JP2008110561A - Multi-layer molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a multi-layer molded article which expresses excellent adhesion with other resin component without damaging excellent barrier property to the organic matter fluid being inherent in a polyarylene sulfide resin, in the application of piping members, containers, or fuel tubes in transferring of the organic matter fluid such as fuel, and components for fuel equipped with these performance. <P>SOLUTION: A multi-layer structure is formed by co-extruding the polyarylene sulfide resin composition (A) containing the polyarylene sulfide resin (a1), a polyfunctionalisocyanate compound (a2) represented by 4,4'-diphenylmethane diisocyanate, and a thermoplastic elastomer (a3) represented by ethylene-glycidyl methacrylate copolymer as essential components, and the thermoplastic resin (B) having one kind or more functional groups selected from amino group such as polyamide or the like, amide group, hydroxy group, carboxy group, acid anhydride group, isocyanate group, and epoxy group. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a multilayer molded body suitable for piping members, containers, and fuel tubes when transporting an organic fluid such as fuel.

  In recent years, piping materials, piping components, and tube products for organic fluids that have fluidity such as solvents, fuels, liquefied gases, and other various polymer raw materials, intermediates, and products have been replaced with metal materials and plastics have been promoted. For example, a polyamide resin having a high barrier performance against fuel such as gasoline is used for fuel piping members and containers for vehicles.

  However, for alcohol-containing gasoline that is rapidly spreading, the barrier property of polyamide resin is never sufficient, and even 12 nylon, which has a relatively high barrier property against alcohol-containing gasoline, can be released into the atmosphere. It was in a situation where it was not possible to obtain a high barrier property that could meet various regulations for preventing fuel diffusion.

  On the other hand, polyphenylene sulfide resin has attracted attention as a resin material having a very high barrier property against alcohol-containing gasoline. However, although polyphenylene sulfide resin has excellent heat resistance and chemical resistance, it has insufficient impact resistance and is difficult to apply to automobile fuel tubes and fuel tanks. Therefore, as a method of manufacturing a fuel tube or a fuel tank for automobiles, the structure of three layers of a polyphenylene sulfide resin layer, an adhesive layer, and a polyethylene layer is used to maintain the barrier property of the polyphenylene sulfide resin. A molded container having impact resistance as a whole product is known (see Patent Document 1 and Patent Document 2).

  However, since polyphenylene sulfide has low adhesiveness with other resin components, the multilayer structure has a problem that peeling between layers is likely to occur, and the barrier property is remarkably lowered. In particular, when used as a member used in an engine room that is in a high temperature environment, problems such as deformation due to significant softening of the polyethylene layer accompanying temperature rise have occurred.

  Therefore, as a method for solving the problem of softening of the polyethylene layer in the multilayer structure using polyphenylene sulfide, a multilayer structure in which a layer made of polyphenylene sulfide and a layer made of polyamide are laminated is known. As such a multilayer structure, specifically, a multilayer structure in which a layer made of a mixture of polyphenylene sulfide and an epoxy group-containing polyolefin, an olefin-based adhesive layer, and a layer made of polyamide is laminated (described below). (See Patent Document 3). However, since such a multilayer structure uses a polyolefin-based adhesive layer, when it is used in a high temperature environment, the peel strength between the layers is insufficient.

  Also, with 100 parts by weight of polyphenylene sulfide resin, containing a functional group having one or more bonds or functional groups selected from polyamide, amide bond, ester bond, urethane bond, carboxyl group, acid anhydride group and epoxy group A technique is known in which a polyphenylene sulfide resin layer containing 10 to 150 parts by weight of at least one thermoplastic resin and a polyamide layer are multilayered without using an adhesive layer to form a multilayer structure ( Patent Document 4) below. However, in order to obtain adhesion to the polyamide resin layer, this multilayer structure needs to contain a large amount of polyamide and modified olefin resin in polyphenylene sulfide, which impairs the inherent barrier properties of polyarylene sulfide. It was an end.

JP-A-5-193060 JP-A-5-193061 JP-A-11-156970 JP 10-138372 A

  Accordingly, the problem to be solved by the present invention is that without impairing the excellent barrier property with respect to the original organic fluid of polyarylene sulfide in applications such as piping members, containers, and fuel tubes when transporting organic fluid such as fuel. Another object of the present invention is to provide a multilayer molded article that exhibits excellent adhesion with other resin components, and a fuel component having these performances.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have coextruded a resin component containing a polyarylene sulfide and a polyvalent isocyanate compound with a thermoplastic resin having a specific functional group. The inventors have found that the adhesion between the layers can be dramatically improved without degrading the performance of the polyarylene sulfide, and the present invention has been completed.

