JP2008213459A - Multilayered molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a multilayer thermoplastic resin molding which is excellent in antifreeze resistance, chemical resistance, gas-barrier properties, flexibility, moldability, and interlaminar adhesion. <P>SOLUTION: The multilayer molding comprising at least three layers includes a layer (i) made of a polyamide resin composition, a layer (ii) made of a resin composition in which 80-300 pts.wt. of a polyamide resin (B) is mixed with 100 pts.wt. of a polyphenylene sulfide resin (A), and a layer (iii) made of a polyphenylene sulfide resin composition not containing an epoxy-modified thermoplastic resin. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention is a multilayer molded article having excellent antifreeze resistance, chemical resistance, gas permeation resistance, flexibility, moldability, and excellent adhesion between layers, at least a layer containing a polyamide resin, a polyamide in a specific ratio It is a multilayer molded article composed of a resin, a polyphenylene sulfide resin (hereinafter referred to as PPS resin), a thermoplastic resin having a functional group, a layer made of a resin composition containing a thermoplastic resin, and a layer containing a polyphenylene sulfide resin.

  For example, a technology for producing a hollow molded article of a thermoplastic resin by blow molding or extrusion molding using a polyamide-based resin or a saturated polyester resin mainly in a duct or a fuel line in an engine room of an automobile is widely used. However, conventional single-layer hollow molded products made of thermoplastic resins such as polyamide resins and saturated polyester resins are not suitable because they are insufficient in heat resistance, chemical resistance, gas permeability resistance, wear resistance, Therefore, products with further improved heat resistance, chemical resistance, gas permeation resistance, wear resistance and the like are required.

  PPS resin is excellent in heat resistance, hot water resistance, chemical resistance, flame retardancy, electrical characteristics and the like, and its demand is increasing for applications such as electricity, electronic parts, and automobile parts. However, PPS resin has a high molding temperature and a low melt viscosity. Moreover, since the solidification speed of the resin is high, it is inferior particularly in blow molding and extrusion moldability, which is not preferable in terms of moldability.

Therefore, in order to obtain a molded product that combines the properties of thermoplastic resins other than PPS resin, such as mechanical properties and moldability, and the properties of PPS resin such as heat resistance, hot water resistance, and chemical resistance, both materials are laminated. It is possible.
Recently, hollow molding materials that take advantage of the characteristics of the PPS resin are disclosed in Patent Documents 1 and 2 and the like.

  Therefore, in order to obtain a molded product that combines the properties of thermoplastic resins other than PPS resin such as mechanical properties, moldability, and economy with the properties of PPS resin such as heat resistance, hot water resistance, and chemical resistance, both materials It is conceivable to laminate the layers. However, even if a PPS resin and a thermoplastic resin other than the PPS resin are simply laminated, there is no adhesion between the two materials, so that peeling occurs between the resin layers, and the intended molded product cannot be obtained.

  Therefore, Patent Documents 1, 2, 3 and the like have already been reported as a method for laminating a PPS resin and another thermoplastic resin.

However, further improvements in adhesion, impact resistance, and flexibility are required.
JP 63-301252 A JP-A-10-298431 Japanese National Patent Publication No. 10-138372

  The present invention has been achieved as a result of studying improvement of the problems possessed by the above-mentioned single-layer molded products of polyamide resin, saturated polyester resin, and PPS resin. Excellent balance of chemical resistance such as water resistance, chemical resistance, gas permeability, wear resistance, heat resistance, chemical resistance such as zinc chloride, calcium chloride, and amine resistance, moldability, adhesion between layers, and flexibility A multilayer molded article is provided.

  A composition produced by blending a specific amount of a specific functional group-containing thermoplastic resin and a non-functional thermoplastic resin with respect to a PPS resin and a polyamide resin, and following a predetermined extrusion order. It has been found that a multilayer molded article in which at least one layer is a polyamide resin or PPS resin group can achieve the above-mentioned object effectively by using as an intermediate layer.

In order to solve the above problems, the present invention is as follows.
1. A multilayer molded article comprising at least three layers,
(I) a layer comprising a polyamide resin composition,
(Ii) (A) a layer comprising a resin composition obtained by blending 80 to 300 parts by weight of (B) polyamide resin with respect to 100 parts by weight of polyphenylene sulfide resin, and (iii) polyphenylene sulfide containing no epoxy-modified thermoplastic resin A multilayer molded article comprising a layer comprising a resin composition.
2. (Ii) Thermoplastic resins 20 to 200 in which the resin composition constituting the layer has (C) at least one functional group selected from an epoxy group, an acid anhydride group, a carboxyl group, a carboxylate, and a carboxylic acid ester. 2. The multilayer molded article according to 1, which is a resin composition obtained by blending parts by weight.
3. (Ii) The resin composition constituting the layer comprises (D) 10 to 100 parts by weight of a thermoplastic resin having no epoxy group, acid anhydride group, carboxyl group, carboxylate, or carboxylic acid ester. 3. A multilayer molded article according to 1 or 2, which is a resin composition.
4). (Ii) The resin composition which comprises a layer is any one of 1-3 which is a resin composition formed by mix | blending 100-250 weight part of (B) polyamide resin with respect to 100 weight part of (A) polyphenylene sulfide resin. Multi-layer molded product.
5. (Ii) Heat having at least one functional group selected from the above-mentioned (C) epoxy group, acid anhydride group, carboxyl group, carboxylate, and carboxylate ester, which is blended in the resin composition constituting the layer The multilayer molded article according to any one of 2 to 4, wherein the plastic resin is a polyolefin resin composition.
6). (Ii) having at least one functional group selected from (C) an epoxy group, an acid anhydride group, a carboxyl group, a carboxylate, and a carboxylic acid ester, which is blended in the resin composition constituting the layer 6. The multilayer molded article according to 5, wherein the thermoplastic resin comprises (C1) a polyolefin resin containing an epoxy group and (C2) a polyolefin copolymer containing an acid anhydride group.
7). (Iii) The polyphenylene sulfide resin composition not including the epoxy-modified thermoplastic resin composition constituting the layer is (C3) at least one kind selected from an acid anhydride group, a carboxyl group, a carboxylate, and a carboxylate The multilayer molded article according to any one of 1 to 6, which is a polyphenylene sulfide resin composition obtained by blending 1 to 50 parts by weight of a thermoplastic resin having a functional group with respect to 100 parts by weight of the polyphenylene sulfide resin.
8). (Iii) The polyphenylene sulfide resin composition not containing the epoxy-modified thermoplastic resin composition constituting the layer is selected from (E) an epoxy group, an amino group, and an isocyanate group with respect to 100 parts by weight of the (A) polyphenylene sulfide resin. The multilayer molded article according to any one of 1 to 7, comprising 0.1 to 5 parts by weight of a compound having at least one kind of group.
9. The multilayer molded article according to any one of 1 to 8, wherein the multilayer molded article is a multilayer hollow molded article obtained by extrusion molding or blow molding.
10. 10. The multilayer molded article according to 9, wherein the multilayer molded article is an extruded multilayer tube.
11. The multilayer molded article according to 9 or 10, wherein the multilayer molded article is an automobile fuel pipe or a coolant pipe.
12 The multilayer molded article according to any one of 1 to 11, wherein the multilayer molded article has an interlayer adhesion of 40 N / cm or more, and the multilayer molded article has a tensile elongation at break of 100% or more.

