JP2003292780A - Polyphenylene sulfide resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a polyphenylene sulfide resin composition for a secondary battery cell having excellent toughness (impact strength) and weld strength as a chassis material or a casing material of household appliances or OA equipment or a structural material for the secondary battery cell (a container, a sheet or a film). <P>SOLUTION: This polyphenylene sulfide resin composition comprises a polyphenylene sulfide resin and a polyphenylene ether. The polyphenylene sulfide resin to be used has a specific content of oligomers and a specified content of functional groups. The polyphenylene ether to be used is obtained by a specific method and contains &ge;0.1 epoxy group on the average per molecular chain. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to toughness (impact strength),
The present invention relates to a polyphenylene sulfide resin composition having excellent weld strength, heat-resistant creep resistance, water vapor permeation resistance and oil resistance, chemical resistance, and heat resistance, and further relates to chassis materials, housing materials for home appliances and OA equipment, and Furthermore, lithium metal batteries, lithium ion batteries (hereinafter abbreviated as lithium batteries), polymer ion batteries, nickel-
The present invention relates to a polyphenylene sulfide resin composition for a secondary battery battery case, which is preferably used as a battery container (container) of a secondary battery such as a hydrogen battery, a lead storage battery, or an alkaline storage battery, or a sheet or film material constituting the secondary battery. .

[0002]

2. Description of the Related Art Conventionally, unreinforced polyphenylene sulfide has good flowability due to its crystallinity. It is used in the electronic field because of its excellent heat resistance and water resistance, but it is difficult to use as a molding material for various molded products (especially large-sized molded products) because it has a defect of poor toughness (impact strength). Therefore, in order to solve these drawbacks of polyphenylene sulfide, many attempts have been proposed to blend or alloy with various resins and various thermoplastic elastomers. For example, Japanese Patent Publication No. 56-34032 proposes a resin composition composed of polyphenylene oxides and polyphenylene sulfides which is excellent in moldability and flame retardancy, and Japanese Patent Application Laid-Open No. 59-164360 discloses polyphenylene sulfide. A resin composition prepared by mixing an epoxy resin into a mixture of a resin and a polyphenylene oxide resin has been proposed.

Further, Japanese Patent Laid-Open No. 58-2 proposed by the present applicant.
7740 discloses a modified block copolymer comprising a polyphenylene sulfide or other engineering resin and a hydrogenated block copolymer modified with a derivative of an α, β-unsaturated carboxylic acid, which is excellent in impact resistance and interfacial peel resistance. Polymer compositions have been proposed and, likewise, JP-A-58-403.
Japanese Patent Publication No. 50 discloses a thermoplastic graft excellent in impact resistance, which comprises a hydrogenated block copolymer modified with a derivative of α, β-unsaturated carboxylic acid and a polyphenylene sulfide or other engineering resin, and an epoxy group-containing polymer. There is a copolymer composition.

Japanese Patent Application Laid-Open No. 58-154757 discloses polyarylene sulfide and α-olefin / α,
A polyarylene sulfide resin composition composed of a glycidyl ester copolymer of β-unsaturated acid and having excellent impact resistance and molding processability has been proposed, and is disclosed in JP-A-59-2079.
JP-A No. 21-21980 proposes a composition having excellent impact resistance, which is composed of a polyolefin obtained by graft-copolymerizing polyphenylene sulfide and an unsaturated carboxylic acid or its anhydride or its derivative, and an epoxy resin, and is further disclosed in JP-A-62-162. Japanese Patent No. 153343, Japanese Patent Laid-Open No. 62-153344.
JP-A No. 62-153345 and JP-A No. 62-153345 propose a polyphenylene sulfide resin composition excellent in impact resistance, which comprises a specific polyphenylene sulfide and a glycidyl ester copolymer of α-olefin / α, β-unsaturated acid. Has been done.

Further, JP-A-62-169854, JP-A-62-172056, and JP-A-62-162.
Japanese Patent No. 172057 also proposes a polyphenylene sulfide resin composition having excellent impact resistance, which is composed of a polyolefin obtained by graft-copolymerizing a specific polyphenylene sulfide and an unsaturated carboxylic acid or an anhydride or derivative thereof. On the other hand, regarding a resin composition containing polyphenylene sulfide and polyphenylene ether, for the purpose of improving miscibility, JP-A-01-266160 is used.
JP-A No. 02-75656 and JP-A No. 02-75656 propose a method of using a copolymer of styrene and an ethylenically unsaturated monomer having an oxazonyl group for improving the miscibility of acid-modified polyphenylene ether and modified polyphenylene sulfide. Kaihei 01-213359, Japanese Patent Laid-Open No. Hei 0
Nos. 1-213361, 02-86652, and 05-339500 disclose copolymers of styrene and an ethylenically unsaturated monomer having a glycidyl group for improving the miscibility of polyphenylene ether and polyphenylene sulfide. A method using is proposed.

Further, Japanese Patent Laid-Open No. 03-20356 proposes a method of using a copolymer of styrene and an ethylenically unsaturated monomer having an oxazonyl group for improving the miscibility of polyphenylene sulfide and polyphenylene ether, and further JP-A-02-155951, JP-A-04-227636, JP-A-05-2
79568, Japanese Patent Laid-Open No. 06-172489.
Further, JP-A 06-271759 discloses a resin composition comprising an epoxy group-containing polyphenylene ether and polyphenylene sulfide.

However, these compositions disclosed in the prior art have not been sufficiently designed in terms of dispersibility, toughness and weld strength of a molded product of a resin composition comprising polyphenylene sulfide and polyphenylene ether. The current situation. Furthermore, Japanese Patent Laid-Open No. 09-161
In Japanese Patent No. 737, a composition using a copolymer of styrene and an ethylenically unsaturated monomer having an oxazonyl group for improving miscibility of polyphenylene sulfide and polyphenylene ether can be used as a battery case of a sealed alkaline secondary battery. The content of the purport is disclosed. However, even in the case of the composition disclosed herein, a sufficient material design has not yet been made from the viewpoints of dispersibility of the dispersed phase, imparting toughness and weld strength of the molded product.