  That is, the present invention relates to a polyarylene sulfide resin composition (A) comprising a polyarylene sulfide resin (a1), a polyvalent isocyanate compound (a2), and a thermoplastic elastomer (a3) as essential components, an amino group, and an amide group. Having a structure obtained by co-extrusion with a thermoplastic resin (B) having one or more functional groups selected from hydroxyl group, carboxyl group, acid anhydride group, isocyanate group and epoxy group The present invention relates to a multilayer molded body.

  The present invention further relates to a fuel component comprising the multilayer molded body.

  According to the present invention, in applications such as piping members, containers, fuel tubes and the like when transporting organic fluids such as fuel, other resin components can be used without impairing excellent barrier properties against the organic fluids inherent to polyarylene sulfide. It is possible to provide a multilayer molded article that exhibits excellent adhesion, and a fuel component having these performances.

  The present invention will be described in detail below.

  As described above, the multilayer molded article of the present invention comprises a polyarylene sulfide resin composition (A) comprising, as essential components, a polyarylene sulfide resin (a1), a polyvalent isocyanate compound (a2), and a thermoplastic elastomer (a3). A structure obtained by coextrusion with a thermoplastic resin (B) having one or more functional groups selected from amino group, amide group, hydroxyl group, carboxyl group, acid anhydride group, isocyanate group and epoxy group It is what you have.

  The polyarylene sulfide resin (a1) used here has a resin structure having a repeating unit of a structure in which an aromatic ring and a sulfur atom are bonded. Specifically, the following structural formula (1)

(In the formula, R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a nitro group, an amino group, a phenyl group, a methoxy group, or an ethoxy group.)
It is resin which makes the structural site represented by a repeating unit.

Here, in the structural part represented by the structural formula (1), R ⁵ and R ⁶ in the formula are preferably hydrogen atoms from the viewpoint of the mechanical strength of the PAS resin (A), In that case, what couple | bonds in the para position represented by following Structural formula (2) and what couple | bonds in the meta position represented by following Structural formula (3) are mentioned.

  Among these, the heat resistance and crystallinity of the PAS resin (A) include that the bond of the sulfur atom to the aromatic ring in the repeating unit is a structure bonded at the para position represented by the structural formula (2). It is preferable in terms of

  In addition, the PAS resin (A) includes not only the structural portion represented by the structural formula (1) but also the following structural formulas (4) to (7).

The structural site represented by the formula (1) may be included in an amount of 30 mol% or less of the total with the structural site represented by the structural formula (1). In particular, in the present invention, the structural site represented by the structural formulas (4) to (7) is preferably 10 mol% or less from the viewpoint of the heat resistance and mechanical strength of the PAS resin (A).
In the case where the PAS resin (A) includes a structural portion represented by the structural formulas (4) to (7), the bonding mode thereof is either a random copolymer or a block copolymer. Also good.

  The PAS resin (A) has the following structural formula (8) in its molecular structure.

May have a trifunctional structural site represented by the formula (1) or a naphthyl sulfide bond, but is preferably 1 mol% or less with respect to the total number of moles with other structural sites.

Such a PAS resin (A) can be produced by, for example, the following (1) to (4).
Method 1: A method of polymerizing polyhalogen aromatic compounds in the presence of sulfur and sodium carbonate.
A method of polymerizing dihalogen aromatic compounds in a polar solvent in the presence of a sulfidizing agent.
Method 2: A method of self-condensing P-chlorothiophenol.
Method 3: N-methylpyrrolidone and polyhalogenoaromatic compound are mixed and heated, and the water-containing sulfidizing agent is added at such a rate that the water content in the reaction system falls within the range of 2 to 50 mol% of the organic polar solvent. In addition, a method of reacting a polyhalogenoaromatic compound with a sulfidizing agent.
Method 4: During the reaction between the alkali metal sulfide and the polyhalogenoaromatic compound in N-methylpyrrolidone, a part of the gas phase in the reaction vessel is condensed by cooling the gas phase portion of the reaction vessel, and this is liquid. A method for producing a polyarylene sulfide resin (PAS) by refluxing the phase;
Method 5: N-methylpyrrolidone, a non-hydrolyzable organic solvent, and a hydrous alkali metal sulfide are mixed, and then the obtained mixed solution is dehydrated to obtain a solid alkali metal sulfide and an alkali metal hydrosulfide ( b) and an alkali metal salt of a hydrolyzate of N-methylpyrrolidone (Step 1), and then in the presence of the slurry, a polyhalogenoaromatic compound, the alkali metal hydrosulfide, Polymerization by reacting with the alkali metal salt of the hydrolyzate of N-methylpyrrolidone prepared (Step 2)

  Among these, the method 3, the method 4, and the method 5 are particularly preferable because a linear high molecular weight polyarylene sulfide resin can be easily obtained.

