THERMOPLASTIC RESIN COMPOSITION FOR REFRIGERANT TRANSPORT HOSE AND REFRIGERANT TRANSPORT HOSE

Abstract

The present invention provides a refrigerant transport hose exhibiting good flexibility, refrigerant permeation resistance, and deterioration resistance. A thermoplastic resin composition for a refrigerant transport hose has an island structure in which an elastomer is present as a domain within a matrix containing a thermoplastic resin, wherein the thermoplastic resin composition comprises: 100 parts by mass of the elastomer; 30 to 100 parts by mass of the thermoplastic resin; and 0.5 to 10 parts by mass of a hydrotalcite and / or a magnesium-aluminum solid solution; wherein the thermoplastic resin contains 50 to 100 parts by mass of a polyamide relative to 100 parts by mass of the thermoplastic resin, and the elastomer comprises an elastomer with a polyisobutylene main chain.

Description

Technical field

[0001] The present invention relates to a thermoplastic resin composition for a refrigerant transport hose and a refrigerant transport hose. More precisely, the present invention relates to a thermoplastic resin composition used for manufacturing a refrigerant transport hose for use in an air conditioning system of an automobile or the like, and to a refrigerant transport hose including a layer composed of the thermoplastic resin composition. State of the art

[0002] Given the increasing demand for weight reduction in automobiles, efforts have been made to achieve this by manufacturing automotive hoses using resin with high barrier properties instead of the rubber previously used, thus reducing the hose's thickness. Specifically, rubber is a primary material for refrigerant transport hoses in current automotive air conditioning systems, and if this primary material can be replaced with resin, which has high barrier properties, weight reduction can be achieved.

[0003] JP 2011-58638 A (Patent Literature 1) describes a refrigerant transport hose having an innermost layer obtained using a polyamide resin composition to which an acid acceptor such as hydrotalcite is added. List of literature on patent literature

[0004] Patent specification 1: JP 2011-58638 A Brief description of the invention: Technical problem

[0005] The refrigerant transport hose described in patent literature 1 can suppress the hydrolysis of polyamide by adding the acid acceptor and thus exhibits high resistance to deterioration, but does not necessarily have sufficient flexibility and refrigerant permeation resistance.

[0006] The present invention provides a thermoplastic resin composition used for manufacturing a refrigerant transport hose with good flexibility, refrigerant permeation resistance and deterioration resistance, as well as a refrigerant transport hose. Solution to the problem

[0007] The present invention (I) may include a thermoplastic resin composition for a refrigerant transport hose having an island structure in which an elastomer is present as a domain in a matrix comprising a thermoplastic resin, wherein the thermoplastic resin composition comprises: 100 parts by mass of the elastomer; 30 to 100 parts by mass of the thermoplastic resin; and 0.5 to 10 parts by mass of a hydrotalcite and / or a magnesium-aluminum solid solution; wherein the thermoplastic resin contains 50 to 100 parts by mass of a polyamide in relation to 100 parts by mass of the thermoplastic resin, and the elastomer comprises an elastomer with a polyisobutylene main chain. The present invention (II) is a refrigerant transport hose including a layer composed of the thermoplastic resin composition for a refrigerant transport hose of the present invention (I).

[0008] The present invention includes the following embodiments. [1] A thermoplastic resin composition for a refrigerant transport hose having an island structure in which an elastomer is present as a domain in a matrix comprising a thermoplastic resin, wherein the thermoplastic resin composition contains: 100 parts by mass of the elastomer; 30 to 100 parts by mass of the thermoplastic resin; and 0.5 to 10 parts by mass of hydrotalcite and / or a magnesium-aluminum solid solution; wherein the thermoplastic resin contains 50 to 100 parts by mass of a polyamide, in relation to 100 parts by mass of the thermoplastic resin, and the elastomer contains an elastomer with a polyisobutylene main chain. [2] The thermoplastic resin composition for a refrigerant transport hose according to [1], comprising at least one selected from the group consisting of zinc oxide, an anti-aging agent based on phenylenediamine or quinoline and a processing aid. [3] The thermoplastic resin composition for a refrigerant transport hose according to [1], wherein the polyamide is at least one selected from the group consisting of polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 610, a polyamide 6 / 66 copolymer, a polyamide 6 / 12 copolymer, polyamide 46, polyamide 6T, polyamide 9T and polyamide MXD6. [4] The thermoplastic resin composition for a refrigerant transport hose according to [1], wherein the elastomer with a polyisobutylene main chain is at least one selected from the group consisting of a butyl rubber, a halogenated butyl rubber, an isobutylene monoalkylstyrene copolymer rubber, a halogenated isobutylene monoalkylstyrene copolymer rubber and a styrene isobutylene styrene block copolymer. [5] The thermoplastic resin composition for a refrigerant transport hose according to [1], wherein the hydrotalcite and / or the magnesium-aluminium solid solution has a specific surface area of ​​100 m² 2 / g or more. [6] The thermoplastic resin composition for a refrigerant transport hose according to [1], further comprising a first fatty acid metal salt and a second fatty acid metal salt having a lower melting point than that of the first fatty acid metal salt. [7] The thermoplastic resin composition for a refrigerant transport hose according to [6], wherein the first fatty acid metal salt has a melting point of 150 °C or more. [8] The thermoplastic resin composition for a refrigerant transport hose according to [7], wherein the second fatty acid metal salt has a melting point of less than 150 °C. [9] The thermoplastic resin composition for a refrigerant transport hose according to [6], which contains 0.5 to 5.0 parts by mass of the first fatty acid metal salt in relation to 100 parts by mass of the elastomer.

[10] The thermoplastic resin composition for a refrigerant transport hose according to [6], which contains 0.5 to 5.0 parts by mass of the second fatty acid metal salt in relation to 100 parts by mass of the elastomer.

[11] The thermoplastic resin composition for a refrigerant transport hose according to [6], wherein the ratio Wd1 / Wd2 of a mass Wd1 of the first fatty acid metal salt to a mass Wd2 of the second fatty acid metal salt is from 0.5 to 5.0.

[12] The thermoplastic resin composition for a refrigerant transport hose according to [6], wherein the first fatty acid metal salt is at least one selected from the group consisting of calcium stearate, zinc 12-hydroxystearate and lithium 12-hydroxystearate.

[13] The thermoplastic resin composition for a refrigerant transport hose according to [6], wherein the second fatty acid metal salt is at least one selected from the group consisting of zinc stearate and magnesium stearate.

[14] A refrigerant transport hose containing: a layer composed of the thermoplastic resin composition according to [1].

[15] The refrigerant transport hose according to

[14] , containing: an inner layer; a reinforcing layer; and an outer layer; wherein the inner layer is composed of the thermoplastic resin composition according to [1].

[16] The refrigerant transport hose according to

[14] , wherein the refrigerant transport hose does not contain a layer made of vulcanized rubber. Advantageous effects of the invention

[0009] The thermoplastic resin composition for a refrigerant transport hose of the present invention is characterized by excellent flexibility, refrigerant permeation resistance and deterioration resistance.

[0010] The refrigerant transport hose of the present invention is characterized by excellent flexibility, refrigerant permeation resistance and deterioration resistance. Brief description of the drawings Fig. Figure 1 is a cross-sectional view of a refrigerant transport hose. Fig. Figure 2 is a diagram illustrating an evaluation procedure for the flexibility of a hose. Description of embodiments

[0011] The present invention (I) relates to a thermoplastic resin composition for a refrigerant transport hose. The thermoplastic resin composition of the present invention is used to manufacture a refrigerant transport hose. The thermoplastic resin composition of the present invention is preferably used as a material forming an inner layer of the refrigerant transport hose.