  The multilayer molded article of the present invention is excellent in low temperature impact resistance, and the tube using the composition is excellent in adhesion and flexibility. Furthermore, surface appearance, heat resistance, antifreeze resistance, low temperature impact resistance, gas barrier resistance, chloride resistance It has a combination of chemical resistance such as zinc and calcium chloride, moldability, economy, etc., especially a fuel line for automobiles used under high temperature conditions or for many years in direct contact with water or aqueous solution, fuel oil. It can be beneficially used in heat medium circulation pipe applications such as cooling pipes, cooling pipes, snow melting or heating heating systems.

  The multilayer molded article of the present invention will be specifically described below.

  The polyamide resin composition constituting the (i) layer used in the present invention is a blend of polyamide resin. Specific examples of the polyamide resin include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polypentamethylene adipamide (nylon 56), polyhexamethylene sebacamide (nylon 610). , Polyhexamethylene dodecanamide (nylon 612), polyundecanamide (nylon 11), polydodecanamide (nylon 12), polycaproamide / polyhexamethylene adipamide copolymer (nylon 6/66), polycaproamide / poly Hexamethylene terephthalamide copolymer (nylon 6 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (nylon 66 / 6T), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer ( Iron 66 / 6I), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 6T / 6I), polyhexamethylene terephthalamide / polydodecanamide copolymer (nylon 6T / 12), polyhexamethylene adipamide / poly Hexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I), polyxylylene adipamide (nylon XD6), polyhexamethylene terephthalamide / poly-2-methylpentamethylene terephthalamide copolymer (nylon 6T / M5T), polynonamethylene terephthalamide (nylon 9T), and mixtures thereof.

  Particularly preferred polyamide resins include nylon 6, nylon 66, nylon 11, and nylon 12 in terms of moldability, mechanical properties, fuel barrier properties, and economy.

  The degree of polymerization of these polyamide resins is not particularly limited, but the relative viscosity measured at 25 ° C. in a 98% concentrated sulfuric acid solution having a sample concentration of 0.01 g / ml is in the range of 1.5 to 7.0. Particularly preferred is a polyamide resin in the range of 2.0 to 6.0.

  In addition to the polyamide resin, a thermoplastic elastomer or a plasticizer can be added to the polyamide resin composition constituting the (i) layer as necessary.

  Examples of the thermoplastic elastomer include olefin-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, polyester-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, and styrene-based thermoplastic elastomers, and olefin-based thermoplastic elastomers are particularly preferable.

  Specific examples of the plasticizer include hexylene glycol, glycerin, octyl p-oxybenzoate, 2-ethylhexyl p-oxybenzoate, heptyl p-oxybenzoate, N-methylbenzenesulfonamide, N-butylbenzenesulfonamide , P-toluenesulfonamide, N-ethyl-p-toluenesulfonamide, N-cyclohexyl-p-toluenesulfonamide, β-naphthol, and dibenzylphenol octylcresol.

  The (A) PPS resin blended in the (ii) resin composition constituting the layer and (iii) the PPS resin composition constituting the layer used in the present invention comprises 70 mol% of repeating units represented by the following structural formula. As mentioned above, it is a polymer containing preferably 90 mol% or more, and if the following repeating unit is less than 70 mol%, the heat resistance is impaired, which is not preferable.

  A PPS resin generally consists of a polymer having a relatively low molecular weight obtained by a production method represented by Japanese Patent Publication No. 45-3368 and an essentially linear product obtained by a production method represented by Japanese Patent Publication No. 52-12240. In the polymer obtained by the method described in the above Japanese Patent Publication No. 45-3368, the polymer is heated in an oxygen atmosphere after polymerization, or a peroxide or the like. It is also possible to increase the polymerization by adding the above crosslinking agent and heating.

  In the present invention, it is possible to use a PPS resin obtained by any method, but an essentially linear and relatively high molecular weight polymer is preferably used.

  Moreover, PPS resin can also comprise less than 30 mol% of the repeating units with repeating units having the following structural formula.

  The (A) PPS resin used in the present invention is preferably one that has been subjected to deionization treatment by an acid aqueous solution washing treatment or an organic solvent washing treatment after being produced through the above steps.

  The above acid aqueous solution cleaning treatment is performed as follows.

  The acid used for the acid aqueous solution cleaning treatment of the PPS resin is not particularly limited as long as it does not have an action of decomposing the PPS resin, and examples thereof include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid, and propyl acid. Of these, acetic acid and hydrochloric acid can be more preferably used, but those that decompose and deteriorate the PPS resin such as nitric acid are not preferable.

  The acid aqueous solution cleaning method includes a method of immersing a PPS resin in an acid aqueous solution, and can be appropriately stirred or heated as required. For example, when acetic acid is used, a PPS resin that has been subjected to an acid treatment, in which a PPS resin powder is immersed and stirred for 30 minutes in an aqueous pH 4 solution heated to 80 to 90 ° C., is obtained. In order to physically remove the remaining acid or salt, it is necessary to wash several times with water or warm water.

  The water used for washing is preferably distilled water or deionized water in the sense that it does not impair the advantageous scientific modification effect of the PPS resin by acid treatment.

  Moreover, when performing a hot water washing process, it is as follows.

  In the hot water treatment of the PPS resin, it is important that the temperature of the hot water is 100 ° C. or higher, more preferably 120 ° C. or higher, further preferably 150 ° C. or higher, particularly preferably 170 ° C. or higher. PPS resin is not preferred because of its small scientific modification effect.

  It is preferable that the water used in order to develop a preferable scientific modification effect of the PPS resin by the hot water washing treatment of the present invention is distilled water or deionized water. The operation of the hot water treatment is usually performed by charging a predetermined amount of PPS resin and heating and stirring in a pressure vessel. The ratio of the PPS resin to water is preferably higher, but usually a bath ratio of 200 g or less of PPS resin is selected for 1 liter of water.

  In addition, since the decomposition of the end groups is not preferable in the hot water treatment atmosphere, it is preferable to use an inert atmosphere in order to avoid this. Furthermore, it is preferable to wash the PPS resin after this hot water treatment operation several times with warm water in order to physically remove the remaining components.

  Further, in the case of the organic solvent cleaning treatment, it is as follows.

  The organic solvent used for washing the PPS resin is not particularly limited as long as it does not have an action of decomposing the PPS resin. For example, N-methylpyrrolidone, dimethylformamide, dimethylacetamide, 1,3-dimethylimidazolide Nitrogen-containing polar solvents such as nonone, hexamethylphosphoramide, and piverazinone, sulfoxides such as dimethyl sulfoxide, dimethyl sulfone, and sulfolane, sulfone solvents, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, and acetophenone, dimethyl ether, dipropyl Ether solvents such as ether, dioxane, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchlorethylene, monochloroethane, dichloroethane, tetrachloroethane Halogen solvents such as ethylene, perchlorethane, chlorobenzene, alcohols such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, polypropylene glycol, phenol solvents and benzene, Examples thereof include aromatic hydrocarbon solvents such as toluene and xylene. Among these organic solvents, use of N-methylpyrrolidone acetone, dimethylformamide, chloroform and the like is particularly preferable. In addition, these organic solvents are used in one or a mixture of two or more.

