CN117642570A - Hose for conveying refrigerant - Google Patents
Hose for conveying refrigerant Download PDFInfo
- Publication number
- CN117642570A CN117642570A CN202280050249.6A CN202280050249A CN117642570A CN 117642570 A CN117642570 A CN 117642570A CN 202280050249 A CN202280050249 A CN 202280050249A CN 117642570 A CN117642570 A CN 117642570A
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- CN
- China
- Prior art keywords
- thermoplastic resin
- resin composition
- elastomer
- transporting hose
- refrigerant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003507 refrigerant Substances 0.000 title claims abstract description 116
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 204
- 239000011342 resin composition Substances 0.000 claims abstract description 148
- 229920001971 elastomer Polymers 0.000 claims abstract description 98
- 239000000806 elastomer Substances 0.000 claims abstract description 79
- 230000035699 permeability Effects 0.000 claims abstract description 79
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000011347 resin Substances 0.000 claims abstract description 37
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 36
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 19
- 239000011159 matrix material Substances 0.000 claims abstract description 12
- 238000002844 melting Methods 0.000 claims description 24
- 230000008018 melting Effects 0.000 claims description 24
- 229920005549 butyl rubber Polymers 0.000 claims description 20
- 229920006122 polyamide resin Polymers 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 239000000853 adhesive Substances 0.000 claims description 15
- 230000001070 adhesive effect Effects 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 12
- -1 polypropylene Polymers 0.000 claims description 12
- 229920002292 Nylon 6 Polymers 0.000 claims description 8
- 229920005555 halobutyl Polymers 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- 239000004636 vulcanized rubber Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000004831 Hot glue Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract description 10
- 229920002647 polyamide Polymers 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 201
- 239000000523 sample Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 16
- 230000002093 peripheral effect Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000012790 adhesive layer Substances 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 229910001868 water Inorganic materials 0.000 description 7
- 229920001400 block copolymer Polymers 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000004898 kneading Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000002274 desiccant Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 229920001384 propylene homopolymer Polymers 0.000 description 4
- 229920005604 random copolymer Polymers 0.000 description 4
- 239000012779 reinforcing material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 229920000299 Nylon 12 Polymers 0.000 description 3
- 229920000572 Nylon 6/12 Polymers 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920001470 polyketone Polymers 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- UHKPXKGJFOKCGG-UHFFFAOYSA-N 2-methylprop-1-ene;styrene Chemical compound CC(C)=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 UHKPXKGJFOKCGG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 229920005557 bromobutyl Polymers 0.000 description 2
- IYYGCUZHHGZXGJ-UHFFFAOYSA-N but-1-ene;ethene;prop-1-ene Chemical compound C=C.CC=C.CCC=C IYYGCUZHHGZXGJ-UHFFFAOYSA-N 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920006132 styrene block copolymer Polymers 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229920003734 UBESTA® Polymers 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920005556 chlorobutyl Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZMUCVNSKULGPQG-UHFFFAOYSA-N dodecanedioic acid;hexane-1,6-diamine Chemical compound NCCCCCCN.OC(=O)CCCCCCCCCCC(O)=O ZMUCVNSKULGPQG-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- UKACHOXRXFQJFN-UHFFFAOYSA-N heptafluoropropane Chemical compound FC(F)C(F)(F)C(F)(F)F UKACHOXRXFQJFN-UHFFFAOYSA-N 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920003253 poly(benzobisoxazole) Polymers 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 description 1
- 229920000927 poly(p-phenylene benzobisoxazole) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Landscapes
- Rigid Pipes And Flexible Pipes (AREA)
- Laminated Bodies (AREA)
Abstract
The invention provides a flexible and lightweight refrigerant conveying hose with low gas permeability such as water vapor and freon. The hose for transporting a refrigerant is characterized by comprising at least an outer layer, a reinforcing layer and an inner layer, wherein the outer layer has a layer formed of a thermoplastic resin composition A, the inner layer has a layer formed of a thermoplastic resin composition B, the thermoplastic resin composition A has a sea-island structure comprising a thermoplastic resin a as a matrix and an elastomer a as a domain, the thermoplastic resin a comprises a polyolefin-based resin, the elastomer a comprises a butyl-based elastomer in an amount of 51 to 85% by mass, the thermoplastic resin composition B has a sea-island structure comprising a thermoplastic resin B as a matrix and an elastomer B as a domain, the thermoplastic resin B comprises a polyamide-based resin, and the elastomer B comprises a butyl-based elastomer.
Description
Technical Field
The present invention relates to a refrigerant transporting hose for an air conditioner of an automobile.
Background
In order to cope with the emission limitation of carbon dioxide, weight reduction of automobiles has become one of the important problems. Therefore, a refrigerant transporting hose for an air conditioner or the like mounted in an automobile is also required to be lightweight. When the inner and outer layers constituting the hose are thinned for weight reduction, gas permeability of the supplied refrigerant, oxygen, water vapor, and the like may be deteriorated. For this reason, it has been proposed to replace the constituent material of the inner layer with a polyamide resin composition excellent in gas permeability from rubber (for example, refer to patent documents 1 and 2).
Air conditioners and the like are mounted in limited confined spaces of automobiles, and therefore, a refrigerant transporting hose is required to be excellent in flexibility and easy to assemble even in confined spaces. Further, durability to withstand long-term use in a high-temperature and high-humidity environment in an engine room is required. However, since the resin hose described in patent document 1 and the refrigerant transport pipe described in patent document 2 are composed of the polyamide resin composition, there is a concern that the water vapor permeability to moisture outside the hose may be deteriorated due to the moisture absorption of the polyamide resin composition. Accordingly, there is room for improvement in terms of obtaining a refrigerant transporting hose that is lightweight and excellent in flexibility while reducing the permeability of the transported refrigerant and the water vapor permeability of the moisture outside the hose.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2013-155793
Patent document 2: japanese patent laid-open No. 2021-46490
Disclosure of Invention
Problems to be solved by the invention
The present invention provides a flexible and lightweight hose for transporting refrigerant, which has low gas permeability such as refrigerant and water vapor.
Technical means for solving the problems
The hose for transporting a refrigerant according to the present invention, which achieves the above object, is characterized by comprising at least an outer layer, a reinforcing layer and an inner layer, wherein the outer layer has at least a layer formed of a thermoplastic resin composition a, the inner layer has at least a layer formed of a thermoplastic resin composition B, the thermoplastic resin composition a has an island structure comprising a thermoplastic resin a as a matrix and an elastomer a as a structural domain, the thermoplastic resin a comprises at least a polyolefin-based resin, the elastomer a comprises at least a butyl-based elastomer, the elastomer a is 51 to 85 mass% of 100 mass% of the thermoplastic resin composition a, the thermoplastic resin composition B has an island structure comprising a thermoplastic resin B as a matrix and an elastomer B as a structural domain, and the thermoplastic resin B comprises at least a polyamide-based resin and the elastomer B comprises at least a butyl-based elastomer.
Effects of the invention
The refrigerant transporting hose of the present invention has an outer layer formed by a layer formed of a thermoplastic resin composition a containing a polyolefin-based resin, and therefore can reduce the water vapor permeability of moisture outside the hose, and has an inner layer formed by a layer formed of a thermoplastic resin composition B containing a polyamide-based resin, and therefore can reduce the permeability of the refrigerant being transported. Further, the outer layer excellent in low water vapor permeability can be thinned, and the inner layer excellent in low permeability of the refrigerant can be thinned, so that the hose can be made lightweight. Further, since the thermoplastic resin composition a and the thermoplastic resin composition B have an island structure in which a butyl elastomer is a domain, the hose can be made excellent in flexibility.