On the other hand, from the viewpoint of using materials,
Although OA equipment has been changed from metal to thermoplastic resin as its chassis material and housing material, these performances still remain as resin materials from the viewpoint of heat resistance, rigidity, warpage of molded products, and dimensional stability. At present, there are applications that are inadequate. In addition, the applications of driving power supplies for mobile devices, data backup power supplies for computers, solar cells for effective use of solar energy, and various secondary batteries are being expanded from the viewpoint of environmental protection. In particular, it is well known that a secondary battery is often used to supply the required power of an internal combustion engine of an automobile, and further, a secondary battery is directly used as a driving power source instead of the internal combustion engine, so-called, The development of electric vehicles is actively carried out from the viewpoint of protecting the global environment.

As described above, with the development of industrial technology, the demand for secondary batteries tends to increase more and more, and the demand for smaller and lighter secondary batteries and larger electric capacity is increasing. In such a secondary battery, a battery case (container) for storing an electrolytic solution and an electrode, a battery sheet or a battery film is indispensable, and the main characteristics required for the resin material for the battery are: Resistance to liquids Long-term stability can be mentioned. As the resistance to the electrolytic solution, for example, an alkaline storage battery is resistant to an alkaline aqueous solution, and a lithium ion battery is an organic electrolytic solution [eg, lithium hexafluorophosphate (LiPF ₆ ) is a solute,
Propylene carbonate / 1,2-dimethoxyethane is an organic solvent composed of an organic solvent as a main component] resistance (when used for automobiles, further oil resistance is required) Tolerance is required. In addition, it is necessary to properly maintain the properties of the electrolytic solution for a long period of time.For example, in alkaline storage batteries, the performance deteriorates when water in the alkaline aqueous solution in the battery case permeates out of the battery container, and in lithium ion batteries, If water enters the battery case from the outside, the lithium salt in the organic solution (for example, lithium hexafluorophosphate (LiPF ₆ ) or lithium borofluoride) is decomposed and the performance is deteriorated.

Further, it is required to have a performance capable of withstanding heat generation and increase in internal pressure due to chemical changes during charging or discharging over a long period of time. Above all, the sealed secondary battery is required to be as small and lightweight as possible, have a large electric capacity, and have a long battery life. Therefore, the battery case of the sealed secondary battery is
A resin that is required to have toughness (impact strength, elongation) when thin, and has excellent heat resistance, heat creep resistance, and heat rigidity that can withstand harsh conditions such as heat generation during charging or discharging and increase in internal pressure. Materials are required, and similar performance is desired in the field of battery case sheets.

Polypropylene resin and ABS resin are often used as the resin material for the battery case of the conventional secondary battery.
Polypropylene resin excels in fluidity, hot water permeation resistance (water vapor permeation resistance), and gas permeation resistance during molding, but it has a large molding shrinkage ratio and rigidity, especially at high temperatures, in injection molding of products with a thin rib structure. It had the drawbacks such as poor rigidity and heat-resistant creep resistance. On the other hand, ABS resin does not have sufficient resistance to gasoline and oil (for example, brake oil, rust preventive agent) in automobile applications, and further has high hot water permeability and high gas permeability, so that the property of the electrolyte after long use is It has a drawback that it cannot be maintained and the long term electric capacity, which is the life of the secondary battery, cannot be achieved.

From these viewpoints, the composition obtained by the prior art of the above-mentioned polyphenylene sulfide resin composition satisfies the above-mentioned required performance as a material for a secondary battery battery case (container, sheet, film), but is dispersed. At present, a sufficient material design has not been made from the viewpoints of phase dispersibility, imparting toughness, and weld strength of a molded product.

[0013]

DISCLOSURE OF THE INVENTION The present invention provides a polyphenylene sulfide resin having improved mixing and dispersibility of a resin composition composed of polyphenylene sulfide and polyphenylene ether, elimination of delamination, and excellent toughness (impact strength) and weld strength. In providing the composition, home appliances / OA
Toughness (impact strength), weld strength, heat resistance to maintain the initial electrolyte performance for a long period of time as a chassis material, housing material, and battery case material for secondary batteries (container or sheet, film) An object of the present invention is to provide a polyphenylene sulfide resin composition for a secondary battery battery case, which is excellent in creep resistance, water vapor permeation resistance, heat resistance, acid resistance, alkali resistance, and oil resistance.

[0014]

In view of such a situation, the present inventors have proposed a resin composition comprising a polyphenylene sulfide resin and a polyphenylene ether, in which the miscibility, toughness (impact strength) and weld strength of these components are combined. Regarding, as a result of repeated intensive studies, a resin composition obtained by melt-mixing a polyphenylene sulfide having a specified functional group amount and an oligomer amount and a functionalized polyphenylene ether obtained by a specific method has significantly improved toughness. And a polyphenylene sulfide resin composition having excellent weld strength, which can be used as a chassis material and a housing material for home electric appliances and OA equipment, and can be used as a secondary battery battery case (container or sheet, film) material. They have found the present invention and reached the present invention.

That is, the present invention is: (A) Polyphenylene sulfide resin 1 having an extraction amount with methylene chloride of 0.7% by weight or less and a -SX group (S is a sulfur atom, X is an alkali metal or hydrogen atom) of 15 μmol / g or more. 99 parts by weight,
(B) A polyfunctional epoxy compound having two or more oxirane rings in one molecule and a polyphenylene ether having a melting point of 140 to 260 ° C. are heated to a temperature (20 to 230) below the melting point.
C.), and an average of 0.1 or more epoxy group-containing polyphenylene ethers 99-1 parts by weight per one molecular chain obtained by reacting in a non-solvent, a polyphenylene sulfide resin composition,

2. 100 in total of component (a) and component (b)
Per part by weight, (c) a block copolymer composed of at least one polymer block A containing a vinyl aromatic compound as a main component and at least one polymer block B containing a conjugated diene compound as a main component, and / or the block. A polyphenylene sulfide resin composition comprising 1 to 50 parts by weight of a hydrogenated block copolymer obtained by hydrogenating the copolymer,

3. Total of (a) component and (b) component 1
3. Polyphenylene sulfide resin composition, characterized in that it comprises 1 to 200 parts by weight of (d) an inorganic filler per 00 parts by weight. Total 1 of component (a), component (b) and component (c)
The present invention relates to a polyphenylene sulfide resin composition comprising (d) 1 to 200 parts by weight of inorganic filler per 100 parts by weight.

