1. A cold-storage appliance comprising:
at least one container defining external surfaces comprising at least first and second side external surfaces;
a structure defining a container compartment from which the container can be withdrawn to open the container and to afford access to its interior and to which the container can be returned to close the container for cold storage of any items within the container; and
heating means for warming at least the first and second side external surfaces of the container when in the container compartment.
2. The appliance of claim 1, wherein the heating means is arranged to warm the external surface of the container to above ambient temperature.
3. The appliance of claim 1, wherein the heating means employs heat recovered from heat-emitting parts of the appliance.
4. The appliance of claim 3, wherein the heat emitting parts include a refrigerator engine, a heat exchanger or a motor.
5. The appliance of claim 1, wherein the container compartment includes a heating element or pad facing the exterior of the container.
6. The appliance of claim 1, wherein the exterior of the container includes a heating element or pad.
7. A cold-storage appliance comprising:
an open-topped insulating container defining external surfaces comprising first and second side external surfaces;
an insulating lid adapted to close the open top of the container;
a cooling means adapted to cool the interior of the container; and
a structure supporting the container, the lid and the cooling means;
wherein the container is mounted to the structure for movement relative to the structure and to the lid to open the container and to afford access to its interior or to close the container, and wherein at least the first and second side external surfaces of the container are exposed to air above ambient temperature when the container is closed by the lid.
8. A cold-storage appliance comprising:
at least one container defining an external surface;
a structure defining a container compartment from which the container can be withdrawn to open the container and afford access to its interior and to which the container can be returned to close the container for cold storage of any items within the container; and
circulating means comprising a fan for circulating air around the container compartment to expose the external surface of the container therein to said circulating air.
9. A cold-storage appliance comprising:
at least one container defining an external surface;
a structure defining a container compartment from which the container can be withdrawn to open the container and afford access to its interior and to which the container can be returned to close the container for cold storage of any items within the container; and
circulating means for circulating air around the container compartment to expose the external surface of the container therein to said circulating air, wherein the circulating means comprises a heater creating a convection current within the container compartment.
10. A cold-storage appliance comprising:
at least one container defining an external surface;
a structure defining a container compartment from which the container can be withdrawn to open the container and afford access to its interior and to which the container can be returned to close the container for cold storage of any items within the container; and
circulating means for circulating air around the container compartment to expose the external surface of the container therein to said circulating air, wherein the circulating means comprises a heater creating a convection current within the container compartment and being positioned below the container when the container is in the container compartment.
11. A cold-storage appliance comprising:
at least one container defining an external surface;
a structure defining a container compartment from which the container can be withdrawn to open the container and afford access to its interior and to which the container can be returned to close the container for cold storage of any items within the container; and
circulating means for circulating air around the container compartment to expose the external surface of the container therein to said circulating air, wherein the circulating means derives warm air from heat-generating parts of the appliance.
12. The appliance of claim 1, further comprising trace heating means for applying heat locally to an interface between the container and a lid closing the container.
13. The appliance of claim 12, wherein the trace heating means employs electric elements andor a fluid conduit.
14. The appliance of claim 13, wherein the fluid conduit contains refrigeration liquid or hot gas.
15. The appliance of claim 12, wherein trace heating is applied continuously.
16. The appliance of claim 12, wherein trace heating is applied only when it is desired to open the container.
17. The appliance of claim 1, wherein the heating means is also for warming bottom and rear external surfaces of the container when in the container compartment.
18. The appliance of claim 1, further comprising circulating means for circulating air around the container compartment to expose the external surface of the container therein to said circulating air.
19. The appliance of claim 18, wherein the circulating means includes a fan.
20. The appliance of claim 18, wherein the circulating means includes a heater creating a convection current within the container compartment.
21. The appliance of claim 20, wherein the heater is positioned below the container when the container is in the container compartment.
22. The appliance of claim 18, wherein the circulating means derives warm air from heat-generating parts of the appliance.
23. The appliance of claim 7, further comprising circulating means for circulating air around the container compartment to expose the external surface of the container therein to said circulating air.
24. The appliance of claim 23, wherein the circulating means includes a fan.
25. The appliance of claim 23, wherein the circulating means includes a heater creating a convection current within the container compartment.
26. The appliance of claim 25, wherein the heater is positioned below the container when the container is in the container compartment.
27. The appliance of claim 23, wherein the circulating means derives warm air from heat-generating parts of the appliance.
The claims below are in addition to those above.
All refrences to claim(s) which appear below refer to the numbering after this setence.