In the refrigerant transporting hose, the elastomer B is preferably 51 to 85 mass% of 100 mass% of the thermoplastic resin composition B, so that the hose can be made softer. The refrigerant transporting hose preferably does not have a layer made of vulcanized rubber, and the productivity of the refrigerant transporting hose can be improved.
The thermoplastic resin composition B preferably has a lower Freon permeability than the thermoplastic resin composition A, and can efficiently reduce the Freon permeability of the hose and suppress the generation of bubbles. On the other hand, the water vapor permeability coefficient of the thermoplastic resin composition a is preferably smaller than that of the thermoplastic resin composition B, and the water permeation/diffusion from the outside of the hose can be suppressed, and the inner layer containing the polyamide resin can be prevented from absorbing moisture, so that the low permeability of freon can be maintained.
In the thermoplastic resin composition a, the thermoplastic resin a preferably contains at least a polypropylene resin, and the elastomer a preferably contains at least a halogenated butyl rubber, and is excellent in flexibility while further reducing the permeability of moisture from outside the hose. In the thermoplastic resin composition B, the thermoplastic resin B preferably contains at least a polyamide 6 resin, and the elastomer B preferably contains at least a halogenated isobutylene para-methylstyrene copolymer rubber, so that the permeability of the refrigerant to be transported can be further reduced and the flexibility can be further improved. Further, it is preferable that a part of the domain of the thermoplastic resin composition A and/or a part of the domain of the thermoplastic resin composition B be crosslinked, so that the durability of the outer layer and/or the inner layer can be further improved.
The refrigerant transporting hose preferably has an aqueous adhesive, a solvent adhesive, a chemical reaction adhesive or a hot melt adhesive interposed between the outer layer and the reinforcing layer and/or between the inner layer and the reinforcing layer, and further improves the durability of the hose.
The thermoplastic resin composition A had a shear rate of 243.2s at 250 ℃ -1 The melt viscosity is preferably 1000 Pa.s or less, and extrusion processability in molding the outer layer can be improved. The thermoplastic isThe thermoplastic resin a preferably contains one or more thermoplastic resins having a melting point of 150 ℃ or more, and the thermoplastic resin b preferably contains one or more thermoplastic resins having a melting point of 200 ℃ or more, and the processability of extrusion molding the outer layer on the outer periphery of the extrusion molded inner layer is improved.
The thermoplastic resin composition A has a tensile stress of 10% or less at 10% deformation and a water vapor permeability coefficient of 3.0 g.mm/(m) 2 24 h) or less, and can achieve both the low water vapor permeability and the flexibility of the outer layer at a high level. Further, the thermoplastic resin composition B has a tensile stress at 10% deformation of 10MPa or less and an oxygen permeability coefficient of 0.05cm 3 ·mm/(m 2 Day mmHg) or less, and can achieve both low permeability and flexibility of the inner layer refrigerant at a high level.
The thermoplastic resin composition A preferably has a tensile breaking strength of 3MPa or more at 23℃and a tensile breaking elongation of 200% or more, and can ensure the durability of the outer layer at room temperature or normal temperature. Further, the thermoplastic resin composition A preferably has a tensile breaking strength of 0.4MPa or more at 150℃and a tensile elongation at break of 50% or more at 150℃and can ensure the durability of the outer layer at high temperature. Further, the thermoplastic resin composition A and the thermoplastic resin composition B preferably have Izod impact strength at-40 ℃ which is not destroyed, and the durability of the outer layer and the inner layer at low temperature can be ensured.
Drawings
Fig. 1 is an explanatory view illustrating a cross section of a hose for transporting a refrigerant of the present invention.
Fig. 2 is an explanatory diagram illustrating a method of measuring flexibility of a hose.
Detailed Description
The refrigerant transporting hose of the present invention is a hose for transporting a refrigerant, which is used for an air conditioner or the like of an automobile. Examples of the refrigerant include Hydrofluorocarbons (HFCs), hydrofluoroolefins (HFOs), hydrocarbon compounds, carbon dioxide, ammonia, and water. Examples of the HFC include R410A, R, R404A, R407C, R507A, R134a, and the like. Further, as HFO, R1234yf, R1234ze, R1233zd, R1123, R1224yd, R1336mzz, and the like can be exemplified. Examples of the hydrocarbon compound include methane, ethane, propane, propylene, butane, isobutane, pentane, heptafluoropropane, and hexafluoropropane.
Fig. 1 is an explanatory view illustrating a cross section of a hose for transporting a refrigerant, for example. The refrigerant transporting hose 1 is formed of at least an outer layer 3, a reinforcing layer 4, and an inner layer 2, wherein the outer layer 3 is disposed on the outer peripheral side of the reinforcing layer 4, and the inner layer 2 is disposed on the inner peripheral side of the reinforcing layer 4. The outer layer 3 and the inner layer 2 are respectively formed in a circular tube shape. Further, a plurality of enhancement layers 4 may be provided, and in this case, it is assumed that: the inner layer 2 is disposed on the inner peripheral side of the innermost reinforcing layer 4, and the outer layer 3 is disposed on the outer peripheral side of the outermost reinforcing layer 4. Examples of the layers other than the outer layer 3, the reinforcing layer 4, and the inner layer 2 include an adhesive layer, a barrier layer, and a rubber layer. The adhesive layer may be sandwiched between the outer layer 3 and the reinforcing layer 4 and/or between the inner layer 2 and the reinforcing layer 4.
The outer layer 3 of the refrigerant transporting hose may have at least a layer made of the thermoplastic resin composition a, or may have a layer other than the layer made of the thermoplastic resin composition a on the inner peripheral side and/or the outer peripheral side thereof. The properties of the layers other than the layer formed from the thermoplastic resin composition a are not particularly limited as long as the objects of the present invention are not hindered.
The inner layer 2 of the refrigerant transporting hose may have at least a layer made of the thermoplastic resin composition B, or may have a layer other than the layer made of the thermoplastic resin composition B on the inner peripheral side and/or the outer peripheral side thereof. The properties of the layers other than the layer formed from the thermoplastic resin composition B are not particularly limited as long as the objects of the present invention are not hindered.
The thermoplastic resin composition a constituting the outer layer has a sea-island structure having a thermoplastic resin a as a matrix and an elastomer a as a domain. The sea-island structure refers to a dispersed form in which the matrix is a sea phase (continuous phase) and the domains are island phases (discontinuous phase, dispersed phase). The shape of the domain is not particularly limited, and may be any of sphere, ellipsoid, cylinder, needle, and irregular shape. The dispersion form of the thermoplastic resin composition a can be observed by SPM (scanning probe microscope) or the like in a vertical section in the extrusion texture direction. The observation magnification can be appropriately determined according to the size of the domain.