The polyphenylene sulfide resin (hereinafter abbreviated as PPS) which is the component (a) of the resin composition of the present invention is
The amount of extraction with methylene chloride is 0.7% by weight or less, preferably 0.6% by weight or less, and particularly preferably 0.5% by weight or less. The above extraction amount range means that there are few low oligomers having a relatively low molecular weight (about 10 to 30 mer) in PPS. When the extracted amount exceeds the upper limit value, the miscibility of the polyphenylene sulfide of the obtained resin composition with the epoxy group-containing polyphenylene ether of the component (b) is poor, and improvement of the weld strength of the obtained resin composition is desired. In addition, the impact resistance as toughness is significantly deteriorated, which is not preferable.

Here, the amount of extraction with methylene chloride can be measured by the following method. That is, P
PS powder (5 g) is added to methylene chloride (80 ml), subjected to Soxhlet extraction for 6 hours, cooled to room temperature, and the extracted methylene chloride solution is transferred to a weighing bottle. Furthermore, the container used for the above extraction was mixed with a total of 60 ml of methylene chloride to obtain 3
The washing solution is collected in batches and the washing solution is collected in the weighing bottle. Next, by heating to about 80 ° C. to evaporate and remove methylene chloride in the weighing bottle, the residue is weighed, and the amount of the oligomer present in the PPS can be determined from the amount of the residue.

Further, the PPS of the component (a) has a --SX group (S is a sulfur atom, X is an alkali metal or hydrogen atom) of 15 μmol / g or more, particularly preferably 20.
˜60 μmol / g. When the amount of the group is less than the above lower limit, the polyphenylene sulfide of the resulting resin composition and (b)
The miscibility with the epoxy group-containing polyphenylene ether as a component is inferior, the improvement of the weld strength of the obtained resin composition cannot be expected, and the impact resistance as toughness is significantly deteriorated, which is not preferable.

The -SX group can be quantified by the following method. That is, 1 PPS powder in advance
After drying at 20 ° C. for 4 hours, 20 g of dried PPS powder was added to N
In addition to 150 g of methyl-2-pyrrolidone, vigorously stir and mix for 30 minutes at room temperature so as to eliminate powder agglomerates, and make a slurry. After filtering this slurry, washing is repeated 7 times with 1 liter of warm water at about 80 ° C. each time.
The filter cake obtained here is slurried again in 200 g of pure water, and then 1N hydrochloric acid is added to adjust the pH of the slurry to 4.5. Then, the mixture is stirred at 25 ° C. for 30 minutes, filtered, and washed 6 times with 1 liter of warm water at about 80 ° C. each time. The obtained filter cake was slurried again in 200 g of pure water, then titrated with 1N sodium hydroxide, and PPS was calculated from the amount of sodium hydroxide consumed.
The amount of -SX groups present in it can be known.

The above-mentioned method for producing PPS is usually carried out by polymerizing a halogen-substituted aromatic compound such as p-dichlorobenzene in the presence of sulfur and sodium carbonate, sodium sulfide or sodium hydrogen sulfide and water in a polar solvent. Examples thereof include a method of polymerizing sodium oxide or hydrogen sulfide with sodium hydroxide or sodium aminoalkanoate, and self-condensation of p-chlorothiophenol. Among them, amide solvents such as N-methylpyrrolidone and dimethylacetamide, A suitable method is to react sodium sulfide with p-dichlorobenzene in a sulfone solvent such as sulfolane.

There is no particular limitation on the manufacturing method as long as it can be obtained by a known method. For example, US Pat. No. 2,513,188, JP-B-44-276.
71, Japanese Patent Publication No. 45-3368, Japanese Patent Publication No. 52
-12240, Japanese Patent Laid-Open No. 61-225217, US Pat. No. 3,274,165, British Patent No. 11
No. 60660, Japanese Patent Publication No. 46-27255, Belgian Patent No. 29437, Japanese Patent Laid-Open No. 5-2221.
The method described in Japanese Patent Publication No. 96, etc. and the prior art methods exemplified in these patents can be used.

Here, the amount of methylene chloride extracted was 0.
Specific examples of the method for producing PPS satisfying 7% by weight or less and -SX group of 15 μmol / g or more include (0041) to (004) of JP-A-8-253587.
4) The manufacturing method of Examples 1 and 2 described in the paragraph and (0046) to (0) of JP-A No. 11-106656.
048), there are Synthesis Examples 1 and 2 and the like.
The PPS used in the present invention has a melt viscosity at 320 ° C. (using a flow tester, 300 ° C., load 20 Kgf / c.
Value held for 6 minutes at m ² and L / D = 10/1. ) Is 1
It may be arbitrarily selected from 10,000 poises, and the structure of PPS may be linear or branched as long as it exhibits the above-mentioned characteristics, and linear is more preferable.

Next, the resin composition of the present invention is used (b).
A polyfunctional epoxy compound containing two or more oxirane rings in one molecule of the component and a polyphenylene ether having a melting point of 140 to 260 ° C. are heated to a temperature below the melting point (20 to 230).
C.) and an average of 0.1 or more epoxy group-containing polyphenylene ethers per one molecular chain obtained by the reaction in a non-solvent, the polyphenylene ether resin (hereinafter simply referred to as PPE) before the reaction is bonded. Unit (Equation 1):

[0026]

[Chemical 1]

(Where R1, R2, R3, and R4
Are hydrogen, halogen, a primary or secondary lower alkyl group having 1 to 7 carbon atoms, a phenyl group, a haloalkyl group, an aminoalkyl group, a hydrocarbonoxy group, or at least two carbon atoms each being a halogen atom. Selected from the group consisting of halohydrocarbonoxy groups separating an oxygen atom, which may be the same or different.
The reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.) is preferably in the range of 0.15 to 2.0, and more preferably in the range of 0.20 to 1.0. It is a homopolymer and / or a copolymer.