  As a cleaning method using an organic solvent, there is a method of immersing a PPS resin in an organic solvent, and it is possible to appropriately stir or heat as necessary.

  There is no restriction | limiting in particular about the washing | cleaning temperature at the time of wash | cleaning PPS resin with an organic solvent, Arbitrary temperature of about normal temperature-about 300 degreeC can be selected. Here, the higher the cleaning temperature, the higher the cleaning efficiency tends to be. However, a sufficient effect is usually obtained at a cleaning temperature of room temperature to 150 ° C.

  It is also possible to wash under pressure at a temperature above the boiling point of the organic solvent in a pressure vessel. There is no particular limitation on the cleaning time. Although depending on the washing conditions, in the case of batch type washing, a sufficient effect is usually obtained by washing for 5 minutes or more. It is also possible to wash in a continuous manner.

  Although it is sufficient to wash the PPS resin produced by the polymerization with an organic solvent, it is preferable to combine it with water washing or warm water washing in order to further exhibit the effects of the present invention. In addition, when a high-boiling water-soluble organic solvent such as N-methylpyrrolidone is used, it is preferable that the remaining organic solvent can be easily removed by washing with water or warm water after washing with the organic solvent. The water used for these washings is preferably distilled water or deionized water.

The melt viscosity of (A) PPS resin used in the present invention is not particularly limited, and is selected from (B) polyamide resin, (C) epoxy group, acid anhydride group, carboxyl group, carboxylate, and carboxylate ester to be blended Any melt viscosity can be used as long as it can be melt kneaded with a thermoplastic resin having at least one kind of functional group or (D) a thermoplastic resin having no functional group. Those having a melt viscosity of 100 to 10,000 poise at a shear rate of 10 sec ⁻¹ are preferably used.

  The (B) polyamide resin blended in the resin composition constituting the (ii) layer used in the present invention is a polyamide mainly composed of amino acids, lactams or diamines and dicarboxylic acids. Representative examples of the main constituents include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and paraaminomethylbenzoic acid, lactams such as ε-caprolactam and ω-laurolactam, pentamethylenediamine , Hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, Metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, Bis (4-aminosi Chlohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, aliphatic, alicyclic, aromatic Diamines, and adipic acid, speric acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid Examples include aliphatic, alicyclic, and aromatic dicarboxylic acids such as acids, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid. In the present invention, nylon derived from these raw materials Homopolymers or copolymers, each alone or in the form of a mixture It can be used.

  In the present invention, a particularly useful polyamide resin is a polyamide resin having a melting point of 150 ° C. or more and excellent in heat resistance and strength. Specific examples include polycaproamide (nylon 6), polyhexamethylene adipamide. (Nylon 66), polypentamethylene adipamide (nylon 56), polyhexamethylene sebamide (nylon 610), polyhexamethylene dodecane (nylon 612), polyundecanamide (nylon 11), polydodecanamide (nylon) 12), polycaproamide / polyhexamethylene adipamide copolymer (nylon 6/66), polycaproamide / polyhexamethylene terephthalamide copolymer (nylon 6 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide Copolymer (Nai 66 / 6T), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 6T / 6I), polyhexamethylene terephthalamide / Polydodecanamide copolymer (nylon 6T / 12), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I), polyxylylene adipamide (nylon XD6) Polyhexamethylene terephthalamide / poly-2-methylpentamethylene terephthalamide copolymer (nylon 6T / M5T), polynonamethylene terephthalamide (nylon 9T) and Mixtures of al and the like.

  Particularly preferred polyamide resins include nylon 6, nylon 66, nylon 11, and nylon 12 in terms of moldability, mechanical properties, fuel barrier properties, and economy.

  The degree of polymerization of these polyamide resins is not particularly limited, but the relative viscosity measured at 25 ° C. in a 98% concentrated sulfuric acid solution having a sample concentration of 0.01 g / ml is in the range of 1.5 to 7.0. Particularly preferred is a polyamide resin in the range of 2.0 to 6.0.

  The blending ratio of (A) PPS resin and (B) polyamide resin in the resin composition constituting the (ii) layer of the multilayer molded article of the present invention is (i) a layer comprising the polyamide resin composition or (iii) PPS resin composition From the viewpoint of adhesion to a layer made of a product, the polyamide resin is preferably 80 parts by weight or more and 300 parts by weight or less with respect to 100 parts by weight of the PPS resin. If the polyamide resin is less than 80 parts by weight, the PPS resin becomes a complete matrix. (I) Adhesive strength with the layer made of the polyamide resin composition decreases, and if it exceeds 300 parts by weight, the PPS resin that becomes the domain is small. Adhesive strength with the layer made of the composition is reduced. A more preferable blending ratio is 100 parts by weight or more and 250 parts by weight or less of polyamide resin with respect to 100 parts by weight of PPS resin. Further, (ii) the resin composition constituting the layer includes (C) a thermoplastic resin having at least one functional group selected from an epoxy group, an acid anhydride group, a carboxyl group, a carboxylate, and a carboxylic acid ester. It is preferable to blend a resin. (C) As a thermoplastic resin having at least one functional group selected from an epoxy group, an acid anhydride group, a carboxyl group, a carboxylate, and a carboxylic ester, an olefin copolymer having these functional groups And fluorine-based copolymers.

  (Ii) The resin composition constituting the layer is preferably blended with (C1) a thermoplastic resin having an epoxy group and / or (C2) a thermoplastic resin having an acid anhydride group. C1) an olefin copolymer having an epoxy group and / or (C2) an olefin copolymer having an acid anhydride group.

  (C1) The olefin copolymer having an epoxy group is an olefin copolymer having an epoxy group in the side chain or main chain, and does not include a normal epoxy resin. As an epoxy group-containing olefin copolymer, the double bond of an olefin copolymer having a glycidyl group such as glycidyl ester, glycidyl ether or glycidyl amine in the side chain or a double bond-containing olefin copolymer is epoxy-oxidized. Things. In the present invention, among these epoxy group-containing olefin copolymers, a copolymer comprising an α-olefin and an α, β-unsaturated glycidyl ester is preferably used. Examples of the α-olefin herein include ethylene, propylene, and butene-1. Further, the glycidyl ester of α, β-unsaturated acid is a compound represented by the following general formula, and specifically includes glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and the like, among which glycidyl methacrylate is particularly preferable. Is preferably used.

(However, R in the formula represents any one selected from a hydrogen atom and an alkyl group having 1 to 6 carbon atoms.)

  The (C1) epoxy group-containing polyolefin copolymer may be any random, block, or graft copolymer of the α-olefin and α, β-unsaturated acid glycidyl.

  The epoxy group content in the (C1) epoxy group-containing polyolefin copolymer of the present invention is preferably 1 to 50% by weight, more preferably 3 to 40% by weight. When the content is 1% by weight or more, the intended effect can be sufficiently exhibited. When the content is 50% by weight or less, no gel is formed during melt-kneading with the PPS resin, and the extrusion stability and moldability. It is preferable because it does not adversely affect the mechanical strength.

