WO2016094762A1 - Revêtements abs améliorés et armoires de refroidissement les contenant - Google Patents

Revêtements abs améliorés et armoires de refroidissement les contenant Download PDF

Info

Publication number
WO2016094762A1
WO2016094762A1 PCT/US2015/065177 US2015065177W WO2016094762A1 WO 2016094762 A1 WO2016094762 A1 WO 2016094762A1 US 2015065177 W US2015065177 W US 2015065177W WO 2016094762 A1 WO2016094762 A1 WO 2016094762A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
liner
blowing agent
interior space
abs
Prior art date
Application number
PCT/US2015/065177
Other languages
English (en)
Inventor
Bin Yu
Rajiv Banavali
Original Assignee
Honeywell International Inc.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Honeywell International Inc. filed Critical Honeywell International Inc.
Priority to CN201580076081.6A priority Critical patent/CN107208956A/zh
Publication of WO2016094762A1 publication Critical patent/WO2016094762A1/fr

Links

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D23/00—General constructional features
    • F25D23/06—Walls
    • F25D23/065—Details
    • F25D23/066—Liners

Definitions

  • the present invention relates to devices, such as cold boxes, refrigerators, freezers and the like which comprise an insulated cooling cabinet having improved liners.
  • Devices such as refrigerators, cold boxes, freezers and the like include a cooling cabinet that usually contains an outer cabinet (usually metal), an inner plastic liner and an insulating foam core, typically polyurethane foam, in the space between the metal cabinet and the liner.
  • the foam insulation contains cells that are filed with the blowing agent that was used to form the polyurethane foam.
  • halogenated methane such as fluorotrichloromethane (CFC-1 1 ) was most commonly used as the blowing agent. More recently, more environmentally acceptable substitutes, such as HCFCs, including 2-fluoro-2,2-dichloroethane (HCFC-141 b) and 2,2-dichloro-1 , 1 ,1 -trifluoroethane (HCFC-123), and HFCs, including HFC-245fa, have been used. More recently, the use of 1 ,1 ,1 -trifluoro,3-chloropropene (HFCO-1233zd) has also been proposed for use a blowing agent in such applications.
  • HCFCs including 2-fluoro-2,2-dichloroethane (HCFC-141 b) and 2,2-dichloro-1 , 1 ,1 -trifluoroethane (HCFC-123)
  • HFCs including HFC-245fa
  • blowing agent used to form polyurethane foams In general, it is not uncommon for some portion of the blowing agent used to form polyurethane foams to escape over time from the cells that contain them. As a result, the design of such devices must take into account the interrelationship that the blowing agent will have with the liner of the refrigerator, freezer and the like. For this reason, many of the blowing agents which have been used to form polyurethane foams (such as Freon (CFC-1 1 ) and Freon substitutes, such as 2-fluoro-2,2 dichloroethane and 2,2- dichloro-1 , 1 ,1 -trifluoroethane,(HCFC 141 b and HCFC 123, respectively), have been studied for their impact on liners and have been found to potentially cause
  • the liner can be formed from a large variety of materials. (See for example, US Patent 6,589,646, which is incorporated herein by reference).
  • One of the most important and commonly used materials to form the liner is acrylonitrile-butadiene- styrene (ABS) resin.
  • ABS resins One particular example of such ABS resins is disclosed in US Patent 5,324,589, which is incorporated herein by reference.
  • GPPS glass-clear polystyrene
  • HIPS impact-modified polystyrene
  • styrene 6 copolymers, such as styrene-butadiene block copolymers
  • ASA styrene-butadiene block copolymers
  • polyolefins such as polyethylene or polypropylene
  • acrylates and methacrylates such as PMMA
  • PCs polycarbonates
  • PVC polyvinyl chloride
  • PET terephthalate
  • the present invention provides devices, such as cold boxes, refrigerators, freezers and the like, and improved liners well adapted for use in such devices and other devices that utilize liners, especially liners made from thermoplastic resins and even more preferably liners made from relatively glassy polymers, such as thermoplastic ABS resin.
  • liners especially liners made from thermoplastic resins and even more preferably liners made from relatively glassy polymers, such as thermoplastic ABS resin.
  • ESC is a particular problem with glassy polymers, like ABS, when exposure to certain organic materials can result in cracking or crazing upon very modest applied stress (often an order of magnitude lower than the actual tensile or flexural strength of the polymer).
  • the present invention provides an improved liner comprising: (a) a first layer formed, and preferably thermoformed, from ABS polymer or resin; and a second layer or coating bound to the first layer, directly and/or indirectly, to provide said first layer with protection against exposure to blowing agent compounds that have or may have a deleterious effect on the properties of the first layer.
  • the second, protective layer or coating comprises a layer or coating formed from an amorphous or semi-crystalline polyamide resin or polymer having sufficient composition and/or thickness to substantially inhibit the migration of blowing agent there through, and even more preferably to inhibit the migration of blowing agent comprising HFCO-1233zd, and even more preferable trans 1233zd (1233zd(E)).
  • the second layer or coating is formed from a resin that forms a semi-crystalline polymer, and even more particularly from Nylon 6.
  • the second, protective layer or coating comprises a layer or coating formed from a material, and preferably a polymeric material, that is capable of absorbing a substantial portion of blowing agent molecules, and particularly HFCO-1233zd, preferably trans 1233zd.
  • the second, protective layer is formed from a thermoplastic polyolefin, and even more preferably from polyethylene or polypropylene.
