JPH11335653A - Welding rod for polyarylene sulfide molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a welding rod giving a high weld strength, when welding PAS molded products to each other, and to provide a PAS molded product welded with the welding rod and having a high weld strength. SOLUTION: This welding rod for polyarylene sulfide molded products comprises (A) 100-0 pt.wt. of a branched polyarylene sulfide having a melt- viscosity V6 of 200-50,000 poises and a non-Newtonian index N of >=1.15 and (B) 0-100 pts.wt. of a thermally oxidatively cross-linked polyarylene sulfide having a melt viscosity V6 of 200-20,000 poises and a non-Newtonian index N of 1.1-2.0 and further satisfying the equality: log [the melt viscosity V6 of the thermally oxidatively cross-linked polyarylene sulfide]/log [the melt viscosity6 of the polyarylene sulfide B before thermally oxidatively treated into the thermally oxidatively cross-linked polyarylene sulfide]=1.01 to 1.55.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a welding rod for molded polyarylene sulfide.

[0002]

2. Description of the Related Art Polyphenylene sulfide (hereinafter referred to as P
Polyarylene sulfide (hereinafter sometimes abbreviated as PAS) resin represented by a resin (which may be abbreviated as PS) is excellent in heat resistance, chemical resistance, moldability, flame retardancy, and dimensional stability. It is widely used for electronic / electric parts and mechanical parts.

Conventionally, when bonding PAS compacts to each other, a method of using an adhesive or a method of heat welding using high frequency or ultrasonic waves has been used. However, in the former method, there is a problem that the heat resistance of the completed PAS molded article is impaired due to the low heat resistance of the adhesive itself, and in the latter method, it is difficult to bond a large molded article. Had.

Although various methods of welding synthetic resin molded articles using synthetic resin welding rods have been proposed, these methods are not suitable for bonding between PAS molded articles. -91634, JP-A-51-602
No. 65, JP-A-60-4032).

[0005]

SUMMARY OF THE INVENTION The present invention relates to a welding rod which provides high welding strength when joining PAS compacts by welding, and a PAS compact having a high welding strength joined by the welding rod. To provide.

[0006]

Means for Solving the Problems The present inventors have conducted various studies to solve the above problems. As a result, the inventors have found that a welding rod containing the following predetermined PAS is extremely excellent in bonding between PAS compacts by welding, and that the welded portion has a high welding strength, and completed the present invention.

That is, the present invention provides (1) (A) a melt viscosity V
₆ is 200 to 50,000 poise, and 100 to 0 parts by weight of a branched polyarylene sulfide having a non-Newton index N of 1.15 or more, and (B) a melt viscosity V
₆ is 200 to 20,000 poise, the non-Newtonian index N is 1.1 to 2.0, and the following formula (1)
Satisfy

[0008]

Log [melt viscosity of the above-mentioned thermally oxidized cross-linked polyarylene sulfide V ₆ ] / log [melt viscosity of the poly-arylene sulfide (b) before being converted into the above-mentioned thermally oxidized cross-linked polyarylene sulfide by the thermal oxidation treatment V ₆ ] = 1.
01 to 1.55 (1) The thermally oxidized crosslinked polyarylene sulfide 0
It is a welding rod for a polyarylene sulfide molded article containing 100 parts by weight.

Japanese Patent No. 2868816 discloses a melt viscosity (measured at 310 ° C. and a shear rate of 1,200 / sec) of 300.
Disclosed is a welding rod for a polyarylene sulfide molded article, which comprises 100 to 30% by weight of a linear polyarylene sulfide having a molecular weight of 10,000 to 10,000 and 0 to 70% by weight of an inorganic filler. Further, in the detailed description of the invention of the publication, the linear PAS is not obtained by thickening treatment by oxidative crosslinking, but is obtained substantially from a monomer mainly composed of a bifunctional monomer. It is disclosed. Furthermore, in a PAS having a crosslinked structure which is heated in the presence of air and partially crosslinked to have a high molecular weight, the weldability is hindered and is not suitable as a welding rod. However, it discloses that excellent welding strength cannot be obtained, the mechanical strength of the welded portion is low, and the welded portion is easily broken.

The present inventors have proposed a P having a thermally oxidized crosslinked structure.
Even with AS, PAS having a predetermined relationship between a predetermined melt viscosity V ₆ , a predetermined non-Newton index N, and a melt viscosity V ₆ before and after the thermal oxidation crosslinking treatment is extremely excellent as a welding rod for a PAS molded product. They have found that they have characteristics. Furthermore, the present inventors have found that even a PAS having a predetermined melt viscosity V ₆ and a predetermined non-Newton index N can be similarly formed in a PAS having a branched structure obtained from a monomer containing a polyfunctional monomer. It has also been found that it has extremely excellent properties as a body welding rod.