1. A process for dyeing tanned leather, which comprises either
(a1) allowing ammonia, primary amines or a mixture of ammonia and primary amines in an aqueous and alkaline medium to act on the tanned leather and (a2) treating this leather in an aqueous and alkaline medium in the presence of ammonia, primary amines or a mixture of ammonia and primary amines with a polyfunctional organic compound comprising at least one aldehyde group as a functional group, or
(b1) allowing a part or all of a polyfunctional organic compound comprising at least one aldehyde group as a functional group to act on the tanned leather in an aqueous and acidic medium and (b2) allowing ammonia, primary amines or a mixture of ammonia and primary amines in an aqueous and alkaline medium and then, if necessary, the remainder of the polyfunctional organic compound to act on the tanned leather;
(c) allowing a dye comprising at least one functional group to act on the treated leather in an aqueous and alkaline medium, wherein this functional group is capable of reacting with one of the functional groups of the organic compound forming a covalent bond; and
(d) draining the dye liquor and washing the dyed leather with water with the proviso that the pH value in (c) is over 8 when using an anionic tanned or retanned leather, if an anionic dye is used.
2. A process according to claim 1, wherein the aqueous, alkaline medium in a1), a2), b2) and c) has a pH of 7 to 10.
3. A process according to claim 1, wherein a1), a2), b2) and c) are conducted at a reaction temperature of 20 to 80\xb0 C.
4. A process according to claim 1, wherein the quantity of the ammonia in a1) or b2) is 0.1 to 20 parts by weight in relation to 100 parts by weight of the shaved weight of the tanned leather.
5. A process according to claim 1, wherein the ammonia in a1) and b2) is generated in situ by hydrolysis of ammonium salts with bases.
6. A process according to claim 5, wherein the ammonium salts are ammonium salts of polymeric water-soluble carboxylic acids or inorganic ammonium salts.
7. A process according to claim 1, wherein the quantity of the polyfunctional organic compound in a2), b1) and b2) is 0.1 to 20 parts by weight in relation to 100 parts by weight of the shaved weight of the tanned leather.
8. A process according to claim 1, wherein the polyfunctional organic compound contains one aldehyde group and a further 1 to 4 functional groups for covalent bonding of the dye, where the functional groups are bonded to the aldehyde group either directly or via an organic bridging group.
9. A process according to claim 8, wherein the bridging group contains 1 to 30 C atoms, where carbon bonds may be broken by O, S, NR, C(O)O or C(O)NR, wherein R is hydrogen or C1-C4alkyl.
10. A process according to claim 8, wherein the functional groups for the formation of covalent bonds are selected from the group consisting of \u2014CHO, \u2014OH, \u2014SH, \u2014NHR, isocyanate, masked isocyanate, carboxyl, carboxylate, carbamide, sulfoxyl, sulfoxylate, and sulfonamide, wherein R is hydrogen or C1-C4alkyl.
11. A process according to claim 10, wherein the functional group is \u2014CHO.
12. A process according to claim 1, wherein the polyfunctional organic compound is a compound of formula I;
OHC\u2014B\u2014(F)x\u2003\u2003(I),
wherein
B is a direct bond or a bivalent or trivalent bridging group with 1 to 12 C atoms,
x is the number 1 or 2, and
F is a functional group which is capable of reacting with the functional group of a dye.
13. A process according to claim 12, wherein B is a bivalent bridging group and x is the number 1.
14. A process according to claim 13, wherein B is linear or branched C1-C12alkylene, C3-C12cycloalkylene, C1-C4alkylene-C5-C8cycloalkylene, C1-C4alkylene-C5-C8cycloalkylene-C1-C4alkylene, C6-C12arylene, C7-C16aralkylene, or C1-C4-alkylene-C6-C12arylene-C1-C4alkylene.
15. A process according to claim 12, wherein the functional group F is selected from the group consisting of \u2014CHO, \u2014OH, \u2014SH, \u2014NHR, \u2014CO2H, \u2014CO2R1, \u2014C(O)\u2014NR2R3, \u2014NCO, \u2014SO3H, \u2014SO2OR1, and \u2014SO2\u2014NR2R3, wherein R is hydrogen or C1-C4alkyl, R1 is C1-C4alkyl, and R2 and R3 are independently of one another hydrogen or C1-C4alkyl.
16. A process according to claim 12, wherein B is a direct bond or C1-C8alkylene and F is \u2014CHO.
17. A process according to claim 1, wherein the polyfunctional organic compound is selected from the group consisting of glyoxal, malondialdehyde, glutardialdehyde, succinaldehyde, dialdehyde starch and mixtures thereof.
18. A process according to claim 1, wherein the quantity of the dye in c) is 0.1 to 20 parts by weight in relation to 100 parts by weight of the shaved weight of the tanned leather.
19. A process according to claim 1, wherein (c) further comprises addition of inorganic bases to maintain the pH value.
20. A process according to claim 19, wherein the inorganic base is added either separately or mixed with the dye.
21. A process according to claim 1, wherein the dyes with functional groups in c) are selected from the group consisting of azo dyes, metal complex azo dyes, anthraquinone dyes, diarylmethane and triarylmethane dyes, sulfur dyes, phthalocyanine dyes, azine dyes, oxazine dyes and thiazine dyes.