  • the second, protective layer or coating comprises a layer or coating formed from a material, and preferably a polymeric material, that includes components capable of reacting with the blowing agent molecules, and preferably blowing agent comprising HFCO-1233zd, and to thereby protect the first layer from exposure to such blowing agent molecules.
  • the device comprises: a cabinet or cabinet-like structure having an inner compartment, preferably for containing food, beverages and the like in a relatively cold condition; insulating foam to prevent passage of heat into or out of the inner compartment; and a liner comprising at least two layers according to the present invention between said insulating foam and said inner compartment, wherein at least a first layer of the liner has a surface facing toward the open space of the inner compartment and at least a second layer of the liner has a surface facing toward said insulating foam.
  • the foam is a closed cell foam, and more preferably a closed cell polyurethane foam, in which the blowing agent comprises in substantial part, and more preferably at least about 50% by weight, and even more preferably at least 75% by weight, of 1 -chloro-3,3,3-trifluoropropene (1233zd), and even more preferably trans 1233zd.
  • the integrity and desirable characteristics associated with ABS liners can be maintained in such devices when a protective layer according to the present invention is configured to inhibit exposure of the first layer to such HFCO-1233zd molecules that are degassed or otherwise emitted from the foam.
  • liners of the present invention are used in the refrigerator which is insulated with a foam containing a highly thermally efficient halogenated olefin blowing agent, and in particular HFCO-1233zd, (preferably trans 1233zd), while maintaining durability of the liner and avoidance of stress cracking or other deleterious effects.
  • a highly thermally efficient halogenated olefin blowing agent and in particular HFCO-1233zd, (preferably trans 1233zd)
  • an object of one embodiment of the inventions is the provision of an thermal insulating device for keeping foodstuffs cool, cold or frozen in which the foam is a closed-cell foam having a halogenated olefin contained in at least a portion of the cells, and more preferably 1 -chloro-3,3,3-trifluoropropene (1233zd), and even more preferably trans 1233zd and a liner according to the present invention, and even more preferably a liner of the present invention having a thickness of not greater than about 6 mm.
  • the present invention relates to a device for containing item(s) or fluid(s) and maintaining for at least an extended period of time (eg, at least 1 hour) a temperature inside said container either below or above ambient temperature.
  • an extended period of time eg, at least 1 hour
  • the devices of the present invention include (a) a container or compartment, preferably having an opening that is either open or closable by a door, hatch, sliding cover or the like, for holding an item(s) or fluid(s), and preferably food and/or beverage items, to be maintained in a cooled or heated condition, and most preferably in a cooled condition, relative to the ambient temperature, said container having an inner liner in accordance with the present invention and which corresponds at least in part to the interior shape of the compartment or container; and (b) thermal insulation comprising a polymeric material having closed cells therein wherein said cells are formed from and/or contain blowing agent comprising, and preferably comprising in major proportion by weight, a haloalkene according to Formula IA:
  • each R is independently CI, F, H, or CF 3 , provided that the total number of carbon atoms is either 3 or 4,
  • Y is CF 3
  • n 0 or 1
  • thermal insulation being disposed with respect to said container or compartment so as to inhibit the flow of heat into and/or out of the compartment and being adjacent or proximate to said liner, particularly such that said liner will be exposed to said blowing agent which escapes from said thermal insulation.
  • the device further includes a heat transfer system for adding and/or removing heat from the compartment or container by use of a heat transfer fluid.
  • the heat transfer fluid comprises a haloalkene Formula IB:
  • each R is independently CI, F or H
  • Y is CF 3
  • n 0 or 1 .
  • the container or compartment for holding an item(s) or fluid(s) of the present invention include refrigerators, freezers, vending machines, reach- in coolers, transport refrigeration units, and water heater heat pumps.
  • the haloalkene according to Formula IA is selected from the group consisting of 1 ,1 ,1 ,4,4,4-hexafluoro-2-butene (1336), 1 -chloro-3,3,3- trifluoropropene (1233zd) (preferably trans 1233zd), 1 ,3,3,3-tetrafluoropropene
  • the monochloro,trifluoropropene comprises, in preferred embodiments comprises at least about 75% by weight, and even more preferably in certain embodiments consists essentially of, trans 1 -chloro-3,3,3- trifluoropropene (transHFCO-1233zd)).
  • FIG. 1 is a schematic representation of a refrigerator cabinet.
  • FIG. 2 is a schematic drawing of the plastic liner serving as plastic wall of the refrigerator shown in FIG. 1 .
  • a liner and particularly and preferably an ABS liner
  • advantageous properties of a liner can be achieved according to the present invention by desirable finish, chemical resistance, and impact resistance via the first layer of the liner, and without losing or negatively impacting those properties, utilizing the second layer to ensure the liner ensure that the liner does not undergo excessive blistering, cracking (crazing) and loss of impact properties (embrittlement), after exposure during use to the halogenated hydrocarbon blowing agents, and particularly HFCO-1233zd, resulting from the insulation.