  More specifically, the method 3 specifically includes heating the mixture of N-methylpyrrolidone and dihaloaromatic compound to 150 ° C. or higher, and then removing the water-containing sulfiding agent from the reaction mixture. By introducing at a rate that can be performed, a method of reacting while adjusting the water content in the reaction system to a range of 0.02 to 0.5 mol relative to 1 mol of the organic polar solvent can be mentioned. Here, the reaction temperature is preferably in the range of 200 to 300 ° C., preferably 210 to 280 ° C., from the viewpoint that the reaction proceeds well.

  After completion of the reaction, the reaction mixture is first added as it is, or after adding an acid or base, it is heated under reduced pressure or normal pressure to distill off only the solvent, and then the residual solid can is water, acetone, methyl ethyl ketone, alcohols. The target product can be recovered by washing once or more with a solvent such as neutralizing, washing with water, filtering and drying.

  Examples of the water-containing sulfiding agent used in Method 3 include water-containing materials such as alkali metal sulfides, alkali metal hydrosulfides, and mixtures thereof.

  Examples of the alkali metal sulfide include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and the like, and are used as hydrates and aqueous solutions. Among these, sodium sulfide and potassium sulfide are preferable, and sodium sulfide is particularly preferable. These alkali metal sulfides can be obtained by reacting an alkali metal hydrosulfide and an alkali metal base, or hydrogen sulfide and an alkali metal base, but those prepared outside the reaction system may also be used.

  Examples of the alkali metal hydrosulfide include lithium hydrosulfide, sodium hydrosulfide, potassium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and the like, and can be used as a hydrate or an aqueous solution.

  Among the alkali metal hydrosulfides, sodium hydrosulfide and potassium hydrosulfide are preferable, and sodium hydrosulfide is particularly preferable. These alkali metal hydrosulfides can be obtained by reacting hydrogen sulfide with an alkali metal base, but those prepared outside the reaction system may also be used.

  The polyhalogenoaromatic compounds used here are, for example, p-dihalobenzene, m-dihalobenzene, o-dihalobenzene, 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, 1,3,5-trihalo. Benzene, 1,2,3,5-tetrahalobenzene, 1,2,4,5-tetrahalobenzene, 1,4,6-trihalonaphthalene, 2,5-dihalotoluene, 1,4-dihalonaphthalene, 1 -Methoxy-2,5-dihalobenzene, 4,4'-dihalobiphenyl, 3,5-dihalobenzoic acid, 2,4-dihalobenzoic acid, 2,5-dihalonitrobenzene, 2,4-dihalonitrobenzene, 2,4-dihaloanisole, p, p′-dihalodiphenyl ether, 4,4′-dihalobenzophenone, 4,4′-dihalodiphenyl sulfone, 4, '- dihalodiphenyl sulfoxide, 4,4'-dihalodiphenyl sulfide, and a compound having an aromatic ring in the alkyl group having 1 to 18 carbon atoms of each of the above compounds as nuclear substituents. Moreover, it is desirable that the halogen atom contained in each compound is a chlorine atom or a bromine atom.

  Among these, the bifunctional dihalogenoaromatic compound is preferable from the viewpoint that the present invention can efficiently produce a linear high molecular weight PAS resin, and in particular, the mechanical strength of the finally obtained PAS resin From the viewpoint of good moldability, p-dichlorobenzene, m-dichlorobenzene, 4,4′-dichlorobenzophenone and 4,4′-dichlorodiphenyl sulfone are preferable, and p-dichlorobenzene is particularly preferable. When it is desired to give a branched structure to a part of the polymer structure of the linear PAS resin, 1,2,3-trihalobenzene, 1,2,4-trihalobenzene, or 1 together with the dihaloaromatic compound. , 3,5-trihalobenzene is preferably used in combination.

  Next, the method 4 will be described in detail. In the method 4, specifically, N-methylpyrrolidone, an alkali metal sulfide, and a polyhalogeno aromatic compound are charged into a reaction vessel, and first, under an inert gas atmosphere. Then, dehydration or water addition is performed as necessary so that the water content of the polymerization system becomes a predetermined amount. The amount of water in the reaction system is preferably 0.5 to 1.7 mol, particularly 0.8 to 1.2 mol, per mol of alkali metal sulfide, from the viewpoint of suppressing the formation of side reaction products. Here, the gas phase portion of the reaction vessel 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 refrigerant through an internal coil installed at the top of a reaction can, a method of flowing a coolant through an external coil or jacket wound around the top of the reaction can, and a reflux condenser installed at the top of the reaction can Examples thereof include a method of spraying water on the upper part outside the reaction can or blowing a gas (air, nitrogen, etc.).

  Moreover, as for the reaction conditions of the method 4, it is preferable to perform reaction for 0.1 to 20 hours on the temperature conditions of 230-275 degreeC.

  After completion of the reaction, the desired polyarylene sulfide resin (a1) can be obtained by filtration, solvent washing, acid treatment, water washing and, if necessary, solvent washing and water washing as necessary after completion of the reaction. .