  The epoxy group-containing polyolefin copolymer of (C1) contains other olefin monomers such as methyl acrylate, methyl methacrylate, acrylonitrile, styrene, vinyl acetate and vinyl ether as long as the effects of the present invention are not impaired. It may be polymerized.

  The polyolefin copolymer having an acid anhydride group (C2) preferably used in the present invention includes polyethylene, polypropylene, polystyrene, ethylene-propylene copolymer, ethylene-butene copolymer, polybutene, and ethylene-propylene. -Maleic to polyolefin resins such as diene copolymer, styrene-butadiene copolymer, polybutadiene, butadiene-acrylonitrile copolymer, polyisoprene, butene-isoprene copolymer, and styrene-ethylene-butadiene-styrene copolymer Acid anhydride, succinic anhydride, fumaric anhydride, acrylic acid, methacrylic acid, vinyl acetate and its salts such as Na, Zn, K, Ca, Mg, methyl acrylate, methyl methacrylate, ethyl acrylate, methacryl Ethyl acid, acrylic acid pro Le, propyl methacrylate, butyl acrylate, butyl methacrylate, and the like copolymerized olefin copolymer. The copolymerization mode of such an olefin polymer is not particularly limited, and any copolymer mode such as a random copolymer, a graft copolymer, or a block copolymer may be used.

  The blending amount of the thermoplastic resin having at least one functional group selected from (C) an epoxy group, an acid anhydride group, a carboxyl group, a carboxylate, and a carboxylic acid ester is (A) 100 parts by weight of a PPS resin. The amount is preferably 20 to 200 parts by weight, more preferably 30 to 150 parts by weight. Since the melt viscosity of a resin composition can be made into an appropriate range by setting it as 20 weight part or more, since a moldability and impact resistance can fully be exhibited, it is preferable. It is preferable that the amount be 200 parts by weight or less because (A) a gel is not generated at the time of melt kneading with the PPS resin and the extrusion stability, moldability, mechanical strength, heat resistance and the like are not adversely affected.

  Two or more thermoplastic resins having at least one functional group selected from (C) an epoxy group, an acid anhydride group, a carboxyl group, a carboxylate, and a carboxylic acid ester may be used in combination. As (C1) an epoxy group-containing olefin copolymer and (C2) an acid anhydride group-containing olefin copolymer.

  A preferred ratio of (C1) epoxy group-containing olefin copolymer and (C2) acid anhydride group-containing olefin copolymer is 10: 1 to 1:10 (weight ratio), and a more preferred range is 5: 1. ˜1: 10 (weight ratio).

  Further, the resin composition constituting the (ii) layer of the present invention is blended with (D) a thermoplastic resin having no epoxy group, acid anhydride group, carboxyl group, carboxylate salt, or carboxylic acid ester. It is preferable to do. Examples of the component (D) include ethylene-propylene copolymers, ethylene-butene copolymers, polybutene, ethylene-propylene-diene copolymers, polyolefin resins such as ethylene-vinyl acetate copolymers, and styrene-butadiene. Copolymer, polybutadiene, butadiene-acrylonitrile copolymer, polyisoprene, diene resins such as butylene-isoprene copolymer and hydrogenated products thereof, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer And acrylic resins such as ethylene-isopropyl acrylate copolymer, ethylene-methyl methacrylate copolymer, and ethylene-ethyl methacrylate copolymer.

Of these, ethylene-propylene copolymer, ethylene-butene copolymer, and ethylene-propylene-diene copolymer are particularly preferable. Two or more thermoplastic resins containing no functional group selected from (D) an epoxy group, an acid anhydride group, a carboxyl group, a carboxylate, and a carboxylic acid ester may be used in combination. The thermoplastic resin not contained is preferably blended in an amount of 10 to 100 parts by weight with respect to 100 parts by weight of the (A) PPS resin, and a more preferred range is 15 to 80 parts by weight.

  By blending 10 parts by weight or more, the low-temperature impact property of the resin composition can be improved, and by setting it to 100 parts by weight or less, compatibility with other resins can be favorably maintained, which is preferable.

  In addition, the resin composition constituting the layer (ii) of the present invention includes a crystal nucleating agent, a mold release agent, an antioxidant, a heat stabilizer, a lubricant, an ultraviolet ray inhibitor, a colorant, and a difficult agent as long as the characteristics are not impaired. Conventional additives such as a flame retardant can be added.

  The method for preparing the resin composition constituting the layer (ii) of the present invention is, for example, by supplying a mixture of raw materials to a generally known melt mixer such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, and a mixing roll. A typical example is a method of melt-kneading at a temperature of 280 to 340 ° C.

  (Ii) When a resin composition constituting the layer is produced, if a PPS resin, a polyamide resin, and a functional group-containing thermoplastic resin are blended together and extruded, a gelation reaction occurs between the functional group-containing thermoplastic resins. In some cases, the reaction between the PPS resin or the polyamide resin and the desired functional group-containing thermoplastic resin does not proceed effectively, and the impact resistance, particularly the low temperature impact resistance, may not be sufficiently exhibited.

  As a method for suppressing abnormal reactions and obtaining good impact resistance, a PPS resin and a polyamide resin are individually extruded, a pellet is prepared, and then a two-stage extrusion method in which the PPS resin and the polyamide resin are alloyed. There is a side feed extrusion method in which a resin is supplied and a polyamide resin is supplied from the middle of a cylinder. Details of this extrusion method are described below.

  In the two-stage extrusion method, at least one selected from (A) a PPS resin and (C) an epoxy group, an acid anhydride group, a carboxyl group, a carboxylate, and a carboxylic acid ester from the hopper of a twin-screw extruder as the first stage. A thermoplastic resin having a seed functional group and a thermoplastic resin not containing (D) a functional group are supplied and melt-kneaded at a resin temperature of 280 ° C. to 340 ° C. to obtain a high impact PPS resin pellet. From the high impact PPS resin pellets obtained as the second stage and (B) polyamide resin or (B) polyamide resin and the remaining (C) epoxy group, acid anhydride group, carboxyl group, carboxylate, and carboxylate ester A thermoplastic resin having at least one selected functional group is blended, supplied to a hopper of a twin-screw extruder, and melt kneaded at a resin temperature of 280 ° C. to 340 ° C. to obtain a resin composition. Of course, at least one functional group selected from (B) polyamide resin and the remaining (C) epoxy group, acid anhydride group, carboxyl group, carboxylate salt, and carboxylate ester supplied during the second stage extrusion A thermoplastic resin having high impact polyamide resin pellets previously melt-kneaded may be used.

  In the side feed extrusion method, at least one functional group selected from (A) a PPS resin and (C) an epoxy group, an acid anhydride group, a carboxyl group, a carboxylate, and a carboxylate ester from a hopper of a twin screw extruder. (D) a thermoplastic resin not containing a functional group and (B) a polyamide resin or (B) a polyamide resin and the remaining (C) an epoxy group, an acid anhydride group, a carboxyl A method for obtaining a resin composition by supplying a blend of a thermoplastic resin having at least one functional group selected from a group, a carboxylate, and a carboxylic acid ester, and melt-kneading at a resin temperature of 280 ° C. to 340 ° C. It is. As the resin composition to be obtained, the two-stage extrusion method is excellent, but the side feed extrusion method is preferable from the viewpoint of economy.