  • the insulation is foamed in place insulation.
  • ABS resin is a grade that provides deep draw capability in thermoforming operations.
  • general purpose ABS grades which are commercially available for extrusion are particularly suitable for use as the first layer of the present liner. It is preferred that the ABS resin layer have a high gloss.
  • the ABS resin layer of this invention comprise three building blocks, unsaturated nitrile monomer, diene rubber, and vinyl aromatic monomer, (for example, acrylonitrile, polybutadiene rubber, and styrene), which can vary widely with respect to the percentage used.
  • the proportion of these components can be tailored to desired needs such as chemical resistance, heat stability, impact resistance, toughness, rigidity, and processing needs.
  • the relative proportion of these components will vary with respect to the desired end use according to the needs of those skilled in the art.
  • butadiene provides impact resistance.
  • a larger proportion of butadiene may be utilized to provide low temperature impact resistance.
  • the styrene component may be high so as to enhance processing ease and reduce costs.
  • ABS is not a random terpolymer of acrylonitrile, butadiene, and styrene but a mixture of styrene-acrylonitrile copolymer grafted with butadiene.
  • the butadiene provides a rubber phase which exists as discrete particles.
  • the ABS resin may be prepared according to any of the methods well known in the art including emulsion, bulk, mass or suspension processes or a combination of these processes.
  • the ABS resin is made by emulsion polymerization in order to have a high gloss appearance.
  • ABS resins examples include those provided by Cheil under the trade designation Starex QU-191 S resin and by Inuos under the trade designation Lustran ABS 620, particularly the general purpose grades, the extrusion grades, and blow molding grades.
  • nylon 6 The amide resins commonly used and known by those skilled in the art generically as “nylon” may be adapted for use according to the present invention in view of the teachings contained herein.
  • the amide resins can be formed from condensation reactions of diamine(s) and dicarboxylic acid(s), such as is the case with nylon 6,6, or by ring opening polymerization of caprolactam (nylon 6).
  • nylon 6 is preferred.
  • polyolefin according to the present invention is selected from high- density polyethylene (HDPE), cross-linked polyethylene (XLPE), medium-density polyethylene (MDPE), linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), very-low-density polyethylene (VLDPE), copolymers with any of the above, and any combinations of any two or more of these.
  • the polyolefin is PE wax.
  • polyethylene waxes according to certain embodiments have average molecular weights in the range of about 1500 grams per mole (g/mol) to about 20,000 g/mol. High grade polyethylene waxes may be obtained by the controlled
  • the second layer comprises a polymeric film, layer or coating having embedded therein a component that reacts with one or more of the blowing agent compounds, and preferably HFCO-1233zd, and in this way inhibit, and preferably substantially inhibit the exposure of those blowing agent compounds to the first layer of the liner.
  • the polymer is polyethylene or polyamide
  • the blowing agent reactive component is an amine and in certain embodiments preferably a tertiary amine.
  • Preferred tertiary amines are triethylenediamine
  • the polymer which is used in the second layer comprises a polyolefin and/or polyamide and the blowing agent reactive component is embedded in at least a portion of one or both thereof.
  • the multi-layer liner of the present invention may be formed by co-extrusion, including in preferred embodiments bilayer co-extrusion.
  • an adhesive or other material may be used to join or bond the first and second layer of the liner.
  • one layer is coated onto the other layer; such a technique is preferred for embodiments in which the second layer is a polyolefin layer but may be used with the other
  • any two or more of the embodiments described herein may be combined to form a three layer liner, or that all three embodiments may combined to form a four layer liner.
  • a variety of techniques may be used to form the multi-layer liner, and all such techniques are considered to be within the scope of the present invention.
  • the liners of the present invention may be used in a variety of applications.
  • the liners are included in in relatively small refrigeration systems such as domestic refrigerators and freezers, vending machines, reach-in coolers, transport refrigeration units and the like, can provide such systems with highly advantageous energy performance while at the same time providing such systems that have extraordinarily low environmental impact and are durable and long-lasting.
  • One aspect of the present invention provides systems, devices and methods for containing item(s) or fluid(s) at a temperature either below or above the ambient temperature, preferably for an extended period of time (such as at least several hours or days).
  • Such systems, devices, and methods include (a) a container or compartment for holding an item(s) or fluid(s) to be maintained in a cooled or heated condition relative to the ambient; (b) thermal insulation disposed with respect to said container or
  • the insulation comprising a polymeric material having closed cells therein wherein said cells are formed from and/or contain a blowing agent.
  • the blowing agent comprises a haloalkene according to Formula IA:
  • each R is independently CI, F, H, or CF 3 , provided that the total number of carbon atoms is either 3 or 4,
  • R' is (CR 2 ) n Y
  • Y is CF 3
  • n 0 or 1 ;
  • each R is independently CI, F or H
  • R' is (CR 2 ) n Y
  • Y is CF 3
  • n 0 or 1 .
