JPH08269201A - Polyarylene sulfide excellent in adhesiveness - Google Patents

Abstract

PURPOSE: To obtain PAS having excellent adhesiveness to an epoxy resin, a silicone resin or the like as well as high heat resistance and mechanical strengths. CONSTITUTION: A polyarylene sulfide comprising p-arylene sulfide units and m-arylene sulfide units and being a substantially linear polyarylene sulfide containing 0.5-10mol% based on the total of m-alylene sulfide units and p-arylene sulfide units, m-arylene sulfide units and having an alkali metal content of 200wt. ppm or below, a melt viscosity V6 of 50-3000P and a strength of bonding to an epoxy resin of 50kgf/cm<2> or above.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyarylene sulfide having excellent adhesiveness (hereinafter sometimes abbreviated as PAS) and a polyarylene sulfide resin composition containing the same.

[0002]

2. Description of the Related Art PAS is widely used for electric / electronic parts or mechanical parts because it has excellent heat resistance and molding processability and further has good chemical resistance, flame retardancy and dimensional stability. . However, PAS has relatively poor adhesiveness with other resins, especially with epoxy resin. Therefore, for example, when the PASs are bonded to each other with an epoxy adhesive, the PASs are bonded to another material, or the electric / electronic components are sealed with an epoxy resin, poor adhesion between the PAS and the epoxy resin is a problem. It was.

In view of such problems, various attempts have been made to improve the adhesion between PAS and epoxy resin. For example, JP-A-2-272063 discloses a polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) resin composition containing carnauba wax, JP-A-4-275368.
Japanese Patent Laid-Open No. 5-1711041 discloses a PPS resin composition prepared by mixing a fibrous and / or non-fibrous filler with a polyalkylene ether compound, and Japanese Patent Laid-Open No. 5-171041 discloses a super absorbent polymer such as a crosslinked polyacrylate. A PPS resin composition containing, an aromatic sulfone compound in JP-A-6-57136,
And P containing a fibrous and / or non-fibrous filler
PS resin composition, a PPS resin composition prepared by blending an aliphatic polyester and a fibrous and / or non-fibrous filler in JP-A-6-107946, and JP-A-6-
No. 166816 discloses a P containing a poly (ethylenecyclohexanedimethylene terephthalate) copolymer.
Each PS resin composition is disclosed. However, in any of the above, since a substance having a lower heat resistance than PPS is added, the heat resistance of the resin composition is lowered, and further, the mechanical strength is remarkably lowered in some resin compositions.

Further, JP-A-4-198267 discloses a PAS resin composition containing a PAS containing a carboxyl group, and JP-A-5-25388 discloses a PAS resin composition containing a PAS containing an amino group. ing. However, these are produced, for example, by copolymerizing dichlorobenzene having a carboxyl group or an amino group, but there is a production problem that these dichlorobenzenes remain in the reaction system, and adhesion of the obtained PAS It was not strong enough.

Japanese Unexamined Patent Publication (Kokai) No. 1-126334 discloses a method for producing a copolymer composed of a paraphenylene sulfide unit and a metaphenylene sulfide unit. However, this method is not intended to improve the adhesive strength, but to produce a block copolymer composed of the above-mentioned units. Further, JP-A-50-83500 discloses that m-dihalobenzene is used in the reaction of m-dihalobenzene, p-dihalobenzene and an alkali metal sulfide in an amount of 35 to 90 mol% of the total number of moles of dihalobenzene. A method of making a PPS is disclosed.
However, the produced PPS has not a high molecular weight, has a low melting point, is non-crystalline, has low heat resistance, and has a problem in practicality. The method is aimed at making soluble PPS and is not directed at improving the adhesive strength.

[0006]

The present invention is based on the conventional PA.
In addition to the high heat resistance and mechanical strength of S, the PAS has excellent adhesiveness to epoxy resin, silicone resin and the like.

[0007]

The present invention provides a polyarylene sulfide containing a paraarylene sulfide unit and a metaarylene sulfide unit, wherein the metaarylene sulfide unit is present in the total amount of the paraarylene sulfide unit and the metaarylene sulfide unit. 0.5-10
Containing mol% and alkali metal content is 200 wtpp
m or less, the melt viscosity V ₆ is 50 to 3000 poise, and the adhesive strength with the epoxy resin is 50 kgf / c.
It is a substantially linear polyarylene sulfide of m ² or more.