Specific examples of this PPE include, for example, poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly ( 2-methyl-6-phenyl-
1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), and the like, and further 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethyl). Also included are polyphenylene ether copolymers such as copolymers with phenol and 2-methyl-6-butylphenol).

Among them, poly (2,6-dimethyl-1,4-)
Phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable, and poly (2,6-dimethyl-1,4-phenylene ether) is more preferable. The method for producing such PPE is not particularly limited as long as it can be obtained by a known method, and for example, a complex of cuprous salt and amine described in US Pat. No. 3,306,874 is used as a catalyst,
For example, it can be easily produced by oxidative polymerization of 2,6-xylenol, and in addition, it can be produced by US Pat. No. 3,30687.
No. 5, No. 3257357 and No. 3257358.
No. 5, Japanese Patent Publication No. 52-18880, Japanese Patent Laid-Open No. 50-51197.
And it can be easily manufactured by the method described in JP-A-63-152628 and the like.

The PPE is usually a powder, and from the viewpoint of handling, it is 10 μm to 1000 μm, and more preferably 30 to 700 μm. The melting point of these powder PPE is 140 to 260 ° C., and the temperature-heat obtained when the PPE is first heated at 20 ° C./min using a differential scanning calorimeter (DSC). It is defined as the peak top temperature of the peak observed in the flow graph. When there are plural peak top temperatures, the highest temperature among them is defined as the melting point of PPE.

Next, the polyfunctional epoxy compound containing two or more oxirane rings in one molecule to be reacted with the powder PPE is a compound selected from the group of compounds collectively referred to as an epoxy resin, and particularly Preferably:

[0032]

[Chemical 2]

(Wherein X1 and X2 are aromatic hydrocarbons,
A is an aliphatic hydrocarbon, n is a bisphenol A type resin represented by 0 or an integer of 1 or more, or:

[0034]

[Chemical 3]

(Wherein R is an aliphatic or aromatic hydrocarbon, n is 0 or an integer of 1 or more) and is a polyglycidyl ether compound containing no unsaturated group. The state of the epoxy compound is not particularly limited, but it is preferably gas or liquid under the temperature and pressure conditions for reacting with the polyphenylene ether described above.

The reaction between these powder PPE and the polyfunctional epoxy compound containing two or more oxirane rings in one molecule is usually carried out at room temperature (20 ° C.) or higher and below the melting point of the powder PPE. Is 20 to 230 ° C., preferably 100 to 2
30 degreeC, More preferably, it is 150-230 degreeC. If the reaction temperature is less than 20 ° C, the polyfunctional epoxy compound and powder P
Insufficient reaction with PE and reaction temperature is 230 ℃
If it exceeds, the reaction rate will be faster, but the secondary reaction of the polyfunctional epoxy group compound will proceed and the crosslinking of the polyfunctional epoxy resin and the crosslinking reaction of the polyfunctional epoxy resin and PPE will occur, resulting in the desired functionalization. It is not preferable because the active epoxy group remaining in the polyphenylene ether is lost.

The reaction time depends on the reaction temperature and the type of polyfunctional epoxy compound used, and the time for obtaining polyphenylene ether containing an average of 0.1 or more epoxy groups can be arbitrarily selected.
To carry out these reactions, an autoclave capable of heating and cooling, a Henschel mixer, a closed type kneader, a tumbler type blender, etc. are usually mentioned, but not limited thereto.

In order to obtain a polyphenylene ether containing an average of 0.1 or more epoxy groups, the amount of the polyfunctional epoxy compound to be provided is usually the amount of terminal phenol groups of the polyphenylene ether (using gel permeation chromatography: GPC). The number-average molecular weight of polyphenylene ether calculated in terms of polystyrene is calculated as a representative molecular chain), and a polyfunctional epoxy compound is used in an amount of 0.1 to 10 times by mole, preferably 0.8 to 5 times by mole,
More preferably, it is 1.1 to 3 times mol. When the addition amount of the polyfunctional epoxy compound is 0.1 times or less, a polyphenylene ether containing 0.1 or more epoxy groups on average cannot be obtained, and when the addition amount is more than 10 times the unreacted polyfunctional epoxy compound. It is not preferable because the compound remains, the reaction between the epoxy compounds and the crosslinking reaction proceed.

As one of such reaction modes, PPE is used.
There is a method of reacting a polyfunctional epoxy compound containing two or more oxirane rings in one molecule in a solution state in which is dissolved in a good solvent. When the polyfunctional epoxy compound is reacted with PPE by this method, the PPE chain is The reaction between PPE and the polyfunctional epoxy compound is difficult to control because the grafting reaction between the PPE and the polyfunctional epoxy compound does not occur at all, or the graft reaction between the PPE and the polyfunctional epoxy compound does not occur at all. Therefore, polyphenylene ether having an average of 0.1 or more epoxy groups cannot be stably obtained, which is not preferable.

In the present invention, the above powder PPE and 1
In the reaction of a polyfunctional epoxy compound containing two or more oxirane rings in the molecule, it is most preferable to add a basic compound to accelerate the reaction. The basic compound, specifically, lithium, sodium, potassium,
Sodium methylate, sodium ethylate, tertiary amines such as triethylamine and tributylamine, imidazole, sodium phenoxide, lithium hydroxide,
Examples thereof include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, etc. Among them, sodium methylate, triethylamine, tributylamine, sodium hydroxide are preferably used. In addition to the above, a quaternary ammonium salt can also be preferably used.