  At this time, a method of supplying (C1) a polyolefin copolymer having an epoxy group from the hopper and (C2) a polyolefin copolymer having an acid anhydride group from the middle of the cylinder is preferably employed.

  In the resin composition constituting the layer (ii) thus obtained, the PPS resin phase is modified with a functional group-containing thermoplastic resin composition such as an epoxy group and a functional group-free thermoplastic resin. The resin phase is modified with an acid anhydride group-containing thermoplastic resin, and a resin composition suitable for the intermediate layer of a multilayer molded article having a very high low temperature impact property is obtained.

  The resin composition constituting the (ii) layer thus obtained preferably has a matrix of polyamide resin and a domain of PPS resin. This is because by using PPS resin as a domain, the dispersed particle size is reduced, the surface area of the domain is increased, and as a result, the outer layer and the inner layer are firmly bonded.

  It is important that the polyphenylene sulfide resin composition constituting the (iii) layer used in the present invention does not contain an epoxy-modified thermoplastic resin. By not containing an epoxy group-modified thermoplastic resin, the viscosity change in the extruder is small, and the continuous formability of extrusion molding is excellent. In the present invention, the resin composition constituting the (iii) layer is at least one selected from (C3) an acid anhydride group, a carboxyl group, a carboxylate, and a carboxylate ester with respect to 100 parts by weight of the (A) PPS resin. It is preferable to blend a thermoplastic resin having various functional groups. (C3) The toughness of the PPS resin composition is improved by blending 1 part by weight or more of a thermoplastic resin having at least one functional group selected from an acid anhydride group, a carboxyl group, a carboxylate, and a carboxylic acid ester. It is preferable because it can be improved. Moreover, it is preferable for it to be 50 parts by weight or less because the gas barrier property of the PPS resin composition is not lowered. More preferably, it is 5 to 40 parts by weight.

  (C3) As a specific example of a thermoplastic resin having at least one functional group selected from an acid anhydride group, a carboxyl group, a carboxylate, and a carboxylic ester, a polyolefin copolymer having an acid anhydride group Polyethylene, polypropylene, polystyrene, ethylene-propylene copolymer, ethylene-butene copolymer, polybutene, ethylene-propylene-diene copolymer, styrene-butadiene copolymer, polybutadiene, butadiene-acrylonitrile copolymer, poly Polyolefin resins such as isoprene, butene-isoprene copolymer, and styrene-ethylene-butadiene-styrene copolymer include maleic anhydride, succinic anhydride, fumaric anhydride, acrylic acid, methacrylic acid, vinyl acetate and Na, Zn, K, C Olefin copolymers such as salts of Mg, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, etc. Can be mentioned. The copolymerization mode of such an olefin polymer is not particularly limited, and any copolymer mode such as a random copolymer, a graft copolymer, or a block copolymer may be used.

  (Iii) The resin composition constituting the layer is selected from (E) an epoxy group, an amino group, and an isocyanate group that are effective as a compatibilizer for the (A) PPS resin and the (C3) functional thermoplastic resin. It is preferable to blend 0.1 to 5 parts by weight of the compound having one or more functional groups with respect to 100 parts by weight of the PPS resin. (E) By making the amount of the compound having one or more functional groups selected from an epoxy group, an amino group, and an isocyanate group to be 0.1 parts by weight or more, the thermoplastic resin having a functional group can be sufficiently dispersed. (I) It is preferable because layer peeling with the layer is difficult to occur and the toughness of a two-layer molded product can be improved. Further, the content of 5 parts by weight or less is preferable because the PPS resin composition does not gel and the appearance when a two-layer molded product is improved.

  (E) Specific examples of the compound having one or more functional groups selected from an epoxy group, an amino group and an isocyanate group include bisphenol A, resorcinol, hydroquinone, pyrocatechol, bisphenol F, saligenin, 1 , 3,5-trihydroxybenzene, bisphenol S, trihydroxy-diphenyldimethylmethane, 4,4′-dihydroxybiphenyl, 1,5-dihydroxynaphthalene, cashew phenol, 2,2,5,5-tetrakis (4- Hydroxyphenyl) glycidyl ethers of bisphenols such as hexane, those using halogenated bisphenol instead of bisphenol, glycidyl ether epoxy compounds such as diglycidyl ether of butanediol, phthalic acid group Glycidyl ester compounds such as sidyl esters, glycidyl epoxy resins such as glycidyl amine compounds such as N-glycidyl aniline, linear epoxy compounds such as epoxidized polyolefin and epoxidized soybean oil, vinylcyclohexene dioxide, dicyclopentadiene dioxide And cyclic non-glycidyl epoxy resins. In addition, other novolac type epoxy resins are also included. The novolac type epoxy resin has two or more epoxy groups and is usually obtained by reacting a novolac type phenol resin with epichlorohydrin. Moreover, a novolac type phenol resin is obtained by a condensation reaction of phenols and formaldehyde. Although there is no restriction | limiting in particular as phenols of a raw material, Phenol, o-cresol, m-cresol, p-cresol, bisphenol A, resorcinol, p-tertiary butylphenol, bisphenol F, bisphenol S, and these condensates are mentioned.

  Furthermore, the alkoxysilane which has an epoxy group is mentioned. Specific examples of such compounds include epoxy group-containing alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. A compound etc. can be illustrated.

  Examples of the amino group-containing compound include alkoxysilanes having an amino group. Specific examples of such compounds include amino group-containing alkoxysilanes such as γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane. Compound etc. are mentioned.

  Examples of the compound containing at least one isocyanate group include isocyanate compounds such as 2,4-tolylene diisocyanate, 2,5-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, polymethylene polyphenyl polyisocyanate, and γ-isocyanate. Propyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanate An isocyanate group-containing alkoxysilane compound such as propyltrichlorosilane can be exemplified.

  In particular, in order to obtain a stable and high toughness expression effect, it is preferably at least one compound selected from a compound containing one or more isocyanate groups or a compound containing two or more epoxy groups, and more preferably one or more isocyanate groups. More preferably, it is a compound containing.

  As the PPS resin composition not including the epoxy-modified thermoplastic resin constituting the (iii) layer used in the present invention, (C3) a PPS resin composition not including the thermoplastic resin having the functional group described above is also useful. is there. (Iii) Specific examples of the PPS resin composition constituting the layer include those obtained by adding 1 to 20 parts by weight of polyamide or polyetherimide to 100 parts by weight of (A) polyphenylene resin. Use of polyamide or polyetherimide in place of the thermoplastic resin having a functional group is preferable because the gas barrier property is greatly improved, and a product having a good appearance without protrusions on the surface of the extruded product is obtained.

  Furthermore, it is also possible to add an unmodified olefin resin to the PPS resin composition constituting the (iii) layer used in the present invention as long as the performance is not impaired. Preferred unmodified olefinic resins are high density polyethylene, medium density polyethylene, low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, polybutene, ethylene-propylene-diene copolymer, ethylene- Polyolefin resins such as vinyl acetate copolymers, styrene-butadiene copolymers, polybutadiene, butadiene-acrylonitrile copolymers, diene resins such as polyisoprene butene-isoprene copolymers and their hydrogenated products, ethylene-acrylic Examples include acrylic resins such as methyl acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-isopropyl acrylate copolymer, ethylene-methyl methacrylate copolymer, and ethylene-ethyl methacrylate copolymer. ,these Et al. May be used in combination of two or more members selected.