The thermoplastic resin a contains at least a polyolefin resin. The thermoplastic resin a may be a polyolefin resin alone or a mixture of the thermoplastic resin with other thermoplastic resins. The inclusion of the polyolefin resin can reduce the water vapor permeability and make the resin excellent. Examples of the polyolefin resin include polyethylene resin, polypropylene resin, and polybutylene resin. Among them, polypropylene resin is preferable. By including the polypropylene resin in the thermoplastic resin a, both low water vapor permeability and heat resistance can be achieved. Examples of the polypropylene resin include propylene homopolymer (propylene homopolymer), propylene/ethylene block copolymer, propylene/ethylene/1-butene block copolymer, propylene/ethylene random copolymer, propylene/1-butene random copolymer, propylene/ethylene random block copolymer, and propylene/ethylene/1-butene random block copolymer. Among them, propylene homopolymers, propylene-ethylene block copolymers and propylene-ethylene random copolymers are preferable. The polyolefin resin may contain at least partially a modified polyolefin resin having a functional group such as anhydrous maleic acid. The polyolefin resin may be used alone or in combination of a plurality of resins.
Examples of other thermoplastic resins other than the polyolefin resin that can be contained in the thermoplastic resin a include polyamide resins, polyester resins, polyvinyl alcohol resins, and polyketone resins. A single or a plurality of other thermoplastic resins may be mixed with the polyolefin-based resin. In the case of mixing another thermoplastic resin, the polyolefin resin is preferably 51 mass% or more, more preferably 60 mass% or more, and still more preferably 70 mass% or more, of 100 mass% of the thermoplastic resin a.
Preferably, the thermoplastic resin a contains one or more thermoplastic resins having a melting point of 150 ℃ or more. By including a thermoplastic resin having a melting point of 150 ℃ or higher, heat resistance required in the hose can be improved. The melting point of the polyolefin resin and/or other thermoplastic resin is preferably 150℃or higher, more preferably 155℃to 170℃and still more preferably 162℃to 170 ℃. In the present specification, the term "a" is used to mean: the melting point of the thermoplastic resin is obtained by measuring the temperature of an endothermic peak accompanying melting during the temperature increase by a DSC (differential scanning calorimetry) method.
The thermoplastic resin a is preferably 15 to 49% by mass, more preferably 15 to 40% by mass, and even more preferably 15 to 31% by mass of 100% by mass of the thermoplastic resin composition a. By setting the thermoplastic resin a to 15 mass% or more, the dispersion form of the island-in-sea structure in which the thermoplastic resin a is a matrix can be ensured, and the water vapor permeability can be reduced. Further, the flexibility can be ensured by setting the thermoplastic resin a to 49 mass% or less.
The elastomer a contains at least a butyl-based elastomer. The elastomer a may be a butyl-based elastomer alone or in combination with other elastomers. By including the butyl-based elastomer, both low water vapor permeability and flexibility can be achieved. The butyl elastomer contained in the elastomer a may be the same as or different from the butyl elastomer contained in the elastomer b. Examples of the butyl elastomer include butyl rubber, halogenated butyl rubber, isobutylene-p-methylstyrene copolymer rubber, halogenated isobutylene-p-methylstyrene copolymer rubber, and styrene-isobutylene-styrene block copolymer rubber. Among them, halogenated butyl rubber is preferable as the elastomer a. Examples of the halogenated butyl rubber include brominated butyl rubber and chlorinated butyl rubber. By incorporating the halogenated butyl rubber into the elastomer a, not only the softness and water vapor permeation resistance of the hose are improved, but also the elastomer is dynamically crosslinked at the time of kneading the thermoplastic resin composition a, whereby the durability is improved. The butyl elastomer may be used alone or in combination of two or more.
Examples of other elastomers other than the butyl-based elastomer that the elastomer a can contain include olefin-based elastomer, styrene-based elastomer, urethane-based elastomer, ester-based elastomer, amide-based elastomer, and acrylic-based elastomer. It is also possible to mix one or more other elastomers with the butyl elastomer. In the case of mixing another elastomer, the butyl elastomer is preferably 51 mass% or more, more preferably 75 mass% or more, and still more preferably 95 mass% or more, based on 100 mass% of the elastomer a.
The elastomer a is 51 to 85 mass%, preferably 60 to 85 mass%, and more preferably 69 to 85 mass% of 100 mass% of the thermoplastic resin composition a. By setting the elastomer a to 51 mass% or more, flexibility can be ensured. Further, by setting the elastomer a to 85 mass% or less, the dispersion form of the island-in-sea structure in which the elastomer a is a domain can be ensured, and the water vapor permeability can be reduced and excellent.
It is preferable that a part of the domains of the thermoplastic resin composition A be crosslinked. By crosslinking a part of the domains, the strength of the thermoplastic resin composition a can be improved, thereby further improving the durability of the outer layer. The method for crosslinking a part of the domain is not particularly limited, and examples thereof include dynamic crosslinking by adding a crosslinking agent and melt-kneading.
Thermoplastic resin composition A for forming outer layer had a shear rate of 243.2s at 250 ℃ -1 The melt viscosity is preferably 1000 Pa.s or less. By setting the melt viscosity to 1000 Pa.s or less, the processability in hose extrusion can be improved. In the present specification, the melt viscosity can be measured using a capillary rheometer under prescribed conditions.
The tensile stress at 10% deformation of the thermoplastic resin composition A is preferably 10MPa or less, more preferably 1MPa to 9MPa, still more preferably 1MPa to 5 MPa. By setting the tensile stress at 10% deformation to 10MPa or less, the flexibility of the outer layer can be made excellent.
The tensile breaking strength of the thermoplastic resin composition A at room temperature (23 ℃) is preferably 3MPa or more, and the tensile breaking elongation is preferably 200% or more. The durability of the outer layer at room temperature (23 ℃) or normal temperature (20 ℃ + -15 ℃) can be ensured by setting the tensile breaking strength to 3MPa or more and the tensile breaking elongation to 200% or more. The tensile break strength is more preferably 3.5MPa or more, still more preferably 4MPa or more. The tensile elongation at break is more preferably 250% or more, and still more preferably 300% or more.
The tensile breaking strength of the thermoplastic resin composition A at 150℃is preferably 0.4MPa or more, and the tensile breaking elongation at 150℃is preferably 50% or more. The durability of the outer layer at high temperature can be ensured by setting the tensile breaking strength at 150 ℃ to 0.4MPa or more and the tensile breaking elongation at 150 ℃ to 50% or more. The tensile break strength at 150℃is more preferably 0.5MPa or more. The tensile elongation at break at 150℃is more preferably 100% or more, still more preferably 200% or more.
In the present specification, the tensile stress at 10% deformation, the tensile breaking strength at 23℃and 150℃and the tensile breaking elongation at 23℃and 150℃can be determined according to the measurement method specified in JIS K6251 "method for determining the vulcanization rubber and thermoplastic rubber-elongation characteristics".
Preferably, the thermoplastic resin composition A has an Izod impact strength of-40 ℃ which is free from damage and ensures the durability of the outer layer at low temperatures. In the present specification, izod impact strength at-40℃can be measured by using a notched test piece according to the measurement method defined in JIS K7110.
The water vapor permeability coefficient of the thermoplastic resin composition A is preferably 3.0 g.mm/(m) 2 24 h) or less, more preferably 1.0 g.mm/(m) 2 ·24h)～3.0g·mm/(m 2 24 h), more preferably 1.0 g.mm/(m) 2 ·24h)～2.0g·mm/(m 2 24 h). By making the water vapor permeability coefficient of the thermoplastic resin composition A3.0g.mm/(m) 2 24 h) or less, the outer layer is excellent in low water vapor permeability. In the present specification, as described in examples below, the water vapor permeability coefficient can be obtained at a temperature of 60℃and a relative humidity of 95% using a member obtained by forming a sheet of the thermoplastic resin composition into a thickness of 0.2mm as a sample.