In a preferred embodiment, (2) the branched polyarylene sulfide (A) has a melt viscosity V ₆ of 300 to 300.
The welding rod according to the above (1), wherein the welding rod is 35,000 poises;
(3) The welding rod according to the above (1) or (2), wherein the non-Newtonian index N of the branched polyarylene sulfide (A) is 1.2 to 2.2. (4) The branched polyarylene sulfide (A) ) Reacts 0.2 to 1.0 mol% of a polyhalo aromatic compound with an alkali metal sulfide, a dihalo aromatic compound and a charged alkali metal sulfide in an organic amide solvent, and reacts during the reaction. Any one of the above (1) to (3), which is produced by cooling a gas phase portion of the can to condense a part of the gas phase in the reaction vessel and refluxing it to a liquid phase. Welding rod according to one, (5)
(6) the welding rod according to any one of (1) to (4) above, wherein the melt viscosity V ₆ of the thermally oxidized crosslinked polyarylene sulfide (B) is 250 to 15,000 poise;
The above-mentioned (1), wherein the non-Newton index N of the thermally oxidized crosslinked polyarylene sulfide (B) is 1.15 to 1.95.
Welding rod according to any one of - (5), (7) polyarylene sulfide (b) is to obtain a polyarylene sulfide having a melt viscosity V ₆ of 70～3,000 poise is thermally oxidized cross-linked The welding rod according to any one of (1) to (6) above, wherein the polyarylene sulfide (b) is an alkali metal sulfide or a dihalo aromatic in an organic amide solvent. 0.2 to 1.0 based on compound and charged alkali metal sulfide
By reacting mol% of a polyhaloaromatic compound and cooling the gas phase portion of the reaction vessel during the reaction, a part of the gas phase in the reaction vessel is condensed and this is refluxed to the liquid phase to produce the reaction vessel. (1) The welding rod according to any one of (1) to (7), (9) a total of 100 weight of the branched polyarylene sulfide (A) and the thermally oxidized crosslinked polyarylene sulfide (B). Parts, inorganic filler (C)
And (10) a welding rod according to any one of the above (1) to (9) containing 0 to 400 parts by weight of Polyarylene sulfide molded article.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a branched PAS is a branched chain (branched structure) obtained by reacting not only a dihalo aromatic compound but also a polyhalo aromatic compound with an alkali metal sulfide during PAS synthesis. ), And a thermally oxidatively crosslinked PAS refers to a PAS having a crosslinked structure obtained by thermally oxidatively crosslinking PAS in an oxygen-containing atmosphere.

The melt viscosity V of the branched PAS (A) of the present invention
₆ has an upper limit of 50,000 poise, preferably 350,000 poise
00 poise, with a lower limit of 200 poise, preferably 3 poise.
00 poise. If the upper limit is exceeded, the thermal stability decreases and molding becomes difficult, and if it is less than the lower limit, the weld strength of the molded article is significantly reduced, which is not preferable. Here, the melt viscosity V ₆ is a value measured using a flow tester after holding at 300 ° C., a load of 20 kgf / cm ² and L / D = 10/1 for 6 minutes.

Non-Newton exponent N of branched PAS (A)
Has a lower limit of 1.15, preferably 1.2, and an upper limit of 2.2. If the lower limit is less than the above lower limit, the welding strength of the molded product is extremely low, which is not preferable. here,
The non-Newtonian index N is calculated using Capillograph as 3
It is a value calculated by using the following formula (2) by measuring the shear rate and the shear stress under the conditions of 00 ° C. and L / D = 40/1. If the N value is 1, it is a Newtonian fluid, and the N value is 1
Exceeding indicates a non-Newtonian fluid.

[0015]

Equation 3] ^{SR = K · SS N (2} ) ( where, SR shear rate (sec ^-1), SS is a shear stress (dyne / cm ^2), and K is a constant.) Branching present invention The type PAS (A) is 0.2 to 1.0 mol%, preferably 0.25 to 0.6 mol% based on the alkali metal sulfide, dihaloaromatic compound and charged alkali metal sulfide in the organic amide solvent. It can be produced by reacting mol% of a polyhalo aromatic compound. If the addition amount of the polyhalo aromatic compound is less than the above lower limit, a sufficient branched structure cannot be obtained, and if it exceeds the above upper limit, the thermal stability is reduced and molding becomes difficult, which is not preferable.

In the above method, the method of adding the polyhalo aromatic compound into the polymerization reaction system is not particularly limited. For example, the alkali metal sulfide and the dihalo-aromatic compound may be added simultaneously, or at an arbitrary point during the reaction, the polyhalo-aromatic compound is dissolved in an organic solvent such as N-methylpyrrolidone, and the reaction vessel is pressurized with a high-pressure pump. It may be press-fitted inside.

The polyhalo aromatic compound is a compound having three or more halogen substituents in one molecule, for example, 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, 1,3,5 -Trichlorobenzene, 1,
3-dichloro-5-bromobenzene, 2,4,6-trichlorotoluene, 1,2,3,5-tetrabromobenzene, hexachlorobenzene, 1,3,5-trichloro-
2,4,6-trimethylbenzene, 2,2 ', 4,4'
-Tetrachlorobiphenyl, 2,2 ', 6,6'-tetrabromo-3,3', 5,5'-tetramethylbiphenyl, 1,2,3,4-tetrachloronaphthalene, 1,
Examples thereof include 2,4-tribromo-6-methylnaphthalene and a mixture thereof, and 1,2,4-trichlorobenzene and 1,3,5-trichlorobenzene are preferred.

Preferably, the branched PAS (A) is obtained by cooling a part of the gas phase in the reaction vessel by cooling the gas phase part of the reaction vessel during the reaction in the method for producing the branched PAS (A). It can be produced by a method of condensing and refluxing the liquid phase.

A method for producing a PAS by cooling a gas phase portion of a reaction vessel to condense a part of a gas phase in the reaction vessel and refluxing the liquid phase to a liquid phase is disclosed in Japanese Patent Application Laid-Open No. 5-222.
The method described in JP 196 can be used.

In this polymerization method, the refluxed liquid has a higher water content than the liquid bulk because of the vapor pressure difference between water and the amide solvent. The reflux liquid having a high water content forms a layer having a high water content at the upper portion of the reaction solution. As a result, residual alkali metal sulfide (eg, Na ₂ S),
Alkali metal halides (eg, NaCl), oligomers, and the like are included in the layer in large amounts. In the conventional method, PAS and N
In a state where the raw materials such as a ₂ S and by-products are uniformly mixed, not only a high molecular weight PAS cannot be obtained, but also
Depolymerization of the produced PAS also occurs, and by-products of thiophenol are observed. However, in the present invention, the above disadvantageous phenomenon can be avoided by actively cooling the gas phase portion of the reaction vessel and returning a large amount of the water-rich reflux liquid to the upper part of the liquid phase so as to inhibit the reaction. It can be considered that such factors can be effectively eliminated and a high molecular weight PAS can be obtained. However, the present invention is not limited only by the effect of the above phenomenon, but by various effects caused by cooling the gas phase part, high molecular weight PAS
Is obtained.

