JPH08333512A - Polyurethane sulfide resin composition for blow forming - Google Patents

Abstract

PURPOSE: To obtain a composition having little drawdown of a parison during blow formation and capable of producing a forming having excellent appearance by compounding a modified olefin elastomer obtained by grafting a specific glycidyl compound in a specific amount. CONSTITUTION: This composition is obtained by compounding (A) 100 pts.wt. of a polyarylene sulfide having a melt viscosity of 2,500-30,000 poise with (B) 3-200 pts.wt. of a modified olefin elastomer obtained by grafting a glycidyl compound of formula I [R is H or a 1-6C alkyl; Ar is a 6-20C aromatic hydrocarbon having a glycidyloxy group; (m)=1-4], e.g. a compound of formula II. Further, the component A is obtained by reacting an alkali metal sulfide with a dihaloaromatic compound in an organic amide solvent while condensing a part of the gaseous phase in a reaction vessel by cooling it and recycling the condensate to the liquid phase during reaction.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyarylene sulfide resin composition for blow molding.

[0002]

2. Description of the Related Art Polyarylene sulfide (hereinafter referred to as P
(Sometimes abbreviated as AS) has excellent resistance to acids, alkalis, various organic solvents and the like. Therefore, a bottle blow-molded from PAS is a container for medical use, food use, or various chemicals, such as a bottle, a tank,
Suitable for applications such as flasks.

However, when the blow molding method commonly used for general thermoplastic resins is applied in the blow molding of PAS, PAS has a weak melt tension most required for blow molding and draws down the parison. There was a problem.

In view of such a problem, Japanese Patent Laid-Open No. 61-2 / 1986
No. 55832 discloses a melt viscosity of 3,000 to 20,0.
Injection stretch blow molding of 00 poise of substantially linear PAS is disclosed. However, in the manufacturing method, a bottomed parison is first molded from the above PAS by injection molding, and then a rod is pushed through the opening of the bottomed parison to stretch it in the longitudinal direction, and then a gas is blown to blow it horizontally. Since the operation procedure of stretching in the direction is taken, there is a problem that the operation is complicated and the apparatus becomes expensive.

Japanese Unexamined Patent Publication No. 3-247436 discloses a PA
Hollow molding characterized by blending 100 parts by weight of an alkoxysilane compound, for example, vinylalkoxysilane, epoxyalkoxysilane, aminoalkoxysilane, allylalkoxysilane or mercaptoalkoxysilane 0.01 to 5 parts by weight, and blow molding The manufacturing method of the product is described. However, the PAS melt tension was not sufficiently improved, and drawdown of the parison during blow molding could not be sufficiently suppressed.

Japanese Patent Publication No. 6-98673 discloses a deionized polyphenylene sulfide (hereinafter referred to as PPS).
A blow hollow molded article having a PPS resin composition as a main constituent, which is obtained by adding an inorganic filler as an optional component to a resin composed of an epoxy group-containing olefin-based copolymer. ing. The epoxy group-containing olefin-based copolymer is composed of α-olefin such as ethylene, propylene and butene-1, and glycidyl ester of α, β-unsaturated acid such as glycidyl acrylate, glycidyl methacrylate and glycidyl ethacrylate. It consists of Even when the composition was used, the PAS melt tension was not sufficiently improved, and drawdown of the parison during blow molding could not be sufficiently suppressed.

[0007]

DISCLOSURE OF THE INVENTION The present invention provides a polyarylene sulfide resin composition which has a small drawdown of a parison during blow molding and gives a blow molded article having good appearance characteristics.

[0008]

Means for Solving the Problems The present inventors have conducted extensive studies to solve the above-mentioned various drawbacks. As a result, by blending PAS having a predetermined melt viscosity V ₆ with a specific modified olefin elastomer, the drawdown of the parison during blow molding of PAS can be remarkably improved, and the PAS blow having excellent appearance characteristics can be obtained. They have found that a molded product can be obtained, and completed the present invention.

That is, according to the present invention, 100 parts by weight of (A) a polyarylene sulfide having a melt viscosity V ₆ of 2,500 to 30,000 poise and (B) an olefin elastomer are added to glycidyl represented by the following formula (I). Modified olefin elastomer grafted with compound 3-20
0 parts by weight

[0010]

Embedded image (In the formula, each R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Ar represents an aromatic hydrocarbon group having 6 to 20 carbon atoms having at least one glycidyloxy group, m represents an integer of 1 to 4), and is a polyarylene sulfide resin composition for blow molding.

The resin composition of the present invention is characterized in that the melt viscosity V _{6 of} PAS is the above-mentioned predetermined value, and that the above-mentioned predetermined modified olefin elastomer is combined therewith. PAS with V ₆ outside the above range
Or the use of a polymer other than the above-mentioned predetermined modified olefin elastomer, the effect of the present invention cannot be exhibited.

Japanese Unexamined Patent Publication Nos. 6-9850 and 5-3
No. 20508, No. 5-320509, No. 6-184432, and No. 6-88024.
The publication describes a resin composition comprising PAS and the above component (B). PA described in the above publication
S is respectively PAS having an alkali metal content reduced to 900 ppm or less by deionization, PAS modified with an epoxy resin, a resin mixture composed of PAS and a polyester resin, a resin mixture composed of PAS and a polyamide resin, and It is a PAS having an amino group in the side chain. PAS of the present invention, the melt viscosity V ₆ 2,500~30,00
It is limited to 0 poise. Further, the PAS resin compositions described in the above publications all have good mechanical strength,
It has significantly improved impact resistance while maintaining elastic modulus and heat resistance. On the other hand, P of the present invention
The AS resin composition is used for blow molding, and has a small drawdown of the parison at the time of blow molding, and provides a blow molded product having good appearance characteristics.

The melt viscosity V ₆ of (A) PAS used in the present invention has an upper limit of 30,000 poises, preferably 15,000 poises, particularly preferably 8,000 poises, and a lower limit of 2,500 poises. Preferably 2,80
0 poise, particularly preferably 3,000 poise. If it exceeds the upper limit, the moldability is deteriorated and blow molding becomes difficult, and if it is less than the lower limit, the effect of the present invention cannot be achieved, and the strength of the molded product is remarkably lowered, which is not preferable. Here, the melt viscosity V ₆ was 300 ° C. using a flow tester, a load of 20 kgf / cm ² , and L / D = 10.
It is the viscosity (poise) measured after holding for 6 minutes.

There is no particular limitation on the method for producing the above (A) PAS. The following method can be preferably used.

That is, in the method for producing PAS by reacting an alkali metal sulfide with a dihalo aromatic compound in an organic amide solvent, in the reaction vessel, the gas phase portion of the reaction vessel is cooled during the reaction. This is a method in which a part of the gas phase is condensed and then refluxed in the liquid phase. As the method, the method described in JP-A-5-222196 can be used.

The refluxed liquid has a high water content compared to the liquid-phase bulk because of the difference in vapor pressure 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. However, the addition of water is not excluded at all. However, with the addition of water, some of the advantages of this method are lost. Therefore,
Preferably, the total amount of water in the polymerization reaction system is constant during the reaction.