The PAS of the present invention contains a para-arylene sulfide unit and a meta-arylene sulfide unit, and is preferably a random copolymer. This can increase the adhesive strength of PAS. In the PAS, the content of the meta-arylene sulfide unit has a lower limit of 0.5 mol%, preferably 1.0 mol%, and an upper limit of 10 mol, based on the total amount of the para-arylene sulfide unit and the meta-arylene sulfide unit. %, Preferably 5.0 mol%. If the content is less than the above lower limit, the adhesiveness of PAS is inferior, and if it exceeds the above upper limit, the melting point of PAS is remarkably lowered, heat resistance which is the original property of PAS is impaired, and problems occur in practicality. Absent. Further, the PAS may contain a unit derived from a polyhalo compound such as 1,3,5-trichlorobenzene or 1,2,4-trichlorobenzene, which is added during the PAS production described below. it can. This unit is preferably 5.0 mol% or less based on the total amount of para-arylene sulfide units and meta-arylene sulfide units.

In the PAS of the present invention, the content of alkali metal is 200 ppm by weight or less, preferably 150 ppm by weight or less. If the upper limit is exceeded, the adhesive strength will be poor. The alkali metal contained in PAS is derived from the alkali metal sulfide used in the production of PAS shown below, and examples thereof include sodium, lithium, potassium, rubidium, and cesium. The alkali metal content is a value obtained by burning PAS powder at 700 ° C., dissolving the residue with hydrochloric acid, and measuring with an atomic absorption spectrometer.

The melt viscosity V ₆ of the PAS of the present invention has an upper limit of 3000 poise, preferably 1500 poise, particularly preferably 1000 poise, and a lower limit of 50 poise, preferably 100 poise, particularly preferably 150 poise. If it exceeds the upper limit, the moldability is deteriorated, and if it is less than the lower limit, the adhesive strength is lowered and the heat resistance and the mechanical strength are lowered, which is not preferable. The melt viscosity V ₆ was 300 ° C. and the load was 20 kgf / cm ² , using a flow tester.
It is a viscosity (poise) measured after holding for 6 minutes at L / D = 10.

The adhesive strength of the PAS of the present invention with an epoxy resin is 50 kgf / cm ² or more, preferably 60 kgf.
/ Cm ² or more. If it is less than the above lower limit, good adhesiveness with the epoxy resin cannot be obtained, which is not preferable. The adhesive strength with the epoxy resin is a value measured as follows. After mixing 40 parts by weight of glass fiber (chopped strand, fiber diameter 10 μm, fiber length 3 mm, urethane resin as a sizing agent, surface-treated with aminosilane surface treatment agent) into 60 parts by weight of PAS, biaxial different direction A pellet is prepared by kneading at 320 ° C. using a rotary extruder. A test piece according to JIS K6850 is prepared from the obtained pellets by an injection molding machine in which the cylinder temperature is 320 ° C. and the mold temperature is 130 ° C. Then, in accordance with JIS K6850, the obtained test piece was treated with an epoxy resin adhesive [main agent (novolak type epoxy resin) / curing agent (amino curing agent) = 100 parts by weight / 3
3.3 parts by weight] at 90 ° C. for 30 minutes for adhesion, and then a pulling speed of 5 mm / min and a chuck distance of 130.
A tensile test is performed in mm to measure the adhesive strength.

Further, the PAS of the present invention is substantially linear. PAS having a crosslinked structure has low adhesive strength and insufficient mechanical strength such as impact resistance.

The above-mentioned PAS of the present invention can be preferably produced by the following method.

That is, in the method for producing a polyarylene sulfide by reacting an alkali metal sulfide with a dihaloaromatic compound in an organic amide solvent, the reaction rate of the paradihaloaromatic compound and the paradihaloaromatic compound in the reaction system is Is 0 to less than 80%, 0.5 to 10 mol% of metadihaloaromatic compound is added to the reaction system with respect to the total amount of charged dihaloaromatic compound, and the gas phase part of the reaction can is cooled during the reaction. This is a method of condensing a part of the gas phase in the reaction vessel and refluxing it in the liquid phase to wash the polyarylene sulfide (a) with water and treat it with an acid.

In the production of the above polyarylene sulfide (a), the lower limit of the amount of the metadihaloaromatic compound added is 0.5 mol%, preferably 1 mol%, based on the total amount of the charged dihaloaromatic compound. The upper limit is 10 mol%,
It is preferably 5.0 mol%. Below the above range, P
The metaarylene sulfide unit in AS is less than the lower limit of the present invention, and exceeding the above range is not preferable because the metaarylene sulfide unit exceeds the upper limit of the present invention.