In this polymerization method, it is not necessary to add water during the reaction as in the conventional method. However, this does not preclude the addition of water at all. However, if the operation of adding water is performed, some of the advantages of the present invention are lost. Therefore, preferably, the total water content in the polymerization reaction system is constant throughout the reaction.

The gas phase of the reaction vessel can be cooled either externally or internally, and can be cooled by a cooling means known per se. For example, a method of flowing a cooling medium through an internal coil installed at an upper part in a reaction can, a method of flowing a cooling medium through an external coil or a jacket wrapped around the upper part of the reaction can, and using a reflux condenser installed at the upper part of the reaction can A method such as spraying water or blowing a gas (air, nitrogen, etc.) on the upper portion of the outside of the reaction vessel is conceivable, but any method can be used as long as it has the effect of increasing the amount of reflux in the vessel as a result. May be used. If the outside air temperature is relatively low (for example, normal temperature), appropriate cooling can be performed by removing a heat insulating material conventionally provided on the upper part of the reaction vessel. In the case of external cooling, water condensed on the reactor wall
The amide-based solvent mixture enters the liquid phase along the reaction vessel wall. 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 down the cooling device surface or the reactor wall and 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. 230-275 for constant temperature
It is preferred 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 for 1 to 6 hours. In order to obtain a higher molecular weight PAS, it is preferable to use two or more reaction temperature profiles. This 2
When performing a step operation, the first step is preferably performed at a temperature of 195 to 240 ° C. If the temperature is low, the reaction rate is too low, which is not practical. If the temperature is higher than 240 ° C., the reaction rate is too high, so that not only a sufficiently high molecular weight PAS cannot be obtained, but also the side reaction rate is significantly increased. The end of the first phase,
The residual ratio of the dihalo aromatic compound in the polymerization reaction system is 1 mol% to 40 mol%.
It is preferable to carry out the reaction at a time point when the molar% is within the range of 3,000 to 20,000. More preferably, the residual ratio of the dihalo aromatic compound in the polymerization reaction system is in the range of 2 mol% to 15 mol%, and the molecular weight is in the range of 5,000 to 15,000. Residual rate is 40 mol%
If it exceeds 2,000, side reactions such as depolymerization are likely to occur in the second stage reaction, while if it is less than 1 mol%, high molecular weight P
It is hard 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
When the temperature is higher than 270 ° C., side reactions such as depolymerization are liable to occur, making it difficult to stably obtain a high molecular weight product.

As an actual operation, first, under an inert gas atmosphere, dehydration or water addition is performed as 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 the alkali metal sulfide 1
It is 0.5 to 2.5 mol, especially 0.8 to 1.2 mol, per mol. If it exceeds 2.5 moles, 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 the amount is less than 0.5 mol, the reaction rate is too high to obtain a product having a sufficient high molecular weight, and undesirable reactions such as side reactions occur.

In the case of a one-stage reaction at a constant temperature, the cooling of the gas phase during the reaction is preferably carried out from the start of the reaction, but must be carried out at least in the course of raising the temperature to 250 ° C. or lower. 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. The degree of the cooling effect is usually the most suitable index of the pressure in the reactor. The absolute value of the pressure varies depending on the characteristics of the reaction vessel, the stirring state, the amount of water in the system, the molar ratio of the dihalo aromatic compound to the alkali metal sulfide, and the like. However, when the pressure in the reaction vessel is reduced as compared with the case where the reaction vessel is not cooled under the same reaction conditions, the amount of the reflux liquid increases, which means that the temperature at the gas-liquid interface of the reaction solution decreases. It is considered that the relative degree of decrease indicates the degree of separation between a layer having a high water content and a layer having no water content. Therefore, it is preferable to perform cooling to such an extent that the internal pressure of the reaction vessel is 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.

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

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

Dihaloaromatic compounds are described in, for example,
It can be selected from those described in JP-A-5-3368, but is preferably p-dichlorobenzene. Further, a copolymer can be obtained by using one or more kinds of para-, meta- or ortho-dihalides of diphenyl ether, diphenyl sulfone or biphenyl in a small amount (20 mol% or less). For example, m-dichlorobenzene, o-dichlorobenzene,
p, p'-dichlorodiphenylether, m, p'-dichlorodiphenylether, m, m'-dichlorodiphenylether, p, p'-dichlorodiphenylsulfone, m, p'-dichlorodiphenylsulfone, m, m '
-Dichlorodiphenyl sulfone, p, p'-dichlorobiphenyl, m, p'-dichlorobiphenyl, m, m'-
Dichlorobiphenyl.

Further, as a small amount of additives, a terminal terminator, a monohalide as a modifying agent, or a molecular weight regulator such as thiophenol or diphenyl disulfide may be used in combination.

The high molecular weight PAS thus obtained is separated from by-products by work-up methods known to those skilled in the art.

The upper limit of the melt viscosity V ₆ of the thermally oxidatively crosslinked PAS (B) of the present invention is 20,000 poise, preferably 1 poise.
It is 5,000 poise, particularly preferably 12,000 poise, and the lower limit is 200 poise, preferably 250 poise, particularly preferably 300 poise. If the upper limit is exceeded, the thermal stability decreases and molding becomes difficult. If the lower limit is less than the lower limit, the adhesive strength of the molded article becomes extremely low, which is not preferable. Here, the melt viscosity V ₆ is measured in the same manner as described above.

The non-Newtonian index N of the thermally oxidized crosslinked PAS (B) has a lower limit of 1.1, preferably 1.15;
The upper limit is 2.0, preferably 1.95. If the amount is less than the above lower limit, a crosslinked structure cannot be sufficiently obtained, and if the amount exceeds the above upper limit, the thermal stability decreases and molding becomes difficult, which is not preferable. Here, the non-Newton index N is the same as the above.