The gas phase portion of the reaction can 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 so that the amount of water in the alkali metal sulfide in the amide solvent becomes a predetermined amount, if necessary. 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 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 it is less than 0.5 mol, the reaction rate is too fast to obtain a sufficiently high molecular weight product.

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.

The organic amide solvent used here is PA
Known for S-polymerization, such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylcaprolactam, etc., and mixtures thereof can be used, with N-methylpyrrolidone 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. Further, hydrosulfides and hydrates corresponding to these can be used after being neutralized with the corresponding hydroxides. Inexpensive sodium sulfide is preferred.

The dihalo-aromatic compound is, for example, Japanese Patent Publication No.
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 a small amount (20 mol% or less) of one or more kinds of para, meta or orthodihalo compounds of diphenyl ether, diphenyl sulfone or biphenyl. For example, m-dichlorobenzene, o-dichlorobenzene,
p, p'-dichlorodiphenyl ether, m, p'-dichlorodiphenyl ether, m, m'-dichlorodiphenyl ether, p, p'-dichlorodiphenyl sulfone, m, p'-dichlorodiphenyl sulfone, m, m '
-Dichlorodiphenyl sulfone, p, p'-dichlorobiphenyl, m, p'-dichlorobiphenyl, m, m'-
It is dichlorobiphenyl.

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.

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

In the present invention, the PAS obtained as described above may preferably be further acid-treated. The acid treatment is performed at a temperature of 100 ° C or lower, preferably 40 ° C.
It is carried out at a temperature of ~ 80 ° C. If the temperature exceeds the above upper limit, the PAS molecular weight after acid treatment decreases, which is not preferable. On the other hand, if the temperature is lower than 40 ° C., the remaining inorganic salt is deposited to reduce the fluidity of the slurry and hinder the continuous treatment process, which is not preferable. The concentration of the acid solution used for the acid treatment is preferably 0.01 to 5.0% by weight. The pH of the acid solution is preferably 4.0 to 5.0 after the acid treatment. By adopting the above concentration and pH, -SX in PAS which is the object to be treated
(X represents an alkali metal) and most of -COOX terminals can be converted to -SH and -COOH terminals, and corrosion of plant equipment can be prevented, which is preferable. The time required for the acid treatment depends on the acid treatment temperature and the concentration of the acid solution, but it is preferably 5 minutes or longer, particularly preferably 10 minutes or longer. If it is less than the above, the -SX and -COOX ends in PAS cannot be sufficiently converted to the -SH and -COOH ends, 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. Therefore, the elution of alkali metal, such as sodium, during use of the product and the deterioration of electrical insulation can be suppressed. The (A) PAS used in the present invention may have a functional group. PAS having an epoxy group can be obtained by reacting the PAS obtained as described above with an epoxy resin. Examples of the method for modifying PAS by reacting PAS with an epoxy resin include, for example, JP-A-5-194706, JP-A-5-194707, JP-A-5-186594 and JP-A-5-2.
The method described in Japanese Patent No. 14071 can be used.

The method described in JP-A-5-194706 is to react PAS with an epoxy resin in a polar organic solvent. As the epoxy resin used,
For example, conjugated or non-conjugated dienes, epoxidized products such as unsaturated carboxylic acid esters having conjugated or non-conjugated cyclic dienes and conjugated or non-conjugated dienes, aliphatic diols, aliphatic polyhydric alcohols, bisphenols, phenol novolacs and cresols. Polyglycidyl ether obtained by reacting novolak with epichlorohydrin or β-methylepichlorohydrin, polyglycidyl obtained by reacting dicarboxylic acid with epichlorohydrin or β-methylepichlorohydrin Esters and the like can be mentioned.

In the reaction, the charging ratio of PAS and epoxy resin is 0.1 part by weight or more, preferably 1 to 100 parts by weight of epoxy resin to 100 parts by weight of PAS. The polar organic solvent used as the reaction medium,
For example, N-methyl-2-pyrrolidone (NMP), dimethylacetamide, dimethylformamide, dimethylsulfoxide and the like can be mentioned. The reaction temperature and reaction time are
Generally, it can be selected from room temperature to 300 ° C., preferably 100 to 280 ° C. and 10 minutes to 20 hours.

After completion of the reaction, the slurry is filtered, the obtained cake is washed with a solvent capable of dissolving an epoxy resin such as acetone and NMP, and then dried. When washed with a high boiling organic solvent such as NMP, it is desirable to further wash with ion-exchanged water or the like in order to facilitate drying.

When carrying out the reaction between PAS and the epoxy resin, if necessary, a curing agent for the epoxy resin or a curing agent for the epoxy resin may be added to the reaction system.
A catalyst that accelerates the reaction between PAS and the epoxy resin may be present. The curing agent has a function of promoting the bonding between the epoxy resin bonded to the PAS and another epoxy resin, and thus serves to increase the amount of the epoxy resin bonded to the PAS. As the curing agent, amines, acid anhydrides, imidazoles, polysulfides, phenol resins and the like which are generally used as curing agents for epoxy resins can be added. A curing accelerator may be used in combination with these curing agents. A tertiary amine and phosphine are preferably used as a catalyst for promoting the reaction between PAS and an epoxy resin. Specific examples thereof include triethylamine, tributylamine, dimethylbenzylamine, tris (dimethylaminomethyl) phenol, tributylphosphine, triphenylphosphine and the like.

The method described in JP-A-5-194707 is to add an epoxy resin to a reaction liquid produced during the synthesis of PAS and to cause the reaction. In the reaction, the amount of the epoxy resin is 0.01 parts by weight or more, preferably 0.1 to 100 parts by weight of the PAS reaction solution.
20 parts by weight.

The epoxy resin may be added immediately after the PAS synthesis (polymerization) is completed and while the temperature of the reaction solution is high, or the reaction solution may be cooled after a sufficient time after the PAS synthesis (polymerization) is completed. You may go from The epoxy resin may be added as it is to the reaction liquid, or may be dissolved in an organic solvent and added as a solution.

The epoxy resin used, the polar organic solvent used as the reaction medium, the reaction conditions and the like can be the same as those described in JP-A-5-194706.

The method described in JP-A-5-186594 discloses a PAS having an amino group at the side chain and / or the terminal.
And an epoxy resin and at least one epoxy group-containing compound selected from epichlorohydrin in a polar organic solvent.

The reaction temperature and reaction time are generally from 0 to 300.
C., preferably 15 to 280.degree. C. and 30 minutes to 50 hours. The ratio of the PAS having an amino group to the epoxy group-containing compound is usually 0.5 parts by weight or more, preferably 1 to 70 parts by weight, based on 100 parts by weight of the PAS having an amino group.

The epoxy resin used and the polar organic solvent used as the reaction medium are described in the above-mentioned JP-A-5-19470.
The same material as described in JP-A-6 can be used.