The thermoplastic resin composition B constituting the inner layer has a sea-island structure having the thermoplastic resin B as a matrix and the elastomer B as a domain. The sea-island structure refers to a dispersed form in which the matrix is a sea phase (continuous phase) and the domains are island phases (discontinuous phase, dispersed phase). The shape of the domain is not particularly limited, and may be any of sphere, ellipsoid, cylinder, needle, and irregular shape. The dispersion form of the thermoplastic resin composition B can be observed by SPM (scanning probe microscope) or the like in a vertical section in the extrusion texture direction. The observation magnification can be appropriately determined according to the size of the domain.
The thermoplastic resin b contains at least a polyamide resin. The thermoplastic resin b may be a polyamide resin alone or a mixture of other thermoplastic resins. The inclusion of the polyamide resin can reduce the oxygen permeability and the refrigerant permeability, thereby making it excellent. Examples of the polyamide resin include polyamide 6 resin, polyamide 66 resin, polyamide 11 resin, polyamide 12 resin, polyamide 610 resin, polyamide 6/66 copolymer, polyamide 6/12 copolymer, polyamide 46 resin, polyamide 6T resin, polyamide 9T resin, polyamide MXD6 resin, and the like. Among them, polyamide 6 resin is preferable. By including the polyamide 6 resin in the thermoplastic resin b, the low refrigerant permeability, the low oxygen permeability, and the heat resistance can be achieved. The polyamide resin may be used alone or in combination of two or more.
Examples of other thermoplastic resins other than the polyamide resin that can be contained in the thermoplastic resin b include polyolefin resins, polyester resins, polyvinyl alcohol resins, and polyketone resins. The polyamide resin may be blended with one or more other thermoplastic resins. In the case of mixing another thermoplastic resin, the polyamide resin is preferably 51 mass% or more, more preferably 75 mass% or more, and still more preferably 95 mass% or more, of 100 mass% of the thermoplastic resin b.
Preferably, the thermoplastic resin b contains one or more thermoplastic resins having a melting point of 200 ℃ or more. By including a thermoplastic resin having a melting point of 200 ℃ or higher, heat resistance can be achieved. The melting point of the polyamide resin and/or other thermoplastic resin is preferably 200℃or higher, more preferably 200℃to 280℃and still more preferably 210℃to 280 ℃.
The thermoplastic resin B is preferably 15 to 49% by mass, more preferably 15 to 40% by mass, and even more preferably 20 to 39% by mass, based on 100% by mass of the thermoplastic resin composition B. When the thermoplastic resin b is 15 mass% or more, the dispersion form of the island-in-sea structure of the thermoplastic resin b as a matrix is easily ensured, and the refrigerant permeability and the oxygen permeability can be reduced. Further, the flexibility can be ensured by setting the thermoplastic resin b to 49 mass% or less.
The elastomer b contains at least a butyl-based elastomer. The elastomer b may be a butyl-based elastomer alone or in combination with other elastomers. By including the butyl elastomer, both low oxygen permeability and low refrigerant permeability and flexibility can be achieved. The butyl elastomer contained in the elastomer b may be the same as or different from the butyl elastomer contained in the elastomer a. Examples of the butyl elastomer include butyl rubber, halogenated butyl rubber, isobutylene-p-methylstyrene copolymer rubber, halogenated isobutylene-p-methylstyrene copolymer rubber, and styrene-isobutylene-styrene block copolymer rubber. Among them, halogenated isobutylene para-methylstyrene copolymer rubber is preferable as the elastomer b. As the halogenated isobutylene para-methylstyrene copolymer rubber, brominated isobutylene para-methylstyrene copolymer rubber and chlorinated isobutylene para-methylstyrene copolymer rubber may be exemplified. By incorporating the halogenated isobutylene para-methylstyrene copolymer rubber in the elastomer B, not only the flexibility, oxygen permeation resistance, and refrigerant permeation resistance of the hose are improved, but also the elastomer is dynamically crosslinked during kneading of the thermoplastic resin composition B, whereby the durability is improved. The butyl elastomer may be used alone or in combination of two or more.
Examples of the other elastomer than the butyl elastomer that can be contained in the elastomer b include an olefin elastomer, a styrene elastomer, a urethane elastomer, an ester elastomer, an amide elastomer, and an acrylic elastomer. It is also possible to mix one or more other elastomers with the butyl elastomer. In the case of mixing another elastomer, the butyl elastomer is preferably 51 mass% or more, more preferably 75 mass% or more, and still more preferably 95 mass% or more, based on 100 mass% of the elastomer b.
The elastomer B is preferably 51 to 85 mass%, more preferably 60 to 85 mass% of 100 mass% of the thermoplastic resin composition B. By setting the elastomer b to 51 mass% or more, flexibility can be ensured. Further, by setting the elastomer b to 85 mass% or less, the dispersion form of the island-in-sea structure in which the elastomer b is a domain can be ensured, and the refrigerant permeability and the oxygen permeability can be reduced to be excellent.
It is preferable that a part of the domains of the thermoplastic resin composition B be crosslinked. By crosslinking a part of the domains, the strength of the thermoplastic resin composition B can be improved, thereby further improving the durability of the inner layer. The method for crosslinking a part of the domain is not particularly limited, and examples thereof include dynamic crosslinking by adding a crosslinking agent and melt-kneading.
The tensile stress at 10% deformation of the thermoplastic resin composition B is preferably 10MPa or less, more preferably 1MPa to 9MPa, and still more preferably 1MPa to 7 MPa. By setting the tensile stress at 10% deformation to 10MPa or less, the flexibility of the inner layer can be made excellent. Further, it is preferable that the thermoplastic resin composition B has an Izod impact strength of-40℃which is free from damage and ensures the durability of the inner layer at low temperatures.
The oxygen permeability coefficient of the thermoplastic resin composition B is preferably 0.05cm 3 ·mm/(m 2 Day mmHg) or less, more preferably 0.0001cm 3 ·mm/(m 2 ·day·mmHg)～0.02cm 3 ·mm/(m 2 Day mmHg), more preferably 0.0001cm 3 ·mm/(m 2 ·day·mmHg)～0.01cm 3 ·mm/(m 2 Day mmHg). By making the oxygen permeability coefficient of the thermoplastic resin composition B0.05 cm 3 ·mm/(m 2 Day mmHg) or less, the low oxygen permeability of the inner layer can be made excellent, and the permeability of the refrigerant can be reduced. In the present specification, it is possible toAs described in examples below, the oxygen permeability coefficient was determined under conditions of 21℃and 50RH% using a member obtained by forming a sheet of the thermoplastic resin composition into a thickness of 0.2mm as a sample.