  • container and compartment are used in the broad sense and are not limited to containers that fully enclose or surround the items or fluid being contained.
  • containers that have relatively permanent openings such as would be the case in reach-in coolers and refrigerators, are encompassed within the meaning of this term.
  • the compound of Formula IA comprises, and preferably comprises at least about 25% by weight, and more preferably comprises at least about 30% by weight, and even more preferably consists essentially of one or more compounds selected from 1 ,1 ,1 ,4,4,4-hexafluoro-2-butene (1336mzz), 1 -chloro- 3,3,3-trifluoropropene (1233zd), and 1 ,3,3,3-tetrafluoropropene (1234ze).
  • the 1 -chloro-3,3,3-trifluoropropene (1233zd) is trans-1 -chloro-3,3,3-trifluoropropene (1233zd(E))
  • the 1 ,3,3,3- tetrafluoropropene (1234ze) is transi ,3,3,3-tetrafluoropropene (1234ze(E))
  • the 1 ,1 ,1 ,4,4,4-hexafluoro-2-butene (1336mzz) is cisl ,1 ,1 ,4,4,4-hexafluoro-2-butene (1336mzz (Z)).
  • the compound of Formula 1 A comprises, and preferably comprises at least about 50% by weight, and more preferably comprises at least about 70% by weight, and even more preferably consists essentially of one or more compounds selected from 1 ,1 ,1 ,4,4,4-hexafluoro-2-butene (1336mzz), 1 -chloro-3,3,3- trifluoropropene (1233zd), and 1 ,3,3,3-tetrafluoropropene (1234ze), and the compound of Formula IB comprises, and preferably comprises at least about 50% by weight, and more preferably comprises at least about 70% by weight, and even more preferably consists essentially of one or more compounds selected from 1 -chloro-3,3,3- trifluoropropene (1233zd) (preferably trans-1233zd), 2,3,3,3-tetrafluoropropene (1234yf) and 1 ,3,3,3-tetrafluoropropene (1234ze), and the compound of Formula IB comprises, and preferably comprises at
  • the 1 -chloro-3,3,3-trifluoropropene (1233zd) is transl -chloro-3,3,3- trifluoropropene (1233zd(E))
  • the 1 ,3,3,3-tetrafluoropropene (1234ze) is transl ,3,3,3- tetrafluoropropene (1234ze(E))
  • the 1 ,1 ,1 ,4,4,4-hexafluoro-2-butene (1336) is cisl ,1 ,1 ,4,4,4-hexafluoro-2-butene (1336(Z)).
  • the compound of Formula 1 A comprises, and preferably comprises at least about 50% by weight, and more preferably comprises at least about 70% by weight, and even more preferably consists essentially of one or more compounds selected from 1 ,1 ,1 ,4,4,4-hexafluoro-2-butene (1336mzz), and 1 - chloro-3,3,3-trifluoropropene (1233zd) (preferably trans 1233zd), and the compound of Formula IB comprises, and preferably comprises at least about 50% by weight, and more preferably comprises at least about 70% by weight, and even more preferably consists essentially of one or more compounds selected from 2,3,3,3-tetrafluoropropene (1234yf) and 1 ,3,3,3-tetrafluoropropene (1234ze) (preferably trans-1234ze).
  • the compound of Formula 1 A comprises, and preferably comprises at least about 50% by weight, and more preferably comprises at least about 70% by weight, and even more preferably consists essentially of one or more compounds selected from 1 ,1 ,1 ,4,4,4-hexafluoro-2-butene (1336mzz) and 1 - chloro-3,3,3-trifluoropropene (1233zd) (preferably trans 1233zd), and the compound of Formula IB comprises, and preferably comprises at least about 50% by weight, and more preferably comprises at least about 70% by weight, and even more preferably consists essentially of 1 ,3,3,3-tetrafluoropropene (1234ze), and even more preferably trans-1234ze.
  • the compound of Formula 1 A comprises, and preferably comprises at least about 50% by weight, and more preferably comprises at least about 70% by weight, and even more preferably consists essentially of 1 ,1 ,1 ,4,4,4- hexafluoro-2-butene (1336mzz) (preferably cis-1336mzz) and the compound of Formula IB comprises, and preferably comprises at least about 50% by weight, and more preferably comprises at least about 70% by weight, and even more preferably consists essentially of 1 ,3,3,3-tetrafluoropropene (1234ze), and even more preferably trans- 1234ze.
  • the compound of Formula 1 A comprises, and preferably comprises at least about 50% by weight, and more preferably comprises at least about 70% by weight, and even more preferably consists essentially of one or more compounds selected from 1 ,1 ,1 ,4,4,4-hexafluoro-2-butene (1336mzz) (preferably cis-1336) and the compound of Formula IB comprises, and preferably comprises at least about 50% by weight, and more preferably comprises at least about 70% by weight, and even more preferably consists essentially of and 1 -chloro-3,3,3- trifluoropropene (1233zd) (preferably trans-1233zd).
  • the compound of Formula 1 A comprises, and preferably comprises at least about 50% by weight, and more preferably comprises at least about 70% by weight, and even more preferably consists essentially of one or more compounds selected from 1 -chloro-3,3,3-trifluoropropene (1233zd) (preferably trans-1233zd) and the compound of Formula IB comprises, and preferably comprises at least about 50% by weight, and more preferably comprises at least about 70% by weight, and even more preferably consists essentially of and 1 ,3,3,3-tetrafluoropropene (1234ze), and even more preferably trans-1234ze.
  • the compound of Formula 1 A comprises at least about 50% by weight, and more preferably comprises at least about 70% by weight, and even more preferably consists essentially of 1 -chloro-3,3,3-trifluoropropene (1233zd) (preferably transHFCO-1233zd), and the compound of Formula IB comprises, and preferably comprises at least about 50% by weight, and more preferably comprises at least about 70% by weight, and even more preferably consists essentially of 2,3,3,3- tetrafluoropropene (1234yf).
  • Figures 1 and 2 showing a refrigerator appliance which includes a cabinet and is defined by an outer cabinet metal wall 1 , an inner liner wall 2, and a body of foamed-in-place insulation 3 therebetween.