  Next, the method 5 will be described in detail. Specifically, in the method 5, first, N-methylpyrrolidone, a polyhalogenoaromatic compound, and a hydrated alkali metal sulfide are mixed, and then the obtained mixed solution is mixed. Dehydration produces a slurry containing solid alkali metal sulfide, alkali metal hydrosulfide, and alkali metal salt of N-methylpyrrolidone hydrolyzate (step 1). Here, the amount of the N-methylpyrrolidone charged is less than the equivalent of N-methylpyrrolidone with respect to the hydrated alkali metal sulfide, and particularly 0.01 to 0 N-methylpyrrolidone with respect to 1 mol of the hydrated alkali metal sulfide. It is preferably used at a ratio of 9 mol.

  Next, water, polyhalogenoaromatic compound, alkali metal sulfide, N-methylpyrrolidone, etc. are added to the slurry obtained through step 1 as necessary, and the range is 180 to 300 ° C., preferably 200 to 280 ° C. The desired polyarylene sulfide resin (a1) can be obtained by reacting or polymerizing with.

  Here, the amount of the polyhalogenoaromatic compound in step 2 is specifically preferably in the range of 0.8 to 1.2 mol, particularly 0.9 to 1.1, per mol of sulfur atom in the reaction system. The molar range is preferable from the viewpoint of obtaining a higher molecular weight polyarylene sulfide resin (a1).

  In Step 2, therefore, in Step 2 of the present invention, the polyarylene sulfide resin (a1) indicates that the polymerization slurry is substantially anhydrous when the consumption rate of the solid alkali metal sulfide is 10%. From the viewpoint of high molecular weight.

  Here, as the polyhalogeno aromatic compound, any of those exemplified in the method 3 can be used, and as the hydrated alkali metal sulfide, any of the hydrated alkali metal sulfides exemplified in the method 3 can be used.

  The polyarylene sulfide resin (a1) thus obtained has a peak molecular weight in the range of 35,000 or more when measured using gel permeation chromatography, and has low temperature impact resistance and toughness. It is preferable because the improvement is remarkable, and 200,000 or less is preferable because the fluidity during molding is good. Especially, it is especially preferable that it is the range of 40,000-100,000 from the point of these performance balances. Here, it can obtain | require by a gel permeation chromatography. Although there is no particular limitation in this measurement method, 1-chloronaphthalene can be used as a dissolving solvent for the PAS resin, and it can be dissolved and measured at a high temperature of about 200 ° C. The molecular weight of the polyarylene sulfide resin (A) used in the present invention is particularly preferably a non-Newton index of 1.00 to 1.30.

  Next, the polyvalent isocyanate compound (a2) used in the present invention includes, for example, tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, 2,2,4 (2,4,4) -trimethyl as specific compounds. Alkylene diisocyanates such as hexamethylene diisocyanate; isocyanurate-type aliphatic polyisocyanates trimerized from the alkylene diisocyanate; urethane bond-containing aliphatic polyisocyanates which are reaction products of the alkylene diisocyanate and ethylene glycol or trimethylolpropane; hexamethylene Diisocyanate pentamerization and heptamization products; cyclophoric diisocyanates such as isophorone diisocyanate and dicyclohexyldimethylmethane diisocyanate; Diisocyanate and aliphatic isocyanate such as diethyl fumarate diisocyanate; phenylene diisocyanate, xylene diisocyanate, toluene diisocyanate, naphthylene-1,5-diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenylpropane diisocyanate, 2 Quantified toluene diisocyanate, carbodiimide modified diphenylmethane diisocyanate, 3,3′-dimethylphenylmethane-4,4′-diisocyanate, 3,3′-dimethyl-4,4′-diphenylene diisocyanate, 3,3′-bitoluene-4, 4′-diisocyanate, bis (4-isocyanatephenyl) ether, bis (4-isocyanatephenyl) thioether, bis (4-isocyanate) Aromatic diisocyanates such as phenyl) sulfone; aromatic triisocyanates such as triphenylmethane triisocyanate, triisocyanate benzene, triisocyanate naphthalene, tris (4-isocyanatephenyl) phosphite, tris (4-isocyanatephenyl) phosphate, polymethylene Examples thereof include polyfunctional isocyanates such as polyphenyl polyisocyanate, and water additions of the aromatic diisocyanate or aromatic triisocyanate.

  Among these, alkylene diisocyanate, isocyanurate type aliphatic polyisocyanate obtained by trimerization of the alkylene diisocyanate, and aromatic diisocyanate are preferable from the viewpoint of excellent adhesion to other resin components.

  Further, the polyarylene sulfide resin composition (A) has a content of the polyvalent isocyanate compound (a2) of 0.1 to 4% by mass, so that the polyarylene sulfide resin composition (A) has a melt stability. It is preferable from the viewpoint that the adhesiveness with the thermoplastic resin (B) becomes good when co-extruded with the thermoplastic resin (B), and is particularly preferable from the viewpoint that these effects appear remarkably. It is preferably 5 to 3% by mass.

