CA2052236C - Method for dyeing fibrous material - Google Patents
Method for dyeing fibrous materialInfo
- Publication number
- CA2052236C CA2052236C CA002052236A CA2052236A CA2052236C CA 2052236 C CA2052236 C CA 2052236C CA 002052236 A CA002052236 A CA 002052236A CA 2052236 A CA2052236 A CA 2052236A CA 2052236 C CA2052236 C CA 2052236C
- Authority
- CA
- Canada
- Prior art keywords
- carrier
- fibers
- aromatic
- fibrous material
- carbonamide
- 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 - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 57
- 239000002657 fibrous material Substances 0.000 title claims abstract description 34
- 238000004043 dyeing Methods 0.000 title claims abstract description 31
- 239000000835 fiber Substances 0.000 claims abstract description 101
- 239000000203 mixture Substances 0.000 claims abstract description 80
- 239000004760 aramid Substances 0.000 claims abstract description 27
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 27
- 125000003118 aryl group Chemical group 0.000 claims abstract description 24
- 239000004642 Polyimide Substances 0.000 claims abstract description 18
- 229920001721 polyimide Polymers 0.000 claims abstract description 18
- 229920006376 polybenzimidazole fiber Polymers 0.000 claims abstract description 16
- 239000004744 fabric Substances 0.000 claims description 56
- 239000003063 flame retardant Substances 0.000 claims description 46
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 43
- 239000003995 emulsifying agent Substances 0.000 claims description 43
- 229920002480 polybenzimidazole Polymers 0.000 claims description 28
- MMOXZBCLCQITDF-UHFFFAOYSA-N N,N-diethyl-m-toluamide Chemical group CCN(CC)C(=O)C1=CC=CC(C)=C1 MMOXZBCLCQITDF-UHFFFAOYSA-N 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 16
- 239000000654 additive Substances 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 15
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 14
- -1 poly(m-phenyleneisophthalamide) Polymers 0.000 claims description 13
- 230000000996 additive effect Effects 0.000 claims description 9
- ZVSKZLHKADLHSD-UHFFFAOYSA-N benzanilide Chemical group C=1C=CC=CC=1C(=O)NC1=CC=CC=C1 ZVSKZLHKADLHSD-UHFFFAOYSA-N 0.000 claims description 8
- IMNDHOCGZLYMRO-UHFFFAOYSA-N n,n-dimethylbenzamide Chemical compound CN(C)C(=O)C1=CC=CC=C1 IMNDHOCGZLYMRO-UHFFFAOYSA-N 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 150000001298 alcohols Chemical class 0.000 claims description 7
- 229920000889 poly(m-phenylene isophthalamide) Polymers 0.000 claims description 4
- 230000002411 adverse Effects 0.000 claims description 3
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 claims description 3
- 239000000975 dye Substances 0.000 description 60
- 229920000784 Nomex Polymers 0.000 description 20
- 239000004763 nomex Substances 0.000 description 20
- 229960001673 diethyltoluamide Drugs 0.000 description 17
- 229920000271 Kevlar® Polymers 0.000 description 11
- 125000002091 cationic group Chemical group 0.000 description 11
- 239000004761 kevlar Substances 0.000 description 11
- WMAVHUWINYPPKT-UHFFFAOYSA-M (e)-3-methyl-n-[(e)-(1-methyl-2-phenylindol-1-ium-3-ylidene)amino]-1,3-thiazol-2-imine;chloride Chemical compound [Cl-].C12=CC=CC=C2N(C)C(C=2C=CC=CC=2)=C1N=NC=1SC=C[N+]=1C WMAVHUWINYPPKT-UHFFFAOYSA-M 0.000 description 9
- MHOFGBJTSNWTDT-UHFFFAOYSA-M 2-[n-ethyl-4-[(6-methoxy-3-methyl-1,3-benzothiazol-3-ium-2-yl)diazenyl]anilino]ethanol;methyl sulfate Chemical compound COS([O-])(=O)=O.C1=CC(N(CCO)CC)=CC=C1N=NC1=[N+](C)C2=CC=C(OC)C=C2S1 MHOFGBJTSNWTDT-UHFFFAOYSA-M 0.000 description 8
- SPWPAFQLIZTXFN-UHFFFAOYSA-M 4-methoxy-n-methyl-n-[(1,3,3-trimethylindol-1-ium-2-yl)methylideneamino]aniline;methyl sulfate Chemical compound COS([O-])(=O)=O.C1=CC(OC)=CC=C1N(C)\N=C\C1=[N+](C)C2=CC=CC=C2C1(C)C SPWPAFQLIZTXFN-UHFFFAOYSA-M 0.000 description 7
- RGJOEKWQDUBAIZ-IBOSZNHHSA-N CoASH Chemical compound O[C@@H]1[C@H](OP(O)(O)=O)[C@@H](COP(O)(=O)OP(O)(=O)OCC(C)(C)[C@@H](O)C(=O)NCCC(=O)NCCS)O[C@H]1N1C2=NC=NC(N)=C2N=C1 RGJOEKWQDUBAIZ-IBOSZNHHSA-N 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- 239000000969 carrier Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 238000009991 scouring Methods 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 239000000080 wetting agent Substances 0.000 description 3
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 description 2
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000002280 amphoteric surfactant Substances 0.000 description 2
- 239000001000 anthraquinone dye Substances 0.000 description 2
- 239000000987 azo dye Substances 0.000 description 2
- 239000000981 basic dye Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004900 laundering Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- DLKDEVCJRCPTLN-UHFFFAOYSA-N 2-butylisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCCC)C(=O)C2=C1 DLKDEVCJRCPTLN-UHFFFAOYSA-N 0.000 description 1
- VPLDXHDOGVIETL-UHFFFAOYSA-N 2-propan-2-ylisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(C(C)C)C(=O)C2=C1 VPLDXHDOGVIETL-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- XRASRVJYOMVDNP-UHFFFAOYSA-N 4-(7-azabicyclo[4.1.0]hepta-1,3,5-triene-7-carbonyl)benzamide Chemical compound C1=CC(C(=O)N)=CC=C1C(=O)N1C2=CC=CC=C21 XRASRVJYOMVDNP-UHFFFAOYSA-N 0.000 description 1
- JBMKAUGHUNFTOL-UHFFFAOYSA-N Aldoclor Chemical class C1=C(Cl)C(S(=O)(=O)N)=CC2=C1NC=NS2(=O)=O JBMKAUGHUNFTOL-UHFFFAOYSA-N 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- 229920013683 Celanese Polymers 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- 229920002821 Modacrylic Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 1
- 229960001413 acetanilide Drugs 0.000 description 1
- 239000000980 acid dye Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000003443 antiviral agent Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 238000010420 art technique Methods 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical class ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- CEDDGDWODCGBFQ-UHFFFAOYSA-N carbamimidoylazanium;hydron;phosphate Chemical class NC(N)=N.OP(O)(O)=O CEDDGDWODCGBFQ-UHFFFAOYSA-N 0.000 description 1
- 125000005521 carbonamide group Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000004456 color vision Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000001177 diphosphate Substances 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000013101 initial test Methods 0.000 description 1
- 239000000077 insect repellent Substances 0.000 description 1
- 229940078863 isopropylphthalimide Drugs 0.000 description 1
- 238000009981 jet dyeing Methods 0.000 description 1
- 238000012886 linear function Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 239000000983 mordant dye Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229940072395 n-butylphthalimide Drugs 0.000 description 1
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 210000001328 optic nerve Anatomy 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000985 reactive dye Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 210000001525 retina Anatomy 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical class C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 239000003451 thiazide diuretic agent Substances 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 239000000984 vat dye Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- 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
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/642—Compounds containing nitrogen
- D06P1/649—Compounds containing carbonamide, thiocarbonamide or guanyl groups
- D06P1/6495—Compounds containing carbonamide -RCON= (R=H or hydrocarbons)
-
- 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
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/24—Polyamides; Polyurethanes
-
- 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
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/24—Polyamides; Polyurethanes
- D06P3/242—Polyamides; Polyurethanes using basic 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
- Y10S8/92—Synthetic fiber dyeing
- Y10S8/924—Polyamide fiber
- Y10S8/925—Aromatic polyamide
Abstract
A method for dyeing fibrous material is provided. The method includes contacting a fibrous material with a carrier and a dye soluble or dispersed with the carrier in a dyebath. The carrier comprises an N-substituted aromatic carbonamide or an N,N-disubstituted aromatic carbonamide or mixture thereof.
The carrier system of the present can be advantageously utilized for improving dye and flame resistant properties of difficult to dye fibers such as aromatic polyamide fibers, polybenzimidazole fibers and aromatic polyimide fibers.
The carrier system of the present can be advantageously utilized for improving dye and flame resistant properties of difficult to dye fibers such as aromatic polyamide fibers, polybenzimidazole fibers and aromatic polyimide fibers.
Description
METHOD FOR DYEING FIBROUS MATERIALS
The present invention relates to a method for dyeing fibrous material, and particularly fibrous materials having flame resistant properties which are difficult to dye such as aromatic polyamides, polybenzimidazoles or aromatic polyimides.
Backqround of the Invention There are various recognized methods for dyeing and/or incorporating additives into fibers and other fibrous materials, including methods which utilize organic solvents such as dimethylsulfoxide ("DMS0"), dimethylacetamide ("DMAc"), dimethylformamide ("DMF"), N-methylpyrrolidone ("NMP"), N-cyclohexyl-2-pyrrolidone (''CHPIl), acetophenone, acetanilide and methyl benzoate. Exemplary systems utilizing these organic solvents have been proposed in U.S. Patent Nos.
3,558,267 to Langenfeld, 3,741,719 to Ramanathan et al, 4,525,168 to Kelly, and U.S. Patent No. 4,898,596 to Riggins et al and U.K. Patent Nos. 1,275,459 to Gruen and 1,282,113 to Burtonshaw et al. In addition to these organic solvents it has been proposed in U. S. Patent No. 4,780,105 to White et al to dye aromatic polyamides with a cationic dye and a dye assistant including N-substituted phthalimides (e.g., a mixture of N-butylphthalimide and isopropylphthalimide).
Despite the general availability of dyeing methods using various carriers, there continues to be a desire for process improvements which enhance the dyeability of fibers and fabrics formed therefrom. For example, improvements in dye exhaustion and more uniform dyeing tend to improve the aesthetic characteristics of the fibers. Another example is that certain dyeing techniques result in the undesirable side effect of retention of solvent by the fibers.
Retention of solvent can adversely affect both the appearance and the flame resistance of the fibers.
This is particularly frustrating when dyeing fibers such as the aromatic polyamides, i.e., poly(_-phenyleneisophthalamide) ("Nomex~") and poly(~-phenyleneterephthalamide) (''KevlarX''), polybenzimidazoles, aromatic polyimides, and the like which have excellent flame resistant properties but also are difficult to dye. In order to dye these fibers, some of the various organic solvents and carriers, e.g., DMAc, DMSO, DMF, acetophenone, etc., and the N-substituted phthalimides have to be used, but these compounds may present health problems for some employees, and if non-water soluble, also tend to be retained by the fibers after dyeing. Thus, prior art techniques for dyeing these fibers can be counter-productive in that one of the problems caused by retention of solvent or carrier, e.g., decreased flame resistance, requires addition of a significantly large portion of a flame retardant to compensate for the reduction in the flame resistant properties of the fibers.