The metadihaloaromatic compound is added when the reaction rate of the paradihaloaromatic compound in the reaction system is 0 to less than 80%. The reaction rate of paradihalo aromatic compounds is 8
When it is 0% or more, the adhesiveness of the produced PAS is poor, the viscosity is lowered, and the metadihaloaromatic compound remains unreacted in the reaction system, which is not preferable. Preferably the para and metadihalo aromatic compounds are added to the reaction system simultaneously. Thus, by simultaneously adding both of them, the adhesiveness of PAS can be further improved. The total amount of para and metadihalo aromatic compounds added to the polymerization reaction system is based on 1 mol of the alkali metal sulfide.
Preferably 0.9 to 1.1 moles, particularly preferably 0.9
It is 6 to 1.05 mol. By using within this range, high molecular weight PAS can be obtained. If the amount added is less than the above range, only PAS having a remarkably low molecular weight can be obtained, and the reaction rates of the para and metadihalo aromatic compounds decrease, which is economically disadvantageous. If it exceeds the above range, depolymerization occurs, which is not preferable. When the metadihaloaromatic compound is charged during the reaction, for example, the metadihaloaromatic compound is directly or dissolved in N-methylpyrrolidone or the like used as an organic amide solvent, and a reaction vessel using a pressure injection pump is used. It can be performed by press-fitting the inside.

The para and metadihalo aromatic compounds used in the production of the above polyarylene sulfide (a) are known. For example, it can be selected from those described in JP-B-45-3368, JP-A-2-103232, or JP-B-4-64618.

Examples of the paradihalo aromatic compound include dihalogenated benzenes such as p-dichlorobenzene, p-dibromobenzene and 1-chloro-4-bromobenzene.
Alternatively, 2,5-dichlorotoluene, 2,5-dichloroxylene, 1-ethyl-2,5-dichlorobenzene, 1
-Ethyl-2,5-dibromobenzene, 1-ethyl-2
-Bromo-5-chlorobenzene, 1,3,4,6-tetramethyl-2,5-dichlorobenzene, 1-cyclohexyl-2,5-dichlorobenzene, 1-phenyl-2
5-dichlorobenzene, 1-benzyl-2,5-dichlorobenzene, 1-phenyl-2,5-dibromobenzene, 1-p-toluyl-2,5-dichlorobenzene, 1
Examples thereof include substituted dihalogenated benzenes such as -p-toluyl-2,5-dibromobenzene and 1-hexyl-2,5-dichlorobenzene. Of the above, dihalogenated benzene is preferable, and of these, p-dichlorobenzene is particularly preferable. Moreover, these compounds can be used individually or as a mixture.

Examples of the metadihalo aromatic compound include dihalogenated benzenes such as m-dichlorobenzene, m-dibromobenzene and 1-chloro-3-bromobenzene.
Alternatively, 2,4-dichlorotoluene, 2,4-dichloroxylene, 1-ethyl-2,4-dibromobenzene, 1
-Ethyl-2-bromo-4-chlorobenzene, 1,2,
4,6-Tetramethyl-3,5-dichlorobenzene, 1
-Cyclohexyl-2,4-dichlorobenzene, 1-phenyl-2,4-dichlorobenzene, 1-benzyl-
2,4-dichlorobenzene, 1-phenyl-2,4-dibromobenzene, 1-p-toluyl-2,4-dichlorobenzene, 1-p-toluyl-2,4-dibromobenzene, 1-hexyl- Substituted dihalogenated benzene such as 2,4-dichlorobenzene and the like can be mentioned. Of the above, dihalogenated benzene is preferable, and of these, m-dichlorobenzene is particularly preferable. These compounds can be used individually or as a mixture.

In the production of PAS (a), a method of cooling a gas phase portion of the reaction can during the reaction to condense a part of the gas phase in the reaction can and then refluxing this to a liquid phase is a special method. The method described in Kaihei 5-222196 can be used.

The refluxed liquid has a high water content compared to the liquid phase bulk due to the vapor pressure difference between water and the amide solvent.
This reflux liquid having a high water content forms a layer having a high water content on the reaction solution. As a result, the residual alkali metal sulfide (for example, Na ₂ S), alkali metal halide (for example, NaCl), oligomer and the like are contained in a large amount in the layer. In the conventional method, at a high temperature of 230 ° C. or higher, when the generated PAS and the raw materials such as Na ₂ S and by-products are uniformly mixed, not only high-molecular-weight PAS cannot be obtained but Depolymerization of PAS also occurred, and thiophenol by-product was observed. However, in the present invention, by positively cooling the gas phase portion of the reaction vessel and returning a large amount of water-rich reflux liquid to the upper portion of the liquid phase, the above-mentioned inconvenient phenomenon can be avoided and the reaction is inhibited. Of high molecular weight PA
It seems that S can be obtained. However, the present invention is not limited only to the effects due to the above-mentioned phenomenon, and high-molecular weight PAS can be obtained by various influences caused by cooling the gas phase portion.

In this method, it is not necessary to add water during the reaction unlike the conventional method. However, the addition of water is not excluded at all. However, if water is added, some of the advantages of the method are lost. Therefore, preferably, the total water content in the polymerization reaction system is constant throughout the reaction.

