What is claimed is:
1. A method for producing environmental friendly artificial leather product, comprising:
coating a first solvent-free elastomer resin composition on a releasing paper to form a top layer,
coating a layer of polyurethane resin composition containing more than 50% by weight solid content of polyurethane resin on said top layer to form an intermediate layer,
coating a layer of a second solvent-free elastomer resin composition on said intermediate layer to form an adhesive layer,
bonding a substrate on said adhesive layer to form an environmental friendly artificial semi-product, and
peeling the releasing paper from said top layer to obtain environmental friendly artificial leather product.
2. A method for producing environmental friendly artificial leather product according to claim 1, wherein said first solvent-free elastomer resin composition is water soluble elastomer resin composition or water dispersed elastomer resin composition.
3. A method for producing environmental friendly artificial leather product according to claim 1, wherein said elastomer of said first solvent-free elastomer resin composition is select from the group consisting polyurethane, polyamino acid and acrylate.
4. A method for producing environmental friendly artificial leather product according to claim 1, wherein said first solvent-free elastomer resin composition comprises about 10% to 90% by weight solid content of elastomer.
5. A method for producing environmental friendly artificial leather product according to claim 1, wherein the step of forming said top layer further comprises a step of drying said first solvent-free elastomer resin composition at a temperature of about 80 to 140 C.
6. A method for producing environmental friendly artificial leather product according to claim 1, wherein said polyurethane resin composition containing more than 50% by weight solid content of polyurethane resin comprises about 0 to 5% by weight of surfactant and about 5% to 10% by weight of curing agent.
7. A method for producing environmental friendly artificial leather product according to claim 1, wherein the step of forming said intermediate layer further comprises a step of drying the said polyurethane resin composition containing more than 50% by weight solid content of polyurethane resin.
8. A method for producing environmental friendly artificial leather product according to claim 1, further comprising subjecting said polyurethane resin composition containing more than 50% by weight solid content of polyurethane resin to vacuum de-gassing prior to coating said polyurethane resin composition.
9. A method for producing environmental friendly artificial leather product according to claim 1, wherein said second solvent-free elastomer resin composition is water soluble elastomer resin composition, water dispersed elastomer resin composition or solvent-free wet curing elastomer resin composition.
10. A method for producing environmental friendly artificial leather product according to claim 1, wherein said elastomer of said second solvent-free elastomer resin composition is select from the group consisting polyurethane, polyamino acid and acrylate.
11. A method for producing environmental friendly artificial leather product according to claim 1, wherein said substrate is bonded to said substrate prior to drying said second solvent-free elastomer resin composition.
12. A method for producing environmental friendly artificial leather product according to claim 1, wherein said substrate is woven fabric, non-woven fabric or animal skin.
13. A method for producing environmental friendly artificial leather product according to claim 1, further comprising a step of subjecting said artificial leather semi-product to a temperature of about 40 to 60 C. for about 24 to 48 hours to form a cross-linking structure in said adhesive layer prior to peeling said releasing paper.
14. An environmental friendly artificial leather product, comprising:
a substrate,
an adhesive layer formed of a first solvent-free elastomer resin composition on a side of said substrate,
an intermediate layer formed of polyurethane resin composition containing more than 50% by weight solid content of polyurethane resin on said adhesive layer, and
a top layer formed of a second solvent-free elastomer resin composition on said intermediate layer.
15. An environmental friendly artificial leather product according to claim 14, wherein said first solvent-free elastomer resin composition is water soluble elastomer resin composition, water dispersed elastomer resin composition or solvent-free wet curing elastomer resin composition.
16. An environmental friendly artificial leather product according to claim 14, wherein said elastomer of said first solvent-free elastomer resin composition is select from the group consisting polyurethane, polyamino acid and acrylate.
17. An environmental friendly artificial leather product according to claim 14, wherein said polyurethane resin composition containing more than 50% by weight solid content of polyurethane resin comprises about 0 to 5% by weight of surfactant and about 5% to 10% by weight of curing agent.
18. An environmental friendly artificial leather product according to claim 14, wherein said second solvent-free elastomer resin composition is water soluble elastomer resin composition or water dispersed elastomer resin composition.