It is therefore an object of the present invention to provide an improved method for dyeing fibrous materials, and particularly to provide a method lo which provides one or more particularly advantageous results, including increased efficiency in dye exhaustion, more uniform dyeing and reduction of the retention of solvent. The improved method is particularly advantageous when used with difficult to dye fibers such as aromatic polyamide fibers including NomexX and KevlarX fibers, polybenzimidazole fibers, aromatic polyimide fibers, fibers of copolymers of the monomers thereof and blends thereof.
8ummary of the Invention This invention relates to a method for dyeing fibrous material which includes the steps of contacting the fibrous material with a mixture (e.g., a solution or dispersion) containing a dye in a dye carrier (e.g., a dyebath) comprising an N-substituted aromatic carbonamide or an N,N-disubstituted aromatic carbonamide or mixture thereof and fixing the dye in the fibrous material. The use of the present carrier results in improved dyeing characteristics. For example, improved efficiency in dye exhaustion may be achieved as compared to comparable levels of other carriers particularly when used to dye fibers such as aromatic polyamide fibers, polybenzimidazole fibers, aromatic polyimide fibers, fibers of copolymers of the monomers thereof and blends thereof.
In accordance with a particularly preferred embodiment of the present invention, the method of the present invention includes the steps of contacting aromatic polyamide fibers, polybenzimidazole fibers, aromatic polyimides fibers, fibers of copolymers of the monomers thereof, or blends thereof with a mixture of a carrier and dye soluble or dispersed with the carrier, the carrier including an N-substituted aromatic carbonamide or an N,N-disubstituted aromatic carbonamide or mixture thereof, an emulsifier and a flame retardant, and fixing the dye in the fibers. The emulsifier provides improved dyeing characteristics (e.g., improved dye exhaustion and more uniform dyeing) whereas the use of the flame retardant in small amounts (e.g. less than about 2 g/100 ml) results in "super flame resistant" properties in the fibers, i.e., less than 25 percent of the fabric formed from the fibers is consumed using Federal Test Method 191-5905 Flame Contact Test).
Detailed Description of the Invention As summarized above, the present invention provides an improved carrier system and carrier-based . ", .."j__.
method for dyeing and/or incorporating other additives into fibrous materials. The carrier and method is particularly adapted for use in reducing the adverse effect of dyeing methods on dye exhaustion, dye uniformity and flame resistant properties of the fibrous material. The carrier preferably comprises an N-substituted aromatic carbonamide or an N,N-disubstituted aromatic carbonamide or mixture thereof.
In a preferred embodiment, the carrier system can include an emulsifier and/or a flame retardant.
The method of the present invention can advantageously be employed using customary dyeing techniques. The dye and the carrier, and the addition of the emulsifier, flame retardant, and/or other additives is typically carried out by forming a mixture (e.g., a bath, solution, dispersion or the like) of the dye and the carrier of the present invention followed by contacting the fiber and/or fabric with this mixture and then fixing the dye in the fiber. In accordance with the present invention, a fibrous textile material, e.g., fiber, web, yarn, thread, sliver, woven fabric, knitted fabric, non-woven fabric, and the like is impregnated, padded, or otherwise contacted with the bath and the dyestuffs and/or additives fixed in the substrate using conventional equipment such as jet dyeing or other appropriate equipment.
The carrier of the present invention comprises an N-substituted aromatic carbonamide or an N,N-disubstituted aromatic carbonamide or mixture thereof.
Generally these compounds can be represented by the formula:
o /R
R-C-I'I~
\R
wherein R is aromatic or substituted aromatic, R' is H or alkyl and R" is alkyl, aromatic, substituted aromatic or aralkyl. Exemplary compounds include:
o 15 Benzanilide ~ C-N
20 N,N-dimethylbenzamide ~ O / Cli~
N,N-diethyl (_-toluamide) ~1 3C ~C- ~/
N-substituted and N,N-disubstituted aromatic carbonamides have previously been utilized as surface plasticizers for nylon such as described in U.S. Patent No. 3,634,023 to Foote. However, applicants are unaware of the use ~ ~, of N-substituted or N,N-disubstituted aromatic carbonamides as a carrier in dyeing fibers.
A particularly preferred N,N-disubstituted aromatic carbonamide is N,N-diethyl(_-toluamide), "DEET". DEET is a liquid at room temperature and is used predominantly as an insect repellant and a resin solvent in addition to being used as a surface plasticizer. Preferably, the carrier system also includes a compound which permits the dye and the carrier and other additives to be held in suspension or dispersion, i.e., an emulsifier. Additionally, the compound can function as a dye assist or levelling agent.
A particularly preferred emulsifier is Phosphoteric T-C6X, an amphoteric surfactant, available from Mona Industries, Inc. of Patterson, New Jersey.
Another particularly preferred emulsifier is Solv-It~, a multicomponent system containing a blend of surfactants and an alkyl ester of an aromatic carboxylic acid available from Apollo Chemical Company of Burlington, North Carolina.
Another particularly preferred emulsifier is WitcomulX AM2-lOC available from Witco Chemical of New York, New York. WitcomulX AM2-lOC is a blend of the free acid form of a phosphated ethoxylated dialkyl phenol containing from about 2 to 20 moles of ethylene oxide and a non-ionic propoxylated-ethoxylated alcohol containing from about 20 to 75 moles of propylene oxide ~2~
and 20 to 75 moles of ethylene oxide. Other compounds suitable for use with the carrier as a dye assist are diphenyl, 1-methylnaphthalene, 2-methyl-naphthalene, alkyl and aryl benzoates, chlorotoluenes, and the like.
Preferably, a flame retardant can also either be included with the carrier in the dyebath, applied as an after-dyeing surface treatment or otherwise incorporated in the fiber to provide super flame resistant properties. A
particularly preferred flame retardant is Antiblaze3 100 flame retardant, a non-cylic chloroalkyl diphosphate ester, available from Albright & Wilson Americas, Inc. of Richmond, Virginia.
Other flame retardants suitable for use are other non-cyclic mono- and poly- phosphonate and/or phosphate-type flame retardants available from Albright ~ Wilson Americas, Inc. In addition, another class of suitable flame retardants are those based on primary guanidine phosphates.
Preferably, the ratio of N-substituted or N,N-disubstituted aromatic carbonamide to emulsifier to flame retardant can be from about 2:3:0.1 to about 8:1:0.5, preferably about 2:3:0.3 to about 3:2:0.3, and more preferably about 4:1:0.3 if Solv-It~ or Phosphoteric T-C6 is used, and about 2:0.1:0.1 to about 8:1:1.5, preferably about 4:0.1:0.1 to 3:0.3:0.5, and more preferably about 4:0.2:0.4 if Witcomul~ AM2-lOC is used. The total weight of the carrier in the dyebath will be in the range from about 1 to about 3 . ~_ ;~
..
2 3 ~
g percent based on the weight of the dyebath. The weight percent can be adjusted using water or any other liquid miscible or dispersible with the carrier.
In view of the desirable results achieved to date, it is thought that the use of the carrier of the present invention is applicable with a wide variety of other additives such as softeners, W absorbers, IR
absorbers, antistatic agents, antifoaming agents, bactericides, fungicides, anti-viral agents or the like, and to a wide variety of fibrous material and includes dyed fibers which have been formed into fabrics including woven, non-woven or knit fabrics, for example.
The carrier can be used advantageously to dye a variety of flame resistant fibers which are difficult to dye, namely, aromatic polyamides, polybenzimidazoles, and aromatic polyimides, copolymers of the monomers thereof, and blends thereof. As noted above the carrier is particularly desirable for use with aromatic polyamides.
Fibers of aromatic polyamides have flame resistant properties and are often generically termed "aramid fibers" and are described, for example, in Kirk-Othmer:
The EncYclopedia of Chemical Technology, Third Edition, Vol. 3, pp. 213-242. The term "aromatic polyamides" or "aramids" includes but is not limited to poly(m-phenyleneisophthalamide) (e.g., Nomex0), poly(p-A
~ 10 phenyleneterephthalamide) (e.g., Kevlar~), polyparabenzamide, copolymers of the monomers thereof, and blends therewith. Nomex~ is available from DuPont of Wilmington, Delaware, in three forms. Nomex~ T-450 is 100 percent, undyed poly(_-phenyleneisophthalamide);
Nomex~ T-456 is 100 percent solution dyed poly(_-phenyleneisophthalamide); and Nomex~ T-455 is a blend of 95 percent Nomex~ (poly(m-phenyleneisophthalamide)) and S
percent Kevlar~ (poly(p-phenyleneterephthalamide)).
Nomex~ T-455 with the 5 percent Kevlar~ fraction is the most common type of Nomex~ used commercially. In view of the ability to dye the Kevlar~ fraction of Nomex~ T-455 more uniformly at a temperature above about 250~F, it is believed that the carrier of the present invention can be used at temperatures above about 250~F to dye blends of other fibers with Kevlar~ in a more uniform manner.
Another group of fibers which have flame resistant properties and are difficult to dye are the polybenzimidazole fibers available from Hoechst-Celanese of Charlotte, North Carolina and are described in U.S.
Patent No. 2,895,948 to Brinker et al.
Polybenzimidazoles use specific dicarboxylic and tetramine compounds as monomers and have the repeating unit of the formula:
3 ~
C~ >R< ~C-R--H H
where R and R' are aromatic moieties.
Another group of fibers having flame resistant properties and are difficult to dye are aromatic polyimide fibers described in U.S. Patent No. 4,758,649 to Asano et al. The aromatic polyimides have the repeating unit of the formula:
O O
R-N~ >R< ~I'J
O O
where R and R' are aromatic moieties.
In addition, copolymers of monomers or blends of the aromatic polyamides, polybenzimidazoles and/or aromatic polyimides can advantageously be dyed using the present carrier. For example, aromatic polyamide fibers and polybenzimidazole fibers can be blended in a weight ratio of about 60:40 to about 80:20 aromatic polyamide fibers to polybenzimidazole fibers. The A
'~ 20~2236 blends can be in the form of intimate blends, draw blends, corespun and the like. Additionally other synthetic fibers such as acrylic, modacrylic, polyesters and aliphatic polyamides can be advantageously dyed using the carrier system of the present invention.
Dyes which can be used advantageously with the present carrier can include acid dyes (e.g., azo, triarylmethane, anthraquinone dyes etc.); basic dyes lo (e.g., triphenylmethane, thiazide dyes, etc.); direct dyes (e.g. sulphonated azo dyes etc.); mordant dyes;
vat dyes; disperse dyes (e.g., nitroarylamine, azo, or anthraquinone dyes and the like with amino groups);
reactive dyes; and mixtures thereof with the proviso that the dyes do not decompose under customary dyeing conditions. Particularly effective dyes for dyeing aromatic polyamide fibers, polybenzimidazole fibers and aromatic polyimide fibers are the basic dyes (sometimes referred to as "cationic dyes"). Examples of this class are the Basacryl0 dyes available from BASF, Charlotte, North Carolina and the Maxillon0 dyes available from Ciba-Geigy Corporation, Greensboro, North Carolina.