The vapor phase portion of the reactor can be cooled by external cooling or internal cooling, and can be performed by a cooling means known per se. For example, a method of flowing a cooling medium into an internal coil installed in the upper part of the reaction can, a method of flowing a cooling medium into an external coil or jacket wound around the upper part of the outside of the reaction can, and a reflux condenser installed in the upper part of the reaction can are used. The method may be such as sprinkling water or blowing gas (air, nitrogen, etc.) on the upper part of the outside of the reaction can. Any method is effective as long as it has the effect of increasing the reflux amount in the can. May be used. If the outside air temperature is relatively low (for example, room temperature), it is also possible to perform appropriate cooling by removing the heat insulating material conventionally provided on the upper part of the reaction can. In the case of external cooling, water condensed on the reactor wall surface
The amide-based solvent mixture enters the liquid phase along the wall of the reaction vessel. Thus, the water-rich mixture pools on top of the liquid phase,
Keep the water content there relatively high. For internal cooling,
The mixture condensed on the cooling surface likewise travels along the surface of the cooling device or the wall of the reaction vessel into the liquid phase.

On the other hand, the temperature of the liquid phase bulk is maintained at a predetermined constant temperature or controlled according to a predetermined temperature profile. 230 to 275 for constant temperature
It is preferable to carry out the reaction at a temperature of ° C for 0.1 to 20 hours. More preferably, the temperature is 240 to 265 ° C. and the time is 1 to 6 hours. To obtain higher molecular weight PAS, it is preferable to use a reaction temperature profile of two or more steps. This 2
When carrying out the stepwise operation, the first step is preferably carried out at a temperature of 195 to 240 ° C. If the temperature is low, the reaction rate is too slow, which is not practical. If the temperature is higher than 240 ° C., the reaction rate is too fast, PAS having a sufficiently high molecular weight cannot be obtained, and the side reaction rate remarkably increases. The end of the first stage is
Dihalo aromatic compound residual rate in the polymerization reaction system is 1 mol% to 40
It is preferable to carry out at a time of mol% and a molecular weight in the range of 3,000 to 20,000. More preferably, the residual ratio of the dihalo-aromatic compound in the polymerization reaction system is 2 mol% to 15 mol% and the molecular weight is 5,000 to 15,000. Residual rate is 40 mol%
When it is more than 1, the side reaction such as depolymerization is likely to occur in the second step reaction, while when it is less than 1 mol%, the high molecular weight P is finally obtained.
It is difficult to get AS. Thereafter, the temperature is raised, and the reaction in the final stage is preferably carried out at a reaction temperature of 240 to 270 ° C. for 1 to 10 hours. PAS with sufficiently high molecular weight at low temperature
At a temperature higher than 270 ° C., side reactions such as depolymerization are likely to occur, making it difficult to stably obtain a high molecular weight product.

As an actual operation, first, dehydration or water addition is carried out in an inert gas atmosphere, if necessary, so that the amount of water in the alkali metal sulfide in the amide solvent becomes a predetermined amount. The water content is preferably alkali metal sulfide 1
The amount is 0.5 to 2.5 mol, especially 0.8 to 1.2 mol per mol. If it exceeds 2.5 mols, the reaction rate will be low, and the amount of by-products such as phenol will increase in the filtrate after the reaction and the degree of polymerization will not increase. If it is less than 0.5 mol, the reaction rate is too fast to obtain a sufficiently high molecular weight product, and unfavorable reactions such as side reactions occur.

In the case of the one-step reaction at a constant temperature, the cooling of the gas phase portion during the reaction is preferably performed from the start of the reaction, but it must be performed at least during the temperature increase of 250 ° C. or less. In the multi-stage reaction, it is preferable to perform cooling from the first-stage reaction, but it is preferable to perform cooling at the latest after the completion of the first-stage reaction. Regarding the degree of cooling effect, the pressure inside the reaction vessel is usually the most suitable index. The absolute value of the pressure varies depending on the characteristics of the reaction vessel, the stirring state, the water content in the system, the molar ratio of the dihalo aromatic compound to the alkali metal sulfide, and the like. However, as compared with the case of not cooling under the same reaction conditions, if the reactor pressure is decreased, the amount of reflux liquid is increased, which means that the temperature at the reaction solution gas-liquid interface is decreased. It is considered that the degree of relative decrease indicates the degree of separation between the layer having a high water content and the layer having no water content. Therefore, it is preferable to cool the reactor so that the internal pressure of the reactor becomes lower than that in the case where no cooling is performed. The degree of cooling can be appropriately set by those skilled in the art according to the equipment used, operating conditions, and the like.

PAS having a desired viscosity can be produced by variously selecting the above reaction conditions.