The thermally oxidatively crosslinked PAS (B) of the present invention must further satisfy the following formula (1).

[0034]

Log [melt viscosity V ₆ of the above-mentioned thermally oxidized crosslinked polyarylene sulfide] / log [melt viscosity V ₆ of the polyarylene sulfide (b) before being converted into the above thermally oxidized crosslinked polyarylene sulfide by the thermal oxidation treatment. ] = 1.
01 to 1.55 (1) The thermally oxidatively crosslinked PAS (B) can be produced by thermally oxidatively crosslinking PAS in an oxygen-containing atmosphere. the ratio of the logarithm of the melt viscosity V ₆ of the PAS of 1.01 to 1.55, preferably 1.10 to 1.50. Below the lower limit,
If the crosslinked structure is not sufficiently obtained, and if the above upper limit is exceeded, the welding strength of the molded article is significantly reduced, which is not preferable.

Thermal oxidation crosslinking PAS by thermal oxidation
The PAS (b) before (B) is not particularly limited, and any PAS produced by a conventionally known method can be used. Preferably PAS is used having a melt viscosity V ₆ of 70～3,000 poise. Further, a branched PAS (A) having a melt viscosity V ₆ in the above range can also be used.

Heat treatment of the above PAS (b) in an oxygen-containing atmosphere to obtain a thermally oxidatively crosslinked PAS (B) can be performed by a known method. The temperature at which the heat treatment is performed is preferably 100 to 280 ° C, particularly preferably 170 to 250 ° C. When the temperature is lower than the above range, the time required for the heat treatment increases, and when the temperature is higher than the above range, thermal stability during melting is poor. The time required for thermal oxidation treatment vary by melt viscosity V ₆ and non-Newtonian index N of the heating temperature or the desired PAS, preferably 0.5 to 120 hours, particularly preferably 1 to 90 hours.

The above-mentioned heat treatment is preferably carried out in an oxygen-containing atmosphere such as air, pure oxygen or the like and a mixture thereof with any suitable inert gas. Examples of the inert gas include water vapor, nitrogen, carbon dioxide, and the like, and a mixture thereof. The concentration of oxygen in the oxygen-containing atmosphere is preferably 0.5 to 50% by volume, particularly preferably 10 to 25% by volume. If the oxygen concentration exceeds the above range, the amount of generated radicals increases and the viscosity at the time of melting becomes remarkable, and the hue becomes dark, which is not preferable. If the oxygen concentration is lower than the above range, the rate of thermal oxidation becomes unfavorably low.

The apparatus for performing the heat treatment may be a batch type or a continuous type, and a known apparatus can be used. For example, a device for bringing PAS into contact with an oxygen-containing gas in a closed vessel equipped with a stirrer can be used, and a fluidized bed thermal oxidation treatment apparatus equipped with a stirrer is preferably used. The use of such a device makes it possible to reduce the temperature distribution in the bath. As a result, thermal oxidation can be promoted, and non-uniformity of the molecular weight can be prevented.

When the above-mentioned oxidative crosslinking is carried out, a radical initiator, a radical polymerization aid and the like can be added to enhance the crosslinking of PAS. Examples of such compounds include peroxides such as benzoyl peroxide, lauroyl peroxide and dicumyl peroxide, and azo compounds such as azoisobutyronitrile.

In the welding rod for a polyarylene sulfide molded article of the present invention, the blending amounts of the branched PAS (A) and the thermally oxidized crosslinked PAS (B) are (A) 100 to 0 parts by weight and (B) 0 to 0 parts by weight. 100 parts by weight.

In the present invention, an inorganic filler (C) can be further blended as an optional component. The inorganic filler (C) is not particularly limited, and for example, a powdery / flaky filler, a fibrous filler, and the like can be used. Examples of the powdery / flaky filler include alumina, talc, mica, kaolin, clay, titanium oxide, calcium carbonate,
Calcium silicate, calcium phosphate, calcium sulfate, magnesium oxide, magnesium phosphate, silicon nitride, glass, hydrotalcite, zirconium oxide,
Glass beads, carbon black and the like can be mentioned. Examples of the fibrous filler include glass fiber, asbestos fiber, carbon fiber, silica fiber, silica / alumina fiber, potassium titanate fiber, and polyaramid fiber. In addition, a filler such as a ZnO tetrapot, a metal salt (eg, zinc chloride, lead sulfate, etc.), an oxide (eg, iron oxide, molybdenum dioxide, etc.), and a metal (eg, aluminum, stainless steel, etc.) may be used. it can. 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 necessary.

The blending amount of the inorganic filler (C) is determined by the amount of the branched PA
The upper limit is 400 parts by weight, preferably 200 parts by weight, based on a total of 100 parts by weight of S (A) and the thermally oxidized crosslinked PAS (B).
Parts by weight, particularly preferably 100 parts by weight. If (C) exceeds the above upper limit, the moldability deteriorates, which is not preferable. In order to increase the mechanical strength, it is preferable to add 0.01 parts by weight or more.

Further, other resins and elastomers can be added to the welding rod of the present invention as long as the object of the present invention is not impaired. As the resin and elastomer, for example, ethylene, propylene, butylene, pentene, butadiene, isoprene, chloroprene, styrene, α-
Homopolymers and copolymers such as methylstyrene, vinyl acetate, vinyl chloride, acrylate, (meth) acrylonitrile, polyamide, polyester, polyurethane, polyacetal, polycarbonate, polysulfone, polyallylsulfone, polyethersulfone, poly Homopolymers such as arylate, polyphenylene oxide, polyetheretherketone, polyimide, silicone resin, phenoxy resin, fluororesin, polyarylether, polysulfide, random copolymer, block copolymer, graft copolymer, other than the above Elastomers.