  • an outer cabinet metal wall 1 an inner liner wall 2
  • a body of foamed-in-place insulation 3 therebetween.
  • the particular shape and configuration shown in Figures 1 and 2 is for illustration only and that numerous and various shapes and configurations of the cabinet, and therefore the cabinet liner wall 2, may be used within the broad scope of the present invention.
  • the thickness of the liner wall 2 is relevant to certain preferred embodiments of the present invention, but otherwise the particular shape and configuration of the cabinet formed by the liner wall can be according to any design as required for the particular application.
  • inner liner wall 2 is thermoformed into the desired configuration, one example of which is shown in figure 2.
  • inner liner wall 2 is a thermoformed product of liner sheet made from one or more of the materials described herein, or a combination of sheets which have been laminated or otherwise integrated to form the liner wall 2.
  • the liner of the present invention has a thickness of not greater than about 10 mm, more preferably not greater than about 5 mm, more preferably not greater than about 4 mm, and even more preferably in certain embodiments not greater than 3 mm, or the other preferred thicknesses described herein.
  • ODP ozone depletion potential
  • GWP low global warming potential
  • transHFCO-1233zd which is sometimes also referred to herein as "1233ZD"
  • 1233ZD transHFCO-1233zd
  • the global warming potential (GWP) of 1233ZD is more than two orders of magnitude lower than that of currently utilized HFCs, and more than one order of magnitude lower than the present language in the EU F-Gas Regulation, and within the rationale of the EU WEEE Directive pertaining to household refrigerator/freezers, with a GWP less than 15.
  • PUR foam properties of lambda (k-factor), compressive strength, and dimensional stability derived from characterization of hand mix foams or foam panels prepared by means of a high pressure foam machine have evidenced efficacy of the present systems in comparison to systems using 245fa foams.
  • k-factor lambda
  • compressive strength compressive strength
  • dimensional stability derived from characterization of hand mix foams or foam panels prepared by means of a high pressure foam machine
  • a single layer, 0.5 inch by 0.5 inch sheet of ABS liner is formed in a thickness of 0.06 inches.
  • the sheet is exposed to 1233zd(E) vapor inside a Fisherport tube at a temperature of 70 Q C.
  • the absorption of 1233zd(E) into the ABS was determined by recording the weight change after a one day and a four day exposure period. The sheet was found to increase in weight by 0.2% after one day and by more than 0.3% after four days.
  • a two layer liner is formed using the ABS sheet of the Comparative Example by coextruding the ABS liner and nylon-6 at a temperature of from about 240 Q C - 260 Q C.
  • a compatibilizer such as Triax 1 120 (Bayer) is used to increase the affinity between these two polymer layers.
  • the thickness of the ABS layer in the coextruded sheet is about 0.06 inch and the thickness of the nylon-6 is from about 0.005 to about 0.01 inch.
  • the side of the sheet containing the Nylon-6 layer is exposed to 1233zd(E) vapor inside a Fisherport tube at a temperature of 70 Q C. The absorption of 1233zd(E) into the liner was determined by recording the weight change after a one day and a two day exposure period.
  • the sheet was found to increase in weight by less than 0.03% after both the one day and the four day period, which is only one tenth of the absorption in the ABS layer of the Comparative Example. It is thus seen that the liner of the present invention had an ABS portion that was substantially protected from exposure to 1233zd(E). Other physical and chemical properties of liner remain substantially unchanged.
  • a two layer liner is formed using the ABS sheet of Comparative Example 1 by spaying a holt melt of PE Wax onto the ABS sheet of Comparative Example liner using a spray gun supplied with hot air. (Alternatively a co-extrusion as in Example 1 is used).
  • the thickness of solidified PE layer is about 0.005 to about 0.01 inch and the thickness of the ABS layer is about 0.06 inch.
  • the side of the sheet containing the Nylon-6 layer is exposed to 1233zd(E) vapor inside a Fisherport tube at a temperature of 70 Q C. The absorption of 1233zd(E) into the liner was determined by recording the weight change after a one day and a two day exposure period.
  • the sheet was found to increase in weight by less than 0.03% after both the one day and the four day period, which is only one tenth of the absorption in the ABS layer of the Comparative Example. It is thus seen that the liner of the present invention had an ABS portion that was substantially protected from exposure to 1233zd(E). Other physical and chemical properties of liner remain substantially unchanged.
  • a layer comprising about 20g of a polybutadiene rubber and about 12g Dabco 33LV (33% triethylenediamine from Air Products) is formed and bonded to the ABS sheet of Comparative Example 1 in a thickness was from about 0.005 to about 0.01 inch.
  • the rubber-coated side of the sheet is exposed to 1233zd(E) vapor inside a Fisherport tube at a temperature of 70 Q C.
  • the absorption of 1233zd(E) into the liner was determined by recording the weight change after a one day and a two day exposure period. The sheet was found to not increase in weight after both the one day and the two day period. It is thus seen that the liner of the present invention had an ABS portion that was substantially protected from exposure to 1233zd(E). Other physical and chemical properties of liner remain substantially unchanged.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Refrigerator Housings (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