  Next, the thermoplastic elastomer (a3) in the polyarylene sulfide resin composition (A) imparts impact resistance to the multilayer laminate and also improves the adhesion to the thermoplastic resin (B). It is an essential ingredient. Specifically, the thermoplastic elastomer (a3) has a melting point of 300 ° C. or less and has rubber elasticity at room temperature, and the dispersibility when melt-kneaded with the polyarylene sulfide resin (A). From the point which is excellent in it. In addition, polyolefin elastomers or nitrile elastomers are preferred from the viewpoints of excellent heat resistance, easy mixing, and remarkable effect of improving impact resistance.

  Examples of the polyolefin-based elastomer include those having a functional group such as a hydroxyl group, a carboxyl group, an amino group, a mercapto group, an epoxy group, an acid anhydride group, an isocyanate group, an ester group, and a vinyl group. It is preferable from the viewpoint of excellent compatibility with a1).

  Furthermore, among these, a functional group or an epoxy group derived from a carboxylic acid such as an acid anhydride, an acid, or an ester is particularly preferable.

  The polyolefin-based elastomer can be obtained, for example, by copolymerization of α-olefins and vinyl polymerizable compounds having the functional group. Examples of the α-olefins include α-olefins having 2 to 8 carbon atoms such as ethylene, propylene, and butene. Examples of the vinyl polymerizable compounds having the functional group include, for example, α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters, and alkyl esters thereof, maleic acid, Fumaric acid, itaconic acid, other unsaturated dicarboxylic acids having 4 to 10 carbon atoms, mono- and diesters thereof, and α, β-unsaturated dicarboxylic acids such as acid anhydrides thereof, anhydrides thereof, glycidyl (meth) acrylate, etc. Is mentioned.

  A copolymer containing a plurality of these functional groups at the same time can be used. Preferable examples thereof include terpolymers of α-olefins, maleic anhydride and glycidyl acrylate.

  Next, the nitrile elastomer is specifically obtained by copolymerization of a nitrile having an unsaturated bond such as acrylonitrile or methacrylonitrile with butadiene having a conjugated double bond, methylbutadiene or the like. Can be mentioned. The copolymer is more preferably of a type in which part or all of the double bonds are hydrogenated to improve heat resistance.

  The thermoplastic elastomer (a3) containing these functional groups has good dispersibility with the polyarylene sulfide resin (A), and it becomes easy to obtain a uniformly mixed resin composition, and is resistant to low temperature rupture. Etc. improve.

  The blending ratio of the thermoplastic elastomer (a3) is preferably 10 to 20% by mass in the polyarylene sulfide resin composition (A) from the viewpoint of excellent balance between adhesion improvement and barrier property, particularly 12 to 12%. It is preferable that it is 18 mass%.

  The polyarylene sulfide resin composition (A) used in the present invention is composed of various inorganic or organic reinforcements in addition to the polyarylene sulfide resin (a1), the polyvalent isocyanate compound (a2), and the thermoplastic elastomer (a3). Materials, fillers, lubricants, stabilizers and the like can be used in combination. These blending amounts are preferably 5% by weight or less in the polyarylene sulfide resin composition (A).

  The method for producing the polyarylene sulfide resin composition (A) is carried out by using a polyarylene sulfide resin (a1), a polyvalent isocyanate compound (a2), a thermoplastic elastomer (a3), and other compounding components in advance such as a Henschel mixer or a tumbler. And a method of obtaining the mixture by feeding to a single or twin screw extruder kneader, kneading at 250 ° C. to 350 ° C., granulating and pelletizing. In particular, the kneading machine is preferably a twin-screw extrusion kneader rotating in the same direction and equipped with a kneading disk for kneading from the viewpoint of good composition uniformity.

  Next, one or more functional groups selected from amino groups, amide groups, hydroxyl groups, carboxyl groups, acid anhydride groups, isocyanate groups and epoxy groups, which are co-extruded with the polyarylene sulfide resin composition (A) described above. Specifically, the thermoplastic resin (B) having a group includes a polycarbonate resin having a hydroxyl group at a molecular end, a polyester resin having a hydroxyl group and a carboxyl group, a polyurethane having a hydroxyl group and an isocyanate group, and an epoxy group, a carboxyl group, Or the modified polyolefin which has an acid anhydride group in a pendant form, a polyamide resin, etc. are mentioned.

  Specific examples of the polycarbonate resin include polymer carbonates of bifunctional phenol compounds. Examples of the bifunctional phenol compounds include bis (4-hydroxyphenyl) methane, 2,2- Bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4,4-bis (hydroxyphenyl) heptane, 2,2-bis (4-hydroxy-3,5) -Dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, bis (4-hydroxyphenyl) ether, bis (3,5-dichloro-4-hydroxyphenyl) ether, bis ( 4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bi Bisphenols such as (4-hydroxyphenyl) sulfoxide and bis (3,5-dibromo-4-hydroxyphenyl) sulfoxide; p, p′-dihydroxybiphenyl, 3,3′-dichloro-4,4′-dihydroxybiphenyl, etc. And dihydroxybenzenes such as resorcinol, hydroquinone, 1,4-dihydroxy-2,5-dichlorobenzene and 1,4-dihydroxy-3-methylbenzene.