[0012] The thermoplastic resin composition of the present invention has an island structure in which an elastomer is present as a domain in a matrix containing a thermoplastic resin. The island structure allows the thermoplastic resin composition to exhibit flexibility. To create the island structure, the rubber is crosslinked (dynamically crosslinked) during kneading.

[0013] The thermoplastic resin composition of the present invention contains 100 parts by mass of the elastomer, 30 to 100 parts by mass of the thermoplastic resin and 0.5 to 10 parts by mass of a hydrotalcite and / or a magnesium-aluminium mixed crystal.

[0014] The term elastomer refers to a polymeric material that exhibits rubber-like elastic properties at normal temperature.

[0015] The elastomer contains an elastomer with a polyisobutylene backbone. The polyisobutylene backbone refers to a chemical structure formed by the polymerization of multiple isobutylenes, that is, a chemical structure formed by -[-CH2-C(CH3)2-] n-is represented (provided n is an integer of 2 or greater). The elastomer with a polyisobutylene main chain is not limited as long as it has a polyisobutylene main chain; however, it is preferably at least one selected from the group consisting of a butyl rubber (IIR), a halogenated butyl rubber, an isobutylene monoalkylstyrene copolymer rubber, a halogenated isobutylene monoalkylstyrene copolymer rubber, and a styrene isobutylene styrene block copolymer (SIBS). Examples of the isobutylene monoalkylstyrene copolymer rubber may include an isobutylene p-methylstyrene copolymer rubber (IPMS). Examples of the halogenated isobutylene monoalkylstyrene copolymer rubber may include a halogenated isobutylene p-methylstyrene copolymer rubber. A brominated isobutylene p-methylstyrene copolymer rubber (BIMS) is more preferred as the elastomer.

[0016] The elastomer may contain a different elastomer than the elastomer with a polyisobutylene main chain, provided that the effect of the present invention is not impaired.

[0017] The thermoplastic resin contains 50 to 100 parts by mass of a polyamide, preferably 70 to 100 parts by mass of a polyamide, and more preferably 80 to 100 parts by mass of a polyamide, per 100 parts by mass of the thermoplastic resin. If the thermoplastic resin contains polyamide, gas barrier properties can be ensured.

[0018] The polyamide is preferably, but not limited to, at least one selected from the group consisting of polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 610, a polyamide 6 / 66 copolymer, a polyamide 6 / 12 copolymer, polyamide 46, polyamide 6T, polyamide 9T and polyamide MXD6.

[0019] The thermoplastic resin may contain a thermoplastic resin other than polyamide. Examples of thermoplastic resins other than polyamide include, but are not limited to, polyester, polyvinyl alcohol, and polyketone.

[0020] The thermoplastic resin may contain a thermoplastic resin other than polyamide, but preferably contains only polyamide.

[0021] The thermoplastic resin content in the thermoplastic resin composition ranges from 30 to 100 parts by mass, preferably from 31 to 95 parts by mass, and more preferably from 31 to 80 parts by mass, relative to 100 parts by mass of the elastomer. If the thermoplastic resin content is within the range described above, both flexibility and resistance to refrigerant permeation can be achieved.

[0022] The thermoplastic resin composition of the present invention contains a hydrotalcite and / or a magnesium-aluminum solid solution. If the thermoplastic resin composition containing the polyamide is used for the inner layer of the refrigerant transport hose, an acid, generated, for example, by the degradation of a lubricant such as an ester-based oil in a refrigerant, promotes the hydrolysis of the polyamide in the inner layer and reduces the degradation resistance of the inner layer. However, if the thermoplastic resin composition contains the hydrotalcite and / or the magnesium-aluminum solid solution, the hydrotalcite and / or the magnesium-aluminum solid solution bind the acid, and the reduction in the degradation resistance of the inner layer can be suppressed.

[0023] Hydrotalcite is a non-stoichiometric compound described by the general formula [M 2+ 1-x M3+ x (OH2) x+ [A n- x / n ·mH2O] x- is shown. M 2+ is a divalent metal like Mg 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ or Zn 2+ . M 3+ is a trivalent metal like Al 3+ , Fe 3+ , Cr 3+ , Co 3+ or In 3+ A n- is an n-valent anion such as OH - , F - , Cl - , Br - , NO3 - , CO3 2- , SO4 2- , Fe(CN)6 3- , CH 3COO - , an oxalation or a salicylation. x lies in the range where x is greater than 0 and 0.33 or less.

[0024] A representative mineral of hydrotalcite is a mineral with a chemical composition of Mg 1-x Al x (OH)2(CO3) x / 2 ·nH2O. The chemical composition of hydrotalcite is (Mg6Al2(OH)2(CO3) 16·4H2O).

[0025] Hydrotalcite includes both natural and synthetic products, and any hydrotalcite can be used in the present invention. Hydrotalcite is commercially available and can be obtained, for example, from SETOLAS Holdings, Inc. under the brand names DHT-4C, DHT-4A, or similar.

[0026] The magnesium-aluminum solid solution is a magnesium-aluminum oxide and has a dehydrating effect. The magnesium-aluminum solid solution preferably has an MgO content of 55 to 65% and an Al₂O₃ content of 30 to 40%. If the chemical composition of the magnesium-aluminum solid solution is modified by the addition of Mg a Al b O c,As shown, a is preferably equal to 0.7, b is equal to 0.3 and c is equal to 1.15. The magnesium-aluminum solid solution is commercially available and can be obtained, for example, from SETOLAS Holdings, Inc. under the brand names KW-2000, KW-2100, KW-2200 or similar.

[0027] The hydrotalcite and / or the magnesium-aluminum solid solution preferably have a specific surface area of ​​100 m². 2 / g or more and preferably a specific surface area of ​​100 to 200 m² 2 / g. If the specific surface area of ​​the hydrotalcite and / or the magnesium-aluminum solid solution is within the range of values ​​described above, the deterioration resistance of the thermoplastic resin composition is improved.

[0028] The hydrotalcite and / or the magnesium-aluminium solid solution may be contained in at least one of the matrix or the domain, but is preferably contained in the matrix.

[0029] The content of hydrotalcite and / or magnesium-aluminum solid solution in the thermoplastic resin composition is 0.5 to 10 parts by mass, preferably 0.5 to 8 parts by mass, and more preferably 0.5 to 6 parts by mass, based on 100 parts by mass of the elastomer. If the content of hydrotalcite and / or magnesium-aluminum solid solution is too low, the deterioration resistance of the thermoplastic resin composition will be insufficient. If the content of hydrotalcite and / or magnesium-aluminum solid solution is too high, the fatigue strength and durability will deteriorate.

[0030] The thermoplastic resin composition may contain either hydrotalcite or magnesium-aluminum solid solution, or it may contain both. If the thermoplastic resin composition contains both hydrotalcite and magnesium-aluminum solid solution, the combined content of hydrotalcite and magnesium-aluminum solid solution is 0.5 to 10 parts by mass per 100 parts by mass of the elastomer.

[0031] The thermoplastic resin composition of the present invention preferably comprises at least one of the following, selected from the group consisting of zinc oxide, a phenylenediamine-based or quinoline-based antioxidant, and a processing aid. The addition of at least one of the following, selected from the group consisting of zinc oxide, a phenylenediamine-based or quinoline-based antioxidant, and a processing aid, results in improved extrusion processability of the thermoplastic resin composition. The three additives—zinc oxide, the phenylenediamine-based or quinoline-based antioxidant, and the processing aid—may comprise only one, two, or all three.

[0032] Zinc oxide is also known as ZnO.

[0033] Zinc oxide acts as a viscosity stabilizer, and when the thermoplastic resin composition contains zinc oxide, an increase in viscosity during extrusion molding of the thermoplastic resin composition is suppressed, and the formation of residues can be effectively reduced, thus improving processability.