The organic amide solvent used here is PA
Known for S polymerization, for example N-methylpyrrolidone (NMP), N, N-dimethylformamide,
N, N-dimethylacetamide, N-methylcaprolactam, etc., and mixtures thereof can be used, with NMP being preferred. They all have a lower vapor pressure than water.

Alkali metal sulphides are also known, for example lithium sulphide, sodium sulphide, potassium sulphide, rubidium sulphide, cesium sulphide and mixtures thereof. These hydrates and aqueous solutions may be used. Further, hydrosulfides and hydrates corresponding to these can be used after being neutralized with the corresponding hydroxides.
Inexpensive sodium sulfide is preferred.

In order to increase the molecular weight of PAS,
For example, 1,3,5-trichlorobenzene, 1,2,4-
A polyhalo compound such as trichlorobenzene can also be used in a concentration of preferably 5 mol% or less based on the total amount of para and metadihalo aromatic compounds.

Further, as a small amount of other additives, a terminal terminating agent and a monohalo compound as a modifying agent can be used in combination.

To produce the PAS of the present invention, the PAS (a) obtained in the above step is washed with water and treated with an acid.

Washing with water is preferably carried out by filtering the slurry produced in the PAS (ii) production step and then dispersing the filter cake in water. For example, the PAS slurry obtained as described above is filtered to obtain a PAS cake containing little solvent. The PAS cake is put into water, preferably 1 to 5 times by weight, stirred and mixed at room temperature to 90 ° C. for preferably 5 minutes to 10 hours, and then filtered. By repeating the stirring and mixing and filtering operations preferably 2 to 10 times, the solvent adhering to the PAS and the by-product salt are removed, and the washing with water is completed. By performing water washing as described above, it becomes possible to perform efficient washing with a small amount of water as compared with the washing method in which water is poured into the filter cake.

The acid treatment is preferably carried out at a temperature of 100 ° C. or lower, particularly preferably at room temperature to 80 ° C.
If the temperature exceeds the above upper limit, the PAS molecular weight after acid treatment decreases, which is not preferable. The pH of the acid solution used for the acid treatment is preferably 3.5 to 6.0, particularly preferably 4.0 to 5.5. By adopting this pH, most of the -SX (X represents an alkali metal) terminal in PAS that is the object to be treated can be converted to the -SH terminal. If the pH is less than the above range, the amount of acid used is large and the cost becomes high. If the pH exceeds the above range, removal of the alkali metal terminal in PAS becomes insufficient. The time required for the acid treatment depends on the acid treatment temperature and the concentration of the acid solution,
It is preferably 5 minutes or longer, particularly preferably 10 minutes or longer. If it is less than the above, the -SX end in PAS cannot be sufficiently converted to the -SH end, which is not preferable. For the acid treatment,
For example, acetic acid, formic acid, oxalic acid, phthalic acid, hydrochloric acid, phosphoric acid, sulfuric acid, sulfurous acid, nitric acid, boric acid, carbonic acid, etc. are used,
Acetic acid is particularly preferred. By applying this treatment, PAS
It is possible to reduce an impurity such as an alkali metal such as sodium.

By performing the above-mentioned washing with water and acid treatment, the amount of alkali metal such as sodium in PAS can be significantly reduced. This improves the dimensional stability of the molded product and also increases the adhesive strength.

The present invention also provides (A) the PA of the present invention.
The PAS resin composition contains 100 parts by weight of S and 0.01 to 400 parts by weight of the filler (B).

In the resin composition of the present invention, the component (A)
With respect to 100 parts by weight, the upper limit of the component (B) is 40.
0 parts by weight, preferably 250 parts by weight, particularly preferably 1
The lower limit is 0.01 part by weight, preferably 1.0 part by weight, particularly preferably 10 parts by weight. When the amount of the component (B) exceeds the above upper limit, the adhesive strength with the epoxy resin decreases and the moldability of the resin composition also deteriorates. When the component (B) is less than the above lower limit, the mechanical strength of the molded product is low.

As the component (B) filler of the present invention, a conventional filler can be used. For example, as the fibrous filler, glass fiber, carbon fiber, silane glass fiber, whiskers, boron fiber, potassium titanate fiber, asbestos fiber, silicon carbide fiber, aramid fiber, ceramics fiber, metal fiber, etc. may be mentioned. Examples of the filler include silicates such as mica and talc, carbonates, sulfates, metal oxides, glass beads, silica and the like. These fillers can be used alone or in combination of two or more. Further, these fillers may be treated with a silane coupling agent or a titanate coupling agent as needed.

The resin composition of the present invention contains P other than PAS of the present invention as long as the object of the present invention is not impaired.
AS can be blended. The blending amount is preferably 0 to 2000 with respect to 100 parts by weight of the component (A).
Parts by weight, particularly preferably 1 to 400 parts by weight. As a result, the P of the present invention is maintained while maintaining excellent adhesiveness.
The amount of AS used can be reduced. Examples of the PAS include linear PAS in which a metadihalo aromatic compound is not copolymerized, or PAS obtained by thermally oxidizing and cross-linking the linear PAS.