  Further, in order to produce the polycarbonate resin, the carbonating agent to be reacted with the bifunctional phenol compound described above specifically includes carbonyl halides such as carbonyl bromide and carbonyl chloride, diphenyl carbonate, di (chlorophenyl). ) Carbonates, carbonate esters such as di (tolyl carbonate and dinaphthyl carbonate), and haloformates such as hydroquinone bischloroformate and ethylene glycol haloformate.

  The polyester resin is preferably an aromatic polyester resin obtained from an aromatic dicarboxylic acid and an aliphatic diol, and in particular, a dicarboxylic acid and an aliphatic diol in which 60 mol% or more of the dicarboxylic acid component is terephthalic acid. Aromatic polyesters obtained from the above are preferred. Here, examples of other compounds of terephthalic acid as the dicarboxylic acid component include azelaic acid, sebacic acid, adipic acid, and dodecanedicarboxylic acid. On the other hand, examples of the aliphatic diol include ethylene glycol, propylene glycol, 1,4-butanediol, trimethylene glycol, hexamethylene glycol, and cyclohexene dimethanol. Specific examples of such a polyester resin include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexene dimethylene terephthalate, and the like. Among these, polyethylene terephthalate and polybutylene terephthalate are particularly preferable from the viewpoint of adhesion to the polyarylene sulfide resin composition (A).

  Moreover, the polyurethane resin used here is obtained from polyisocyanate and diol, and as polyisocyanate, 2,4-tolylene diisocyanate, hexamethylene diisocyanate, metaxylene diisocyanate, and 4,4′- Examples thereof include diphenylmethane diisocyanate.

  Next, the modified polyolefin having an epoxy group, a carboxyl group, or an acid anhydride group in a pendant shape has a polyolefin as a main chain, and has an epoxy group, a carboxyl group, or an acid anhydride group in a pendant shape on its side chain. is there.

  Specific examples of the polyolefin containing an epoxy group include a copolymer of glycidyl (meth) acrylate such as glycidyl acrylate and glycidyl methacrylate and an α-olefin, and a carboxyl group or an acid anhydride group. Examples of the polyolefin containing olefin include those obtained by reacting a polyolefin resin with maleic acid, succinic acid, phthalic acid, or acid anhydrides thereof.

  Specific examples of the α-olefin used here include ethylene, propylene, butene-1,4-methylpentene-1, hexene 1, decene-1, and octene-1.

  Next, examples of the polyamide resin include amino acid compounds, polymers of lactam compounds, and polycondensates of diamine compounds and dicarboxylic acid compounds.

  Specific examples of the amino acid compound include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and paraaminomethylbenzoic acid. Examples of the lactam compound include ε-aminocaprolactam and ω-laurolactam.

  Next, the diamine compound used for the polycondensate of the diamine compound and the dicarboxylic acid compound is tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2,2,4- / 2,4,4. -Aliphatic diamines such as trimethylhexamethylenediamine and 5-methylnonamethylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3 , 5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, Alicyclic diamines such as aminoethylpiperazine, meta Cyclohexylene diamine, aromatic diamines of p-xylylenediamine, and the like.

  On the other hand, dicarboxylic acid compounds are aliphatic dicarboxylic acids such as adipic acid, speric acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methyl Aromatic dicarboxylic acids such as isophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid and the like can be mentioned.

  Of these, polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon), in particular because of its excellent barrier properties and impact resistance to fuels such as gasoline. 46), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecane (nylon 612), polydodecanamide (nylon 12), polyundecanamide (nylon 11), polyhexamethylene terephthalamide (nylon 6T), Polyxylylene adipamide (nylon XD6) is preferable, and 6-nylon, 66-nylon and 12-nylon are particularly preferable.

  These polyamide resins have a relative viscosity measured at 25 ° C. in a concentrated sulfuric acid solution having a degree of polymerization of 1% in the range of 1.5 to 7.0, particularly in the range of 2.0 to 6.5. It is preferable from the viewpoint of excellent impact resistance.

  Among the thermoplastic resins (B) having one or more functional groups selected from amino groups, amide groups, hydroxyl groups, carboxyl groups, acid anhydride groups, isocyanate groups, and epoxy groups described in detail above, particularly fuels. Polyamide resin is preferred from the viewpoint of excellent impact resistance and fuel barrier properties in the use of fuel piping members such as tubes.