The amount of epoxy groups bonded to the polyphenylene ether obtained by the above reaction method can be determined by the following procedure. (1) After the reaction, a 5% solution of powdered PPE in toluene was added dropwise to a large excess of methanol to cause precipitation. The precipitate was separated and the precipitated polymer was dried under reduced pressure at 150 ° C. × 0.1 mmHg for 1 hour and dried. Obtained as a polymer. (2) The dry polymer was dissolved in deuterated chloroform, and the peak chemical shift was tetramethylsilane peak (0.
00 ppm) as a reference, and the number of epoxy groups per one molecule of polyphenylene ether was measured by 270 MHz-NMR.
Peaks (6.47 ppm) due to protons at positions and peaks (2.74 ppm, 2.89 p) due to epoxy groups
pm, 3.34 ppm).

Next, a block composed of at least one polymer block A containing a vinyl aromatic compound as a main component and at least one polymer block B containing a conjugated diene compound as a main component used as the component (c) of the present invention. The hydrogenated block copolymer obtained by hydrogenating the copolymer and the block copolymer is dispersed in the epoxy group-containing polyphenylene ether as the component (b) or dispersed in the polyphenylene sulfide resin as the component (a). However, it exerts a great effect in imparting toughness to the obtained composition.

Here, a block copolymer composed of at least one polymer block A mainly containing a vinyl aromatic compound and at least one polymer block B mainly containing a conjugated diene compound is, for example, A -B, AB-
A, B-A-B-A, (A-B-) 4-Si, A-B-
It is a vinyl aromatic compound-conjugated diene compound block copolymer having a structure such as A-B-A, and the bound vinyl aromatic compound is 5 to 95% by weight, preferably 10 to 80%.
It is a block copolymer containing wt%.

Further, referring to the block structure, the polymer block A containing a vinyl aromatic compound as a main component is preferably a homopolymer block of a vinyl aromatic compound or a vinyl aromatic compound in an amount of preferably more than 50% by weight, and more preferably. Has a structure of a copolymer block of a vinyl aromatic compound and a conjugated diene compound, the content of which is 70% by weight or more, and the polymer block B mainly containing the conjugated diene compound is a conjugated diene compound. Preferably more than 50% by weight of homopolymer block or conjugated diene compound,
More preferably, it has a structure of a copolymer block of a conjugated diene compound and a vinyl aromatic compound, the content of which is 70% by weight or more.

The polymer block A containing a vinyl aromatic compound as a main component and the polymer block B containing a conjugated diene compound as a main component are a conjugated diene compound or a vinyl aromatic compound in the molecular chain of each polymer block. The distribution may be random, tapered (in which the monomer component increases or decreases along the molecular chain), partially block-shaped or any combination thereof, and the polymer block mainly contains the vinyl aromatic compound. When there are two or more polymer blocks mainly containing the conjugated diene compound, the respective polymer blocks may have the same structure or different structures.

The vinyl aromatic compound constituting the block copolymer is, for example, one or more of styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene and the like. It can be selected, and styrene is particularly preferable. Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3.
One or more selected from butadiene and the like, and among them, butadiene, isoprene and combinations thereof are preferable.

In the polymer block mainly composed of the conjugated diene compound, the microstructure of the bonding form in the block can be arbitrarily selected. For example, in the polymer block mainly composed of butadiene, 1,2-vinyl is used. The bond is preferably 2 to 90%, more preferably 8 to 80%.
Is. In addition, in the polymer block mainly containing isoprene, the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds is 2 to 80%, more preferably 3 to 70%.

The number average molecular weight of the block copolymer of the component (c) used in the present invention is 5,000 to 1,000,000.
It is preferably 0, particularly preferably 20,000.
It is preferably in the range of up to 500,000, and the molecular weight distribution [ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography and converted into polystyrene] is 10 or less. Further, the molecular structure of this block copolymer may be linear, branched, radial, or any combination thereof.

The block copolymer having such a structure is obtained by subjecting the aliphatic double bond of the polymer block B mainly composed of the conjugated diene compound of the above block copolymer to a hydrogenation reaction, and carrying out the present invention. It can be used as the hydrogenated block copolymer of the component (c) used in (1). The hydrogenation rate of such aliphatic double bonds is preferably at least 20%, more preferably 50% or more, and particularly preferably 8%.
It is 0% or more. The hydrogenation rate can be known using, for example, a nuclear magnetic resonance apparatus (NMR).

Further, the inorganic filler used as the component (d) in the present invention means the above-mentioned (a), (b) and (c).
It is a component that gives many functions to the resin composition consisting of components, for example, imparting rigidity, imparting heat resistance, imparting thermal conductivity, imparting conductivity, improving molding shrinkage, and improving linear expansion coefficient. The inorganic filler as the component (d) that brings out these effects can be selected according to the purpose such as improvement, and the following are mentioned.

For example, inorganic salts, glass fibers (long glass fibers, chopped strand glass fibers), glass flakes, glass beads, carbon fibers, whiskers, kaolin, mica, talc, carbon black, titanium oxide,
Calcium carbonate, potassium titanate, wollastonite,
Thermally conductive substances (graphite, aluminum nitride, boron nitride, alumina, beryllium oxide, silicon dioxide, magnesium oxide, aluminum nitrate, barium sulfate, etc.), conductive metal fibers, conductive metal flakes, conductive carbon black, conductive Examples include carbon fibers that exhibit properties. These inorganic fillers are the polyphenylene sulfide resin of the above-mentioned component (a), (b)
A material treated with a known surface treatment agent for the purpose of improving the dispersibility of the components in the polyphenylene ether resin or a known sizing agent for the purpose of improving the handling property during processing can also be preferably used.

The polyphenylene sulfide resin composition of the present invention comprises 1 to 99% by weight of the above-mentioned essential component (a) polyphenylene sulfide resin and 99 to 1% by weight of the epoxy group-containing polyphenylene ether (b). At least one polymer block A which is a resin composition and mainly comprises a vinyl aromatic compound as the component (c) per 100 parts by weight of the components (a) and (b).
And at least one polymer block B containing a conjugated diene compound as a main component and a resin containing 1 to 50 parts by weight of a hydrogenated block copolymer obtained by hydrogenating the block copolymer. It is a composition.

