JP2006281507A - Laminated structure - Google Patents

Abstract

An object of the present invention is to provide a laminated structure excellent in alcohol gasoline permeation prevention, interlayer adhesion, low temperature impact resistance, heat resistance, and chemical resistance.
A laminated structure having at least two layers of a layer A comprising a polyolefin resin composition (A) containing a polyolefin resin as a main component and a layer B comprising a polyamide resin composition (B). The polyamide resin composition (B) is composed of a dicarboxylic acid unit containing 50 to 100 mol% of terephthalic acid units and / or naphthalenedicarboxylic acid units, and 60 to 100 mol of aliphatic diamine units having 9 to 13 carbon atoms. The polyamide resin (X) comprising 50% to 97% by mass of the diamine unit containing 50% and 50% to 3% by mass of the impact resistance improver (Y), and the total A of the laminated structure A laminated structure characterized in that a ratio of the sum of the thickness of the layer and the thickness of the B layer is 80 to 100%.
[Selection figure] None

Description

  The present invention is a laminated structure having at least two layers, the two layers including a layer made of a polyolefin resin composition containing a polyolefin resin as a main component and a polyamide resin having a specific structural unit In particular, the present invention relates to a laminated structure excellent in alcohol gasoline permeation prevention, interlayer adhesion, low-temperature impact resistance, heat resistance, and chemical resistance.

  In automobile-related fuel tubes, hoses, tanks, etc., the problem of rusting due to antifreezing agents on roads, and in recent years, from the viewpoint of energy saving, the weight reduction of automobile components has been promoted, and the main material from metal to resin Substitution is progressing. For example, saturated polyester resins, polyolefin resins, polyamide resins, thermoplastic polyurethane resins, etc. are mentioned, but in the case of single layer molded products using these, heat resistance, chemical resistance, etc. are insufficient. The applicable range was limited.

Furthermore, in recent years, from the viewpoint of preventing environmental pollution, strict exhaust gas regulations including prevention of leakage into the atmosphere due to diffusion of volatile hydrocarbons through fuel tubes, hoses, and tank partition walls have been implemented. In the future, more and more strict laws and regulations will be imposed, and it is desirable to limit the amount of fuel that permeates and evaporates from the fuel tube, hose, and tank partition. From the viewpoint of saving gasoline consumption and improving performance, oxygen-containing gasoline blended with alcohols having a low boiling point such as methanol and ethanol, or ethers such as methyl-t-butyl ether (MTBE) has come to be used. I came. For this reason, conventionally used polyamide 11 (PA11) resin, polyamide 12 (PA12) resin, and the like are not sufficient in permeation-preventing property for the above-mentioned fuel, and particularly, improvement in permeation-preventing property for alcohol gasoline is required.
For this reason, it is necessary to increase the wall thickness in order to improve the permeation prevention performance of alcohol gasoline, but this leads to the disadvantage that the flexibility of the molded product decreases or becomes heavy, and in terms of material and productivity. There was a problem of high costs.

  As a method for solving this problem, polyamide 11 or polyamide 12 is used as an outer layer or outermost layer, and a resin having a good alcohol gasoline permeation-preventing property, such as saponified ethylene / vinyl acetate copolymer (EVOH), polymetaxylylene adipamide (Polyamide MXD6), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyvinylidene fluoride (PVDF), ethylene / tetrafluoroethylene copolymer (ETFE), ethylene / chlorotri Fluoroethylene copolymer (ECTFE), tetrafluoroethylene / hexafluoropropylene copolymer (TFE / HFP, FEP), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (TFE / HFP / VDF) Layered structure of a resin having excellent fuel barrier property such as THV) was placed in the innermost layer has been proposed (e.g., see Patent Document 1).

  Polyamide 11 and polyamide 12 do not necessarily have excellent alcohol-gasoline permeation-preventing properties, but play a role of maintaining resistance to calcium chloride, which is a road anti-freezing agent, and protecting a fuel barrier layer disposed in the inner layer. Yes. A material that has these roles, has a lower cost, and is sufficiently bonded to the inner layer resin has been desired.

  A fuel transfer tube and a laminated body for automobile parts having a layer containing a polyamide resin such as MXD6 and a layer containing a polyolefin resin are known (see Patent Document 2 or 3). However, these fuel transfer tubes and laminated parts for automobile parts are still insufficient from the viewpoint of achieving higher fuel barrier properties.

  Furthermore, a layer composed of nylon 11 and / or nylon 12, a dicarboxylic acid component in which 60 to 100 mol% of all dicarboxylic acid components are terephthalic acid, 60 to 100 mol% of all diamine components are 1,9-nonanediamine and A laminated structure including a layer made of a polyamide resin composed of a diamine component selected from 2-methyl-1,8-octanediamine has been proposed (see Patent Document 4). However, in order to obtain a laminated structure that can be manufactured at a lower cost and is excellent in alcohol gasoline permeation-preventing property, there is room for further study.

JP 7-507739 JP-A-4-272592 JP 2003-1770 A JP 2004-203012 A

  An object of the present invention is to provide a laminated structure that solves the above problems, has excellent alcohol gasoline permeation prevention properties, is excellent in interlayer adhesion, low-temperature impact resistance, and heat resistance, and can be further reduced in cost. It is to provide.

  As a result of intensive studies to solve the above problems, the present inventors have a laminated structure having at least two layers, and the two layers contain a polyolefin resin as a main component. A layer composed of a product and a layer composed of a polyamide resin composition containing a polyamide resin having a specific structural unit, wherein the ratio of the sum of the thicknesses of the two layers to the total thickness is within a specific range It has been found that the body exhibits excellent alcohol gasoline permeation-preventing properties and satisfies various properties such as interlayer adhesion, low-temperature impact resistance, and heat resistance, and can further reduce the cost.

That is, the present invention is as follows.
(1) A laminated structure having at least two layers of an A layer made of a polyolefin resin composition (A) containing a polyolefin resin as a main component and a B layer made of a polyamide resin composition (B). And
The polyamide resin composition (B) includes a dicarboxylic acid unit containing 50 to 100 mol% of a terephthalic acid unit and / or a naphthalenedicarboxylic acid unit and a diamine containing 60 to 100 mol% of an aliphatic diamine unit having 9 to 13 carbon atoms. 50 to 97% by mass of the polyamide resin (X) composed of units and 50 to 3% by mass of the impact resistance improver (Y), and the thickness of the layer A relative to the total thickness of the laminated structure And the ratio of the sum of the thickness of the B layer is 80 to 100%,
A laminated structure characterized by the above.
(2) The laminated structure according to (1), which has only an A layer and a B layer.
(3) The laminated structure according to the above (1) or (2), which has a two-layer structure composed of one A layer and one B layer.
(4) Any one of the above (1) to (3), wherein the aliphatic diamine unit having 9 to 13 carbon atoms is a 1,9-nonanediamine unit and / or a 2-methyl-1,8-octanediamine unit. The laminated structure described in 1.
(5) The laminated structure according to any one of (1) to (4), wherein the polyolefin-based resin is an acid-modified polyolefin.
(6) A molded article comprising the laminated structure according to any one of (1) to (5) above.
(7) The molded article according to (6), which is selected from the group consisting of a hose, a tube, a bottle, a tank, a film, and a sheet.
(8) The molded product according to (6) or (7), wherein the A layer is the outermost layer.
(9) The molded article according to any one of (6) to (8), which is a fuel transport tube.