Further, if necessary, additives such as an antioxidant, a heat stabilizer, a lubricant, a release agent and a coloring agent may be added.

The method for mixing the above components is not particularly limited. A generally widely used method, for example, a method of mixing each component with a mixer such as a Henschel mixer can be used.

The resin composition of the present invention is usually melt-kneaded in an extruder and pelletized, and then, for example, injection-molded or compression-molded into a desired shape.

Since the PAS resin composition of the present invention does not undergo rapid crystallization, it can suppress the occurrence of cracks due to molding shrinkage and the like, and has high adhesiveness with epoxy resins, silicone resins and the like. Therefore, it is useful in the field of sealing electric / electronic parts.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

[0045]

EXAMPLES Each characteristic value in the examples was measured as follows. <Melt viscosity V ₆ > Shimadzu flow tester CFT-
It measured using 500C. <Sodium content> PPS powder was burned in a muffle furnace at 700 ° C. and then used as an atomic absorption spectrometer, manufactured by Shimadzu Corporation A
It was measured using A-670. <Adhesive Strength> As the glass fiber, CS 3J-961S (trademark) manufactured by Nitto Boseki Co., Ltd. was used. Regarding the epoxy resin adhesive, XNR3101 (trademark) manufactured by Nagase Ciba Co., Ltd. was used as a main agent, and XNH3101 (trademark) manufactured by Nagase Ciba Co., Ltd. was used as a curing agent. <Crystallization temperature _Tc and melting point _Tm > Measured by DSC. The device is a differential scanning calorimeter SS manufactured by Seiko Denshi.
It measured using C / 5200 as follows. 10 mg of the sample was heated from room temperature to 320 ° C. at a heating rate of 20 ° C./min in a nitrogen stream, and then held at 320 ° C. for 5 minutes to melt. It was then cooled at a rate of 10 ° C / min. The exothermic peak temperature at this time was defined as the crystallization temperature _Tc . The endothermic peak temperature when the temperature was raised from room temperature to 320 ° C. at a rate of 10 ° C./min was defined as the melting point T _m .

[0046]

Example 1 Flake-shaped sodium sulfide (60.4 wt% Na ₂ S) 19.38 was placed in a 150 liter autoclave.
1 kg and N-methyl-2-pyrrolidone (hereinafter NM
45.0 kg was charged. While stirring under a nitrogen stream, the temperature was raised to 209 ° C. and water was reduced to 4.640
kg was distilled (the residual water content was 1.12 mol per mol of sodium sulfide). Then, the autoclave was sealed and cooled to 180 ° C., and 21.609 kg of paradichlorobenzene (hereinafter sometimes abbreviated as p-DCB) and 0.441 kg of metadichlorobenzene (hereinafter sometimes abbreviated as m-DCB). (2.0 mol% relative to total DCB) and 18.0 kg of NMP were charged. Liquid temperature 150 ℃
Then, the temperature was started by pressurizing to 1 kg / cm ² G with nitrogen gas. The reaction was allowed to proceed while stirring at a liquid temperature of 260 ° C. for 2 hours, and the upper portion of the autoclave was cooled by watering. Next, the temperature was lowered and the cooling of the upper part of the autoclave was stopped. During cooling of the upper part of the autoclave, the liquid temperature was kept constant so as not to drop. The maximum pressure during the reaction is 8.5
It was 9 kg / cm ² G.

The resulting slurry was filtered to remove the solvent, and then the filter cake was put into warm water of about 80 ° C. (about twice the weight of the filter cake by weight) and stirred sufficiently for about 30 minutes. , Filtered. This operation of washing with water and filtration was repeated 5 times. Next, the filter cake was slurried with water at about 50 ° C., acetic acid was added to the slurry to adjust the pH to 5, and acid treatment was carried out. After the acid treatment, washing with water was repeated three times. Then, it was dried in a hot air circulation dryer at 120 ° C. for about 8 hours to obtain a white powdery polymer (P-1). The characteristic values of the polymer were measured.

The reaction rate of p-DCB is 98.4%,
The reaction rate of m-DCB was 100%.

[0049]

Example 2 21.940 kg of p-DCB, m-DC
0.110 kg of B (0.5 mol% based on total DCB)
Under the same conditions as in Example 1 except that
2) was obtained and each characteristic value was measured.

The reaction rate of p-DCB is 98.9%,
The reaction rate of m-DCB was 100%.

[0051]

Example 3 p-DCB of 20.948 kg, m-DC
1.103 kg of B (5.0 mol% based on total DCB)
Under the same conditions as in Example 1 except that
3) was obtained and each characteristic value was measured.