  The multilayer laminate of the present invention is obtained by coextrusion of the polyarylene sulfide resin composition (A) and the thermoplastic resin (B). Here, the method of co-extrusion specifically, in order to obtain a tubular molded body such as a fuel tube, the polyarylene sulfide resin composition (A) and the thermoplastic resin (B), There is a method in which it is put into an extruder, melted and kneaded, and then formed into a laminated tube through a die while contacting in a molten state. Here, the extruder is preferably a uniaxial or biaxial extruder, and is provided with a tube die that unifies the plasticized resin in each cylinder at a die portion into one multilayer tube. The temperature in the cylinder when the polyarylene sulfide resin composition (A) is melt-kneaded is preferably 280 to 320 ° C., and the temperature in the cylinder when the thermoplastic resin (B) is melt-kneaded is 230 to 320 ° C. It is preferable that it is 270 degreeC.

  When obtaining the said tube molded object, the layer structure is the layer which consists of the said polyarylene sulfide resin composition (A) in an inner layer (henceforth abbreviated as "(A) layer"), and the said thermoplastic resin (henceforth "A" layer). It may be a two-layer structure having a layer made of B) (hereinafter abbreviated as “(B) layer”), and further, the (A) layer is disposed on the outer side of the (B) layer. A three-layer structure or a four-layer structure in which the (A) layer is disposed outside the (A) layer may be used. In the present invention, in particular, a two-layer structure is preferable from the viewpoint of a good balance between impact resistance and fuel barrier properties.

  Further, the thickness per layer in the multilayer laminate of the present invention varies depending on the application, but for example, when used for a fuel tube, the total thickness of the tubular molded body is preferably 0.8 to 1.2 mm, The ratio of the thickness of one layer of the (A) layer and the thickness of one layer of the (B) layer is (A) layer / (B) layer = 10/90 to 40/60. From the point of balance with the nature.

  In order to obtain a molded body such as a fuel tank or a container as the multilayer laminate of the present invention, the polyarylene sulfide resin composition (A) and the thermoplastic resin (B) are coextruded into a multilayer sheet and rolled. In addition to a stretching method, a tenter stretching method, a tubular stretching method, a stretching blow method, etc., it can be produced by shaping by a molding method such as deep drawing or vacuum forming. In applications such as fuel tanks and containers, the liquid contact surface side with the fuel or the like is a layer made of the polyarylene sulfide resin composition (A) and the outside is a layer made of the thermoplastic resin (B). It is preferable from the viewpoint of fuel barrier properties.

  As described above, the multilayer molded body of the present invention described in detail above is suitable for piping members, containers, and fuel tubes when transporting an organic fluid such as fuel. Specific applications include pipes, lining pipes, Cap nuts, pipe joints (elbow, header, cheese, reducer, joint, coupler, etc.), various valves, flow meters, gaskets (seal, packing), etc. Various parts, housings such as fuel pumps and canisters, fuel tanks and the like can be mentioned. The member of the present invention may of course be combined with other materials by combining with other materials, bonding, caulking, or the like.

The effects of the present invention will be described below with reference to examples and reference examples.
(Measurement method and evaluation method)
[Measurement of peak molecular weight]
The peak molecular weight of the polyarylene sulfide resin obtained in Synthesis Example 1 below was measured by gel permeation chromatography.

Apparatus: Ultra-high temperature polymer molecular weight distribution measuring apparatus (“SSC-7000” manufactured by Senshu Kagaku Co., Ltd.)
Column: UT-805L (made by Showa Denko KK)
Column temperature: 210 ° C
Solvent: 1-chloronaphthalene 6 types of monodisperse polystyrene are calibrated with UV detector (360nm)
The molecular weight distribution and peak molecular weight were measured.
[Shock resistance]
Each polyarylene sulfide resin composition prepared by blending the following Table-1 was evaluated by performing notched Izod impact strength at 23 ° C. in accordance with ASTM D-256.
[Fuel barrier properties]
For each polyarylene sulfide resin composition prepared by blending the following Table-1, the gas permeation coefficient at 40 ° C. of fuel C fuel (isooctane / toluene / ethanol = 45/45/10 vol%) conforms to JIS K7126 A method The pressure was measured by differential pressure GC detection.

Apparatus; Gas permeability / moisture permeability measuring device: “GTR-30VAD” manufactured by GTR Tech
GC detector: “GC-14A” manufactured by Shimadzu Corporation
[Peel strength]
Using the tube obtained by the multilayer tube manufacturing method manufactured in each example and comparative example, the tube was cut open in the length direction to form a sheet, and the sheet was cut to a width of 10 mm. The peel strength was measured at a predetermined temperature.

Production Example 1
(Synthesis of PPS resin)
First, the following materials were mixed to prepare a hydrous sulfiding agent.