  The method for preparing the PPS resin composition constituting the layer (iii) used in the present invention is, for example, by mixing a raw material mixture into a generally known melt mixer such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, and a mixing roll. As a typical example, a method of supplying and melt-kneading at a temperature of 280 to 340 ° C. can be given as a typical example, but melt kneading with a twin-screw extruder is particularly preferable.

  In the multilayer molded article of the present invention, (ii) layer (layer made of resin composition) is an intermediate layer, and (i) layer (layer made of polyamide resin composition), (iii) layer (polyphenylene sulfide resin) It is preferable that the layer comprising the composition is present on the outside or the inside. (Ii) When the PPS resin of the resin composition constituting the layer is a matrix, high chemical resistance of the PPS resin can be expected, but (i) layer: the adhesive strength with the layer made of the polyamide resin composition is lowered. There is a tendency. (Ii) When the resin composition constituting the layer has a PPS resin domain, a high interlayer adhesion can be obtained, but the high chemical resistance of the PPS resin cannot be expected. Therefore, it is possible to overcome the weak point by arranging the (iii) layer (a layer made of a polyphenylene sulfide resin composition) as a chemical resistant layer, and a multilayer molded product excellent in antifreezing liquid resistance, chemical resistance and the like can be obtained. can get.

  As a method for producing such a multilayer molded article, the above resin composition and polyamide resin or PPS resin are separately supplied to a normal co-extrusion method and three extruders, and these three kinds of molten resins are separately provided. The extruded flows are pressure-fed into a common die to form an annular flow, and then merged in the die. The resin composition of the present invention is used as an intermediate layer, and the polyamide resin or PPS resin is used as an inner layer. Alternatively, it can be formed as an outer layer and then co-extruded out of the die to obtain a multilayer tubular body by a generally known tube forming method, blow molding method or the like.

  In the multilayer molded product of the present invention, the flexural modulus of the molded product comprising the resin composition constituting the layer (ii) is 1500 MPa or less, and the polyamide resin composition constituting the layer (i) or (iii) constituting the layer It is preferable that the bending elastic modulus of the molded article made of the PPS resin composition to be 3000 MPa or less. Here, the flexural modulus is a value measured by molding an ASTM type 1/4 inch bending test piece with each resin composition and performing a bending test in accordance with ASTM D790.

  Moreover, when the multilayer molded article of the present invention is a multilayer hollow molded article, the flexibility (R) can be 50 or less. Here, for flexibility (R), a tube having an outer diameter of 8 mm × inner diameter of 6 mm is prepared, wound around a cylinder, and the radius (mm) of the cylinder at which the flatness of the tube is 50% is obtained. It was.

  The multilayer molded article of the present invention can be suitably used for automobile fuel pipes and coolant conduits because of excellent mechanical properties, low-temperature impact properties, gas barrier properties, flexibility, and interlayer adhesion.

  In the resin composition constituting each layer of the multilayer molded article of the present invention, the fibrous and / or non-fibrous filler is not an essential component, but can be blended as necessary (ii) layer or (iii) In the resin composition which comprises a layer, it is possible to mix | blend in the range which does not exceed 100 weight part with respect to 100 weight part of (A) PPS resin. In general, by blending in the range of 10 to 90 parts by weight, it is possible to improve strength, rigidity, heat resistance and dimensional stability.

  Such fibrous and / or non-fibrous fillers include glass fibers, alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers, stone fiber, metal fibers and carbon fibers, wollastonite, zeolite , Silicates such as sericanite, kaolin, mica, clay, pyroferrite, bentonite, asbestos, talc, alumina silicate, metal compounds such as alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, calcium carbonate, magnesium carbonate, dolomite Carbonates such as calcium sulfate, sulfate such as barium sulfate, glass. Non-fibrous fillers such as beads, boron nitride, silicon carbide and silica may be mentioned, and these may be hollow. Two or more kinds of these fillers can be used in combination, and can be used after pretreatment with a coupling agent such as silane or titanium if necessary.

  The multilayer molded article of the present invention thus obtained is excellent in hot water resistance, antifreeze resistance, chemical resistance, heat resistance, moldability and interlayer adhesion, and blow molded articles such as bottles, tanks and ducts, and sheets. As an extruded product such as tubes, pipes and films, it is effective for automobile fuel pipes such as water pipes, fuel tubes and fuel fillers, pipes for coolant, electrical and electronic parts, and chemical applications.

  Hereinafter, the present invention will be described in detail with reference to examples.

  The physical properties of the resin compositions and the interlayer adhesion, antifreeze resistance, gasohol resistance, and low temperature impact resistance of the resin compositions described in Examples and Comparative Examples described below were measured by the following methods.

(Physical properties of resin composition)
It is melt-kneaded at a predetermined temperature using a twin screw extruder, pelletized, dried by hot air drying at 130 ° C. for 3 hours, and then controlled by ASTM 1 type dumbbell with an injection molding machine adjusted to a cylinder temperature of 300 ° C. and a mold temperature of 40 ° C. A 1/4 inch bending test piece and a 1/4 inch thick Izod impact test piece were obtained.

(1) Tensile properties The ASTM No. 1 dumbbell obtained by the above method was subjected to a tensile test according to ASTM D638, and the tensile yield strength and tensile elongation at break were measured. When there was no clear yield point, the intersection of the rising straight portion (elastic portion) and the straight portion of the stretched portion (plastic deformation portion) was taken as the yield point.

(2) Flexural modulus The ASTM type 1/4 inch bending test piece obtained by the above method was subjected to a bending test according to ASTM D790, and the flexural modulus (MPa) was measured.

(3) Low temperature impact strength The notched impact strength of the ASTM 1/4 inch thick Izod test piece obtained by the above method was measured according to ASTM D256. The test piece was measured with an impact tester equipped with a thermostatic bath adjusted to -40 ° C after cooling for 3 hours in a -40 ° C atmosphere.

(Physical properties of multi-layer molded products)
Polyamide resin in a 40 mm extruder for the outer layer adjusted to 260 ° C., PPS to a 30 mm extruder for the inner layer adjusted to 310 ° C. The resin is charged, melted and kneaded inside the extruder, supplied to a coextrusion die adjusted to 310 ° C., melted and joined in multiple layers at the joint inside the coextrusion die, and three layers from the die face at the tip Coextruded as a parison. A three-layer tube having an outer diameter of 8 mm and an inner diameter of 6 mm was formed by cooling and solidifying with a sizing device. The take-up speed at this time was 5 m / min. Obtained. The thickness of the three-layer tube was 0.6 mm for the outer layer, 0.2 mm for the intermediate layer, and 0.2 mm for the inner layer.

(1) Interlayer adhesion A three-layer tube having an outer diameter of 8 mm and an inner diameter of 6 mm obtained by the above method was cut into a length of 150 mm, and further divided into two in the longitudinal direction to obtain strip-shaped test pieces. The interlayer is peeled off from one end of the obtained test piece and forcedly peeled up to a position of 50 mm from the end. The peeled layer was pulled up and down at a speed of 10 mm / min with a tensile tester, and the value obtained by dividing the average load (N) between 0 to 20 mm of the movement amount of the crosshead by the width (cm) of the test piece. Interlayer adhesion strength (N / cm) was used.