The Freon permeability coefficient of the thermoplastic resin composition B is preferably smaller than that of the thermoplastic resin composition A. This can effectively reduce the permeability of freon transported by the hose and suppress the generation of bubbles (blister). Therefore, the Freon permeability coefficient of the thermoplastic resin composition for the outer layer is preferably larger than that of the thermoplastic resin composition for the inner layer, and the ratio of the Freon permeability coefficient of the thermoplastic resin composition for the outer layer to that of the thermoplastic resin composition for the inner layer [ outer layer/inner layer ] is preferably 1.0 or more, more preferably 10 or more. In the present specification, as described in examples below, a member obtained by forming a sheet of the thermoplastic resin composition into a thickness of 0.2mm was used as a sample, and Freon HFO-1234yf was used to determine the Freon permeability coefficient from the permeation quantity at 80℃for 72 hours.
On the other hand, the water vapor permeability coefficient of the thermoplastic resin composition A is preferably smaller than that of the thermoplastic resin composition B. This can inhibit the permeation/diffusion of moisture from the outside of the hose, prevent the moisture absorption of the inner layer containing the polyamide resin, and maintain the low permeability of freon. Therefore, the water vapor permeability coefficient of the thermoplastic resin composition for the outer layer is preferably smaller than that of the thermoplastic resin composition for the inner layer, and the ratio of the water vapor permeability coefficient of the thermoplastic resin composition for the outer layer to that of the thermoplastic resin composition for the inner layer [ outer layer/inner layer ] is preferably smaller than 1.0, more preferably 0.4 or less.
The refrigerant transporting hose is composed of at least an outer layer having a layer formed of the thermoplastic resin composition A, a reinforcing layer, and an inner layer having a layer formed of the thermoplastic resin composition B. The outer diameter of the refrigerant transporting hose is not particularly limited, and for example, it is preferably 4mm to 30mm, and the inner diameter thereof is preferably 3mm to 25 mm.
The outer layer may be constituted only by a layer formed of the thermoplastic resin composition a, or may be laminated with other layers. The thickness of the outer layer is not particularly limited, and is preferably, for example, 0.5mm to 4 mm.
The inner layer may be constituted only by a layer formed of the thermoplastic resin composition B, or may be laminated with other layers. The thickness of the inner layer is not particularly limited, but is preferably, for example, 0.2mm to 3 mm.
The refrigerant transporting hose has a reinforcing layer between the outer layer and the inner layer. By having the reinforcing layer, the strength of the hose can be ensured, and the pressure resistance can be made excellent. The thickness of the reinforcing layer is not particularly limited, but is preferably, for example, 0.3mm to 3 mm.
The reinforcing material capable of forming the reinforcing layer is not particularly limited, and may be any of an organic material and an inorganic material. For example, the organic material may be a polymer (fibrous material), and examples thereof include polyester, polyamide, aramid, vinylon, rayon, PBO (poly (p-phenylene benzobisoxazole)), polyketone, and polyarylate. Examples of the inorganic material include metals, and hard steel wires such as brass-plated wires and galvanized wires are exemplified. The reinforcing material may also be a surface treated reinforcing material. From the viewpoints of excellent fatigue resistance and excellent cost performance, the reinforcing layer is preferably a polyester fiber.
The form of the reinforcing layer (reinforcing material) may be, for example, a form woven into a spiral structure and/or a woven layer (woven) structure. In addition, the reinforcing layer may be any one of a single reinforcing layer and a plurality of reinforcing layers.
The refrigerant transporting hose preferably has an adhesive layer interposed between the outer layer and the reinforcing layer and/or between the inner layer and the reinforcing layer. The durability of the hose can be further improved by the adhesive layer. The adhesive layer is preferably composed of, for example, an aqueous adhesive, a solvent-based adhesive, a chemical reaction-based adhesive, or a hot melt adhesive.
The refrigerant transporting hose may have an adhesive layer, a barrier layer, a rubber layer, or the like as the outer layer, the reinforcing layer, and the layers other than the inner layer, but preferably has no layer formed of vulcanized rubber. By not having a layer made of vulcanized rubber, the vulcanizing step can be omitted, and the man-hours for manufacturing the refrigerant transporting hose can be reduced to improve productivity.
The moisture permeability of the refrigerant transporting hose is preferably 1.5 mg/(cm) 2 240 h) or less, more preferably 1.3 mg/(cm) 2 240 h) is preferably as follows. When the moisture permeability of the refrigerant transporting hose was 1.5 mg/(cm) 2 240 h) or less, the permeation/diffusion of moisture and/or water vapor in the air into the hose can be suppressed, moisture absorption of the inner layer containing the polyamide resin can be prevented, and low permeability of freon can be maintained. In the present specification, the water permeation amount of the refrigerant transporting hose means a water permeation amount per 1cm at a temperature of 50℃and a relative humidity of 95% 2 The mass (mg) of water vapor that permeated from the outer surface to the inner surface during 240 hours. Regarding the moisture permeation amount of the refrigerant transporting hose, the refrigerant transporting hose filled with the weighed desiccant and having the opening sealed was placed in an environment having a temperature of 50℃and a relative humidity of 95%, the increase in the mass of the desiccant after 120 hours to 360 hours was measured, and the increase in the mass of 240 hours was divided by the inner surface area of the test sample to calculate the moisture permeation amount [ mg/(240 h cm) 2 )]。
The Freon HFO-1234yf permeation quantity (hereinafter, sometimes referred to as "refrigerant permeation quantity") of the refrigerant transporting hose is preferably 10 kg/(m) 2 Year) or less, more preferably 3.0 kg/(m) 2 Year) below. When the refrigerant permeation quantity of the refrigerant transporting hose is 3.0 kg/(m) 2 Year) or less, the transported freon can be prevented from penetrating and diffusing, and leaking to the outside. In the present specification, the refrigerant permeation amount of the refrigerant transporting hose means that the amount of the refrigerant permeation amount is 1m per 1m at 80 ℃ 2 The mass (kg) of refrigerant that permeated from the inner surface to the outer surface during one year (8760 hours) of the surface area of the inner peripheral surface of the hose. The refrigerant permeation amount of the refrigerant transporting hose was measured according to SAE J2064 AUG 2015. In each test sample of length 1.07m, every 1cm 3 Is filled with 70% + -3% refrigerant (HFO-1234 yf).The test sample was left to stand at 80℃for 25 days, the decrease in mass (refrigerant permeation amount) in the final predetermined period (5 to 7 days) of the 25-day period was measured, and the refrigerant permeation amount [ kg/(m) was calculated by unit conversion based on the value obtained by dividing the decrease by the inner surface area of the test sample 2 ·year)]。
The method for producing the refrigerant transporting hose is not particularly limited, and examples thereof include the following production methods: the thermoplastic resin composition B thus prepared is extruded in a circular tube shape by extrusion molding to form an inner layer, a reinforcing layer is formed on the outer peripheral surface of the inner layer, and an adhesive layer is optionally formed on the outer peripheral surface of the inner layer, and then the thermoplastic resin composition A thus prepared is extruded in a circular tube shape by extrusion molding to form an outer layer.
The present invention will be further described with reference to examples, but the scope of the present invention is not limited to these examples.
Examples
The thermoplastic resin compositions a and B shown in tables 1 to 2 were prepared by the following methods. First, butyl rubber was processed into particles by a rubber granulator (manufactured by sen mountain manufacturing company). In preparing the thermoplastic resin compositions (A-1 to A-5, A '-6 to A' -8, B-1, B '-2 to B' -3) each having the formulation shown in Table 1 to Table 2, the thermoplastic resin compositions were fed into a twin-screw kneading extruder (manufactured by Nippon Steel Co., ltd.) at a compounding ratio shown in Table 1 to Table 2, and kneaded at 235℃for 3 minutes. The kneaded material was extruded continuously in a strand form from an extruder, and after water cooling, cut with a cutter, thereby obtaining a thermoplastic resin composition a and a thermoplastic resin composition B in the form of pellets. Dynamic crosslinking is performed in a twin screw compounding extruder.