  The laminated structure of the present invention is excellent in alcohol gasoline permeation prevention, heat resistance, chemical resistance, low temperature impact resistance and interlayer adhesion, and can be produced at low cost. Therefore, the laminated structure of the present invention is effective as a film, a hose, a tube, a bottle, and a tank for automobile parts, industrial materials, industrial materials, electrical and electronic parts, machine parts, office equipment parts, household goods, and container applications. In particular, it is useful as a tube or hose for automobile fuel piping.

The present invention is described in detail below.
The laminated structure of the present invention comprises at least two layers of an A layer composed of a polyolefin resin composition (A) containing a polyolefin resin as a main component and a B layer composed of a polyamide resin composition (B). Have. The polyamide resin composition (B) includes a dicarboxylic acid unit containing 50 to 100 mol% of a terephthalic acid unit and / or a naphthalenedicarboxylic acid unit and a diamine containing 60 to 100 mol% of an aliphatic diamine unit having 9 to 13 carbon atoms. The polyamide resin (X) composed of units is contained in an amount of 50 to 97% by mass, and the impact resistance improver (Y) is contained in an amount of 50 to 3% by mass.
Here, “containing a polyolefin-based resin as a main component” means that the content of the polyolefin-based resin is the largest among all the components in the polyolefin-based resin composition (A).

  The polyolefin resin used as the main component of the polyolefin resin composition (A) is not particularly limited, and examples thereof include polybutadiene (PB), high density polyethylene (HDPE), low density polyethylene (LDPE), Ultra high molecular weight polyethylene (UHMWPE), polypropylene (PP), polybutene, polymethylpentene, styrene / butadiene block copolymer (SBR), ethylene / propylene / diene rubber (EPDM), ethylene / vinyl acetate copolymer (EVA), Polyacrylic acid ester, polyisoprene, hydrogenated polyisoprene, acrylic elastomer, diblock or triblock copolymer consisting of polystyrene block and hydrogenated polyisoprene block (for example, Kuraray Co., Ltd. ), Ethylene / butene copolymer (EBR), hydrogenated styrene / butadiene block copolymer (H-SBR), ethylene / propylene copolymer (EPR), ethylene / propylene / ethylidene norbornene copolymer, Hydrogenated polystyrene / ethylene / butylene (SEBS) elastomer (for example, manufactured by Shell Chemical Co., Ltd., trade name Clayton G), ethylene-α olefin copolymer and propylene-α olefin copolymer (for example, manufactured by Mitsui Petrochemical Co., Ltd.) No. Tafmer) and ethylene methacrylic acid-based special elastomer (for example, trade name “Tafrit T3000” manufactured by Mitsui DuPont Polychemical Co., Ltd.). Among these, high-density polyethylene (HDPE), low-density polyethylene (LDPE), and polypropylene (PP) are preferably used in terms of heat resistance and availability. These may be a blend of two or more.

  Moreover, considering the adhesiveness with B layer which consists of a polyamide resin composition (B), it is preferable to use what was modified | denatured by functional groups, such as an acid, for the polyolefin-type resin used in this invention. The compound used for the modification is not particularly limited. For example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid, maleic anhydride, itaconic anhydride, anhydrous Citraconic acid or the like is used. These may be used alone or in combination of two or more.

  Specific examples of the polyolefin resin modified with a functional group such as acid include maleic anhydride-modified HDPE, a blend of HDPE and maleic anhydride-modified HDPE, and a blend of HDPE and maleic anhydride-modified PP. , Blend of maleic anhydride modified HDPE and ethylene / butene copolymer, blend of maleic anhydride modified HDPE and ethylene / propylene copolymer, blend of PP and maleic anhydride modified HDPE, maleic anhydride Examples thereof include a blend of a modified PP and an ethylene / butene copolymer, a blend of a maleic anhydride-modified PP and an ethylene / propylene copolymer. Among these, maleic anhydride modified HDPE, blend of HDPE and maleic anhydride modified HDPE, blend of HDPE and maleic anhydride modified PP, blend of maleic anhydride modified HDPE and ethylene / butene copolymer It is preferable to use acid-modified polyolefin such as a product, a blend of maleic anhydride-modified HDPE and an ethylene / propylene copolymer, from the viewpoint of cost and interlayer adhesion.

  The acid modification rate of the polyolefin resin with the acid is preferably about 0.01 to 5%, more preferably about 0.03 to 3%, and still more preferably about 0.05 to 1.5%. If the modification rate is too low or too high, it tends to be difficult to ensure adhesion to the B layer made of the polyamide resin composition (B), and if too high, the heat resistance of the acid-modified polyolefin resin There is a tendency for stability and retention stability to decrease. In the present specification, the acid modification rate is expressed as a percentage by weight of the acid used to modify the polyolefin resin per 100 parts by weight of the polyolefin resin.

  Furthermore, the polyolefin resin used in the present invention preferably has a melt mass flow rate (MFR) value (190 ° C .: JIS K 7210) of 0.01 to 100 g / 10 min, and 0.05 to 50 g / 10. It is more preferable that it is a minute, and it is still more preferable that it is 0.1-5 g / 10min. If the MFR is less than 0.01 g / 10 min, the fluidity is too short, and there is a possibility that it cannot be stably molded. On the other hand, if the MFR exceeds 100 g / 10 min, the resulting laminated structure may have insufficient impact resistance, which is not preferable.

  The content of the polyolefin resin in the polyolefin resin composition (A) used in the present invention is 50% as a percentage of the total mass of the polyolefin resin composition (A) from the viewpoint of fuel barrier properties and heat resistance. It is preferable that it is -100 mass%, It is more preferable that it is 70-100 mass%, It is further more preferable that it is 80-100 mass%. In addition, in this specification, when the content of the polyolefin resin in the polyolefin resin composition (A) is 100% by mass (that is, when the layer A is made of only a polyolefin resin), the polyolefin resin The resin is included in the term “polyolefin resin composition (A)”.

  As the polyolefin-based resin used in the present invention, commercially available resins can be used as they are. Moreover, you may manufacture by the conventionally well-known manufacturing method of polyolefin resin.

The polyolefin resin composition (A) used in the present invention may contain components other than the polyolefin resin. The other components include polyacetal (POM), polymethyl methacrylate (PMMA), various aliphatic polyamides and aromatic polyamides, polyphenylene sulfide, polyether ether ketone, polysulfone, liquid crystal polymer, ethylene / tetrafluoroethylene copolymer. And other thermoplastic resins such as (ETFE). The content of these other components is preferably 0 to 50% by mass, more preferably 0 to 30% by mass, as a proportion of the total mass of the polyolefin-based resin composition (A). More preferably, it is 20 mass%. When the content of these other components exceeds 50% by mass, the interlayer adhesion with the B layer made of the polyamide resin composition (B) is lowered, or the alcohol gasoline permeation preventive property of the resulting laminated structure is lowered. There is a case.
In addition, the polyolefin resin composition (A) used in the present invention is a further component (for example, conductive filler, antioxidant, heat stabilizer, ultraviolet absorber, light stabilizer, lubricant, inorganic filling) Agents, antistatic agents, flame retardants, crystallization accelerators, plasticizers, colorants, lubricants, etc.).