(1) Water-containing flaky sodium sulfide (manufactured by Nagao): 1.5kg
Purity / Na ₂ S (58.9% by mass), NaSH (1.3% by mass)
(2) Hydrous flaky sodium hydrosulfide (manufactured by Nagao); 0.225 kg
Purity / NaSH (71.2% by mass), Na ₂ S (2.7% by mass)
(3) Water 0.425kg
As described above, 2.15 kg of a water-containing sulfiding agent was prepared by mixing three types.

  Next, paradichlorobenzene (1.838 kg), N-methylpyrrolidone (4.958 kg), water (0.09 kg) were added to a reaction tank equipped with a temperature sensor, a cooler, a dropping tank, a distillate separation tank, and a stirring blade. Was heated to 100 ° C. with stirring under a nitrogen atmosphere. After sealing the reaction vessel, the water-containing sulfidizing agent (2.15 kg) was added dropwise at 220 ° C. and an internal pressure of 0.22 MPa.

  During the dropping reaction, dehydration is performed, the paradichlorobenzene co-evaporated is returned to the reaction tank, and water is discharged out of the system, so that the amount of water in the system is 0.02 to 0.5 mol per 1 mol of N-methylpyrrolidone. The reaction was carried out with adjustment. The reaction was carried out until the temperature reached 240 ° C. by heating, and then the reaction was terminated by maintaining at 240 ° C. for 1 hour.

It can be confirmed that water is 0.17 mol% of the polar solvent (N-methylpyrrolidone) at the end of the reaction, and the polymer is 0.02 to 0 with respect to 1 mol of the polar solvent during and after the reaction. It was confirmed that it was in a 5 mol range.
The reaction product was washed with water and dried to obtain a white powdered polymer. This polymer is designated as “PPS-1”. PPS-1 had a peak molecular weight of 40,700 and a non-Newton index of 1.05.

(Preparation of polyarylene sulfide resin composition (A))
The various materials shown in Table-1 were uniformly mixed at the mass percentages shown in Table-1, and then kneaded and extruded at 290 to 330 ° C. using a 35 mmφ twin-screw extruder to form a composition “A-1” to “A-8” was obtained.

The abbreviations in Table 1 are as follows.
ADD-1: 4,4′-diphenylmethane diisocyanate ADD-2: Isocyanurate type aliphatic polyisocyanate (“Bernock DN-980S” manufactured by Dainippon Ink & Chemicals, Inc.)
ELA-1: Ethylene / glycidyl methacrylate copolymer
("Bond First E" manufactured by Sumitomo Chemical Co., Ltd.)
ELA-2: ethylene butene copolymer (“Tuffmer A-4085” manufactured by Mitsui Chemicals, Inc.)

Examples 1-4, Comparative Examples 1-3
[Production of multilayer tube]
A two-layer tube having two plasticizing cylinders (inner diameter 20 mmφ, single-screw extrusion screw) and a die for a tube in which the plasticized resin in each cylinder is united into one two-layer tube at the die portion. Using the production apparatus, the tube shown in Table-2 was used to extrude the tube at the temperature shown in Table-2, and the winding speed was adjusted to produce a two-layer tube having an outer diameter of 8 mmφ and an inner diameter of 6 mmφ. In these two-layer tubes, the inner layer had a thickness of 0.2 to 0.3 mm, and the outer layer had a thickness of 0.8 to 0.7 mm.

[Evaluation of tube]
The peel strength was evaluated based on the above evaluation method.

Abbreviations in Table-2 are as follows.
PA-12: 12-nylon ("Mills amide L25W40" manufactured by EMS Showa Denko KK)

Claims (7)

A polyarylene sulfide resin composition (A) comprising the polyarylene sulfide resin (a1), the polyvalent isocyanate compound (a2), and the thermoplastic elastomer (a3) as essential components, an amino group, an amide group, a hydroxyl group, a carboxyl group, A multilayer molded article having a structure obtained by co-extrusion with a thermoplastic resin (B) having one or more functional groups selected from an acid anhydride group, an isocyanate group and an epoxy group. The multilayer molded article according to claim 1, wherein the thermoplastic resin (B) is an aliphatic polyamide. The multilayer molded article according to claim 1 or 2, wherein a content of the polyvalent isocyanate compound (a2) in the polyarylene sulfide resin composition (A) is 0.1 to 4% by mass. The multilayer molded article according to claim 1, 2, or 3, wherein the content of the thermoplastic elastomer (a3) in the polyarylene sulfide resin composition (A) is 10 to 20% by mass. The polyarylene sulfide resin (a1) in the polyarylene sulfide resin composition (A) has a peak molecular weight of 35,000 to 200,000 in a molecular weight distribution determined by gel permeation chromatography. A multilayer molded article according to any one of the above. The multilayer molded article according to claim 5, wherein the polyarylene sulfide resin (a1) in the polyarylene sulfide resin composition (A) is a linear polyarylene sulfide having a non-Newton index of 1.00 to 1.30. A fuel component comprising the multilayer molded body according to any one of claims 1 to 6.