The reaction rate of p-DCB is 98.2%,
The reaction rate of m-DCB was 100%.

[0053]

Example 4 A polymer (P-4) was obtained under the same conditions as in Example 1 except that the reaction was carried out at a liquid temperature of 220 ° C. for 5 hours and then at a liquid temperature of 260 ° C. for 5 hours. The characteristic value was measured. The reaction rate of p-DCB is 98.7% and m-DC
The reaction rate of B was 100%.

[0054]

Example 5 A polymer (P-5) was obtained under the same conditions as in Example 1 except that the reaction was carried out at a liquid temperature of 240 ° C. for 2 hours and then at a liquid temperature of 260 ° C. for 2 hours. The characteristic value was measured. The reaction rate of p-DCB is 98.7% and m-DC
The reaction rate of B was 100%.

[0055]

Example 6 20.286 kg of p-DCB and m-DC
1.764 kg of B (8.0 mol% based on total DCB)
Except that the polymer (P-
6) was obtained and each characteristic value was measured.

The reaction rate of p-DCB is 98.5%,
The reaction rate of m-DCB was 100%.

[0057]

Example 7 22.185 kg of p-DCB, m-DC
0.453 kg of B (2.0 mol% based on total DCB)
The polymer (P-7) was obtained under the same conditions as in Example 1, except that the reaction was allowed to proceed while stirring at a liquid temperature of 260 ° C. for 3 hours. The characteristic values of the polymer were measured. The maximum pressure during the reaction was 8.52 kg / cm ² G.

The reaction rate of p-DCB is 98.1%,
The reaction rate of m-DCB was 100%.

[0059]

[Comparative Example 1] 22.06 kg of p-DCB, m-DC
0.044 kg of B (0.2 mol% based on total DCB)
Under the same conditions as in Example 1 except that
C1) was obtained and each characteristic value was measured.

The reaction rate of p-DCB is 98.8%,
The reaction rate of m-DCB was 100%.

[0061]

[Comparative Example 2] p-DCB was added without adding m-DCB.
A polymer (PC-2) was obtained under the same conditions as in Example 1 except that the amount was 2.050 kg, and each characteristic value was measured.

The reaction rate of p-DCB was 98.8%.

[0063]

[Comparative Example 3] 19.404 kg of p-DCB, m-DC
A polymer (P-C3) was obtained under the same conditions as in Example 1 except that B was 2.646 kg (12.0 mol% based on the total DCB), and each characteristic value was measured.

The reaction rate of p-DCB is 98.5%,
The reaction rate of m-DCB was 100%.

[0065]

[Comparative Example 4] 21.609 kg of p-DCB was charged, and when the reaction temperature reached 240 ° C. (reaction rate of p-DCB was 85%), 0.441 kg of m-DCB (total DC
Polymer (P-C4) was obtained under the same conditions as in Example 5 except that (2.0 mol% relative to B) was pressed into the autoclave by a pressure injection pump, and each characteristic value was measured. p-
The reaction rate of DCB was 98.6%, and the reaction rate of m-DCB was 100%.

[0066]

Comparative Example 5 A polymer (P-C5) was obtained under the same conditions as in Example 4, except that the upper part of the autoclave was not cooled. The characteristic values of the polymer were measured. The maximum pressure during the reaction was 10.31 kg / cm ² G.

The reaction rate of p-DCB is 99.1%,
The reaction rate of m-DCB was 100%.

[0068]

Comparative Example 6 A polymer (P-C6) was obtained under the same conditions as in Example 1 except that the washing and filtering operations were carried out 9 times without acetic acid treatment. Was measured.

[0069]

[Comparative Example 7] p-DCB was added without adding m-DCB.
A polymer (P-C7) was obtained under the same conditions as in Example 7, except that the amount was 2.638 kg. The characteristic values of the polymer were measured. Maximum pressure during reaction is 8.60 kg
/ Cm ² G It was.

The reaction rate of p-DCB was 98.4%.

In Examples 1 to 7 and Comparative Examples 1 to 7,
The reaction rates of p-DCB and m-DCB were calculated from the measurement results by gas chromatography. Here, each reaction rate was calculated by the following formula.

[0072]

## EQU1 ## Reaction rate (%) of p-DCB = (1-remaining p-D
CB weight / p-DCB weight) × 100

[0073]

## EQU2 ## Reaction rate (%) of m-DCB = (1-remaining m-D
CB weight / prepared m-DCB weight) × 100 The above results are shown in Tables 1 and 2.