In operation, the dye and/or other additive is preferably applied to the fibers of a fabric using a one-step batch-type process at 100~F to 300~F at 1 to 4 atm pressure. Pre-scouring and after-scouring of the fabric is preferred. The fabric can be scoured by "~ 2052236 passing the fabric through a hot aqueous scour in a jet dye machine or other scouring equipment. The jet is then charged with water and other auxiliaries including the dye and the present carrier with or without an emulsifier and with or without a flame retardant or other additive. The temperature and pressure are then increased to a temperature above about 250~F and preferably about 270~F and a pressure above about 2.5 atm and held for about 30 minutes to about 1.5 hours lo while the jet is working. The fabric is allowed to cool, the dyebath dropped, the fabric rinsed and then an after-scour is performed using a wetting agent and soda ash in the jet. The resulting fabric has greater than 90 percent of the charged dyestuff, preferably about 98 percent exhausted into the fabric. The dye, flame retardant and/or additive is fixed into the fiber during the dye cycle.
Additional benefits and advantages of the invention will be apparent from the following illustrative examples.
EXAMPL~ 1 Using Nomex0 T-455 (95% Nomex~ and 5%
Kevlar0) fibers and a jet dye apparatus, the jet is loaded at a 10:1 liquor-to-goods ratio with fresh water, 2.0% owf soda ash and 2.0% owf wetting agent, and the temperature of the fabric formed from the fibers raised to 160~F. The jet is run at 160~F for 30 20522~6 minutes. The bath is then dropped and the fabric is rinsed clear using cold water.
A dye run is performed using a 10:1 liquor-to-goods ratio with a dyebath including 2 g/100 ml of S dyebath of N,N-diethyl(_-toluamide) (referred to hereinafter in the examples as "DEET") as a carrier.
The bath is set below about 120~F and run for 10 minutes. A navy blue cationic dye formulation containing 11.25% owf ("on weight of fabric") 100%
Basacryl Blue X-3GL, 1.41% owf Basacryl Red GL and 0.90% owf 200% Basacryl Golden Yellow X-GFL is added and run in the jet for 10 minutes. 2 g/100 ml of dyebath of sodium nitrate is added over a 10 minute period followed by 2% owf formic acid. The temperature is raised to 270~F at a rate of 3~F/minute. The fabric is then dyed for an extended period of 60 minutes at an elevated temperature of about 270~F and at a pressure of about 2.85 atm. The dyed fabric is cooled to 160~F
and the shade checked. When the shade is acceptable, the dyebath is dropped and the fabric is rinsed clean in cold water.
An after-scour is done at a 10:1 liquor-to-goods ratio in a bath comprising about 2% owf of wetting agent and about 2% owf of soda ash. The temperature is raised to 160~F and the fibers of the fabric scoured for 30 minutes at 160~F. The scouring bath is dropped and the fabric rinsed until the rinse is clear. The fabric is then dried.
~ 20~2236 The depth of shade of the fabrics are determined subjectively by sight, and objectively using the L*, a*, b* scale. The latter uses a colorimeter available from HunterLab of Fairfax, Virginia set at 10~ illumination and having a D65 light source. The L*, a*, b* scale is based on the opponent-colors theory of color vision which presumes that in the human eye there is an intermediate signal-switching stage between the light receptors in the retina and the optic nerve taking color signals to the brain. In this switching stage, red responses are compared with green to generate a red-to-green color dimension. The green (or red and green together, depending on theory used) response is compared in a similar manner with the blue to generate a yellow-to-blue color dimension. These two dimensions are often, though not always, associated with the symbols "a*" and "b*", respectively. The necessary third dimension, "L*", for lightness, is usually a non-linear function such as the square root or cube root of one of the dimensions. The resulting fabric of Example 1 had a deep shade of blue, and an L*
value of 20.27, an a* value of -0.19 and a b* value of -6.99. The values obtained for L*, a*, b* depth of shade compare satisfactorily to those obtained with other carriers such as CHP and substituted N-phthalimides.
.i'~.....
In order to demonstrate the effectiveness of an N-substituted carbonamide instead of an N,N-disubstituted aromatic carbonamide, the steps of Example 1 are repeated except 1.5 g/100 ml of dyebath of benzanilide is used as the carrier. The resulting fabric had a deep shade of blue and an L* value of 19.77, an a* value of -0.14 and a b* value of -6.09.
In order to demonstrate the effectiveness of a different N,N-disubstituted aromatic carbonamide, the steps of Example 1 are repeated except N,N-dimethylbenzamide is used as the carrier. The resulting fabric had a deep shade of blue and an L*
value of 19.31, an a* value of 1.03 and a b* value of -9.32.
The results of Examples 1-3 indicate that the use of the various N-substituted and N,N-disubstituted aromatic carbonamides as carriers provide excellent depth of shade properties when added to the dye baths.
In order to demonstrate the effectiveness of the inclusion of an emulsifier, the steps of Example 1 are repeated except 0.2 g/100 ml of dyebath of an amphoteric surfactant (Phosphoteric T-C6X) emulsifier is included in the carrier system. The resulting fabric had a deep shade of blue, and an L* of 18.57, an a* value of 0.44 and a b* value of -6.19.
'~ 20~2236 In order to demonstrate the effectiveness of the inclusion of a different emulsifier, the steps of Example 1 are repeated except 0.5 g/100 ml of dyebath of Solv-ItX is included in the carrier. The resulting fabric had a deep shade of blue, and an L* value of 18.81, an a* value of 0.05 and a b* value of -5.96.
EXAMPL~ 6 In order to demonstrate the effectiveness of the present carrier when a flame retardant is included with the carrier, the steps of Example 1 are repeated except the carrier system includes 0.92 g/100 ml of dyebath of AntiblazeX 100 flame retardant. The resulting fabric had a deep shade of blue, and a L*
value of 17.35 an a* value of 0.95 and a b* value of -6.71. This indicates that improved dye characteristics results when a flame retardant is included in the carrier. When the steps of Example 1 are repeated using 2.0 g/100 ml of dyebath of CHP and 0.9 g/100 ml of dyebath of AntiblazeX 100 as the carrier system, the fabric has an L* value of 18.89, an a* value of 0.72 and a b* value of -5.92. This indicates that improved dye characteristics result with the use of the present carrier as compared to the use of CHP and Antiblaze~
100 as the carrier system.
In order to demonstrate the effectiveness of the present carrier when an emulsifier and a flame !~ 2 0 5 2 2 3 6 retardant are included with the carrier, the steps of Example 1 are repeated except the carrier system used at 2.65 g/100 ml of dyebath includes 0.5 g/100 ml of dyebath of Phosphoteric T-C6~ and 0.15 g/100 ml of dyebath of AntiblazeX 100 flame retardant in a weight ratio of 4:1:0.3 DEET to emulsifier to flame retardant.
The resulting fabric had a deep shade of blue, and a L*
value of 17.01, an a* value of 0.25 and a b* value of -6.00.
EXANP~E 8 In order to demonstrate the effectiveness of the present carrier when a different emulsifier is included with the carrier, Example 7 is repeated except Solv-It~ is used, and the navy blue cationic dye comprises 11.25% owf 100% Basacryl Blue X-3GL, 1.41%
owf Basacryl Red GL and 0.90% owf 200% Basacryl Golden Yellow X-GFL. The resulting fabric had a deep shade of blue, and an L* value of 18.00, an a* value of 1.09 and a b* value of -6.68.
In order to demonstrate the effectiveness of the present carrier when a different emulsifier is included with the carrier, Example 7 is repeated except O.5 g/100 ml of dyebath of WitcomulX AM2-lOC is used instead of the Phosphoteric T-C6~, and the navy blue cationic dye comprises 11.25% owf 100% Basacryl Blue X-3GL, 1.41% owf Basacryl Red GL and 0.90% owf 200%
Basacryl Golden Yellow X-GFL. The resulting fabric had 20~2236 "i~ --19--a deep shade of blue, and an L* value of 17.45, an a*
value of 0.40 and a b* value of -5.99.
The results of Examples 6-9 indicate that excellent depth of shade properties can be provided when emulsifier and/or a flame retardant are included with the carrier system.
The dyed fabrics of Examples 6 and 8 were also tested for flame resistance using Federal Test Method 191-5905 Flame Contact Test. Test Method 191-5905 is a measurement of the resistance of fabric and other textiles to flame propagation due to a flame source. An initial test specimen, 2 3/4 inches by 12 inches, (70mm by 120mm) is exposed to high temperature butane gas flame 3 inches (76 mm) in height by vertical suspension in the flame for 12 seconds, the lowest portion of the specimen always 1 1/2 inches (38 mm) above the center of the burner. At the end of 12 seconds, the specimen is withdrawn from the flame slowly, and the after-flaming is timed. Then the specimen is re-introduced into the flame and again slowly withdrawn after 12 seconds and after-flame timed. Additionally, a second specimen is tested after five launderings at 140~F under the conditions specified in AATCC Method 135-3II, B. The results are reported as percent consumed of the original specimen ("Original") and after five launderings ("after/5") wherein -20~
Percent consumed = L-A
L x 100 where L = original length of specimen A = Length of uncharred part of specimen from the top of the specimen down the side with less charred area to the point at which the uncharred area first reaches a width of less than 1 inch (25 mm).
The results are reported in Table 1 with a scoured-only Nomex~ T-455 sample used as a standard.
TABLE
Example No. Ave % Consumed Warp Ave % Consumed Fill Standardoriginal 19.9 17.3 After/5 14.9 13.8 6original 9.9 10.2 After/5 9.9 8.1 8original 9.2 8.9 After/5 13.5 11.8 The results indicate that super flame resistant properties (i.e., less than 25~ consumed) can be provided by the use of a carrier with a flame retardant alone and/or a carrier with an emulsifier and a flame retardant. Moreover, the flame retardant properties obtained by use of the present carrier system, compared favorably to those of the standard, scoured only Nomex~ T-455.
In order to demonstrate the effectiveness of the carrier with an emulsifier and a flame retardant at .
different weight ratios, the steps of Example 8 are repeated using only 2.0 g/100 ml of dyebath total carrier system except the weight ratio is 3:2:0.3 DEET
to Solv-ItX to flame retardant. The resulting fabric had a deep shade of blue, and an L* value of 18.06, an a* value of 0.14 and a b* value of -7.75.
In order to demonstrate further the effectiveness of the carrier with an emulsifier and a flame retardant at different weight ratios, the steps of Example 10 are repeated except the weight ratio is 2:3:0.3 DEET to Solv-It~ to flame retardant. The resulting fabric had a deep shade of blue, and an L*
value of 19.30, an a* value of 0.66 and a b* value of -10.56. This indicates that at ratio of less than 2:3:0.3, the improved dyeing characteristics obtained with this carrier system combination will begin to decrease, and thus the effectiveness of the carrier will decrease.
In order to demonstrate further the effectiveness of the present carrier, the steps of the Example 1 are repeated except the fiber used is 100%
Kevlar~, the carrier is 4:1 DEET to Solv-It~ at 2.0 g/100 ml of dyebath, and the navy blue cationic dye comprises 14.63% owf Basacryl Blue X-3GL, 0.93% owf Basacryl Red GL and 1.00% owf 200% Basacryl Golden Yellow X-GFL. The resulting fabric had an L* value of 20.12, an a* value of -1.57 and a b* value of -6.97.