(2) Gasohol resistance A 30 cm long outer diameter 8 mm x inner diameter 6 mm tube is filled with Fuel C (toluene / isooctane = 50/50 (heavy waste)) + ethanol 20 wt%, and both ends of the tube are metal plugs And sealed. The tube was placed in an explosion-proof oven at 60 ° C. and the weight loss was measured and plotted. The weight loss per unit time (W) when the rate of weight reduction showed linearity was divided by the inner surface area (S) of the tube to obtain gasohol resistance.
Gasohol property (g / m ² · day) = W (g / hr) / S (m ² ) × 24 (hr)

(3) Low-temperature impact property An outer diameter 8mm x inner diameter 6mm tube created by tube molding is cut into a length of 30cm, placed on a flat surface in an atmosphere of -30 ° C, and a 0.5kg spherical weight from a height of 30cm. It was dropped and the number of fractures of n number 10 was examined, and the number of fractures relative to the number of tests is shown in the table.

(4) Flexibility A tube having an outer diameter of 8 mm × inner diameter of 6 mm created by tube molding was wound around a cylinder, and the radius (mm) of the cylinder at which the tube flatness was 50% was defined as flexibility.
Flatness ratio (%) = tube thickness at the time of cylindrical winding / initial tube thickness × 100.

(5) Tensile elongation at break 8 mm outer diameter x 6 mm inner diameter tube created by tube forming was cut into a length of 250 mm and measured with a tensile tester at 100 mm between chucks and at a pulling speed of 10 mm / min. The crosshead movement distance was calculated from the following formula.
Tensile elongation at break (%) = crosshead moving distance (mm) / 100 (mm) × 100.

Reference Example 1 (Polymerization of PPS-1)
In an autoclave, sodium sulfide 3.25 kg (25 mol, containing 40% crystal water), sodium hydroxide 40 g (1.0 mol), sodium acetate trihydrate 1.36 kg (about 10 mol) and N-methyl-2 -7.9 kg of pyrrolidone (hereinafter abbreviated as NMP) was charged, and the temperature was gradually raised to 205 ° C while stirring, and about 1.5 liters of distilled water containing 1.30 kg was removed.

To the residual mixture, 3.75 kg (25.5 mol) of 1,4-dichlorobenzene and 2 kg of NMP were added, sealed under an inert gas such as nitrogen gas, and heated at 270 ° C. for 3 hours. The reaction product was washed 5 times with warm water at 70 ° C. and dried under reduced pressure at 80 ° C. for 24 hours to obtain a powdery PPS resin (P-1) having a melt viscosity of about 2500 poise (320 ° C., shear rate 10 sec ⁻¹ ). 2 kg was obtained.

  Similar operations were repeated and used in the examples described below.

Reference Example 2 (PPS-2 PPS-1 acid aqueous solution cleaning treatment)
About 2 kg of the PPS resin powder obtained in Reference Example 1 is put into 20 liters of a pH 4 acetic acid aqueous solution heated to 90 ° C., and stirred for about 30 minutes, followed by filtration. The pH of the filtrate becomes 7. Was washed with deionized water at about 90 ° C. and dried under reduced pressure at 120 ° C. for 24 hours to obtain a powder to obtain an acid solution washing treated PPS resin (P-2).

Reference Example 3 (Polymerization of PPS-3)
The autoclave was charged with 3.25 kg of sodium sulfide (25 mol, containing 40% crystal water), 16 g of sodium hydroxide (0.4 mol), 0.16 kg of sodium acetate (2.0 mol) and N-methyl-2-pyrrolidone ( (Hereinafter abbreviated as NMP) was charged, and gradually heated to 205 ° C. while stirring, and about 1.5 liters of distilled water containing 1.30 kg of water was removed.

1,4-Dichlorobenzene (3.82 kg, 26.0 mol) and NMP (3.3 kg) were added to the residual mixture, sealed under an inert gas such as nitrogen gas, and heated at 270 ° C. for 2.5 hours. The reaction product was washed 5 times with warm water at 70 ° C. and dried under reduced pressure at 80 ° C. for 24 hours to obtain about PPS resin (P-3) having a melt viscosity of about 300 poise (320 ° C., shear rate 10 sec ⁻¹ ). 2 kg was obtained.

Reference Example 4 (Polymerization of PPS-4)
An autoclave is charged with 3.25 kg of sodium sulfide (25 mol, containing 40% crystal water), 16 g of sodium hydroxide (0.4 mol), and 4.1 kg of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP). While stirring, the temperature was gradually raised to 205 ° C., and about 1.5 liters of distilled water containing 1.30 kg of water was removed.
1,4-Dichlorobenzene (3.82 kg, 26.0 mol) and NMP (3.3 kg) were added to the residual mixture, sealed under an inert gas such as nitrogen gas, and heated at 275 ° C. for 1 hour. The reaction product was washed 5 times with warm water at 70 ° C. and dried under reduced pressure at 80 ° C. for 24 hours to obtain about PPS resin (P-4) having a melt viscosity of about 150 poise (320 ° C., shear rate 10 sec ⁻¹ ). 2 kg was obtained.

Reference Example 5 (Adjustment of PPS-5)
80 parts by weight of PPS-1, (C-2) 20 parts by weight of an acid-modified ethylene / 1-butene copolymer, and (E) 0.3 parts by weight of 3-isocyanatopropyltriethoxysilane were dry blended and tumbled. After premixing for 2 minutes, the mixture was put into a hopper of a twin screw extruder set at a cylinder temperature of 280 ° C. to 320 ° C., melt-kneaded, pelletized with a strand cutter and dried at 120 ° C. overnight to obtain PPS-5. The bending elastic modulus of the obtained pellet was 2000 MPa.

Reference Example 6 (Adjustment of PPS-6)
Dry 90 parts by weight of PPS-1, 20 parts by weight of polyetherimide (GE Plastic Japan 1010) acid-modified ethylene / 1-butene copolymer, and 0.3 parts by weight of (E) 3-isocyanatopropyltriethoxysilane. After blending and premixing for 2 minutes with a tumbler, it is put into a hopper of a twin screw extruder set at a cylinder temperature of 280 ° C to 320 ° C, melt kneaded, pelletized with a strand cutter and dried at 120 ° C overnight and then PPS -6 was obtained. The bending elastic modulus of the obtained pellet was 3000 MPa.