The polyamide resin (X) used in the present invention contains 60 to 100 mol of a dicarboxylic acid unit containing 50 to 100 mol% of a terephthalic acid unit and / or a naphthalenedicarboxylic acid unit and an aliphatic diamine unit having 9 to 13 carbon atoms. % Diamine units.
The content of terephthalic acid units and / or naphthalenedicarboxylic acid units in the polyamide resin (X) is 50 to 100 mol%, preferably 60 mol% to 100 mol%, more preferably based on all dicarboxylic acid units. It is 75 mol%-100 mol%, More preferably, it is 90 mol%-100 mol%. When the content of the terephthalic acid unit and / or naphthalenedicarboxylic acid unit is less than 50 mol%, the physical properties such as heat resistance, chemical resistance, and alcohol gasoline permeation-preventing property of the resulting laminated structure are lowered.
Examples of the naphthalenedicarboxylic acid unit include units derived from 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and 1,4-naphthalenedicarboxylic acid. Among the naphthalenedicarboxylic acid units, units derived from 2,6-naphthalenedicarboxylic acid are preferred.

  The dicarboxylic acid unit in the polyamide resin (X) includes other dicarboxylic acid units other than the terephthalic acid unit and / or the naphthalenedicarboxylic acid unit as long as the object of the laminated structure of the present invention can be achieved. May be. Examples of the other dicarboxylic acid units include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 2,2- Aliphatic dicarboxylic acids such as diethylsuccinic acid, azelaic acid, sebacic acid and suberic acid, alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,3 / 1,4-cyclohexanedicarboxylic acid, isophthalic acid, 1,3 / 1,4-phenylenedioxydiacetic acid, diphenic acid, 4,4′-oxydibenzoic acid, diphenylmethane-4,4′-dicarboxylic acid, diphenylsulfone-4,4′-dicarboxylic acid, 4,4 Examples thereof include units derived from aromatic dicarboxylic acids such as' -biphenyldicarboxylic acid. It can be used. Among the above units, units derived from aromatic dicarboxylic acids are preferred. The content of these other dicarboxylic acid units is 50 mol% to 0 mol%, preferably 40 mol% to 0 mol%, preferably 25 mol% to 0 mol%, based on all dicarboxylic acid units. More preferably, it is 10 mol% to 0 mol%. Furthermore, units derived from polyvalent carboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid can be contained within a range where melt molding is possible.

  Content of a C9-C13 aliphatic diamine unit in polyamide resin (X) is 60-100 mol% with respect to all the diamine units, Preferably it is 75-100 mol%, More preferably, it is 90- 100 mol%. When the content of the aliphatic diamine unit having 9 to 13 carbon atoms is less than 60 mol%, the heat resistance and impact resistance of the resulting laminated structure are lowered, and the low water absorption is impaired.

  As the aliphatic diamine unit having 9 to 13 carbon atoms, either a linear aliphatic diamine unit or a branched aliphatic diamine unit may be used. As the linear aliphatic diamine unit, 1,9-nonanediamine, 1 , 10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, and units derived from 1,13-tridecanediamine. Examples of the branched aliphatic diamine unit include units derived from a branched aliphatic diamine such as 2-methyl-1,8-octanediamine and 5-methyl-1,9-nonanediamine.

  Among the aliphatic diamine units having 9 to 13 carbon atoms shown above, it is derived from 1,9-nonanediamine and 2-methyl-1,8-octanediamine from the viewpoint of alcohol gasoline permeation prevention and economy. Units are preferred, and units derived from 1,12-dodecanediamine are preferred from the viewpoint of low-temperature impact resistance. Furthermore, it is preferable that a 1,9-nonanediamine unit and a 2-methyl-1,8-octanediamine unit coexist, and the molar ratio in that case is a balance of moldability, impact resistance and coextrusion moldability. From this viewpoint, the ratio of the former to the latter is preferably 30:70 to 98: 2 mol%, and more preferably in the range of 40:60 to 95: 5 mol%.

  The diamine unit in the polyamide resin (X) includes units derived from other diamines other than aliphatic diamines having 9 to 13 carbon atoms as long as the object of the laminated structure of the present invention can be achieved. You may go out. Examples of the other diamine units include ethylenediamine, propylenediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1, 14-tetradecanediamine, 1,15-pentadecanediamine, 1,16-hexadecanediamine, 1,17-heptadecanediamine, 1,18-octadecanediamine, 1,19-nonadecanediamine, 1,20-eicosanediamine, Aliphatic diamines such as 2 / 3-methyl-1,5-pentanediamine, 1,3 / 1,4-cyclohexanediamine, 1,3 / 1,4-cyclohexanedimethylamine, bis (4-aminocyclohexyl) methane, Bis (4-aminocyclohexyl) propane, bis (3-methyl-4-amino) Nocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) propane, 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine, 5-amino-1,3,3-trimethylcyclohexanemethyl Cycloaliphatic diamines such as amine, bis (aminopropyl) piperazine, bis (aminoethyl) piperazine, norbornanedimethylamine, tricyclodecanedimethylamine, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m- Examples include units derived from aromatic diamines such as xylylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 4,4′-diaminodiphenyl ether. Or two or more can be used . The content of these diamine units is 40 mol% to 0 mol%, preferably 25 mol% to 0 mol%, more preferably 10 mol% to 0 mol%, based on the total diamine units. preferable.

  In addition, the end of the molecular chain of the polyamide resin (X) is preferably sealed with an end-capping agent, more preferably 40% or more of the end groups are sealed, and 60% of the end groups are sealed. % Or more is more preferably sealed, and 70% or more of the end groups are particularly preferably sealed.

  The end capping agent is not particularly limited as long as it is a monofunctional compound having reactivity with the amino group or carboxyl group at the end of the polyamide, but from the viewpoint of reactivity and stability of the capping end, monocarboxylic acid is used. An acid or a monoamine is preferable, and a monocarboxylic acid is more preferable from the viewpoint of easy handling. In addition, acid anhydrides, monoisocyanates, monoacid halides, monoesters, monoalcohols, and the like can also be used.

  The monocarboxylic acid used as the end-capping agent is not particularly limited as long as it has reactivity with an amino group. For example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, laurin Aliphatic monocarboxylic acids such as acids, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid and isobutyric acid; cycloaliphatic monocarboxylic acids such as cyclohexanecarboxylic acid; benzoic acid, toluic acid, α-naphthalenecarboxylic acid , Β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, aromatic monocarboxylic acid such as phenylacetic acid, or any mixture thereof. Of these, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, in terms of reactivity, stability of the sealing end, price, etc. Benzoic acid is particularly preferred.

  The monoamine used as the end-capping agent is not particularly limited as long as it has reactivity with a carboxyl group. For example, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearyl Aliphatic monoamines such as amine, dimethylamine, diethylamine, dipropylamine, dibutylamine; cycloaliphatic monoamines such as cyclohexylamine, dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine, naphthylamine, or any mixture thereof Can be mentioned. Of these, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline are particularly preferable from the viewpoints of reactivity, boiling point, stability of the sealing end, and price.

  Furthermore, the polyamide resin (X) preferably has an intrinsic viscosity [η] measured in concentrated sulfuric acid at 30 ° C. of 0.4 to 3.0 dl / g, preferably 0.5 to 2.5 dl / g. Is more preferable, and it is still more preferable that it is 0.6-2.0 dl / g. When a material having an intrinsic viscosity [η] within the above range is used, a material excellent in mechanical properties, heat resistance and the like can be obtained. If the value is smaller than the above value, the resulting laminated structure may have insufficient mechanical properties. If the value is larger than the above value, the extrusion pressure and torque become too high, making it difficult to produce the laminated structure. It may become. The intrinsic viscosity [η] of the polyamide resin (X) can be adjusted to the above range by appropriately adjusting, for example, the ratio of diamine and dicarboxylic acid, the amount of terminal blocking agent introduced, the polymerization conditions, and the like.

