymer is designated as PA46.

Examples 1 to 3, Comparative Examples 1 to 5 Polyphenylene sulfide obtained in Reference Examples 1 to 3, polyamide (nylon) obtained in Reference Examples 4 to 5, Reference Examples 6 to 8
The hydrogenated block copolymer obtained in the above was dry-blended with the composition shown in Table 1, melt-kneaded using a co-rotating twin-screw extruder set at 290 ° C to 360 ° C under conditions of a screw rotation speed of 200 rpm, and extruded. The resulting strand was pelletized.

The pellets obtained here are supplied to a screw in-line type injection molding machine set at 290 ° C. to 360 ° C., and a mold temperature of 135 ° C.
A test piece for a tensile test and a test piece for an Izod impact test were injection molded under the following conditions. Using these test pieces, a tensile test (ASTM D-638) and a high load (18.
56kg / cm ²⁾ Thermal deformation temperature (ASTM D-648), Izod (notched) impact strength (ASTM D-256: 23 ℃ ) measured shows these results in Table 1.

According to the results, the two-component resin composition of Comparative Example 4 has improved impact strength to some extent, but sacrifices heat resistance. In addition, the resin composition comprising two components of Comparative Example 5 has insufficient impact strength due to poor compatibility. Also, in the resin compositions composed of the three components of Comparative Examples 1, 2, and 3, only insufficient impact strength was obtained due to poor compatibility between polyphenylene sulfide and polyamide. On the other hand, the resin compositions of the examples give a sufficient impact strength without impairing heat resistance by introducing a carboxyl group into polyphenylene sulfide to have reactivity with an amino group at the terminal of polyamide. It is considered that the impact strength is surprisingly improved due to the synergistic effect of the interaction of the three components by introducing a carboxyl group into polyphenylene sulfide.

Claims (1)

(57) [Claims] 1. A hydrogenated block having (a) carboxyl group-containing polyphenylene sulfide 99 to 50% by weight, (b) at least one vinyl aromatic compound polymer block and at least one hydrogenated conjugated diene compound polymer block. (1) Polyphenylene sulfide resin composition characterized by comprising 1 to 63 parts by weight based on 100 parts by weight of a total of (c) polyamide (a) + (b).