In order to further demonstrate the effectiveness of the present carrier, the steps of the Example 1 are repeated except the fiber used is 100% Kevlar~, the carrier is 4:1:0.3 DEET to Solv-It~ to Antiblaze~ 100 flame retardant at 2.0 g/100 ml of dyebath and the navy blue cationic dye comprises 14.63% owf Basacryl Blue X-3GL, 0.93% owf Basacryl Red GL and 1.00% owf 200% Basacryl Golden Yellow X-GFL. The resulting fabric had an L* value of 19.06, an a* value of -1.39 and a b* value of -6.78.
Examples 12 and 13 illustrate that the carrier with an emulsifier or with an emulsifier and flame retardant can be used to dye Kevlar~ effectively.
In order to further demonstrate the effectiveness of the present Example 1 are repeated except the fiber used is 100% PBI (polybenzimidazoles), the carrier used at 2.0 g/100 ml of dyebath is 4:1 DEET to Solv-It~ emulsifier and the trigger blue cationic dye comprises 6.00~ owf 100~
Basacryl Blue X3GL, 1.00% owf Basacryl Red GL and 0.01% owf 200% Basacryl Golden Yellow X-GFL. The resulting fabric had an L* value of 23.95, an a* value to -3.47 and a b* value of 0.27.
.
20~~236 ."~ ...
In order to further demonstrate the effectiveness of the present carrier in dyeing 100%
PBI, the steps of Example 14 are repeated except the carrier is 4:1 DEET to Phosphoteric T-C6~. The resulting fabric had an L* value of 21.32, an a* value of -2.78 and a b* value of -2.23.
Examples 14 and 15 illustrate that the carrier with an emulsifier can be used to effectively dye 100% PBI.
In order to further demonstrate the effectiveness of the present carrier with a blend of PBI and Nomex~ fibers, the steps of Example 1 are repeated except the fiber used is a PBI/Nomex0 T-455 20:80 blend, the carrier used at 2.0 g/100 ml of dyebath is 4:1 DEET to Solv-ItX emulsifier, and the trigger blue cationic dye comprises 6.00% owf 100~
Basacryl Blue X-3GL, 1.00% owf Basacryl Red GL and 0.01% owf 200% Basacryl Golden Yellow X-GFL. The resulting fabric had an L* value of 23.78, an a* value of 0.50 and a b* value of -16.31.
In order to further demonstrate the effectiveness of the present carrier with a blend of PBI and NomexX fibers, the steps of Example 16 are repeated except the carrier used is 4:1 DEET to Phosphoteric T-C6~. The resulting fabric had an L*
.,"
value of 23.63, an a* value of 0.74 and a b* value of -17.47.
Examples 16-17 indicate that a PBI/Nomex~
blend can be dyed effectively with the carrier and the emulsifier.
In order to demonstrate further the effectiveness of the present carrier with a blend of PBI and Nomex0 fibers and to demonstrate the criticality of the presence of the carrier, the steps of Example 16 are repeated except only 0.38 g/lOO ml of dyebath of Solv-It0 is used. The resulting fabric had an L* value of 28.59, and a* value of -O.99 and a b*
value of -15.95.
In order to demonstrate further the effectiveness of the present carrier with a blend of PBI and Nomex~ fibers and to demonstrate the criticality of the presence of the carrier, the steps of Example 16 are repeated except only 0.38 g/lOO ml of dyebath of Phosphoteric T-C6~ is used. The resulting fabric had an L* value of 28.93, an a* value of -O.9O
and a b* value of -16.13.
In order to demonstrate further the effectiveness of the present carrier with a blend of PBI and Nomex~ fibers and to demonstrate the criticality of the presence of the carrier, the steps 20~2236 .. ..
of Example 16 are repeated except only 0.38 g/100 ml of dyebath of Witcomul~ AM2-lOC is used. The resulting fabric had an L* value of 29.30, an a* value of -0.88 and a b* value of -14.20.
Examples 18-20 and the high L* values demonstrate the need for the use of the present carrier inasmuch as the use of an emulsifier without the present carrier results in poor dyeing.
In order to demonstrate further the effectiveness of the present carrier including a flame retardant with a blend of PBI and Nomex~ fibers, the steps of Example 16 are repeated except, the carrier is 4:1:0.3 DEET to Solv-It~ to AntiblazeX 100 flame retardant. The resulting fabric had an L* value of 23.66, an a* value of 0.63 and a b* value of -16.31.
In order to demonstrate further the effectiveness of the present carrier including a flame retardant with a blend of PBI and Nomex~ fibers, the steps of Example 16 are repeated except, the carrier is 4:1:0.3 DEET to Phosphoteric T-C6~ to Antiblaze~ 100 flame retardant. The resulting fabric had an L* value of 24.87, an a* value of 0.17 and a b* value of -17.19.
In order to demonstrate further the effectiveness of the present carrier including a flame retardant with a blend of PBI and Nomex~ fibers, the '~ 20~2236 .,.~, steps of Example 16 are repeated except, the carrier is 4:1:0.3 DEET to Witcomul~ AM2-lOC to Antiblaze0 lOO
flame retardant. The resulting fabric had an L* value of 21.43, an a* value of 1.24 and a b* value of -13.27.
Examples 21-23 indicate that a PBI/Nomex~
blend can be dyed effectively with the carrier, an emulsifier and a flame retardant.
In order to demonstrate further the effectiveness of the present carrier with a blend of PBI and Kevlar0 fibers, the steps of Example 1 are repeated except the fiber used is a PBI/Kevlar0 40:60 blend, the carrier used at 2.0 g/lOO ml of dyebath is 4:1 DEET to Solv-It~, and the navy blue cationic dye comprises 69.00% owf 100% Basacryl Blue X-3GL and 15.00% owf Basacryl Red GL. The resulting fabric had an L* value of 23.44, an a* value of 1.68 and a b*
value of -5.34 indicating that a PBI/Kevlar0 blend can be dyed effectively with the carrier and an emulsifier.
In order to demonstrate further the effectiveness of the present carrier including a flame retardant with a blend of PBI and Kevlar0 fibers, the steps of Example 1 are repeated except the fiber used is a PBI/Kevlar~ 40:60 blend, the carrier used at 2.0 g/lOO ml of dyebath is 4:1:0.3 DEET to Solv-It~ to Antiblaze0 lOO flame retardant, and the navy blue cationic dye comprises 69.00% owf 100% Basacryl Blue X-" ,...
3GL and 15.00% owf Basacryl Red GL. The resulting fabric had an L* value of 24.03, an a* value of 1.68 and a b* value of -5.44 indicating that a PBI/Kevlar~
blend can be dyed effectively with the carrier and an emulsifier and a flame retardant.
The results of Examples 24-25 indicate that blends of Kevlar~ and PBI can be dyed effectively by the use of the carrier system of the present invention.
In the specification and examples, there have been disclosed preferred embodiments of the invention, although specific terms are employed, they are used in a generic and descriptive sense only and not for the purpose of limitation, the scope of the invention being defined by the following claims.
The present invention relates to a method for dyeing fibrous material, and particularly fibrous materials having flame resistant properties which are difficult to dye such as aromatic polyamides, polybenzimidazoles or aromatic polyimides.
Backqround of the Invention There are various recognized methods for dyeing and/or incorporating additives into fibers and other fibrous materials, including methods which utilize organic solvents such as dimethylsulfoxide ("DMS0"), dimethylacetamide ("DMAc"), dimethylformamide ("DMF"), N-methylpyrrolidone ("NMP"), N-cyclohexyl-2-pyrrolidone (''CHPIl), acetophenone, acetanilide and methyl benzoate. Exemplary systems utilizing these organic solvents have been proposed in U.S. Patent Nos.
3,558,267 to Langenfeld, 3,741,719 to Ramanathan et al, 4,525,168 to Kelly, and U.S. Patent No. 4,898,596 to Riggins et al and U.K. Patent Nos. 1,275,459 to Gruen and 1,282,113 to Burtonshaw et al. In addition to these organic solvents it has been proposed in U. S. Patent No. 4,780,105 to White et al to dye aromatic polyamides with a cationic dye and a dye assistant including N-substituted phthalimides (e.g., a mixture of N-butylphthalimide and isopropylphthalimide).
Despite the general availability of dyeing methods using various carriers, there continues to be a desire for process improvements which enhance the dyeability of fibers and fabrics formed therefrom. For example, improvements in dye exhaustion and more uniform dyeing tend to improve the aesthetic characteristics of the fibers. Another example is that certain dyeing techniques result in the undesirable side effect of retention of solvent by the fibers.
Retention of solvent can adversely affect both the appearance and the flame resistance of the fibers.
This is particularly frustrating when dyeing fibers such as the aromatic polyamides, i.e., poly(_-phenyleneisophthalamide) ("Nomex~") and poly(~-phenyleneterephthalamide) (''KevlarX''), polybenzimidazoles, aromatic polyimides, and the like which have excellent flame resistant properties but also are difficult to dye. In order to dye these fibers, some of the various organic solvents and carriers, e.g., DMAc, DMSO, DMF, acetophenone, etc., and the N-substituted phthalimides have to be used, but these compounds may present health problems for some employees, and if non-water soluble, also tend to be retained by the fibers after dyeing. Thus, prior art techniques for dyeing these fibers can be counter-productive in that one of the problems caused by retention of solvent or carrier, e.g., decreased flame resistance, requires addition of a significantly large portion of a flame retardant to compensate for the reduction in the flame resistant properties of the fibers.
It is therefore an object of the present invention to provide an improved method for dyeing fibrous materials, and particularly to provide a method lo which provides one or more particularly advantageous results, including increased efficiency in dye exhaustion, more uniform dyeing and reduction of the retention of solvent. The improved method is particularly advantageous when used with difficult to dye fibers such as aromatic polyamide fibers including NomexX and KevlarX fibers, polybenzimidazole fibers, aromatic polyimide fibers, fibers of copolymers of the monomers thereof and blends thereof.
8ummary of the Invention This invention relates to a method for dyeing fibrous material which includes the steps of contacting the fibrous material with a mixture (e.g., a solution or dispersion) containing a dye in a dye carrier (e.g., a dyebath) comprising an N-substituted aromatic carbonamide or an N,N-disubstituted aromatic carbonamide or mixture thereof and fixing the dye in the fibrous material. The use of the present carrier results in improved dyeing characteristics. For example, improved efficiency in dye exhaustion may be achieved as compared to comparable levels of other carriers particularly when used to dye fibers such as aromatic polyamide fibers, polybenzimidazole fibers, aromatic polyimide fibers, fibers of copolymers of the monomers thereof and blends thereof.
In accordance with a particularly preferred embodiment of the present invention, the method of the present invention includes the steps of contacting aromatic polyamide fibers, polybenzimidazole fibers, aromatic polyimides fibers, fibers of copolymers of the monomers thereof, or blends thereof with a mixture of a carrier and dye soluble or dispersed with the carrier, the carrier including an N-substituted aromatic carbonamide or an N,N-disubstituted aromatic carbonamide or mixture thereof, an emulsifier and a flame retardant, and fixing the dye in the fibers. The emulsifier provides improved dyeing characteristics (e.g., improved dye exhaustion and more uniform dyeing) whereas the use of the flame retardant in small amounts (e.g. less than about 2 g/100 ml) results in "super flame resistant" properties in the fibers, i.e., less than 25 percent of the fabric formed from the fibers is consumed using Federal Test Method 191-5905 Flame Contact Test).
