US2457838A - Fluorescent cellulose acetate filaments - Google Patents
Fluorescent cellulose acetate filaments Download PDFInfo
- Publication number
- US2457838A US2457838A US667499A US66749946A US2457838A US 2457838 A US2457838 A US 2457838A US 667499 A US667499 A US 667499A US 66749946 A US66749946 A US 66749946A US 2457838 A US2457838 A US 2457838A
- Authority
- US
- United States
- Prior art keywords
- fluorescent
- color
- filaments
- cellulose acetate
- dyed
- 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 - Lifetime
Links
- 229920002301 cellulose acetate Polymers 0.000 title description 17
- 239000000049 pigment Substances 0.000 description 25
- 239000000463 material Substances 0.000 description 16
- 238000009987 spinning Methods 0.000 description 12
- 239000004744 fabric Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 229920002678 cellulose Polymers 0.000 description 9
- 239000001913 cellulose Substances 0.000 description 9
- 238000004043 dyeing Methods 0.000 description 8
- 239000005083 Zinc sulfide Substances 0.000 description 7
- 229910052984 zinc sulfide Inorganic materials 0.000 description 7
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- -1 for example Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000004627 regenerated cellulose Substances 0.000 description 4
- 238000007127 saponification reaction Methods 0.000 description 4
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 2
- 108010043121 Green Fluorescent Proteins Proteins 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- ZLFVRXUOSPRRKQ-UHFFFAOYSA-N chembl2138372 Chemical compound [O-][N+](=O)C1=CC(C)=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 ZLFVRXUOSPRRKQ-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical class CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 2
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- QOSTVEDABRQTSU-UHFFFAOYSA-N 1,4-bis(methylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NC)=CC=C2NC QOSTVEDABRQTSU-UHFFFAOYSA-N 0.000 description 1
- ILDXSRFKXABMHH-UHFFFAOYSA-N 2-(2-aminophenyl)ethanol Chemical compound NC1=CC=CC=C1CCO ILDXSRFKXABMHH-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920013683 Celanese Polymers 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241000692870 Inachis io Species 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- YVNQAIFQFWTPLQ-UHFFFAOYSA-O [4-[[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfophenyl)methyl]amino]-2-methylphenyl]methylidene]-3-methylcyclohexa-2,5-dien-1-ylidene]-ethyl-[(3-sulfophenyl)methyl]azanium Chemical compound C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S(O)(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S(O)(=O)=O)C)C=C1 YVNQAIFQFWTPLQ-UHFFFAOYSA-O 0.000 description 1
- NAKDZSIMLMUSKQ-UHFFFAOYSA-N [Cr](=O)(=O)([O-])O[Cr](=O)(=O)[O-].[Th+4].[Cr](=O)(=O)([O-])O[Cr](=O)(=O)[O-] Chemical compound [Cr](=O)(=O)([O-])O[Cr](=O)(=O)[O-].[Th+4].[Cr](=O)(=O)([O-])O[Cr](=O)(=O)[O-] NAKDZSIMLMUSKQ-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- JPIYZTWMUGTEHX-UHFFFAOYSA-N auramine O free base Chemical compound C1=CC(N(C)C)=CC=C1C(=N)C1=CC=C(N(C)C)C=C1 JPIYZTWMUGTEHX-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- QFFVPLLCYGOFPU-UHFFFAOYSA-N barium chromate Chemical compound [Ba+2].[O-][Cr]([O-])(=O)=O QFFVPLLCYGOFPU-UHFFFAOYSA-N 0.000 description 1
- 229940083898 barium chromate Drugs 0.000 description 1
- 229960001506 brilliant green Drugs 0.000 description 1
- HXCILVUBKWANLN-UHFFFAOYSA-N brilliant green cation Chemical compound C1=CC(N(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](CC)CC)C=C1 HXCILVUBKWANLN-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GIOZLVMCHDGNNZ-UHFFFAOYSA-N magnesium;oxido-(oxido(dioxo)chromio)oxy-dioxochromium Chemical compound [Mg+2].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O GIOZLVMCHDGNNZ-UHFFFAOYSA-N 0.000 description 1
- 229940101209 mercuric oxide Drugs 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229940079938 nitrocellulose Drugs 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- BBCHGPOXBBSEMV-UHFFFAOYSA-K rhodium(3+);trithiocyanate Chemical compound [Rh+3].[S-]C#N.[S-]C#N.[S-]C#N BBCHGPOXBBSEMV-UHFFFAOYSA-K 0.000 description 1
- CKMPIIPZKJISCU-UHFFFAOYSA-M sodium;4,8-diamino-1,5-dihydroxy-9,10-dioxoanthracene-2-sulfonate Chemical compound [Na+].O=C1C2=C(N)C=C(S([O-])(=O)=O)C(O)=C2C(=O)C2=C1C(O)=CC=C2N CKMPIIPZKJISCU-UHFFFAOYSA-M 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/60—Optical bleaching or brightening
- D06L4/657—Optical bleaching or brightening combined with other treatments, e.g. finishing, bleaching, softening, dyeing or pigment printing
-
- 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
- Y10S8/921—Cellulose ester or ether
Definitions
- This invention relates to the preparation of colored fabrics, and relates more particularly to the production of fabrics woven of continuous or staple lengths of artificial filamentary materials such as, for example, regenerated cellulose.