Furthermore, the total of the components (a) and (b) is 10
A resin composition containing 1 to 200 parts by weight of (d) an inorganic filler with respect to 0 parts by weight, and further a component (a),
It is a resin composition containing 1 to 200 parts by weight of the inorganic filler (d) based on 100 parts by weight of the total of the components (b) and (c). Among them, the composition of the most preferred embodiment is
The polyphenylene sulfide resin as the component (a) is used in an amount of 30 to 9
A polyphenylene sulfide resin composition containing 0 part by weight, 10 to 70 parts by weight of the epoxy group-containing polyphenylene ether as the component (b), and 3 to 30 parts by weight of the block copolymer and / or the hydrogenated block copolymer as the component (c). Is.
The most preferable embodiment of the resin composition containing the inorganic filler of the component (d) in addition to these components is the above (a),
It is 1 to 150 parts by weight based on 100 parts by weight of the total of the components (b), (c) and (d).

The method for producing the polyphenylene sulfide resin composition of the present invention will be described below. The most preferable embodiment of the method for industrially easily obtaining the polyphenylene sulfide resin composition of the present invention is (1) a melt-kneading machine for melt-kneading each of the above-mentioned components, and a kneading block of any screw It is a multi-screw extruder with two or more screws that can be installed in a position, and the entire kneading block part of the screw used is substantially (L /
D) ≧ 1.5, more preferably (L / D) ≧ 5 [wherein L represents the total length of the kneading block, and D represents the maximum outer diameter of the kneading block],
And (π · D · N / h) ≧ 50 [where π = 3.1
4, D = screw outer diameter corresponding to the metering zone,
N = screw rotation speed (revolutions / second), h = groove depth of the metering zone],

(2) These extruders have a first raw material supply port on the upstream side with respect to the flow direction of the raw material and a second raw material supply port on the downstream side thereof. One or more raw material supply ports may be further provided downstream, and a twin-screw extruder in which a vacuum vent port is provided between these raw material supply ports is used if necessary.

In the method for producing the polyphenylene sulfide resin composition of the present invention, the basic raw material supply method is to supply all of the components (a) to (c) from the first raw material supply port, (b) Supply in the coexistence of the PPS of the component (a) within a range not exceeding 50% of the total amount of the polyphenylene ether containing an epoxy group of the component and the total amount of the PPS of the component (a),
The extrusion method of supplying the remaining PPS of the component (a) from the second raw material supply port is preferable, and at this time, the block copolymer and / or the hydrogenated block copolymer of the component (c) is supplied.
A method in which PPS as the component (a) and the epoxy group-containing polyphenylene ether as the component (b) are mixed and supplied from the first raw material supply port is preferable. Further, in the case of further supplying the inorganic filler of the component (d), it is preferable to supply it under the state where the components (a) to (c) are completely melted and kneaded, and usually, after the second raw material supply port. It is preferable to supply the raw material to the raw material supply port.

The extruder barrel set temperature is usually 280 to 350 ° C., preferably 280, in the zone for melt kneading.
~ 310 ° C, screw speed 100 ~ 1200rp
m, preferably 100 to 500 rpm, and melt kneaded. In the present invention, in addition to the above components, other additional components may be added, if necessary, within a range that does not impair the characteristics and effects of the present invention, such as an epoxy group and / or an oxazonyl group for the purpose of further improving impact resistance. A copolymer prepared by copolymerizing an unsaturated monomer contained with an α-olefin (preferably ethylene) in a proportion of 1 to 20% by weight is contained in an amount of 1 to 20 with respect to 100 parts by weight of the resin composition of the present invention.
It is also possible to add by weight.

Other commonly used antioxidants, metal deactivators, flame retardants (organic phosphate ester compounds, condensed phosphate ester compounds, ammonium polyphosphate flame retardants, aromatic halogen flame retardants, silicone compounds) Flame retardants, etc.), fluoropolymers, plasticizers (low molecular weight polyethylene, epoxidized soybean oil, polyethylene glycol, fatty acid esters, etc.), flame retarding aids such as antimony trioxide, weathering (light) improving agents, nucleation Agents, slip agents, various colorants,
A release agent or the like may be added.

The polyphenylene sulfide resin composition of the present invention thus obtained eliminates the drawbacks of the conventional polyphenylene sulfide resin composition, and provides not only toughness (impact resistance) but also weld strength of the molded product. Because it is excellent, it can be preferably used for electric / electronic, molded parts of automobile parts, and in addition to this improved performance, it can be used in combination with heat creep resistance, water vapor permeation resistance, chemical resistance of polyphenylene sulfide itself. It is particularly useful as a material for a secondary battery battery case (injection molded product, sheet or film) directly incorporating electrodes, an electrolytic solution and a separator. And the polyphenylene sulfide resin composition of the present invention, various conventionally known processing methods, for example,
Various moldings can be molded according to the intended purpose by compression molding, injection molding, extrusion molding, multi-layer extrusion molding, profile extrusion molding and the like.

[0060]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Component (a), polyphenylene sulfide resin a-1: Melt viscosity (using a flow tester, 300
Value measured after holding for 6 minutes at a temperature of 20 ° C., a load of 20 Kgf / cm ² , and L / D = 10/1. ) Is 500 poise, the amount of methylene chloride extracted is 0.4% by weight, and the amount of -SX group is 29μ.
Mol / g PPS was set to a-1. a-2: Melt viscosity is 500 poise, extraction amount with methylene chloride is 0.7% by weight, and -SX group amount is 30 μmol / g.
Of PPS was set to a-2. a-3: Melt viscosity of 500 poise, methylene chloride extraction amount of 1.2% by weight, -SX group amount of 31 μmol / g
Of PPS was set to a-3. a-4: Melt viscosity of 500 poise, methylene chloride extraction amount of 3.0% by weight, -SX group amount of 29 μmol / g
Of PPS was designated as a-4.