Detailed Description of the Invention As summarized above, the present invention provides an improved carrier system and carrier-based . ", .."j__.
method for dyeing and/or incorporating other additives into fibrous materials. The carrier and method is particularly adapted for use in reducing the adverse effect of dyeing methods on dye exhaustion, dye uniformity and flame resistant properties of the fibrous material. The carrier preferably comprises an N-substituted aromatic carbonamide or an N,N-disubstituted aromatic carbonamide or mixture thereof.
In a preferred embodiment, the carrier system can include an emulsifier and/or a flame retardant.
The method of the present invention can advantageously be employed using customary dyeing techniques. The dye and the carrier, and the addition of the emulsifier, flame retardant, and/or other additives is typically carried out by forming a mixture (e.g., a bath, solution, dispersion or the like) of the dye and the carrier of the present invention followed by contacting the fiber and/or fabric with this mixture and then fixing the dye in the fiber. In accordance with the present invention, a fibrous textile material, e.g., fiber, web, yarn, thread, sliver, woven fabric, knitted fabric, non-woven fabric, and the like is impregnated, padded, or otherwise contacted with the bath and the dyestuffs and/or additives fixed in the substrate using conventional equipment such as jet dyeing or other appropriate equipment.
The carrier of the present invention comprises an N-substituted aromatic carbonamide or an N,N-disubstituted aromatic carbonamide or mixture thereof.
Generally these compounds can be represented by the formula:
o /R
R-C-I'I~
\R
wherein R is aromatic or substituted aromatic, R' is H or alkyl and R" is alkyl, aromatic, substituted aromatic or aralkyl. Exemplary compounds include:
o 15 Benzanilide ~ C-N
20 N,N-dimethylbenzamide ~ O / Cli~
N,N-diethyl (_-toluamide) ~1 3C ~C- ~/
N-substituted and N,N-disubstituted aromatic carbonamides have previously been utilized as surface plasticizers for nylon such as described in U.S. Patent No. 3,634,023 to Foote. However, applicants are unaware of the use ~ ~, of N-substituted or N,N-disubstituted aromatic carbonamides as a carrier in dyeing fibers.
A particularly preferred N,N-disubstituted aromatic carbonamide is N,N-diethyl(_-toluamide), "DEET". DEET is a liquid at room temperature and is used predominantly as an insect repellant and a resin solvent in addition to being used as a surface plasticizer. Preferably, the carrier system also includes a compound which permits the dye and the carrier and other additives to be held in suspension or dispersion, i.e., an emulsifier. Additionally, the compound can function as a dye assist or levelling agent.
A particularly preferred emulsifier is Phosphoteric T-C6X, an amphoteric surfactant, available from Mona Industries, Inc. of Patterson, New Jersey.
Another particularly preferred emulsifier is Solv-It~, a multicomponent system containing a blend of surfactants and an alkyl ester of an aromatic carboxylic acid available from Apollo Chemical Company of Burlington, North Carolina.
Another particularly preferred emulsifier is WitcomulX AM2-lOC available from Witco Chemical of New York, New York. WitcomulX AM2-lOC is a blend of the free acid form of a phosphated ethoxylated dialkyl phenol containing from about 2 to 20 moles of ethylene oxide and a non-ionic propoxylated-ethoxylated alcohol containing from about 20 to 75 moles of propylene oxide ~2~
and 20 to 75 moles of ethylene oxide. Other compounds suitable for use with the carrier as a dye assist are diphenyl, 1-methylnaphthalene, 2-methyl-naphthalene, alkyl and aryl benzoates, chlorotoluenes, and the like.
Preferably, a flame retardant can also either be included with the carrier in the dyebath, applied as an after-dyeing surface treatment or otherwise incorporated in the fiber to provide super flame resistant properties. A
particularly preferred flame retardant is Antiblaze3 100 flame retardant, a non-cylic chloroalkyl diphosphate ester, available from Albright & Wilson Americas, Inc. of Richmond, Virginia.
Other flame retardants suitable for use are other non-cyclic mono- and poly- phosphonate and/or phosphate-type flame retardants available from Albright ~ Wilson Americas, Inc. In addition, another class of suitable flame retardants are those based on primary guanidine phosphates.
Preferably, the ratio of N-substituted or N,N-disubstituted aromatic carbonamide to emulsifier to flame retardant can be from about 2:3:0.1 to about 8:1:0.5, preferably about 2:3:0.3 to about 3:2:0.3, and more preferably about 4:1:0.3 if Solv-It~ or Phosphoteric T-C6 is used, and about 2:0.1:0.1 to about 8:1:1.5, preferably about 4:0.1:0.1 to 3:0.3:0.5, and more preferably about 4:0.2:0.4 if Witcomul~ AM2-lOC is used. The total weight of the carrier in the dyebath will be in the range from about 1 to about 3 . ~_ ;~
..
2 3 ~
g percent based on the weight of the dyebath. The weight percent can be adjusted using water or any other liquid miscible or dispersible with the carrier.
In view of the desirable results achieved to date, it is thought that the use of the carrier of the present invention is applicable with a wide variety of other additives such as softeners, W absorbers, IR
absorbers, antistatic agents, antifoaming agents, bactericides, fungicides, anti-viral agents or the like, and to a wide variety of fibrous material and includes dyed fibers which have been formed into fabrics including woven, non-woven or knit fabrics, for example.
The carrier can be used advantageously to dye a variety of flame resistant fibers which are difficult to dye, namely, aromatic polyamides, polybenzimidazoles, and aromatic polyimides, copolymers of the monomers thereof, and blends thereof. As noted above the carrier is particularly desirable for use with aromatic polyamides.
Fibers of aromatic polyamides have flame resistant properties and are often generically termed "aramid fibers" and are described, for example, in Kirk-Othmer:
The EncYclopedia of Chemical Technology, Third Edition, Vol. 3, pp. 213-242. The term "aromatic polyamides" or "aramids" includes but is not limited to poly(m-phenyleneisophthalamide) (e.g., Nomex0), poly(p-A
~ 10 phenyleneterephthalamide) (e.g., Kevlar~), polyparabenzamide, copolymers of the monomers thereof, and blends therewith. Nomex~ is available from DuPont of Wilmington, Delaware, in three forms. Nomex~ T-450 is 100 percent, undyed poly(_-phenyleneisophthalamide);
Nomex~ T-456 is 100 percent solution dyed poly(_-phenyleneisophthalamide); and Nomex~ T-455 is a blend of 95 percent Nomex~ (poly(m-phenyleneisophthalamide)) and S
percent Kevlar~ (poly(p-phenyleneterephthalamide)).
Nomex~ T-455 with the 5 percent Kevlar~ fraction is the most common type of Nomex~ used commercially. In view of the ability to dye the Kevlar~ fraction of Nomex~ T-455 more uniformly at a temperature above about 250~F, it is believed that the carrier of the present invention can be used at temperatures above about 250~F to dye blends of other fibers with Kevlar~ in a more uniform manner.
Another group of fibers which have flame resistant properties and are difficult to dye are the polybenzimidazole fibers available from Hoechst-Celanese of Charlotte, North Carolina and are described in U.S.
Patent No. 2,895,948 to Brinker et al.
Polybenzimidazoles use specific dicarboxylic and tetramine compounds as monomers and have the repeating unit of the formula:
3 ~
C~ >R< ~C-R--H H
where R and R' are aromatic moieties.
Another group of fibers having flame resistant properties and are difficult to dye are aromatic polyimide fibers described in U.S. Patent No. 4,758,649 to Asano et al. The aromatic polyimides have the repeating unit of the formula:
O O
R-N~ >R< ~I'J
O O
where R and R' are aromatic moieties.
In addition, copolymers of monomers or blends of the aromatic polyamides, polybenzimidazoles and/or aromatic polyimides can advantageously be dyed using the present carrier. For example, aromatic polyamide fibers and polybenzimidazole fibers can be blended in a weight ratio of about 60:40 to about 80:20 aromatic polyamide fibers to polybenzimidazole fibers. The A
'~ 20~2236 blends can be in the form of intimate blends, draw blends, corespun and the like. Additionally other synthetic fibers such as acrylic, modacrylic, polyesters and aliphatic polyamides can be advantageously dyed using the carrier system of the present invention.
Dyes which can be used advantageously with the present carrier can include acid dyes (e.g., azo, triarylmethane, anthraquinone dyes etc.); basic dyes lo (e.g., triphenylmethane, thiazide dyes, etc.); direct dyes (e.g. sulphonated azo dyes etc.); mordant dyes;
vat dyes; disperse dyes (e.g., nitroarylamine, azo, or anthraquinone dyes and the like with amino groups);
reactive dyes; and mixtures thereof with the proviso that the dyes do not decompose under customary dyeing conditions. Particularly effective dyes for dyeing aromatic polyamide fibers, polybenzimidazole fibers and aromatic polyimide fibers are the basic dyes (sometimes referred to as "cationic dyes"). Examples of this class are the Basacryl0 dyes available from BASF, Charlotte, North Carolina and the Maxillon0 dyes available from Ciba-Geigy Corporation, Greensboro, North Carolina.
In operation, the dye and/or other additive is preferably applied to the fibers of a fabric using a one-step batch-type process at 100~F to 300~F at 1 to 4 atm pressure. Pre-scouring and after-scouring of the fabric is preferred. The fabric can be scoured by "~ 2052236 passing the fabric through a hot aqueous scour in a jet dye machine or other scouring equipment. The jet is then charged with water and other auxiliaries including the dye and the present carrier with or without an emulsifier and with or without a flame retardant or other additive. The temperature and pressure are then increased to a temperature above about 250~F and preferably about 270~F and a pressure above about 2.5 atm and held for about 30 minutes to about 1.5 hours lo while the jet is working. The fabric is allowed to cool, the dyebath dropped, the fabric rinsed and then an after-scour is performed using a wetting agent and soda ash in the jet. The resulting fabric has greater than 90 percent of the charged dyestuff, preferably about 98 percent exhausted into the fabric. The dye, flame retardant and/or additive is fixed into the fiber during the dye cycle.
Additional benefits and advantages of the invention will be apparent from the following illustrative examples.
EXAMPL~ 1 Using Nomex0 T-455 (95% Nomex~ and 5%
Kevlar0) fibers and a jet dye apparatus, the jet is loaded at a 10:1 liquor-to-goods ratio with fresh water, 2.0% owf soda ash and 2.0% owf wetting agent, and the temperature of the fabric formed from the fibers raised to 160~F. The jet is run at 160~F for 30 20522~6 minutes. The bath is then dropped and the fabric is rinsed clear using cold water.
A dye run is performed using a 10:1 liquor-to-goods ratio with a dyebath including 2 g/100 ml of S dyebath of N,N-diethyl(_-toluamide) (referred to hereinafter in the examples as "DEET") as a carrier.