- cellulose acetate, or other organic derivative of cellulose dyed in shades which are extremely fast to light and which, in addition, exhibit a pronounced fluorescence under the excitation of ultra-violet light.
- An object of this invention is the provision of colored fabrics made of or containing artificial filamentary materials which are dyed in shades fast to light and capable of fluorescence under the excitation of ultra-violet light in a color substantially identical with that of the fabric under visible light.
- Another object of this invention is to provide colored fabrics of artificial filamentary materials containing fluorescent pigments and dyed in shades fast to light whereby the respective colorations produced will not interfere with each other, the fabric obtained being of the same color whether viewed by visible light or under ultraviolet light.
- the colored fluorescent filaments prepared in accordance with the process of our invention may have a basis of any suitable filament-forming -material.
- the filaments may be formed by extruding a solution of the desired filament-forming material-containing the desired finely-divided fluorescent pigment through a spinning jet containing a plurality of orifices into a medium adapted to effect the formation or solidification of the filaments.
- thefilaments may have a basis of regenerated cellulose which may be made by the viscose, cuprammonium, nitro cellulose, or any other process adapted for the production of said regenerated cellulose filaments.
- They may also have a basis of a synthetic linear polyamide condensation product or other suitable polymeric material such as polyvinyl chloride, polymerized vinylidene chloride, or a co-bolymer of vinyl chloride and viny tinued exposure, which shade may be undesirable.
- derivative of cellulose may be prepared by dismamas a 3 solving the organic derivative of cellulose in a suitable volatile solvent, such as acetone, and extruding such solution, after the desired amount of finely-divided fluorescent pigment has been added thereto, through an orifice or plurality of orifices into an evaporative atmosphere as in the dry spinning method or into a liquid coagulating medium as in the wet spinning method, which spinning methods are well known in the art.
- suitable volatile solvent such as acetone
- the fluorescent pigment- Prior to incorporation in the spinning solution, the fluorescent pigment-is reduced to a very finely-divided form by a suitable treatment which may comprise grinding the pigment in a ball mill, colloid mill or the like, adapted to reduce the pigment to the desired finely-divided form.
- a suitable treatment which may comprise grinding the pigment in a ball mill, colloid mill or the like, adapted to reduce the pigment to the desired finely-divided form.
- the particles are reduced in size to a diameter of from less than 0.1 up to about 5 microns.
- the amount of pigment added will vary depending upon the particular shade which is desired in thefilaments and the nature of the pigment employed. A satisfactory color of high intensity and brilliance under both daylight and ultra-violet light may beobtained by adding to the spinning solution an amount of fluorescent pigment of from about 0.01% to about 5 to by weight, based on the amount of the filamentforming material present in the spinning solution.
- the finely-divided colored fluorescent pigment may be added at any point in the manufacture of the filaments prior to extrusion.
- a spinning solution may be prepared with the desired amount of fluorescent pigment incorporated therein and the pigmented spinning solution thus obtained then extruded through orifices to form filaments in the manner well known to the art.
- the pigments may be added to the spinning dope at a point near the spinning jet or orifices through which it is extruded so that the system employed for spinning the filaments will not be contaminated with any particular color. This avoids extensive and time-consuming cleaning operations if it is desired'to spin filaments in various other colors. 4
- the filaments obtained possess substantially the same tenacity and elongation characteristics as filaments which do not contain a finely-divided pigment. Consequently, the pigmented filaments prepared in accordance with my invention may be employed satisfactorily y in any application where substantial tenacity and elongation characteristics are necessary.
- fluorescent pigments which may be employed to impart the desired brilliant fluorescent color to the filaments, the following may be mentioned.
- a yellow fluorescent color specially prepared mixtures of zinc sulfide and cadmium sulfide, or cadmium tungstate are satisfactory.
- a red fluorescent color specially prepared zinc sulfide, or mercuric oxide, potassium dichromate, magnesium dichromate,.barium chromate, thorium dichromate, rhodium thiocyanate, as well as Rhodamine BX tungstate lake and Barium red lakeC toner, are suitable.