Other compounding materials B-1: Nylon 12 (AESNOTL: flexural modulus 1500 MPa) manufactured by Arkema
B-2: Nylon 11 manufactured by Arkema (BESNOTL: bending elastic modulus 1200 MPa)
B-3: Nylon 6 “Amilan” CM1026 manufactured by Toray Industries, Inc. (flexural modulus 2800 MPa)
C-1: Ethylene / glycidyl methacrylate copolymer (“Bondfast” E, manufactured by Sumitomo Chemical)
C-2: Acid-modified ethylene / 1-butene copolymer (“Tuffmer” MH7020 manufactured by Mitsui Chemicals)
D: ethylene 1-butene copolymer (Mitsui Chemicals "Toughmer" A4085)
F-1: 3,9-bis [2- (3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl] -2,4,8,10 -Tetraoxaspiro [5,5] undecane.
F-2: Bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol di-phosphite.
G: Polyetherimide (GE Plastics Japan 1010)

Reference Examples 7-16
The hopper input material shown in Table 2 and the side feed material are dry blended in the ratio shown in Table 2 and premixed for 2 minutes with a tumbler, and then the hopper of the twin screw extruder set at a cylinder temperature of 280 ° C to 320 ° C. PPS resin, unmodified polyolefin resin, modified polyolefin resin, and heat stabilizer are added to and melt-kneaded. Polyamide resin and modified polyolefin resin are supplied from a side feeder, melt-mixed, and then pelletized with a strand cutter. Dried overnight.

Reference Example 17
All of the same type and amount of compounded material as in Reference Example 8 are dry-blended all together, premixed for 2 minutes with a tumbler, put into a twin-screw extruder hopper set at a cylinder temperature of 280 to 320 ° C., melt-kneaded, and strands Pelletized with a cutter and dried at 120 ° C. overnight.

Examples 1-6, 9
Nylon 12 (B-1) as an outer layer extruder adjusted to 260 ° C., and an intermediate layer extruder adjusted to 300 ° C. as a multilayer molding resin composition obtained in Reference Examples 7 to 12 and 17 above. , PPS (PPS-5) was charged into the inner layer extruder controlled at 300 ° C. and melt-bonded in a multi-layer shape at the joint in the co-extrusion die, and from the die face at the tip, as a multi-layer tubular body or multi-layer parison Coextruded. A three-layer tube having an outer diameter of 8 mm and an inner diameter of 6 mm was obtained by cooling and solidifying with a sizing device. The outer layer thickness was 0.6 mm, the intermediate layer thickness was 0.2 mm, and the inner layer thickness was 0.2 mm. Table 2 shows the characteristics of the obtained tube. In Example 9, since the low-temperature toughness of the multilayer molding resin composition used in the intermediate layer (Reference Example 17) was low, cracks occurred in the low-temperature impact test of the tube, and the results were slightly inferior to those in Examples 1 to 6. It became.

Comparative Examples 1 and 2
It was the same as Examples 1-6 except that the resin composition for multilayer molding used for the intermediate layer was changed to Reference Examples 15 and 16. In Comparative Example 1, since the polyamide component of Reference Example 15 is small, the adhesive force between the outer layer and the intermediate layer is low. On the contrary, in Comparative Example 2, the PPS component of Reference Example 16 is too small and the adhesive force between the intermediate layer and the inner layer is low. There is a tendency. Example 7
Example 11 was the same as Example 1 except that nylon 11 (B-2) was used as the outer layer resin and composition 7 was used as the multilayer molding resin composition for the intermediate layer. The resulting tube had good adhesion to the inner and outer layers, and excellent impact properties and flexibility.

Example 8
Example 6 was the same as Example 1 except that nylon 6 (B-3) was used for the outer layer resin and composition 8 was used for the multilayer molding resin composition for the intermediate layer. The resulting tube had good adhesion to the inner and outer layers, and excellent impact properties and flexibility.

Example 10
Example 12 was the same as Example 1 except that nylon 12 (B-1) was used as the outer layer resin, Reference Example 7 was used as the multilayer molding resin composition for the intermediate layer, and PPS-6 was used as the inner layer resin. The obtained tube had good adhesion to the inner and outer layers, and particularly excellent fuel barrier properties.

Comparative Example 3
PPS (PPS-5) was charged into an inner layer extruder temperature-controlled at 300 ° C. to obtain a single-layer tube having an outer diameter of 8 mm and an inner diameter of 6 mm. A PPS single-layer tube is excellent in gasohol resistance but inferior in impact resistance and flexibility.

Claims (12)

A multilayer molded article comprising at least three layers,
(I) a layer comprising a polyamide resin composition,
(Ii) (A) a layer comprising a resin composition obtained by blending 80 to 300 parts by weight of (B) polyamide resin with respect to 100 parts by weight of polyphenylene sulfide resin, and (iii) polyphenylene sulfide containing no epoxy-modified thermoplastic resin A multilayer molded article comprising a layer comprising a resin composition. (Ii) Thermoplastic resins 20 to 200 in which the resin composition constituting the layer has (C) at least one functional group selected from an epoxy group, an acid anhydride group, a carboxyl group, a carboxylate, and a carboxylic acid ester. The multilayer molded article according to claim 1, which is a resin composition formed by blending parts by weight. (Ii) The resin composition constituting the layer comprises (D) 10 to 100 parts by weight of a thermoplastic resin having no epoxy group, acid anhydride group, carboxyl group, carboxylate, or carboxylic acid ester. The multilayer molded article according to claim 1, wherein the multilayer molded article is a resin composition. (Ii) The resin composition constituting the layer is a resin composition obtained by blending 100 to 250 parts by weight of (B) polyamide resin with respect to 100 parts by weight of (A) polyphenylene sulfide resin. The multilayer molded article as described. (Ii) Heat having at least one functional group selected from the above-mentioned (C) epoxy group, acid anhydride group, carboxyl group, carboxylate, and carboxylate ester, which is blended in the resin composition constituting the layer The multilayer molded article according to any one of claims 2 to 4, wherein the plastic resin is a polyolefin resin composition. (Ii) having at least one functional group selected from (C) an epoxy group, an acid anhydride group, a carboxyl group, a carboxylate, and a carboxylic acid ester, which is blended in the resin composition constituting the layer The multilayer molded article according to claim 5, wherein the thermoplastic resin comprises two types of (C1) a polyolefin resin containing an epoxy group and (C2) a polyolefin copolymer containing an acid anhydride group. (Iii) The polyphenylene sulfide resin composition not including the epoxy-modified thermoplastic resin composition constituting the layer is (C3) at least one kind selected from an acid anhydride group, a carboxyl group, a carboxylate, and a carboxylate The multilayer molded article according to any one of claims 1 to 6, which is a polyphenylene sulfide resin composition obtained by blending 1 to 50 parts by weight of a thermoplastic resin having a functional group with respect to 100 parts by weight of the polyphenylene sulfide resin. (Iii) The polyphenylene sulfide resin composition not containing the epoxy-modified thermoplastic resin composition constituting the layer is selected from (E) an epoxy group, an amino group, and an isocyanate group with respect to 100 parts by weight of the (A) polyphenylene sulfide resin. The multilayer molded article according to any one of claims 1 to 7, comprising 0.1 to 5 parts by weight of a compound having at least one kind of group. The multilayer molded article according to any one of claims 1 to 8, wherein the multilayer molded article is a multilayer hollow molded article obtained by extrusion molding or blow molding. The multilayer molded article according to claim 9, wherein the multilayer molded article is an extruded multilayer tube. The multilayer molded article according to claim 9 or 10, wherein the multilayer molded article is an automobile fuel pipe or a coolant pipe. The multilayer molded article according to any one of claims 1 to 11, wherein the multilayer molded article has an interlayer adhesive strength of 40 N / cm or more, and the multilayer molded article has a tensile elongation at break of 100% or more.