  The polyamide resin (X) can be produced by using a known polyamide polymerization method known as a method for producing crystalline polyamide. Production equipment includes known polyamides such as batch reaction kettles, single tank or multi-tank continuous reaction apparatuses, tubular continuous reaction apparatuses, kneading reaction extruders such as uniaxial kneading extruders and biaxial kneading extruders, etc. Manufacturing equipment can be used. As the polymerization method, a known method such as melt polymerization, solution polymerization or solid phase polymerization can be used, and polymerization can be carried out by repeating normal pressure, reduced pressure, and pressure operation. These polymerization methods can be used alone or in appropriate combination.

  Moreover, when manufacturing polyamide resin (X), you may use the terminal blocker illustrated above, The usage-amount is the intrinsic viscosity of the polyamide resin finally obtained, and the sealing rate of a terminal group. Determined from. The specific amount used varies depending on the reactivity, boiling point, reaction apparatus, reaction conditions, etc. of the end-capping agent to be used, but is usually 0.3 to 10 mol% with respect to the total number of moles of dicarboxylic acid and diamine. Used within range.

  In the present invention, the polyamide resin composition (B) constituting the B layer contains the specific amount of the polyamide resin (X) and the impact resistance improver (Y), and the impact resistance improver (Y ) Is 50 to 3% by mass, preferably 40 to 5% by mass, and more preferably 30 to 10% by mass. When the content of the impact resistance improver (Y) exceeds 50% by mass, the alcohol gasoline permeation-preventing property of the entire laminated structure is lowered, whereas when it is less than 3% by mass, the impact resistance of the entire laminated structure is reduced. Properties and elongation are reduced.

  The impact resistance improver (Y) used in the present invention is not particularly limited as long as it improves the impact resistance of the polyamide resin (X). For example, polyolefin, polyolefin elastomer, polystyrene elastomer, Examples include acrylic elastomers, polyamide elastomers, and polyester elastomers. Among these, polyolefin, polyolefin elastomer, polystyrene elastomer, and polyester elastomer are preferable.

Examples of the polyolefin include polybutadiene (PB), high density polyethylene (HDPE), low density polyethylene (LDPE), ultrahigh molecular weight polyethylene (UHMWPE), polypropylene (PP), polyisoprene, and hydrogenated polyisoprene. It is done.
Examples of the polyolefin elastomer include ethylene / propylene / diene rubber (EPDM), ethylene / butene copolymer (EBR), ethylene / propylene copolymer (EPR), and ethylene / propylene / ethylidene norbornene copolymer. , Ethylene-α olefin copolymer and propylene-α olefin copolymer (for example, trade name Toughmer, manufactured by Mitsui Petrochemical Co., Ltd.).
Examples of the polystyrene elastomer include styrene-butene copolymer (SBR), hydrogenated styrene / butadiene block copolymer (H-SBR), diblock or triblock composed of a polystyrene block and a hydrogenated polyisoprene block. Examples include block copolymers (for example, Kuraray Co., Ltd., trade name Septon), hydrogenated polystyrene / ethylene / butylene (SEBS) elastomers (for example, Shell Chemical Co., Ltd., trade name Clayton G) and the like.
Examples of the acrylic elastomer include polyacrylic acid ester, ethylene methacrylic acid special elastomer (for example, trade name Taffrit T3000, manufactured by Mitsui DuPont Polychemical Co., Ltd.), acrylic (reaction type) elastomer (for example, Manufactured by Kureha Chemical Co., Ltd., trade name Paraloid EXL), core / shell type elastomer having a core made of silicon rubber and a shell made of acrylic rubber or acrylic resin (for example, grade name S2001 or RK120 made by Mitsubishi Rayon Co., Ltd.) ) And the like.

  Among these, polypropylene (PP), ethylene / butene copolymer (EBR), hydrogenated styrene / butadiene block copolymer (H-SBR), ethylene / propylene copolymer (EPR), hydrogenated SEBS elastomer, ethylene An α-olefin copolymer and a propylene-α-olefin copolymer are preferably used, and polypropylene (PP), an ethylene / butene copolymer (EBR), and an ethylene / propylene copolymer (EPR) are more preferably used.

  The polyamide resin composition (B) used in the present invention contains 50 to 97% by mass of the above polyamide resin (X) and 50 to 3% by mass of the above impact resistance improver (Y). %, Other components other than the polyamide resin (X) and the impact modifier (Y) may be contained. Examples of the other components include POM, PMMA, various aliphatic polyamides and aromatic polyamides, polyesters, polyphenylene sulfide, polyether ether ketone, polysulfone, liquid crystal polymer, ETFE and other thermoplastic resins, and antioxidants. , Heat stabilizers, ultraviolet absorbers, light stabilizers, lubricants, inorganic fillers, antistatic agents, flame retardants, crystallization accelerators, plasticizers, colorants, lubricants, mold release agents and the like. Moreover, you may contain the electroconductive filler mentioned later.

As described above, the laminated structure of the present invention includes an A layer composed of a polyolefin resin composition (A) containing a polyolefin resin as a main component, and a B layer composed of a polyamide resin composition (B). It is a laminated structure having at least two layers. Here, the ratio of the sum of the thickness of the A layer and the thickness of the B layer to the total thickness of the laminated structure is 80 to 100%, preferably 90 to 100%, more preferably 95. ~ 100%. When the ratio is less than 80%, it is not preferable from the viewpoint of productivity of the laminated structure and alcohol gasoline permeation prevention.
In the preferable aspect of this invention, a laminated structure has only A layer and B layer. In the laminated structure of the present invention, as long as it is an A layer that satisfies the above conditions, it may have only one A layer, or may have two or more identical or different A layers. Good. Moreover, as long as it is B layer which satisfy | fills said conditions, it may have only one B layer, or may have two or more same or different B layers. As a more preferred embodiment of the present invention, a laminated structure having a two-layer structure composed of one A layer and one B layer, a three-layer structure composed of one A layer and two different B layers A laminated structure having Among these, a laminated structure having a two-layer structure composed of one A layer and one B layer is particularly preferable in terms of productivity, cost, interlayer adhesion, and the like.
In this specification, when the laminated structure of the present invention has a plurality of A layers and / or a plurality of B layers, the thickness of the A layer is the thickness of all the A layers in the laminated structure. The thickness of the B layer represents the total thickness of all the B layers in the laminated structure.

  The laminated structure of the present invention has the A layer and the B layer, and the ratio of the sum of the thickness of the A layer and the thickness of the B layer to the total thickness of the laminated structure is 80 As long as it is -100%, you may have other layers other than A layer and B layer. By having other layers, it is possible to give a further function to the laminated structure of the present invention, or to obtain a more economically advantageous laminated structure. Examples of the other layer include a layer made of a thermoplastic resin.

