Laminate

Abstract

The present invention relates to a laminate. Provided is a laminate which has excellent low-temperature impact resistance and compressive strength at high temperatures even if the layer of a modified polyolefin is thick. A laminate having two or more layers including a layer (a) and a layer (b), the layer (a) including an aliphatic polyamide composition (A), and the layer (b) including a modified polyolefin (B), the modified polyolefin (B) contains a unit derived from a monomer based on an alpha-olefin having 2-10 carbon atoms and a unit derived from an unsaturated compound having a functional group. The unsaturated compound having a functional group is at least one selected from the group consisting of an unsaturated compound having at least one group selected from the group consisting of a carboxyl group, a hydroxyl group, an epoxy group, an amino group, an amide group, an imide group, a nitrile group, a thiol group, and an isocyanate group, and a derivative of an unsaturated compound having a carboxyl group. The modified polyolefin (B) has a Shore hardness (D scale) of 30 to 61 (inclusive) as measured in accordance with ASTM D2240.

Description

[0001] This application is a divisional application of the invention patent application with application number 202080025790.2, application date March 27, 2020, and invention title "Laminated Body". Technical Field

[0002] This invention relates to laminates. Background Technology

[0003] Hose / tubes are widely used in various pressure lines such as hydraulic lines, water lines, vacuum lines, and automotive fuel lines, brake lines, coolant hoses, air conditioning lines, SCR (diesel engine exhaust gas removal system) lines, and control cable sleeves. These hoses / tubes transport chemical solutions such as coolant (alcohol and water), refrigerant, oil, and urea solution. For hoses / tubes used in the automotive industry, extremely high performance is required, including high compressive strength at high temperatures, long-term heat resistance, chemical resistance, water vapor and / or chemical solution barrier properties, and flexibility.

[0004] In particular, if the circulating fluid is not sufficiently barrier to these chemical solutions, such as ethylene glycol-based coolant (LLC) used to prevent freezing in winter, urea solution sealed in as a catalyst to remove NOx released from diesel engines, and refrigerants like carbon dioxide, Freon, Freon alternatives, propane, and water used in air conditioners / radiators, the cooling and catalytic effects cannot be fully realized in actual use. Furthermore, with stricter controls on the evaporation of ozone-depleting gases, the requirements for refrigerant barrier properties in refrigerant transport pipes used in automobiles and other applications have become increasingly stringent.

[0005] On the other hand, with the strengthening of controls on the evaporation of ozone-depleting gases, the quality of refrigerants used in automobiles and other applications has improved in recent years. For example, R-1234yf refrigerant has been developed as a replacement for HFC-134a refrigerant. Compared with HFC-134a refrigerant, it has a lower ozone depletion potential and global warming potential, making it an extremely environmentally friendly refrigerant. However, R-1234yf refrigerant is particularly prone to hydrolysis and acid production (such as formic acid) when in contact with water at high temperatures. Due to the presence of this acid, depending on the materials in contact with the chemical solution, hydrolysis and deterioration can easily occur. In the worst case, this can lead to cracks, fluid leakage, and failure to achieve the purpose of fluid transport. Alternatively, chemical solutions or water can sometimes seep through the pipe body and adversely affect the contacting components.

[0006] The single-layer tubes obtained by using polyamide resins alone, especially polyamide 11 or polyamide 12 which have excellent strength, toughness, chemical resistance and flexibility, are not sufficiently durable and barrier to the aforementioned chemical solutions in the long term.

[0007] Fluoropolymers such as ethylene / tetrafluoroethylene copolymer (ETFE) are considered to be among the materials used for components that exhibit excellent resistance to various chemical solutions and provide barrier properties against water vapor. In recent years, the development of fluoropolymers with adhesive properties to polyamides has become active (see Patent Documents 1-3). However, while avoiding the use of halogen-containing materials is beneficial for environmental protection, issues such as high density and high cost exist. Therefore, there is a search for developing piping systems that utilize halogen-free materials, offer excellent barrier properties against chemical solutions, and are resistant to various chemical solutions.

[0008] On the other hand, polyolefins are inexpensive and exhibit excellent resistance to chemical solutions and long-term chemical solution resistance. For example, a cooling pipe composed of an outer layer containing polyamide and an inner layer containing cross-linked polyethylene has been proposed (see Patent Document 4). Another cooling pipe composed of an outer layer containing polyamide and an inner layer of polypropylene having a certain thickness and containing specific additives has been proposed (see Patent Document 5). Similarly, a cooling pipe has been proposed, characterized by being formed of an inner layer that is inactive to coolant and cannot swell, and an outer layer containing polyamide. The inner layer is composed of halogenated or non-halogenated homopolymer or copolymer olefin. This cooling pipe is manufactured by extrusion blow molding, and the wall thickness of the layers varies along the entire length of the conduit, with significant differences in the flexibility of the polymers in the inner and outer layers (see Patent Document 6). Furthermore, a multilayer pipe has been proposed, comprising, from the inside to the outside, an inner layer of polyolefin, a first intermediate layer based on an adhesive, a second intermediate layer of ethylene / vinyl alcohol copolymer, a third intermediate layer of polyamide, and an outer protective layer (see Patent Document 7). Furthermore, a fuel cell piping is proposed, wherein an outer layer is made of an outer layer material with polyamide resin and styrene-isobutylene block copolymer as essential components, and an inner layer is made of an inner layer material with polyolefin resin and styrene-isobutylene block copolymer as essential components (see Patent Document 8).

[0009] Existing technical documents

[0010] Patent documents

[0011] Patent Document 1: International Publication No. 2001 / 058686

[0012] Patent Document 2: International Publication No. 2001 / 060606

[0013] Patent Document 3: Japanese Patent Application Publication No. 2004-301247

[0014] Patent Document 4: Japanese Patent Application Publication No. 9-29869

[0015] Patent Document 5: Japanese Patent Publication No. 2008-507436

[0016] Patent Document 6: Japanese Patent Application Publication No. 7-214647

[0017] Patent Document 7: Japanese Patent Application Publication No. 2006-116966

[0018] Patent Document 8: Japanese Patent Application Publication No. 2005-216725 Summary of the Invention

[0019] The problem the invention aims to solve

[0020] The aim is to find a way to vary the thickness of the polyamide and polyolefin layers according to the requirements of the application, with any layer thickness exhibiting excellent mechanical properties at both high and low temperatures.

[0021] However, the piping disclosed in Patent Document 4, when using polyethylene as the inner layer, has poor long-term durability and pipe properties at high temperatures.

[0022] In addition, due to the increased thickness of the polyolefin layer, it is difficult to balance the mechanical strength at both high and low temperatures, but patent documents 5-8 do not provide specific technical data or technical inspiration.

[0023] In particular, for electric vehicles, there is a need to further improve the barrier properties and high-temperature resistance of LLC. For laminates, there is a need for excellent barrier properties and high-temperature resistance, as well as to increase the thickness of inexpensive polyolefins. On the other hand, it is also required to balance the high pressure resistance of LLC under high-temperature atmospheres and the impact resistance at low temperatures.

[0024] The purpose of this invention is to solve the aforementioned problems and provide a laminate that exhibits excellent low-temperature impact resistance and high-temperature compressive strength, even when the modified polyolefin layer is relatively thick.

[0025] Solution for solving the problem

[0026] In order to solve the aforementioned problems, the inventors conducted in-depth research and found that even if the modified polyolefin is thickened, the laminate containing a layer of aliphatic polyamide resin composition and a layer of modified polyolefin with specific mechanical and material properties has excellent low-temperature impact resistance and high-temperature compressive strength.

[0027] That is, the present invention is a laminated body, which is a laminated body comprising two or more layers including layer (a) and layer (b).

[0028] The aforementioned layer (a) comprises an aliphatic polyamide composition (A).

[0029] The aforementioned layer (b) comprises a modified polyolefin (B).

[0030] The aforementioned modified polyolefin (B) comprises units derived from monomers of α-olefins having 2 or more and 10 or fewer carbon atoms, and units derived from unsaturated compounds having functional groups. The unsaturated compounds having functional groups are selected from at least one group selected from unsaturated compounds having at least one group selected from carboxyl, hydroxyl, epoxy, amino, amide, imide, nitrile, thiol, and isocyanate groups, and derivatives of unsaturated compounds having carboxyl groups.

[0031] The aforementioned modified polyolefin (B) has a Shore hardness (D scale) of 30 or higher and 61 or lower as measured according to ASTM D2240.

[0032] The following shows preferred embodiments of the laminate. Multiple combinations of preferred embodiments are possible.

[0033] [1] A laminate, wherein the aforementioned aliphatic polyamide composition (A) comprises a polyamide (A1), wherein the aforementioned polyamide (A1) is an aliphatic polyamide having a ratio of methylene to amide groups of 7.0 or more.

[0034] [2] A laminate, wherein the aforementioned polyamide (A1) is a homopolymer selected from the group consisting of polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 1010, polyamide 1012 and polyamide 1212, and / or a copolymer obtained by using a variety of raw material monomers forming them.

[0035] [3] A laminate, wherein the aforementioned aliphatic polyamide composition (A) further comprises one or more other components selected from the group consisting of plasticizers, impact resistant agents and heat resistant agents.

[0036] [4] A laminate, wherein the aforementioned (a) layer and (b) layer are adjacent to each other.

[0037] [5] A laminate wherein the aforementioned modified polyolefin (B) has a tensile yield stress of less than 23 MPa as measured by ASTM D638 and a tensile fracture stress of more than 25 MPa as measured by ASTM D638.

[0038] [6] A laminate wherein the aforementioned modified polyolefin (B) has an MFR (230°C, 2160g) of 3.5g / 10min or more as measured according to ASTM D1238.

[0039] [7] A laminate wherein the aforementioned modified polyolefin (B) has a wavenumber of 710 cm⁻¹ in FT-IR measurements. -1 Above and 740cm -1 The wavenumber showing the greatest intensity among the following absorptions is 721 cm⁻¹. -1 above.

[0040] [8] A laminate wherein the aforementioned modified polyolefin (B) is manufactured by melting the unmodified polyolefin and graft copolymerizing it by adding the aforementioned unsaturated compound having a functional group.

[0041] [9] A laminate, wherein the aforementioned modified polyolefin (B) is maleic anhydride modified polypropylene.

[0042]

[10] A laminate consisting only of the aforementioned (a) and (b) layers.

[0043]

[11] A laminate manufactured by co-extrusion molding.

[0044]

[12] A layered hollow shaped body comprising the aforementioned layered body.

[0045]

[13] A layered hollow molded body, which is arranged from the outside in the order of the aforementioned (a) and (b) layers.

[0046]

[14] A layered hollow shaped body, wherein the aforementioned (b) layer is disposed in the innermost layer.

[0047]

[15] A layered hollow shaped body, wherein the innermost layer contains other layers.

