USA - Water-reducible dye compositions comprising solvent dyes and citrus solvents - Google Patents

Water-reducible dye compositions comprising solvent dyes and citrus solvents Download PDF

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Publication number

USA

USA US08/445,230 USA USA US A US A US A US A US A US A US A US A US A

Authority

US

United States

Prior art keywords

solvent

water

cas

dye

dyes

Prior art date

-05-18

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.)

Expired - Fee Related

Application number

US08/445,230

Inventor

Alejandro Zimin, Sr.

Peter A. Caputo

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Morton International LLC

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Morton International LLC

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-05-18

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-05-19

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-02-18

-05-19 Application filed by Morton International LLC filed Critical Morton International LLC

-05-19 Priority to US08/445,230 priority Critical patent/USA/en

-07-05 Assigned to MORTON INTERNATIONAL, INC. reassignment MORTON INTERNATIONAL, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CAPUTO, PETER A., ZIMIN, ALEJANDRO, SR.

-02-18 Application granted granted Critical

-02-18 Publication of USA publication Critical patent/USA/en

-02-18 Anticipated expiration legal-status Critical

Status Expired - Fee Related legal-status Critical Current

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• dye Substances 0.000 title claims abstract description 59
• solvent Substances 0.000 title claims abstract description 46
• Citrus Species 0.000 title claims abstract description 19
• citrus fruits Nutrition 0.000 title claims abstract description 19
• solvent dye Substances 0.000 title claims abstract description 19
• mixture Substances 0.000 title claims description 21
• XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
• nonionic surfactant Substances 0.000 claims abstract description 4
• PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 8
• salts Chemical class 0.000 claims description 6
• anthraquinones Chemical class 0.000 claims description 5
• solvent mixture Substances 0.000 claims description 5
• QBMJKIBIEWDYAY-UHFFFAOYSA-N 1,2-bis(2-methylphenyl)guanidine 7-[[5-[(6,8-disulfonaphthalen-2-yl)diazenyl]-2,4-dihydroxyphenyl]diazenyl]naphthalene-1,3-disulfonic acid Chemical compound Cc1ccccc1NC(=N)Nc1ccccc1C.Cc1ccccc1NC(=N)Nc1ccccc1C.Cc1ccccc1NC(=N)Nc1ccccc1C.Cc1ccccc1NC(=N)Nc1ccccc1C.Oc1cc(O)c(cc1N=Nc1ccc2cc(cc(c2c1)S(O)(=O)=O)S(O)(=O)=O)N=Nc1ccc2cc(cc(c2c1)S(O)(=O)=O)S(O)(=O)=O QBMJKIBIEWDYAY-UHFFFAOYSA-N 0.000 claims description 4
• QPQKUYVSJWQSDY-UHFFFAOYSA-N 4-phenyldiazenylaniline Chemical compound C1=CC(N)=CC=C1N=NC1=CC=CC=C1 QPQKUYVSJWQSDY-UHFFFAOYSA-N 0.000 claims description 4
• aqueous medium Substances 0.000 claims description 4
• hydrogen Inorganic materials 0.000 claims description 4
• hydrogen Substances 0.000 claims description 4
• hydrogen atom Chemical class [H]* 0.000 claims description 4
• DKBXPLYSDKSFEQ-UHFFFAOYSA-L turquoise gll Chemical compound [Na+].[Na+].[Cu+2].N1=C(N=C2[N-]3)[C]4C(S(=O)(=O)[O-])=CC=CC4=C1N=C([N-]1)C4=CC=CC(S([O-])(=O)=O)=C4C1=NC(C=1C4=CC=CC=1)=NC4=NC3=C1[C]2C=CC=C1 DKBXPLYSDKSFEQ-UHFFFAOYSA-L 0.000 claims description 4
• alkyl phenyl group Chemical group 0.000 claims description 3
• GBTNCRZBGFMBGM-UHFFFAOYSA-N copper 2-ethyl-N-(2-ethylhexyl)hexan-1-amine (10Z,29Z)-2,11,20,29,38,40-hexaza-37,39-diazanidanonacyclo[28.6.1.13,10.112,19.121,28.04,9.013,18.022,27.031,36]tetraconta-1,3(40),4(9),5,7,10,12,14,16,19,21(38),22,24,26,29,31,33,35-octadecaene-6,15-disulfonic acid Chemical compound [Cu++].CCCCC(CC)CNCC(CC)CCCC.CCCCC(CC)CNCC(CC)CCCC.OS(=O)(=O)C1=CC2=C3N=C(\N=C4/[N-]C([N-]C5=N\C(=N/C6=N/C(=N\3)/c3ccc(cc63)S(O)(=O)=O)c3ccccc53)c3ccccc43)C2C=C1 GBTNCRZBGFMBGM-UHFFFAOYSA-N 0.000 claims description 3
• IRGKJPHTQIWQTD-UHFFFAOYSA-N 2,7-dibromopyrene-1,3,6,8-tetrone Chemical compound O=C1C(Br)C(=O)C2=CC=C3C(=O)C(Br)C(=O)C4=CC=C1C2=C43 IRGKJPHTQIWQTD-UHFFFAOYSA-N 0.000 claims description 2
• YLNJGHNUXCVDIX-UHFFFAOYSA-N bis(2-methylpropyl) perylene-3,9-dicarboxylate Chemical compound C=12C3=CC=CC2=C(C(=O)OCC(C)C)C=CC=1C1=CC=CC2=C1C3=CC=C2C(=O)OCC(C)C YLNJGHNUXCVDIX-UHFFFAOYSA-N 0.000 claims description 2
• primary amino group Chemical group [H]N([H])* 0.000 claims description 2
• XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 29
• -1 amine salts Chemical class 0.000 description 14
• dispersion Substances 0.000 description 12
• surface-active agent Substances 0.000 description 10
• terpenes Chemical class 0.000 description 10
• terpenes Nutrition 0.000 description 9
• limonene Nutrition 0.000 description 7
• limonene Drugs 0.000 description 7
• loading method Methods 0.000 description 6
• CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
• long chain fatty acid esters Chemical class 0.000 description 5
• oil Substances 0.000 description 5
• xylene Substances 0.000 description 5
• azo dye Substances 0.000 description 4
• ink Substances 0.000 description 4
• ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
• LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
• RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical group CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 3
• OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
• DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
• cosolvent Substances 0.000 description 3
• organic solvent Substances 0.000 description 3
• IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 3
• ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
• DZNJMLVCIZGWSC-UHFFFAOYSA-N 3',6'-bis(diethylamino)spiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(N(CC)CC)C=C1OC1=CC(N(CC)CC)=CC=C21 DZNJMLVCIZGWSC-UHFFFAOYSA-N 0.000 description 2
• KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
• MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 2
• GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
• acyclic group Chemical group 0.000 description 2
• alkyl group Chemical class 0.000 description 2
• UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 description 2
• butyl (2R)-2-hydroxypropanoate Substances 0.000 description 2
• carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
• carrier Substances 0.000 description 2
• compounds Chemical class 0.000 description 2
• LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
• formulation Methods 0.000 description 2
• metal Substances 0.000 description 2
• QFVDKARCPMTZCS-UHFFFAOYSA-N methylrosaniline Chemical compound C1=CC(N(C)C)=CC=C1C(O)(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 QFVDKARCPMTZCS-UHFFFAOYSA-N 0.000 description 2
• FKORGLNGEASTQE-UHFFFAOYSA-N naphthalene-1,3-disulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC(S(O)(=O)=O)=C21 FKORGLNGEASTQE-UHFFFAOYSA-N 0.000 description 2
• nontoxic Toxicity 0.000 description 2
• nontoxic effect Effects 0.000 description 2
• nuclear magnetic resonance spectrum Methods 0.000 description 2
• pigment Substances 0.000 description 2
• GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
• substance Substances 0.000 description 2
• terpinene Natural products 0.000 description 2
• terpinene derivatives Chemical class 0.000 description 2
• trolamine Drugs 0.000 description 2
• YHQGMYUVUMAZJR-UHFFFAOYSA-N α-terpinene Chemical compound CC(C)C1=CC=C(C)CC1 YHQGMYUVUMAZJR-UHFFFAOYSA-N 0.000 description 2
• YKFLAYDHMOASIY-UHFFFAOYSA-N γ-terpinene Chemical compound CC(C)C1=CCC(C)=CC1 YKFLAYDHMOASIY-UHFFFAOYSA-N 0.000 description 2
• YTTFFPATQICAQN-UHFFFAOYSA-N 2-methoxypropan-1-ol Chemical compound COC(C)CO YTTFFPATQICAQN-UHFFFAOYSA-N 0.000 description 1
• JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 1
• JKYIIKTWBPGPNV-UHFFFAOYSA-N 4-[(2-hydroxy-5-nonylphenyl)diazenyl]-N-[4-[(2-hydroxy-5-nonylphenyl)diazenyl]phenyl]benzamide Chemical compound CCCCCCCCCc1ccc(O)c(c1)N=Nc1ccc(NC(=O)c2ccc(cc2)N=Nc2cc(CCCCCCCCC)ccc2O)cc1 JKYIIKTWBPGPNV-UHFFFAOYSA-N 0.000 description 1
• IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Polymers CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
• LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
• RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 description 1
• SAIKULLUBZKPDA-UHFFFAOYSA-N Bis(2-ethylhexyl) amine Chemical compound CCCCC(CC)CNCC(CC)CCCC SAIKULLUBZKPDA-UHFFFAOYSA-N 0.000 description 1
• Bos taurus Species 0.000 description 1
• WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 description 1
• Citrus aurantifolia Nutrition 0.000 description 1
• Citrus limon Nutrition 0.000 description 1
• Citrus pyriformis Species 0.000 description 1
• Citrus tangerina Species 0.000 description 1
• Citrus x paradisi Species 0.000 description 1
• Cocos nucifera Nutrition 0.000 description 1
• Cocos nucifera Species 0.000 description 1
• Embryophyta Species 0.000 description 1
• WSTYNZDAOAEEKG-UHFFFAOYSA-N Mayol Natural products CC1=C(O)C(=O)C=C2C(CCC3(C4CC(C(CC4(CCC33C)C)=O)C)C)(C)C3=CC=C21 WSTYNZDAOAEEKG-UHFFFAOYSA-N 0.000 description 1
• Tilia x europaea Nutrition 0.000 description 1
• Tilia x europaea Species 0.000 description 1
• YJVBLROMQZEFPA-UHFFFAOYSA-L acid red 26 Chemical compound [Na+].[Na+].CC1=CC(C)=CC=C1N=NC1=C(O)C(S([O-])(=O)=O)=CC2=CC(S([O-])(=O)=O)=CC=C12 YJVBLROMQZEFPA-UHFFFAOYSA-L 0.000 description 1
• addition Methods 0.000 description 1
• agitation Methods 0.000 description 1
• alkyl amino group Chemical group 0.000 description 1
• MOYAFQVGZZPNRA-UHFFFAOYSA-N alpha-Terpinolene Natural products CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 1
• VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 description 1
• anthraquinone dye Substances 0.000 description 1
• aryl amino group Chemical group 0.000 description 1
• beta-terpinene Natural products 0.000 description 1
• betanaphthol Drugs 0.000 description 1
• bicyclic group Chemical group 0.000 description 1
• citral Drugs 0.000 description 1
• coating method Methods 0.000 description 1
• coloring Methods 0.000 description 1
• constituent Substances 0.000 description 1
• cyclic group Chemical group 0.000 description 1
• diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
• dietary fatty acids Nutrition 0.000 description 1
• ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
• dispersing agent Substances 0.000 description 1
• ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
• edible vegetable oil Substances 0.000 description 1
• effects Effects 0.000 description 1
• environmental effect Effects 0.000 description 1
• esters Chemical class 0.000 description 1
• ethyl lactate Drugs 0.000 description 1
• fatty acid Substances 0.000 description 1
• fatty acid Natural products 0.000 description 1
• WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 description 1
• guanidines Chemical class 0.000 description 1
• hydroxy functional group Chemical class O* 0.000 description 1
• ingredient Substances 0.000 description 1
• lime Substances 0.000 description 1
• limonene group Chemical group 0.000 description 1
• material Substances 0.000 description 1
• NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
• methyl lactate Drugs 0.000 description 1
• mixing Methods 0.000 description 1
• monocyclic group Chemical group 0.000 description 1
• SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Polymers CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
• oleoresin Substances 0.000 description 1
• oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 1
• paint Substances 0.000 description 1
• phthalocyanine dye Substances 0.000 description 1
• spectrum Methods 0.000 description 1
• stirring Methods 0.000 description 1
• substrate Substances 0.000 description 1
• terpinolene group Chemical group 0.000 description 1
• unsaturated hydrocarbon Natural products 0.000 description 1
• volatile oil Substances 0.000 description 1
• SCWPFSIZUZUCCE-UHFFFAOYSA-N β-terpinene Chemical compound CC(C)C1=CCC(=C)CC1 SCWPFSIZUZUCCE-UHFFFAOYSA-N 0.000 description 1

Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
  • C09B67/—Dispersions of dyes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
  • C09B67/—Solutions of dyes
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
  • Y10S8/907—Nonionic emulsifiers for dyeing
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
  • Y10S8/938—Solvent dyes

Definitions

• the present invention is directed to water-reducible dye compositions which, upon mixing with water, form aqueous dispersions of the dyes and to the aqueous dispersions formed therefrom.
• dyes which are water-immiscible.
• a major advantage of water-immiscible dyes is that such dyes tend to be permanent, at least with respect to exposure to water.
• a disadvantage of such dyes is that they require organic solvent carriers, such as xylene, which are problematic from a health and environmental standpoint.
• the present invention is directed to compositions of water-immiscible dyes which form stable dispersions in aqueous media and therefor provide the permanence of water-immiscible dyes without the accompanying disadvantage of containing substantial amounts of harmful organic solvent carriers.
• Dye solutions typically must be formulated with a variety of additional ingredients which dilute the coloring effect of the dye; hence, the need for high dye loading.
• the solvent used to dissolve the dye may not be desirably used at a high level in the formulation. Accordingly, it is a further object of the invention that the water-reducible dye solutions have high dye loadings.
• a water-reducible dye solution of the present invention comprises between about 35 wt % and about 70 wt % of a) a water-immiscible solvent dye or mixture of solvent dyes, at least about 25 wt % of said dye solution being a solvent dye or mixture of solvent dyes selected from the dye types consisting of azo dyes, phthalocyanine dyes, and anthraquinone dyes; between about 10 and about 64 wt % of b) a solvent system for said water-immiscible dye or dye mixture in sufficient quantities to dissolve said water-immiscible dye or dye mixture, said solvent system comprising between about 30 and about 100 wt % of b1) a citrus solvent(s) and b2) between 0 and about 70 wt % of a compatible co-solvent(s) which is either water-immiscible or water-immiscible; and c) between about 1 and about 55 wt % of a non-ionic surfactant
• the water-reducible solutions When mixed into water, the water-reducible solutions form stable micro dispersions of the water-immiscible dye solutions in the water, which dispersions are infinitely reducible.
• the dyes of such aqueous dispersions become permanently fixed to the material to which they are applied.
• Solvent dyes are dyes that have at least some solubility in one or more organic solvents in which solvent the dye may be dissolved and by which the cye may be carried to the substrate. Solvent dyes are completely or substantially immiscible in water. Solvent dyes are discussed more fully in Colour Index International, 3rd ed., Additions and Amendments no. 67, April , p. 147-148.
• the water-immiscible solvent dyes which comprise at least 25 wt % of the dye solutions of the present invention are of the dye types:
• Azo dyes which includes monoazo, disazo and tetrazo's of both the metallized and non-metallized varieties.
• Metallized dyes are typically described as amine salts of monatomic metal chelates with one or two molecules of dye, depending upon the metal used.
• Non-metallized azo dyes include guanidine salt types typical of the Luxol R product line.
• Specific examples of water-immiscible azo dyes include but are not limited to are:
• 4--Morfast® Red 101 c.i.
• Solvent Red 68 1,3-naphthalenedisulfonic acid, 7-hydroxy-8-4-(phenyl-azo) phenyl azo-, compound with 2-ethyl-N-(2-ethylhexyl)-1-hexanamine (1:2).
• CAS # -82-8.
• 5--Morfast® Black 101 c.i.
• Solvent Black 48 cobaltate bis-2, 2'dioxy-4-di 2"-hydroxy-3"-alkyloxy-propyl amino-4-phenylazo-5-methyl-azobenzene, hydrogen dibutanammonium salt.
• Solvent Brown 20 1,3-naphthalenedisulfonic acid,7,7' (4,6-dihydroxy-1,3-phenylene) bis (azo) bis arylguanidine salt. CAS # -28-7.
• Phthalocyanine derived dyes mainly of the sulfonated versions derived from coppered pigments. Specific examples include but are not limited to:
• 1--Morfast® Blue 100 c.i.
• Solvent Blue 129 cuprate (2-), 29H, 31H phthalocyanine disulfonato (4-) N29, N30, N31, N32 di-1-alkanammonium, -N-(alkyl) salt CAS # -92-0.
• Anthraquinones predominantly, mono, di and mixed substituted alkylamino derivatives as well as mono, di and mixed substituted arylamino types. Specific examples include but are not limited to:
• solvent dyes used in solvent dye solutions in accordance with the invention if not of one of the dye types listed above, used in admixture with a dye or dyes of the type(s) mentioned above include, but are not limited to (according to their color index designations): Solvent Violet 9, CAS # 467-63-0; Solvent Black 7, CAS # -03-5; Solvent Blue 100, CAS # -50-6; Solvent Orange 97, CAS # -04-0; and Solvent Red 49, CAS # 509-34-2.
• Citride Solvent is used herein inclusively to include chemicals defined as citrus peel oils, terpene, terpinene, and dipentene. The definitions of these classes in Hawley's Condensed Chemical Dictionary, Eleventh Edition overlap:
• Citrirus Peel Oils - Edible oils expressed from the peel or rind of grapefruit, lemon, lime, orange and tangerine; Constituents: limonene, citral, and terpenes in varying percentages.
• Terpene C 10 H 16 An unsaturated hydrocarbon occurring inmost essential oils and oleoresins of plants.
• the terpenes are based on the isoprene unit C 5 H 8 , and may be either acyclic or cyclic with one or more benzenoid groups. There are classified as monocyclic (dipentene), dicyclic (pinene) or acyclic Myrcene, according to the molecular structure.
• Tepinene C 10 H 16 A mixture of three isomeric cyclic terpenes, alpha, beta and gamma terpinene.
• Diapentene (cinene; limonene, inactive; dl-p-mentha-1,8-diene; cajputene); Commercial form is high in dipentene content, but also contains other terpenes and related compounds in varying amounts.
• Citrus solvents are found to be particularly useful solvents in providing dispersions of a wide variety of dyes.
• citrus solvents are non-toxic, environmentally safe and biodegradable.
• the citrus solvent may comprise 100% of the solvent of the water-reducible dye composition, or may be admixed with a co-solvent up to a 30/70 citrus solvent/co-solvent wt. ratio, preferably one which is likewise non-toxic and environmentally benign.
• suitable co-solvents include but are not limited to ethyl lactate, butyl lactate, propylene glycol, triethanolamine, methyl ethyl ketone, ethanol, methanol, diethanolamine, methyl lactate, xylene, 1-methoxy-2-propanol, 2-methoxy-1-propanol.
• the third essential component is a non-ionic surfactant.
• Suitable surfactants include fatty acid esters; polyoxyethylated nonyl phenol derivatives; Rhone Poulene--CO-720 and CO630 nonylphenoxypoly (ethyleneoxy) ethanol CAS # -45-9; Union Carbide--Tergitol D-683 alkoxylated alkylphenol CAS # -69-7; Rhone Poulene--Alkamide modified coconut diethanolamide CAS # -42-9; Rhone Poulene--Alkamuls EL-985 polyethoxylated caster oil CAS # 75-21-8; and Morton International--Sotex N long chain fatty acid esters.
• the dye solution is typically provided free of water for shipment and storage.
• the end user adds the dye solution to water (or aqueous medium) with appropriate agitation to produce a dispersion of the dye solution in water (or aqueous medium).
• stable dispersions are achieved at a 1:1 ratio of water reducible dye solution to water.
• the dye solution can accommodate more or less water, so as to provide the dye content the user desires.
• Aqueous dispersions of the dye solution of the present invention can be used for example in felt tip pens, ball point pens, printing inks, hand stamps, ink jet inks, coatings, paints and woodstains.
• This solution when mixed with 204 ml. water with stirring formed a dispersion of the dye solution.
• a water-reducible solution was prepared in the manner of Example 1 containing 40 wt % 4-(2-hydroxy-5-nonylphenylazo)-[N[4-(2-hydroxy-5-nonylphenylazo)-phenyl]] benzamide, 36 wt % ATR-P citrus solvent and 24 wt % Igepal R CO630.
• a water-reducible solution was prepared in the manner of example 1 containing 35 wt % 1,4 dialkylamino anthraquinone, 46 wt % Vortex R citrus solvent and 19 wt % long chain fatty acid ester.
• a water-reducible solution was prepared in the manner of Example 1 containing 40 wt % cuprate (2-), 29H, 31H phthalocyanine disulfonato (4-) N29, N30, N31, N32 di-1-alkanammonium, -N-(alkyl) salt, 20 wt % butyl lactate, 20 wt % Vortex R citrus solvent, 5 wt % long chain fatty acid ester, 10 wt % triethanol amine, and 5 wt % Pegospherse R dispersing agent.
• a water-reducible solution was prepared in the manner of Example 1 containing 46 wt % cobaltate bis-2,2"dioxy-4-di 2"-hydroxy-3"-alkyloxy-propyl amino-4-phenylazo-5-methyl-azobenzene, hydrogen dibutanammonium salt, 40 wt % dipentene and 14 wt % long chain fatty acid ester.
• ATR-C The major component appears to be limonene.
• the surfactant was identified as a mixture of ethoxylated alkyl phenols with the average structure C 12 .7 H 26 .4 - p C 6 H 4 -O-(CH 2 CH 2 -O) 7 H . Assuming an average molecular weight of 580, the surfactant was estimated to be approximately 7 wt % of the sample.
• Vortex This sample appears to be very similar to ATR-C.
• the major component is limonene; the surfactant appears to be a mixture of ethoxylated alkyl phenols.
• ATR-HI FLASH The major component is terpinolene.
• the surfactant was identified as an ethoxylated alkyl phenol with an average surface structure C 17 .7 H 36 .8 - p C 6 H 4 -O-(CH 2 CH 2 -O) 5 .3 H.
• IGEPAL 630 this sample was a surfactant that was known to be an ethoxylated alkyl phenol. NMR spectra determined an average structure C 8 .7 H 18 .5 - p C 6 H 4 -O-(CH 2 CH 2 -O) 8 .6 H.
• ATR-P The NMR spectra of this sample are very complex.
• the terpenoid component is a complex mixture, containing limonene as well as many other components.
• An ethoxylated surfactant appears to be present at a higher level in this sample.
• the ethoxylated segments appear to contain some oxymethylene groups.
• the surfactant may be an ethoxylated alkyl phenol, but due to the complexity of the spectra and the diversity in the structures, positive identification is very difficult. A small carbonyl component, possibly an ester, was also detected in this sample.
• Dipentene This sample also appears to be quite complex.
• the terpenoid solvent contains limonene as well as a number of other components. Its distribution is somewhat similar to that of ATR-P.
• the surfactant in this sample is similar to that of ATR-P. No carbonyl component was detected.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• Dispersion Chemistry (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Colloid Chemistry (AREA)
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Abstract

Water-immiscible solvent dyes are mixed with citrus solvents and non-ionic surfactants to form a water-reducible true dye solution containing at least 35 wt % of the water-immiscible dye. The dye solution is dispersible in water and infinitely reducible.

Description

This is a continuation in part of application Ser. No. 08/214,334 filed Mar. 16, , now abandoned, which is a Continuation-In-Part of U.S. Ser. No. 08/063,833 filed May 18, , now abandoned. The present invention is directed to water-reducible dye compositions which, upon mixing with water, form aqueous dispersions of the dyes and to the aqueous dispersions formed therefrom. BACKGROUND OF THE INVENTION There are a wide variety of types of dyes which are water-immiscible. A major advantage of water-immiscible dyes is that such dyes tend to be permanent, at least with respect to exposure to water. A disadvantage of such dyes is that they require organic solvent carriers, such as xylene, which are problematic from a health and environmental standpoint. The present invention is directed to compositions of water-immiscible dyes which form stable dispersions in aqueous media and therefor provide the permanence of water-immiscible dyes without the accompanying disadvantage of containing substantial amounts of harmful organic solvent carriers. For many industrial applications, such as for forming inks, high dye loadings are required. Dye solutions typically must be formulated with a variety of additional ingredients which dilute the coloring effect of the dye; hence, the need for high dye loading. Furthermore, the solvent used to dissolve the dye may not be desirably used at a high level in the formulation. Accordingly, it is a further object of the invention that the water-reducible dye solutions have high dye loadings. SUMMARY OF THE INVENTION A water-reducible dye solution of the present invention comprises between about 35 wt % and about 70 wt % of a) a water-immiscible solvent dye or mixture of solvent dyes, at least about 25 wt % of said dye solution being a solvent dye or mixture of solvent dyes selected from the dye types consisting of azo dyes, phthalocyanine dyes, and anthraquinone dyes; between about 10 and about 64 wt % of b) a solvent system for said water-immiscible dye or dye mixture in sufficient quantities to dissolve said water-immiscible dye or dye mixture, said solvent system comprising between about 30 and about 100 wt % of b1) a citrus solvent(s) and b2) between 0 and about 70 wt % of a compatible co-solvent(s) which is either water-immiscible or water-immiscible; and c) between about 1 and about 55 wt % of a non-ionic surfactant. When mixed into water, the water-reducible solutions form stable micro dispersions of the water-immiscible dye solutions in the water, which dispersions are infinitely reducible. The dyes of such aqueous dispersions become permanently fixed to the material to which they are applied. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Solvent dyes are dyes that have at least some solubility in one or more organic solvents in which solvent the dye may be dissolved and by which the cye may be carried to the substrate. Solvent dyes are completely or substantially immiscible in water. Solvent dyes are discussed more fully in Colour Index International, 3rd ed., Additions and Amendments no. 67, April , p. 147-148. The water-immiscible solvent dyes which comprise at least 25 wt % of the dye solutions of the present invention are of the dye types: 1. Azo dyes which includes monoazo, disazo and tetrazo's of both the metallized and non-metallized varieties. Metallized dyes are typically described as amine salts of monatomic metal chelates with one or two molecules of dye, depending upon the metal used. Non-metallized azo dyes include guanidine salt types typical of the LuxolR product line. Specific examples of water-immiscible azo dyes include but are not limited to are: 1--Automate® Black 104 =color index (c.i.) Solvent Black 49 =benzene azobenzene naphthyl benzeneamino hydroxy, alkyl derivatives/alkylamino-cuprate. CAS Accession # . 2--Automate® Yellow D--c.i. Solvent Yellow, 4--(2-hydroxy-5-nonylphenylazo)-[N-[4--(2-hydroxy-5-nonylphenylazo)-phenyl]]benzamide. CAS # PMN Notice No. P-91-890. 3--Automate® Red B=c.i. Solvent Red 164=2-naphthalenol(phenylazo)phenyl azo alkyl derivatives. CAS #=TSCA accession # . 4--Morfast® Red 101 =c.i. Solvent Red 68=1,3-naphthalenedisulfonic acid, 7-hydroxy-8-4-(phenyl-azo) phenyl azo-, compound with 2-ethyl-N-(2-ethylhexyl)-1-hexanamine (1:2). CAS #=-82-8. 5--Morfast® Black 101 =c.i. Solvent Black 48 =cobaltate bis-2, 2'dioxy-4-di 2"-hydroxy-3"-alkyloxy-propyl amino-4-phenylazo-5-methyl-azobenzene, hydrogen dibutanammonium salt. 6 --Luxol® Brown K=c.i. Solvent Brown 20=1,3-naphthalenedisulfonic acid,7,7' (4,6-dihydroxy-1,3-phenylene) bis (azo) bis arylguanidine salt. CAS # -28-7. 7-Automate® Yellow 126--c.i. Solvent Yellow 126=1,3 benzenediol, 2,4-bis (alkyl phenyl) azo-. CAS # -28-1; -00-5; and -04-3. 8--c.i. Solvent Brown 52 =ferrate bis-2,2'dioxy-4-di 2"-hydroxy-3"alkoxy-propyl amino-5'-chloroazobenzene, hydrogen dibutanammonium salt. CAS" -76-3. 2. Phthalocyanine derived dyes, mainly of the sulfonated versions derived from coppered pigments. Specific examples include but are not limited to: 1--Morfast® Blue 100 =c.i. Solvent Blue 129 =cuprate (2-), 29H, 31H phthalocyanine disulfonato (4-) N29, N30, N31, N32 di-1-alkanammonium, -N-(alkyl) salt CAS # -92-0. 2--Luxol® Blue MBSN=c.i. Solvent Blue 38 =cuprate (2-), 29H, 31H-phthalocyanine-disulfonato (4)-N29, N30, N31, N32-arylguanidine salt. CAS # -51-4. 3. Anthraquinones, predominantly, mono, di and mixed substituted alkylamino derivatives as well as mono, di and mixed substituted arylamino types. Specific examples include but are not limited to: 1--Automate® Blue 8 =c.i. Solvent Blue 98=1,4-dialkylamino anthraquinone. CAS # -36-8. 2--Automate® Green 5 =c.i. Solvent Green 5=9,10-anthracenedione, 1,4-bis [(alkylphenyl) amino] anthraquinone. CAS # : none assigned. 3--BASF's Flussig Blue 672 =c.i. Solvent Blue 79= 1,4-dialkoxyamino anthraquinone. Other solvent dyes used in solvent dye solutions in accordance with the invention, if not of one of the dye types listed above, used in admixture with a dye or dyes of the type(s) mentioned above include, but are not limited to (according to their color index designations): Solvent Violet 9, CAS # 467-63-0; Solvent Black 7, CAS # -03-5; Solvent Blue 100, CAS # -50-6; Solvent Orange 97, CAS # -04-0; and Solvent Red 49, CAS # 509-34-2. The term "Citrus Solvent" is used herein inclusively to include chemicals defined as citrus peel oils, terpene, terpinene, and dipentene. The definitions of these classes in Hawley's Condensed Chemical Dictionary, Eleventh Edition overlap: "Citrus Peel Oils"- Edible oils expressed from the peel or rind of grapefruit, lemon, lime, orange and tangerine; Constituents: limonene, citral, and terpenes in varying percentages. "Terpene"- C10 H16 An unsaturated hydrocarbon occurring inmost essential oils and oleoresins of plants. The terpenes are based on the isoprene unit C5 H8, and may be either acyclic or cyclic with one or more benzenoid groups. There are classified as monocyclic (dipentene), dicyclic (pinene) or acyclic Myrcene, according to the molecular structure. "Terpinene"- C10 H16 A mixture of three isomeric cyclic terpenes, alpha, beta and gamma terpinene. "Dipentene"- (cinene; limonene, inactive; dl-p-mentha-1,8-diene; cajputene); Commercial form is high in dipentene content, but also contains other terpenes and related compounds in varying amounts. "Limonene"- a widely distributed optically active terpene, closely related to isoprene. It occurs naturally in both D- and L- forms. The racemic mixture of two isomers is known as dipentene. Citrus solvents are found to be particularly useful solvents in providing dispersions of a wide variety of dyes. In addition, citrus solvents are non-toxic, environmentally safe and biodegradable. The citrus solvent may comprise 100% of the solvent of the water-reducible dye composition, or may be admixed with a co-solvent up to a 30/70 citrus solvent/co-solvent wt. ratio, preferably one which is likewise non-toxic and environmentally benign. Examples of suitable co-solvents include but are not limited to ethyl lactate, butyl lactate, propylene glycol, triethanolamine, methyl ethyl ketone, ethanol, methanol, diethanolamine, methyl lactate, xylene, 1-methoxy-2-propanol, 2-methoxy-1-propanol. The third essential component is a non-ionic surfactant. Suitable surfactants include fatty acid esters; polyoxyethylated nonyl phenol derivatives; Rhone Poulene--CO-720 and CO630 nonylphenoxypoly (ethyleneoxy) ethanol CAS # -45-9; Union Carbide--Tergitol D-683 alkoxylated alkylphenol CAS # -69-7; Rhone Poulene--Alkamide modified coconut diethanolamide CAS # -42-9; Rhone Poulene--Alkamuls EL-985 polyethoxylated caster oil CAS # 75-21-8; and Morton International--Sotex N long chain fatty acid esters. The specific solvent dyes discussed above can be loaded in citrus solvent compositions to high levels, i.e., at least about 35 wt % and some up to about 70 wt %. This high loading is unexpected. U.S. Pat. No. 5,092,907 describes dispersions of pigments in terpene oil. It also suggests that soluble dyes may be dissolved in terpene oil, but to a maximum of 30%. Thus that it is found that loading levels of 35 wt % or greater of particular dyes and dye mixtures in citrus solvents can be achieved is unexpected. As stated above, high dye levels are advantageous in that the industry requires high dye loadings, particularly for dye compositions which will be subsequently diluted by other components of particular formulations. These components a)-c) are blended together to form a stable water-reducible true dye solution in accordance with the present invention. The dye solution is typically provided free of water for shipment and storage. The end user adds the dye solution to water (or aqueous medium) with appropriate agitation to produce a dispersion of the dye solution in water (or aqueous medium). Generally, stable dispersions are achieved at a 1:1 ratio of water reducible dye solution to water. However, the dye solution can accommodate more or less water, so as to provide the dye content the user desires. Aqueous dispersions of the dye solution of the present invention can be used for example in felt tip pens, ball point pens, printing inks, hand stamps, ink jet inks, coatings, paints and woodstains. The invention will now be described in greater detail by way of specific examples. EXAMPLE 1 To a 1 liter round bottom flask was charged 200 grams of a xylene solution of benzene azobenzene naphthyl benzeneaminohydroxy, alkyl derivatives/alkylaminocuprate. The dye was heated to 120° C. under full vacuum to distill out all xylene (approximately 48%). The xylene is replaced with 90 grams ATR-High FlashR citrus solvent and 10 grams long chain fatty acid ester. This solution when mixed with 204 ml. water with stirring formed a dispersion of the dye solution. EXAMPLE 2 A water-reducible solution was prepared in the manner of Example 1 containing 40 wt % 4-(2-hydroxy-5-nonylphenylazo)-[N[4-(2-hydroxy-5-nonylphenylazo)-phenyl]] benzamide, 36 wt % ATR-P citrus solvent and 24 wt % IgepalR CO630. EXAMPLE 3 A water-reducible solution was prepared in the manner of example 1 containing 35 wt % 1,4 dialkylamino anthraquinone, 46 wt % VortexR citrus solvent and 19 wt % long chain fatty acid ester. EXAMPLE 4 A water-reducible solution was prepared in the manner of Example 1 containing 40 wt % cuprate (2-), 29H, 31H phthalocyanine disulfonato (4-) N29, N30, N31, N32 di-1-alkanammonium, -N-(alkyl) salt, 20 wt % butyl lactate, 20 wt % VortexR citrus solvent, 5 wt % long chain fatty acid ester, 10 wt % triethanol amine, and 5 wt % PegospherseR dispersing agent. EXAMPLE 5 A water-reducible solution was prepared in the manner of Example 1 containing 46 wt % cobaltate bis-2,2"dioxy-4-di 2"-hydroxy-3"-alkyloxy-propyl amino-4-phenylazo-5-methyl-azobenzene, hydrogen dibutanammonium salt, 40 wt % dipentene and 14 wt % long chain fatty acid ester. Commercial citrus solvent/surfactant compositions useful in the present invention are analyzed as follows: ATR-C: The major component appears to be limonene. The surfactant was identified as a mixture of ethoxylated alkyl phenols with the average structure C12.7 H26.4 -p C6 H4 -O-(CH2 CH2 -O)7 H . Assuming an average molecular weight of 580, the surfactant was estimated to be approximately 7 wt % of the sample. Vortex: This sample appears to be very similar to ATR-C. The major component is limonene; the surfactant appears to be a mixture of ethoxylated alkyl phenols. ATR-HI FLASH: The major component is terpinolene. The surfactant was identified as an ethoxylated alkyl phenol with an average surface structure C17.7 H36.8 -p C6 H4 -O-(CH2 CH2 -O)5.3 H. IGEPAL 630: this sample was a surfactant that was known to be an ethoxylated alkyl phenol. NMR spectra determined an average structure C8.7 H18.5 -p C6 H4 -O-(CH2 CH2 -O)8.6 H. ATR-P: The NMR spectra of this sample are very complex. The terpenoid component is a complex mixture, containing limonene as well as many other components. An ethoxylated surfactant appears to be present at a higher level in this sample. The ethoxylated segments appear to contain some oxymethylene groups. The surfactant may be an ethoxylated alkyl phenol, but due to the complexity of the spectra and the diversity in the structures, positive identification is very difficult. A small carbonyl component, possibly an ester, was also detected in this sample. Dipentene: This sample also appears to be quite complex. The terpenoid solvent contains limonene as well as a number of other components. Its distribution is somewhat similar to that of ATR-P. The surfactant in this sample is similar to that of ATR-P. No carbonyl component was detected.

Claims (2)

What is claimed is: 1. A water-reducible dye solution comprisingbetween about 35 wt % and about 70 wt % of a) a water immiscible solvent dye or mixture of solvent dyes, at least about 25 wt % of said dye solution being an azo, pthalocyanine, or anthraquinone solvent dye selected from the group consisting of Solvent Black 49 (CAS Accession # ), Solvent Yellow (CAS # PMN Notice No. P-91-890), Solvent Red 164 (CAS #=TSCA Accession # ), Solvent Red 68 (CAS # -82-8), Solvent Black 48 (cobaltate bis-2,2'-dioxy-4-di-2"-hydroxy-3"-alkyloxy-propyl amino-4-phenylazo-5-methyl-azobenzene, hydrogen dibutanammonium salt), Solvent Brown 20 (CAS # -28-7), Solvent Yellow 126 (CAS # -28-1; -00-5 and -04-3), Solvent Brown 52 (CAS # -76-3), Solvent Blue 129 (CAS # -92-0), Solvent Blue 38 (CAS # -51-4), Solvent Blue 98 (CAS # -36-8), Solvent Green 5 (9,10-anthracenedione-1,4-bis-{(alkylphenyl)amino}anthraquinone), Solvent Blue 79 (1,4-dialkoxyamino anthraquinone), and mixtures thereof; between about 10 and about 64 wt % of b) a solvent system for said water-immiscible solvent dye or mixture of dyes in sufficient quantities to dissolve said water-immiscible solvent dye or mixture of solvent dyes, said solvent system comprising between about 30 and about 100 wt % ofb1) a citrus solvent or mixture of citrus solvents and b2) between 0 and about 70 wt % of an additional solvent or mixture of additional solvents which is either water-miscible or water-immiscible; and c) between about 1 and about 55 wt % of a non-ionic surfactant. 2. The composition of claim 1 dispersed in an aqueous medium. US08/445,230 -05-18 -05-19 Water-reducible dye compositions comprising solvent dyes and citrus solvents Expired - Fee Related USA (en)

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Cited By (12)

* Cited by examiner, † Cited by third party Publication number Priority date Publication date Assignee Title USA (en) * -07-31 -11-17 Morton International, Inc. Stable oil-in-water ink emulsions based upon water-reducible solvent dyes for ink-jet printers and felt-tip and roller-ball pens USA (en) * -03-06 -08-10 Pomp; Paul R. Firearm cleaning agent for cleaning a firearm bore USA (en) * -11-21 -11-23 University Of Massachusetts Apparatus and method for measuring components of a solute stream USB1 (en) * -12-05 -03-25 Basf Aktiengesellschaft Dye preparations containing azo dyes USA1 (en) * -06-07 -12-28 Kimball James F Composition for application to a surface USA1 (en) * -06-06 -12-06 Shah Ketan N Method of neutralizing a stain on a surface USA1 (en) * -06-07 -11-20 Shah Ketan N Method of affixing a design to a surface USA1 (en) * -06-07 -01-22 Frazee Glenn R Composition for application to a surface USA1 (en) * -06-07 -11-05 S.C. Johnson & Son, Inc. Composition For Application To A Surface USA1 (en) * -05-14 -11-19 Bass Benjamin A Design devices for applying a design to a surface USB2 (en) -06-07 -10-15 S.C. Johnson & Son, Inc. Devices for applying a colorant to a surface USB2 (en) -06-07 -09-30 S.C. Johnson & Son, Inc. Carpet décor and setting solution compositions

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* Cited by examiner, † Cited by third party Publication number Priority date Publication date Assignee Title USA (en) * -04-08 -01-13 Morton International, Inc. Water-reducible nigrosine dye compositions USA (en) * -07-31 -05-05 Morton International, Inc. Stable oil-in-water ink emulsions based upon water-reducible nigrosine dyes for ink-jet printers and felt-tip and roller-ball pens

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* Cited by examiner, † Cited by third party Publication number Priority date Publication date Assignee Title USA (en) * -07-31 -11-17 Morton International, Inc. Stable oil-in-water ink emulsions based upon water-reducible solvent dyes for ink-jet printers and felt-tip and roller-ball pens USA (en) * -11-21 -11-23 University Of Massachusetts Apparatus and method for measuring components of a solute stream USB1 (en) * -12-05 -03-25 Basf Aktiengesellschaft Dye preparations containing azo dyes USB2 (en) -12-05 -12-30 Basf Aktiengesellschaft Dye preparations comprising azo dyes USA (en) * -03-06 -08-10 Pomp; Paul R. Firearm cleaning agent for cleaning a firearm bore USA (en) * -03-06 -06-20 Heritage Institute, Inc. Method for cleaning a firearm bore USB2 (en) -06-07 -07-07 S. C. Johnson & Son, Inc. Method of applying a design to a surface USB2 (en) -06-07 -06-01 S.C. Johnson & Son, Inc. Composition for application to a surface USA1 (en) * -06-07 -04-26 Kimball James F Design devices for applying a design to a surface USA1 (en) * -06-07 -12-06 Shah Ketan N Method of neutralizing a stain on a surface USB2 (en) -06-07 -09-30 S.C. Johnson & Son, Inc. Carpet décor and setting solution compositions USA1 (en) * -06-07 -11-20 Shah Ketan N Method of affixing a design to a surface USA1 (en) * -06-07 -12-18 Shah Ketan N Carpet decor and setting solution compositions USA1 (en) * -06-07 -01-22 Frazee Glenn R Composition for application to a surface USA1 (en) * -06-07 -12-28 Kimball James F Composition for application to a surface USA1 (en) * -06-07 -11-05 S.C. Johnson & Son, Inc. Composition For Application To A Surface USB2 (en) -06-07 -06-10 S.C. Johnson & Son, Inc. Composition for application to a surface USA1 (en) * -06-07 -01-18 Kimball James F Method of applying a design to a surface USB2 (en) -06-07 -07-27 S.C. Johnson & Son, Inc. Composition for application to a surface USB2 (en) -06-07 -08-17 S.C. Johnson & Son, Inc. Composition for application to a surface USB2 (en) -06-07 -08-24 S.C. Johnson & Son, Inc. Carpet decor and setting solution compositions USB2 (en) -06-07 -11-09 S.C. Johnson & Son, Inc. Method of neutralizing a stain on a surface USB2 (en) -06-07 -05-24 S.C. Johnson & Son, Inc. Method of neutralizing a stain on a surface USB2 (en) -06-07 -11-01 S.C. Johnson & Son, Inc. Composition for application to a surface USB2 (en) -06-07 -05-27 S.C. Johnson & Son, Inc. Composition for application to a surface USB2 (en) -06-07 -10-15 S.C. Johnson & Son, Inc. Devices for applying a colorant to a surface USA1 (en) * -06-06 -12-06 Shah Ketan N Method of neutralizing a stain on a surface USB2 (en) -05-14 -08-06 S. C. Johnson & Son, Inc. Kit including multilayer stencil for applying a design to a surface USB2 (en) -05-14 -11-22 S.C. Johnson & Son, Inc. Multilayer stencils for applying a design to a surface USA1 (en) * -05-14 -11-19 Bass Benjamin A Design devices for applying a design to a surface

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The present invention is directed to water-reducible dye compositions which, upon mixing with water, form aqueous dispersions of the dyes and to the aqueous dispersions formed therefrom.

BACKGROUND OF THE INVENTION

There are a wide variety of types of dyes which are water-immiscible. A major advantage of water-immiscible dyes is that such dyes tend to be permanent, at least with respect to exposure to water. A disadvantage of such dyes is that they require organic solvent carriers, such as xylene, which are problematic from a health and environmental standpoint.

The present invention is directed to compositions of water-immiscible dyes which form stable dispersions in aqueous media and therefor provide the permanence of water-immiscible dyes without the accompanying disadvantage of containing substantial amounts of harmful organic solvent carriers.

For many industrial applications, such as for forming inks, high dye loadings are required. Dye solutions typically must be formulated with a variety of additional ingredients which dilute the coloring effect of the dye; hence, the need for high dye loading. Furthermore, the solvent used to dissolve the dye may not be desirably used at a high level in the formulation. Accordingly, it is a further object of the invention that the water-reducible dye solutions have high dye loadings.

SUMMARY OF THE INVENTION

A water-reducible dye solution of the present invention comprises between about 35 wt % and about 70 wt % of a) a water-immiscible solvent dye or mixture of solvent dyes, at least about 25 wt % of said dye solution being a solvent dye or mixture of solvent dyes selected from the dye types consisting of azo dyes, phthalocyanine dyes, and anthraquinone dyes; between about 10 and about 64 wt % of b) a solvent system for said water-immiscible dye or dye mixture in sufficient quantities to dissolve said water-immiscible dye or dye mixture, said solvent system comprising between about 30 and about 100 wt % of b1) a citrus solvent(s) and b2) between 0 and about 70 wt % of a compatible co-solvent(s) which is either water-immiscible or water-immiscible; and c) between about 1 and about 55 wt % of a non-ionic surfactant. When mixed into water, the water-reducible solutions form stable micro dispersions of the water-immiscible dye solutions in the water, which dispersions are infinitely reducible. The dyes of such aqueous dispersions become permanently fixed to the material to which they are applied.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Solvent dyes are dyes that have at least some solubility in one or more organic solvents in which solvent the dye may be dissolved and by which the cye may be carried to the substrate. Solvent dyes are completely or substantially immiscible in water. Solvent dyes are discussed more fully in Colour Index International, 3rd ed., Additions and Amendments no. 67, April , p. 147-148.

The water-immiscible solvent dyes which comprise at least 25 wt % of the dye solutions of the present invention are of the dye types:

1. Azo dyes which includes monoazo, disazo and tetrazo's of both the metallized and non-metallized varieties. Metallized dyes are typically described as amine salts of monatomic metal chelates with one or two molecules of dye, depending upon the metal used. Non-metallized azo dyes include guanidine salt types typical of the Luxol.sup.R product line. Specific examples of water-immiscible azo dyes include but are not limited to are:

1--Automate.RTM. Black 104 =color index (c.i.) Solvent Black 49 =benzene azobenzene naphthyl benzeneamino hydroxy, alkyl derivatives/alkylamino-cuprate. CAS Accession # .

2--Automate.RTM. Yellow D--c.i. Solvent Yellow, 4--(2-hydroxy-5-nonylphenylazo)-[N-[4--(2-hydroxy-5-nonylphenylazo)-phenyl ]]benzamide. CAS # PMN Notice No. P-91-890.

3--Automate.RTM. Red B=c.i. Solvent Red 164=2-naphthalenol(phenylazo)phenyl azo alkyl derivatives. CAS #=TSCA accession # .

4--Morfast.RTM. Red 101 =c.i. Solvent Red 68=1,3-naphthalenedisulfonic acid, 7-hydroxy-8-4-(phenyl-azo) phenyl azo-, compound with 2-ethyl-N-(2-ethylhexyl)-1-hexanamine (1:2). CAS #=-82-8.

5--Morfast.RTM. Black 101 =c.i. Solvent Black 48 =cobaltate bis-2, 2'dioxy-4-di 2"-hydroxy-3"-alkyloxy-propyl amino-4-phenylazo-5-methyl-azobenzene, hydrogen dibutanammonium salt.

6 --Luxol.RTM. Brown K=c.i. Solvent Brown 20=1,3-naphthalenedisulfonic acid,7,7' (4,6-dihydroxy-1,3-phenylene) bis (azo) bis arylguanidine salt. CAS # -28-7.

7-Automate.RTM. Yellow 126--c.i. Solvent Yellow 126=1,3 benzenediol, 2,4-bis (alkyl phenyl) azo-. CAS # -28-1; -00-5; and -04-3. 8--c.i. Solvent Brown 52 =ferrate bis-2,2'dioxy-4-di 2"-hydroxy-3"alkoxy-propyl amino-5'-chloroazobenzene, hydrogen dibutanammonium salt. CAS" -76-3.

2. Phthalocyanine derived dyes, mainly of the sulfonated versions derived from coppered pigments. Specific examples include but are not limited to:

1--Morfast.RTM. Blue 100 =c.i. Solvent Blue 129 =cuprate (2-), 29H, 31H phthalocyanine disulfonato (4-) N29, N30, N31, N32 di-1-alkanammonium, -N-(alkyl) salt CAS # -92-0.

2--Luxol.RTM. Blue MBSN=c.i. Solvent Blue 38 =cuprate (2-), 29H, 31H-phthalocyanine-disulfonato (4)-N29, N30, N31, N32-arylguanidine salt. CAS # -51-4.

3. Anthraquinones, predominantly, mono, di and mixed substituted alkylamino derivatives as well as mono, di and mixed substituted arylamino types. Specific examples include but are not limited to:

1--Automate.RTM. Blue 8 =c.i. Solvent Blue 98=1,4-dialkylamino anthraquinone. CAS # -36-8.

2--Automate.RTM. Green 5 =c.i. Solvent Green 5=9,10-anthracenedione, 1,4-bis [(alkylphenyl) amino] anthraquinone. CAS # : none assigned.

3--BASF's Flussig Blue 672 =c.i. Solvent Blue 79= 1,4-dialkoxyamino anthraquinone.

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Other solvent dyes used in solvent dye solutions in accordance with the invention, if not of one of the dye types listed above, used in admixture with a dye or dyes of the type(s) mentioned above include, but are not limited to (according to their color index designations): Solvent Violet 9, CAS # 467-63-0; Solvent Black 7, CAS # -03-5; Solvent Blue 100, CAS # -50-6; Solvent Orange 97, CAS # -04-0; and Solvent Red 49, CAS # 509-34-2.

The term "Citrus Solvent" is used herein inclusively to include chemicals defined as citrus peel oils, terpene, terpinene, and dipentene. The definitions of these classes in Hawley's Condensed Chemical Dictionary, Eleventh Edition overlap:

"Citrus Peel Oils"- Edible oils expressed from the peel or rind of grapefruit, lemon, lime, orange and tangerine; Constituents: limonene, citral, and terpenes in varying percentages.

"Terpene"- C.sub.10 H.sub.16 An unsaturated hydrocarbon occurring inmost essential oils and oleoresins of plants. The terpenes are based on the isoprene unit C.sub.5 H.sub.8, and may be either acyclic or cyclic with one or more benzenoid groups. There are classified as monocyclic (dipentene), dicyclic (pinene) or acyclic Myrcene, according to the molecular structure.

"Terpinene"- C.sub.10 H.sub.16 A mixture of three isomeric cyclic terpenes, alpha, beta and gamma terpinene.

"Dipentene"- (cinene; limonene, inactive; dl-p-mentha-1,8-diene; cajputene); Commercial form is high in dipentene content, but also contains other terpenes and related compounds in varying amounts.

"Limonene"- a widely distributed optically active terpene, closely related to isoprene. It occurs naturally in both D- and L- forms. The racemic mixture of two isomers is known as dipentene.

Citrus solvents are found to be particularly useful solvents in providing dispersions of a wide variety of dyes. In addition, citrus solvents are non-toxic, environmentally safe and biodegradable. The citrus solvent may comprise 100% of the solvent of the water-reducible dye composition, or may be admixed with a co-solvent up to a 30/70 citrus solvent/co-solvent wt. ratio, preferably one which is likewise non-toxic and environmentally benign. Examples of suitable co-solvents include but are not limited to ethyl lactate, butyl lactate, propylene glycol, triethanolamine, methyl ethyl ketone, ethanol, methanol, diethanolamine, methyl lactate, xylene, 1-methoxy-2-propanol, 2-methoxy-1-propanol.

The third essential component is a non-ionic surfactant. Suitable surfactants include fatty acid esters; polyoxyethylated nonyl phenol derivatives; Rhone Poulene--CO-720 and CO630 nonylphenoxypoly (ethyleneoxy) ethanol CAS # -45-9; Union Carbide--Tergitol D-683 alkoxylated alkylphenol CAS # -69-7; Rhone Poulene--Alkamide modified coconut diethanolamide CAS # -42-9; Rhone Poulene--Alkamuls EL-985 polyethoxylated caster oil CAS # 75-21-8; and Morton International--Sotex N long chain fatty acid esters.

The specific solvent dyes discussed above can be loaded in citrus solvent compositions to high levels, i.e., at least about 35 wt % and some up to about 70 wt %. This high loading is unexpected. U.S. Pat. No. 5,092,907 describes dispersions of pigments in terpene oil. It also suggests that soluble dyes may be dissolved in terpene oil, but to a maximum of 30%. Thus that it is found that loading levels of 35 wt % or greater of particular dyes and dye mixtures in citrus solvents can be achieved is unexpected. As stated above, high dye levels are advantageous in that the industry requires high dye loadings, particularly for dye compositions which will be subsequently diluted by other components of particular formulations.

These components a)-c) are blended together to form a stable water-reducible true dye solution in accordance with the present invention. The dye solution is typically provided free of water for shipment and storage. The end user adds the dye solution to water (or aqueous medium) with appropriate agitation to produce a dispersion of the dye solution in water (or aqueous medium). Generally, stable dispersions are achieved at a 1:1 ratio of water reducible dye solution to water. However, the dye solution can accommodate more or less water, so as to provide the dye content the user desires.

Aqueous dispersions of the dye solution of the present invention can be used for example in felt tip pens, ball point pens, printing inks, hand stamps, ink jet inks, coatings, paints and woodstains.

The invention will now be described in greater detail by way of specific examples.

EXAMPLE 1

To a 1 liter round bottom flask was charged 200 grams of a xylene solution of benzene azobenzene naphthyl benzeneaminohydroxy, alkyl derivatives/alkylaminocuprate. The dye was heated to 120.degree. C. under full vacuum to distill out all xylene (approximately 48%). The xylene is replaced with 90 grams ATR-High Flash.sup.R citrus solvent and 10 grams long chain fatty acid ester.

This solution when mixed with 204 ml. water with stirring formed a dispersion of the dye solution.

EXAMPLE 2

A water-reducible solution was prepared in the manner of Example 1 containing 40 wt % 4-(2-hydroxy-5-nonylphenylazo)-[N[4-(2-hydroxy-5-nonylphenylazo)-phenyl]] benzamide, 36 wt % ATR-P citrus solvent and 24 wt % Igepal.sup.R CO630.

EXAMPLE 3

A water-reducible solution was prepared in the manner of example 1 containing 35 wt % 1,4 dialkylamino anthraquinone, 46 wt % Vortex.sup.R citrus solvent and 19 wt % long chain fatty acid ester.

EXAMPLE 4

A water-reducible solution was prepared in the manner of Example 1 containing 40 wt % cuprate (2-), 29H, 31H phthalocyanine disulfonato (4-) N29, N30, N31, N32 di-1-alkanammonium, -N-(alkyl) salt, 20 wt % butyl lactate, 20 wt % Vortex.sup.R citrus solvent, 5 wt % long chain fatty acid ester, 10 wt % triethanol amine, and 5 wt % Pegospherse.sup.R dispersing agent.

EXAMPLE 5

A water-reducible solution was prepared in the manner of Example 1 containing 46 wt % cobaltate bis-2,2"dioxy-4-di 2"-hydroxy-3"-alkyloxy-propyl amino-4-phenylazo-5-methyl-azobenzene, hydrogen dibutanammonium salt, 40 wt % dipentene and 14 wt % long chain fatty acid ester.

Commercial citrus solvent/surfactant compositions useful in the present invention are analyzed as follows:

ATR-C: The major component appears to be limonene. The surfactant was identified as a mixture of ethoxylated alkyl phenols with the average structure C.sub.12.7 H.sub.26.4 -.sub.p C.sub.6 H.sub.4 -O-(CH.sub.2 CH.sub.2 -O).sub.7 H . Assuming an average molecular weight of 580, the surfactant was estimated to be approximately 7 wt % of the sample.

Vortex: This sample appears to be very similar to ATR-C. The major component is limonene; the surfactant appears to be a mixture of ethoxylated alkyl phenols.

ATR-HI FLASH: The major component is terpinolene. The surfactant was identified as an ethoxylated alkyl phenol with an average surface structure C.sub.17.7 H.sub.36.8 -.sub.p C.sub.6 H.sub.4 -O-(CH.sub.2 CH.sub.2 -O).sub.5.3 H.

IGEPAL 630: this sample was a surfactant that was known to be an ethoxylated alkyl phenol. NMR spectra determined an average structure C.sub.8.7 H.sub.18.5 -.sub.p C.sub.6 H.sub.4 -O-(CH.sub.2 CH.sub.2 -O).sub.8.6 H.

ATR-P: The NMR spectra of this sample are very complex. The terpenoid component is a complex mixture, containing limonene as well as many other components. An ethoxylated surfactant appears to be present at a higher level in this sample. The ethoxylated segments appear to contain some oxymethylene groups. The surfactant may be an ethoxylated alkyl phenol, but due to the complexity of the spectra and the diversity in the structures, positive identification is very difficult. A small carbonyl component, possibly an ester, was also detected in this sample.

Dipentene: This sample also appears to be quite complex. The terpenoid solvent contains limonene as well as a number of other components. Its distribution is somewhat similar to that of ATR-P. The surfactant in this sample is similar to that of ATR-P. No carbonyl component was detected.

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