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

The welding rod of the present invention can be produced by extruding the above-mentioned PAS or its composition into a rod shape using a conventional melt-kneading extruder such as a twin-screw extruder. The dimensions of the welding rod can be arbitrarily selected according to the size of the molded article to be welded, the location to be welded, and the like. The diameter of the welding rod is preferably 2 to 4 mm from the viewpoint of workability and the like.

Although the composition of the PAS compact to be welded by the welding rod of the present invention is not particularly limited, it is preferable that the PAS compact has the same composition as the welding rod used in order to obtain better welding strength. The PAS compact may be PAS alone, or may be a mixture of PAS and the above-mentioned inorganic filler or the like. Examples of the PAS molded body include a sheet, a plate, and a tube.

The welding between the PAS compacts can be performed using a known hot jet welding machine. For example,
Heated air is circulated by a hot jet welding machine and PA
Welding can be performed while melting the joint of the S compact and the PAS welding rod.

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

[0049]

【Example】

[0050]

Examples 1 to 14 and Comparative Examples 1 to 3
Flow tester was used in the measurement of melt viscosity V ₆ is a Shimadzu flow tester CFT-500C. The capillograph used for obtaining the non-Newton index N is Capillograph 1BP-TOYO SEIKI SEISAKUSHO.
C.

PPS used in Examples and Comparative Examples
Was produced as follows. <Production of Branched PPS (A)> Synthesis Example 1 15.400 kg of flaky sodium sulfide (60.81% by weight Na ₂ S) and N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) were placed in a 150-liter autoclave. 45.0 kg was charged. The temperature was raised to 209 ° C. while stirring under a nitrogen stream to distill 3.75 kg of water. Thereafter, the autoclave was sealed and cooled to 180 ° C., and 18.000 kg of paradichlorobenzene (hereinafter sometimes abbreviated as p-DCB) [Na ₂ S / p-D
CB (molar ratio) = 0.980], 128.7 g of 1,2,4-trichlorobenzene (hereinafter sometimes abbreviated as 1,2,4-TCB) [1,2,4-TCB / Na ₂ S]
(Molar ratio) = 0.006] and 18.0 kg of NMP. 1 kg / cm using nitrogen gas at a liquid temperature of 150 ° C
^The temperature was increased by pressurizing to ² G. When the liquid temperature reached 240 ° C., cooling was started by sprinkling water on the top of the autoclave, and thiophenol 6 was added using a pressure injection machine.
5.1 g [thiophenol / Na ₂ S (molar ratio) = 0.
005] was added into the autoclave. P at the time of the addition
-The conversion of DCB was 89.1%. After the addition of thiophenol was completed, the temperature was raised to 260 ° C., and the reaction was allowed to proceed while stirring at this temperature for 3 hours. Next, the temperature was lowered and the cooling at the top of the autoclave was stopped. During the 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 was 8.91 kg / cm ² G.

The obtained slurry was filtered to remove the solvent, and then washed with warm water three times according to a conventional method. Next, the filter cake was slurried with water at about 50 ° C., and acid treatment was performed by adding acetic acid to the slurry to adjust the pH to 5. After the acid treatment, the washing with warm water was repeated twice. Next, the product was dried in a hot air circulating drier at 120 ° C. for about 5 hours to obtain a white powdery product.

The melt viscosity V ₆ of the obtained PPS (branched PPS-1) was 680 poise, and the non-Newton index N
Was 1.49.

The conversion of p-DCB was 98.7%, and the conversion of 1,2,4-TCB was 100%.

Synthesis Example 2 In a 150-liter autoclave, 19.478 kg of flaky sodium sulfide (60.1% by weight Na ₂ S) and N
45.0 kg of MP was charged. The temperature was raised to 209 ° C. while stirring under a nitrogen stream to distill out 4.856 kg of water. Thereafter, the autoclave was sealed and cooled to 180 ° C., and 22.780 kg of p-DCB [Na ₂ S / p-D
CB (molar ratio) = about 0.968] and NMP 18.0k
g. 1 kg using nitrogen gas at a liquid temperature of 150 ° C
/ Cm ² G and the temperature was raised. While stirring at a liquid temperature of 215 ° C. for 7 hours, cooling was started by sprinkling water on the upper part of the autoclave. Next, 1,3,5-TCB0.
129 kg (about 0.475 mol% based on sodium sulfide)
Was dissolved in 0.5 kg of NMP and injected into an autoclave with a small high-pressure pump. Thereafter, the temperature was raised, and the mixture was stirred at a liquid temperature of 260 ° C. for 3 hours. Then, the temperature was lowered and water spraying to the upper part of the autoclave was stopped. During the 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 was 8.89 kg / cm ² G.

The obtained slurry was filtered and washed three times with warm water by a conventional method, and then dried in a hot air circulating drier at 120 ° C. for about 5 hours to obtain a white powdery product.

The obtained PPS (branched PPS-2) has a melt viscosity V ₆ of 2330 poise and a non-Newtonian index N
Was 1.57.

The conversion of p-DCB was 98.4%, and the conversion of 1,3,5-TCB was 100%.

Synthesis Example 3 In a 150-liter autoclave, 19.000 kg of flaky sodium sulfide (60.1% by weight Na ₂ S) and N were added.
45.0 kg of MP was charged. The temperature was raised to 209 ° C. while stirring under a nitrogen stream to distill 4.91 kg of water.
Thereafter, the autoclave was closed and cooled to 180 ° C., and 21.639 kg of p-DCB [Na ₂ S / p-DC
B (molar ratio) = about 0.994], 1,2,4-TCB7
4.3 g (about 0.28 mol% based on sodium sulfide) and 18.0 kg of NMP were charged. At a liquid temperature of 150 ° C., the pressure was increased to 1 kg / cm ² G using nitrogen gas, and the temperature was raised. While stirring at a liquid temperature of 220 ° C. for 5 hours, the upper part of the autoclave was sprinkled to cool the gas phase of the autoclave. Thereafter, the temperature was raised, and the mixture was stirred at a liquid temperature of 260 ° C. for 5 hours. Then, the temperature was lowered and the cooling at the top of the autoclave was stopped. During the 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 8.6
It was 0 kg / cm ² G.