19. An environmental friendly artificial leather product according to claim 14, wherein said elastomer of said second solvent-free elastomer resin composition is select from the group consisting polyurethane, polyamino acid and acrylate.
20. An environmental friendly artificial leather product according to claim 14, wherein said second solvent-free elastomer resin composition comprises about 10% to 90% by weight solid content of elastomer.
The claims below are in addition to those above.
All refrences to claim(s) which appear below refer to the numbering after this setence.
What is claimed is:
1. A composition with extended storage stability and resistant to yellowing under the action of UV light comprising
a1) at least one oligomer, co-oligomer, polymer or copolymer or a mixture thereof having at least one ethylenically unsaturated bond; or
a2) a mixture of at least one ethylenically unsaturated monomer with at least one oligomer, co-oligomer, polymer or copolymer having at least one ethylenically unsaturated bond; and
b) at least one stable sterically hindered nitroxyl free-radical or at least one compound of the benzofuran-2-one type or a mixture of the two compounds.
2. A composition according to claim 1, wherein the monomer, oligomer, co-oligomer, polymer or copolymer has at least 2 ethylenically unsaturated bonds.
3. A composition according to claim 1, wherein the monomer, oligomer, co-oligomer, polymer or copolymer contains at least one acrylate or methacrylate functionality or is a polyester derived from an unsaturated acid.
4. A composition according to claim 1, wherein the stable sterically hindered nitroxyl free-radicals have the following structural feature,
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wherein R is alkyl and T is a group required to complete a 5- or 6-membered ring.
5. A composition according to claim 1, wherein the stable sterically hindered nitroxyl free-radicals are selected from the group consisting of
bis(1-oxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 4-hydroxy-1-oxy-2,2,6,6-tetramethyl-piperidine, 4-ethoxy-1-oxy-2,2,6,6-tetramethylpiperidine, 4-propoxy-1-oxy-2,2,6,6-tetra-methylpiperidine, 4-acetamido-1-oxy-2,2,6,6-tetramethylpiperidine, 1-oxy-2,2,6,6-tetra-methylpiperidine, 1-oxy-2,2,6,6-tetramethylpiperidin-4-one, 1-oxy-2,2,6,6-tetramethyl-piperidin-4-yl acetate, 1-oxy-2,2,6,6-tetramethylpiperidin-4-yl 2-ethylhexanoate, 1-oxy-2,2,6,6-tetramethylpiperidin-4-yl stearate, 1-oxy-2,2,6,6-tetramethylpiperidin-4-yl benzoate, 1-oxy-2,2,6,6-tetramethylpiperidin-4-yl 4-tert-butyl-benzoate, bis(1-oxy-2,2,6,6-tetramethyl-piperidin-4-yl) succinate, bis(1-oxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate, bis(1-oxy-2,2,6,6-tetramethylpiperidin-4-yl) n-butylmalonate, bis(1-oxy-2,2,6,6-tetramethylpiperidin-4-yl) phthalate, bis(1-oxy-2,2,6,6-tetramethylpiperidin-4-yl) isophthalate, bis(1-oxy-2,2,6,6-tetramethylpiperidin-4-yl) terephthalate, bis(1-oxy-2,2,6,6-tetramethylpiperidin-4-yl) hexa-hydroterephthalate, N,N-bis(1-oxy-2,2,6,6-tetramethylpiperidin-4-yl)adipamide, N-(1-oxy-2,2,6,6-tetramethylpiperidin-4-yl)caprolactam, N-(1-oxy-2,2,6,6-tetramethylpiperidin-4-yl)-dodecylsuccinimide, 2,4,6-trisN-butyl-N-(1-oxy-2,2,6,6-tetramethylpiperidin-4-yl)-s-triazine, 4,4-ethylenebis(1-oxy-2,2,6,6-tetramethylpiperazin-3-one), 2-oxy-1,1,3,3-tetramethyl-2-iso-benzazole, 1-oxy-2,2,5,5-tetramethylpyrrolidine and N,N-bis(1,1,3,3-tetramethylbutyl)-nitroxide.
6. A composition according to claim 1, comprising as component (b) a compound of formula I
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wherein, when n is 1,
R1 is naphthyl, phenanthryl, anthryl, 5,6,7,8-tetrahydro-2-naphthyl, 5,6,7,8-tetrahydro-1-naphthyl, thienyl, benzobthienyl, naphtho2,3-bthienyl, thianthrenyl, dibenzofuryl, chromenyl, xanthenyl, phenoxathiinyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, cinnolinyl, pteridinyl, carbazolyl, -carbolinyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, biphenyl, terphenyl, fluorenyl or phenoxazinyl, each unsubstituted or substituted by C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, hydroxy, halogen, amino, C1-C4alkylamino, phenylamino or by di(C1-C4alkyl)amino, or R1 is a radical of formula II
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when n is 2,
R1 is phenylene or naphthylene, each unsubstituted or substituted by C1-C4alkyl or by hydroxy; or is R12XR13,
R2, R3, R4 and R5 are each independently of the others hydrogen, chlorine, hydroxy,
C1-C25alkyl, C7-C9phenylalkyl, unsubstituted or C1-C4alkyl-substituted phenyl; unsubstituted or C1-C4alkyl-substituted C5-C8cycloalkyl; C1-C18alkoxy, C1-C18alkylthio, C1-C4alkylamino, di(C1-C4alkyl)amino, C1-C25alkanoyloxy, C1-C25alkanoylamino, C3-C25alkenoyloxy,
C3-C25alkanoyloxy interrupted by oxygen, sulfur or by
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C6-C9cycloalkyl-carbonyloxy, benzoyloxy or C1-C12alkyl-substituted benzoyloxy; or the radicals R2 and R3 or the radicals R3 and R4 or the radicals R4 and R5 together with the carbon atoms to which they are bonded form a benzo ring, or R4 may additionally be (CH2)pCOR15 or (CH2)qOH, or when R3, R5 and R6 are hydrogen, R4 may additionally be a radical of formula III
51
wherein R1 is as defined above for n1,
R6 is hydrogen or a radical of formula IV
52
wherein R4 is not a radical of formula III and R1 is as defined above for n1,
R7, R8, R9, R10 and R11 are each independently of the others hydrogen, halogen, hydroxy, C1-C25alkyl, C2-C25alkyl interrupted by oxygen, sulfur or by
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C1-C25alkoxy,
C2-C25alkoxy interrupted by oxygen, sulfur or by
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C1-C25alkylthio, C3-C25alkenyl,
C3-C25alkenyloxy, C3-C25alkynyl, C3-C25alkynyloxy, C7-C9phenylalkyl, C7-C9phenylalkoxy, unsubstituted or C1-C4alkyl-substituted phenyl; unsubstituted or C1-C4alkyl-substituted phenoxy; unsubstituted or C1-C4alkyl-substituted C5-C8cycloalkyl; unsubstituted or C1-C4alkyl-substituted C5-C8cycloalkoxy; C1-C4alkylamino, di(C1-C4alkyl)amino,
C1-C25alkanoyl, C3-C25alkanoyl interrupted by oxygen, sulfur or by
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C1-C25alkanoyloxy, C3-C25alkanoyloxy interrupted by oxygen, sulfur or by
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C1-C25alkanoylamino, C3-C25alkenoyl, C3-C25alkenoyl interrupted by oxygen, sulfur or by
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C3-C25alkenoyloxy, C3-C25alkenoyloxy interrupted by oxygen, sulfur or by
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C6-C9cycloalkylcarbonyl, C6-C9cycloalkylcarbonyloxy, benzoyl or C1-C12alkyl-substituted benzoyl; benzoyloxy or C1-C12alkyl-substituted benzoyloxy;
59
or in formula II the radicals R7 and R8 or the radicals R8 and R11 together with the carbon atoms to which they are bonded form a benzo ring,
R12 and R13 are each independently of the other unsubstituted or C1-C4alkyl-substituted phenylene or naphthylene,
R14 is hydrogen or C1-C8alkyl,
R15 is hydroxy,
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C1-C18alkoxy or
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R16 and R17 are each independently of the other hydrogen, CF3, C1-C12alkyl or phenyl, or R16 and R17 together with the carbon atom to which they are bonded form a C5-C8cycloalkylidene ring that is unsubstituted or substituted by from 1 to 3 C1-C4alkyl groups;
R18 and R19 are each independently of the other hydrogen, C1-C4alkyl or phenyl,
R20 is hydrogen or C1-C4alkyl,
R21 is hydrogen, unsubstituted or C1-C4alkyl-substituted phenyl; C1-C25alkyl, C2-C25alkyl interrupted by oxygen, sulfur or by
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C7-C9phenylalkyl that is unsubstituted or substituted on the phenyl radical by from 1 to 3 C1-C4alkyl groups; C7-C25phenylalkyl that is unsubstituted or substituted on the phenyl radical by from 1 to 3 C1-C4alkyl groups and interrupted by oxygen, sulfur or by
63
or the radicals R20 and R21 together with the carbon atoms to which they are bonded form a C5-C12cycloalkylene ring that is unsubstituted or substituted by from 1 to 3 C1-C4alkyl groups;
R22 is hydrogen or C1-C4alkyl,
R23 is hydrogen, C1-C25alkanoyl, C3-C25alkenoyl, C3-C25alkanoyl interrupted by oxygen, sulfur or by
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C2-C25alkanoyl substituted by a di(C1-C6alkyl)phosphonate group; C6-C9cycloalkylcarbonyl, thenoyl, furoyl, benzoyl or C1-C12alkyl-substituted benzoyl;
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R24 and R25 are each independently of the other hydrogen or C1-C18alkyl,
R26 is hydrogen or C1-C8alkyl,
R27 is a direct bond, C1-C18alkylene, C2-C18alkylene interrupted by oxygen, sulfur or by
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C2-C18alkenylene, C2-C20alkylidene, C7-C20phenylalkylidene, C5-C8cyclo-alkylene, C7-C8bicycloalkylene, unsubstituted or C1-C4alkyl-substituted phenylene,
67
R28 is hydrogen
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C1-C18alkoxy or
69
R29 is oxygen, NH or
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R30 is C1-C18alkyl or phenyl,
R31 is hydrogen or C1-C18alkyl,
M is an r-valent metal cation,
X is a direct bond, oxygen, sulfur or NR31,
n is 1 or 2,
p is 0, 1 or 2,
q is 1, 2, 3, 4, 5 or 6,
r is 1, 2 or 3, and
s is 0, 1 or 2.
7. A composition according to claim 6, comprising as component (b) a compound of formula V
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wherein
R2 is hydrogen or C1-C6alkyl,
R3 is hydrogen,
R4 is hydrogen or C1-C6alkyl,
R1 is hydrogen,
R7, R8, R9, R10 and R11 are each independently of the others hydrogen, C1-C4alkyl, C1-C4-alkoxy or
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with the proviso that at least two of the radicals R7, R8,
R9, R10 and R11 are hydrogen,
R20, R21 and R22 are hydrogen, and
R23 is C2-C4alkanoyl.
8. A composition according to claim 7, wherein component (b) is a compound of formula Va or Vb
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or a mixture of the two compounds of formulae Va and Vb.
9. A composition according to claim 1, wherein component (b) is present in an amount of from 0.0001 to 10% by weight, based on the total amount of monomer, oligomer, co-oligomer, polymer or copolymer.
10. A method of increasing the storage stability and preventing premature polymerisation or crosslinking of
a1) at least one oligomer, co-oligomer, polymer or copolymer or a mixture thereof having at least one ethylenically unsaturated bond; or
a2) a mixture of at least one ethylenically unsaturated monomer with at least one oligomer, co-oligomer, polymer or copolymer having at least one ethylenically unsaturated bond, which method comprises adding at least one stable sterically hindered nitroxyl free-radical or at least one compound of the benzofuran-2-one type or a mixture of the two compounds.
11. Use of a stable sterically hindered nitroxyl free-radical or a compound of the benzofuran-2-one type or a mixture of the two compounds for increasing the storage stability and preventing premature polymerisation or crosslinking of
a1) at least one oligomer, co-oligomer, polymer or copolymer or a mixture thereof having at least one ethylenically unsaturated bond; or
a2) a mixture of at least one ethylenically unsaturated monomer with at least one oligomer, co-oligomer, polymer or copolymer having at least one ethylenically unsaturated bond.