In the method described in JP-A-5-214071, PAS having an amino group at a side chain and / or a terminal and an epoxy group-containing compound are melt-kneaded and reacted. For example, it is preferable to use a kneading machine such as a single-screw or twin-screw extruder under the reaction conditions described below. You may perform in the atmosphere of inert gas, such as nitrogen gas. The reaction temperature is at least the melting point of PAS (usually 230 to 285 ° C), preferably 290 to 350 ° C. If the temperature is lower than the melting point, the reaction between PAS and the epoxy group-containing compound does not occur, and if it exceeds 400 ° C., the resin is significantly deteriorated, which is not practical. The temperature range of 290 to 350 ° C. is preferable in order to improve the adhesiveness with an inorganic material such as a metal and the compatibility with other polymers. The reaction time is 10 seconds to 20 minutes. If it is less than the above lower limit, the reaction rate is low. If the amount exceeds the upper limit, the viscosity of PAS increases due to crosslinking, making kneading difficult, which is not practical. Further, the mixing ratio of PAS and epoxy group-containing compound is 0.1 to 40 parts by weight, preferably 1 to 2 parts by weight of epoxy group-containing compound per 100 parts by weight of PAS.
0 parts by weight. If it is less than the above lower limit, sufficient effect cannot be exhibited, and if it exceeds the above upper limit, mechanical properties of PAS are lost, or depending on the epoxy group-containing compound used,
It may significantly reduce the melt flow stability of the product.

Examples of the epoxy group-containing compound used include epoxy resin and epichlorohydrin or its derivative. Examples of the epoxy resin include the same ones described in JP-A-5-194706, and examples of the derivative of epichlorohydrin include β
-Methylepichlorohydrin and the like can be mentioned. Also, P
When kneading the AS and the epoxy group-containing compound, the same curing agent and catalyst as described in JP-A-5-194706 can be used.

The (A) PAS of the present invention may have a functional group other than an epoxy group. Examples of the functional group include an active hydrogen-containing group, that is, --NH ₂ , --SH, --O.
_{H, -NHR, -COOH, -CONH 2} , -CONH
R can be mentioned. R in the above functional groups represents an alkyl group, a cycloalkyl group, an aryl group, an alkaryl group, or an aryl-substituted alkyl group. Of these functional groups, —NH ₂ and —COOH are preferable.

The method for producing PAS having a functional group is not particularly limited. For example, in a method for producing a polyarylene sulfide by contacting a dihalogenated aromatic compound with an alkali metal sulfide in a polar solvent, a method in which a dihalogenated aromatic compound containing active hydrogen is present in a reaction system (Patent Document 1) No. 62-95320), or in the above method, a method in which an active hydrogen-containing halogen aromatic compound is present in the reaction system and an alkali metal halogen compound is used as a catalyst (Japanese Patent Laid-Open No. 62-185717) and the like. Can be mentioned. The amount of the active hydrogen-containing halogen aromatic compound is determined from the viewpoint of blow moldability of the obtained PAS, and the upper limit is preferably 5.0 mol%, particularly preferably 3.5 mol%, and the lower limit is preferably 0. It is 0.01 mol%, particularly preferably 0.05 mol%.

Examples of the active hydrogen-containing halogen aromatic compound used for producing the PAS having a functional group include:
Having at least one aromatic ring, and having active hydrogen on at least one carbon atom among the carbon atoms forming the aromatic ring and / or at least one carbon atom forming the side chain of the aromatic ring An aromatic compound having a group and having a halogen atom bonded to at least two carbon atoms among the carbon atoms forming the aromatic ring at the same time can be mentioned. Here, examples of the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring. Of these, a benzene ring is preferable.