A-5: Melt viscosity of 500 poise, methylene chloride extraction amount of 0.6% by weight, -SX group amount of 7 μm.
The mol / g PPS was set to a-5. a-6: Melt viscosity of 200 poise, methylene chloride extraction amount of 0.5% by weight, —SX group amount of 36 μmol / g
The PPS of was set to a-6. a-7: PPS (L3340) manufactured by Toray Industries, Inc. having a melt viscosity of 250 poise, an extraction amount with methylene chloride of 3.1% by weight, and an SX group content of 40 μmol / g was designated as a-7. a-8: PPS having a melt viscosity of 500 poise, an amount of methylene chloride extracted of 1.8% by weight, and an amount of -SX group of 9 μmol / g was designated as a-8.

Component (b) epoxy group-containing polyphenylene ether b-1: Bisphenol A based on 100 parts by weight of polyphenylene ether having a reduced viscosity of 0.37 dl / g.
Type epoxy resin (Grade 2 manufactured by Asahi Kasei Epoxy Co., Ltd.)
50) 10 parts by weight and 0.8 of tri-n-butylamine
By mixing 1 part by weight, polyphenylene ether was heated and stirred in a powder state for 1 hour using a closed heating type autoclave controlled at 150 ° C. to carry out a reaction. The reaction product polymer obtained here was made into a 5% toluene solution, dropped into a large excess of methanol, and filtered to obtain a polymer at 150 ° C.
It was dried under reduced pressure for 1 hour under the condition of 0.1 mmHg to obtain a dry polymer. (As component b-1)

This dried polymer was subjected to proton NMR measurement, and an average of 1.6 per minute of polyphenylene ether.
It contained 1 epoxy group. In order to confirm the presence or absence of a change in the molecular weight of the polyphenylene ether before and after the reaction, 0.02 g of each of the polyphenylene ether and the dry polymer before the reaction was dissolved in 20 ml of chloroform and GPC (gel permeation chromatography) was performed.
As a result, it was confirmed that no change was observed in the molecular weight curve and that the crosslinking reaction did not occur in the above reaction.

B-2: Bisphenol A used in b-1
Type epoxy resin instead of

[0065]

[Chemical 4]

Ethylene glycol diglycidyl (A)
Was reacted and purified in the same manner as in b-1 except that 4 parts by weight of was used to contain an average of 1.3 epoxy groups per minute of polyphenylene ether. In addition, in order to confirm the presence or absence of a change in the molecular weight of the polyphenylene ether before and after the reaction, 0.02 g of each of the polyphenylene ether and the dry polymer before the reaction was dissolved in 20 ml of chloroform, and GPC (gel permeation) was used. Application
As a result of confirmation by chromatography, no change was observed in the molecular weight curve, and it was confirmed that the crosslinking reaction did not occur in the above reaction.

B-3: Reaction was carried out by the same method and conditions as in b-2 except that the addition amount of ethylene glycol glycidyl (A) used in b-2 was changed to 0.6 part, and per 1 minute of polyphenylene ether. It contained an average of 0.17 epoxy groups. In addition, in order to confirm the presence or absence of a change in the molecular weight of the polyphenylene ether before and after the reaction, 0.02 g of each of the polyphenylene ether and the dry polymer before the reaction was dissolved in 20 ml of chloroform, and GPC (gel permeation) was used. Application
As a result of confirmation by chromatography, no change was observed in the molecular weight curve, and it was confirmed that the crosslinking reaction did not occur in the above reaction.

B-4: To 100 parts by weight of polyphenylene ether having a reduced viscosity of 0.37 dl / g, 10 parts by weight of a bisphenol A type epoxy resin (Grade 250 manufactured by Asahi Kasei Epoxy Co., Ltd.) and 0 of tri-n-butylamine. 0.8 parts by weight was dissolved in toluene to give a 10% by weight solution. This toluene solution was placed in a closed heating type autoclave and the temperature was controlled at 150 ° C., and the reaction was carried out by stirring for 1 hour. After the reaction, the mixture was cooled to room temperature, toluene was further added to make a polymer solution of 5% by weight in toluene, which was added dropwise to a large excess of methanol, and the polymer obtained by filtration was further filtered at 150 ° C. × 0.1 mmHg. It was dried under reduced pressure for 1 hour to obtain a dried polymer. (As component b-4)

In order to confirm whether or not the molecular weight of polyphenylene ether before and after the reaction is changed, this dried polymer 0.0
2 g was dissolved in 20 ml of chloroform, but many solids insoluble in chloroform were found. When the chloroform-soluble component was confirmed by GPC (gel permeation chromatography), it showed a molecular weight curve in which a polymer chain was present on the high molecular weight side, which was not found in the polyphenylene ether before the reaction. It was confirmed by the above solution reaction that some kind of cross-linking reaction had occurred with polyphenylene ether.

B-5: The reaction was carried out by the same method and conditions as in b-2 except that the addition amount of ethylene glycol glycidyl (A) used in b-2 was changed to 0.3 part by weight, and 1 minute of polyphenylene ether was added. It contained on average 0.05 epoxy groups. In addition, in order to confirm the presence or absence of a change in the molecular weight of the polyphenylene ether before and after the reaction, 0.02 g of each of the polyphenylene ether and the dry polymer before the reaction was dissolved in 20 ml of chloroform, and GPC (gel permeation) was used. Application
As a result of confirmation by chromatography, no change was observed in the molecular weight curve, and it was confirmed that the crosslinking reaction did not occur in the above reaction.

(C) Component block copolymer, hydrogenated block copolymer C-1: polystyrene-hydrogenated polybutadiene-polystyrene structure, wherein the bound styrene content is 33% by weight and the number average molecular weight is 175. 1,000, a hydrogenated block copolymer in which the amount of 1,2-vinyl bonds in the polybutadiene portion before hydrogenation is 46%. C-2: Polystyrene-hydrogenated polyisoprene-polystyrene structure, wherein the bound styrene amount is 43% by weight, the number average molecular weight is 137,000, and the 1,2-vinyl bond in the polyisoprene portion before hydrogenation Quantity and 3,4-
A hydrogenated block copolymer having a total vinyl bond content of 5%.