[0048]

[16] A layered hollow shaped body, which is a tube.

[0049] The effects of the invention

[0050] According to the present invention, a laminate can be provided that exhibits excellent low-temperature impact resistance and high-temperature compressive strength, even with a thicker modified polyolefin layer. Detailed Implementation

[0051] A laminate consists of two or more layers, including layer (a) and layer (b).

[0052] The aforementioned layer (a) comprises an aliphatic polyamide composition (A).

[0053] The aforementioned layer (b) comprises a modified polyolefin (B), which contains units derived from monomers of α-olefins having 2 or more and 10 or fewer carbon atoms, and units derived from unsaturated compounds. The unsaturated compounds are selected from at least one group selected from unsaturated compounds having at least one group selected from carboxyl, hydroxyl, epoxy, amino, amide, imide, nitrile, thiol, and isocyanate groups, and derivatives of unsaturated compounds having a carboxyl group.

[0054] The aforementioned modified polyolefin (B) has a Shore hardness (D scale) of ≥30 and ≤61 as measured according to ASTM D2240.

[0055] Even when the laminate is composed of thick layers of modified polyolefin, it exhibits excellent low-temperature impact resistance and high-temperature compressive strength.

[0056] 1.(a) layer

[0057] Layer (a) of the laminate contains an aliphatic polyamide composition (A).

[0058] <Aliphatic polyamide composition (A)>

[0059] The aliphatic polyamide composition (A) is not particularly limited as long as it contains an aliphatic polyamide having an amide bond (-CONH-) in the main chain. Examples of aliphatic polyamides include polyamide 6 (polyhexamethylene amide), polyamide 11 (polyundecanoamide), polyamide 12 (polydodecanoamide), polyamide 26 (polyethylene adipamide), polyamide 44 (polybutylene succinate), polyamide 45 (polybutylene glutaramide), polyamide 46 (polybutylene adipamide), polyamide 48 (polybutylene octanoate), polyamide 49 (polybutylene nonanoate), polyamide 410 (polybutylene sebacate), polyamide 412 (polybutylene dodecanoate), and polyamide 54 (polybutylene succinate). Polyamide 55 (polypentyl glutamate), polyamide 56 (polypentyl adipate), polyamide 58 (polypentyl adipate), polyadenosyl glutamate (polyamide 59), polydecanoyl glutamate (polyamide 510), polydodecanoyl glutamate (polyamide 512), polysuccinyl hexamethylenediamine (polyamide 64), polypentyl hexamethylenediamine (polyamide 65), polyhexamethylene adipate (polyamide 66), polycaprylyl hexamethylenediamine (polyamide 68), polyadenosyl hexamethylenediamine (polyamide 69), polydecanoyl hexamethylenediamine... Amines (polyamide 610), polydodecanediylhexanediamine (polyamide 612), polytetradecanediylhexanediamine (polyamide 614), polyhexadecanylhexanediamine (polyamide 616), polyoctadecanediylhexanediamine (polyamide 618), polyadiponylnonadiamine (polyamide 96), polyoctylnonadiamine (polyamide 98), polyadenosylnonadiamine (polyamide 99), polydecanoylnonadiamine (polyamide 910), polydodecanediamine (polyamide 912), polyadiponyldecanadiamine (polyamide 106), polyoctyldecanadiamine (polyamide 910), polydodecanediamine (polyamide 912), polyadiponyldecanadiamine (polyamide 106), polyoctyldecanadiamine (polyamide 910), polyadiponyldecanadiamine (polyamide 912), polyadiponyldecanadiamine (polyamide 910), polyoctyldecanadiamine (polyamide 910), polyadipon ... Homopolymers such as polyamide 108, polynonadienoyldecanediamine (polyamide 109), polydecanediamine (polyamide 1010), polydodecanoyldecanediamine (polyamide 1012), polyadipoyldodecanediamine (polyamide 126), polyoctyldodecanediamine (polyamide 128), polynonadienoyldodecanediamine (polyamide 129), polydecanoyldodecanediamine (polyamide 1210), and polydodecanoyldodecanediamine (polyamide 1212), as well as copolymers obtained using various raw material monomers that form them.

[0060] The aliphatic polyamide composition (A) preferably comprises polyamide (A1).

[0061] [Polyamide (A1)]

[0062] Polyamide (A1) is an aliphatic polyamide (hereinafter sometimes referred to as polyamide (A1)) with a methylene group to amide group ratio (hereinafter sometimes referred to as [CH2] / [NHCO]) of 7.0 or higher. By using aliphatic polyamides with a [CH2] / [NHCO] ratio of 7.0 or higher, excellent mechanical properties and other physical properties of the laminate can be achieved. There is no particular upper limit to the [CH2] / [NHCO] ratio, but practically it is 11.0 or lower.

[0063] Examples of polyamides (A1) include polyamide 11 ([CH2] / [NHCO] = 10.0), polyamide 12 ([CH2] / [NHCO] = 11.0), polyamide 412 ([CH2] / [NHCO] = 7.0), polyamide 512 ([CH2] / [NHCO] = 7.5), polyamide 610 ([CH2] / [NHCO] = 7.0), and polyamide 612 ([CH2] / [NHCO] = 10.0). Polyamides include: [CH2] / [NHCO] = 8.0, polyamide 614 ([CH2] / [NHCO] = 9.0), polyamide 616 ([CH2] / [NHCO] = 10.0), polyamide 618 ([CH2] / [NHCO] = 11.0), polyamide 98 ([CH2] / [NHCO] = 7.5), polyamide 99 ([CH2] / [NHCO] = 8.0), and polyamide 910 ([CH2] / [NHCO] = 8.0). 5) Polyamide 912 ([CH2] / [NHCO] = 9.5), Polyamide 106 ([CH2] / [NHCO] = 7.0), Polyamide 108 ([CH2] / [NHCO] = 8.0), Polyamide 109 ([CH2] / [NHCO] = 8.5), Polyamide 1010 ([CH2] / [NHCO] = 9.0), Polyamide 1012 ([CH2] / [NHCO] = 10.0), Homopolymers such as polyamide 126 ([CH2] / [NHCO] = 8.0), polyamide 128 ([CH2] / [NHCO] = 9.0), polyamide 129 ([CH2] / [NHCO] = 9.5), polyamide 1210 ([CH2] / [NHCO] = 10.0), and polyamide 1212 ([CH2] / [NHCO] = 11.0), and / or copolymers obtained using various raw material monomers that form them.

[0064] As for polyamide (A1), from the viewpoints of ensuring sufficient mechanical properties, heat resistance and other physical properties of the laminate, as well as from the viewpoints of economy and ease of acquisition, it is preferable to use at least one homopolymer selected from the group consisting of polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 1010, polyamide 1012 and polyamide 1212, and / or at least one copolymer obtained by using a variety of raw material monomers that form them.

[0065] [Properties of Polyamide (A1)]

[0066] From the viewpoint of ensuring the mechanical properties of the laminate and ensuring the desired formability of the laminate by keeping the viscosity at melt within an appropriate range, the relative viscosity of the polyamide (Al) measured according to JIS K-6920 under the conditions of 96% sulfuric acid, 1% polymer concentration, and 25°C is preferably 1.5 or more and 5.0 or less, more preferably 2.0 or more and 4.5 or less.

[0067] When the concentration of terminal amino groups per 1g of polyamide (A1) is denoted as [A] (μeq / g) and the concentration of terminal carboxyl groups is denoted as [B] (μeq / g), from the viewpoint of sufficiently ensuring the interlayer adhesion of the laminate, it is preferable that [A] > [B] + 5, more preferably [A] > [B] + 10, and particularly preferably [A] > [B] + 15. Furthermore, from the viewpoint of polyamide melt stability and suppression of gel formation, it is preferable that [A] > 20, and particularly preferably 30 < [A] < 120.

[0068] Here, the concentration of the terminal amino group [A] (μeq / g) can be determined by dissolving the polyamide in a phenol / methanol mixture and titrating it with 0.05N hydrochloric acid. The concentration of the terminal carboxyl group [B] (μeq / g) can be determined by dissolving the polyamide in benzyl alcohol and titrating it with 0.05N sodium hydroxide solution.

[0069] The polyamide (A1) is preferably a mixture of two or more aliphatic polyamides with different terminal amino and / or terminal carboxyl concentrations, provided that the terminal group concentrations are satisfied as described above. In this case, the terminal amino and / or terminal carboxyl concentrations of the aliphatic polyamide mixture are determined based on the terminal amino and terminal carboxyl concentrations of the aliphatic polyamides constituting the mixture and their mixing ratio.

[0070] [Manufacturing method of polyamide (A1)]

[0071] Polyamide (A1) is manufactured by polymerizing or copolymerizing polyamide raw materials using known methods such as melt polymerization, solution polymerization, solid-state polymerization, or combinations thereof in the presence of amines. Alternatively, polyamide (A1) is manufactured by polymerizing polyamide raw materials and then melt-blending them in the presence of amines. Here, the polymerization of polyamide raw materials can be repeatedly performed under normal pressure, reduced pressure, and increased pressure.

[0072] As raw materials for polyamide (A1), aliphatic lactams, aliphatic aminocarboxylic acids, or combinations of aliphatic diamines and aliphatic dicarboxylic acids can be listed.

[0073] Examples of aliphatic lactams include caprolactam, heptanolactam, undecanolactam, dodecalactam, α-pyrrolidone, and α-piperidinone. One or more of these can be used.

[0074] Examples of aliphatic aminocarboxylic acids include 6-aminohexanoic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. One or more of these compounds can be used.

[0075] Examples of aliphatic diamines include 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,15-pentadecanediamine, and 1,16-hexadecanediamine. Examples of amino acids used include 1,17-heptadecanediamine, 1,18-octadecanediamine, 1,19-nonadecanediamine, 1,20-eicosanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, and 5-methyl-1,9-nonanediamine. One or more of these amino acids may be used.

[0076] Examples of aliphatic dicarboxylic acids include glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, octadecanoic acid, and eicosanoic acid. One or more of these can be used.

[0077] As amines, examples include monoamines, diamines, triamines, and polyamines. One or more of these can be used. However, when the raw material for polyamide (A1) is a combination of an aliphatic diamine and an aliphatic dicarboxylic acid, the amine does not include aliphatic diamines.

[0078] Examples of monoamines include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, octadecenylamine, eicosylamine, and docosylamine; alicyclic monoamines such as cyclohexylamine and methylcyclohexylamine; aromatic monoamines such as benzylamine and β-phenylmethylamine; and N,N- Symmetrical secondary amines such as dimethylamine, N,N-diethylamine, N,N-dipropylamine, N,N-dibutylamine, N,N-dihexylamine, and N,N-dioctylamine; and mixed secondary amines such as N-methyl-N-ethylamine, N-methyl-N-butylamine, N-methyl-N-dodecylamine, N-methyl-N-octadecylamine, N-ethyl-N-hexadecylamine, N-ethyl-N-octadecylamine, N-propyl-N-hexadecylamine, and N-propyl-N-benzylamine. One or more of these can be used.

[0079] Examples of diamines include 1,2-ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,15-pentadecanediamine, 1,16-hexadecanediamine, 1,17-heptadecanediamine, 1,18-octadecanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, and 5-methyl-1,9-nonanediamine. Aliphatic diamines; alicyclic diamines such as 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane, bis(3-methyl-4-aminocyclohexyl)methane, 2,2-bis(3-methyl-4-aminocyclohexyl)propane, 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine, 5-amino-1,3,3-trimethylcyclohexanemethylamine, bis(aminopropyl)piperazine, bis(aminoethyl)piperazine, 2,5-bis(aminomethyl)norbornane, 2,6-bis(aminomethyl)norbornane, 3,8-bis(aminomethyl)tricyclodecane, and 4,9-bis(aminomethyl)tricyclodecane; aromatic diamines such as m-phenylenediamine and p-phenylenediamine. One or more of these can be used.

[0080] Amines can be added at any stage of the polymerization of the polyamide raw material, or at any stage of melt mixing after the polymerization of the polyamide raw material. Considering the interlayer adhesion of the laminate, it is preferable to add them during the polymerization stage. In addition, regarding amines, in order to meet the above-mentioned terminal amino group concentration conditions, it is preferable to add diamines and / or polyamines during the polymerization of the polyamide raw material. From the viewpoint of suppressing gel formation, it is particularly preferable to add at least one selected from the group consisting of aliphatic diamines, alicyclic diamines, and polyalkylene imides during the polymerization of the polyamide raw material.

[0081] Furthermore, within the range of terminal group concentrations mentioned above, carboxylic acids such as monocarboxylic acids, dicarboxylic acids, and tricarboxylic acids can be added as needed. In this case, amines and carboxylic acids can be added simultaneously or separately.

[0082] As carboxylic acids, examples include aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, heptanoic acid, octanoic acid, decanoic acid, nonanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, myristenoic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, arachidic acid, behenic acid, and erucic acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid and methylcyclohexanecarboxylic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, ethylbenzoic acid, and phenylacetic acid; and malonic acid, succinic acid, glutaric acid, adipic acid, heptanoic acid, octanoic acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, hexadecanoic acid, hexadecenoic acid, octadecenoic acid, octadecenoic acid, eicosenoic acid, and eicosenoic acid. Aliphatic dicarboxylic acids such as docosanoic acid, diethylene glycol, 2,2,4-trimethyladipic acid, and 2,4,4-trimethyladipic acid; alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and norbornanedicarboxylic acid; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, isophthalimidedicarboxylic acid, terephthalimidedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid; and tricarboxylic acids such as 1,2,4-butanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, 1,2,6-hexanetricarboxylic acid, 1,3,6-hexanetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, and pyromellitic acid. One or more of these can be used.

[0083] The amount of amine used is appropriately determined by known methods, taking into account the concentration of terminal amino groups, the concentration of terminal carboxyl groups, and the relative viscosity of the polyamide (Al). Generally, from the viewpoint of obtaining sufficient reactivity and easily manufacturing polyamides with the desired viscosity, the amount of amine added is preferably 0.5 meq / mol or more and 20 meq / mol or less, more preferably 1.0 meq / mol or more and 10 meq / mol or less, relative to 1 mole of polyamide raw material (1 mole of monomer or monomer unit constituting a repeating unit). Here, regarding the amino equivalent (eq), the amount of amino group that reacts with the carboxyl group in a 1:1 ratio to form an amide group is defined as 1 equivalent.

[0084] As for polyamide (A1) manufacturing equipment, examples include batch reactors, single-tank to multi-tank continuous reaction equipment, tubular continuous reaction equipment, single-screw compounding extruders, twin-screw compounding extruders, and other known polyamide manufacturing equipment.

[0085] [Other ingredients]

[0086] The aliphatic polyamide composition (A) may contain other components as needed. Examples of such other components include polyamides other than polyamide (A1), such as aliphatic polyamides with [CH2] / [NHCO] ratio less than 7.0, polyamide resins having alicyclic or aromatic groups in the main chain or side chains, etc.; impact resistant agents, plasticizers, heat resistant agents selected from antioxidants and heat stabilizers; ultraviolet absorbers, light stabilizers, lubricants, inorganic fillers, antistatic agents, flame retardants, crystallization promoters, colorants, etc. Preferably, one or more of these other components are included, selected from the group consisting of plasticizers, impact resistant agents, and heat resistant agents. One or more of these components may be used.

[0087] [Impact Resistant Agent]

[0088] From the viewpoint of imparting impact resistance to the laminate, the aliphatic polyamide composition (A) preferably contains an impact-resistant agent. It should be noted that the impact-resistant agent is not a modified polyolefin (B). That is, the impact-resistant agent has a Shore hardness (D scale) of less than 30, preferably less than 20, as measured according to ASTM D2240. The lower limit of the Shore hardness (D scale) of the impact-resistant agent as measured according to ASTM D2240 is not particularly limited and can be set to 0.5 or higher. Examples of impact-resistant agents include elastomeric polymers containing structural units derived from unsaturated compounds having carboxyl and / or anhydride groups, and having a Shore hardness (D scale) of less than 30 as measured according to ASTM D2240.

[0089] Examples of elastomeric polymers include (ethylene and / or propylene) / α-olefin copolymers and (ethylene and / or propylene) / (α,β-unsaturated carboxylic acid ester) copolymers, and one or more of these can be used.

[0090] The aforementioned (ethylene and / or propylene) / α-olefin copolymers are polymers obtained by copolymerizing ethylene and / or propylene with α-olefins having 3 or more carbon atoms. Examples of α-olefins having 3 or more carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecadecene, 1-hexadecene, and 1-heptadecene. Carbene, 1-octadecene, 1-nonadecanene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene, etc. One or more of these can be used. Additionally, it can copolymerize conjugated dienes such as 1,3-butadiene; 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 4-ethimide-8-methyl-1,7-nonadiene, and 4,8-dimethyl-1,4,8-decadiene (…). Polyenes such as DMDT, dicyclopentadiene, cyclohexadiene, cyclooctadiene, 5-vinylnorbornene, 5-ethimide-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethimide-3-isopropylidene-5-norbornene, and 2-propenyl-2,5-norbornene are non-conjugated dienes. One or more of these can be used.

[0091] The aforementioned (ethylene and / or propylene) / (α,β-unsaturated carboxylic acid ester) copolymers are polymers obtained by copolymerizing ethylene and / or propylene with α,β-unsaturated carboxylic acid ester monomers. Examples of α,β-unsaturated carboxylic acid ester monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, pentyl acrylate, pentyl methacrylate, hexyl acrylate, hexyl methacrylate, heptyl acrylate, heptyl methacrylate, octyl acrylate, octyl methacrylate, nonyl acrylate, nonyl methacrylate, decyl acrylate, decyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, monomethyl maleate, itaconic acid, dimethyl maleate, and dimethyl itaconic acid. One or more of these monomers may be used.

[0092] Examples of α,β-unsaturated carboxyl compounds in elastomeric polymers include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, nicotinic acid, citraconic acid, penteneic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, intrabicyclo-[2.2.1]-5-heptene-2,3-dicarboxylic acid, and metal salts of these carboxylic acids. Examples of α,β-unsaturated carboxylic anhydrides with an anhydride group include maleic anhydride, itaconic anhydride, citraconic anhydride, and intrabicyclo-[2.2.1]-5-heptene-2,3-dicarboxylic anhydride. One or more of these can be used. Among these, dicarboxylic anhydrides with α,β-unsaturated bonds are preferred, and maleic anhydride and itaconic anhydride are more preferred.

[0093] From the viewpoint of exhibiting good compatibility with the aforementioned polyamide (A1) and the flowability of the aliphatic polyamide composition (A), the concentration of carboxyl groups and / or anhydride groups in the elastomeric polymer is preferably 25 μeq / g or more and 200 μeq / g or less, more preferably 50 μeq / g or more and 150 μeq / g or less.

[0094] Alternatively, the concentration of carboxyl and / or anhydride groups in the elastomer polymer can be determined by titrating a sample solution prepared by dissolving the elastomer polymer in toluene solution and then adding ethanol, using phenolphthalein as an indicator, with a 0.1N KOH ethanol solution.

[0095] [Plasticizer]

[0096] From the viewpoint of imparting flexibility to the laminate, the aliphatic polyamide composition (A) preferably contains a plasticizer. Examples of plasticizers include N-butylbenzenesulfonamide and 2-hexyldecyl p-hydroxybenzoate. One or more of them can be used.

[0097] [Heat resistant agent]

[0098] The aliphatic polyamide composition (A) preferably contains a heat-resistant agent selected from antioxidants and heat stabilizers. Examples of antioxidants include phenolic compounds. Heat stabilizers, also known as processing stabilizers, include, for example, sulfide-based, phosphorus-based, and metal halide-based compounds, preferably phosphorus-based compounds. One or more antioxidants and heat stabilizers can be used.

[0099] [Characteristics of the Aliphatic Polyamide Composition (A)]

[0100] The flexural modulus of the aliphatic polyamide composition (A), as measured according to ISO 178, is preferably 400 MPa or more and 1000 MPa or less, more preferably 450 MPa or more and 950 MPa or less, and particularly preferably 500 MPa or more and 900 MPa or less. By keeping the flexural modulus of the aliphatic polyamide composition (A) within the aforementioned range, the compressive strength of the laminate at high temperatures can be maintained, and the laminate exhibits excellent flexibility. The flexural modulus of the aliphatic polyamide composition (A) can be adjusted by appropriately varying the amount of impact-resistant agent and plasticizer added.

[0101] [Composition of Aliphatic Polyamide Composition (A)]

[0102] The content of polyamide (A1) in the aliphatic polyamide composition (A) is preferably 55% by mass or more and 95% by mass or less, more preferably 60% by mass or more and 95% by mass or less, and particularly preferably 70% by mass or more and 89% by mass or less, relative to 100% by mass of the aliphatic polyamide composition (A). By keeping the content of polyamide (A1) in the aliphatic polyamide composition (A) within the aforementioned range, the laminate can achieve sufficiently excellent properties such as breaking compressive strength at high temperatures. Furthermore, if the content of polyamide (A1) is above the aforementioned lower limit, the breaking compressive strength of the laminate at high temperatures can be sufficiently obtained. If the content of polyamide (A1) is below the aforementioned upper limit, the flexibility and low-temperature impact resistance of the laminate can be sufficiently obtained.

[0103] The content of the impact-resistant agent in the aliphatic polyamide composition (A) is preferably 5% by mass or more and 30% by mass or less, more preferably 7% by mass or more and 25% by mass or less, and particularly preferably 10% by mass or more and 20% by mass or less, relative to 100% by mass of the aliphatic polyamide composition (A). By keeping the content of the impact-resistant agent in the aliphatic polyamide composition (A) within the aforementioned range, the mechanical properties of the laminate can be maintained, and the flexibility and low-temperature impact resistance are improved. In addition, if the content of the impact-resistant agent is above the aforementioned lower limit, the flexibility and low-temperature impact resistance of the laminate can be sufficiently obtained. If the content of the impact-resistant agent is below the aforementioned upper limit, the breaking compressive strength and other mechanical properties of the laminate at high temperatures can be sufficiently obtained.

[0104] The content of plasticizer in the aliphatic polyamide composition (A) is preferably 0% by mass or more and 15% by mass or less, and particularly preferably 1% by mass or more and 10% by mass or less, relative to 100% by mass of the aliphatic polyamide composition (A). By keeping the content of plasticizer within the aforementioned range, the compressive strength of the laminate at high temperature can be maintained, and the flexibility of the laminate is excellent. Furthermore, if the content of plasticizer is below the aforementioned upper limit, the compressive strength of the laminate at high temperature can be sufficiently obtained.

[0105] The content of the heat-resistant agent in the aliphatic polyamide composition (A) is preferably 0% or more and 5% or less, and particularly preferably 0.5% or more and 2% or less, relative to 100% by mass of the aliphatic polyamide composition (A). If the content of the heat-resistant agent is within the aforementioned range, a balance can be achieved in the mechanical properties, heat resistance, etc. of the laminate.

[0106] The content of other components in the aliphatic polyamide composition (A), excluding impact-resistant agents, plasticizers and heat-resistant agents, can be appropriately set according to the required properties.

[0107] [Method for manufacturing aliphatic polyamide composition (A)]

[0108] The method for manufacturing the aliphatic polyamide composition (A) is not particularly limited, and various methods known in the art can be used. For example, it can be manufactured by methods such as: using a drum or mixer to uniformly dry-mix the polyamide (A1), impact resistant agent, plasticizer, and heat resistant agent with other components added as needed, in the aforementioned mixing ratio; pre-dry-mixing the polyamide (A1), impact resistant agent, plasticizer, and heat resistant agent with other components added as needed, and then performing melt mixing; pre-dry-mixing the polyamide (A1), impact resistant agent, plasticizer, and heat resistant agent with other components added as needed, feeding them separately, and then performing melt mixing, etc. Melt mixing can be performed using a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, or other mixing mills.

[0109] 2.(b) layer

[0110] Layer (b) of the laminate contains a modified polyolefin (B).

[0111] <Modified Polyolefin (B)>

[0112] Modified polyolefin (B) is a polymer (hereinafter sometimes referred to as modified polyolefin (B)) containing units derived from monomers of α-olefins having 2 or more and 10 or fewer carbon atoms, and units derived from unsaturated compounds having functional groups, wherein the unsaturated compounds having functional groups are selected from at least one unsaturated compound having at least one group selected from the group consisting of carboxyl, hydroxyl, epoxy, amino, amide, imide, nitrile, thiol and isocyanate groups, and derivatives of unsaturated compounds having carboxyl groups, and the polymer has a Shore hardness (D scale) of 30 or more and 61 or less as measured according to ASTM D2240.

[0113] [Monomers based on α-olefins with 2 or more but less than 10 carbon atoms]

[0114] The polyolefin (B1) constituting the modified polyolefin (B) contains units derived from monomers based on α-olefins having 2 or more and 10 or fewer carbon atoms.

[0115] Examples of monomers based on α-olefins having 2 or more but less than 10 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, and 3-ethyl-1-hexene. One or more of these monomers can be used. Among these, monomers based on α-olefins having 2 or more but less than 8 carbon atoms are preferred from the viewpoint of enabling particularly superior mechanical properties and flexibility of the laminate.

[0116] [Other monomers]

[0117] As long as it does not impair the excellent properties of the laminate, polyolefins (B1) can include monomers other than α-olefins with 2 or more but less than 10 carbon atoms and unsaturated compounds with functional groups, such as styrene, conjugated dienes like 1,3-butadiene, non-conjugated dienes, cyclic olefins, and oxygen-containing olefins. Examples of styrene monomers include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,5-dimethylstyrene, 2,4-dimethylstyrene, vinylnaphthalene, vinylanthracene, 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, and 4-(phenylbutyl)styrene. Examples of non-conjugated dienes include 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 4-ethide-8-methyl-1,7-nonadiene, and 4,8-dimethyl-1,4,8-decanetriene (DMDT). Examples of cyclic alkenes include dicyclopentadiene, cyclohexadiene, cyclooctadiene, 5-vinylnorbornene, 5-ethide-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethidene-3-isopropylidene-5-norbornene, and 2-propenyl-2,5-norbornediene. Examples of oxygen-containing alkenes include hexenol, hexenoic acid, and methyl octenate.

[0118] As the polyolefin (B1), preferred are crystalline polyolefins such as polyethylene, polypropylene, polybutene-1, poly(4-methylpentene-1); ethylene, propylene, 1-butene, or α-olefin copolymers of 4-methylpentene-1 with other monomers. One or more of these can be used.

[0119] [Composition of polyolefin (B1)]

[0120] In the polyolefin (B1), the content of units derived from monomers of α-polyolefins having 2 or more and 10 or less carbon atoms is preferably 60 mol% or more, more preferably 70 mol% or more, and particularly preferably 90 mol% or more, relative to 100 mol% of all polymeric units in the polyolefin (B1). By ensuring that the content of units derived from monomers of α-polyolefins having 2 or more and 10 or less carbon atoms is at or above the aforementioned values, the mechanical properties and flexibility of the laminate are improved. Furthermore, in the polyolefin (B1), the content of units derived from other monomers is preferably less than 40 mol%, more preferably less than 30 mol%, and particularly preferably less than 10 mol% of 100 mol% of all polymeric units in the polyolefin (B1).

[0121] Therefore, as a polyolefin (B1), it is more preferably a polypropylene homopolymer, a random copolymer of propylene and other α-olefins of 20 mol% or less, or a block copolymer of propylene and other α-olefins of 30 mol% or less.

[0122] [Manufacturing method of polyolefin (B1)]

[0123] Polyolefin (B1) can be manufactured using any method known in the art, such as polymerization using titanium-based catalysts, vanadium-based catalysts, or metallocene catalysts. Furthermore, polyolefin (B1) can be in any form of resin or elastomer; both isotactic and syndiotactic structures are acceptable, with no particular limitation on stereoregularity. When polyolefin (B1) is a copolymer, it can be any of alternating copolymerization, random copolymerization, or block copolymerization.

[0124] [Unsaturated compounds with functional groups]

[0125] The modified polyolefin (B) contains units derived from unsaturated compounds having functional groups, wherein the unsaturated compounds having functional groups are selected from at least one group selected from carboxyl, hydroxyl, epoxy, amino, amide, imide, nitrile, thiol, and isocyanate groups, and derivatives of unsaturated compounds having carboxyl groups. By comprising units derived from unsaturated compounds having functional groups (i.e., unsaturated compounds having at least one group selected from the group consisting of specific groups and / or derivatives of unsaturated compounds having carboxyl groups), the modified polyolefin (B) enables high interlayer adhesion between layers (a) and (b) and high durability of the laminate.

[0126] Examples of unsaturated carboxylic acids with a carboxyl group include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclic [2,2,1]hept-2-en-5,6-dicarboxylic acid, and intrabicyclic [2,2,1]-5-heptene-2,3-dicarboxylic acid. One or more of these carboxyl groups may be used.

[0127] Derivatives of unsaturated compounds having a carboxyl group include, for example, the aforementioned carboxyl-containing unsaturated compounds such as acid anhydrides, acyl halides, amides, imides, and / or esters. Examples of derivatives of unsaturated compounds having a carboxyl group include maleic chloride, maleimide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic anhydride, intrabicyclo[2,2,1]-5-heptene-2,3-dicarboxylic anhydride, dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconic acid, diethyl citraconic acid, dimethyl tetrahydrophthalate, and dimethyl bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic acid. One or more of these derivatives may be used.

[0128] Examples of unsaturated compounds containing hydroxyl groups include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, glyceryl mono(meth)acrylate, pentaerythritol mono(meth)acrylate, and other hydroxyl-containing (meth)acrylates; 10-undecen-1-ol, 1-octen-3-ol, glyceryl monoallyl ether, allyl alcohol, 2-buten-1,4-diol, etc. One or more of these compounds may be used.

[0129] Examples of unsaturated compounds with epoxy groups include glycidyl acrylate, glycidyl methacrylate, and other glycidyl esters of unsaturated carboxylic acids; or monoglycidyl esters of unsaturated dicarboxylic acids such as maleic acid and fumaric acid (in the case of monoglycidyl esters, the alkyl group has 1 or more but less than 12 carbon atoms), alkyl glycidyl esters of p-styrene carboxylic acids, 2-methylallyl glycidyl ether, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1-hexene, vinylcyclohexene monooxide, etc. One or more of these compounds may be used.

[0130] Examples of unsaturated compounds containing an amino group include aminoalkyl ester derivatives of acrylic acid or methacrylic acid such as urethane acrylate, urethane methacrylate, dimethylaminoethyl methacrylate, aminopropyl acrylate, aminopropyl methacrylate, and cyclohexylaminoethyl methacrylate; and vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine. One or more of these compounds may be used.

[0131] Examples of acrylamide derivatives, such as acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, and N,N-dimethylaminopropylacrylamide, are examples of unsaturated compounds containing an amide group. One or more of these derivatives may be used.

[0132] Examples of unsaturated compounds containing an imide group include N-acryloyloxyethyl-1,2,3,6-tetrahydrophthalimide (manufactured by Toa Synthetic Co., Ltd., trade name: ARONIX TO-1428), N-acryloyloxyethyl hexahydrophthalimide (manufactured by Toa Synthetic Co., Ltd., trade name: ARONIX TO-1429), and N-acryloyloxyethyl-3,4,5,6-tetrahydrophthalimide (manufactured by Toa Synthetic Co., Ltd., trade name: ARONIX TO-1534). One or more of these compounds may be used.

[0133] Examples of unsaturated compounds containing a nitrile group include acrylonitrile, methacrylonitrile, 5-hexenonium, 5-methyl-5-hexenonium, methyl-2-cyanoacrylate, ethyl-2-cyanoacrylate, butyl-2-cyanoacrylate, cyclohexyl-2-cyanoacrylate, 2-ethylhexyl-2-cyanoacrylate, and ethoxyethyl-2-cyanoacrylate. One or more of these compounds may be used.

[0134] Examples of unsaturated compounds containing a thiol group include esters formed by combining aliphatic or aromatic thiol alcohols or dithiols with acrylic acid or methacrylic acid. One or more of these compounds can be used.

[0135] Examples of unsaturated compounds having an isocyanate group include 2-methacryloyloxyethyl isocyanate (manufactured by Showa Denko Corporation, trade name: Karenz MOI (registered trademark)) and 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko Corporation, trade name: Karenz AOI (registered trademark)). One or more of these compounds may be used.

[0136] The unsaturated compounds having functional groups are preferably maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, intrabicyclo-[2.2.1]-5-heptene-2,3-dicarboxylic anhydride, acrylic acid, methacrylic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, glycidyl methacrylate, and aminopropyl methacrylate, more preferably maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, and intrabicyclo-[2.2.1]-5-heptene-2,3-dicarboxylic anhydride, and particularly preferably maleic anhydride.

[0137] From the viewpoint of obtaining a laminate with good mechanical properties, long-term resistance to chemical solutions and good interlayer adhesion, the modified polyolefin (B) is preferably maleic anhydride modified polypropylene.

[0138] [Properties of Modified Polyolefin (B)]

[0139] From the viewpoint of obtaining a laminate with mechanical properties and flexibility at low temperatures, the upper limit of the Shore hardness (D scale) of the modified polyolefin (B) measured according to ASTM D2240 is 61 or less, preferably 59 or less.

[0140] Furthermore, from the viewpoint of the mechanical strength of the laminate, the lower limit of the Shore hardness (D scale) measured according to ASTM D2240 is 30 or more, preferably 45 or more, and particularly preferably 50 or more.

[0141] From the viewpoint of obtaining a laminate with mechanical properties and flexibility at low temperatures, the tensile yield stress of the modified polyolefin (B), as measured according to ASTM D638, is preferably 23 MPa or less, and particularly preferably 21 MPa or less. Furthermore, from the same viewpoint, the tensile fracture stress, as measured according to ASTM D638, is preferably 25 MPa or more, and particularly preferably 27 MPa or more.

[0142] The modified polyolefin (B) preferably has an MFR value of 3.5 g / 10 min or more and 10.0 g / 10 min or less, more preferably 4.0 g / 10 min or more and 7.0 g / 10 min or less, as measured according to ASTM D1238 at 230°C and 2160 g. By ensuring that the MFR value of the modified polyolefin (B) is within the aforementioned range, the impact resistance at low temperatures is improved, and the molding stability of the laminate is enhanced.

[0143] Generally, in the FT-IR determination of polyolefins, the wavenumber is 710 cm⁻¹. -1 ~740cm -1 The maximum absorption varies depending on whether the polyolefin is a homopolymer or a random copolymer, showing a trend that the closer to 710 cm⁻¹, the better. -1 The closer it is to a homopolymer, the closer it is to 740 cm⁻¹ -1 The closer it is to the structure of a random copolymer, the better. In the FT-IR measurement of modified polyolefin (B), the wavenumber is around 710 cm⁻¹. -1 Above and 740cm -1 The wavenumber exhibiting the greatest intensity among the following absorptions is preferably 721 cm⁻¹. -1 The above. If it falls within this range, it is possible to obtain laminated tubes with excellent flexibility and superior impact resistance at low temperatures.

[0144] [Composition of modified polyolefin (B)]

[0145] In the modified polyolefin (B), the content of the aforementioned unsaturated compound with functional groups is preferably an amount similar to the grafting amount of the unsaturated compound with functional groups described later, relative to 100% by mass of the modified polyolefin (B). Furthermore, when the modified polyolefin (B) is maleic anhydride-modified polypropylene, the content of polypropylene in the maleic anhydride-modified polypropylene is preferably 50% by mass or more and 99.5% by mass or less, more preferably 60% by mass or more and 97% by mass or less, and particularly preferably 70% by mass or more and 95% by mass or less, relative to 100% by mass of the maleic anhydride-modified polypropylene. By ensuring that the content of polypropylene in the maleic anhydride-modified polypropylene is at or above the aforementioned values, sufficient flexibility of the laminate can be achieved, and superior resistance to leaching of low molecular weight compounds and ions can be obtained. Here, the content of polypropylene in the maleic anhydride-modified polypropylene can be measured in the same manner as the grafting amount of the unsaturated compound with functional groups described later.

[0146] [Method for manufacturing modified polyolefin (B)]

[0147] The modified polyolefin (B) can be manufactured using known methods for introducing the aforementioned units derived from the functionalized unsaturated compound into the polyolefin (B1). Examples include methods for graft copolymerization of the aforementioned functionalized unsaturated compound with polyolefin (B1); methods for free radical copolymerization of olefin monomers with the aforementioned functionalized unsaturated compound; and preferably, methods for graft copolymerization of the aforementioned functionalized unsaturated compound with polyolefin (B1).

[0148] Furthermore, various known methods can be used as methods for graft copolymerization of the aforementioned functionalized unsaturated compound with polyolefin (B1). Examples include: melting the unmodified polyolefin, adding the aforementioned functionalized unsaturated compound, and graft copolymerizing it; or dissolving the unmodified polyolefin in a solvent, adding the graft monomer, and graft copolymerizing it. In any case, to ensure efficient graft polymerization of the aforementioned functionalized unsaturated compound, it is preferable to carry out the reaction in the presence of a free radical polymerization initiator.

[0149] There are no particular limitations on the free radical polymerization initiator as long as it promotes the reaction between the polyolefin backbone and the unsaturated compound having the aforementioned functional groups; organic peroxides and organic peresters are preferred. Specifically, examples include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(benzoyl peroxide)hexyn-3, 1,4-bis(tert-butylperoxide isopropyl)benzene, lauroyl peroxide, tert-butyl peracetate, 2,5-dimethyl-2,5-di(tert-butylperoxide)hexyn-3, 2,5-dimethyl-2,5-di(tert-butylperoxide)hexane, tert-butyl benzoate, tert-butyl peroxyphenylacetate, tert-butyl peroxyisobutyrate, tert-butyl peroxyoctanoate, tert-butyl peroxypentanoate, cumyl peroxypentanoate, and tert-butyl peroxydiethylacetate. Other azo compounds include azobisisobutyronitrile and dimethylazoisobutyronitrile. One or more of these compounds may be used. Among these, more preferred are dialkyl peroxides such as dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxide)hexyn-3, 2,5-dimethyl-2,5-di(tert-butylperoxide)hexane, and 1,4-bis(tert-butylperoxide isopropyl)benzene.

[0150] The free radical polymerization initiator is preferably used in an amount of about 0.001 to 10 parts by mass relative to 100 parts by mass of polyolefin (B1).

[0151] The grafting amount of the aforementioned unsaturated compound with functional groups relative to 100% by mass of polyolefin (B1) is preferably 0.05% by mass or more and 20% by mass or less, more preferably 0.05% by mass or more and 10% by mass or less, further preferably 0.05% by mass or more and 5% by mass or less, and particularly preferably 0.05% by mass or more and 3% by mass or less. Furthermore, the grafting amount of polyolefin (B1) is the net weight grafting amount measured after removing the unsaturated compound with the aforementioned functional groups from polyolefin (B1). Additionally, the grafting amount can be determined by... 13 C-NMR, 1 This is performed using known methods such as ¹H-NMR determination. Furthermore, when using monomers with acidic functional groups, such as unsaturated carboxylic acids and their anhydrides, as the aforementioned unsaturated compounds with functional groups, the amount of functional group introduced into the polyolefin (B1) can be measured, for example, by the acid value. Additionally, when using maleic anhydride as the aforementioned unsaturated compound with functional groups, an infrared spectrophotometer can be used, typically based on a range of 1780–1790 cm⁻¹. -1 The grafting amount was determined by the absorption spectrum of the carbonyl group of maleic anhydride detected nearby.

[0152] Modified polyolefin (B) can be used in combination with various additives as needed. In this case, layer (b) can contain various additives in addition to the modified polyolefin. Examples of such additives include conductive fillers, antioxidants, heat stabilizers, UV absorbers, light stabilizers, lubricants, inorganic fillers, antistatic agents, flame retardants, crystallization promoters, plasticizers, colorants, lubricants, and other thermoplastic resins. One or more of these additives can be used.

[0153] 3. Layered structure

[0154] The laminate contains two or more layers, including (a) and (b).

[0155] By including layer (a) in the laminate, a laminate with excellent mechanical properties, chemical resistance, and flexibility can be obtained. Furthermore, by including layer (b) in the laminate, the chemical solution barrier properties of the laminate, especially its barrier properties against water vapor, coolant (LLC), and urea solution, and its long-term chemical solution resistance are improved.

[0156] The laminate is preferably arranged in the order of layer (a) and layer (b) from the outside to the inside. This effectively imparts both the mechanical properties achieved by layer (a) and the chemical solution barrier properties achieved by layer (b). Here, when the laminate is sheet-like, and two or more surfaces of the laminate are in contact with air but not with a chemical solution, the surface in contact with air but not with a chemical solution is designated as the outside, and the opposite surface is designated as the inside. Furthermore, when the laminate is a hollow laminate, the inside refers to the side of the laminate in contact with the chemical solution, and the outside refers to the side of the laminate in contact with air but not with a chemical solution.

[0157] Preferably, layers (a) and (b) of the laminate are adjacent to each other. This results in a laminate with excellent interlayer adhesion.

[0158] The laminate is preferably composed of only layer (a) and layer (b). This allows the effects of layer (a) and layer (b) to be effectively utilized. In this case, layer (a) and layer (b) can each be one layer, or there can be two or more layers.

[0159] More preferably, layer (a) is disposed in the outermost layer of the laminate. By disposing layer (a) in the outermost layer, a laminate with superior breaking compressive strength at high temperatures can be obtained. More preferably, layer (b) is disposed in the innermost layer of the laminate. By disposing layer (b) in the innermost layer, the reduction in mechanical properties caused by contact with chemical solutions can be further suppressed.

[0160] In addition to layers (a) and (b), the laminate may include one or more other layers to provide additional functionality or to achieve an economically advantageous laminate. Examples of such other layers include layers comprising other thermoplastic resins and / or layers comprising any substrate other than thermoplastic resins. When the laminate includes other layers, it is preferable that the innermost layer of the laminate also includes other layers. By including other layers in the innermost layer of the laminate, the functions achieved by the other layers can be effectively imparted.

[0161] Examples of thermoplastic resins constituting layers containing other thermoplastic resins include polyamide resins, fluorinated polymers, polyester resins, polyether resins, polysulfone resins, polysulfide resins, polyketide resins, polyacrylonitrile resins, polymethyl methacrylate resins, polyethylene ester resins, polyvinyl chloride resins, cellulose resins, polycarbonate resins, polyimide resins, and thermoplastic polyurethane resins.

[0162] In addition, any substrate other than thermoplastic resin can be laminated, such as paper, metallic materials, unstretched, uniaxial or biaxial stretched plastic films or sheets, woven fabrics, nonwoven fabrics, metal wool, wood, etc. Examples of metallic materials include metals and / or their metal compounds such as aluminum, iron, copper, nickel, gold, silver, titanium, molybdenum, magnesium, manganese, lead, tin, chromium, beryllium, tungsten, and cobalt, as well as alloy steels such as stainless steel, aluminum alloys, brass, bronze, and other copper alloys, nickel alloys, etc.

[0163] Regarding the total number of layers in the laminate, there is no particular limitation as long as it has at least two layers, having at least one layer (a) and at least one layer (b). The total number of layers in the laminate is determined by the structure of the laminate manufacturing apparatus, and is preferably 8 layers or less, more preferably 2 layers or more and 7 layers or less. In addition, due to limitations in material management and the lamination manufacturing apparatus, the total number of layers in the laminate is particularly preferably two layers.

[0164] The shape of the laminate is arbitrary; it can be sheet-like or hollow (tubular, bottle-like, or other shapes with internal cavities). As a hollow shape, a tubular shape is preferred. The laminate can have wavy regions. Wavy regions refer to areas formed in a wave-like shape, a serpentine shape, an accordion shape, or a corrugated shape, etc. Wavy regions can not only be present throughout the entire length of the laminate, but also locally in appropriate areas along its length.

[0165] Specific examples of laminated bodies include laminated hollow molded bodies, laminated films, and laminated plates, with laminated hollow molded bodies being the most preferred. Additionally, specific examples of laminated hollow molded bodies include laminated tubes.

[0166] The thickness of layer (a) in the laminate is preferably 30% or more and 95% or less of the total wall thickness of the laminate, more preferably 40% or more and 85% or less, and particularly preferably 45% or more and 80% or less. By keeping the thickness of layer (a) within the aforementioned range, the aforementioned properties can be effectively utilized.

[0167] The thickness of layer (b) in the laminate is preferably greater than 5% and less than 70% of the total wall thickness of the laminate, more preferably greater than 15% and less than 60%, and particularly preferably greater than 20% and less than 55%. By keeping the thickness of layer (b) within the aforementioned range, the aforementioned properties can be effectively utilized.

[0168] The total wall thickness of the laminate is preferably 0.5 mm or more and 25 mm or less.

[0169] When the laminate is a laminated tube, regarding the outer diameter of the laminated tube, considering the flow rate of circulating chemical solutions and / or gases (e.g., engine coolant), the wall thickness is designed to ensure that the permeability of the chemical solution does not increase, and that the thickness can maintain the normal breaking pressure of the tube. Furthermore, this thickness maintains a degree of flexibility that allows for easy installation and good vibration resistance during use, but is not limited to this. Preferably, the outer diameter is 4 mm or more and 300 mm or less, the inner diameter is 3 mm or more and 250 mm or less, and the wall thickness is 0.5 mm or more and 25 mm or less.

[0170] Methods for manufacturing laminates include: melt extrusion using an extruder corresponding to the number of layers or materials, and simultaneous lamination inside or outside the die (co-extrusion molding); or, pre-manufacturing a single-layer tube or a laminate manufactured by the above methods, and then, as needed, using an adhesive to sequentially integrate and laminate resins on the outer side (coating method). Laminates are preferably manufactured by co-extrusion, where various materials are co-extruded in a molten state, thermally fused together (melt bonding), thereby manufacturing a tube with a laminated structure in one stage. That is, the manufacturing method of the laminate preferably includes co-extrusion molding.

[0171] In addition, when the laminate has a complex shape and the molded article is produced by heating and bending after forming, in order to remove the residual strain of the molded article, the target molded article can be obtained by heat treatment at a temperature lower than the lowest melting point of the resin constituting the laminate for 0.01 hours to 10 hours after forming the laminate.

[0172] Laminated bodies with wavy regions can be easily formed by first shaping them into straight tubular laminates and then molding them into specific wavy shapes. The presence of these wavy regions provides impact absorption and facilitates installation. Furthermore, by adding necessary components such as connectors or by performing bending processes, L-shaped or U-shaped forms can be created.

[0173] For the entirety or part of the outer periphery of such a formed laminate, considering flystone, wear from other components, and fire resistance, it can be equipped with natural rubber (NR), butadiene rubber (BR), isoprene rubber (IR), butyl rubber (IIR), chloroprene rubber (CR), carboxylated butadiene rubber (XBR), carboxylated chloroprene rubber (XCR), epichlorohydrin rubber (ECO), acrylonitrile butadiene rubber (NBR), hydrogenated acrylonitrile butadiene rubber (HNBR), carboxylated acrylonitrile butadiene rubber (XNBR), a mixture of NBR and polyvinyl chloride, acrylonitrile isoprene rubber (NIR), chlorinated polyethylene rubber (CM), sulfonated polyethylene rubber (CSM), and ethylene propylene rubber (EPR). Protective components (parts) are solid or sponge-like structures composed of thermoplastic elastomers such as ethylene propylene diene rubber (EPDM), ethylene vinyl acetate rubber (EVM), mixtures of NBR and EPDM, acrylic rubber (ACM), ethylene acrylic rubber (AEM), acrylate butadiene rubber (ABR), styrene butadiene rubber (SBR), carboxylated styrene butadiene rubber (XSBR), styrene isoprene rubber (SIR), styrene isoprene butadiene rubber (SIBR), urethane rubber, silicone rubber (MQ, VMQ), fluororubber (FKM, FFKM), fluorosilicone rubber (FVMQ), chlorinated vinyl, olefin, ester, urethane, and amide thermoplastic elastomers. These protective components can be made into sponge-like porous bodies using known methods. By creating porous bodies, lightweight protective parts with excellent thermal insulation can be formed. Additionally, material costs can be reduced. Alternatively, glass fibers can be added to improve their strength. The shape of the protective member is not particularly limited, and it is usually a cylindrical member or a block-shaped member with a recess for accommodating a laminated tube as one form of a laminate. When it is a cylindrical member, the laminated tube can be subsequently inserted into a pre-fabricated cylindrical member, or the cylindrical member can be extruded over the laminated tube and the two can be sealed together. To bond the two, an adhesive is applied to the inner surface of the protective member or the aforementioned recessed surface as needed, and the laminated tube is inserted or embedded therein, sealing the two together, thereby forming a structure in which the laminated tube and the protective member are integrated. Alternatively, reinforcement with metal or the like can be used.

[0174] Applications of laminates

[0175] Laminated materials can be used for a variety of applications, including automotive parts, internal combustion engine components, power tool housings, industrial materials, electrical / electronic components, medical and food products, household / office supplies, building materials, and furniture components.

[0176] Furthermore, laminates are suitable for use as chemical solution transport tubes due to their excellent resistance to chemical solution permeation. Examples of chemical solutions include, for instance, aromatic hydrocarbon solvents such as benzene, toluene, xylene, and alkylbenzenes; alcohols such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, diethylene glycol, phenol, cresol, polyethylene glycol, polypropylene glycol, and polyalkylene glycol; phenol solvents; ether solvents such as dimethyl ether, dipropyl ether, methyl tert-butyl ether, ethyl tert-butyl ether, dioxane, tetrahydrofuran, polyol esters, and polyvinyl ethers; and ether solvents such as HFC-23, HFC-32, HFC-41, HFC-123, HFC-125, HFC-134, HFC-134a, HFC-143, HFC-143a, HFC-152, HFC-152a, HFC-161, and HFC- 227ea, HFC-227ca, HFC-236fa, HFC-236ea, HFC-236cb, HFC-236ca, HFC-245ca, HFC-245ea, HFC-245eb, HFC-245fa, HFC-245cb, HFC-254eb, HFC-2 54cb, HFC-254ca, HFC-263fb, HFC-263ca, HFC-272fb, HFC-272ea, HFC-272fa, HFC-272ca, HFC-281fa, HFC-281ea, HFC-329p, HFC-329mmz, HFC-33 8mf, HFC-338mcc, HFC-338pcc, HFC-347s, HFC-365mfc, HFC-4310mee, HFC-1123, HFC-1132a, FC-1216, HFC-1223, HFC-1225zc, HFC-1225ye, HFC-1 225yc, HFC-1232xf, HFC-1234ye, HFC-1234ze, HFC-1234yf, HFC-1234yc, HFC-1234zc, HFC-1243yf, HFC-1243zc, HFC-1243ye, HFC-1243ze, HFC-1 243zf, HFC-1243yc, HFC-1261yf, FC-1318my, FC-1318cy, HFC-1327my, HFC-1327ye, HFC-1327py, HFC-1327et, HFC-1327cz, HFC-1327cye, HFC-13 27cyc, HFC-1336yf, HFC-1336ze, HFC-1336eye, HFC-1336eyc, HFC-1336pyy, HFC-1336pz, HFC-1336mzy, HFC-1336mzz, HFC-1336qc, HFC-1336pe,HFC-1336ft、HFC-1345qz、HFC-1345mzy、HFC-1345fz、HFC-1345mzz、HFC-1345sy、HFC-1345fyc、HFC-1345pyz、HFC-1345cyc、HFC-1345pyy、HFC-1345eyc、HFC-1345ctm、HFC-1345ftp、HFC1345fye、HFC-1345eyf、HFC-1345eze、HFC-1345ezc、HFC-1345eye、HFC-1354fzc、HFC-1354ctp、HFC-1354etm、HFC-1354tfp、HFC-1354my、HFC-1354mzy、FC-141-10myy、FC-141-10cy、HFC-1429mzt、HFC-1429myz、HFC-1429mzy、HFC-1429eyc、HFC-1429czc、HFC-1429cycc、HFC-1429pyy、HFC-1429myyc、HFC-1429myye、HFC-1429eyym、HFC-1429cyzm、HFC-1429mzt、HFC-1429czym、HFC-1438fy、HFC-1438eycc、HFC-1438ftmc(、HFC-1438czzm、HFC-1438ezym、HFC-1438ctmf、HFC-1447fzy、HFC-1447fz、HFC-1447fycc、HFC-1447cz、HFC-1447mytm、HFC-1447fyz、HFC-1447ezz、HFC-1447qzt、HFC-1447syt、HFC-1456szt、HFC-1456szy、HFC-1456mstz、HFC-1456fzce、HFC-1456ftmf、FC-151-12c、FC-151-12mcy、FC-151-12mmtt、FC-151-12mmzz、HFC-152-11mmtz、HFC-152-11mmyyz、HFC-152-11mmyyz、HFC-1549fz(PFBE)、HFC-1549fztmm、HFC-1549mmtts、HFC-1549fycz、HFC-1549myts、HFC-1549mzzz、HFC-1558szy、HFC-1558fzccc、HFC-1558mmtzc、HFC-1558ftmf、HFC-1567fts、HFC-1567szz、HFC-1567fzfc、HFC-1567sfyy, HFC-1567fzfy, HFC-1567myzzm(, HFC-1567mmtyf, FC-161-14myy, FC-161-14mcyy, HFC-162-13mzy, HFC162-13myz, HFC-162-13mczy, HFC-162-13mcy z, CFC-11 (, CFC-114, CFC-114a, CFC-115, HCFC-21, HCFC-22, HCFC-122, HCFC-123, HCFC-124, HCFC-124a, HCFC-132, HCFC-133a, HCFC-141b, HCFC-142, HCFC-142b, HC Halogenated olefins such as FC-225ca, HCFC-225cb, HCFC-240db, HCFC-243db, HCFC-243ab, HCFC-244eb, HCFC-244bb, HCFC-244db, HCFC-1111, HCFC-1113, HCFC-1223xd, HCFC-1224xe, HCFC-1232xf, HCFC-1233xf, HCFC-1233zd, and mixtures thereof; ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, and acetophenone; mineral oils, silicone oils, natural paraffins, cycloalkanes, synthetic paraffins, polyalphaolefins, gasoline, kerosene, diesel, rapeseed oil methyl ester, soybean oil methyl ester, palm oil methyl ester, coconut oil methyl ester, and liquefied natural gas (Gas) To Liquid (GTL), Coal To Liquid (CTL), Biomass To Liquid (BTL), Alcohol-containing gasoline, Ethyl tert-butyl ether blended oxygenated gasoline, Amine-containing gasoline, Acid gasoline, Compressed natural gas (CNG), Liquefied petroleum gas (LPG), Liquefied hydrocarbon gas (LHG), Liquefied natural gas (LNG), Dimethyl ether for fuel (DME), Castor oil-based brake fluid, Glycol ether-based brake fluid, Boron ester-based brake fluid, Polar brake fluid, Silicone oil-based brake fluid, Mineral oil-based brake fluid, Power steering fluid, Hydrogen sulfide-containing oil, Windshield washer fluid, Engine coolant, Urea solution, Pharmaceuticals, Ink, Paint, etc.

[0177] The laminate is suitable as a pipe for transporting the aforementioned chemical solutions. Specifically, it is preferably a fuel pipe such as a feed pipe, return pipe, evaporator pipe, fuel supply pipe, ORVR pipe, storage pipe, and ventilation pipe; an oil pipe, oil excavation pipe, compressed air pipe, hydraulic pipe, clutch pipe, brake pipe, brake negative pressure pipe, suspension pipe, air pipe, turbine air pipe, duct, leak pipe, EGR valve control pipe, windshield washer fluid pipe, coolant (LLC) cooler pipe, storage tank pipe, urea solution transport pipe, battery cooling and heating pipe, fuel cell pipe, air conditioning pipe, heater pipe, heat dissipation pipe, road heater pipe, underfloor heating pipe, infrastructure supply pipe, fire extinguisher and fire extinguishing equipment pipe, medical cooling machine material pipe, ink dispensing pipe, paint dispensing pipe, and other chemical solution pipes. It is particularly preferred to be any one of coolant (LLC) cooler pipe, urea solution transport pipe, battery cooling and heating pipe, and air conditioning pipe.

[0178] Example

[0179] The following examples and comparative examples illustrate the present invention in detail, but the invention is not limited thereto. First, the analytical and property determination methods in the examples and comparative examples, as well as the materials used in the examples and comparative examples, are shown.

[0180] 1. The properties of polyolefins were determined using the following methods.

[0181] [Shore Hardness (D scale)]

[0182] Shore hardness was determined according to ASTM D2240 (D scale).

[0183] [Tension Test]

[0184] The tensile yield stress and tensile fracture stress are determined according to ASTM D638.

[0185] [MFR (Melting Rate)]

[0186] MFR was determined according to ASTM D1238 at 230°C and 2160g.

[0187] [FT-IR]

[0188] Using the JASCO FT / IR-4700, at 4000cm -1 ~650cm -1 Measurements were taken within the specified range. The survey covered an area of ​​710cm. -1 ~740cm -1 The maximum wave value within the absorption range.

[0189] 2. The physical properties of the laminates were determined using the following methods.

[0190] [Low-temperature impact resistance]

[0191] For 10 laminated tubes, an impact test was conducted at -40°C using the method described in SAE J 2260 7.5. Subsequently, the presence or absence of fractures in the laminated tubes was confirmed.

[0192] High-Temperature Destructive Compressive Strength

[0193] For five laminated tubes, the breaking compressive strength test was conducted at a temperature of 125°C using the method described in SAE J 2260 7.2. The average values ​​of the measured breaking compressive strength are shown in Table 1.

[0194] 3. Materials used in the Examples and Comparative Examples

[0195] (1) Aliphatic polyamide (A1)

[0196] [Manufacturing of Polyamide 12 (A1-1)]

[0197] 19.73 kg (100.0 mol) of dodecanolactam, 45.0 g (0.264 mol) of 5-amino-1,3,3-trimethylcyclohexanemethylamine, and 0.5 L of distilled water were added to a 70 L pressure-resistant reaction vessel equipped with a stirrer. After purging the polymerization tank with nitrogen, the mixture was heated to 180 °C and stirred at this temperature to achieve a homogeneous reaction system. Next, the temperature of the polymerization tank was raised to 270 °C, and the pressure was adjusted to 3.5 MPa while polymerization was carried out under stirring for 2 hours. Afterward, the pressure was released to atmospheric pressure (0.1 MPa) over approximately 2 hours, and then reduced to 53 kPa, where polymerization was carried out for 5 hours under reduced pressure. Finally, nitrogen was introduced into an autoclave, and after restoring the pressure to atmospheric pressure, the nitrogen gas was discharged in a stream from the lower nozzle of the reaction vessel for cutting into granules. The granules were subjected to vacuum drying to obtain polyamide 12 (hereinafter referred to as (A1-1)) with a relative viscosity of 2.20, a terminal amine concentration of 48 μeq / g, and a terminal carboxyl concentration of 24 μeq / g. The ratio of the number of methylene groups to the number of amide groups in polyamide 12 (A1-1) [CH2] / [NHCO] is 11.0, which satisfies 7.0 or higher. In addition, the terminal amine concentration [A] (μeq / g) and the terminal carboxyl concentration [B] (μeq / g) of polyamide 12 (A1-1) satisfy [A]>[B]+5.

[0198] (2) Impact resistant agent (A2)

[0199] Maleic anhydride modified ethylene / 1-butene copolymer (A2-1) (Mitsui Chemicals Co., Ltd., Tafmer (registered trademark) MH5020, anhydride concentration: 100 μeq / g, Shore hardness (D scale): <20)

[0200] (3) Plasticizer (A3)

[0201] N-Butylbenzenesulfonamide (A3-1) (Proviron, Proviplast (registered trademark) 024) (4) Aliphatic polyamide composition (A)

[0202] [Preparation of the aliphatic polyamide composition (A-1)]

[0203] To polyamide 12 (A1-1), premix maleic anhydride-modified ethylene / 1-butene copolymer (A2-1) as an impact resistant agent, N-butylbenzene sulfonamide (A3-1) as a plasticizer, triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate] (manufactured by BASF JAPAN, IRGANOX (registered trademark) 245) as an antioxidant, and tris(2,4-di-tert-butylphenyl) phosphite (BASF) as a phosphorus-based processing stabilizer. The resin (manufactured by JAPAN Corporation, IRGAFOS168) is fed into a twin-screw melt mixer (manufactured by Nippon Steel Corporation, model: TEX (registered trademark) 44) and melt-mixed at a barrel temperature of 180°C to 270°C. The molten resin is extruded into strands and then introduced into a water tank for cooling, cutting, and vacuum drying to obtain granules of an aliphatic polyamide composition (A-1) containing 0.8 parts by mass of antioxidant and 0.2 parts by mass of phosphorus-based processing stabilizer, with a total of 100 parts by mass of polyamide 12 (A1-1) / impact resistant agent (A2-1) / plasticizer (A3-1) of 85.0 / 10.0 / 5.0 (mass%).

[0204] (5) Modified polyolefin (B)

[0205] Modified polyolefin (B-1) maleic anhydride modified polypropylene (Mitsui Chemicals Co., Ltd., Admer (registered trademark) QF551, Shore hardness (D scale): 58, tensile yield stress: 19 MPa, tensile fracture stress: 31 MPa, MFR: 5.2 g / 10 min, in FT-IR measurement, wavenumber was at 710 cm⁻¹. -1 Above and 740cm -1 The wavenumber showing the greatest intensity among the following absorptions is 722.2 cm⁻¹. -1 )

[0206] Modified polyolefin (B-2) maleic anhydride modified polypropylene (Mitsui Chemicals Co., Ltd., Admer (registered trademark) QB516, Shore hardness (D scale): 62, tensile yield stress: 23MPa, tensile fracture stress: 25MPa, MFR: 2.8g / 10min, in FT-IR measurement, wavenumber was at 710cm. -1 Above and 740cm-1 The wavenumber showing the greatest intensity among the following absorptions is 720.3 cm⁻¹. -1 )

[0207] Modified polyolefin (B-3) maleic anhydride modified polypropylene (Mitsui Chemicals Co., Ltd., Admer (registered trademark) QF500, Shore hardness (D scale): 66, tensile yield stress: 24MPa, tensile fracture stress: 38MPa, MFR: 3.5g / 10min, in FT-IR measurement, wavenumber was at 710cm. -1 Above and 740cm -1 The wavenumber showing the greatest intensity among the following absorptions is 718.4 cm⁻¹. -1 )

[0208] Modified polyolefin (B-4) maleic anhydride modified polypropylene (Made by Mitsui Chemicals, Admer (registered trademark) QB510, Shore hardness (D scale): 65, tensile yield stress: 28MPa, tensile fracture stress: 33MPa, MFR: 2.7g / 10min)

[0209] Modified polyolefin (B-5) maleic anhydride modified polypropylene (Made by Mitsui Chemicals, Admer (registered trademark) QB520E, Shore hardness (D scale): 64, tensile yield stress: 24MPa, tensile fracture stress: 35MPa, MFR: 1.8g / 10min)

[0210] 4. Fabrication of laminated bodies

[0211] (Example 1-1)

[0212] Using the aforementioned aliphatic polyamide composition (A-1) and modified polyolefin (B-1), a PAL32 (Milfa Co., Ltd.) double-layer tube forming machine was used. (A-1) was melted at an extrusion temperature of 270°C, and (B-1) was melted at an extrusion temperature of 220°C. The discharged molten resin was then combined using a confluencer to form a laminated tube. Next, the tube was cooled and removed using a sizing mold for dimensional control, resulting in a laminated tube with a layer (a) (outermost layer) formed from (A-1) and a layer (b) (innermost layer) formed from (B-1), with a layer configuration of (a) / (b) = 0.80 / 0.20 mm and an inner diameter of 6.0 mm and an outer diameter of 8.0 mm. The physical property test results of this laminated tube (i.e., the results of high-temperature breaking compressive strength for 5 laminated tubes and the test results of low-temperature impact resistance for 10 laminated tubes) are shown in Table 1.

[0213] (Examples 1-2)

[0214] In Example 1-1, the layer thickness was changed, but otherwise, a laminated tube with a layer configuration of (a) / (b) = 0.65 mm / 0.35 mm, an inner diameter of 6.0 mm, and an outer diameter of 8.0 mm was obtained using the same method as in Example 1-1. The physical property test results of this laminated tube are shown in Table 1.

[0215] (Examples 1-3)

[0216] In Example 1-1, the layer thickness was changed, but otherwise, the same method as in Example 1-1 was used to obtain a laminated tube with a layer configuration of (a) / (b) = 0.50 mm / 0.50 mm, an inner diameter of 6.0 mm, and an outer diameter of 8.0 mm. The physical property test results of this laminated tube are shown in Table 1.

[0217] (Comparative Example 1-1)

[0218] In Example 1-1, the modified polyolefin (B-1) was changed to (B-2). Otherwise, the same method as in Example 1-1 was used to obtain the laminated tube with the layer composition shown in Table 1. The physical property test results of the laminated tube are shown in Table 1.

[0219] (Comparative Examples 1-2)

[0220] In Examples 1-2, the modified polyolefin (B-1) was replaced with (B-2). Otherwise, the laminated tubes with the layer composition shown in Table 1 were obtained using the same method as in Examples 1-2. The physical property test results of the laminated tubes are shown in Table 1.

[0221] (Comparative Examples 1-3)

[0222] In Examples 1-3, the modified polyolefin (B-1) was replaced with (B-2). Otherwise, the same method as in Examples 1-3 was used to obtain the laminated tubes with the layer composition shown in Table 1. The physical property test results of the laminated tubes are shown in Table 1.

[0223] (Comparative Example 2-1)

[0224] In Example 1-1, the modified polyolefin (B-1) was changed to (B-3). Otherwise, the same method as in Example 1-1 was used to obtain the laminated tube with the layer composition shown in Table 1. The physical property test results of the laminated tube are shown in Table 1.

[0225] (Comparative Example 2-2)

[0226] In Examples 1-2, the modified polyolefin (B-1) was changed to (B-3). Otherwise, the same method as in Examples 1-2 was used to obtain the laminated tubes with the layer composition shown in Table 1. The physical property test results of the laminated tubes are shown in Table 1.

[0227] (Comparative Examples 2-3)

[0228] In Examples 1-3, the modified polyolefin (B-1) was replaced with (B-3). Otherwise, the laminated tubes with the layer composition shown in Table 1 were obtained using the same method as in Examples 1-3. The physical property test results of the laminated tubes are shown in Table 1.

[0229] (Comparative Example 3-1)

[0230] In Example 1-1, the modified polyolefin (B-1) was changed to (B-4). Otherwise, the same method as in Example 1-1 was used to obtain the laminated tube with the layer composition shown in Table 1. The physical property test results of the laminated tube are shown in Table 1.

[0231] (Comparative Example 3-2)

[0232] In Examples 1-2, the modified polyolefin (B-1) was changed to (B-4). Otherwise, the same method as in Examples 1-2 was used to obtain the laminated tubes with the layer composition shown in Table 1. The physical property test results of the laminated tubes are shown in Table 1.

[0233] (Comparative Example 3-3)

[0234] In Examples 1-3, the modified polyolefin (B-1) was changed to (B-4). Otherwise, the laminated tubes with the layer composition shown in Table 1 were obtained using the same method as in Examples 1-3. The physical property test results of the laminated tubes are shown in Table 1.

[0235] (Comparative Example 4-1)

[0236] In Example 1-1, the modified polyolefin (B-1) was changed to (B-5). Otherwise, the same method as in Example 1-1 was used to obtain the laminated tube with the layer composition shown in Table 1. The physical property test results of the laminated tube are shown in Table 1.

[0237] (Comparative Example 4-2)

[0238] In Examples 1-2, the modified polyolefin (B-1) was changed to (B-5). Otherwise, the laminated tubes with the layer composition shown in Table 1 were obtained using the same method as in Examples 1-2. The physical property test results of the laminated tubes are shown in Table 1.

[0239] (Comparative Example 4-3)

[0240] In Examples 1-3, the modified polyolefin (B-1) was changed to (B-5). Otherwise, the laminated tubes with the layer composition shown in Table 1 were obtained using the same method as in Examples 1-3. The physical property test results of the laminated tubes are shown in Table 1.

[0241] [Table 1]

[0242]

[0243] As shown in Table 1, the laminated tubes of the embodiments exhibit excellent low-temperature impact resistance and high-temperature compressive strength even when the modified polyolefin layer is thickened.

Claims

1. A laminated hollow shaped body, comprising a laminated body, said laminated body being a laminated body with two or more layers including (a) layer and (b) layer, The stacked hollow shaped body is arranged in the order of layer (a) and layer (b) from the outside, with layer (b) being the innermost layer. Layer (a) comprises an aliphatic polyamide composition (A). Layer (b) comprises a modified polyolefin (B). The modified polyolefin (B) is maleic anhydride-modified polypropylene. The modified polyolefin (B) has a Shore hardness (D scale) of 30 or higher and 61 or lower, as measured according to ASTM D2240. The aliphatic polyamide composition (A) comprises polyamide (A1), an impact-resistant agent, and a plasticizer, and the aliphatic polyamide composition (A) does not contain any polyamide other than polyamide (A1). The polyamide (A1) is a homopolymer selected from the group consisting of polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 1010, polyamide 1012, and polyamide 1212, or a copolymer obtained using a variety of raw material monomers that form them. The impact-resistant agent is selected from elastomeric polymers comprising structural units derived from unsaturated compounds having carboxyl and / or anhydride groups, and having a Shore hardness (D scale) of less than 20 as measured according to ASTM D2240. The content of the impact-resistant agent in the aliphatic polyamide composition (A) is more than 5% by mass and less than 30% by mass relative to 100% by mass of the aliphatic polyamide composition (A). The content of plasticizer in the aliphatic polyamide composition (A) is more than 1% by mass and less than 10% by mass relative to 100% by mass of the aliphatic polyamide composition (A). In the laminate, the thickness of layer (a) is 65% to 80% of the total wall thickness of the laminate, the thickness of layer (b) is 20% to 35% of the total wall thickness of the laminate, and the total wall thickness of the laminate is 0.5 mm to 25 mm. For a hollow laminated body constructed from the outside in the order of layer (a) and layer (b), with a total thickness of 1.0 mm, an inner diameter of 6.0 mm, and an outer diameter of 8.0 mm: (1) For the 10 stacked hollow molded bodies, when subjected to an impact test at -40°C using the method described in SAE J 2260 7.5, the fracture rate was 0 / 10; and (2) For the five stacked hollow molded bodies, the average value of the breaking compressive strength obtained by changing the test temperature to 125°C and carrying out the breaking compressive strength test using the method described in SAE J 2260 7.2 is above 1.4 MPa.

2. The laminated hollow shaped body according to claim 1, wherein, The content of the impact resistant agent in the aliphatic polyamide composition (A) is more than 5% by mass and less than 25% by mass relative to 100% by mass of the aliphatic polyamide composition (A).

3. The laminated hollow molded body according to claim 1 or 2, wherein, The content of the impact resistant agent in the aliphatic polyamide composition (A) is 5% by mass or more and 10.0% by mass or less relative to 100% by mass of the aliphatic polyamide composition (A), and the content of the plasticizer in the aliphatic polyamide composition (A) is 5.0% by mass or more and 10% by mass or less relative to 100% by mass of the aliphatic polyamide composition (A).

4. The laminated hollow molded body according to claim 1 or 2, wherein, The polyamide (A1) is a homopolymer selected from the group consisting of polyamide 11, polyamide 12, polyamide 612, polyamide 1010, polyamide 1012 and polyamide 1212, or a copolymer obtained by using a variety of raw material monomers that form them.

5. The laminated hollow molded body according to claim 1 or 2, wherein, The polyamide (A1) is polyamide 11 or polyamide 12.

6. The laminated hollow molded body according to claim 1 or 2, wherein, The polyamide (A1) is polyamide 12.

7. The laminated hollow molded body according to claim 1 or 2, wherein, According to JIS K-6920, the relative viscosity of polyamide (Al) measured under the conditions of 96% sulfuric acid, 1% polymer concentration, and 25°C is greater than 2.0 and less than 4.

5.

8. The laminated hollow molded body according to claim 1 or 2, wherein, When the concentration of terminal amino groups per 1g of polyamide (A1) is denoted as [A] (μeq / g) and the concentration of terminal carboxyl groups is denoted as [B] (μeq / g), [A] > [B] + 5.

9. The laminated hollow molded body according to claim 1 or 2, wherein, When the concentration of terminal amino groups per 1g of polyamide (A1) is denoted as [A] (μeq / g) and the concentration of terminal carboxyl groups is denoted as [B] (μeq / g), [A] > [B] + 15.

10. The laminated hollow molded body according to claim 1 or 2, wherein, The aliphatic polyamide composition (A) also contains a heat-resistant agent.

11. The laminated hollow shaped body according to claim 10, wherein, The content of the heat-resistant agent in the aliphatic polyamide composition (A) is more than 0.5% by mass and less than 2% by mass relative to 100% by mass of the aliphatic polyamide composition (A).

12. The laminated hollow molded body according to claim 1 or 2, wherein, Layer (a) and layer (b) are adjacent to each other.

13. The laminated hollow molded body according to claim 1 or 2, wherein, The modified polyolefin (B) has a tensile yield stress of less than 23 MPa as measured by ASTM D638 and a tensile fracture stress of more than 25 MPa as measured by ASTM D638.

14. The laminated hollow molded body according to claim 1 or 2, wherein, The modified polyolefin (B) has an MFR (230°C, 2160g) of ≥3.5g / 10min as measured according to ASTM D1238.

15. The laminated hollow molded body according to claim 1 or 2, wherein, The modified polyolefin (B) was measured at a wavenumber of 710 cm⁻¹ in FT-IR. -1 Above and 740cm -1 The wavenumber showing the greatest intensity among the following absorptions is 721 cm⁻¹. -1 above.

16. The laminated hollow molded body according to claim 1 or 2, wherein, The modified polyolefin (B) is manufactured by melting the unmodified polyolefin and graft copolymerizing it by adding the unsaturated compound with functional groups.

17. The laminated hollow molded body according to claim 1 or 2, which consists only of layer (a) and layer (b).

18. The laminated hollow molded article according to claim 1 or 2, which is manufactured by co-extrusion molding.

19. The laminated hollow shaped body according to claim 1 or 2, wherein it is a tube.

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