When the active hydrogen-containing halogen aromatic compound has two or more aromatic rings, the aromatic rings may be directly bonded by a single bond, and a divalent group may be interposed therebetween. May be combined. Examples of the divalent group include an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group,
Examples thereof include a divalent hydrocarbon residue such as a carbonyl group, an oxyalkylene group, a carbonylalkylene group, and a polymethylene group. Examples of the halogen-containing aromatic compound containing active hydrogen include JP-A-62-95320 and JP-A-6-95320.
What was described in the 2-185717 publication can be used. Examples of the active hydrogen-containing halogen aromatic compound having -NH ₂ as a functional group include 2,5-dichloroaniline, 2,6-dichloroaniline, 2,4-dichloroaniline, 2,3-dichloroaniline, 3,5 -Dichloroaniline, 2,4-dibromoaniline, 2,2'-diamino-4,4'-dichlorodiphenyl ether, 2,4
′ -Diamino-2 ′, 4-dichlorodiphenyl ether, 2,2′-diamino-4,4′-dichlorodiphenylthioether, 2,4′-diamino-2 ′, 4-dichlorodiphenylthioether, 2,2′-diamino -
4,4'-dichlorodiphenyl sulfoxide, 2,4 '
-Diamino-2 ', 4-dichlorodiphenyl sulfoxide, 2,2'-diamino-4,4'-dichlorodiphenylmethane, 2,4'-diamino-2', 4-dichlorodiphenylmethane, 2,5-dichloro-4 ' -Aminodiphenyl ether, 2,5-dibromo-4'-aminodiphenyl ether, 2,5-dichloro-4'-aminodiphenylthioether, 2,5-dibromo-4'-aminodiphenylthioether, 2,5-dichloro-4 ' -Aminodiphenyl sulfoxide, 2,5-dibromo-4 '
-Aminodiphenyl sulfoxide, 2,5-dichloro-
4'-aminodiphenylmethane, 2,5-dibromo-4
′ -Aminodiphenylmethane and other dihaloaromatic compounds and 2,3,4-trichloroaniline, 2,3,5-trichloroaniline, 2,3,6-trichloroaniline,
2,4,5-trichloroaniline, 2,4,6-trichloroaniline, 3,4,5-trichloroaniline, 2,
3,4-tribromoaniline, 2,3,5-tribromoaniline, 2,3,6-tribromoaniline, 2,4
5-tribromoaniline, 2,4,6-tribromoaniline, 3,4,5-tribromoaniline, 2,5-dichloro-4-bromoaniline, 2,2'-diamino-3
4,4'-trichlorodiphenyl ether, 2,4'-
Diamino-2 ', 5', 4-trichlorodiphenyl ether, 2,4,5-trichloro-4'-aminodiphenyl ether, 2,3,4-trichloro-4'-aminodiphenyl ether, 2,4,5-tribromo-4 ′ -Aminodiphenyl ether, 2,4,6-tribromo-4
'-Aminodiphenyl ether, 2,5-dichloro-6
-Bromo-4'-aminodiphenyl ether, 2,4
5-trichloro-2'-aminodiphenyl ether,
2,2'-diamino-3,4,4'-trichlorodiphenylthioether, 2,4,5-trichloro-4'-aminothioether, 2,2'-diamino-4,5,4 '
-Trichlorodiphenyl sulfoxide, 2,4,5-trichloro-4'-aminodiphenyl sulfoxide, 2,
2'-diamino-3,4,4'-trichlorodiphenylmethane, 2,4,5-trichloro-4'-aminodiphenylmethane, 2,4,4'-trichloro-2'-aminodiphenylpropane, 3,4,4 ′ -Trichloro-3 ′
Trihaloaromatic compounds such as -aminobiphenyl and 2,
3,4,5-tetrachloroaniline, 2,3,5,6-
Examples thereof include polyhaloaromatic compounds such as tetrachloroaniline, tetrachloroaminodiphenyl ether, and tetrachloroaminodiphenylthioether. Examples of the active hydrogen-containing halogen aromatic compound having -COOH as a functional group include 2,6-dichlorobenzoic acid, 2,5-dichlorobenzoic acid, 2,4-dichlorobenzoic acid, 2,3-
Dichlorobenzoic acid, 2,6-dibromobenzoic acid, 2,5
-Dibromobenzoic acid, 2,4-dibromobenzoic acid, 2,
Dihalo aromatic compounds such as 3-dibromobenzoic acid and 2,
3,4-trichlorobenzoic acid, 2,3,5-trichlorobenzoic acid, 2,3,6-trichlorobenzoic acid, 2,4
5-trichlorobenzoic acid, 2,4,6-trichlorobenzoic acid, 3,4,5-trichlorobenzoic acid, 2,3,4-
Tribromobenzoic acid, 2,3,5-tribromobenzoic acid, 2,3,6-tribromobenzoic acid, 2,4,5-tribromobenzoic acid, 2,4,6-tribromobenzoic acid,
Trihalo aromatic compounds such as 3,4,5-tribromobenzoic acid may be mentioned. Examples of the active hydrogen-containing halogen aromatic compound having -SH as a functional group include 2,6-dichlorothiophenol, 2,5-dichlorothiophenol, 2,4-dichlorothiophenol, 2,3-dichlorothiophenol, 2,2'-dimercapto-4,4 '
-Dichlorodiphenyl ether, 2,4'-dimercapto-2 ', 4-dichlorodiphenyl ether, 2,2'
-Dimercapto-4,4'-dichlorodiphenylthioether, 2,4'-dimercapto-2 ', 4-dichlorodiphenylthioether, 2,2'-dimercapto-
4,4'-dichlorodiphenyl sulfoxide, 2,4 '
-Dimercapto-2 ', 4-dichlorodiphenyl sulfoxide, 2,2'-dimercapto-4,4'-dichlorodiphenylmethane, 2,4'-dimercapto-2', 4
-Dichlorodiphenylmethane, 2,5-dichloro-4 '
-Mercaptodiphenyl ether, 2,5-dibromo-
4'-mercaptodiphenyl ether, 2,5-dichloro-4'-mercaptodiphenyl thioether, 2,5
-Dibromo-4'-mercaptodiphenyl thioether, 2,5-dichloro-4'-mercaptodiphenyl sulfoxide, 2,5-dibromo-4'-mercaptodiphenyl sulfoxide, 2,5-dichloro-4'-mercaptodiphenylmethane, 2, Dihalo aromatic compounds such as 5-dibromo-4'-mercaptodiphenylmethane and 2,5-dibromo-4'-mercaptodiphenyl ether and 2,3,4-trichlorothiophenol, 2,3,5
-Trichlorothiophenol, 2,3,6-trichlorothiophenol, 2,4,5-trichlorothiophenol, 2,4,6-trichlorothiophenol, 3,4
5-trichlorothiophenol, 2,3,4-tribromothiophenol, 2,3,5-tribromothiophenol, 2,3,6-tribromothiophenol, 2,
4,5-tribromothiophenol, 2,4,6-tribromothiophenol, 3,4,5-tribromothiophenol, 2,2'-dimercapto-3,4,4'-trichlorodiphenyl ether, 2, 4,5-Trichloro-4'-mercaptodiphenyl ether, 2,2'-dimercapto-4,5,4'-trichlorodiphenylthioether, 2,4,5-trichloro-4'-mercaptodiphenylthioether, 2,2'- Dimercapto-
3,5,4'-trichlorodiphenyl sulfoxide,
2,4,5-Trichloro-4'-mercaptodiphenyl sulfoxide, 3,3'-dimercapto-4,4 ', 5
-Trichlorodiphenylmethane, 2,4,5-trichloro-4'-mercaptodiphenylmethane, 3,3'-dimercapto-4,4 ', 5-trichlorobiphenyl,
Examples include trihaloaromatic compounds such as 3,4,5-trichloro-4'-mercaptobiphenyl. Examples of the active hydrogen-containing halogen aromatic compound having -OH as a functional group include 2,6-dichlorophenol, 2,5-dichlorophenol, 2,4-dichlorophenol, 2,3
-Dichlorophenol, 3,4-dichlorophenol,
3,5-dichlorophenol, 2,4-dibromophenol, 2,6-dibromophenol, 2,2'-dihydroxy-4,4'-dichlorodiphenyl ether, 2,
4'-dihydroxy-2 ', 4-dichlorodiphenyl ether, 2,2'-dihydroxy-4,4'-dichlorodiphenyl thioether, 2,4'-dihydroxy-2
′, 4-Dichlorodiphenyl thioether, 2,2′-
Dihydroxy-4,4'-dichlorodiphenyl sulfoxide, 2,4'-dihydroxy-2 ', 4-dichlorodiphenyl sulfoxide, 2,2'-dihydroxy-4
4'-dichlorodiphenylmethane, 2,4'-dihydroxy-2 ', 4-dichlorodiphenylmethane, 2,5-
Dichloro-4'-hydroxydiphenyl ether, 2,
5-dibromo-4'-hydroxydiphenyl ether,
2,5-dichloro-4'-hydroxydiphenyl thioether, 2,5-dibromo-4'-hydroxydiphenyl thioether, 2,5-dichloro-4'-hydroxydiphenyl sulfoxide, 2,5-dibromo-4'-hydroxydiphenyl Sulfoxide, 2,5-dichloro-
Dihalo aromatic compounds such as 4'-hydroxydiphenylmethane, 2,5-dibromo-4'-hydroxydiphenylmethane, 2,5-dibromo-4'-hydroxydiphenyl ether and 2,3,4-trichlorophenol,
2,3,5-trichlorophenol, 2,3,6-trichlorophenol, 2,4,5-trichlorophenol, 2,4,6-trichlorophenol, 3,4,5-
Trichlorophenol, 2,3,4-tribromophenol, 2,3,5-tribromophenol, 2,3,6
-Tribromophenol, 2,4,5-tribromophenol, 2,4,6-tribromophenol, 3,4
5-tribromophenol, 2,2'-dihydroxy-
3,4,4'-trichlorodiphenyl ether, 2,
4,5-Trichloro-4'-hydroxydiphenyl ether, 2,2'-dihydroxy-3,4,4'-trichlorodiphenylthioether, 2,4,5-trichloro-4'-hydroxydiphenylthioether, 2,2 '
-Dihydroxy-4,4 ', 5-trichlorodiphenyl sulfoxide, 2,4,5-trichloro-4'-hydroxydiphenyl sulfoxide, 2,2'-dihydroxy-4,4', 5-trichlorodiphenylmethane, 2,
Trihalo aromatic compounds such as 4,6-trichloro-4'-hydroxydiphenylmethane, 3-hydroxy-3,4,4'-trichlorobiphenyl, and 3,4,5-trichloro-4'-hydroxybiphenyl can be mentioned. Examples of the active hydrogen-containing halogen aromatic compound having -NHR as a functional group include 2,6-dichloro (phenyl) aminobenzene, 2,5-dichloro (phenyl) aminobenzene, and 2,4-dichloro (phenyl) aminobenzene. ,
Dihaloaromatic compounds such as 2,3-dichloro (phenyl) aminobenzene and 2,3,4-trichloro (phenylamino) benzene, 2,3,5-trichloro (phenylamino) benzene, 2,3,6-trichloro (Phenylamino) benzene, 2,4,5-trichloro (phenylamino) benzene, 2,4,6-trichloro (phenylamino) benzene, 3,4,5-trichloro (phenylamino) benzene, 2,3,4 -Tribromo (phenylamino) benzene, 2,3,5-tribromo (phenylamino) benzene, 2,3,6-tribromo (phenylamino) benzene, 2,4,5-tribromo (phenylamino) benzene, 2,4 , 6-Tribromo (phenylamino) benzene, 3,4,5-Tribromo (phenylamino) benzene Include trihalo aromatic compounds. Among the above, an active hydrogen-containing halogen aromatic compound having —NH ₂ as a functional group is preferably used, and dichloroaniline is particularly preferable.