(D) Inorganic filler d-1: Glass flakes: Aminosilane-treated glass flakes having an average particle size of 600 μm, an average thickness of 5 μm and an average aspect ratio of 5120 d-2: glass fibers: diameter 13 μm, average length Three
mm aminosilane-treated glass fiber d-3: mica: aminosilane-treated mica having an average flake diameter of 90 μm

[0073]

Examples 1 to 17 and Comparative Examples 1 to 18 Components (a) to (d) shown in Tables 1 to 3 were added at temperatures of 290 to 310.
℃, screw speed 500rpm twin screw extruder (ZSK-40; WERNER & PFLEIDERE
R company, Germany), components (a) to (c) are supplied from the first raw material supply port of the extruder and melt-kneaded, and component (d) is supplied from the second raw material supply port. The melt-kneaded polyphenylene sulfide resin composition was obtained as pellets. The pellets were supplied to a screw in-line type injection molding machine set at 290 to 310 ° C., and a tensile test piece, a weld tensile test piece, an Izod impact test piece and a mold temperature of 130 ° C. A test piece for measuring a deflection temperature under load (DTUL) was injection-molded.

Next, using these test pieces, a tensile strength test (in accordance with ASTM D-638: measurement temperature 2
Tensile strength and weld tensile strength are measured, and Izod (thickness ⅛, notched) impact strength (in accordance with ASTM D-256: measurement temperature 23 ° C.) and load deflection temperature: DTUL (ASTM D) -648:
1.82 MPa load) was measured. These results are put together in Tables 1 to 3.

From these results, the toughness (impact strength) and weld tensile strength of the polyphenylene sulfide resin, which is an index of the amount of oligomer in the polyphenylene sulfide resin, when the extraction amount with methylene chloride exceeds 0.7% by weight is used. It became clear that it decreased remarkably. Furthermore, even when the amount of extraction with methylene chloride, which is an indicator of the amount of oligomer in the polyphenylene sulfide resin, is 0.7% by weight or less, the -SX group (S is a sulfur atom, X is an alkali metal) present in the polyphenylene sulfide resin. It was revealed that the toughness (impact strength) and the weld tensile strength are remarkably lowered when a polyphenylene sulfide resin whose amount (or hydrogen atom) is less than 15 μmol / g is used.

Furthermore, when the epoxy group-containing polyphenylene ether as the component (b) used is one obtained by the method disclosed in the present invention, the toughness (impact strength) and weld tensile strength are improved. However, it was revealed that the one using the modified polyphenylene ether epoxidized by the solution reaction did not show improvement in toughness (impact strength) and weld tensile strength.

[0077]

[Table 1]

[0078]

[Table 2]

[0079]

[Table 3]

[0080]

The polyphenylene sulfide resin composition of the present invention is provided with a polyphenylene sulfide resin having a specified oligomer amount and a specified functional group amount, and a polyphenylene sulfide resin having a specified functional group amount obtained by a specified method. The use of ether brings about an effect of significantly improving toughness (impact strength) and weld strength with respect to a resin composition comprising a polyphenylene sulfide resin, a polyphenylene ether and a block copolymer.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4J002 BP013 CH07X CN01W DA026                       DA036 DA066 DD046 DE066                       DE076 DE136 DE146 DE186                       DE206 DE236 DF016 DF036                       DG046 DJ006 DJ016 DJ036                       DJ046 DJ056 DL006 FA016                       FA046 FA066 FA086 FD016                       FD130 GQ00                 4J031 AA47 AA53 AB04 AC04 AD01                       AE11 AE15 AF23

Claims (5)

[Claims] 1. The amount of (a) methylene chloride extracted is 0.
7 wt% or less, and -SX group (S is a sulfur atom,
X is an alkali metal or hydrogen atom) is 15 μmo
1 to 9 polyphenylene sulfide resin having 1 / g or more
9 parts by weight, (b) a polyfunctional epoxy compound containing two or more oxirane rings in one molecule and a polyphenylene ether having a melting point of 140 to 260 ° C.
0 to 230 ° C.) and 1 obtained by reacting in a non-solvent
A polyphenylene sulfide resin composition comprising 99 to 1 part by weight of epoxy group-containing polyphenylene ether on average of 0.1 or more per molecular chain. 2. At least one polymer block A containing (c) a vinyl aromatic compound as a main component and at least one polymer containing a conjugated diene compound as a main component per 100 parts by weight of the total of the components (a) and (b). 2. The polyphenylene according to claim 1, which comprises 1 to 50 parts by weight of a block copolymer composed of the polymer block B and a hydrogenated block copolymer prepared by hydrogenating the block copolymer. Sulfide resin composition. 3. The polyphenylene sulfide resin composition according to claim 1, which comprises 1 to 200 parts by weight of the inorganic filler (d) per 100 parts by weight of the total of the components (a) and (b). 4. A total of 100 parts by weight of the component (a), the component (b) and the component (c) per 100 parts by weight of the (d) inorganic filler 1 to
The polyphenylene sulfide resin composition according to claim 2, wherein the polyphenylene sulfide resin composition comprises 200 parts by weight. 5. The inorganic filler of component (d) is an inorganic salt,
Glass fiber (long glass fiber, chopped strand glass fiber), glass flake, glass beads, carbon fiber, whiskers, kaolin, mica, talc, carbon black, titanium oxide, calcium carbonate, potassium titanate, wollastonite, thermal conductivity Substances (graphite, aluminum nitride, boron nitride, alumina, beryllium oxide, silicon dioxide, magnesium oxide, aluminum nitrate, barium sulfate), conductive metal fibers, conductive metal flakes, conductive carbon black, conductive carbon The polyphenylene sulfide resin composition according to claim 3, wherein the polyphenylene sulfide resin composition is one or more selected from fibers.