22. A process according to claim 21, wherein the functional group is selected from the group consisting of \u2014CHO, \u2014OH, \u2014SH, \u2014NHR, \u2014CO2H, \u2014CO2R1, \u2014C(O)\u2014NR2R3, \u2014NCO, \u2014SO3H, \u2014SO2OR1, and \u2014SO2\u2014NR2R3, wherein R is hydrogen or C1-C4alkyl, R1 is C1-C4alkyl, and R2 and R3 are independently of one another hydrogen or C1-C4alkyl.
23. A process according to claim 1, wherein the dye is a dye of formula II,
Dye-(X\u2014Z)y\u2003\u2003(II),
wherein
dye is the backbone chain of a water-soluble, organic or metal organic dye,
X is a direct bond or a bivalent bridging group,
Z is a functional group which is capable of reacting with the functional groups of the polyfunctional organic compound, forming a covalent bond, and
y is a number from 1 to 10.
24. A process according to claim 23, wherein the bridging group is C1-C12alkylene, which may be broken by O, S or NR, where R is H or C1-C4alkyl.
25. A process according to claim 23, wherein Z is \u2014OH, \u2014SH or \u2014NH2.
26. A process according to claim 25, wherein Z is \u2014NH2.
27. A process according to claim 23, wherein y is a number from 1 to 6.
28. A process according to claim 1, wherein a part of the dye is added in a1) or b1) and the remainder of the dye is added in c).
29. A process according to claim 1, wherein a sulfur dye is concomitantly added in c).
30. A tanned and dyed leather wherein the dye is permanently and covalently bonded to the leather via a bridging group, and the bridging group is essentially bonded to the leather via \u2014N\u2550CH\u2014 groups, with the proviso that the leather is not anionic tanned or retanned.
31. A leather according to claim 30, wherein a large number of groups of formula XXII are covalently bonded in the region of the surface of the leather,
\u2014N\u2550CH\u2014B\u2014(Y\u2014X-dye)r\u2003\u2003(XXII),
wherein
B is a direct bond or a bivalent or trivalent bridging group with 1 to 12 C atoms,
X is a direct bond or a bivalent bridging group,
r is the number 1 or 2, and
Y is a group formed from a functional group of a polyfunctional organic compound and a functional group of a dye.
32. A leather according to claim 31, wherein r in formula XXII is the number 1.
33. A leather according to claim 31, wherein X is a direct bond or a bridging group which is C1-C12alkylene, which may be broken by O, S or NR, where R is H or C1-C4alkyl.
34. A leather according to claim 31, wherein B is a bivalent bridging group and r is the number 1.
35. A leather according to claim 34, wherein B is linear or branched C1-C12alkylene, C3-C12cycloalkylene, C1-C4alkylene-C5-C8cycloalkylene, C1-C4alkylene-C5-C8cycloalkylene-C1-C4alkylene, C6-C12arylene, C7-C16aralkylene, or C1-C4-alkylene-C6-C12arylene-C1-C4alkylene.
36. A leather according to claim 31, wherein the group Y is selected from the group of consisting of imine, ester, amide, urea and urethane groups.
37. A leather according to claim 36, wherein Y is selected from the group consisting of \u2014HC\u2550N\u2014, \u2014N\u2550CH\u2014, \u2014C(O)\u2014O\u2014, \u2014O\u2014C(O)\u2014, \u2014C(O)\u2014S\u2014, \u2014S\u2014C(O)\u2014, \u2014C(O)\u2014NR\u2014, \u2014NR\u2014C(O)\u2014, \u2014NH\u2014C(O)\u2014NR\u2014, \u2014NR\u2014C(O)\u2014NH\u2014, \u2014O\u2014C(O)\u2014NR\u2014, \u2014NR\u2014C(O)\u2014O\u2014, \u2014S\u2014C(O)\u2014NR\u2014, and \u2014NR\u2014C(O)\u2014S\u2014.
38. A leather according claim 36, wherein the group Y is \u2014CH\u2550NH\u2014.
39. A leather according to claim 31, wherein B in formula XXII is a bivalent bridging group with 1 to 8 C atoms, X is a direct bond, r is the number 1, and Y is \u2014HC\u2550N\u2014.
40. A leather according to claim 31, wherein the dyes of formula XXII are selected from the group consisting of azo dyes, metal complex azo dyes, anthraquinone dyes, diarylmethane and triarylmethane dyes, sulfur dyes, phthalocyanine dyes, azine dyes, oxazine dyes and thiazine dyes.
41. A tanned and dyed leather, obtainable by the process according to claim 1.
42. A tanned and dyed leather according to claim 30, wherein the dye is bonded to the leather via the bridging group in the region of the surface of the leather.
43. A process according to claim 1, wherein up to 60% of the dye is allowed to act on the leather after b1) and before b2).