The obtained slurry was repeatedly filtered and washed with warm water by a conventional method, and dried at 120 ° C. for about 8 hours in a circulating hot air drier to obtain a white powdery product.

The melt viscosity V ₆ of the obtained PPS (branched PPS-3) was 30,300 poise, and the non-Newton index N was 2.00.

The conversion of p-DCB was 99.2%, and the conversion of 1,2,4-TCB was 100%.

Synthesis Example 4 A 150-liter autoclave was charged with 15.400 kg of flaky sodium sulfide (60.81% by weight Na ₂ S) and 45.0 kg of NMP. The temperature was raised to 209 ° C. while stirring under a nitrogen stream to distill 3.75 kg of water. Thereafter, the autoclave was sealed and cooled to 180 ° C., and 18.186 kg of p-DCB [Na ₂ S / p-D
CB (molar ratio) = 0.970], 1,2,4-TCB1
28.7 g [1,2,4-TCB / Na ₂ S (molar ratio)
= 0.006] and 18.0 kg of NMP. At a liquid temperature of 150 ° C., the pressure was increased to 1 kg / cm ² G using nitrogen gas, and the temperature was raised. When the liquid temperature reached 240 ° C., cooling was started by sprinkling water on the upper part of the autoclave, and 65.1 g of thiophenol was used using a pressure injector.
[Thiophenol / Na ₂ S (molar ratio) = 0.005]
Was added to the autoclave. P-DCB at the time of the addition
Was 89.0%. After the addition of thiophenol was completed, the temperature was raised to 260 ° C., and the reaction was allowed to proceed while stirring at this temperature for 3 hours. Next, the temperature was lowered and the cooling at the top of the autoclave was stopped. During the 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 was 8.88 kg / cm ² G.

The obtained slurry was filtered to remove the solvent, and then washed with warm water three times in a usual manner. Next, the filter cake was slurried with water at about 50 ° C., and acid treatment was performed by adding acetic acid to the slurry to adjust the pH to 5. After the acid treatment, the washing with warm water was repeated twice. Next, the product was dried in a hot air circulating drier at 120 ° C. for about 5 hours to obtain a white powdery product.

The melt viscosity V ₆ of the obtained PPS (branched PPS-4) is 340 poise, and the non-Newton index N
Was 1.17.

The conversion of p-DCB was 98.3%, and the conversion of 1,2,4-TCB was 100%. <Production of Thermal Oxidation Crosslinkable PPS (B)> Synthesis Example 5 18.743 kg of flaky sodium sulfide (60.9% by weight Na ₂ S) and N were placed in a 150-liter autoclave.
45.0 kg of MP was charged. The temperature was raised to 209 ° C. while stirring under a nitrogen stream to distill 4.600 g of water.
Thereafter, the autoclave was sealed and cooled to 180 ° C., and p-DCB (22.165 kg [Na ₂ S / p-DC
B (molar ratio) = 0.970] and 0.064 kg of diphenyl disulfide (hereinafter may be abbreviated as DDS)
(0.2 mol% based on the charged sodium sulfide) and NMP1
8.0 kg was charged. At a liquid temperature of 150 ° C., the pressure was increased to 1 kg / cm ² G using nitrogen gas, and the temperature was raised. Liquid temperature 2
The mixture was stirred at 60 ° C. for 3 hours to advance the reaction, and then the temperature was lowered.

The obtained slurry was filtered to remove the solvent, and then the solvent-containing filter cake was heated at 220 ° C. for about 6 hours in a nitrogen stream to remove the solvent. Next, water washing and filtration were repeated 7 times on the obtained PPS powder by a conventional method.
The product was dried in a hot air circulating drier at 0 ° C. for about 8 hours to obtain a white powdery product.

The melt viscosity V ₆ of the obtained PPS (b) is 1
It was 20 poise. The reaction rate of p-DCB is 9
It was 8.2% and the conversion of DDS was 100%.

Next, the PPS was charged into a simple thermal oxidation treatment apparatus and heat-treated at 230 ° C. for 24 hours to obtain a melt viscosity V _6.
Is 310 poise and the non-Newtonian index N is 1.13.
(Thermally oxidized crosslinked PPS-5) was obtained.

Synthesis Example 6 The same procedure as in Synthesis Example 5 was carried out except that heat treatment was performed at 230 ° C. for 130 hours. PPS (thermal oxidation) having a melt viscosity V ₆ of 980 poise and a non-Newton index N of 1.33 was performed. Crosslinked PPS-6) was obtained.

Synthesis Example 7 In a 150-liter autoclave, 18.743 kg of flaky sodium sulfide (60.9 wt% Na ₂ S) and N
45.0 kg of MP was charged. The temperature was raised to 209 ° C. while stirring under a nitrogen stream to distill 4.600 kg of water. Thereafter, the autoclave was sealed and cooled to 180 ° C., and 21.828 kg of p-DCB [Na ₂ S / p-D
CB (molar ratio) = 0.985] and 18.0 kg of NMP. 1 kg / c using nitrogen gas at a liquid temperature of 150 ° C
The temperature was increased by pressurizing to m ² G. The mixture was stirred at a liquid temperature of 260 ° C. for 3 hours to advance the reaction, and then cooled.

The obtained slurry was filtered to remove the solvent, and then the solvent-containing filter cake was heated at 220 ° C. for about 6 hours in a nitrogen stream to remove the solvent. Next, water washing and filtration were repeated 7 times on the obtained PPS powder by a conventional method.
The product was dried in a hot air circulating drier at 0 ° C. for about 8 hours to obtain a white powdery product.