L'invention concerne des dispositifs et revêtements destinés à contenir un ou plusieurs article(s) à une température inférieure à la température ambiante, comprenant : (a) un récipient comprenant un espace intérieur et (b) une isolation thermique comprenant un matériau polymère comportant en son sein des alvéoles fermées, lesdites alvéoles étant formées à partir de et/ou contenant un agent d'expansion, ledit récipient comprenant un revêtement comprenant (i) une première couche comprenant de l'ABS et possédant une surface faisant face audit espace intérieur ; et (ii) au moins une deuxième couche possédant une surface tournée à l'écart dudit espace intérieur, ladite deuxième couche dudit revêtement étant au moins une couche parmi (1) une couche formée d'une résine polyamide amorphe ou semi-cristalline ; (2) une couche formée d'un matériau polymère pouvant absorber une partie importante desdites molécules d'agent d'expansion émises à partir de ladite isolation ; et (3) une couche contenant un matériau susceptible de réagir avec une partie importante dudit agent d'expansion émis à partir de ladite isolation.
PCT/US2015/065177 2014-12-12 2015-12-11 Revêtements abs améliorés et armoires de refroidissement les contenant WO2016094762A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201580076081.6A CN107208956A (zh) 2014-12-12 2015-12-11 改善的abs衬垫和包含其的冷却柜