[0074]

[Table 1]

[0075]

[Table 2] Examples 1 to 3 are PPS of the present invention produced by changing the addition amount of m-DCB, and the contents of the metaphenylene sulfide unit are different from each other. When the content of the metaphenylene sulfide unit increases, the adhesive strength with the epoxy resin also increases. In Examples 4 and 5, the reaction in the PPS manufacturing process has two stages. Compared to Example 1, PPS having a larger melt viscosity V ₆ was obtained, and in each case, the adhesive strength with the epoxy resin was higher than that in Example 1. Example 6 is the same as Example 4 under the conditions of m-
It is PPS manufactured by increasing the amount of DCB added. Compared to Example 4, the content of the metaphenylene sulfide unit was large and the adhesive strength with the epoxy resin was high. Example 7 is
P produced under the same conditions as in Example 1 but with a longer reaction time
It is PS. Similar to Example 1, the adhesive strength with the epoxy resin is high.

On the other hand, Comparative Example 1 is a PPS produced under the same conditions as in Example 1, except that the amount of m-DCB added was 0.2 mol%. The content of the metaphenylene sulfide unit is below the range of the present invention, and the adhesive strength with the epoxy resin is also low. Comparative Example 2 is a m-DC under the same conditions as in Example 1.
It is PPS manufactured without adding B. The PPS does not contain a metaphenylene sulfide unit and has low adhesive strength with an epoxy resin. The PPS of Comparative Example 3 is the same as that of Example 1.
It was produced under the same conditions as above but with an addition amount of m-DCB of 12 mol%. Metaphenylene sulfide units are beyond the scope of the present invention, V ₆ , T _c and T _m are significantly lower and PP
The original heat resistance of S was impaired and it was impractical. Comparative Example 4 is the m-DC under the same conditions as in Example 5.
It is a PPS produced by adding B when the reaction rate of p-DCB is 85%. The obtained PPS has low adhesive strength with the epoxy resin. Comparative Example 5 was prepared under the same conditions as in Example 4,
It is PPS manufactured without cooling the upper part of the autoclave. The melt viscosity V ₆ is small, and the adhesive strength with the epoxy resin is extremely low. Comparative Example 6 is PPS produced under the same conditions as in Example 1 but without acetic acid treatment. High sodium content and low adhesive strength with epoxy resin. Comparative Example 7 is a PPS produced without adding m-DCB under the same conditions as in Example 7. It does not contain a metaphenylene sulfide unit, and has a lower adhesive strength with an epoxy resin as compared with Example 7.

[0077]

Examples 8 to 10 and Comparative Examples 8 and 9 Using the PPS (P-7 and P-C7) produced in the above Example 7 and Comparative Example 7, the compounding amounts (parts by weight) shown in Table 3 were used. A resin composition was prepared to prepare each test piece, and the adhesive strength with the silicone resin was measured.

The adhesive strength with the silicone resin was measured as follows. PAS, glass fiber (CS 3
J-961S, a trademark, manufactured by Nitto Boseki Co., Ltd.) and calcium carbonate (SL-1000, a trademark, manufactured by Takehara Chemical Industry Co., Ltd.) were mixed at a predetermined compounding ratio (Table 3), and then the adhesive strength of the epoxy resin was adjusted. Same as measurement, JIS K68
A test piece according to 50 was prepared. Then, JIS K68
In accordance with 50, the obtained test piece was bonded using a silicone adhesive (Shin-Etsu Silicone KE1833, trademark, manufactured by Shin-Etsu Chemical Co., Ltd.) under curing conditions of 100 ° C. for 1 hour, and then a pulling speed of 5 mm / min. , Chuck distance 130m
A tensile test was performed at m to measure the adhesive strength.

The above results are shown in Table 3.

[0080]

[Table 3] Each of Examples 8 and 9 was superior in adhesive strength with the silicone resin, as compared with Comparative Examples 8 and 9, respectively. Also,
Example 10 includes PAS (P-C7) other than the present invention. Although the adhesive strength was somewhat lowered, the effect of the present invention was not impaired.

[0081]

INDUSTRIAL APPLICABILITY The present invention provides a PAS excellent in adhesiveness with an epoxy resin, a silicone resin and the like in addition to the high heat resistance and mechanical strength of the conventional PAS.

Claims (2)

[Claims] 1. A polyarylene sulfide containing a para-arylene sulfide unit and a meta-arylene sulfide unit, wherein the meta-arylene sulfide unit is contained in an amount of 0.5 to 10 mol% based on the total amount of the para-arylene sulfide unit and the meta-arylene sulfide unit. And the alkali metal content is 200 ppm by weight or less, and the melt viscosity V
₆ is 50 to 3000 poise, and the adhesive strength with the epoxy resin is 50 kgf / cm ² or more, and a substantially linear polyarylene sulfide. 2. (A) 100 parts by weight of the polyarylene sulfide according to claim 1, and (B) a filler 0.01 to 4
A polyarylene sulfide resin composition containing 100 parts by weight.