Using a T-die with a width of 200mmA single screw extruder (PLA technical Co., ltd.) was set to a barrel temperature and a die temperature higher than the melting point of the highest melting point component in the thermoplastic resin composition by 10℃and the temperature was set at a chill roll temperatureThe obtained pellets of the thermoplastic resin composition for inner/outer layers were molded into sheets having an average thickness of 0.2mm and sheets having an average thickness of 2mm at a temperature of 50℃and a collecting speed of 3 m/min. The sheet having a thickness of 0.2mm was cut and used, and the water vapor permeability coefficient, the oxygen permeability coefficient, and the Freon permeability coefficient, the tensile stress, the tensile breaking strength at 23℃and 150℃and the tensile breaking elongation at 23℃and 150℃were measured. In addition, izod impact strength at-40℃was measured using a sheet having a thickness of 2 mm.
Using dies with circular slotsA single screw extruder (manufactured by PLA technology and research), wherein the barrel temperature and the die temperature were set to a temperature 10 ℃ higher than the melting point of the highest melting point component in the thermoplastic resin composition B, and the pellets of the thermoplastic resin composition B for the inner layer were extruded into a circular tube-shaped inner layer on a mandrel coated with a release agent in advance so as to have a thickness of 0.8 mm. An adhesive was applied to the outer periphery of the obtained inner layer, and polyester fibers were woven using a weaving machine, thereby forming a reinforcing layer, and then an adhesive was applied. Further, use is made of +.A.with a die having a circular slot >The barrel temperature and the die temperature of a single screw extruder (manufactured by PLA skill and Co., ltd.) were set to a temperature 10℃higher than the melting point of the highest melting point component in the thermoplastic resin composition A, and pellets of the thermoplastic resin composition A for the outer layer were extruded into a tubular outer layer on the outer periphery of the reinforcing layer so as to have a thickness of 0.4 mm. The mandrel was pulled out, whereby hoses for transporting a refrigerant, which were formed of the inner layer, the reinforcing layer, and the outer layer, were produced (examples 1 to 7, comparative examples 1 to 3). Any refrigerant transporting hose does not have a layer formed of vulcanized rubber.
Using the obtained refrigerant transporting hose, the presence or absence of bubbles, the refrigerant permeation amount of the refrigerant transporting hose, and the moisture permeation amount were measured.
Further, the characteristics of the thermoplastic resin composition for the inner layer and the thermoplastic resin composition for the outer layer were measured by the following methods.
(1) Melt viscosity of thermoplastic resin composition for outer layer
The thermoplastic resin composition was dried at 100℃for 4 hours in advance, and a capillary having a length of 10mm and an inner diameter of 1mm was used by a capillary rheometer (manufactured by Toyo Seisakusho Co., ltd.) at a temperature of 250℃and a shearing rate of 243.2s -1 The melt viscosity (pa·s) was measured by detecting the load under the conditions of (a). The results obtained are shown in Table 1.
(2) Thermoplastic resin composition for inner layer and thermoplastic resin composition for outer layer
The sheet having a thickness of 0.2mm of the thermoplastic resin composition obtained as described above was used, and the water vapor permeation coefficient (unit: g.mm/(m) was measured using a water vapor permeation tester manufactured by GTRTEC Co., ltd.) under the conditions of a temperature of 60℃and a relative humidity of 95RH% 2 24 h)). The water vapor permeation coefficient of the thermoplastic resin composition for the outer layer is shown in Table 1. The ratio of the water vapor permeability coefficient of the thermoplastic resin composition for inner layer to the water vapor permeability coefficient of the thermoplastic resin composition for outer layer [ outer layer/inner layer ] was calculated]Will be compared with the outer/inner layer]The result of 0.4 or less was "excellent", and the ratio [ outer layer/inner layer ]]The results of more than 0.4 and less than 1.0 were set as "good", and the ratio [ outer layer/inner layer ]]The results of 1.0 or more are "poor", and are shown in tables 3 and 4.
(3) Thermoplastic resin composition for inner layer and thermoplastic resin composition for outer layer
The oxygen permeability coefficient (unit: cm) was measured using a sheet of the thermoplastic resin composition obtained as described above and an OXTRAN1/50 manufactured by MOCON, inc. under conditions of a temperature of 21℃and a relative humidity of 50RH% 3 ·mm/(m 2 Day mmHg)). The oxygen permeation coefficient of the thermoplastic resin composition for the outer layer is shown in Table 1, and the oxygen permeation coefficient of the thermoplastic resin composition for the inner layer is shown in Table 1The results are shown in Table 2.
(4) Freon permeability coefficient of thermoplastic resin composition for inner layer and thermoplastic resin composition for outer layer
The Freon permeability coefficient was measured using a sheet (hereinafter referred to as "sample sheet") of 0.2mm in thickness of the thermoplastic resin composition obtained as described above and using Freon HFO-1234 yf. Freon HFO-1234yf was poured into a stainless steel cup until half the cup volume, and the opening was sealed with a sample piece using a predetermined jig so as to cover the cup opening. In this state, a standing test was performed at a temperature of 80℃for 72 hours. Before and after the static test, the mass of the freon-containing cup sealed with the specimen was measured, the mass of the freon reduction was obtained, and the Freon permeability coefficient (unit: g.mm/(72 h.cm) 2 )). Regarding the obtained results, the ratio of the Freon permeability coefficient of the thermoplastic resin composition for outer layer to the Freon permeability coefficient of the thermoplastic resin composition for inner layer [ outer layer/inner layer ]Will be compared with the outer/inner layer]Results greater than 10 were set to "excellent" and will be compared [ outer/inner]The result of greater than 1.0 and less than 10 was set as "good", and the ratio [ outer layer/inner layer]The results of 1.0 or less are shown in tables 3 and 4, with the "difference".
(5) Tensile test characteristics of thermoplastic resin composition for inner layer and thermoplastic resin composition for outer layer
Using a sheet having a thickness of 0.2mm of the thermoplastic resin composition obtained as described above, it was die-cut into a JIS No. 3 dumbbell shape, and tensile tests at 23℃and 150℃were conducted at a tensile speed of 500 mm/min in accordance with the measurement method prescribed in JIS K6251 "method for determining the vulcanized rubber and thermoplastic rubber-tensile characteristics". From the obtained stress-strain curve, the tensile stress, tensile breaking strength, tensile elongation at break at 10% deformation at 23℃and tensile breaking strength and tensile elongation at break at 150℃were measured. The results obtained are shown in tables 1 and 2.
(6) Ehrlich test characteristics of thermoplastic resin composition for inner layer and thermoplastic resin composition for outer layer
Using a sheet of the thermoplastic resin composition obtained as described above, which had a thickness of 2mm, a notched test piece of 63.5mm in length, 10mm in width and 2mm in thickness was processed according to JIS K7110, and an Izod impact test was performed at-40 ℃. The results obtained are shown in tables 1 and 2. In the table, the term "NB" is used when the notched test piece was not broken even when the ehrlich impact test was performed.