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US201462091306P 2014-12-12 2014-12-12
US62/091,306 2014-12-12
US14/964,775 2015-12-10
US14/964,775 US20160169575A1 (en) 2014-12-12 2015-12-10 Abs liners and cooling cabinets containing same

Publications (1)

Publication Number Publication Date
WO2016094762A1 true WO2016094762A1 (fr) 2016-06-16

Family

ID=56108241

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2015/065177 WO2016094762A1 (fr) 2014-12-12 2015-12-11 Revêtements abs améliorés et armoires de refroidissement les contenant

Country Status (3)

Country Link
US (1) US20160169575A1 (fr)
CN (1) CN107208956A (fr)
WO (1) WO2016094762A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018015215A1 (fr) 2016-07-20 2018-01-25 Brugg Rohr Ag Holding Couches barrières
US11879586B2 (en) * 2016-07-20 2024-01-23 Brugg Rohr Ag Holding Thermally insulated medium pipes having HFO-containing cell gas

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20180074514A (ko) 2016-12-23 2018-07-03 삼성전자주식회사 냉장고
MX2019012621A (es) * 2017-05-19 2020-01-30 Chemours Co Fc Llc Compuestos fluorados utiles como agentes de expansion de espuma.
CN112063096A (zh) * 2020-09-07 2020-12-11 海信（山东）冰箱有限公司 冰箱、冰箱内胆、冰箱内胆材料及其制备方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4196950A (en) * 1978-07-19 1980-04-08 Monsanto Company Refrigerator construction
US5118174A (en) * 1991-05-17 1992-06-02 Whirlpool Corporation Method to prevent chemical (HCFC) attack of plastic foodliner from foam insulation chemicals
US5227245A (en) * 1990-04-04 1993-07-13 The Dow Chemical Company Barrier films for preventing solvent attack on plastic resins
US5486407A (en) * 1993-06-08 1996-01-23 General Electric Co. High rubber backing multi-layer ABS system which exhibits improved chemical resistance to HCFC blowing agents
US6164739A (en) * 1993-10-18 2000-12-26 The Dow Chemical Company Multilayer protective film
US20110031254A1 (en) * 2008-04-21 2011-02-10 Dow Global Technologies Inc. Units insulated with foams and having flexible outer skins
US20130149452A1 (en) * 2011-12-09 2013-06-13 Honeywell International, Inc. Foams and articles made from foams containing 1-chloro-3,3,3-trifluoropropene (1233zd)
US20130306655A1 (en) * 2011-02-14 2013-11-21 Panasonic Corporation Heat-insulating box

Family Cites Families (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5219665A (en) * 1991-01-30 1993-06-15 E. I. Du Pont De Nemours And Company Fabricated articles with improved resistance to hydrohalocarbons
US5324589A (en) * 1992-11-30 1994-06-28 General Electric Company Thermoformable, multilayer ABS films and equipment liners
US5834126A (en) * 1994-12-30 1998-11-10 Basf Corporation Barrier layer for use in refrigerator cabinets
JPH08337691A (ja) * 1995-03-29 1996-12-24 Basf Corp プラスチック上への化学的攻撃を低減するための保護組成物
US20090253820A1 (en) * 2006-03-21 2009-10-08 Honeywell International Inc. Foaming agents and compositions containing fluorine sustituted olefins and methods of foaming
US6658857B1 (en) * 2003-02-20 2003-12-09 Hatho M. George Portable thermoelectric cooling and heating appliance device and method of using
JP2005106312A (ja) * 2003-09-29 2005-04-21 Hitachi Home & Life Solutions Inc 冷蔵庫並びに真空断熱パネル及びその製造方法
DE102004036248A1 (de) * 2004-07-26 2006-02-16 Bayer Aktiengesellschaft Verwendung von polyamidbasierten Deckschichten für die Produktion von Inlinern für Kältegeräte
TWI482748B (zh) * 2005-06-24 2015-05-01 Honeywell Int Inc 含有經氟取代之烯烴之組合物
JP2012500741A (ja) * 2008-08-25 2012-01-12 スティロン ヨーロッパ ゲゼルシャフト ミット ベシュレンクテル ハフツング 多層熱可塑性シート材料およびそれから調製された熱成形物品
EP2230260A1 (fr) * 2009-03-10 2010-09-22 Total Petrochemicals Research Feluy Composition de polymère monovinyle aromatique modifiée au caoutchouc
PL2452138T3 (pl) * 2009-07-07 2014-01-31 Arcelik As Lodówka zawierająca wewnętrzną powłokę z tworzywa sztucznego
MX359434B (es) * 2009-12-22 2018-09-27 Du Pont Composiciones que comprenden 2,3,3,3-tetrafluoropropeno, 1,1,2,3-tetracloropropeno, 2-cloro-3,3,3-trifluoropropeno, o 2-cloro-1,1,1,2-tetrafluoropropano.
DE102010007141A1 (de) * 2010-02-05 2011-08-11 Aht Cooling Systems Gmbh Kühltruhe
US8961812B2 (en) * 2010-04-15 2015-02-24 E I Du Pont De Nemours And Company Compositions comprising Z-1,2-difluoroethylene and uses thereof
US20140190978A1 (en) * 2010-07-27 2014-07-10 Honeywell International Inc. Devices for maintaining food products at low temperature
US9556303B2 (en) * 2011-02-21 2017-01-31 Honeywell International Inc. Catalysts for polyurethane foam polyol premixes containing halogenated olefin blowing agents
US9051442B2 (en) * 2011-02-21 2015-06-09 Honeywell International Inc. Polyurethane foam premixes containing halogenated olefin blowing agents and foams made from same