The bath is set below about 120~F and run for 10 minutes. A navy blue cationic dye formulation containing 11.25% owf ("on weight of fabric") 100%
Basacryl Blue X-3GL, 1.41% owf Basacryl Red GL and 0.90% owf 200% Basacryl Golden Yellow X-GFL is added and run in the jet for 10 minutes. 2 g/100 ml of dyebath of sodium nitrate is added over a 10 minute period followed by 2% owf formic acid. The temperature is raised to 270~F at a rate of 3~F/minute. The fabric is then dyed for an extended period of 60 minutes at an elevated temperature of about 270~F and at a pressure of about 2.85 atm. The dyed fabric is cooled to 160~F
and the shade checked. When the shade is acceptable, the dyebath is dropped and the fabric is rinsed clean in cold water.
An after-scour is done at a 10:1 liquor-to-goods ratio in a bath comprising about 2% owf of wetting agent and about 2% owf of soda ash. The temperature is raised to 160~F and the fibers of the fabric scoured for 30 minutes at 160~F. The scouring bath is dropped and the fabric rinsed until the rinse is clear. The fabric is then dried.
~ 20~2236 The depth of shade of the fabrics are determined subjectively by sight, and objectively using the L*, a*, b* scale. The latter uses a colorimeter available from HunterLab of Fairfax, Virginia set at 10~ illumination and having a D65 light source. The L*, a*, b* scale is based on the opponent-colors theory of color vision which presumes that in the human eye there is an intermediate signal-switching stage between the light receptors in the retina and the optic nerve taking color signals to the brain. In this switching stage, red responses are compared with green to generate a red-to-green color dimension. The green (or red and green together, depending on theory used) response is compared in a similar manner with the blue to generate a yellow-to-blue color dimension. These two dimensions are often, though not always, associated with the symbols "a*" and "b*", respectively. The necessary third dimension, "L*", for lightness, is usually a non-linear function such as the square root or cube root of one of the dimensions. The resulting fabric of Example 1 had a deep shade of blue, and an L*
value of 20.27, an a* value of -0.19 and a b* value of -6.99. The values obtained for L*, a*, b* depth of shade compare satisfactorily to those obtained with other carriers such as CHP and substituted N-phthalimides.
.i'~.....
In order to demonstrate the effectiveness of an N-substituted carbonamide instead of an N,N-disubstituted aromatic carbonamide, the steps of Example 1 are repeated except 1.5 g/100 ml of dyebath of benzanilide is used as the carrier. The resulting fabric had a deep shade of blue and an L* value of 19.77, an a* value of -0.14 and a b* value of -6.09.
In order to demonstrate the effectiveness of a different N,N-disubstituted aromatic carbonamide, the steps of Example 1 are repeated except N,N-dimethylbenzamide is used as the carrier. The resulting fabric had a deep shade of blue and an L*
value of 19.31, an a* value of 1.03 and a b* value of -9.32.
The results of Examples 1-3 indicate that the use of the various N-substituted and N,N-disubstituted aromatic carbonamides as carriers provide excellent depth of shade properties when added to the dye baths.
In order to demonstrate the effectiveness of the inclusion of an emulsifier, the steps of Example 1 are repeated except 0.2 g/100 ml of dyebath of an amphoteric surfactant (Phosphoteric T-C6X) emulsifier is included in the carrier system. The resulting fabric had a deep shade of blue, and an L* of 18.57, an a* value of 0.44 and a b* value of -6.19.
'~ 20~2236 In order to demonstrate the effectiveness of the inclusion of a different emulsifier, the steps of Example 1 are repeated except 0.5 g/100 ml of dyebath of Solv-ItX is included in the carrier. The resulting fabric had a deep shade of blue, and an L* value of 18.81, an a* value of 0.05 and a b* value of -5.96.
EXAMPL~ 6 In order to demonstrate the effectiveness of the present carrier when a flame retardant is included with the carrier, the steps of Example 1 are repeated except the carrier system includes 0.92 g/100 ml of dyebath of AntiblazeX 100 flame retardant. The resulting fabric had a deep shade of blue, and a L*
value of 17.35 an a* value of 0.95 and a b* value of -6.71. This indicates that improved dye characteristics results when a flame retardant is included in the carrier. When the steps of Example 1 are repeated using 2.0 g/100 ml of dyebath of CHP and 0.9 g/100 ml of dyebath of AntiblazeX 100 as the carrier system, the fabric has an L* value of 18.89, an a* value of 0.72 and a b* value of -5.92. This indicates that improved dye characteristics result with the use of the present carrier as compared to the use of CHP and Antiblaze~
100 as the carrier system.
In order to demonstrate the effectiveness of the present carrier when an emulsifier and a flame !~ 2 0 5 2 2 3 6 retardant are included with the carrier, the steps of Example 1 are repeated except the carrier system used at 2.65 g/100 ml of dyebath includes 0.5 g/100 ml of dyebath of Phosphoteric T-C6~ and 0.15 g/100 ml of dyebath of AntiblazeX 100 flame retardant in a weight ratio of 4:1:0.3 DEET to emulsifier to flame retardant.
The resulting fabric had a deep shade of blue, and a L*
value of 17.01, an a* value of 0.25 and a b* value of -6.00.
EXANP~E 8 In order to demonstrate the effectiveness of the present carrier when a different emulsifier is included with the carrier, Example 7 is repeated except Solv-It~ is used, and the navy blue cationic dye comprises 11.25% owf 100% Basacryl Blue X-3GL, 1.41%
owf Basacryl Red GL and 0.90% owf 200% Basacryl Golden Yellow X-GFL. The resulting fabric had a deep shade of blue, and an L* value of 18.00, an a* value of 1.09 and a b* value of -6.68.
In order to demonstrate the effectiveness of the present carrier when a different emulsifier is included with the carrier, Example 7 is repeated except O.5 g/100 ml of dyebath of WitcomulX AM2-lOC is used instead of the Phosphoteric T-C6~, and the navy blue cationic dye comprises 11.25% owf 100% Basacryl Blue X-3GL, 1.41% owf Basacryl Red GL and 0.90% owf 200%
Basacryl Golden Yellow X-GFL. The resulting fabric had 20~2236 "i~ --19--a deep shade of blue, and an L* value of 17.45, an a*
value of 0.40 and a b* value of -5.99.
The results of Examples 6-9 indicate that excellent depth of shade properties can be provided when emulsifier and/or a flame retardant are included with the carrier system.
The dyed fabrics of Examples 6 and 8 were also tested for flame resistance using Federal Test Method 191-5905 Flame Contact Test. Test Method 191-5905 is a measurement of the resistance of fabric and other textiles to flame propagation due to a flame source. An initial test specimen, 2 3/4 inches by 12 inches, (70mm by 120mm) is exposed to high temperature butane gas flame 3 inches (76 mm) in height by vertical suspension in the flame for 12 seconds, the lowest portion of the specimen always 1 1/2 inches (38 mm) above the center of the burner. At the end of 12 seconds, the specimen is withdrawn from the flame slowly, and the after-flaming is timed. Then the specimen is re-introduced into the flame and again slowly withdrawn after 12 seconds and after-flame timed. Additionally, a second specimen is tested after five launderings at 140~F under the conditions specified in AATCC Method 135-3II, B. The results are reported as percent consumed of the original specimen ("Original") and after five launderings ("after/5") wherein -20~
Percent consumed = L-A
L x 100 where L = original length of specimen A = Length of uncharred part of specimen from the top of the specimen down the side with less charred area to the point at which the uncharred area first reaches a width of less than 1 inch (25 mm).
The results are reported in Table 1 with a scoured-only Nomex~ T-455 sample used as a standard.
TABLE
Example No. Ave % Consumed Warp Ave % Consumed Fill Standardoriginal 19.9 17.3 After/5 14.9 13.8 6original 9.9 10.2 After/5 9.9 8.1 8original 9.2 8.9 After/5 13.5 11.8 The results indicate that super flame resistant properties (i.e., less than 25~ consumed) can be provided by the use of a carrier with a flame retardant alone and/or a carrier with an emulsifier and a flame retardant. Moreover, the flame retardant properties obtained by use of the present carrier system, compared favorably to those of the standard, scoured only Nomex~ T-455.
In order to demonstrate the effectiveness of the carrier with an emulsifier and a flame retardant at .
different weight ratios, the steps of Example 8 are repeated using only 2.0 g/100 ml of dyebath total carrier system except the weight ratio is 3:2:0.3 DEET
to Solv-ItX to flame retardant. The resulting fabric had a deep shade of blue, and an L* value of 18.06, an a* value of 0.14 and a b* value of -7.75.
In order to demonstrate further the effectiveness of the carrier with an emulsifier and a flame retardant at different weight ratios, the steps of Example 10 are repeated except the weight ratio is 2:3:0.3 DEET to Solv-It~ to flame retardant. The resulting fabric had a deep shade of blue, and an L*
value of 19.30, an a* value of 0.66 and a b* value of -10.56. This indicates that at ratio of less than 2:3:0.3, the improved dyeing characteristics obtained with this carrier system combination will begin to decrease, and thus the effectiveness of the carrier will decrease.
In order to demonstrate further the effectiveness of the present carrier, the steps of the Example 1 are repeated except the fiber used is 100%
Kevlar~, the carrier is 4:1 DEET to Solv-It~ at 2.0 g/100 ml of dyebath, and the navy blue cationic dye comprises 14.63% owf Basacryl Blue X-3GL, 0.93% owf Basacryl Red GL and 1.00% owf 200% Basacryl Golden Yellow X-GFL. The resulting fabric had an L* value of 20.12, an a* value of -1.57 and a b* value of -6.97.
In order to further demonstrate the effectiveness of the present carrier, the steps of the Example 1 are repeated except the fiber used is 100% Kevlar~, the carrier is 4:1:0.3 DEET to Solv-It~ to Antiblaze~ 100 flame retardant at 2.0 g/100 ml of dyebath and the navy blue cationic dye comprises 14.63% owf Basacryl Blue X-3GL, 0.93% owf Basacryl Red GL and 1.00% owf 200% Basacryl Golden Yellow X-GFL. The resulting fabric had an L* value of 19.06, an a* value of -1.39 and a b* value of -6.78.
Examples 12 and 13 illustrate that the carrier with an emulsifier or with an emulsifier and flame retardant can be used to dye Kevlar~ effectively.
In order to further demonstrate the effectiveness of the present Example 1 are repeated except the fiber used is 100% PBI (polybenzimidazoles), the carrier used at 2.0 g/100 ml of dyebath is 4:1 DEET to Solv-It~ emulsifier and the trigger blue cationic dye comprises 6.00~ owf 100~
Basacryl Blue X3GL, 1.00% owf Basacryl Red GL and 0.01% owf 200% Basacryl Golden Yellow X-GFL. The resulting fabric had an L* value of 23.95, an a* value to -3.47 and a b* value of 0.27.
.
20~~236 ."~ ...
In order to further demonstrate the effectiveness of the present carrier in dyeing 100%
PBI, the steps of Example 14 are repeated except the carrier is 4:1 DEET to Phosphoteric T-C6~. The resulting fabric had an L* value of 21.32, an a* value of -2.78 and a b* value of -2.23.
Examples 14 and 15 illustrate that the carrier with an emulsifier can be used to effectively dye 100% PBI.
In order to further demonstrate the effectiveness of the present carrier with a blend of PBI and Nomex~ fibers, the steps of Example 1 are repeated except the fiber used is a PBI/Nomex0 T-455 20:80 blend, the carrier used at 2.0 g/100 ml of dyebath is 4:1 DEET to Solv-ItX emulsifier, and the trigger blue cationic dye comprises 6.00% owf 100~
Basacryl Blue X-3GL, 1.00% owf Basacryl Red GL and 0.01% owf 200% Basacryl Golden Yellow X-GFL. The resulting fabric had an L* value of 23.78, an a* value of 0.50 and a b* value of -16.31.
In order to further demonstrate the effectiveness of the present carrier with a blend of PBI and NomexX fibers, the steps of Example 16 are repeated except the carrier used is 4:1 DEET to Phosphoteric T-C6~. The resulting fabric had an L*
.,"
value of 23.63, an a* value of 0.74 and a b* value of -17.47.
Examples 16-17 indicate that a PBI/Nomex~
blend can be dyed effectively with the carrier and the emulsifier.
In order to demonstrate further the effectiveness of the present carrier with a blend of PBI and Nomex0 fibers and to demonstrate the criticality of the presence of the carrier, the steps of Example 16 are repeated except only 0.38 g/lOO ml of dyebath of Solv-It0 is used. The resulting fabric had an L* value of 28.59, and a* value of -O.99 and a b*
value of -15.95.
In order to demonstrate further the effectiveness of the present carrier with a blend of PBI and Nomex~ fibers and to demonstrate the criticality of the presence of the carrier, the steps of Example 16 are repeated except only 0.38 g/lOO ml of dyebath of Phosphoteric T-C6~ is used. The resulting fabric had an L* value of 28.93, an a* value of -O.9O
and a b* value of -16.13.
In order to demonstrate further the effectiveness of the present carrier with a blend of PBI and Nomex~ fibers and to demonstrate the criticality of the presence of the carrier, the steps 20~2236 .. ..
of Example 16 are repeated except only 0.38 g/100 ml of dyebath of Witcomul~ AM2-lOC is used. The resulting fabric had an L* value of 29.30, an a* value of -0.88 and a b* value of -14.20.
Examples 18-20 and the high L* values demonstrate the need for the use of the present carrier inasmuch as the use of an emulsifier without the present carrier results in poor dyeing.
In order to demonstrate further the effectiveness of the present carrier including a flame retardant with a blend of PBI and Nomex~ fibers, the steps of Example 16 are repeated except, the carrier is 4:1:0.3 DEET to Solv-It~ to AntiblazeX 100 flame retardant. The resulting fabric had an L* value of 23.66, an a* value of 0.63 and a b* value of -16.31.
In order to demonstrate further the effectiveness of the present carrier including a flame retardant with a blend of PBI and Nomex~ fibers, the steps of Example 16 are repeated except, the carrier is 4:1:0.3 DEET to Phosphoteric T-C6~ to Antiblaze~ 100 flame retardant. The resulting fabric had an L* value of 24.87, an a* value of 0.17 and a b* value of -17.19.
In order to demonstrate further the effectiveness of the present carrier including a flame retardant with a blend of PBI and Nomex~ fibers, the '~ 20~2236 .,.~, steps of Example 16 are repeated except, the carrier is 4:1:0.3 DEET to Witcomul~ AM2-lOC to Antiblaze0 lOO
flame retardant. The resulting fabric had an L* value of 21.43, an a* value of 1.24 and a b* value of -13.27.
Examples 21-23 indicate that a PBI/Nomex~
blend can be dyed effectively with the carrier, an emulsifier and a flame retardant.
In order to demonstrate further the effectiveness of the present carrier with a blend of PBI and Kevlar0 fibers, the steps of Example 1 are repeated except the fiber used is a PBI/Kevlar0 40:60 blend, the carrier used at 2.0 g/lOO ml of dyebath is 4:1 DEET to Solv-It~, and the navy blue cationic dye comprises 69.00% owf 100% Basacryl Blue X-3GL and 15.00% owf Basacryl Red GL. The resulting fabric had an L* value of 23.44, an a* value of 1.68 and a b*
value of -5.34 indicating that a PBI/Kevlar0 blend can be dyed effectively with the carrier and an emulsifier.
In order to demonstrate further the effectiveness of the present carrier including a flame retardant with a blend of PBI and Kevlar0 fibers, the steps of Example 1 are repeated except the fiber used is a PBI/Kevlar~ 40:60 blend, the carrier used at 2.0 g/lOO ml of dyebath is 4:1:0.3 DEET to Solv-It~ to Antiblaze0 lOO flame retardant, and the navy blue cationic dye comprises 69.00% owf 100% Basacryl Blue X-" ,...
3GL and 15.00% owf Basacryl Red GL. The resulting fabric had an L* value of 24.03, an a* value of 1.68 and a b* value of -5.44 indicating that a PBI/Kevlar~
blend can be dyed effectively with the carrier and an emulsifier and a flame retardant.
The results of Examples 24-25 indicate that blends of Kevlar~ and PBI can be dyed effectively by the use of the carrier system of the present invention.
In the specification and examples, there have been disclosed preferred embodiments of the invention, although specific terms are employed, they are used in a generic and descriptive sense only and not for the purpose of limitation, the scope of the invention being defined by the following claims.
Claims (47)
1. A method for dyeing fibrous material comprising the steps of:
contacting a fibrous material formed from fibers selected from the group of aromatic polyamide fibers, polybenzimidazole fibers, aromatic polyimide fibers, fibers of copolymers of the monomers thereof, or blends thereof with a mixture of a carrier and a dye soluble or dispersed with the carrier, the carrier comprising an N-substituted aromatic carbonamide or an N,N-disubstituted aromatic carbonamide or mixture thereof; and fixing the dye within the fibrous material.
contacting a fibrous material formed from fibers selected from the group of aromatic polyamide fibers, polybenzimidazole fibers, aromatic polyimide fibers, fibers of copolymers of the monomers thereof, or blends thereof with a mixture of a carrier and a dye soluble or dispersed with the carrier, the carrier comprising an N-substituted aromatic carbonamide or an N,N-disubstituted aromatic carbonamide or mixture thereof; and fixing the dye within the fibrous material.
2. A method according to claim 1 wherein the fiber is aromatic polyamide fibers, polybenzimidazole fibers, aromatic polyimide fibersl fibers of copolymers of the monomers thereof, or blends thereof.
3. A method according to claim 1 wherein the carrier includes an emulsifier.
4. A method according to claim 3 wherein the emulsifier is a blend of the free acid form of a phosphated ethoxylated dialkyl phenol containing from about 2 to 20 moles of ethylene oxide and a non-ionic propoxylated-ethoxylated alcohol containing from about 20 to 75 moles of propylene oxide and 20 to 75 moles of ethylene oxide.
5. A method according to claim 1 or 3 wherein the carrier includes a flame retardant.
6. A method according to claim 1 or 3 wherein the N,N-disubstituted aromatic carbonamide is N,N-diethyl(m-toluamide) or N,N-dimethylbenzamide.
7. A method according to claim 1 or 3 wherein the N-substituted aromatic carbonamide is benzanilide.
8. A method according to claim 2 wherein the aromatic polyamide is poly(m-phenyleneisophthalamide), poly(p-phenyleneterephthalamide), copolymers of the monomers thereof, or blends thereof.
9. A method according to claim 2 wherein the fiber comprises a blend of aromatic polyamide and polybenzimidazole fibers.
10. A method according to claim 1 or 3 wherein the fibrous material is contacted with the mixture of the carrier and the dye at a temperature of from about 100°F to about 300°F and at from about 1 to about 4 atm pressure.
11. A method according to claim 10 wherein the fibrous material is contacted with the mixture of the carrier and the dye at a temperature of above about 250°F and at a pressure above about 2.5 atm, and held at the temperature and pressure for about 30 minutes to about 1.5 hours.
12. A fabric formed from the fibrous material dyed by the method of claim 1 or 3.
13. A method for dyeing fibrous material particularly adapted for use in reducing the adverse affect of dyeing methods on the flame resistant properties of fibrous material having inherent flame resistant properties, the method comprising the steps of:
contacting aromatic polyamide fibers, polybenzimidazole fibers, aromatic polyimide fibers, fibers of copolymers of the monomers thereof, or blends thereof with a mixture of a carrier and a dye soluble or dispersed with the carrier, the carrier comprising an N-substituted aromatic carbonamide or an N,N-disubstituted aromatic carbonamide or mixture thereof, an emulsifier and a flame retardant; and fixing the dye and flame retardant within the fibers.
contacting aromatic polyamide fibers, polybenzimidazole fibers, aromatic polyimide fibers, fibers of copolymers of the monomers thereof, or blends thereof with a mixture of a carrier and a dye soluble or dispersed with the carrier, the carrier comprising an N-substituted aromatic carbonamide or an N,N-disubstituted aromatic carbonamide or mixture thereof, an emulsifier and a flame retardant; and fixing the dye and flame retardant within the fibers.
14. A method according to claim 13 wherein the N,N-disubstituted aromatic carbonamide is N,N-diethyl (m-toluamide) or N,N-dimethylbenzamide.
15. A method according to claim 13 wherein the N-substituted aromatic carbonamide is benzanilide.
16. A method according to claim 13 wherein the emulsifier is a blend of the free acid form of a phosphated ethoxylated dialkyl phenol containing from about 2 to 20 moles of ethylene oxide and a non-ionic propoxylated-ethoxylated alcohol containing from about 20 to 75 moles of propylene oxide and 20 to 75 moles of ethylene oxide.
17. A method according to claim 13 wherein the fibers are contacted with the mixture of the carrier and the dye at a temperature of from about 100°F to about 300°F and at from about 1 to about 4 atm pressure.
18. A method according to claim 17 wherein the fibers are contacted with the mixture of the carrier and the dye at a temperature of above about 2500F and at a pressure above about 2.5 atm, and held at the temperature and pressure for about 30 minutes to about 1.5 hours.
19. A fabric in which the fibers are dyed by the method of claim 13.
20. In a method for treating fibers selected from the group of aromatic polyamide fibers, polybenzimidazole fibers, aromatic polyimide fibers, fibers of copolymers of the monomers thereof or blends thereof, with an additive which includes the step of contacting fibrous material formed from such fibers with a mixture of a carrier and an additive soluble or dispersed with the carrier, the improvement comprising the use, as the carrier, of an N-substituted aromatic carbonamide or an N,N-disubstituted aromatic carbonamide or mixture thereof.
21. In a method according to claim 20 wherein the carrier includes an emulsifier.
22. In a method according to claim 21 wherein the emulsifier is a blend of the free acid form of a phosphated ethoxylated dialkyl phenol containing from about 2 to 20 moles of ethylene oxide and a nonionic propoxylated-ethoxylated alcohol containing from about 20 to 75 moles of propylene oxide and 20 to 75 moles of ethylene oxide.
23. In a method according to claim 20 or 21 wherein the carrier includes a flame retardant.
24. In a method according to claim 20 or 21 wherein the N,N-disubstituted aromatic carbonamide is N,N-diethyl (m-toluamide) or N,N-dimethylbenzamide.
25. In a method according to claim 20 or 21 wherein the N-substituted aromatic carbonamide is benzanilide.
26. In a method according to claim 20 or 21 wherein the fibrous material is contacted with the mixture of the carrier and the additive at a temperature of from about 100°F to about 300°F and at from about 1 to about 4 atm pressure.
27. In a method according to claim 26 wherein the fibrous material is contacted with the mixture of the carrier and the additive at a temperature of above about 250°F and at a pressure above about 2.5 atm, and held at the temperature and pressure for about 30 minutes to about 1.5 hours.
28. In a method for dyeing aromatic polyamide fibers, polybenzimidazole fibers, aromatic polyimide fibers, fibers of copolymers of the monomers thereof, or blends thereof with a dye which includes the step of contacting the fibers with a mixture of a carrier and a dye soluble or dispersed with the carrier, the improvement comprising the use, as the carrier of an N-substituted aromatic carbonamide or an N,N-disubstituted aromatic carbonamide or mixture thereof, an emulsifier and a flame retardant.
29. In a method according to claim 28 wherein the N,N-disubstituted aromatic carbonamide is N,N-diethyl (m-toluamide) or N,N-dimethylbenzamide.
30. In a method according to claim 28 wherein the N-substituted aromatic carbonamide is benzanilide.
31. In a method according to claim 28 wherein the emulsifier is a blend of the free acid form of a phosphated ethoxylated dialkyl phenol containing from about 2 to 20 moles of ethylene oxide and a nonionic propoxylated-ethoxylated alcohol containing from about 20 to 75 moles of propylene oxide and 20 to 75 moles of ethylene oxide.
32. In a method according to claim 28 wherein the fibrous material is contacted with the mixture of the carrier and the additive at a temperature of from about 100OF to about 300'F and at from about 1 to about 4 atm pressure.
33. In a method according to claim 32 wherein the fibrous material is contacted with the mixture of the carrier and the additive at a temperature of above about 250'F and at a pressure above about 2.5 atm, and held at the temperature and pressure for about 30 minutes to about 1.5 hours.
34. A fibrous material formed from fibers selected from the group of aromatic polyamide fibers, polybenzimidazole fibers, aromatic polyimide fibers, fibers of copolymers of the monomers thereof or blends thereof, which has been dyed with a mixture of a carrier and a dye soluble or dispersed with the carrier in a dyebath, the carrier comprising an N-substituted aromatic carbonamide or an N,N-disubstituted aromatic carbonamide or mixture thereof.
35. A fibrous material according to claim 34 wherein the carrier includes an emulsifier.
36. A fibrous material according to claim 35 wherein the emulsifier is a blend of the free acid form of a phosphated ethoxylated dialkyl phenol containing from about 2 to 20 moles of ethylene oxide and a nonionic propoxylated-ethoxylated alcohol containing from about 20 to 75 moles of propylene oxide and 20 to 75 moles of ethylene oxide.
37. A fibrous material according to claim 34 or 35 wherein the carrier includes a flame retardant.
38. A fibrous material according to claim 34 or 35 wherein the N,N-disubstituted aromatic carbonamide is N,N-diethyl (m-toluamide) or N,N-dimethylbenzamide.
39. A fibrous material according to claim 34 or 35 wherein the N-substituted aromatic carbonamide is benzanilide.
40. A fabric formed from the fibrous material of claim 34 or 35.
41. A fiber of aromatic polyamides, polybenzimidazoles, aromatic polyimides, copolymers of the monomers thereof or blends thereof dyed with a mixture of a carrier and a dye soluble or dispersed with the carrier, the carrier comprising an N-substituted aromatic carbonamide or an N,N-disubstituted aromatic carbonamide or mixture thereof, an emulsifier, and a flame retardant.
42. A fiber according to claim 41 wherein the N,N-substituted aromatic carbonamide is N,N-diethyl (m-toluamide) or N,N-dimethylbenzamide.
43. A fiber according to claim 41 wherein the emulsifier is a blend of the free acid form of a phosphated ethoxylated dialkyl phenol containing from about 2 to 20 moles of ethylene oxide and a non-ionic propoxylated-ethoxylated alcohol containing from about 20 to 75 moles of propylene oxide and 20 to 75 moles of ethylene oxide.
44. A fiber according to claim 41 wherein the N-substituted aromatic carbonamide is benzanilide.
45. A fiber according to claim 41 wherein the aromatic polyamide is poly(m-phenylene-isophthalamide), poly(p-phenyleneterephthalamide), copolymers of the monomers thereof, or blends thereof.
46. A fiber according to claim 41 wherein the fiber comprises a blend of aromatic polyamide and polybenzimidazole fibers.
47. A fabric formed from the fibers of claim 41.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/589,919 US5207803A (en) | 1990-09-28 | 1990-09-28 | Method for dyeing aromatic polyamide fibrous materials: n,n-diethyl(meta-toluamide) dye carrier |
US589,919 | 1990-09-28 |
Publications (2)
Publication Number | Publication Date |
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CA2052236A1 CA2052236A1 (en) | 1992-03-29 |
CA2052236C true CA2052236C (en) | 1999-03-09 |
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Application Number | Title | Priority Date | Filing Date |
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CA002052236A Expired - Fee Related CA2052236C (en) | 1990-09-28 | 1991-09-25 | Method for dyeing fibrous material |
Country Status (11)
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US (1) | US5207803A (en) |
EP (1) | EP0478301B1 (en) |
JP (1) | JP2530782B2 (en) |
KR (1) | KR940011839B1 (en) |
CN (1) | CN1060126A (en) |
AT (1) | ATE124101T1 (en) |
AU (1) | AU647342B2 (en) |
CA (1) | CA2052236C (en) |
DE (1) | DE69110603T2 (en) |
DK (1) | DK0478301T3 (en) |
ES (1) | ES2073689T3 (en) |
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US5306312A (en) * | 1990-10-31 | 1994-04-26 | Burlington Industries, Inc. | Dye diffusion promoting agents for aramids |
US5427589A (en) * | 1993-03-03 | 1995-06-27 | Springs Industries, Inc. | Method for dyeing fibrous materials |
US5437690A (en) * | 1994-05-25 | 1995-08-01 | Springs Industries, Inc. | Method for dyeing fibrous materials and dye assistant relating to the same |
WO1999052971A1 (en) | 1998-04-09 | 1999-10-21 | Majilite Corporation | Fire retardant compositions and methods for their preparation and use |
USD435217S (en) * | 1999-04-15 | 2000-12-19 | Supreme Corq | Synthetic cork for a liquid container |
US6551362B2 (en) * | 2001-02-02 | 2003-04-22 | Bgb Stockhausen Gmbh | Composition for dyeing material of synthetic aromatic polyamide fibers comprising a cationic dye and novel dye assistant |
US20040062782A1 (en) * | 2002-10-01 | 2004-04-01 | John Van Winkle | Addition of insect repellent during rinse cycle |
US20050204487A1 (en) * | 2004-03-18 | 2005-09-22 | Reiyao Zhu | Dyeing of modacrylic/aramid fiber blends |
US20060040575A1 (en) * | 2004-08-18 | 2006-02-23 | Kelleher Karen A | Reflective printing on flame resistant fabrics |
EP1959771B1 (en) | 2005-12-16 | 2014-06-18 | Southern Mills, Inc. | Protective garments that provide thermal protection |
US7967873B1 (en) * | 2006-03-29 | 2011-06-28 | Bozzetto, Inc. | Dyed textile article and dye bath assistant |
US7811952B2 (en) | 2006-04-20 | 2010-10-12 | Southern Mills, Inc. | Ultraviolet-resistant fabrics and methods for making them |
US20080153372A1 (en) * | 2006-04-20 | 2008-06-26 | Southern Mills | Insect-Repellant Fabrics and Methods for Making Them |
EP2069571A2 (en) * | 2006-09-08 | 2009-06-17 | Southern Mills, Inc. | Methods and systems for providing dyed, stretchable flame resistant fabrics and garments |
CA2685894A1 (en) * | 2007-05-08 | 2008-11-20 | Southern Mills, Inc. | Systems and methods for dyeing inherently flame resistant fibers withoutusing accelerants or carriers |
CN102187023B (en) * | 2008-10-17 | 2014-07-09 | 索维高级聚合物股份有限公司 | Fiber or foil from polymers with high tg and process for their manufacture |
US20120171918A1 (en) | 2011-01-05 | 2012-07-05 | Pbi Performance Products, Inc. | Flame resistant fabric with tracing yarns |
CN103541214B (en) * | 2013-10-21 | 2016-05-11 | 绍兴文理学院 | For improving the method for polyimide fiber basic dyeing performance |
CN104532622B (en) * | 2014-12-19 | 2016-08-24 | 东华大学 | A kind of method of polyimide fiber disperse dyeing |
CA3039312A1 (en) * | 2016-11-01 | 2018-05-11 | Teijin Limited | Fabric, method for manufacturing same, and fiber product |
CN107447553B (en) * | 2017-08-15 | 2020-01-17 | 江南大学 | Ketone ester carrier dyeing method for polyimide fiber and fabric |
CN108060594A (en) * | 2017-12-25 | 2018-05-22 | 江南大学 | A kind of preparation method of the environmentally friendly carrier of polylactic acid dyeing |
US20190338462A1 (en) | 2018-05-03 | 2019-11-07 | Milliken & Company | Textile materials containing aramid fibers and dyed polyphenylene sulfide fibers |
RU2744118C1 (en) * | 2020-10-23 | 2021-03-02 | Акционерное общество «Каменскволокно» | Method for dying aramide fiber |
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-
1990
- 1990-09-28 US US07/589,919 patent/US5207803A/en not_active Expired - Fee Related
-
1991
- 1991-09-23 CN CN91109377A patent/CN1060126A/en active Pending
- 1991-09-25 AT AT91308736T patent/ATE124101T1/en not_active IP Right Cessation
- 1991-09-25 DK DK91308736.7T patent/DK0478301T3/en active
- 1991-09-25 ES ES91308736T patent/ES2073689T3/en not_active Expired - Lifetime
- 1991-09-25 EP EP91308736A patent/EP0478301B1/en not_active Expired - Lifetime
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- 1991-09-25 CA CA002052236A patent/CA2052236C/en not_active Expired - Fee Related
- 1991-09-26 AU AU84753/91A patent/AU647342B2/en not_active Ceased
- 1991-09-27 JP JP3249382A patent/JP2530782B2/en not_active Expired - Lifetime
- 1991-09-28 KR KR1019910016990A patent/KR940011839B1/en not_active IP Right Cessation
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DE69110603T2 (en) | 1996-01-18 |
EP0478301B1 (en) | 1995-06-21 |
JP2530782B2 (en) | 1996-09-04 |
KR940011839B1 (en) | 1994-12-26 |
KR920004660A (en) | 1992-03-27 |
DE69110603D1 (en) | 1995-07-27 |
JPH04257376A (en) | 1992-09-11 |
CA2052236A1 (en) | 1992-03-29 |
EP0478301A1 (en) | 1992-04-01 |
ATE124101T1 (en) | 1995-07-15 |
ES2073689T3 (en) | 1995-08-16 |
AU8475391A (en) | 1992-04-02 |
US5207803A (en) | 1993-05-04 |
AU647342B2 (en) | 1994-03-17 |
CN1060126A (en) | 1992-04-08 |
DK0478301T3 (en) | 1995-11-20 |
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