(7) Bubble of refrigerant conveying hose
The refrigerant transporting hose obtained as described above was observed and evaluated for the presence or absence of bubbles. The results obtained are shown in tables 3 and 4.
(8) Flexibility of refrigerant transporting hose
As shown by way of example in fig. 2, one end portion of the refrigerant transporting hose in the longitudinal direction is fixed by a fixing member such as a clip, and a spring scale is attached to a position separated from the fixing position by a predetermined length L ((120+hose outer diameter/2) ×pi [ mm ]), and is stretched, so that the refrigerant transporting hose is semicircular-arc-shaped from the state shown by the broken line to the state shown by the solid line. Then, in a bent state where the hose inside radius R was 120mm, the tensile force F (unit: N) measured by a spring balance that stretched in the horizontal direction was obtained. The results obtained are shown in tables 3 and 4 as an index having a value of 100 in comparative example 1. The thicknesses of the inner layer and the outer layer of the hose of comparative example 3 were different from those of other hoses, and therefore, the evaluation was not performed.
(9) Refrigerant permeation amount of refrigerant transporting hose
The refrigerant permeation amount of the refrigerant transporting hose was measured according to SAE J2064 AUG 2015. The refrigerant transporting hose was cut into a length of 1.07m as a test sample, and was cut into pieces every 1cm 3 Is filled with 70% + -3% refrigerant (freon HFO-1234 yf). The test sample was allowed to stand in an environment of 80℃for 25 days, and the decrease in mass per day (24 hours) (refrigerant permeation amount) in the last predetermined period (5 to 7 days) of the 25-day period was measured. The amount of reduction was divided by the internal surface area of the test sample to calculate the annual (8760 hours) refrigerantRefrigerant permeation amount of the hose for transportation (unit: kg/(m) 2 Year)). The smaller the value of the refrigerant permeation amount, the more excellent the refrigerant permeation resistance is. If the refrigerant permeability is 3 kg/(m) 2 Year) or less, it can be evaluated as having refrigerant permeation resistance that is practically sufficient. The results obtained are shown in tables 3 and 4 as follows: the refrigerant permeation quantity was 3.0 kg/(m) 2 Year) is "excellent", and the refrigerant permeation amount is more than 3.0 kg/(m) 2 Year) and less than or equal to 10 kg/(m) 2 Year) is "good", and the refrigerant permeation amount is more than 10 kg/(m) 2 Year) is set to "bad".
(10) Moisture permeation amount of refrigerant transporting hose
After leaving the refrigerant transporting hose to stand in an oven at 50 ℃ for 5 hours, the test sample was filled with a desiccant having a volume corresponding to 80% of the internal volume and sealed. The test sample was left standing at 50℃and a humidity of 95RH%, and the increase in mass of the desiccant after 120 hours to 360 hours was measured. The increase in mass (unit: mg) of the 240 hour amount obtained was divided by the internal surface area (unit: cm) of the test sample 2 ) The moisture permeation amount of the refrigerant transporting hose was calculated (unit: mg/(cm) 2 240 h)). The results obtained are shown in tables 3 and 4 as follows: the water permeability was set to 1.3 mg/(cm) 2 240 h) was set to "excellent", and the water permeation amount was set to be more than 1.3 mg/(cm) 2 240 h) and less than or equal to 1.5 mg/(cm) 2 The result of 240 h) was "good", and the moisture permeation amount was more than 1.5 mg/(cm) 2 240 h) is set to "bad".
TABLE 1
TABLE 2
The types of the raw materials used in tables 1 and 2 are shown below.
Resin a-1: propylene homopolymer, prime Polypro J108M, manufactured by Prime Polymer Co., ltd., melting point 165 ℃.
Resin a-2: propylene-ethylene random copolymer, novatecMG05ES, manufactured by JapanPolypropylene Corporation, melting point 147 ℃.
Resin a-3: propylene-ethylene block copolymer, novatecBC06C, manufactured by JapanPolypropylene Corporation, melting point 165 ℃.
Resin b-1: polyamide 6, nylon 6"UBE Nylon" 1011FB, manufactured by Yu Xingjingsu Co., ltd, melting point 225 ℃.
Resin b-2: polyamide 12, nylon 12"UBESTA" (registered trademark) 3012U, manufactured by Yu Xingjingsu Co., ltd, melting point 176 ℃.
Resin b-3: polyamide 612, nylon 6/12 copolymer "UBE nylon" 7024B, manufactured by Yu Xingzhi Co., ltd., melting point 201 ℃.
Elastomer a: brominated butyl rubber, manufactured by ExxonMobil Chemical, exxon Bromobutyl2255".
Elastomer b: brominated isobutylene p-methylstyrene copolymer rubber, "EXXPRO" (registered trademark) 3745 manufactured by ExxonMobil Chemical agency.
Zinc oxide: three types of zinc oxide are manufactured by chemical industry.
Crosslinking agent: N-phenyl-N' - (1, 3-dimethylbutyl) -p-phenylenediamine, "SANTOFLEX" (registered trademark) 6PPD, manufactured by Solutia corporation.
Viscosity stabilizer: calcium stearate, made by Sakai chemical industry Co., ltd.
TABLE 3
TABLE 4
| Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Resin composition for forming outer layer | A'-6 | A'-7 | A'-8 |
| Thickness of outer layer [ mm ]] | 0.4 | 0.4 | 0.8 |
| Adhesive between outer layer/reinforcing layer | Adhesive-1 | Adhesive-2 | Adhesive-2 |
| Construction of the reinforcing layer | PET fiber | PET fiber | PET fiber |
| Adhesive between inner layer/reinforcing layer | Adhesive-2 | Adhesive-2 | Adhesive-1 |
| Resin constituting inner layerComposition and method for producing the same | B-1 | B-1 | B'-3 |
| Thickness of inner layer [ mm ]] | 0.8 | 0.8 | 0.4 |
| With or without bubbles | Without any means for | Without any means for | Has the following components |
| Flexible pipe (index) | 100 | 77 | - |
| Freon permeability ratio (outer/inner)] | Excellent (excellent) | Good grade (good) | Difference of difference |
| Refrigerant permeation quantity | Excellent (excellent) | Excellent (excellent) | Difference of difference |
| Ratio of water vapor permeability coefficients] | Good grade (good) | Good grade (good) | Difference of difference |
| Moisture penetration amount | Good grade (good) | Difference of difference | Excellent (excellent) |
The types of the raw materials used in tables 3 and 4 are shown below.
Thermoplastic resin compositions A-1 to A-5, A '-6 to A' -8 constituting the outer layer: refer to table 1.
PET fiber: polyethylene terephthalate fibers.
Adhesive-1: an acid-modified polyolefin adhesive.
Adhesive-2: moisture-curable urethane adhesives.
Thermoplastic resin composition B-1, B '-2, B' -3 constituting the inner layer: refer to table 2.
As apparent from table 3, it was confirmed that: the refrigerant transporting hoses of examples 1 to 7 were low in water vapor permeability and freon permeability, and the hoses were soft and lightweight. In the refrigerant transporting hose of example 7, since the elastomer B in the resin composition (B' -2) constituting the inner layer is less than 51 mass%, the effect of improving the flexibility of the hose tends to be small.