  Examples of the thermoplastic resin constituting the layers other than the A layer and the B layer include polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), polycyclohexylene terephthalate (PCT), and PET / PEI. Polyesters such as copolymers, polyarylate (PAR), polybutylene naphthalate (PBN), polyethylene naphthalate (PEN), and liquid crystalline polyester (LCP), polyethers such as polyacetal (POM) and polyphenylene oxide (PPO) Resins, polysulfone resins such as polysulfone (PSF) and polyethersulfone (PES), polythioether resins such as polyphenylene sulfide (PPS) and polythioethersulfone (PTES), polyether ether Ton (PEEK), polyketone resins such as polyallyl ether ketone (PEAK), polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, acrylonitrile / Polynitrile resins such as budadiene / styrene copolymer (ABS), methacrylonitrile / styrene / butadiene copolymer (MBS), polymethacrylate resins such as polymethyl methacrylate (PMMA), polyethyl methacrylate (PEMA) Polyvinyl chloride resins such as polyvinyl acetate (PVAc), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymer, vinylidene chloride / methyl acrylate copolymer, etc. Vinyl tree , Cellulose resins such as cellulose acetate and cellulose butyrate, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), ethylene / tetrafluoroethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), ethylene / Chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene / hexafluoropropylene copolymer (TFE / HFP, FEP), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (TFE / HFP / VDF, THV), fluororesins such as tetrafluoroethylene / fluoro (alkyl vinyl ether) copolymer (PFA), polycarbonate resins such as polycarbonate (PC), thermoplastic polyimide (PI), polyamide Polyimide resins such as imide (PAI) and polyetherimide (PEI), thermoplastic polyurethane resins, polyethylene adipamide (polyamide 26), polytetramethylene adipamide (polyamide 46), polyhexamethylene adipamide ( Polyamide 66), polyhexamethylene azelamide (polyamide 69), polyhexamethylene sebamide (polyamide 610), polyhexamethylene undecamide (polyamide 611), polyhexamethylene dodecamide (polyamide 612), polyhexamethylene Terephthalamide (polyamide 6T), polyhexamethylene isophthalamide (polyamide 6I), polynonamethylene dodecamide (polyamide 912), polydecamethylene dodecamide (polyamide 1012), polydodecamethylene dodecami (Polyamide 1212), polymetaxylylene adipamide (polyamide MXD6), polybis (4-aminocyclohexyl) methane dodecamide (polyamide PACM12), polybis (3-methyl-4-aminocyclohexyl) methane dodecamide (polyamide dimethyl PACM12) Polynonamethylene hexahydroterephthalamide (polyamide 9T (H)), polydecamethylene hexahydroterephthalamide (polyamide 10T (H)), polyundecamethylene hexahydroterephthalamide (polyamide 11T (H)), Polyamide resin such as polydodecamethylenehexahydroterephthalamide (polyamide 12T (H)) and copolymers using several types of polyamide raw material monomers, polyurethane elastomer, polyester elastomer Examples include tomers and polyamide elastomers.

  Among these, polyester resins, polyamide resins, polythioether resins, and fluorine resins are preferably used, and polyester resins, polyamide resins, and fluorine resins are more preferably used.

In addition, the laminated structure of the present invention includes a layer composed only of the above-mentioned polyamide resin (X) or a resin containing the polyamide resin (X) but not satisfying the provisions of the above-mentioned polyamide resin composition (B). You may have the layer which consists of a composition.
Furthermore, in the laminated structure of the present invention, as a layer other than the A layer and the B layer, in addition to the layer made of the thermoplastic resin, any base material such as paper, metal-based material, unstretched, It is also possible to laminate a layer made of uniaxial or biaxially stretched plastic film or sheet, woven fabric, non-woven fabric, metallic cotton, wood or the like. Examples of the metal-based material include aluminum, iron, copper, nickel, gold, silver, titanium, molybdenum, magnesium, manganese, lead, tin, chromium, beryllium, tungsten, cobalt, and other metals and metal compounds, and two or more of these. Examples thereof include alloy steels such as stainless steel, aluminum alloys, copper alloys such as brass and bronze, and alloys such as nickel alloys.
In addition, only one layer may be sufficient as layers other than A layer and B layer, and the same or different two or more layers may be sufficient as it.

  The total number of layers in the multilayer structure of the present invention is not particularly limited as long as the multilayer structure has at least two layers of the A layer and the B layer.

  In the laminated structure of the present invention, as long as the ratio of the sum of the thickness of the A layer and the thickness of the B layer to the total thickness of the laminated structure is 80 to 100%, the thicknesses of the A layer and the B layer Is not particularly limited, and can be adjusted according to the type of polymer constituting each layer, the total number of layers, the use, etc., but the thickness of each layer is the alcohol gasoline permeation-preventing property, low-temperature impact resistance of the laminated structure It is determined in consideration of characteristics such as property and flexibility. In general, the thicknesses of the A layer and the B layer are each preferably 3 to 97% with respect to the thickness of the entire laminated structure. Considering the alcohol gasoline permeation prevention property, the thicknesses of the A layer and the B layer are more preferably 5 to 95%, and further preferably 10 to 90%, respectively, with respect to the thickness of the entire laminated structure.

The laminated structure of the present invention can be effectively used as molded articles such as hoses, tubes, bottles, tanks and the like, and particularly has an effect such as excellent alcohol-gasoline permeation-preventing properties, and is therefore suitable as a fuel transport tube. Can be used. Moreover, the laminated structure of the present invention can be effectively used as a molded product such as a film or a sheet.
When the laminated structure of the present invention is used as a molded product such as a hose, a tube, a bottle, or a tank including a fuel transport tube, either the A layer or the B layer may be disposed outside, but alcohol gasoline permeation is possible. From the viewpoint of ensuring prevention and impact resistance, the A layer is preferably arranged outside the B layer, and the A layer is more preferably arranged in the outermost layer of these molded products. From the viewpoint of interlayer adhesion, it is preferable that the A layer and the B layer are directly laminated in at least a part of the laminated structure of the present invention.

  When the laminated structure of the present invention is used for a fuel transport tube or the like, in order to prevent static electricity generated by internal friction of the fuel circulating in the pipe or friction with the pipe wall from accumulating and igniting the fuel. In addition, it is preferable that a conductive filler is blended in the innermost layer to make this layer a conductive layer. As a result, it is possible to prevent an explosion due to static electricity generated when a fluid such as fuel is conveyed. At that time, by disposing the non-conductive layer on the outer side with respect to the conductive layer, it is possible to achieve both low temperature impact resistance and conductivity, and it is economically advantageous.

  Here, the conductive filler referred to in the present invention includes all fillers added to impart conductivity, for example, granular fillers having such properties, flaky fillers, fibrous fillers, etc. Is mentioned.

  As the particulate filler, carbon black, graphite or the like can be preferably used. As the flaky filler, aluminum flakes, nickel flakes, nickel-coated mica and the like can be suitably used. As the fibrous filler, carbon fibers, carbon-coated ceramic fibers, carbon whiskers, aluminum fibers, copper fibers, brass fibers, stainless fibers, and other metal fibers can be preferably used. Of these conductive fillers, carbon black is most preferred.

  The carbon black that can be used as the conductive filler in the present invention includes at least one carbon black generally used for imparting conductivity. Preferred carbon blacks include acetylene black obtained by incomplete combustion of acetylene gas, ketjen black, oil black, naphthalene black, thermal black, lamp black, and channel produced by furnace-type incomplete combustion using crude oil as a raw material. Examples thereof include black, roll black, and disk black, but are not limited thereto. Of these, acetylene black and furnace black (Ketjen black) are particularly preferably used.

Carbon black is produced in various carbon powders having different characteristics such as particle size, surface area, dibutyl phthalate (DBP) oil absorption, and ash content. The carbon black that can be used in the present invention is not particularly limited in these properties, but preferably has a good chain structure and a high aggregation density. A large amount of carbon black is not preferable in terms of impact resistance, and the average particle size is 500 nm or less, more preferably 5 to 100 nm, particularly 10 to 70 nm, from the viewpoint of obtaining excellent electrical conductivity with a smaller amount. it is preferred, the surface area (BET method) is ^{10 m} 2 / g or more, further 300 meters ² / g or more, particularly preferably from 500 to 1500 ² / g, DBP oil absorption 50 ml / 100 g or more, further 100ml / 100g or more, particularly preferably 300ml / 100g or more. The ash content is preferably 0.5% by weight or less, more preferably 0.3% by weight or less. In addition, DBP oil absorption here is the value measured by the method defined in ASTM-D2414. The carbon black preferably has a volatile content of less than 1.0% by weight.