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4196950A (en) * 1978-07-19 1980-04-08 Monsanto Company Refrigerator construction
US5227245A (en) * 1990-04-04 1993-07-13 The Dow Chemical Company Barrier films for preventing solvent attack on plastic resins
US5118174A (en) * 1991-05-17 1992-06-02 Whirlpool Corporation Method to prevent chemical (HCFC) attack of plastic foodliner from foam insulation chemicals
US5486407A (en) * 1993-06-08 1996-01-23 General Electric Co. High rubber backing multi-layer ABS system which exhibits improved chemical resistance to HCFC blowing agents
US6164739A (en) * 1993-10-18 2000-12-26 The Dow Chemical Company Multilayer protective film
US20110031254A1 (en) * 2008-04-21 2011-02-10 Dow Global Technologies Inc. Units insulated with foams and having flexible outer skins
US20130306655A1 (en) * 2011-02-14 2013-11-21 Panasonic Corporation Heat-insulating box
US20130149452A1 (en) * 2011-12-09 2013-06-13 Honeywell International, Inc. Foams and articles made from foams containing 1-chloro-3,3,3-trifluoropropene (1233zd)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018015215A1 (fr) 2016-07-20 2018-01-25 Brugg Rohr Ag Holding Couches barrières
CH712779A1 (de) * 2016-07-20 2018-01-31 Brugg Rohr Ag Holding Barriereschichten.
US11879586B2 (en) * 2016-07-20 2024-01-23 Brugg Rohr Ag Holding Thermally insulated medium pipes having HFO-containing cell gas

Also Published As

Publication number Publication date
US20160169575A1 (en) 2016-06-16
CN107208956A (zh) 2017-09-26

Similar Documents

Publication Publication Date Title
US20160169575A1 (en) Abs liners and cooling cabinets containing same
US20140190978A1 (en) Devices for maintaining food products at low temperature
US5340208A (en) Refrigerator liner structures
EP2318208B1 (fr) Matériaux en feuille à base de thermoplastique multicouches et articles thermoformés préparés à partir de tells matériaux
US5834126A (en) Barrier layer for use in refrigerator cabinets
US9181410B2 (en) Systems for efficient heating and/or cooling and having low climate change impact
EP0474831A1 (fr) Films de barrage destines a empecher l'attaque de solvants sur des resines plastiques.
WO2011003711A2 (fr) Réfrigérateur comprenant une cuve interne en plastique
JP5649175B2 (ja) ポリスチレン系樹脂積層発泡シートからなる容器を容器本体として用いた内嵌合容器
JP2021062622A (ja) 耐熱性および加工性が優秀な食品容器用複合シートおよびそれで形成された食品容器
KR20190022490A (ko) 폴리락티드 수지의 외장 층을 갖는 폴리머 발포체 단열 구조물
JP2018507383A (ja) アクリロニトリルブタジエンスチレン（ａｂｓ）ポリマー及びライナー
WO2006085713A8 (fr) Composition de resine thermoplastique resistante aux agents chimiques
US20210253817A1 (en) Azeotropic and azeotrope-like compositions of z-1,1,1,4,4,4-hexafluorobut-2-ene
US5338601A (en) Polyolefin barrier films for preventing solvent attack on plastic resins
JP7496678B2 (ja) ポリスチレン系樹脂発泡シート及び容器
TW201213413A (en) Expandable polystyrene and methods of forming the same
JP4434382B2 (ja) ポリスチレン系樹脂発泡シートの製造方法
CN109312099B (zh) 屏障层
WO2017206819A1 (fr) Couche structurale écologique à économie d'énergie pour dispositif de réfrigération et application associée
WO2017206818A1 (fr) Couche structurale écologique et à économie d'énergie pour dispositif de réfrigération, et applications associées
CN114502373A (zh) 复合体
Spada et al. Effect of the innovations on the quality of the processes and of the products: Fluorocarbons
JP2019524477A5 (fr)
TR201706505A3 (tr) Plasti̇k i̇ç duvar i̇çeren buzdolabi

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15867177

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15867177

Country of ref document: EP

Kind code of ref document: A1