As apparent from table 4, it was confirmed that: in the refrigerant transporting hose of comparative example 1, since the elastomer a in the resin composition (a' -6) constituting the outer layer was less than 51 mass%, the flexibility of the hose was inferior to that of examples 1 to 7.
In the refrigerant transporting hose of comparative example 2, the thermoplastic resin a contained a polyamide resin instead of a polyolefin resin in the resin composition (a' -7) constituting the outer layer, and thus was poor in water vapor permeation.
In the refrigerant transporting hose of comparative example 3, the thermoplastic resin a contained a polyamide resin instead of a polyolefin resin in the resin composition (a '-8) constituting the outer layer, and the thermoplastic resin B contained a polyolefin resin instead of a polyamide resin in the resin composition (B' -3) constituting the inner layer, so that the refrigerant permeability was poor.
Description of the reference numerals
1: a refrigerant transporting hose;
2: an inner layer;
3: a reinforcing layer;
4: an outer layer.
Claims (16)
1. A refrigerant transporting hose comprising at least an outer layer, a reinforcing layer and an inner layer, characterized in that,
the outer layer having at least a layer formed of a thermoplastic resin composition A, the inner layer having at least a layer formed of a thermoplastic resin composition B,
the thermoplastic resin composition A has an island structure comprising a thermoplastic resin a as a matrix and an elastomer a as a domain, the thermoplastic resin a contains at least a polyolefin resin, the elastomer a contains at least a butyl elastomer, and the elastomer a is 51 to 85 mass% of 100 mass% of the thermoplastic resin composition A,
the thermoplastic resin composition B has an island structure having a matrix of a thermoplastic resin B and a domain of an elastomer B, and the thermoplastic resin B contains at least a polyamide resin and the elastomer B contains at least a butyl elastomer.
2. The refrigerant transporting hose according to claim 1, wherein,
in 100 mass% of the thermoplastic resin composition B, the elastomer B is 51 to 85 mass%.
3. The refrigerant transporting hose according to claim 1 or 2, wherein,
the refrigerant transporting hose does not have a layer formed of vulcanized rubber.
4. A refrigerant transporting hose according to any one of claims 1 to 3, wherein,
the Freon permeability coefficient of the thermoplastic resin composition B is smaller than that of the thermoplastic resin composition A.
5. The refrigerant transporting hose according to any one of claims 1 to 4, wherein,
the water vapor permeability coefficient of the thermoplastic resin composition a is smaller than that of the thermoplastic resin composition B.
6. The refrigerant transporting hose according to any one of claims 1 to 5, wherein,
the thermoplastic resin a at least comprises a polypropylene resin, and the elastomer a at least comprises halogenated butyl rubber.
7. The refrigerant transporting hose according to any one of claims 1 to 6, wherein,
the thermoplastic resin b at least comprises a polyamide 6 resin, and the elastomer b at least comprises halogenated isobutylene p-methylstyrene copolymer rubber.
8. The refrigerant transporting hose according to any one of claims 1 to 7, wherein,
a portion of the domains of the thermoplastic resin composition a and/or a portion of the domains of the thermoplastic resin composition B are crosslinked.
9. The refrigerant transporting hose according to any one of claims 1 to 8, wherein,
the refrigerant transporting hose is provided with an aqueous adhesive, a solvent adhesive, a chemical reaction adhesive or a hot melt adhesive interposed between the outer layer and the reinforcing layer and/or between the inner layer and the reinforcing layer.
10. The refrigerant transporting hose according to any one of claims 1 to 9, wherein,
the thermoplastic resin composition A had a shear rate of 243.2s at 250 ℃ -1 The melt viscosity is 1000 Pa.s or less.
11. The refrigerant transporting hose according to any one of claims 1 to 10, wherein,
the thermoplastic resin a includes one or more thermoplastic resins having a melting point of 150 ℃ or more, and the thermoplastic resin b includes one or more thermoplastic resins having a melting point of 200 ℃ or more.
12. The refrigerant transporting hose according to any one of claims 1 to 11, wherein,
The thermoplastic resin composition A has a tensile stress of 10% or less at 10% deformation and a water vapor permeability coefficient of 3.0 g.mm/(m) 2 24 h) or below.
13. The refrigerant transporting hose according to any one of claims 1 to 12, wherein,
the thermoplastic resin composition B has a tensile stress of 10% or less at 10% deformation and an oxygen permeability coefficient of 0.05cm 3 ·mm/(m 2 Day mmHg) or less.
14. The refrigerant transporting hose according to any one of claims 1 to 13, wherein,
the thermoplastic resin composition A has a tensile breaking strength of 3MPa or more at 23 ℃ and a tensile breaking elongation of 200% or more.
15. The refrigerant transporting hose according to any one of claims 1 to 14, wherein,
the thermoplastic resin composition A has a tensile breaking strength of 0.4MPa or more at 150 ℃ and a tensile breaking elongation of 50% or more at 150 ℃.
16. The refrigerant transporting hose according to any one of claims 1 to 15, wherein,
the thermoplastic resin composition A and the thermoplastic resin composition B were nondestructive in Izod impact strength at-40 ℃.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-124601 | 2021-07-29 | ||
| JP2021-162526 | 2021-10-01 | ||
| JP2021162526 | 2021-10-01 | ||
| PCT/JP2022/027057 WO2023008137A1 (en) | 2021-07-29 | 2022-07-08 | Hose for refrigerant transportation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117642570A true CN117642570A (en) | 2024-03-01 |
Family
ID=90016768
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280050249.6A Pending CN117642570A (en) | 2021-07-29 | 2022-07-08 | Hose for conveying refrigerant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117642570A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06294485A (en) * | 1993-04-07 | 1994-10-21 | Bridgestone Corp | Refrigerant transporting hose |
| CN1212041A (en) * | 1996-02-20 | 1999-03-24 | 株式会社明治橡胶化成 | Refrigerant conveying hose |
| CN1498763A (en) * | 2002-10-28 | 2004-05-26 | ס��� �ҵ��ʽ���� | Ink tube of ink-jetting printer |
| JP2006322325A (en) * | 2005-05-17 | 2006-11-30 | Japan Servo Co Ltd | Motor fan and method of correcting balance of the motor fan |
| JP2013047489A (en) * | 2011-08-29 | 2013-03-07 | Minebea Motor Manufacturing Corp | Blower |
| JP2020045470A (en) * | 2018-09-21 | 2020-03-26 | 横浜ゴム株式会社 | Inner liner for tier and pneumatic tire |
-
2022
- 2022-07-08 CN CN202280050249.6A patent/CN117642570A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06294485A (en) * | 1993-04-07 | 1994-10-21 | Bridgestone Corp | Refrigerant transporting hose |
| CN1212041A (en) * | 1996-02-20 | 1999-03-24 | 株式会社明治橡胶化成 | Refrigerant conveying hose |
| CN1498763A (en) * | 2002-10-28 | 2004-05-26 | ס��� �ҵ��ʽ���� | Ink tube of ink-jetting printer |
| JP2006322325A (en) * | 2005-05-17 | 2006-11-30 | Japan Servo Co Ltd | Motor fan and method of correcting balance of the motor fan |
| JP2013047489A (en) * | 2011-08-29 | 2013-03-07 | Minebea Motor Manufacturing Corp | Blower |
| JP2020045470A (en) * | 2018-09-21 | 2020-03-26 | 横浜ゴム株式会社 | Inner liner for tier and pneumatic tire |
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