  The conductive filler may be subjected to a surface treatment with a surface treatment agent such as titanate, aluminum or silane. Moreover, in order to improve melt-kneading workability | operativity, it is also possible to use what was granulated.

The blending amount of the conductive filler varies depending on the type of the conductive filler to be used, and thus cannot be specified unconditionally. However, as long as the laminated structure of the present invention as described above is taken, the conductivity, fluidity, mechanical From the viewpoint of balance with strength and the like, it is generally preferably 3 to 30% by mass with respect to the total mass of the layer containing the conductive filler.
In addition, such a conductive filler has a surface specific resistance value of 10 ⁸ Ω / square or less, particularly 10 ⁶ Ω / square or less, in a molded article having a layer containing the conductive filler, in the sense that sufficient antistatic performance is obtained. It is preferable that However, the blending of the conductive filler tends to cause deterioration in strength and fluidity. Therefore, if the target conductivity level is obtained, it is desirable that the amount of the conductive filler is as small as possible.

  As a method for producing a laminated structure, a method of melt extrusion using an extruder corresponding to the number of layers or the number of materials, and a method of simultaneously laminating inside or outside the die (coextrusion method), or once, a single layer A method (coating method) in which a structure or a laminated structure manufactured by the above method is manufactured in advance, and an adhesive is used on the outside in order to integrate the resins and laminate them. Can do.

  In addition, when the obtained laminated structure has a complicated shape, or when it is subjected to heat bending after molding to form a molded product, the above-mentioned laminated structure is formed in order to remove residual distortion of the molded product. After that, it is possible to obtain a desired molded article by heat treatment for 0.01 to 10 hours at a temperature lower than the lowest melting point of the resins constituting the structure.

  The laminated structure may have a corrugated region. The waveform region is a region formed in a waveform shape, a bellows shape, an accordion shape, a corrugated shape, or the like. The laminated structure may not only have a corrugated region over its entire length, but may also have a corrugated region partially in an appropriate region in the middle. For example, in the case of a laminated tube, the corrugated region can be easily formed by first forming a straight tube and then molding it to obtain a predetermined corrugated shape. By having such a corrugated region, it has shock absorption and attachment is easy. Furthermore, for example, necessary parts such as a connector can be added, or an L shape or a U shape can be formed by bending.

  All or part of the outer periphery of the laminated structure molded in this way is considered to be epichlorohydrin rubber (ECO), acrylonitrile / butadiene rubber (NBR), NBR, taking into account stones, abrasion with other parts, and flame resistance. Mixture with polyvinyl chloride, chlorosulfonated polyethylene rubber, chlorinated polyethylene rubber, acrylic rubber (ACM), chloroprene rubber (CR), ethylene / propylene rubber (EPR), ethylene / propylene / diene rubber (EPDM), NBR and EPDM A solid or sponge-like protective member (protector) composed of a rubber elastomer, a vinyl chloride-based, an olefin-based, an ester-based, an amide-based thermoplastic elastomer or the like can be disposed. The protective member may be a sponge-like porous body by a known method. By using a porous body, a protective part that is lightweight and excellent in heat insulation can be formed. Moreover, material cost can also be reduced. Alternatively, the strength may be improved by adding glass fiber or the like. The shape of the protective member is not particularly limited, but when the laminated structure is, for example, a laminated tube, it is usually a block-like member having a recess for receiving the laminated tube, a cylindrical member into which the laminated tube can be inserted later. Further, it may be a protective member formed by coating and extruding a cylindrical member on a laminated tube and bringing them into close contact with each other. In order to bond the two, the adhesive is applied to the inner surface of the protective member or the concave surface as necessary, and the laminated tube is inserted or fitted into the inner surface, and the laminated tube and the protective member are integrated. Forming a structured structure. Further, it can be reinforced with metal or the like.

  When the laminated structure is in the form of a tube, the outer diameter thereof considers the flow rate of fuel (for example, gasoline), the wall thickness does not increase the permeability of gasoline, and the normal tube breaking pressure is reduced. Although it is designed to have a thickness that can be maintained and can maintain flexibility such that the ease of assembling the tube and vibration resistance during use are maintained, the present invention is not limited thereto. Preferably, the outer diameter is 4 to 30 mm, the inner diameter is 3 to 25 mm, and the wall thickness is 0.5 to 5 mm.

Applications of the laminated structure of the present invention include machine parts such as automobile parts, internal combustion engines, power tool housings, industrial materials, industrial materials, electrical / electronic parts, medical, food, household / office supplies, and building materials. There are various uses such as parts, furniture parts, and household goods.
Moreover, since the laminated structure of the present invention is excellent in alcohol gasoline permeation-preventing properties, it is suitable for a chemical solution transport pipe. Examples of the chemical liquid include gasoline, kerosene, diesel gasoline, methanol, ethanol, propanol, butanol, alcohol-containing gasoline, methyl-t-butyl ether, oxygen-containing gasoline, amine-containing gasoline, sour gasoline, castor oil base brake fluid, glycol ether system. Examples include brake fluids, borate ester brake fluids, cryogenic brake fluids, silicone oil brake fluids, mineral oil brake fluids, power steering oils, window washer fluids, engine coolants, pharmaceutical agents, inks and paints. The laminated structure of the present invention is suitable as a tube for conveying the above chemical solution. Specifically, a fuel transport tube such as a feed tube, a return tube, an evaporation tube, a fuel filler tube, an ORVR tube, a reserve tube, a vent tube, etc. , Oil tube, Brake tube, Window washer fluid tube, Radiator tube, Cooling water, Cooler tube for refrigerant, Air conditioner refrigerant tube, Floor heating tube, Fire extinguisher and fire extinguishing equipment tube, Medical cooling equipment tube, Ink , Paint spray tubes, and other chemical solution tubes. In particular, it is suitable as a fuel transport tube.

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these.
In addition, the analysis and measurement of physical properties in Examples and Comparative Examples were performed as follows.

[Intrinsic viscosity]
Polyamide is dissolved in concentrated sulfuric acid to prepare sample solutions having concentrations of 0.05 g / dl, 0.1 g / dl, 0.2 g / dl and 0.4 g / dl, and the intrinsic viscosity η _inh at 30 ° C. is determined. The value measured and extrapolated to 0 was defined as the intrinsic viscosity [η].

[Evaluation of the physical properties]
(Low temperature impact resistance)
Evaluation was performed by the method described in SAE J2260.
(Alcohol gasoline permeation prevention)
One end of a tube cut to 200 mm was sealed, and alcohol / gasoline mixed with Fuel C (isooctane / toluene = 50/50 volume ratio) and methanol in an 85/15 volume ratio was put inside, and the other end was also sealed. . Thereafter, the entire weight was measured, and then the test tube was placed in an oven at 60 ° C., and the change in weight was measured every day. The change in weight per day was divided by the inner layer surface area of the tube to calculate the alcohol gasoline permeability coefficient (g / m ² · day).

(Interlayer adhesion)
The tube cut to 200 mm was further cut in half in the vertical direction to produce a test piece. Using a Tensilon universal testing machine, a 180 ° peel test was performed at a tensile speed of 50 mm / min. The peel strength was read from the maximum point of the SS curve, and the interlayer adhesion was evaluated.

(Interlayer adhesion after immersion in alcohol gasoline)
Seal one end of the tube cut to 200 mm, and put alcohol / gasoline mixed with Fuel C (isooctane / toluene = 50/50 volume ratio) and methanol in an 85/15 volume ratio inside, and the other end also Sealed. Next, the test tube was put in an oven at 60 ° C., taken out after 500 hours, and interlayer adhesion was evaluated by the above method.

[Materials Used in Examples and Comparative Examples]
Polyamide resin (X):
A polyamide resin produced by the following method was used.
(A-1) Production of polyamide 9T Terephthalic acid 32960 g (198.4 mol), 1,9-nonanediamine 26909 g (170 mol), 2-methyl-1,8-octanediamine 4748.7 g (30 mol), benzoic acid 390.8 g (3.2 mol), 60 g of sodium hypophosphite monohydrate (0.1% by weight based on the raw material) and 40 L of distilled water were placed in an autoclave and purged with nitrogen.
The mixture was stirred at 100 ° C. for 30 minutes, and the internal temperature was raised to 210 ° C. over 2 hours. At this time, the autoclave was pressurized to 2.2 MPa. The reaction was continued for 1 hour, then the temperature was raised to 230 ° C., and then the temperature was maintained at 230 ° C. for 2 hours. The reaction was carried out while gradually removing water vapor and keeping the pressure at 2.2 MPa. Next, the pressure was reduced to 1.0 MPa over 30 minutes, and the reaction was further continued for 1 hour to obtain a prepolymer. This was dried at 100 ° C. under reduced pressure for 12 hours and pulverized to a size of 2 mm or less. This was subjected to solid state polymerization at 230 ° C. and 0.013 kPa for 10 hours to obtain polyamide 9T having a melting point of 300 ° C. and an intrinsic viscosity of 1.92 dl / g (hereinafter, this polyamide is referred to as (a-1)). Sometimes).

(A-2) Production of polyamide 9T (a-1) In production of polyamide 9T, 26909 g (170 mol) of 1,9-nonanediamine was converted to 15829 g (100 mol) and 2-methyl-1,8-octanediamine 4748. (A-1) Polyamide 9T having a melting point of 275 ° C. and an intrinsic viscosity of 1.85 dl / g in the same manner as the production method of polyamide 9T except that 7 g (30 mol) was changed to 15829 g (100 mol) (Hereinafter, this polyamide may be referred to as (a-2)).

(B) Preparation of polyamide 9N 2,6-naphthalenedicarboxylic acid 42892 g (198.4 mol), 1,9-nonanediamine 26909 g (170 mol), 2-methyl-1,8-octanediamine 4748.7 g (30 mol) Then, 390.8 g (3.2 mol) of benzoic acid, 60 g of sodium hypophosphite monohydrate (0.1% by weight with respect to the raw material) and 40 L of distilled water were placed in an autoclave and purged with nitrogen.
The mixture was stirred at 100 ° C. for 30 minutes, and the internal temperature was raised to 210 ° C. over 2 hours. At this time, the autoclave was pressurized to 2.2 MPa. The reaction was continued as it was for 1 hour, then the temperature was raised to 240 ° C., and then the temperature was maintained at 230 ° C. for 2 hours, and the reaction was carried out while gradually removing water vapor and keeping the pressure at 2.2 MPa. Next, the pressure was reduced to 1.0 MPa over 30 minutes, and the reaction was further continued for 1 hour to obtain a prepolymer. This was dried at 100 ° C. under reduced pressure for 12 hours and pulverized to a size of 2 mm or less. This was subjected to solid phase polymerization at 240 ° C. and 0.013 kPa for 10 hours to obtain polyamide 9N having a melting point of 302 ° C. and an intrinsic viscosity of 1.90 dl / g (hereinafter, this polyamide may be referred to as (b)). is there).

Polyamide resin composition (B):
A polyamide resin composition produced by the following method was used.
(A-1) Preparation of polyamide 9T resin composition Preliminary mixing of polyamide 9T (a-1) with JSR T7761P (manufactured by JSR Corporation, ethylene-propylene copolymer) as an impact resistance improver (Y) This is supplied to a twin screw extruder (BT-30, manufactured by Plastics Engineering Laboratory Co., Ltd.), melt kneaded and extruded at a cylinder temperature of 320 ° C., cooled, cut, and polyamide 9T resin. A pellet of polyamide 9T resin composition comprising 80 parts by weight and 20 parts by weight of impact modifier was obtained (hereinafter, this polyamide 9T resin composition may be abbreviated as A-1).

(A-2) Production of polyamide 9T resin composition Polyamide 9T resin 90 was produced in the same manner as in the production method (A-1) except that polyamide 9T was changed from (a-1) to (a-2). Pellets of polyamide 9T resin composition comprising 10 parts by weight of an impact modifier (Y) were obtained (hereinafter, this polyamide 9T resin composition may be abbreviated as A-2).

(B) Production of polyamide 9N resin composition JSR T7761P (manufactured by JSR Corporation, ethylene-propylene copolymer) as an impact resistance improver (Y) was premixed in polyamide 9N (b), Supply to a twin screw extruder (BT-30, manufactured by Plastics Engineering Laboratory Co., Ltd.), melt knead and extrude under the condition of a cylinder temperature of 320 ° C., cool and cut, 85 parts by weight of polyamide 9N resin, A pellet of polyamide 9T resin composition comprising 15 parts by weight of an impact resistance improver was obtained (hereinafter, this polyamide 9N resin composition may be abbreviated as B).

(C) Production of polyolefin-based resin composition HDPE resin [Hi-Zex 6300M] (Mitsui Chemicals, MFR value (190 ° C.): 0.11 g / 10 min) and maleic anhydride-modified HDPE resin [Admer HF500] (Mitsui Chemicals) MFR value (190 ° C.): 1.0 g / 10 min) is preliminarily mixed in advance, and this is supplied to a twin screw extruder (BT-30, manufactured by Plastic Engineering Laboratory Co., Ltd.) and the cylinder temperature The mixture was melt-kneaded and extruded under a condition of 210 ° C., cooled and cut to obtain polyolefin resin composition pellets comprising 80 parts by weight of HDPE resin and 20 parts by weight of maleic anhydride-modified HDPE resin (hereinafter referred to as “this”). A polyolefin resin composition may be abbreviated as C).

(D) Production of polyolefin-based resin composition HDPE resin [Hi-Zex 6300M] (Mitsui Chemicals, MFR value (190 ° C.): 0.11 g / 10 min) and maleic anhydride-modified HDPE resin [Admer HF500] (Mitsui Chemicals) MFR value (190 ° C.): 1.0 g / 10 min) and an ethylene-α olefin copolymer [Tafmer P-0775] (manufactured by Mitsui Chemicals) are preliminarily mixed, and this is a twin screw extruder. (BT-30, manufactured by Plastics Engineering Laboratory Co., Ltd.), melt-kneaded under conditions of a cylinder temperature of 210 ° C., extruded, cooled, cut, and 80 parts by weight of HDPE resin, maleic anhydride-modified HDPE A pellet of a polyolefin resin composition comprising 10 parts by weight of a resin and 10 parts by weight of an ethylene-α-olefin copolymer resin was obtained (hereinafter referred to as “this”). The polyolefin resin composition is sometimes abbreviated as D).

(E) Manufacture of polyamide-based resin composition MXD-6 (Nylon T-600 manufactured by Toyobo Co., Ltd.) and an ethylene-α olefin copolymer [Tuffmer P-0775] (manufactured by Mitsui Chemicals) were premixed in advance. Then, this is supplied to a twin-screw extruder (BT-30, manufactured by Plastic Engineering Laboratory Co., Ltd.), melt-kneaded and extruded under the condition of a cylinder temperature of 270 ° C., cooled, cut, and MXD. Pellets of a polyamide resin composition comprising 85 parts by weight of -6 resin and 15 parts by weight of an ethylene-α-olefin copolymer resin were obtained (hereinafter, this polyamide resin composition may be abbreviated as E).

Example 1
Using the polyolefin resin composition (C) and the polyamide 9T resin composition (A-1) shown above, (C) was extruded at 210 ° C. with a tube molding machine manufactured by Plastic Engineering Laboratory Co., Ltd. , (A-1) were melted separately at an extrusion temperature of 320 ° C., and the discharged molten resin was joined by an adapter to form a laminated tubular body. Subsequently, it is cooled by a sizing die that controls dimensions and taken up, and the (I) layer (outermost layer) comprising the polyolefin-based resin composition (C) and the (III) layer comprising the polyamide 9T resin composition (A-1). A laminated tube having a thickness (I) / (III) = 0.80 / 0.20 mm, an inner diameter of 6 mm, and an outer diameter of 8 mm was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 2
In Example 1, except that (A-1) was changed to (A-2) and (A-2) was melted at an extrusion temperature of 300 ° C., the same method as in Example 1 was used, as shown in Table 1. A laminated tube having the layer structure shown in FIG. The physical property measurement results of the laminated tube are shown in Table 1.

Example 3
In Example 1, except that (C) was changed to polyolefin resin composition (D) and (A-1) was changed to polyamide 9N resin composition (B), the same method as in Example 1 was used. The laminated tube of the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 4
Example 1 is the same as Example 1 except that (C) is changed to the polyolefin resin composition (D) and the layer structure is changed to thickness (I) / (III) = 0.70 / 0.30 mm. The laminated tube of the layer structure shown in Table 1 was obtained by the same method. The physical property measurement results of the laminated tube are shown in Table 1.

Example 5
Using the above-described polyolefin resin composition (D), polyamide 9T resin composition (A-2) and polyamide 9N resin composition (B), a tube molding machine manufactured by Plastic Engineering Laboratory Co., Ltd. , (D) is melted separately at an extrusion temperature of 210 ° C., (A-2) is melted at an extrusion temperature of 300 ° C., and (B) is melted at 320 ° C., and the discharged molten resin is merged by an adapter to form a laminated tubular body. did. Subsequently, it is cooled by a sizing die that controls dimensions and taken up, and the (I) layer (outermost layer) comprising the polyolefin resin composition (D) and the (II) layer comprising the polyamide 9T resin composition (A-2) (Intermediate layer) When the layer (III) composed of the polyamide 9N resin composition (B) is used (innermost layer), the layer configuration is thickness (I) / (II) / (III) = 0.70 / 0. A laminated tube having an inner diameter of 6 mm and an outer diameter of 8 mm was obtained at 15 / 0.15 mm. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 1
Using the polyolefin-based resin composition (C) and the polyamide-based resin composition (E) shown above, (C) was extruded at 210 ° C. with a tube molding machine manufactured by Plastic Engineering Laboratory Co., Ltd. ( E) was melted separately at an extrusion temperature of 270 ° C., and the discharged molten resin was joined by an adapter to form a laminated tubular body. Subsequently, it is cooled by a sizing die for dimension control and taken up, and the (I) layer (outermost layer) made of the polyolefin resin composition (C) and the (III) layer (outermost layer) made of the polyamide resin composition (E). A laminated tube having a thickness (I) / (III) = 0.80 / 0.20 mm and an inner diameter of 6 mm and an outer diameter of 8 mm was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 2
In Comparative Example 1, (C) is changed to the polyolefin resin composition (D), and the (I) layer (outermost layer) made of the polyolefin resin composition (D) and the polyamide resin composition (E) ( Table 1 is the same as Comparative Example 1 except that the layer structure when the layer (III) (the innermost layer) is set to thickness (I) / (III) = 0.70 / 0.30 mm. A laminated tube having the layer structure shown in FIG. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 3
Using the polyolefin-based resin composition (C) shown above, (C) was melted at an extrusion temperature of 210 ° C. with a tube molding machine manufactured by Plastic Engineering Laboratory Co., Ltd. Molded into a tubular body. Then, it cooled by the sizing die which controls a dimension, and it took up, and obtained the single layer tube of the internal diameter 6mm and outer diameter 8mm which consist of a polyolefin-type resin composition (C). Table 1 shows the physical property measurement results of the single-layer tube.

Comparative Example 4
A single-layer tube having a layer structure shown in Table 1 was obtained in the same manner as in Comparative Example 3 except that (C) was changed to the polyolefin resin composition (D) in Comparative Example 3. Table 1 shows the physical property measurement results of the single-layer tube.

From Table 1, the laminated tubes of Examples 1 to 5 have a remarkably small alcohol gasoline permeability coefficient (that is, excellent alcohol gasoline permeation prevention property), and the interlaminar adhesion is maintained without being significantly reduced even after immersion in alcohol gasoline. In addition, it can be seen that the low-temperature impact resistance is excellent.
On the other hand, the laminated tubes of Comparative Examples 1 and 2 using a layer made of a polyamide resin composition that does not use polyamide resin (X) as the innermost layer have a remarkably large alcohol gasoline permeability coefficient (that is, alcohol gasoline permeation preventive property). Inferior), the interlaminar adhesion was remarkably reduced after immersion in alcohol gasoline, and the low temperature impact resistance was inferior. In addition, the single-layer tubes of Comparative Examples 3 and 4 had an alcohol gasoline permeation coefficient that was abnormally large (that is, the alcohol gasoline permeation preventive property was remarkably inferior).

  The laminated structure of the present invention is excellent in alcohol gasoline permeation prevention, heat resistance, chemical resistance, low temperature impact resistance, and interlayer adhesion. Therefore, the laminated structure of the present invention is effective as a film, a hose, a tube, a bottle, and a tank for automobile parts, industrial materials, industrial materials, electrical and electronic parts, machine parts, office equipment parts, household goods, and container applications. Particularly useful as an automotive fuel transport tube or hose.

Claims (9)

A laminated structure having at least two layers of a layer A composed of a polyolefin resin composition (A) containing a polyolefin resin as a main component and a layer B composed of a polyamide resin composition (B),
The polyamide resin composition (B) includes a dicarboxylic acid unit containing 50 to 100 mol% of a terephthalic acid unit and / or a naphthalenedicarboxylic acid unit and a diamine containing 60 to 100 mol% of an aliphatic diamine unit having 9 to 13 carbon atoms. 50 to 97% by mass of the polyamide resin (X) composed of units and 50 to 3% by mass of the impact resistance improver (Y), and the thickness of the layer A relative to the total thickness of the laminated structure And the ratio of the sum of the thickness of the B layer is 80 to 100%,
A laminated structure characterized by the above.   The laminated structure according to claim 1, comprising only an A layer and a B layer.   The laminated structure according to claim 1 or 2, having a two-layer structure composed of one A layer and one B layer.   The laminated structure according to any one of claims 1 to 3, wherein the aliphatic diamine unit having 9 to 13 carbon atoms is a 1,9-nonanediamine unit and / or a 2-methyl-1,8-octanediamine unit. body.   The laminated structure according to any one of claims 1 to 4, wherein the polyolefin-based resin is an acid-modified polyolefin.   The molded article which consists of a laminated structure of any one of Claims 1-5.   The molded article according to claim 6, which is selected from the group consisting of a hose, a tube, a bottle, a tank, a film and a sheet.   The molded article according to claim 6 or 7, wherein the A layer is an outermost layer.   The molded article according to any one of claims 6 to 8, which is a fuel transport tube.