The melt viscosity V ₆ of the obtained PPS (b) was 4
It was 30 poise. The reaction rate of p-DCB is 9
It was 8.8%.

Next, the PPS was charged into a simple thermal oxidation treatment apparatus and heat-treated at 230 ° C. for 35 hours to obtain a melt viscosity V _6.
Is 1,120 poise and the non-Newton index N is 1.
A PPS of 19 (thermo-oxidatively crosslinked PPS-7) was obtained.

Synthesis Example 8 The same procedure as in Synthesis Example 7 was carried out except that the heat treatment was carried out at 230 ° C. for 48 hours. PPS having a melt viscosity V ₆ of 1940 poise and a non-Newton index N of 1.29 was used. Oxidative crosslinking type PPS-8) was obtained.

Synthesis Example 9 In a 150-liter autoclave, 19.000 kg of flaky sodium sulfide (60.1% by weight Na ₂ S) and N were added.
45.0 kg of MP was charged. The temperature was raised to 209 ° C. while stirring under a nitrogen stream to distill 4.91 kg of water.
Thereafter, the autoclave was closed and cooled to 180 ° C., and 21.639 kg of p-DCB [Na ₂ S / p-DC
B (molar ratio) = 0.994] and 18.0 kg of NMP. 1 kg / c using nitrogen gas at a liquid temperature of 150 ° C
The temperature was increased by pressurizing to m ² G. While stirring at a liquid temperature of 220 ° C. for 5 hours, the upper part of the autoclave was cooled by sprinkling water. Thereafter, the temperature was raised, and the reaction was allowed to proceed while stirring at 260 ° C. for 5 hours. Next, the temperature was lowered and the cooling at the top of the autoclave was stopped. While cooling the top of the autoclave,
The liquid temperature was kept constant so as not to drop. The maximum pressure during the reaction was 8.60 kg / cm ² G.

The obtained slurry was repeatedly filtered and washed with warm water in a usual manner, and dried in a hot air circulating drier at 120 ° C. for about 8 hours to obtain a white powdery product.

The melt viscosity V ₆ of the obtained PPS (b) was 1,080 poise. The conversion of p-DCB was 98.6%.

Next, the PPS was charged into a simple thermal oxidation treatment apparatus and heat-treated at 230 ° C. for 18 hours to obtain a melt viscosity V _6.
Is 9080 poise and the non-Newton index N is 1.8
As a result, PPS (Thermal Oxidation Crosslinkable PPS-9) was obtained. <Production of Comparative PPS> Synthesis Example 10 A 150-liter autoclave was charged with 15.400 kg of flaky sodium sulfide (60.81% by weight Na ₂ S) and 45.0 kg of NMP. The temperature was raised to 209 ° C. while stirring under a nitrogen stream to distill 3.75 kg of water. Thereafter, the autoclave was sealed and cooled to 180 ° C., and 18.242 kg of p-DCB [Na ₂ S / p-D
CB (molar ratio) = 0.967], 1,2,4-TCB1
28.7 g (0.6 mol% based on sodium sulfide) and 18.0 kg of NMP were charged. At a liquid temperature of 150 ° C., the pressure was increased to 1 kg / cm ² G using nitrogen gas, and the temperature was raised. When the liquid temperature reached 240 ° C., cooling was started by sprinkling water on the top of the autoclave, and 65.1 g (0.5 mol% based on sodium sulfide) of thiophenol was introduced into the autoclave using a pressure injection machine. Was added. The conversion of p-DCB at the time of the addition was 88.9%. After the addition of thiophenol was completed, the temperature was raised to 260 ° C.
The reaction was allowed to proceed while stirring at this temperature for 3 hours. Next, the temperature was lowered and the cooling at the top of the autoclave was stopped. During the 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 8.93 kg / cm ² G
Met. After completion of the reaction, the conversion of p-DCB was 98.
7%.

The obtained slurry was filtered to remove the solvent, and the washing with warm water was repeated three times according to a conventional method. Next, the filter cake was slurried with water at about 50 ° C., and acetic acid was added to the slurry to adjust the pH to 5 to perform an acid treatment. After the acid treatment, the washing with warm water was repeated twice. Next, the product was dried in a hot air circulating drier at 120 ° C. for about 5 hours to obtain a white powdery product.

The resulting PPS (branched PPS-10) had a melt viscosity V ₆ of 150 poise and a non-Newtonian index N
Was 1.09.

Synthesis Example 11 PPS having a melt viscosity V ₆ of 1,980 poise and a non-Newton index N of 1.61 was carried out in the same manner as in Synthesis Example 5 except that the heat treatment was carried out at 230 ° C. for 340 hours. A thermally oxidized crosslinked PPS-11) was obtained.

Synthesis Example 12 PPS having a melt viscosity V ₆ of 18,200 poise and a non-Newton index N of 2.06 was carried out in the same manner as in Synthesis Example 7 except that the heat treatment was performed at 230 ° C. for 144 hours. A thermally oxidized crosslinked PPS-12) was obtained.

Table 1 shows the properties of each PPS.

[0085]

Here, the value of the formula (1) is defined as log [melt viscosity V _{6 of} thermo-oxidatively crosslinked polyarylene sulfide (B)].
/ Log [the melt viscosity V ₆ of the polyarylene sulfide (b) before being converted into the above-mentioned thermo-oxidative cross-linked polyarylene sulfide by the thermal oxidation treatment] is shown.