[0034] Zinc oxide is commercially available and can be obtained, for example, from Seido Chemical Industry Co., Ltd. under the brand name Zinc Oxide III or similar.

[0035] The zinc oxide content is not limited as long as a desired effect is achieved, but is preferably from 0.1 to 30 parts by mass, more preferably from 0.5 to 20 parts by mass and even more preferably from 0.5 to 6 parts by mass, in relation to the total amount of 100 parts by mass of the thermoplastic resin and the elastomer.

[0036] The zinc oxide can be contained in at least one of the matrix and the domain; however, preferably 50% or more by weight of the zinc oxide is contained in the matrix. The addition of 50% or more by weight of zinc oxide to the matrix suppresses an increase in viscosity during extrusion of the thermoplastic resin composition and can effectively reduce residue generation, thus improving processability.

[0037] The phenylenediamine-based or quinoline-based anti-aging agent acts as an anti-aging agent and / or a crosslinking agent, improves the heat aging resistance of the thermoplastic resin composition and contributes to improved extrusion processability.

[0038] The phenylenediamine-based anti-aging agent refers to an anti-aging agent having an aromatic ring in its molecular structure which has two secondary amines as substituents, and is preferably at least one selected from the group consisting of N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine, N-phenyl-N'-(1-methylheptyl)-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N,N'-Di-2-naphthyl-p-phenylenediamine and N,N'-Diphenyl-p-phenylenediamine, and is more preferably N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine.

[0039] The phenylenediamine-based antioxidant is commercially available and can be obtained, for example, from Solutia Inc. or similar companies under the brand name 6PPD.

[0040] The quinoline-based antioxidant refers to an antioxidant with a quinoline scaffold in its molecular structure and is preferably a 2,2,4-trimethyl-1,2-dihydroquinoline polymer. The quinoline-based antioxidant is commercially available and can be obtained, for example, from Ouchi Shinko Chemical Industrial Co., Ltd. under the brand name "Nocrac" (brand name) 224 or similar.The content of the phenylenediamine-based or quinoline-based antioxidant in the thermoplastic resin composition (if both the phenylenediamine-based and the quinoline-based antioxidant are included, the total content of the phenylenediamine-based and quinoline-based antioxidants) is not limited as long as the desired effect is achieved, but is preferably 0.1 to 10 parts by mass and more preferably 0.1 to 5.0 parts by mass, based on 100 parts by mass of the total amount of the thermoplastic resin and the elastomer. The phenylenediamine-based or quinoline-based antioxidant may be contained in at least one of the matrix and the domain, but is preferably contained in the domain.

[0041] The processing aid contributes to improved extrusion processability of the thermoplastic resin composition. The processing aid is not particularly limited, but preferably comprises at least one selected from a fatty acid, a fatty acid metal salt, a fatty acid ester, and a fatty acid amide. Examples of fatty acids include stearic acid, palmitic acid, lauric acid, oleic acid, and linoleic acid, with stearic acid being preferred. Examples of fatty acid metal salts include calcium stearate, aluminum stearate, zinc 12-hydroxystearate, lithium 12-hydroxystearate, potassium stearate, zinc stearate, magnesium stearate, and sodium stearate. Examples of fatty acid esters include glycerol monostearate, sorbitan stearate, stearyl stearate, and ethylene glycol distearate.

[0042] Examples of fatty acid amides include stearic acid monoamides, oleic acid monoamides, and ethylene-bis-stearic acid amides.

[0043] The content of the processing aid in the thermoplastic resin composition is not limited as long as a desired effect is achieved, but is preferably from 0.2 to 10 parts by mass, more preferably from 1 to 8 parts by mass and even more preferably from 1 to 5 parts by mass, in relation to the total quantity of 100 parts by mass of the thermoplastic resin and the elastomer.

[0044] The processing aid can be contained in at least one of the components matrix and domain, but is preferably contained in the matrix.

[0045] In the present invention, the thermoplastic resin composition preferably contains both a first fatty acid metal salt and a second fatty acid metal salt with a melting point that is lower than that of the first fatty acid metal salt.

[0046] By adding the first fatty acid metal salt with a high melting point as a processing aid, the first fatty acid metal salt exhibits favorable mobility at the temperature at which an alloy of the thermoplastic resin and the elastomer is kneaded and extruded, and thus performs well as a processing aid. However, at the operating temperature (e.g., 150°C or less) of the refrigerant transport hose, the first fatty acid metal salt exhibits insufficient molecular mobility and has limited function as an acid acceptor. Flexibility is only improved by increasing the amount of the fatty acid metal salt to enhance acid absorption, but there is concern that the barrier properties will be inadequate.

[0047] The second metal fatty acid salt with a low melting point exhibits high molecular mobility at the operating temperature (for example, 150°C or less) of the refrigerant transport hose and can show a high effectiveness as an acid acceptor.

[0048] In the present invention, the hydrolysis resistance is improved without impairing the flexibility and barrier properties at the operating temperature of the refrigerant transport hose by adding a second fatty acid metal salt, which has a low melting point, in addition to the first fatty acid metal salt, which has a high melting point.

[0049] From the perspective of processability and the resistance to deterioration of the thermoplastic resin composition, the melting point of the first fatty acid metal salt is preferably 150 °C or higher. From the same perspective, the melting point of the second fatty acid metal salt is preferably less than 150 °C. The melting point of the first fatty acid metal salt may be 150 °C or higher, 160 °C or higher, 170 °C or higher, 180 °C or higher, 190 °C or higher, 200 °C or higher, or 210 °C or higher. Conversely, the melting point of the second fatty acid metal salt may be less than 150 °C, 145 °C or lower, 140 °C or lower, 135 °C or lower, 130 °C or lower, or 125 °C or lower.

[0050] From the perspective of flexibility, barrier properties, and processability, the first fatty acid metal salt in the thermoplastic resin composition preferably comprises 0.5 to 5.0 parts by mass per 100 parts by mass of the elastomer. The first fatty acid metal salt in the thermoplastic resin composition preferably comprises 1.0 to 3.0 parts by mass, and even more preferably 2.0 to 2.5 parts by mass, per 100 parts by mass of the elastomer.

[0051] From the perspective of deterioration resistance, the second fatty acid metal salt in the thermoplastic resin composition preferably comprises 0.5 to 5.0 parts by mass, based on 100 parts by mass of the elastomer. More preferably, the second fatty acid metal salt in the thermoplastic resin composition comprises 0.5 to 2.0 parts by mass, and even more preferably, 0.5 to 1.0 parts by mass, based on 100 parts by mass of the elastomer.

[0052] From the perspective of the balance between flexibility, barrier properties, processability and deterioration resistance, the ratio Wd1 / Wd2 of a mass Wd1 of the first fatty acid metal salt to a mass Wd2 of the second fatty acid metal salt is preferably 0.5 to 5.0.

[0053] The first fatty acid metal salt is preferably at least one selected from the group consisting of calcium stearate (melting point: 155 ± 5 °C), zinc 12-hydroxystearate (melting point: 150 ± 10 °C), and lithium 12-hydroxystearate (melting point: 212 ± 10 °C). Furthermore, the second fatty acid metal salt is preferably at least one selected from the group consisting of zinc stearate (melting point: 125 ± 5 °C) and magnesium stearate (melting point: 145 ± 5 °C).

[0054] The thermoplastic resin composition may contain other additives besides those described above, as long as the effects of the present invention are not impaired.

[0055] The thermoplastic resin composition of the present invention preferably exhibits, upon tensile testing after being immersed at 150 °C for 96 hours in a refrigerant-containing composition comprising a refrigerant, a refrigerant oil, and water (EB after treatment), an elongation at break of 30 to 100% of the elongation at break of the thermoplastic resin composition before treatment (EB before treatment). The ratio EB after treatment / EB before treatment × 100 [%] is hereinafter referred to as the "EB residual ratio after treatment". The EB residual ratio after treatment is more preferably 35 to 100% and even more preferably 50 to 100%.If a refrigerant transport hose is manufactured using the thermoplastic resin composition which, after treatment, has an EB residual ratio within the range of numbers described above, a refrigerant transport hose with excellent deterioration resistance can be obtained.

[0056] The elongation at break (EB) is measured as follows. The thermoplastic resin composition is formed into a sheet with an average thickness of 1.0 mm using a single-screw extrusion press with a 40 mm diameter (available from Pla Giken Co., Ltd.) equipped with a 200 mm wide T-shaped die, with the cylinder and die temperatures set to 10 °C plus the melting point of the polymer component with the highest melting point in the thermoplastic resin composition, a cooling roller temperature of 50 °C, and a feed rate of 3 m / min. The formed sheet is then punched into a JIS No. 6 dumbbell mold to produce a test piece of the thermoplastic resin composition.

[0057] The prepared test piece made of thermoplastic resin composition is subjected to a tensile test according to JIS K7161 at a temperature of 25 °C, a relative humidity of 50% and a speed of 500 mm / min, a tensile strain is determined from the resulting stress-strain curve and the strain is defined as elongation at break (EB).

[0058] The measurement procedure for EB after treatment is as follows. A dumbbell-shaped test piece of the thermoplastic resin composition according to JIS No. 6, prepared for measuring elongation at break, is hermetically sealed in a constant-volume container together with water, a refrigerant oil, and a refrigerant, and subjected to heat treatment at a predetermined temperature for a predetermined time. The enclosed quantities of water, refrigerant oil, and refrigerant have a mass ratio of 1:80:160.

[0059] After treatment, the test piece made of thermoplastic resin composition is removed from the container of constant volume and the elongation at break of the test piece is measured and the measured value is defined as EB after treatment.

[0060] The residual EB ratio after treatment is measured as follows. The elongation at break of an untreated test piece of the thermoplastic resin composition is measured, and the measured value is defined as EB before treatment.

[0061] The residual EB ratio after treatment is calculated using the following formula. EB residual ratio (%) after treatment = EB after the Treatment / EB before treatment×100

[0062] For the thermoplastic resin composition of the present invention, a 10% modulus at a temperature of 25 °C is preferably 10 MPa or less, more preferably 2 to 10 MPa, and even more preferably 5 to 9 MPa. If a refrigerant transport hose is manufactured using the thermoplastic resin composition having a 10% modulus at a temperature of 25 °C within the range described above, a refrigerant transport hose with excellent flexibility can be obtained.

[0063] The 10% modulus is measured according to JIS K7161.

[0064] In the thermoplastic resin composition of the present invention, the oxygen permeability coefficient at a temperature of 21 °C and a relative humidity of 50% is preferably 0.03 cm. 3 mm / (m 2 ·day·mmHg) or less, preferably from 0.0001 to 0.0300 cm 3 mm / (m 2·day·mmHg) and even more preferably from 0.0050 to 0.0200 cm 3 mm / (m 2 ·day·mmHg). If a refrigerant transport hose is manufactured using a thermoplastic resin composition that has an oxygen permeability coefficient at a temperature of 21 °C and a relative humidity of 50% within the range described above, a refrigerant transport hose with excellent refrigerant permeation resistance can be obtained. The oxygen permeability coefficient is the amount of oxygen that passes through an area of ​​1 m² within one day. 2 and penetrates a thickness of 1 mm per 1 mmHg pressure under defined temperature and humidity conditions.

[0065] The present invention (II) relates to a refrigerant transport hose. The refrigerant transport hose is defined as a hose for transporting a refrigerant for an air conditioning system or the like. The refrigerant transport hose of the present invention (II) is used in a particularly suitable manner as a hose for transporting a refrigerant for an air conditioning system of a motor vehicle. Examples of refrigerants for an air conditioning system include hydrofluorocarbons (HFCs), hydrofluoroolefins (HFOs), hydrocarbons, carbon dioxide, ammonia, and water. Examples of HFCs include R410A, R32, R404A, R407C, R507A, and R134a. Examples of HFOs include R1234yf, R1234ze, R1233zd, R1123, R1224yd, and R1336mzz. Examples of hydrocarbons include methane, ethane, propane, propylene, butane, isobutane, hexafluoropropane, and pentane.

[0066] Fig.Figure 1 is a cross-sectional view of a refrigerant transport hose of the present invention. However, one embodiment of the present invention is not limited to the illustration in Figure 1. Fig. 1 limited.

[0067] The refrigerant transport hose 1 encloses an inner layer 2, a reinforcement layer 3, and an outer layer 4. The reinforcement layer 3 is located outside the inner layer 2, and the outer layer 4 is located outside the reinforcement layer 3.

[0068] The refrigerant transport hose of the present invention (II) can enclose a layer composed of the thermoplastic resin composition of the present invention (I). Fig. 1 is the layer composed of the thermoplastic resin composition of the present invention (I), the inner layer 2.

[0069] The inner layer 2 is preferably composed of the thermoplastic resin composition of the present invention (I). When the inner layer 2 is composed of the thermoplastic resin composition of the present invention (I), the refrigerant permeation resistance of the refrigerant transport hose is improved.

[0070] The thickness of the inner layer is not limited, but can be, for example, 0.2 to 3 mm.

[0071] The reinforcing layer is a layer provided between the inner and outer layers, and the reinforcing material that can form the reinforcing layer is not particularly restricted and can be at least one organic material and one inorganic material. For example, the organic material can be a polymer (fiber material) such as polyester, polyamide, aramid, vinylon, rayon, polyparaphenylbenzobisoxazole (PBO), polyketone, and polyarylate. Furthermore, examples of the inorganic material include metals, such as hardened steel wires, which can be, for example, brass-plated wire and galvanized wire. The reinforcing material can be surface-treated. With a view to achieving excellent fatigue strength performance and excellent cost-effectiveness, the reinforcing layer is preferably polyester fiber.The inclusion of a reinforcing layer ensures the hose's strength and maintains excellent pressure resistance. The thickness of the reinforcing layer is not limited, but can range from 0.3 to 3 mm, for example.

[0072] Preferred examples for the shape of the reinforcing layer (reinforcing material) include a shape woven into a spiral structure and / or a braided structure. Furthermore, the reinforcing layer can be either a single reinforcing layer or multiple reinforcing layers.

[0073] Examples of the material forming the outer layer 4 include, but are not limited to, a thermoplastic elastomer and a vulcanized rubber, with a thermoplastic elastomer being preferred. Preferred examples of the thermoplastic elastomer include, but are not limited to, a polyolefin elastomer, a polyester elastomer, a polyamide elastomer, and a polyurethane elastomer. More preferred examples include a thermoplastic elastomer using polypropylene and a thermoplastic elastomer using polyamide 12.

[0074] The thickness of the outer layer is not limited, but can be, for example, 0.2 to 3 mm.

[0075] The refrigerant transport hose preferably does not include a layer composed of vulcanized rubber. If the refrigerant transport hose does not include a layer composed of vulcanized rubber, the number of hose manufacturing steps is reduced (in particular, a vulcanization step is omitted), thus resulting in energy savings.

[0076] The process for manufacturing a refrigerant transport hose is not particularly limited, but the refrigerant transport hose can be manufactured as follows: First, the inner layer (the inner tube) is extruded into a tubular shape, a reinforcing material is woven onto the tube to form a reinforcing layer, and the outer layer (the outer tube) is extruded onto the reinforcing layer, thus creating a refrigerant transport hose. Examples<<Beispiele 1 bis 11 und Vergleichsbeispiele 1 bis 3> >Raw materials

[0077] BIMS: Brominated isobutylene p-methylstyrene copolymer rubber “EXXPRO” (brand name) 3745, available from ExxonMobil Chemical Co. Acid-modified PO elastomer: Maleic acid-modified α-olefin copolymer “TAFMER” (brand name) MH7010, available from Mitsui Chemicals, Inc. PA6: Polyamide 6 “UBE Nylon” (brand name) 1011FB, available from Ube Industries, Ltd. PA6 / 12: Polyamide 6 / 12 copolymer “UBE Nylon” (brand name) 7024B, available from Ube Industries, Ltd. PA12: Polyamide 12 “UBESTA” (brand name) 3012U, available from Ube Industries, Ltd. Magnesium-aluminum solid solution: Magnesium-aluminum solid solution KW-2200 (specific surface area: 145 m²) 2 / g), available from SETOLAS Holdings, Inc. (“Magnesium-Aluminium Solid Solution” is hereinafter also referred to as “Mg-Al Solid Solution”). Hydrotalcite: Hydrotalcite “DHT” (brand name)-4C, available from SETOLAS Holdings, Inc. (specific surface area: 15 m²) 2 / G) Zinc oxide: Zinc oxide III, available from Seido Chemical Industry Co., Ltd. (added as zinc oxide content, which is shown in the table in the form of a masterbatch obtained by mixing zinc oxide with polyamide 6) 6PPD: Phenylenediamine-based antioxidant “SANTOFLEX” (brand name) 6PPD, available from Solutia Inc. (substance name: N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine) Calcium stearate: Calcium stearate SC-PG, available from Sakai Chemical Industry Co., Ltd. Stearic acid: industrial stearic acid, available from Chiba Fatty Acid Co., Ltd. (1) Production of the thermoplastic resin composition

[0078] The respective starting materials were placed in a twin-screw extrusion press (available from The Japan Steel Works, Ltd.) at the mixing ratios listed in Tables 1 and 2 and kneaded for 3 minutes at 235 °C. Each of the kneaded products was continuously extruded from the extrusion press into a strand shape, cooled with water, and cut with a cutting device to obtain pellet-shaped thermoplastic resin compositions A1 to A14.

[0079] The resulting thermoplastic resin compositions A1 to A14 were measured with respect to the residual EB ratio after treatment, the 10% modulus, and the oxygen permeability coefficient. The measurement results are shown in Tables 1 and 2. (2) Production of the resin composition of the outer layer

[0080] Into a twin-screw wrought extrusion press (available from The Japan Steel Works, Ltd.) 100 parts by mass of IIR (Butyl Rubber “Exxon Butyl” 268, available from ExxonMobil Chemical Co., Ltd.), 19 parts by mass of a crosslinkable resin (Silane-Modified Polypropylene “RINKLON” (brand name) XPM800HM, available from Mitsubishi Chemical Corporation), 19 parts by mass of polypropylene (Propylene Homopolymer “Prime Polypro” (brand name) J108M, available from Prime Polymer Co., Ltd.), 3 parts by mass of a resin-based crosslinking agent (Alkylphenol-Formaldehyde Resin “Hitanol” (brand name) 2501Y, available from Hitachi Chemical Co., Ltd.), 6 parts by mass of zinc oxide (Zinc Oxide III, available from Seido Chemical Industry Co., Ltd.), and 5 parts by mass of an oxidizer (Irganox 1010) were added, and the mixture was Kneaded for 3 minutes at 235 °C.After kneading, two parts by mass of a silanol condensation catalyst (silane crosslinking agent masterbatch "Catalyst MB" PZ010, available from Mitsubishi Chemical Corporation) were added to the pellet by dry mixing to produce an outer layer resin composition B1. An outer layer formed within 30 minutes of adding the catalyst MB.

[0081] A twin-screw wrought extrusion press (available from The Japan Steel Works, Ltd.) was used to process 100 parts by mass of BIMS (brominated isobutylene-p-methylstyrene copolymer rubber “EXXPRO” (brand name) 3745, available from ExxonMobil Chemical Corporation), 39 parts by mass of PA12 (polyamide 12 “UBE Nylon” (brand name) 3012U, available from Ube Industries, Ltd.), 5 parts by mass of zinc oxide (zinc oxide III, available from Seido Chemical Industry Co., Ltd.), 3 parts by mass of 6PPD (phenylenediamine-based antioxidant “SANTOFLEX” (brand name) 6PPD (substance name: N-phenyl-N'-1,3-dimethylbutyl)-p-phenylenediamine, available from Solutia Inc.), and 1 part by mass of calcium stearate (calcium stearate SC-PG, available from Sakai Chemical Industry). Co., Ltd.) and 1 part by mass of stearic acid (industrial stearic acid, available from Chiba Fatty acid Co., Ltd.) and kneaded for 3 minutes at 235 °C to produce an outer layer resin composition B2. (3) Manufacture of the refrigerant transport hose

[0082] Each of the thermoplastic resin compositions prepared in (1) above was extruded by an extrusion press into a tubular shape having a thickness specified in Tables 3 and 4 onto a mandrel pre-coated with a release agent. A reinforcing polyester yarn was braided onto each of the tubular thermoplastic resin compositions using a braiding machine. The outer layer resin composition B1 or B2 was extruded by an extrusion press into a tubular shape having a thickness specified in Tables 3 and 4 onto the braided reinforcing yarn, and the mandrel was removed, thus producing a tube consisting of an inner layer, a reinforcing layer, and an outer layer.

[0083] The refrigerant permeability resistance and flexibility of the hoses produced in this way were evaluated. The evaluation test results are shown in Tables 3 and 4.

[0084] The measurement and evaluation procedures are as follows. Measurement of elongation at break (EB)

[0085] Each of the thermoplastic resin compositions was formed into a sheet with an average thickness of 1.0 mm using a single-screw extrusion press with a 40 mm diameter (available from Pla Giken Co., Ltd.) fitted with a 200 mm wide T-shaped die, with the cylinder and die temperatures set to 10 °C plus the melting point of the polymer component with the highest melting point in each of the thermoplastic resin compositions at a cooling roller temperature of 50 °C and a feed rate of 3 m / min, and each of the formed sheet was punched into a dumbbell mold according to JIS No. 6 to produce a test piece of each of the thermoplastic resin compositions.

[0086] The prepared test piece of each of the thermoplastic resin compositions was subjected to a tensile test according to JIS K7161 at a temperature of 25 °C, a relative humidity of 50% and a speed of 500 mm / min, a tensile strain was determined from the obtained stress-strain curve, and the strain was defined as a tensile strain (ES). Measurement of the residual EB ratio after treatment

[0087] The dumbbell-shaped test piece according to JIS No. 6 of each of the thermoplastic resin compositions, prepared for measuring elongation at break, was hermetically sealed in a constant-volume container together with water, a refrigerant oil, and a refrigerant, and subjected to heat treatment at a predetermined temperature for a predetermined time. The sealed quantities of water, refrigerant oil, and refrigerant had a mass ratio of 1:80:160.

[0088] After treatment, the test piece of each of the thermoplastic resin compositions was removed from the container of constant volume, and the elongation at break of the test piece was measured, and the measured value was defined as EB after treatment.

[0089] The elongation at break of an untreated test piece of each of the thermoplastic resin compositions was measured, and the measured value was defined as EB before treatment.

[0090] The residual EB ratio after treatment was calculated using the following formula. EB residual ratio (%) after treatment = EB after the Treatment / EB before treatment×100 Measurement of the 10% module

[0091] Each of the thermoplastic resin compositions was formed into a sheet with an average thickness of 1.0 mm using a single screw extrusion press with a 40 mm Ø (available from Pla Giken Co., Ltd.) equipped with a 200 mm wide T-shaped die, with the cylinder and die temperatures set to 10 °C plus the melting point of the polymer component with the highest melting point in each of the thermoplastic resin compositions, a cooling roller temperature of 50 °C, and a feed rate of 3 m / min.

[0092] Each of the manufactured sheet components with an average thickness of 1.0 mm was die-cut into a dumbbell shape according to JIS No. 6 and subjected to a tensile test at a temperature of 25 °C, a relative humidity of 50%, and a speed of 500 mm / min according to JIS K7161. From the resulting stress-strain curve, a stress at 10% strain was determined, and this stress was defined as the 10% modulus. Measurement of the oxygen permeability coefficient

[0093] Each of the thermoplastic resin compositions was formed into a sheet with an average thickness of 0.2 mm using a single screw extrusion press with a 40 mm Ø (available from Pla Giken Co., Ltd.) equipped with a 200 mm wide T-shaped die, with the temperatures of the cylinder and the die set to a temperature of 10 °C plus the melting point of the polymer component with the highest melting point in each of the thermoplastic resin compositions, at a cooling roller temperature of 50 °C, and a feed rate of 3 m / min.

[0094] Each of the prepared surface structures was cut out, and the oxygen permeability coefficient was measured at a temperature of 21 °C and a relative humidity of 50% using OXTRAN 1 / 50, available from MOCON Corporation. Evaluation of refrigerant permeation resistance

[0095] The measurement was performed according to SAE J2064 AUG2015. Samples of hoses, each 1.07 m long, were filled with a refrigerant (HFO-1234yf) at a concentration of 70% ±3% per cm. 3 The internal volume of each sample was filled. These samples were left in an atmosphere at 80 °C for 25 days, and the rate of mass reduction (rate of refrigerant permeation) per day [kg / day] was measured for a predetermined period (five to seven days) at the end of the 25-day period. A numerical value obtained by dividing each of these reduction amounts by the internal surface area of ​​each sample was converted into a value per year, thus yielding a refrigerant permeation coefficient [kg / m²]. 2[·year)] calculated. A smaller numerical value for the refrigerant permeation coefficient indicates better refrigerant permeation resistance. A case where this numerical value was 6 or less can be considered to have sufficient refrigerant permeation resistance for practical use. In Tables 3 and 4, a case where this numerical value was 6 or less was indicated as O, and a case where this numerical value was greater than 6 was indicated as ×. Assessment of flexibility

[0096] As in Fig.As illustrated in Figure 2, one end section of each of the tube samples S was secured longitudinally by a fastening device, such as a clamp. A spring scale was attached to the other end section, which was a predetermined length L (120 + tube outer diameter / 2) × n [mm] away from the fastening position. Each sample S was then bent into a semicircular arc from a state illustrated by dashed lines to a state illustrated by solid lines. Subsequently, a tensile force F, measured with the spring scale and applied horizontally in the bent state with an inner radius R in the bent tube of 120 mm, was used as an indicator for evaluation. A smaller value of this tensile force F indicates easy bendability and superior flexibility of the sample S.In Tables 3 and 4, a case where this tensile force F was less than 20 N was marked with ◯, and a case where this tensile force F was 20 N or more was marked with ×. [Table 1] Table 1 Mixing ratio of the thermoplastic resin composition (1) A1 A2 A3 A4 A5 A6 A7 A8 A9 A10 BIMS Mass parts 100 100 100 100 100 100 100 100 100 100 Acid-modified PO elastomer Mass parts PA6 Mass parts 75 25 59 51 24 51 51 51 51 51 PA6 / 12 Mass parts 17 6 8 33 8 8 8 8 8 PA12 Mass parts Mg-Al solid solution Mass parts 2 2 2 2 0,5 5 10 Hydrotalcite Mass parts 2 5 9 zinc oxide Mass parts 6 5 5 5 5 5 5 5 5 5 6PPD Mass parts 4 3 3 3 3 3 3 3 3 3 Calcium stearate Mass parts 2 1 1 1 1 1 1 1 1 1 Stearic acid Mass parts 2 1 1 1 1 1 1 1 1 1 EB residual ratio after treatment % 35 85 74 83 84 59 68 36 32 81 10% module MPa 9,9 2,0 7,4 7,5 7,3 7,7 6,8 7,5 7,2 7,0 oxygen permeability coefficient *1 0,0061 0,0130 0,0060 0,0070 0,0080 0,0069 0,0084 0,0072 0,0069 0,0083 *1 Unit of oxygen permeability coefficient: (cm3·mm / (m2·Tag·mmH))

[0097] [Table 2] Table 2 Mixing ratio of the thermoplastic resin composition (2) A11 A12 A13 A14 BIMS Mass parts 100 100 Acid-modified PO elastomer Mass parts 100 100 PA6 Mass parts 42 51 57 133 PA6 / 12 Mass parts 8 23 53 PA12 Mass parts 16 Mg-Al solid solution Mass parts 2 2 Hydrotalcite Mass parts 2 zinc oxide Mass parts 5 5 5 5 6PPD Mass parts 3 3 3 2 Calcium stearate Mass parts 1 1 1 2 Stearic acid Mass parts 1 1 1 1 EB residual ratio after treatment % 31 21 92 46 10% module MPa 5,3 6,5 5,2 17,7 oxygen permeability coefficient *1 0,0265 0,0088 Upper device measurement limit (0.1) or more 0,0059 *1 Unit of oxygen permeability coefficient: (cm3·mm / (m2·day·mmHg))

[0098] [Table 3] Table 3 Configuration and evaluation of hoses (1) EXAMPLE 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 inner layer composition A1 A2 A3 A4 A5 A6 A7 A8 Layer thickness mm 0,4 0,8 0,8 0,8 0,8 0,8 0,8 0,8 Reinforcing layer material polyester polyester polyester polyester polyester polyester polyester polyester Layer thickness mm 0,5 0,5 0,5 0,5 0,5 0,5 0,5 0,5 structure Braided Braided Braided Braided Braided Braided Braided Braided outer layer composition B1 B2 B2 B2 B2 B2 B2 B2 Layer thickness mm 1,2 0,5 0,5 0,5 0,5 0,5 0,5 0,5 Evaluation Refrigerant permeation resistance ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ flexibility ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯

[0099] [Table 4] Table 4 Configuration and evaluation of the hose (2) Example 9 Example 10 Example 11 Comparative example 1 Comparative example 2 Comparative example 3 inner layer composition A9 A10 A11 A12 A13 A14 Layer thickness mm 0,8 0,8 0,8 0,8 0,8 0,8 Reinforcing layer material polyester polyester polyester polyester polyester polyester Layer thickness mm 0,5 0,5 0,5 0,5 0,5 0,5 structure Braided Braided Braided Braided Braided Braided outer layer composition B2 B2 B2 B2 B2 B2 Layer thickness mm 0,5 0,5 0,5 0,5 0,5 0,5 Evaluation Refrigerant permeation resistance ◯ ◯ ◯ ◯ × ◯ flexibility ◯ ◯ ◯ ◯ ◯ × <<Beispiele 12 bis 19 und Vergleichsbeispiele 1 bis 3> >Raw materials

[0100] BIMS: Brominated isobutylene-p-methylstyrene copolymer rubber “EXXPRO” (brand name) 3745, available from ExxonMobil Chemical Co. SIBS: Isobutylene-based thermoplastic elastomer “SIBSTAR” (brand name), available from Kaneka Corporation 6PPD: Phenylenediamine-based antioxidant “SANTOFLEX” (brand name) 6PPD, available from Solutia Inc. (substance name: N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine) Zinc oxide: Zinc oxide III, available from Seido Chemical Industry Co., Ltd. (added as zinc oxide content, which is shown in the table in the form of a masterbatch obtained by mixing zinc oxide with polyamide 6) PA6: Polyamide 6 “UBE Nylon” (brand name) 1011FB, available from Ube Industries, Ltd. PA6 / 12: Polyamide 6 / 12 copolymer “UBE Nylon” (brand name) 7024B, available from Ube Industries, Ltd. PA11: Polyamide 11, “Rilsan” (brand name) OTL, available from Arkema Co., Ltd. Hydrotalcite: Hydrotalcite “DHT” (brand name)-4C, available from SETOLAS Holdings, Inc. (specific surface area: 15 m²) 2 / G) Stearic acid: industrial stearic acid, available from Chiba Fatty Acid Co., Ltd. Calcium stearate: calcium stearate SC-PG, available from Sakai Chemical Industry Co., Ltd. (melting point: 155 ± 5 °C) Zinc stearate: Zinc stearate SZ-PG, available from Sakai Chemical Industry Co., Ltd. (melting point: 125 ± 5 °C) Magnesium stearate: Magnesium stearate SM-PG, available from Sakai Chemical Industry Co., Ltd. (melting point: 145 ± 5 °C) (1) Production of the thermoplastic resin composition

[0101] The starting materials shown under the conditions listed in Table 5 were placed in a twin-screw kneader (available from The Japan Steel Works, Ltd.) at each of the mixing ratios shown in the respective example and kneaded for 3 minutes at 200 to 225 °C. Each of the resulting kneaded products was continuously extruded into a strand shape, cooled with water, and cut with a cutting device to produce a pellet-shaped thermoplastic resin composition. (2) Film education

[0102] The resulting thermoplastic resin compositions were formed into sheet structures using a single-screw extrusion press with a 40 mm diameter (available from Pla Giken Co., Ltd.) equipped with a 200 mm wide T-shaped die. Specifically, sheet structures with an average thickness of 1.0 mm were obtained by setting the cylinder and die temperatures to 200–240 °C and selecting the cooling roller temperature and feed rate as desired. Measurement of the 10% module

[0103] Each of the resulting sheet shapes was stamped into a dumbbell shape according to JIS No. 6 and then subjected to a tensile test at a temperature of 25 °C and a speed of 500 mm / min according to JIS K7161. From the resulting stress-strain curve, a stress at 10% strain was obtained, and this stress was defined as the 10% modulus. Measurement of the oxygen permeability coefficient

[0104] Each of the resulting surface structures was cut out and subjected to a measurement of the oxygen permeability coefficient (cm²). 3 mm / (m 2 ·Day·mmHg) using OXTRAN 1 / 50 available from MOCON Corporation at a temperature of 21 °C and a relative humidity of 50%. Measurement of kneading energy

[0105] In the production of the thermoplastic resin composition, the specific energy of the twin-screw kneader, i.e. the electricity consumption of the extrusion press electric motor (kWh / kg), taking into account the efficiency of the electric motor and the mechanical efficiency of the kneader per 1 kg of starting material during kneading, was measured and defined as kneading energy. Measurement of the residual EB ratio after treatment

[0106] The resulting flat shapes were stamped into a dumbbell shape according to JIS No. 6 to produce test pieces.

[0107] Each test piece was subjected to a tensile test at a temperature of 25 °C, a relative humidity of 50%, and a speed of 500 mm / min according to JIS K7161. The elongation at break was determined from the resulting stress-strain curve and defined as the pre-treatment elongation at break (EB). Subsequently, the thermoplastic resin composition was treated in a refrigerant-containing mixture (comprising a refrigerant, refrigerant oil, and water) at 150 °C for 96 hours, and the post-treatment elongation at break (EB) was measured in the tensile test.

[0108] The EB residual ratio was calculated using the following formula. EB−Residual ratio (%) = EB after treatment / EB before treatment × 100

[0109] The production conditions and measurement results are shown in Table 5 below. In Table 5, the values ​​of the 10% modulus, the oxygen permeability coefficient, the kneading energy, and the residual EB ratio are shown not as measured values, but as relative values ​​when measuring the residual EB ratio after treatment in each example, with the measured values ​​in comparison example 1 being set to 100.

[0110] [Table 5-I] Table 5 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Conditions Elastomer (mass-produced parts) BIMS 100,0 100,0 100,0 100,0 100,0 100,0 SIBS - - - - - - 6PPD (Mass Parts) 3,0 3,0 3,0 3,0 3,0 3,0 Zinc oxide (by mass) 5,0 5,0 5,0 5,0 5,0 5,0 Polyamide (mass-produced parts) PA6 51,0 51,0 51,0 51,0 51,0 51,0 PA6 / 12 8,0 3,0 8,0 8,0 8,0 8,0 PA11 Hydrotalcite (bulk fractions) 2,0 2,0 2,0 2,0 2,0 2,0 Stearic acid (by mass) 1,0 1,0 1,0 - - 1,0 Calcium stearate (parts by mass) 2,0 3,5 5,0 2,5 2,5 2,0 Zinc stearate (bulk) 1,0 1,0 1,0 0,5 5,0 - Magnesium stearate (mass fraction) - - - - - 1,0 Total quantity (mass fractions) 173,0 171,5 176,0 172,0 176,5 173,0 Wd1 / Wd2 2,0 0,5 5,0 5,0 0,5 2,0 Evaluation 10% module 88 95 89 93 85 89 oxygen permeability coefficient 75 73 85 75 85 77 Kneading energy 70 85 75 85 70 70 EB residual ratio before and after the autoclave test 135 130 130 125 140 128 [Table 5-II] Table 5 Example 18 Example Comparison Comparison Comparison19 example 1 example 2 example 3 Conditions Elastomer (mass-produced parts) BIMS 100,0 - 100,0 100,0 100,0 SIBS - 100,0 - - - 6PPD (Mass Parts) 3,0 3,0 3,0 3,0 3,0 Zinc oxide (by mass) 5,0 5,0 5,0 5,0 5,0 Polyamide (mass-produced parts) PA6 51,0 51,0 51,0 51,0 51,0 PA6 / 12 8,0 8,0 8,0 8,0 PA11 8,0 Hydrotalcite (bulk fractions) 2,0 2,0 2,0 5,0 2,0 Stearic acid (by mass) 1,0 1,0 1,0 1,0 1,0 Calcium stearate (parts by mass) 2,0 2,0 2,0 2,0 5,0 Zinc stearate (bulk) 1,0 1,0 - - - Magnesium stearate (mass fraction) - - - - - Total quantity (mass fractions) 173,0 173,0 172,0 175,0 175,0 Wd1 / Wd2 2,0 2,0 - - - Evaluation 10% module 88 85 100 110 95 oxygen permeability coefficient 90 75 100 95 120 Kneading energy 80 80 100 110 95 EB residual ratio before and after the autoclave test 130 136 100 86 93

[0111] The present disclosure includes the following inventions. Invention [1] A thermoplastic resin composition for a refrigerant transport hose, having an island structure in which an elastomer is present as a domain in a matrix comprising a thermoplastic resin, wherein the thermoplastic resin composition comprises: 100 parts by mass of the elastomer; 30 to 100 parts by mass of the thermoplastic resin; and 0.5 to 10 parts by mass of hydrotalcite and / or a magnesium-aluminum solid solution; wherein the thermoplastic resin comprises 50 to 100 parts by mass of a polyamide, in relation to 100 parts by mass of the thermoplastic resin, and the elastomer comprises an elastomer with a polyisobutylene main chain. Invention [2] The thermoplastic resin composition for a refrigerant transport hose according to invention [1], comprising at least one selected from the group consisting of zinc oxide, an aging inhibitor based on phenylenediamine or quinoline, and a processing aid.

[0112] Invention [3] The thermoplastic resin composition for a refrigerant transport hose according to invention [1] or [2], wherein the polyamide is at least one selected from the group consisting of polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 610, a polyamide 6 / 66 copolymer, a polyamide 6 / 12 copolymer, polyamide 46, polyamide 6T, polyamide 9T and polyamide MXD6.

[0113] Invention [4] The thermoplastic resin composition for a refrigerant transport hose according to any one of inventions [1] to [3], wherein the elastomer with a polyisobutylene main chain is at least one selected from the group consisting of a butyl rubber, a halogenated butyl rubber, an isobutylene monoalkylstyrene copolymer rubber, a halogenated isobutylene monoalkylstyrene copolymer rubber, and a styrene-isobutylene-styrene block copolymer. Invention [5] The thermoplastic resin composition for a refrigerant transport hose according to any one of inventions [1] to [4], wherein the hydrotalcite and / or the magnesium-aluminum solid solution has a specific surface area of ​​100 m². 2 / g or more.

[0114] [6] The thermoplastic resin composition for a refrigerant transport hose according to one of the inventions [1] to [5], further comprising a first fatty acid metal salt and a second fatty acid metal salt having a lower melting point than that of the first fatty acid metal salt.

[0115] [7] The thermoplastic resin composition for a refrigerant transport hose according to the invention [6], wherein the first fatty acid metal salt has a melting point of 150 °C or more.

[0116] [8] The thermoplastic resin composition for a refrigerant transport hose according to the invention [7], wherein the second fatty acid metal salt has a melting point of less than 150 °C.

[0117] [9] The thermoplastic resin composition for a refrigerant transport hose according to one of the inventions [6] to [8], which contains 0.5 to 5.0 parts by mass of the first fatty acid metal salt in relation to 100 parts by mass of the elastomer.

[0118]

[10] The thermoplastic resin composition for a refrigerant transport hose according to one of the inventions [6] to [9], which contains 0.5 to 5.0 parts by mass of the second fatty acid metal salt in relation to 100 parts by mass of the elastomer.

[0119]

[11] The thermoplastic resin composition for a refrigerant transport hose according to one of the inventions [6] to

[10] , wherein the ratio Wd1 / Wd2 of a mass Wd1 of the first fatty acid metal salt to a mass Wd2 of the second fatty acid metal salt is from 0.5 to 5.0.

[0120]

[12] The thermoplastic resin composition for a refrigerant transport hose according to one of the inventions [6] to

[11] , wherein the first fatty acid metal salt is at least one selected from the group consisting of calcium stearate, zinc 12-hydroxystearate and lithium 12-hydroxystearate.

[0121]

[13] The thermoplastic resin composition for a refrigerant transport hose according to one of the inventions [6] to

[12] , wherein the second fatty acid metal salt is at least one selected from the group consisting of zinc stearate and magnesium stearate. Invention

[14] A refrigerant transport hose comprising: a layer composed of the thermoplastic resin composition according to one of the inventions [1] to

[13] .

[0122] Invention

[15] The refrigerant transport hose according to invention

[14] , comprising: an inner layer; a reinforcing layer; and an outer layer; wherein the inner layer is composed of the thermoplastic resin composition according to one of inventions [1] to

[13] . Invention

[16] The refrigerant transport hose according to

[14] or

[15] , wherein the refrigerant transport hose does not contain a layer formed from vulcanized rubber. Industrial applicability

[0123] The thermoplastic resin composition of the present invention can be used in a suitable manner to manufacture a refrigerant transport hose. List of reference symbols 1 refrigerant transport hose 2 inner layer 3 Reinforcing layer 4 Outer layer F tractive force L Predetermined length R hose inner radius S Sample QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Cited patent literature

[0000] JP 2011-58638 A [0003, 0004]

Claims

[1] Thermoplastic resin composition for a refrigerant transport hose having an island structure in which an elastomer is present as a domain in a matrix comprising a thermoplastic resin, wherein the thermoplastic resin composition comprises: 100 parts by mass of the elastomer; 30 to 100 parts by mass of the thermoplastic resin; and 0.5 to 10 parts by mass of hydrotalcite and / or a magnesium-aluminum solid solution; wherein the thermoplastic resin comprises 50 to 100 parts by mass of a polyamide, in relation to 100 parts by mass of the thermoplastic resin, and The elastomer comprises an elastomer with a polyisobutylene main chain. [2] Thermoplastic resin composition for a refrigerant transport hose according to claim 1, comprising at least one selected from the group consisting of zinc oxide, an anti-aging agent based on phenylenediamine or quinoline and a processing aid. [3] Thermoplastic resin composition for a refrigerant transport hose according to claim 1, wherein the polyamide is at least one selected from the group consisting of polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 610, a polyamide 6 / 66 copolymer, a polyamide 6 / 12 copolymer, polyamide 46, polyamide 6T, polyamide 9T and polyamide MXD6. [4] Thermoplastic resin composition for a refrigerant transport hose according to claim 1, wherein the elastomer with a polyisobutylene main chain is at least one selected from the group consisting of a butyl rubber, a halogenated butyl rubber, an isobutylene monoalkylstyrene copolymer rubber, a halogenated isobutylene monoalkylstyrene copolymer rubber and a styrene isobutylene styrene block copolymer. [5] Thermoplastic resin composition for a refrigerant transport hose according to claim 1, wherein the hydrotalcite and / or the magnesium-aluminium mixed crystal has a specific surface area of ​​100 m² 2 / g or more. [6] Thermoplastic resin composition for a refrigerant transport hose according to claim 1, further comprising a first fatty acid metal salt and a second fatty acid metal salt having a lower melting point than that of the first fatty acid metal salt. [7] Thermoplastic resin composition for a refrigerant transport hose according to claim 6, wherein the first fatty acid metal salt has a melting point of 150 °C or more. [8] Thermoplastic resin composition for a refrigerant transport hose according to claim 7, wherein the second fatty acid metal salt has a melting point of less than 150 °C. [9] Thermoplastic resin composition for a refrigerant transport hose according to claim 6, comprising 0.5 to 5.0 parts by mass of the first fatty acid metal salt in relation to 100 parts by mass of the elastomer. [10] Thermoplastic resin composition for a refrigerant transport hose according to claim 6, comprising 0.5 to 5.0 parts by mass of the second fatty acid metal salt in relation to 100 parts by mass of the elastomer. [11] Thermoplastic resin composition for a refrigerant transport hose according to claim 6, wherein the ratio Wd1 / Wd2 of a mass Wd1 of the first fatty acid metal salt to a mass Wd2 of the second fatty acid metal salt is from 0.5 to 5.

0. [12] Thermoplastic resin composition for a refrigerant transport hose according to claim 6, wherein the first fatty acid metal salt is at least one selected from the group consisting of calcium stearate, zinc 12-hydroxystearate and lithium 12-hydroxystearate. [13] Thermoplastic resin composition for a refrigerant transport hose according to claim 6, wherein the second fatty acid metal salt is at least one selected from the group consisting of zinc stearate and magnesium stearate. [14] Refrigerant transport hose comprising: a layer composed of the thermoplastic resin composition according to claim 1. [15] Refrigerant transport hose according to claim 14, comprising: an inner layer; a reinforcing layer; and an outer layer; wherein the inner layer is a layer composed of the thermoplastic resin composition according to claim 1. [16] Refrigerant transport hose according to claim 14, wherein the refrigerant transport hose does not include a layer composed of vulcanized rubber.

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