In the method for producing a PAS having a functional group, a part of the gas phase in the reaction vessel is cooled by cooling the gas phase portion of the reaction vessel during the reaction as described in JP-A-5-222196. It is preferred to condense and bring this to reflux in the liquid phase. In addition, acid treatment can be performed using the same method as described above, and it is possible to react with an epoxy resin to form PA.
It is also possible to denature S.

In the present invention, as the (A) PAS, various PASs produced as described above can be used alone or in combination.

The (B) modified olefin elastomer used in the present invention is obtained by modifying (i) the olefin elastomer with (ii) a specific glycidyl compound.

Examples of the above-mentioned (i) olefin-based elastomer include ethylene and α other than ethylene such as propylene, 1-butene, 1-hexene and 4-methyl-1-pentene.
A copolymer rubber with one or more olefins. Preferably ethylene-butene copolymer rubber (hereinafter,
EBR), ethylene-propylene copolymer rubber (hereinafter sometimes referred to as EPR) and ethylene-propylene-diene copolymer rubber (hereinafter referred to as EPDM)
May be abbreviated) and the like. As the diene in EPDM, non-conjugated dienes such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene and methylene norbornene, or conjugated dienes such as butadiene and isoprene can be used.

The content of ethylene in the olefin elastomer is preferably 5 to 95% by weight, particularly preferably 10 to 90% by weight. If the ethylene content is less than the above lower limit or more than the above upper limit, it becomes difficult to exhibit properties as an elastomer. The crystallinity of such an olefin elastomer is usually 40% by weight or less.

EPR, which is a typical example of the olefinic elastomer used in the present invention, has a content of repeating units derived from ethylene of 50 to 80 mol%, and a content of repeating units derived from propylene of 20 to 50.
Preferably it is mol%. A more preferable range is 60 to 70 mol% of ethylene-based repeating units and 30 to 40 mol% of propylene-based repeating units. Also EP
R melt flow rate (MFR, 230 ° C, 2.16)
(kg load) is preferably in the range of 0.01 to 50 g / 10 minutes, and more preferably 0.5 to 30 g / 10 minutes.

EBR, which is another typical example of the olefin elastomer, has a repeating unit content of ethylene of 50 to 90 mol% and a repeating unit content of butene of 10 to 50 mol%. Preferably there is. A more preferable range is 60 to 80 mol% of ethylene-based repeating units and 20 to 40 of butene-based repeating units.
Mol%. Also, the EBR melt flow rate (M
FR, 230 ° C, 2.16 kg load) is 0.01 to 50
It is preferably in the range of g / 10 minutes, more preferably 0.5 to 30 g / 10 minutes.

EPDM, which is another typical example of the olefin elastomer, has a content of repeating units derived from ethylene of 40 to 70 mol% and a content of repeating units derived from propylene of 30 to 60. It is preferable that the content of the repeating unit derived from the mol% and the diene is 1 to 10 mol%. More preferable ranges are 50 to 60 mol% of ethylene-based repeating units, 40 to 50 mol% of propylene-based repeating units, and 3 to 6 mol% of diene-based repeating units. Furthermore, EPD
Melt flow rate (MFR, 230 ° C, 2.16)
(kg load) is preferably in the range of 0.01 to 50 g / 10 minutes, more preferably 0.1 to 30 g / 10 minutes.

The ethylene-propylene copolymer, the ethylene-butene copolymer rubber and the ethylene-propylene-diene copolymer, which are typical examples of the olefin elastomer, basically have the above repeating units. A repeating unit or the like derived from other α-olefin such as 4-methyl-1-pentene may be contained at a ratio of 10 mol% or less within a range that does not impair the properties of these copolymers.

In the present invention, if desired, a polyolefin may be added to the above-mentioned (i) olefin elastomer.
An olefin-based elastomer composition mixed in an amount of 0% by weight or less can be used as (B). As the polyolefin that can be used in addition to the olefin elastomer,
Ethylene, propylene, 1-butene, 1-hexene, 4
Homopolymers of α-olefins such as 1-methyl-1-pentene, non-elastomeric copolymers of ethylene and propylene or other α-olefins, or non-elastomeric copolymers of two or more of these α-olefins It is possible to use a combination, a homopolymer thereof, a copolymer thereof, or a blend of a homopolymer and a copolymer.

When a polyolefin is mixed, the mixing amount is 10 parts by weight of olefin elastomer + polyolefin.
0% by weight is 80% by weight or less, preferably 50% by weight or less. When the amount of the polyolefin mixed exceeds 80% by weight, the properties as an elastomer are lost.

In the present invention, the glycidyl compound (ii) used for modifying the olefin elastomer is represented by the following formula (I).

[0056]

Embedded image (In the formula, each R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Ar represents an aromatic hydrocarbon group having 6 to 20 carbon atoms having at least one glycidyloxy group, m represents an integer of 1 to 4).

Preferred glycidyl compounds include compounds represented by the following formula (II)

[0058]

[Chemical 4] (In the formula, R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms).

Such a glycidyl compound can be produced by the following method, as disclosed in, for example, JP-A-60-130580. First, an aromatic hydrocarbon having at least one phenolic hydroxyl group and N-methylolacrylamide or N-methylolmethacrylamide or an alkyl ether derivative of N-methylolmethacrylamide (hereinafter, these are referred to as N-methylolacrylamides) A compound represented by the following formula (III) is produced by condensation using an acid catalyst.

[0060]

Embedded image (In the formula, each R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Ar 'represents an aromatic hydrocarbon group having 6 to 20 carbon atoms having at least one hydroxyl group,
m represents an integer of 1 to 4).

The aromatic hydrocarbon having at least one phenolic hydroxyl group is not particularly limited,
For example, phenol, o-cresol, m-cresol,
p-cresol, 2,6-xylenol, 2,4-xylenol, o-chlorophenol, m-chlorophenol, o-phenylphenol, p-chlorophenol,
Phenolic compounds such as 2,6-diphenylphenol, polyphenolic compounds such as hydroquinone, catechol and phloroglucinol, polycyclic hydroxy compounds such as 1-naphthol, 2-naphthol and 9-hydroxyanthracene, 2,2-bis (4-hydroxyphenyl)
Examples thereof include bisphenols such as propane (bisphenol-A) and bis (4-hydroxyphenyl) methane.

Then, the hydroxyl group of the compound represented by the formula (III) is glycidylated to obtain the glycidyl compound represented by the formula (I). This glycidylation is preferably carried out by performing an addition reaction between the compound represented by the formula (III) and epihalohydrin, and then dehydrohalogenating with caustic alkali. As the above epihalohydrin, epichlorohydrin, epibromhydrin, epiiodohydrin and the like can be used.

The addition reaction with epihalohydrin is carried out using a phase transfer catalyst. As the phase transfer catalyst, for example, tetrabutylammonium bromide, trioctylmethylammonium chloride, quaternary ammonium salts such as benzyltriethylammonium chloride, tetraphenylphosphonium chloride, quaternary phosphonium salts such as triphenylmethylphosphonium chloride, etc. are used. be able to. The amount of the phase transfer catalyst used is represented by the formula (I
It is preferably in the range of 0.01 to 100 mol% with respect to the compound represented by II). A particularly preferred amount of the phase transfer catalyst used is 0.05 to 10 mol%. The reaction temperature and the reaction time are 50 to 120 ° C. for 5 minutes to 2 hours, and more preferably 80 to 110 ° C. for 10 to 30 minutes.

Following the addition of epihalohydrin, dehydrohalogenation is carried out with caustic. As the caustic alkali, caustic soda, caustic potash, lithium hydroxide and the like can be used. These can be used as solids or as aqueous solutions. As the dehydrohalogenation catalyst, the same one as the above-mentioned phase transfer catalyst can be used. Further, catalysts other than the above phase transfer catalysts can be used, and examples of such catalysts include crown ethers, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol and the like.

The caustic alkali is preferably used in an equimolar amount or more with respect to the compound represented by the formula (III). More preferably, 1.1 to 1.5 times the molar amount is used. The reaction temperature and the reaction time are 20 to 90 ° C. and 1
It is 0 minutes to 3 hours, more preferably 30 minutes to 2 hours at 40 to 70 ° C.

The modification (graft polymerization) of the olefinic elastomer (or the olefinic elastomer composition) with the glycidyl compound can be carried out by either a solution method or a melt-kneading method. In the case of the melt kneading method, the olefin elastomer and the above-mentioned glycidyl compound for modification,
And, if necessary, the catalyst is put into an extruder, a twin-screw kneader, or the like, and heated to a temperature of 180 to 300 ° C. and kneaded for 0.1 to 20 minutes while melting. In the case of the solution method, the above-mentioned starting materials are dissolved in an organic solvent such as xylene, and the solution is stirred at a temperature of 90 to 200 ° C for 0.1 to 100 hours. In any case, a usual radical polymerization catalyst can be used as a catalyst, and specific examples thereof include benzoyl peroxide, lauroyl peroxide, ditertiary butyl peroxide,
Acetyl peroxide, tertiary butyl peroxybenzoic acid, dicumyl peroxide, peroxybenzoic acid, peroxyacetic acid, tertiary butyl peroxypivalate, 2,
Examples thereof include peroxides such as 5-dimethyl-2,5-ditertiarybutylperoxyhexyne and diazo compounds such as azobisisobutyronitrile. The amount of the catalyst added is 0.1 to 10 with respect to 100 parts by weight of the glycidyl compound.
It is about parts by weight. A phenolic antioxidant can be added during the graft reaction. However, when the radical polymerization catalyst is not added, it is preferable not to add it.

The mixing ratio of the (ii) glycidyl compound is 100 parts by weight of the (i) olefin elastomer (or olefin elastomer composition).
It is 0.01 to 30 parts by weight, preferably 0.1 to 10 parts by weight. If the blending amount of the glycidyl compound is less than 0.01 parts by weight, it is difficult to achieve a high graft ratio, and if it exceeds 30 parts by weight, the moldability and mechanical properties of the obtained modified olefin elastomer are deteriorated, which is not preferable. .

In the blow molding PAS resin composition of the present invention, the compounding ratio of the component (A) and the component (B) is such that the upper limit of the component (B) is 20 with respect to 100 parts by weight of the component (A).
0 parts by weight, preferably 100 parts by weight, particularly preferably 5 parts by weight
It is 0 part by weight, and the lower limit of the component (B) is 3 parts by weight, preferably 5 parts by weight, particularly preferably 8 parts by weight. When the amount of the component (B) is less than the lower limit, the drawdown of the parison during blow molding becomes large and the appearance characteristics of the molded product deteriorate. If the upper limit is exceeded, PAS properties such as heat resistance and chemical resistance are lost, which is not preferable.

The blow molding PAS resin composition of the present invention may further contain a filler in an amount of preferably 200 parts by weight or less, particularly preferably 100 parts by weight or less, based on 100 parts by weight of the resin composition. You can Thereby, mechanical strength such as impact resistance of the molded product can be enhanced. If the blending amount of the filler exceeds the above upper limit, moldability is deteriorated, which is not preferable.

As the filler, a conventional one can be used. For example, glass fibers, carbon fibers, metal fibers, aramid fibers, fibrous potassium titanate, fibrous inorganic and organic fillers such as asbestos and various whiskers such as silicon carbide and silicon nitride, graphite, calcium carbonate, Mica, silica, boron nitride, barium sulfate, calcium sulfate, kaolin, clay, bilophyllite, bentonite, sericite, zeolite, mica,
Nepheline sinite, ferrite, attapulgite,
Wollastonite, calcium silicate, magnesium carbonate, dolomite, antimony trioxide, magnesium oxide, zinc oxide, titanium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass powder, glass beads, quartz, quartz glass, iron, Inorganic particulate fillers such as zinc, copper, aluminum and nickel are mentioned. 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.

Further, the resin composition of the present invention may be blended with other resins and elastomers within a range not impairing the object of the present invention. Examples of the resins and elastomers include homopolymers of ethylene, propylene, butylene, pentene, butadiene, isoprene, chloroprene, styrene, α-methylstyrene, vinyl acetate, vinyl chloride, acrylic acid ester, (meth) acrylonitrile, and the like. Copolymer, polyamide, polyester, polyurethane, polyacetal, polycarbonate, polysulfone, polyallylsulfone, polyethersulfone,
Homopolymers such as polyarylate, polyphenylene oxide, polyether ether ketone, polyimide, silicone resin, phenoxy resin, fluororesin, polyaryl ether, polysulfide, random copolymers, block copolymers, graft copolymers, other than the above Elastomers.

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

In the resin composition of the present invention, the above components are prepared by using a single-screw extruder, a twin-screw extruder, a Banbury mixer, a kneading roll,
It can be obtained by kneading in a heating and melting state at 275 ° C. or higher, preferably 285 to 340 ° C. using a kneader such as Brabender Plastograph (registered trademark).

The production of blow-molded articles from the PAS resin composition of the present invention can be carried out by a known method using a blow molding machine generally used for blow molding of thermoplastic resins. That is, the PAS resin composition is plasticized by an extruder or the like, and this is extruded or injected by an annular die to form an annular molten or softened intermediate parison, and a gas is blown inside the parison in the mold. It is filled, expanded, cooled and solidified to obtain a hollow body. As the PAS molding conditions, the cylinder and die temperatures are preferably 28.
The temperature is 0 to 350 ° C, particularly preferably 290 to 320 ° C. The mold temperature is preferably 40 to 200 ° C, particularly preferably 80 to 150 ° C. The gas blown into the interior may be air, nitrogen or the like, but air is generally used in consideration of economy. The blowing pressure is preferably 4 to 10 kg / cm ² .

The blow-molded article produced from the PAS resin composition of the present invention is useful for medical, food or various chemical containers such as bottles, tanks and flasks.

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

[0077]

EXAMPLES In the examples, the melt viscosity V _{6 of} PPS is
It measured using Shimadzu flow tester CFT-500C.

Hereinafter, Synthesis Examples 1 to 6 are PPS production examples, and Synthesis Examples 7 and 8 are modified olefin elastomer production examples.

Synthesis Example 1 In a 150-liter autoclave, 19.478 kg of flaky sodium sulfide (60.1 wt% Na ₂ S) and N-
45.0 kg of methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP) was charged. While stirring under a nitrogen stream, the temperature was raised to 204 ° C. to distill 5.072 kg of water (the amount of residual water was 1.0 mol per mol of sodium sulfide). After that, the autoclave was closed and cooled to 180 ° C., and paradichlorobenzene (hereinafter sometimes abbreviated as p-DCB) 22.51 kg and NMP 18.0 k
g and 1,2,4-trichlorobenzene 40.8 g (about 0.15 mol% with respect to sodium sulfide) were charged. The temperature was raised by pressurizing to 1 kg / cm ² G with nitrogen gas at a liquid temperature of 150 ° C. While stirring at a liquid temperature of 215 ° C. for 7 hours, a refrigerant at 20 ° C. was caused to flow through a coil wound around the upper portion of the autoclave to cool the gas phase portion of the autoclave. After that, the temperature is raised and stirred for 3 hours while maintaining the liquid temperature at 260 ° C.,
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. Maximum pressure during reaction is 8.69k
It was g / cm ² G.

The obtained slurry was repeatedly filtered and washed with warm water by a conventional method and then dried in a hot air circulation dryer at 120 ° C. for about 5 hours to obtain a white powdery product. Obtained P
The melt viscosity V ₆ of PS (P-1) was 3,700 poise.

Synthesis Example 2 The PPS slurry obtained in the same manner as in Synthesis Example 1 was filtered and washed with warm water twice by a conventional method. The obtained filter cake (containing about 50% by weight of water) was slurried with water, 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 warm water was repeated 4 times. Then, it was dried in a hot air circulation dryer at 120 ° C. for about 5 hours to obtain a white powdery product. The melt viscosity V ₆ of the obtained PPS (P-2) was 3,520 poise.

Synthesis Example 3 A PPS containing an amino group was produced.

Flake sodium sulfide (60.7 wt% Na ₂ S) 19.28 was placed in a 150 liter autoclave.
5 kg and 45.0 kg of NMP were charged. The temperature was raised to 204 ° C. with stirring under a nitrogen stream, and 4.600 kg of water was distilled off (the amount of residual water was 1.08 mol per mol of sodium sulfide). Then, close the autoclave 1
Cooled to 80 ℃, p-DCB21.940kg and 2,
0.365 kg of 5-dichloroaniline (about 1.5 mol% with respect to sodium sulfide) and 18.0 kg of NMP were charged. The temperature was raised by pressurizing to 1 kg / cm ² G with nitrogen gas at a liquid temperature of 150 ° C. While stirring at a liquid temperature of 220 ° C. for 3 hours, a cooling medium of 80 ° C. was passed through a coil wound around the upper part of the autoclave to cool it. After that, the temperature was raised and the liquid temperature was maintained at 260 ° C. and stirred for 3 hours, then 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 was 8.73 kg / cm ² G.

The obtained slurry was repeatedly filtered and washed with warm water by a conventional method, and then dried at 120 ° C. for 5 hours in a hot air circulation dryer to obtain a white powdery product. The amino group-containing PPS (P-3) thus obtained had a melt viscosity V ₆ of 3,300.
Poise.

Synthesis Example 4 A PPS containing an epoxy group was produced.

The same PPS (P-
2) N of 8.0 kg and 0.80 kg of epoxy resin (Epicoat 828, trademark, manufactured by Yuka Shell Epoxy Co., Ltd.)
The reaction was carried out in 240 kg of MP at 240 ° C. for 3 hours. After the reaction, it was cooled to 100 ° C. and then filtered. The obtained filter cake was washed with acetone and vacuum dried at 150 ° C. for about 3 hours to obtain an epoxy-modified PPS (P-4).

When the IR spectrum of the obtained PPS was measured by the film method, the absorption due to the epoxy resin was 2980, 1520, 1260, 960, 570 cm.
^It was found near ^-1 .

The addition ratio [(weight of bound epoxy resin / weight of PPS resin) × 100 (%)] of the obtained PPS (P-4) to the epoxy resin was determined from the IR spectrum as follows. By using a calibration curve prepared in advance by blending PPS before reaction used for modification and epoxy resin used for modification at various ratios, the absorbance at 1520 cm ^-1 based on epoxy resin and 1400 cm ^-1 based on PPS was used. Calculated from the ratio. The addition rate was 3.2%.

Further, the melt viscosity V _{6 of the} PPS (P-4) is
Was 5,120 poise.

Synthetic Example 5 Epoxy-modified PPS under the same conditions as in Synthetic Example 4 except that the same PPS (P-3) as obtained in Synthetic Example 3 was used.
(P-5) was produced.

The melt viscosity V ₆ of the obtained PPS was 4,77.
It is 0 poise and the addition rate of epoxy resin is 3.1%
Met.

Synthesis Example 6 (for Comparative Example) 1,2,4-trichlorobenzene was not added, and p-
A white powdery product was obtained in the same manner as in Synthesis Example 1 except that the amount of DCB added was 21.941 kg. Obtained P
The melt viscosity V ₆ of PS (P-6) was 1,070 poise.

Synthesis Example 7 As the olefin elastomer, ethylene-propylene copolymer rubber (EPR) [propylene content 70% by weight, melt flow rate (230 ° C., 2.16 kg load) 1.7 g / 10 minutes] was used. As a glycidyl compound for modification, a glycidyl compound represented by the following formula (IV) (manufactured by Kanegafuchi Chemical Industry Co., Ltd.)

[0094]

[Chemical 6] And POX: Perhexin 2-5B (trademark, manufactured by NOF CORPORATION) was used as a radical generator.

The above olefinic elastomer, the glycidyl compound for modification and the radical generator were mixed with 100: 3:
Dry blending was performed with a Henschel mixer at a ratio of 0.1 (parts by weight). Then, in a single-screw extruder with 30 mmφ and L / D = 25, the mixture was melt-kneaded at 200 ° C. and 30 rpm for graft polymerization.

The resulting modified olefin elastomer (modified ethylene-propylene copolymer rubber, hereinafter M
The melt flow rate of the abbreviated as EPR) is 0.
It was 41 g / 10 minutes, and the grafting ratio of the modifying glycidyl compound was 2.0% by weight.

Here, the melt flow rate (MFR)
Was measured according to JIS K7210 (temperature 190 ° C., load 1.05 kg). Further, the grafting ratio of the modifying glycidyl compound was such that the modified olefin elastomer was dissolved in boiling xylene, the insoluble matter was removed, and then the dissolved component was precipitated with methanol, and this was pressed to a thickness of about 50 μm, and an IR spectrum was obtained. The peak of stretching of the C = O bond of the glycidyl compound for modification (1648 cm ^-1 ) was measured.
And one of the peaks peculiar to isotactic PP (84
It was calculated from the ratio with 0 cm ⁻¹ ).

Synthesis Example 8 As an olefin elastomer, ethylene-butene copolymer rubber (EBR) [butene content 80% by weight, melt flow rate (230 ° C., 2.16 kg load) 1.5
g / 10 min] was used, and the same procedure as in Synthesis Example 7 was performed.

The obtained modified olefin elastomer (modified ethylene-butene copolymer rubber, hereinafter MEB
(It may be abbreviated as R) has a melt flow rate of 0.32
It was g / 10 minutes, and the graft ratio of the modifying glycidyl compound was 2.2% by weight.

[0100]

Examples 1 to 21 and Comparative Examples 1 to 11 The ratio (parts by weight) of PPS and modified olefin elastomers, optional resins, and glass fibers obtained in each synthesis example are shown in Table 1.
Were mixed with each other in a Henschel mixer for 5 minutes to make the mixture uniform, and then melt-kneaded at a temperature of 300 ° C. and a rotation speed of 400 rpm using a 20 mmφ biaxial counter-rotating extruder to prepare pellets. The pellets obtained are supplied to a blow molding machine, the cylinder temperature is 320 ° C., the die diameter is 55 mmφ,
At a mold temperature of 130 ° C. and an air blowing pressure of 6 kg / cm ² , a cylindrical container having an average thickness of 2.4 mm and an internal volume of 500 cc was formed. At this time, the following evaluation was carried out. <Drawdown of parison> The drawdown of the parison at the time of blow molding was performed by extruding the parison to a length of 200 mm and measuring the length of the parison after 10 seconds, and evaluated as large, medium or small as follows. -Large: more than 250 mm-Medium: 210-250 mm-Small: less than 210 mm <Appearance characteristics> The appearance characteristics of the molded cylindrical container were evaluated according to the following criteria.・ Good: The surface smoothness was visually inspected and judged to be smooth, and the cylindrical container was not broken. ・ Available: The same as above, the unevenness was judged, and the cylindrical container There was no tear on the surface. ・ Poor: There was tear on the cylindrical container. The above results are shown in Table 1.

[0101]

[Table 1] * 1: Polyethylene terephthalate (RE-530, trademark, manufactured by Toyobo Co., Ltd.) * 2: A28, trademark, manufactured by EMS * 3: 3J961S, trademark, manufactured by Nitto Boseki Co., Ltd. Example 1 is (A) P- 1 and (B) MEPR. The drawdown of the parison was small and the appearance characteristics were well tolerated. Example 2 is
(A) P-1 and P-2 are used as PAS. The appearance characteristics were improved as compared with Example 1. In Examples 3 to 8, as (A) PAS, P-1 and P-
2, P-3 and P-4 were blended in the ratios shown in Table 1, respectively. In both cases, the drawdown of the parison is small,
The appearance characteristics were good. When PPS having an epoxy group, an amino group or PPS treated with an acid is used (Examples 2 to 8), it is compared with that using PPS not having the above group and not treated with an acid (Example 1). It was found that the appearance characteristics were further improved. Examples 9 to 13
PET as an optional resin in addition to (A) and (B)
It is a mixture of. When PET was blended, the drawdown of the parison was slightly increased, but the effects of the present invention could be sufficiently achieved. Also, the appearance characteristics were good. In Examples 14 to 16, nylon 6 was blended in addition to (A) and (B). When nylon 6 was blended, the drawdown of the parison was slightly increased as in the case of blending PET, but the effects of the present invention could be sufficiently achieved. In Example 17, (B) MEPR of Example 5 was replaced with MEBR. As in Example 5, the drawdown of the parison was small and the appearance characteristics were good. In Examples 18 and 21, the compounding amount of (B) MEPR of Example 5 was increased or decreased within the scope of the present invention. In all cases, the drawdown of the parison was small as in Example 5, and the appearance characteristics were good. In Examples 19 and 20, the glass fiber content was increased or decreased as compared with Example 5. In both cases, the drawdown of the parison was small and the appearance characteristics were good.

On the other hand, in Comparative Example 1, the (B) modified olefin elastomer (MEPR) of Example 1 was replaced with an unmodified olefin elastomer (EPR).
Further, in Comparative Example 2, (B) MEPR of Example 2 is EPR
Instead of. In each case, the drawdown of the parison was small, but the appearance characteristics were significantly deteriorated. Comparative Example 3 is EBR which is an unmodified olefin elastomer.
Is used. The appearance characteristics were extremely poor. Comparative Examples 4 and 5 are (B) MEPR of Examples 5 and 4, respectively.
Instead of EPR. In both cases, the appearance characteristics were significantly deteriorated. In Comparative Example 6, P-4 of Comparative Example 5 was replaced with P-5.
Instead of. The appearance characteristics were remarkably poor as in Comparative Example 5. In Comparative Examples 7 and 8, EPR was used as (B), and PET or nylon 6 was further compounded as an optional resin. In all cases, the appearance characteristics were extremely poor. In Comparative Example 9, instead of the PPS (P-1) of Example 1, the melt viscosity V ₆ was less than the range of the present invention.
6) is used. The drawdown of the parison was large and the appearance characteristics were extremely poor. In Comparative Example 10, the compounding amount of (B) MEPR of Example 2 was set to be less than the range of the present invention. The drawdown of the parison was large and the appearance characteristics were also extremely poor. In Comparative Example 11, the blending amount of (B) MEPR in Example 1 exceeds the range of the present invention. The parison drawdown was small,
The appearance characteristics were significantly deteriorated.

[0103]

EFFECTS OF THE INVENTION The present invention provides a polyarylene sulfide resin composition which gives a blow-molded article having a small drawdown of the parison during blow molding and good appearance characteristics.

[Table 2]

[Table 3]

Claims (3)

[Claims] 1. (A) Melt viscosity V ₆ is 2,500 to 30,
000 Poise Polyarylene Sulfide 100
3 to 200 parts by weight of a modified olefinic elastomer obtained by grafting a glycidyl compound represented by the following formula (I) on an olefinic elastomer (B) by weight. (In the formula, each R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Ar represents an aromatic hydrocarbon group having 6 to 20 carbon atoms having at least one glycidyloxy group, m represents an integer of 1 to 4), and a polyarylene sulfide resin composition for blow molding. 2. A polyarylene sulfide (A) reacts an alkali metal sulfide with a dihaloaromatic compound in an organic amide solvent, and cools the gas phase portion of the reaction can during the reaction. Part of the gas phase inside is condensed,
It is produced by refluxing this in a liquid phase.
The resin composition described. 3. The (A) polyarylene sulfide is one or more polyarylene sulfides selected from polyarylene sulfides having an epoxy group and polyarylene sulfides having an active hydrogen-containing group.
Or the resin composition according to 2.