The inorganic filler (C) used is as follows. <Glass fiber> CS 3J-961S (trademark), manufactured by Nitto Boseki Co., Ltd. <Calcium carbonate> SL-1000 (trademark), manufactured by Takehara Chemical Co., Ltd. Examples and comparative examples were measured as follows. . (1) Preparation of welding rod After mixing each amount of PPS, glass fiber or calcium carbonate in the amount (parts by weight) shown in Tables 2 and 3 with a Henschel mixer, kneading was performed at 320 ° C. using a biaxial counter-rotating extruder. The PPS welding rod was extruded to have a diameter of about 3 mm. (2) Preparation of test piece Each PPS, glass fiber or calcium carbonate in the amount (parts by weight) shown in Tables 2 and 3 was mixed with a Henschel mixer, and then kneaded at 320 ° C. using a biaxially different-direction rotary extruder. Thus, a pellet was prepared. Next, the pellets were supplied to an injection molding machine, and a cylinder temperature of 320 ° C. and a mold temperature of 130 ° C.
A test piece of 127 × 75 × 3 mm was prepared at a temperature of ° C. (3) Measurement of welding strength Two test pieces were butt-joined at short sides and welded at 430 ° C. using a welding rod by a hot jet welding machine. The tensile strength of the welded dumbbell pieces was measured by a tensile tester (distance between chucks: 200 mm, tensile speed: 5 mm / min).

The above results are shown in Tables 2 and 3.

[0088]

[Table 2]

[0089]

Table 3 shows the results of welding test pieces having the same composition using the welding rod of the present invention composed of branched PPS and glass fiber. Good welding strength was obtained. Example 2 is the result of using the same PPS as in Example 1 and using a welding rod made of a mixture of glass fiber and calcium carbonate. The welding strength was slightly reduced as compared with Example 1, but did not impair the effects of the present invention.
Example 3 is different from PPS used in Example 1 in that
V ₆ and N both use higher PPS.
Higher welding strength was obtained compared to Example 1. Example 4 uses PPS in which both V ₆ and N are significantly higher than the previous two PPS. Higher welding strength was obtained. Example 14 is based on the PP used in Example 1.
Compared to S, V ₆ and N both use lower PPS. The welding strength was slightly reduced as compared with Example 1, but did not impair the effects of the present invention.

Example 5 shows the results of welding test pieces having the same composition using the welding rod of the present invention composed of thermally oxidized crosslinked PPS and glass fiber. Although the welding strength was slightly reduced as compared with Example 1 using the branched PPS, the effect of the present invention was sufficiently exhibited. Example 6 is a result of using the same PPS as in Example 5 and using a welding rod made of a mixture of glass fiber and calcium carbonate. The welding strength was slightly reduced as compared with Example 5, but did not impair the effects of the present invention. Examples 7 to 9
Is the one using PPS having both higher V ₆ and N than the PPS used in Example 5. In each case, the welding strength was good. Example 10 uses V ₆ and N
Are those using a thermally oxidatively crosslinked PPS. High welding strength was obtained.

In Example 11, the branched PPS and the crosslinked PP were used.
It is the result of welding the test piece which has the same composition using the welding rod of this invention which consists of S and glass fiber. High welding strength was obtained. In Examples 12 and 13, both the composition of the welding rod and the composition of the test piece were different. In each case, high adhesive strength was obtained.

Comparative Example 1 uses a branched PPS having both V ₆ and N less than the range of the PPS (A) of the present invention. The welding strength was significantly lower. Comparative Example 2
The thermal oxidative crosslinking type PPS having a value of the formula (1) exceeding the range of the PPS (B) of the present invention is used. The welding strength was remarkably low. Comparative Example 3 uses a thermally oxidized crosslinked PPS in which both N and the value of formula (1) exceed the range of the PPS (B) of the present invention. The welding strength was remarkably low.

[0093]

According to the present invention, there is provided a welding rod which provides high welding strength when bonding PAS molded bodies to each other by welding.
And a P having high welding strength joined by the welding rod
An AS molded article is provided.

Claims (6)

[Claims] (A) a melt viscosity V ₆ of 200 to 50,000
Branched polyarylene sulfide having a poise of 0 and a non-Newton index N of 1.15 or more
Parts, and (B) a melt viscosity V ₆ is 200～20,00
0 poise and the non-Newton index N is 1.1 to
2.0, and further satisfies the following formula (1): 0-100 parts by weight of the thermal oxidative crosslinking type polyarylene sulfide log [melt viscosity V _{6 of the} thermal oxidative crosslinking type polyarylene sulfide] / log [Melt viscosity V ₆ of polyarylene sulfide (b) before thermal oxidation crosslinkable polyarylene sulfide is formed by thermal oxidation treatment] = 1.
A welding rod for a polyarylene sulfide molded body, comprising: 2. A branched polyarylene sulfide (A)
Is 0.1% with respect to alkali metal sulfide, dihalo aromatic compound and charged alkali metal sulfide in an organic amide solvent.
Reacting 2 to 1.0 mole% of a polyhalo aromatic compound;
2. The welding method according to claim 1, wherein during the reaction, a part of a gas phase in the reaction vessel is condensed by cooling a gas phase part of the reaction vessel, and this is refluxed to a liquid phase. rod. 3. The polyarylene sulfide (b) having a molecular weight of 7
0～3,000 poise welding rod of a polyarylene sulfide according to claim 1 or 2, wherein the polyarylene sulfide which is produced by treating thermally oxidized bridge having a melt viscosity V ₆ of. 4. The method according to claim 1, wherein the polyarylene sulfide (b) is used in an organic amide-based solvent in an amount of from 0.2 to 0.2 mol% with respect to the alkali metal sulfide, the dihaloaromatic compound and the charged alkali metal sulfide.
1.0 mol% of a polyhalo aromatic compound is reacted, and during the reaction, a part of a gas phase in the reaction vessel is condensed by cooling a gas phase part of the reaction vessel, and this is refluxed to a liquid phase. The welding rod according to claim 1, wherein the welding rod is manufactured. 5. A branched polyarylene sulfide (A)
And an inorganic filler (C) in an amount of 0 to 40 with respect to a total of 100 parts by weight of the polyarylene sulfide (B).
The welding rod according to any one of claims 1 to 4, comprising 0 parts by weight. 6. A polyarylene sulfide molded article welded by the welding rod according to claim 1. Description: