GB1591135A - Uniformly dyed water-swellable cellulose fibres - Google Patents
Uniformly dyed water-swellable cellulose fibres Download PDFInfo
- Publication number
- GB1591135A GB1591135A GB4723577A GB4723577A GB1591135A GB 1591135 A GB1591135 A GB 1591135A GB 4723577 A GB4723577 A GB 4723577A GB 4723577 A GB4723577 A GB 4723577A GB 1591135 A GB1591135 A GB 1591135A
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- United Kingdom
- Prior art keywords
- carbon atoms
- dye
- fibers
- alkyl
- alkoxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- 229920003043 Cellulose fiber Polymers 0.000 title description 5
- 239000000835 fiber Substances 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002270 dispersing agent Substances 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 60
- 125000000217 alkyl group Chemical group 0.000 claims description 32
- -1 phenoxy, methylphenoxy Chemical group 0.000 claims description 27
- 125000003545 alkoxy group Chemical group 0.000 claims description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 17
- 239000000460 chlorine Substances 0.000 claims description 16
- 229910052801 chlorine Inorganic materials 0.000 claims description 15
- 229920000742 Cotton Polymers 0.000 claims description 14
- 238000009472 formulation Methods 0.000 claims description 14
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 12
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052794 bromium Inorganic materials 0.000 claims description 12
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 12
- 229920000728 polyester Polymers 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 125000006353 oxyethylene group Chemical group 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000005083 alkoxyalkoxy group Chemical group 0.000 claims description 5
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000645 desinfectant Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 3
- 239000012209 synthetic fiber Substances 0.000 claims description 3
- 229920002994 synthetic fiber Polymers 0.000 claims description 3
- 125000005078 alkoxycarbonylalkyl group Chemical group 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims description 2
- 125000005359 phenoxyalkyl group Chemical group 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000007900 aqueous suspension Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000975 dye Substances 0.000 abstract description 37
- 229920002678 cellulose Polymers 0.000 abstract description 6
- 239000001913 cellulose Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 238000004043 dyeing Methods 0.000 abstract description 3
- 238000007639 printing Methods 0.000 abstract description 3
- 238000002360 preparation method Methods 0.000 abstract description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 6
- 239000004744 fabric Substances 0.000 description 5
- 239000007859 condensation product Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000002877 alkyl aryl group Chemical group 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 229920001732 Lignosulfonate Polymers 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical class OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 239000000986 disperse dye Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005108 dry cleaning Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical class CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 1
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- GGQADPAYPSXAMP-UHFFFAOYSA-N 1,4-dianilino-5-hydroxy-8-nitroanthracene-9,10-dione Chemical compound C1=CC(NC=2C=CC=CC=2)=C2C(=O)C=3C(O)=CC=C([N+]([O-])=O)C=3C(=O)C2=C1NC1=CC=CC=C1 GGQADPAYPSXAMP-UHFFFAOYSA-N 0.000 description 1
- GJCHQJDEYFYWER-UHFFFAOYSA-N 1,8-dihydroxy-4,5-dinitroanthracene-9,10-dione Chemical compound O=C1C2=C([N+]([O-])=O)C=CC(O)=C2C(=O)C2=C1C([N+]([O-])=O)=CC=C2O GJCHQJDEYFYWER-UHFFFAOYSA-N 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- 125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 description 1
- 125000006275 3-bromophenyl group Chemical group [H]C1=C([H])C(Br)=C([H])C(*)=C1[H] 0.000 description 1
- 125000004800 4-bromophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Br 0.000 description 1
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004861 4-isopropyl phenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- 101100460386 Arabidopsis thaliana NHX3 gene Proteins 0.000 description 1
- 101100412102 Haemophilus influenzae (strain ATCC 51907 / DSM 11121 / KW20 / Rd) rec2 gene Proteins 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000013011 aqueous formulation Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- JHAYEQICABJSTP-UHFFFAOYSA-N decoquinate Chemical group N1C=C(C(=O)OCC)C(=O)C2=C1C=C(OCC)C(OCCCCCCCCCC)=C2 JHAYEQICABJSTP-UHFFFAOYSA-N 0.000 description 1
- 125000004772 dichloromethyl group Chemical group [H]C(Cl)(Cl)* 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 235000012701 green S Nutrition 0.000 description 1
- 239000004120 green S Substances 0.000 description 1
- WDPIZEKLJKBSOZ-UHFFFAOYSA-M green s Chemical compound [Na+].C1=CC(N(C)C)=CC=C1C(C=1C2=CC=C(C=C2C=C(C=1O)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](C)C)C=C1 WDPIZEKLJKBSOZ-UHFFFAOYSA-M 0.000 description 1
- 125000003707 hexyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- HRDXJKGNWSUIBT-UHFFFAOYSA-N methoxybenzene Chemical group [CH2]OC1=CC=CC=C1 HRDXJKGNWSUIBT-UHFFFAOYSA-N 0.000 description 1
- JIQNWFBLYKVZFY-UHFFFAOYSA-N methoxycyclohexatriene Chemical compound COC1=C[C]=CC=C1 JIQNWFBLYKVZFY-UHFFFAOYSA-N 0.000 description 1
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical class C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010022 rotary screen printing Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 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
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
- C09B1/51—N-substituted amino-hydroxy anthraquinone
- C09B1/516—N-acylated derivatives
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
- D06P3/58—Material containing hydroxyl groups
- D06P3/60—Natural or regenerated cellulose
- D06P3/6033—Natural or regenerated cellulose using dispersed dyes
- D06P3/6041—Natural or regenerated cellulose using dispersed dyes using specified dyes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Coloring (AREA)
Abstract
The dye preparations contain dispersants, water retention aids, water and dyes of the formula I. The substituents indicated in the formula I are defined in Claim 1. The dyes are used for dyeing and printing cellulose or cellulose-containing fibre materials. <IMAGE>
Description
(54) UNIFORMLY DYED WATER-SWELLABLE
CELLULOSE FIBERS
(71) We, BASF AKTIENGESELLSCHAFT, a German Joint Stock
Company of 6700 Ludwigshafen, Federal Republic of Germany, do hereby declare -the invention, for which we pray that a Patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following Statement:- The present invention relates to uniformly dyed (as hereinafter defined) waterswellable cellulose fibers which are fast to washing, dry-cleaning, sublimation and light. By the expression "uniformly dyed" as used herein to describe the cellulosic
fibers we mean fibers in which the dye is homogeneously distributed in the cellulosic fibers in the dyed regions as opposed to fibers in which the dye is solely positioned on the surface of the cellulosic fibers in the dyed regions.The dye need not be distributed along the entire length of the fibers or over the entire area of fabrics composed of such fibers and printed fibers and fabrics are included within the expression if the dye is homogeneously distributed in this way in the printed regions.
According to the invention such uniformly dyed fibers are produced by
contacting water-swellable cellulose fibers with water and an oxyethylene swellersolvent (as hereinafter defined) to swell the fibers and, simultaneously or subsequently whilst the fibers are still swollen, with an essentially water-insoluble dye of the formula
where A and A', which are identical or different, are alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine, bromine, phenoxy, methylphenoxy or chlorophenoxy, n and n', which are identical or different, are 0, 1, 2 or 3, and X is hydrogen or
where R is hydrogen alkoxy of 1 to 10 carbon atoms, alkoxyalkoxy of a total of 3 to 7 carbon atoms, alkyl of 1 to 10 carbon atoms (which is unsubstituted or is monosubstituted, disubstituted or trisubstituted by chlorine), phenalkyl of 7 to 9 carbon atoms, phenyl (which is unsubstituted or is substituted by chlorine, bromine, nitro, alkyl of 1 to 4 carbon atoms or alkoxy of I to 4 carbon atoms), phenoxy, phenalkoxy of 7 to 9 carbon atoms, phenoxy-alkyl (where alkyl is of 1 to 3 carbon atoms), phenoxy-alkoxy (where alkoxy is of 2 to 4 carbon atoms), alkoxycarbonyl-alkyl (where alkoxy is of 1 to 4 carbon atoms and alkyl is of 2 to 4 carbon atoms), or phenylamino (which is unsubstituted or is substituted by chlorine, bromine or alkyl of 1 to 4 carbon atoms).
Specific examples of substituents A and A', are methyl, ethyl, propyl, isopropyl, n-butyl, sec.-butyl, tert.-butyl, methoxy, ethoxy, propoxy, isopropoxy, n butoxy, isobutoxy, chlorine, bromine, phenoxy, p-methylphenoxy and pchlorophenoxy.
Specific examples of R, in addition to hydrogen, are methoxy, ethoxy, propoxy, n-butoxy, isobutoxy, pentoxy, 2-methylbutoxy-1, 3-methylbutoxy-l, hexoxy, heptoxy-l, 2-ethylhexoxy-l, nonoxy and decoxy; o5-methoxyethoxy, A- ethoxyethoxy, -propoxyethoxy, A-butoxyethoxy, ,B-isopropoxyethoxy and /3- isobutoxypropoxy; methyl, ethyl propyl, isopropyl, butyl, isobutyl, heptyl-l, heptyl3, chloromethyl, dichloromethyl, trichloromethyl, 3-chloropropyl, 2-chloroethyl and l-chloroethyl; benzyl and p-phenylethyl; phenoxymethyl and p-phenoxyethyl; methoxycarbonylethyl, methoxycarbonylpropyl and ethoxycarbonylethyl ethoxycarbonylpropyl, methoxycarbonyl-butyl, ethoxycarbonylbutyl, butoxycarbonylbutyl, butoxycarbonylpropyl and butoxycarbonylethyl; ,B- phenoxyethoxy, A-phenoxypropoxy and phenoxybutoxy; phenoxy; phenyl, 2-, 3and 4-chlorophenyl, 3- and 4-bromophenyl, 3- and 4-nitrophenyl, 2-, 3- and 4methylphenyl, 4-ethylphenyl, 4-tert.-butylphenyl, 4-n-butylphenyl, 4isopropylphenyl, 2-, 3- and 4-methoxyphenyl and 4-ethoxyphenyl; benzyloxy, A- phenylethoxy and A-phenylpropoxy; phenylamino, 4-tolylamino, 4chlorophenylamino, 4-isopropylphenylamino, 4-tert.-butylphenylamino and 4bromophenylamino.
Preferred dyes of the formula I for use in the invention are those in which A and A' are identical and are 2-, 3- or 4-methyl, 4-methoxy or 4-phenoxy and n and n' are identical and are 0 or 1. Amongst these, in turn, more particularly preferred dyes of the formula I are those in which A and A' are identical and are 2-, 3- or 4methyl, 4-methoxy or 4-phenoxy, n and n' are identical and are 0 or 1 and X is
where R is alkoxy of 1 to 10 carbon atoms, alkoxyalkoxy of a total of 3 to 7 carbon atoms, alkyl of 1 to 10 carbon atoms, alkyl of 1 to 10, especially 1 to 5, carbon atoms which is monosubstituted, disubstituted or trisubstituted by chlorine, phenyl which is unsubstituted or substituted by chlorine, bromine, alkyl of I to 4 carbon atoms or nitro, or phenylamino which is unsubstituted or substituted by chlorine, bromine or alkyl of I to 4 carbon atoms.
Especially preferred dyes of the formula I are those in which A and A' are identical and are 2-methyl or 4-phenoxy, n and n' are 0 or 1 and X is
where R is alkoxy of 1 to 4 carbon atoms, alkyl of I to 10 carbon atoms or phenyl.
Examples of such dyes are those of the formulae
where R is alkoxy of 1 to 4 carbon atoms or alkyl of I to 10 carbon atoms,
where R is alkoxy of I to 4 carbon atoms, alkyl of 1 to 10 carbon atoms or phenyl and
where R is alkoxy of I to 4 carbon atoms.
Dyes of the formula (Ib) where R is alkyl of 1 to 4 carbon atoms are preferred above all. Amongst the dyes of the formula (Ib), the 8-acetylamino, 8propionylamino, 8-butyrylamino and 8-isobutyrylamino compounds should be singled out particularly.
The dyes of the formula I can be prepared in accordance with the process described in German Laid-Open Application DOS 1,950,679, Example 5, paragraph 2, by reacting 1,8-dihydroxy-4,5-dinitroanthraquinone with an amine of the formula
in the presence of boric acid, and reducing the resulting 1,4-bis-(phenylamino)-5hydroxy-8-nitroanthraquinone to the 8-amino compound, with or without subsequent acylation.
On the basis of their structure, the dyes of the formula (I) are appropriately described as essentially insoluble disperse dyes which as a rule cannot be applied to, for example, cottdn. This is confirmed by the data in German Laid-Open
Application DOS 1,950,679.
However, U.S. Patent 3,706,525 discloses a process by means of which dyes which are water-insoluble or sparingly water-insoluble can be printed onto cellulose or cellulosic textiles. The general sense of the data relating to process conditions, given in the said U.S. patent, also applies to dyeing with the dyes of the formula (I).
According to the process disclosed in that patent the water-swellable cellulosic material to be dyed is contacted with water in an amount sufficient to swell the cellulosic material, the dye and an amount sufficient to maintain swelling of the cellulose if water is removed of a solvent having the properties given below, referred to in this specification as an oxyethylene sweller-solvent, provided that at some stage during the process the interior of the swollen cellulose is contacted with a solution of the dye in the solvent or aqueous solvent. The oxyethylene swellersolvent is required to have the following properties:
a) it is at least 2.5 weight percent soluble in water at 250C;
b) it boils above 150"C at atmospheric pressure;
c) it is a solvent for the dye at some temperature in the range from 0 to 2250C; and
d) it has the formula:
where n is 0 or 1,
m is a positive integer, X1 is H, C18 alkyl, C7is aralkyl or alkaryl,
X2 is -OH, -OX3, -SX3, NHX3, NX3(C1~8 alkyl), NX3(C,~1s aralkyl or alkaryl), -OCX3, -OSO2X3, -OCOX3, II II 0 0 -NH(phenyl) or NH(naphthyl),
X3 is C18 alkyl, Cs 1o cycloalkyl, C71 aralkyl or alkaryl, C6aryl, C,0 aryl or
furfuryl,
x is the number of unsatisfied valencies in Y',
Y' is X1OCH2CHOX1CH2-, -CH2CHOX1CH2-,CH2CHCH2, -CH2C(CH2OX1)3, (-CH2)2 -C(CH2OX1)2, (--CH,),CCH,OX', (-CH2)4C, CH2(CHOX1)v CH2OX', CH2(CHOX1)vCH2 or -CH2(COHX1 )vz(CH2)zCH2 y is 2, 3 or 4, and
z is 0, 1, 2, 3 or 4 but no greater than y.
Essentially, therefore, the oxyethylene sweller-solvent has an oxyethylene chain (which may be substituted by methyl) present one or more times in the molecule and may thus be regarded as ethylene glycol or a derivative thereof.
Examples of solvents which may be t sed in con junction with water in producing the fibers of the invention are ethylene glycol, di-, tri- and higher polyethylene glycols (polyethylene oxides), e.g. of molecular weight about 300, and esters of such materials, e.g. carboxylic acid esters and boric acid esters.
Further, German Laid-Open Applications DOS 2,524,243 and 1,528,743 disclose other processes by means of which the fibers according to the invention may be obtained. Printing processes are preferred. In addition to cellulose fibers, blends of cellulose fibers and synthetic fibers, especially cotton and polyester, may also be dyed and printed.
The dyed fibers according to the invention have very good fastness properties, above all wet fastness, fastness to crocking, fastness to dry-cleaning and lightfastness. In the case of prints, no staining or any white ground occurs, on, for example, washing.
For dyeing and printing, the dyes of the formula (II) are advantageously converted to dye formulations which contain the dye together with a dispersant, a water-retaining agent and water, with or without one or more other assistants conventionally used in fluid formulations, e.g. disinfectants or anti-foaming agents.
The formulations are advantageously prepared by milling a suspension of from 15 to 40, preferably from 20 to 35, parts by weight of dye (I), from 4 to 10 parts by weight of dispersant, from 5 to 15 parts by weight of water-retaining agent and from 0.5 to 1.5 parts by weight of disinfectant in from 75.5 to 35.5 parts by weight of water in a stirred ball mill, a bead mill or a sand mill, until the particle size is 0.5 ,um or less. The dye dispersions thus obtained are stable on storage.
Dispersants which may be used include the anionic and non-ionic dispersants conventionally employed for the preparation of finely divided formulations of disperse dyes. Examples of anionic dispersants are ligninsulfonates, salts of phenol/formaldehyde/sodium sulfite condensation products (German Laid-Open
Application DOS 2,301,638), salts of 2-napthalenesulfonic acid/formaldehyde condensation products, salts of phenolsulfonic acid/urea/formaldehyde condensation products and salts of phenosulfonic acid/urea/formaldehyde condensation products, which have been post-condensed with phenol and formaldehyde.
Preferred non-ionic dispersants are ethylene oxide adducts and propylene oxide/ethylene oxide adducts. Such dispersants are dislosed in, for example, U.S.
Patents 2,979,528 and 3,841,888.
The amount of dispersant depends on the dye and on its concentration in the dispersion. As a rule, the amount of dispersant is from 4 to 10 per cent by weight, based on the formulation.
Preferred water-retaining agents are glycols, e.g. ethylene glycol, propylene glycol, diethylene glycol and, preferably, dipropylene glycol. Their amount is in general from 5 to 15, preferably from 8 to 12, per cent by weight based on the formulation.
In the following Examples parts are by weight.
EXAMPLE I
a) A print paste is prepared from 10 parts of the finely dispersed dye of the formula
used as a formulation obtained as described in c), 100 parts of polyethylene oxide of molecular weight 300 and 790 parts of a 3 per cent strength alginate thickener.
A cotton fabric is. printed with this print paste on a rotary screen printing machine and the print is dried at 1000C. It is then heated for 1 minute at 2000C by means of hot air, rinsed cold, soaked at the boil, again rinsed cold and dried. A washfast print in a clear green hue on a white ground is obtained.
If a union fabric of cotton and polyester fibers is printed in the same manner, fixed and washed, a print in which both fibers are dyed in the same hue is obtained.
b) The dye used was prepared as follows: 40 parts of l,8-dihydroxy-4,5-dinitro- anthraquinone in 200 parts of o-toluidine are heated for 2 hours at 1500C. 20 parts of boric acid are then introduced and the reaction mixture is heated for 8 hours at 160"C. After it has cooled to 600C, 400 parts of methanol are added. The mixture is stirred for 2 hours and the 1 ,4-di-o-toluidino-5-hydroxy-8-nitro-anthraq uinone which has precipitated is filtered off, washed with methanol and water, and dried.
19.2 parts of this compound in 80 parts of o-dichlorobenzene are heated at 1500C and 4 parts of hydrazine hydrate are added in the course of 30 minutes, whilst stirring. After stirring for 2 1/2 hours at 1500C, 8 parts of methyl chloroformate is added dropwise. The mixture is stirred for a further hour at from 130 to 1500C and is then cooled to 600 C, and 150 parts of methanol are added. The reaction product which has precipitated is filtered off, washed with methanol and water and dried.
12.9 parts of the dye having the above formula are obtained.
c) The dye obtained as described in b) is converted to an aqueous dye formulation as follows: 30 parts of the dye lb), 6 parts of ligninsulfonate and 10 parts of dipropylene glycol are stirred in 50 parts of water and the suspension is milled in a sand mill until the particle size is about 0.5 ,um or less. 1 part of pentachlorophenol is then added and the dye content is brought to 30 /,, (based on the formulation) by adding water. The formulation obtained is stable on storage.
EXAMPLES 2 to 58
a) Print pastes are prepared as' described under la), using aqueous formulations of the dyes specified in the Table which follows. Prints having the hues shown in the right-hand column are obtained on cotton or polyester/cotton fabrics.
b) The dyes specified in the Table which follows were prepared by the method described in Example lb) and converted to a fluid formulation by the method described in Example Ic).
Ex- -B = -B' X- Hue on cotton and ample cotton/polyester
2 w H - green 0 3 n -C-OCH3 green -C-OCH3 0 II 4 1I " -C-CH3 green CH 0 5 II green 5 reC2'CH3 green 0 6 n -C-CH-CH3 green CH3 93 7 2 -C-CH(CH2)3-CH3 green C2H5 0 8 n O MH-COt- yellowish 9 nOCqHg(n) 9 green 9 -C-0C4H9(n) yellowish green 10 C?: green 0 11 OCn- -O-CH-C:H3 green CF 0 11 12 e -C-OC4Hg yellowish < green green 13 " -H green Ex- -B = -B' X- Hue on cotton and ample cotton/polyester
0 14 n O NH-C- green 15 01C'- green 0 16 n cr 8 - green \==/ green 0 17 n -C-OCH3 yellowish green 0 'I 18 tt CH3(CH2)3-C,H-C- green C2Hs 0 11 19 C 2 CH3-CH2-C- green 20 a -H green S CH3 21 n ' C- green 0 11 22 1' H C-OH-C- green IH3 23 o C1 -H green 0 11 24 1t -C-OCH3 green 0 / 3 O 0 CH3 26 0 -H yellowish - green Ex- -B = -B' X- Hue on cotton and ample cotton/polyester
0 11 yellowish 27 -C-OCH) yellowish green 0 ., 28 n CH2-CH2-CH2-C- green 0 It 29 OH -C- green o 30 e O O-CH2-C- green 31 0OH3 -H green o 32oCH3 II 32 0OH3 11 green 0, 33 fl ClOH2O green 0 34 9 O 0-CH2-CH2-0-C- green H3C O 0 11 11 '1 CH -0-035 CH3-0-C-CH2-CH2-C~ green 0 0 36 CH30-C-OH2-CH2-C O green 36 e CH30-C-CH2-CH2-CH2-C- green 37 P -C-O-CH2-FH-C4H9(n) green - 0 25 OH3 0 38 11 Cl C-0C4H yellowish - green 39 C e -C-OCH2-Cli-CIH9 n C2H9 Ex- 3= -B' X- Hue on cotton ample and cotton/
polyester
40 o green 9 -C-OC4Hg CH3 3 41 O CH3 n green 0 CH It 42 9 -0-0-OH -OH 3 green H3 2 CH3 0 11 43 n CH30-CH2-CH2-0-C- 'I 0 44 ? CH3 -C-O-CH3 11 0 45 e 0CH -C-OCH3 n 46 n -0"-0O4H9 cr 0 47 H OCH3 11 n -C-0O4H9 48 011 "0113 48 O -C-O-CH2-CH2-CzH 3 3 0 It 49 n CH3-CH2-0-CH2-CH2-0-C-green 0 50 9 C1 O NHC- 11 CH3 51 O C1 O NH-C- 1? 0 52 e C;;'3 i3C O IQ=.-C- 'V Ex ample -3 = -3' X, Hue on polyester
polyester
0 o 55 e C1 e NH-C- green o " H3 0 55 9 O NH-C- " H3 OH H, 0 56 9 C3H70-C CH3 113 C 57 < CH30-C- '1 H3 o 11 58 OH3 (H3C)2-CH-C- n CH3 WHAT WE CLAIM IS:
1. Uniformly dyed (as hereinbefore defined) water-swellable cellulosic fibers produced by contacting water-swellable cellulosic fibers with water and an oxyethylene sweller-solvent (as hereinbefore defined) to swell the fibers and, simultaneously or subsequently while the fibers are still swollen, with an essentially water-insoluble dye of the formula
where A and A', which are identical or different, are alkyl of I to 4 carbon atoms,
alkoxy of I to 4 carbon atoms, chlorine, bromine, phenoxy, methylphenoxy or
chlorophenoxy, n and n', which are identical or different, are 0, 1, 2 or 3, and X is hydrogen or
where R is hydrogen, alkoxy of I to 10 carbon atoms, alkoxyalkoxy of a total of 3 to 7 carbon atoms, alkyl of I to 10 carbon atoms (which is unsubstituted or is
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (17)
- **WARNING** start of CLMS field may overlap end of DESC **.Ex ample -3 = -3' X, Hue on polyester polyester0 o 55 e C1 e NH-C- green o " H3 0 55 9 O NH-C- " H3 OH H, 0 56 9 C3H70-C CH3 113 C 57 < CH30-C- '1 H3 o 11 58 OH3 (H3C)2-CH-C- n CH3 WHAT WE CLAIM IS: 1.Uniformly dyed (as hereinbefore defined) water-swellable cellulosic fibers produced by contacting water-swellable cellulosic fibers with water and an oxyethylene sweller-solvent (as hereinbefore defined) to swell the fibers and, simultaneously or subsequently while the fibers are still swollen, with an essentially water-insoluble dye of the formulawhere A and A', which are identical or different, are alkyl of I to 4 carbon atoms, alkoxy of I to 4 carbon atoms, chlorine, bromine, phenoxy, methylphenoxy or chlorophenoxy, n and n', which are identical or different, are 0, 1, 2 or 3, and X is hydrogen orwhere R is hydrogen, alkoxy of I to 10 carbon atoms, alkoxyalkoxy of a total of 3 to 7 carbon atoms, alkyl of I to 10 carbon atoms (which is unsubstituted or ismonosubsituted, disubstituted or trisubstituted by chlorine), phenalkyl of 7 to 9 carbon atoms, phenyl (which is unsubstituted or is substituted by chlorine, bromine, nitro, alkyl of 1 to 4 carbon atoms or alkoxy of I to 4 carbon atoms), phenoxy, phenalkoxy of 7 to 9 carbon atoms, phenoxy-alkyl (where alkyl is of I to 3 carbon atoms), phenoxy-alkoxy (where alkoxy is of 2 to 4 carbon atoms), alkoxycarbonyl-alkyl (where alkoxy is of I to 4 carbon atoms and alkyl is of 2 to 4 carbon atoms), or phenylamino (which is unsubstituted or is substituted by chlorine, bromine or alkyl of 1 to 4 carbon atoms).
- 2. Dyed fibers as claimed in claim 1, wherein A and A' in the formula of the dye are identical and are 2-, 3- or 4-methyl, 4-methoxy or 4-phenoxy and n and n' in the formula of the dye are identical and are zero or 1.
- 3. Dyed fibers as claimed in claim I or 2, wherein X in the formula of the dye iswhere R is alkoxy of I to 10 carbon atoms, alkoxyalkoxy of 3 to 7 carbon atoms, alkyl of I to 10 carbon atoms (which is unsubstituted or is monosubstituted, disubstituted or trisubstituted by chlorine), phenyl (which is unsubstituted or is substituted by chlorine, bromine, alkyl of 1 to 4 carbon atoms or nitro), or phenylamino (which is unsubstituted or substituted by chlorine, bromine or alkyl of I to 4 carbon atoms).
- 4. Dyed fibers as claimed in claim 1, wherein in the formula of the dye A and A' are identical and are 2-methyl or 4-phenoxy, n and n' are identical and are 0 or I and X iswhere R is alkoxy of 1 to 4 carbon atoms, alkyl of I to 10 carbon atoms or phenyl.
- 5. Dyed fibers as claimed in claim 1, wherein in the formula of the dye n and n' are zero and X iswhere R is alkoxy of I to 4 carbon atoms or alkyl of 1 to 10 carbon atoms.
- 6. Dyed fibers as claimed in claim 1, wherein in the formula of the dye n and n' are 1, A and A' are each 2-methyl and X iswhere R is alkoxy of I to 4 carbon atoms, alkyl of I to 10 carbon atoms or phenyl.
- 7. Dyed fibers as claimed in claim 1, wherein in the formula of the dye n and n' are 1, A and A' are each 4-phenoxy and X iswhere R is alkoxy of 1 to 4 carbon atoms.
- 8. Dyed fibers as claimed in claim 1, wherein in the formula of the dye n and n' are 1, A and A' are each 2-methyl and X iswhere R is alkyl of I to 4 carbon atoms.
- 9. Dyed fibers as claimed in claim 1, wherein in the formula of the dye n and n' are 1, A and A' are 2-methyl and X iswhere R is -CH3, C2Hs, -C3H7 or -CH(CH)2.
- 10. Dyed fibers as claimed in claim I wherein the dye is a dye specified in any of the foregoing Examples I to 58.
- II. Dyed fibers as claimed in any of claims I to 10, wherein the cellulosic fibers are cotton fibers.
- 12. Dyed fibers as claimed in any of claims 1 to 10, wherein the cellulosic fibers are admixed or blended with synthetic fibers.
- 13. Dyed fibers as claimed in claim 12, wherein the synthetic fibers are polyester fibers.
- 14. Dyed fibers as claimed in any of claims I to 13 wherein the dye has been printed onto the fibers.
- 15. A dye formulation for use in manufacturing dyed fibers as claimed in claim I comprising an aqueous suspension made by milling from 15 to 40 parts by weight of a dye as specified in claim 1, from 4 to 10 parts by weight of a dispersant, from 5 to 15 parts by weight of a water-retaining agent and from 0.5 to 1.5 parts by weight of disinfectant in from 75.5 to 35.5 parts by weight of water until the particle size is 0.5 ,u or less.
- 16. A dye formulation as claimed in claim 15 in which the dye is a dye as specified in any of the foregoing Examples.
- 17. A dye formulation as claimed in claim 15 and substantially as described in any of the foregoing Examples.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19762651975 DE2651975A1 (en) | 1976-11-15 | 1976-11-15 | DYE PREPARATIONS FOR CELLULOSE OR CELLULOSIC FIBER MATERIAL |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1591135A true GB1591135A (en) | 1981-06-17 |
Family
ID=5993173
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB4723577A Expired GB1591135A (en) | 1976-11-15 | 1977-11-14 | Uniformly dyed water-swellable cellulose fibres |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5361782A (en) |
| CH (1) | CH629837A5 (en) |
| DE (1) | DE2651975A1 (en) |
| FR (1) | FR2370779A1 (en) |
| GB (1) | GB1591135A (en) |
| IT (1) | IT1089010B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2851751A1 (en) * | 1978-11-30 | 1980-06-19 | Basf Ag | DYE PREPARATIONS FOR CELLULOSE OR CELLULOSE-CONTAINING FIBER MATERIAL |
| DE3233948A1 (en) * | 1982-09-14 | 1984-03-15 | Basf Ag, 6700 Ludwigshafen | ANTHRACHINOID DYES |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE757225A (en) * | 1969-10-08 | 1971-03-16 | Bayer Ag | CONTINUOUS DYEING PROCESS OF SYNTHETIC FIBROUS MATERIALS |
| BE756586A (en) * | 1969-11-25 | 1971-03-24 | Du Pont | CELLULOSIC FIBERS CAN SWELL WITH WATER AND UNIFORMLY TINTED RED TO GREEN |
| US3752647A (en) * | 1971-07-30 | 1973-08-14 | Du Pont | Water swollen cellulose and blends dyed with insoluble, non-vattable anthraquinone dyes in a glycol ether solution |
-
1976
- 1976-11-15 DE DE19762651975 patent/DE2651975A1/en not_active Withdrawn
-
1977
- 1977-10-28 IT IT2916177A patent/IT1089010B/en active
- 1977-11-08 FR FR7733548A patent/FR2370779A1/en active Granted
- 1977-11-11 CH CH1380377A patent/CH629837A5/en not_active IP Right Cessation
- 1977-11-14 GB GB4723577A patent/GB1591135A/en not_active Expired
- 1977-11-15 JP JP13633677A patent/JPS5361782A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CH629837A5 (en) | 1982-05-14 |
| DE2651975A1 (en) | 1978-05-18 |
| IT1089010B (en) | 1985-06-10 |
| FR2370779B1 (en) | 1982-09-17 |
| JPS5361782A (en) | 1978-06-02 |
| FR2370779A1 (en) | 1978-06-09 |
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| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed | ||
| PCNP | Patent ceased through non-payment of renewal fee |