- pigments,v such as specially prepared zinc sulfide of a blue fluorescent color, Peacock blue lake or certain blue dyestufl's in substance such as Milling Blue BC;
- Alizarine Blue SE for a green fluorescent color, I have found that the addition of specially prepared zinc' sulfide of a green daylight color as well as a green fluorescent color is suitable, as well as other pigments such as brilliant Green tungstate or Auramine 00 tungstate lake or Malaobtain any other colors, the fluorescent pigments may be mixed as is well understood in the art.
- the artificial filamentary materials containing the above finely-divided fluorescent pigments are then dyed with a suitable dyestufl resistant to the detrimental eflects of ultra-violet light.
- the filaments may be dyed in hankor in bobbin form or they may be woven in the desired fabric form and the fabric obtained then dyed in the piece.
- the dyestufl's preferably employed in dyeing pigmented cellulose acetate or other pigmented organic derivative of cellulose filaments comprise acid dyestuffs, such as those normally employed in the dyeing of wool, and those dyestuffs which are applied in dispersed form in the dyeing of cellulose acetate or other organic derivative of cellulose materials.
- Examples of said acid dyestufls are Brilliant Sulfanine Red B, Artol Blue GL, Artol Yellow SG, Xylene Brilliant Cyanine G and. Fast Red A, whileexamples of satisfactory dyestuffs applied in dispersed form are 1,4-dimethylaminoanthraquinone, the azo dyestuif obtained by coupling p-aminoiacetanilide with p-cresol, and the azo dyestufl.
- the yarns may be stretched to the desired degree when they are in a somewhat softened condition, which condition may be obtained by treating the fluorescent pigmented cellulose acetate yarns, or other organic ester of cellulose yarns, with organic solvents, latent sol-' vents, or swelling agents therefor, or by subjecting the yarns to the action of hot water or steam at elevated temperature 'or pressure.
- the stretching of the yarns may be effected during, continuously with, or after their formation and the stretched yarns may then be taken up in suitable package form.
- the stretching operation causes cellulose acetate yarns to acquire a relatively high tenacity and this increased tenacity may be enhanced by subjecting the stretched cellulose acetate or other organic acid ester of cellulose yarns to saponification with a suitable alkaline medium.
- the saponifying agent employed may be inorganic, such as, for example, sodium hydroxide, potassium hydroxide, ammonium hydroxide or other organic basic agent, or may be an organic saponifying agent, such as, methyl amine, ethylene diamine, triethanolamine, or other organic base.
- the saponifying agents may be employed in varying concentrations in aqueous, alcoholic or aqueous/alcoholic solutions and saponification may be effected satisfactorily at temperatures of 20 to C.
- the stretched cellulose acetate or' other organic acid ester of cellulose yarns containing a fluorescent pigment may be dyed after stretching with any of the dyestufls heretofore mentioned or the stretched yam may be dyed, after saponification, with suitable dyestuffs resistant to light and having an affinity for the regenerated cellulose material formed by saponification.
- the finelydivided fluorescent pigment contained therein does not afiect the tenacity of the stretched and saponifled yarns and they may be employed wherever such dyed, fluorescent yarns of high tenacity characteristics are desired.
- Example I Cellulose acetate filaments containing a finelydivided fluorescent pigment are prepared by adding 1 part'by weight of specially prepared zinc sulfide, fluorescent in a red color, to 400 parts by weight of a 25% solution of cellulose acetate in acetone and then extruding the mixture obtained through a spinning jet into an evaporative atmosphere where-the volatile solvent is removed and the desired pigmented filaments are formed.
- the yarn obtained is then dyed in hank form by padding the hank of yarn with an aqueous dyebath comprising 0.5 part by weight of p-nitrobenzene-azo-4-methyl-2-di-hydroxyethyl amino-benzene on the weight of the yarn dispersed in 30 parts by weight of water, on the weight of the yarn, with the aid of sulfonated ricinoleic acid.
- Dyeing is effected at a temperature of 180 F.
- the yarn obtained is dyed in a bright red color and is fluorescent under ultra-violet light in a bright red color substantially identical with that under daylight.
- the yarn may also be dyed by padding the hank with 0.5 part by weight of Fast Red A (Color Index No.
- Pigmented cellulose acetate fllaments fluorescent in a yellow color are prepared by adding 1 part by weight of a mixture of specially prepared zinc sulfide and cadmium sulfide, fluorescent in a yellow color. to 400 parts by weight of a 25% solution of cellulose acetate in acetone and then'extruding the mixture obtained through a maintained at F. during dyeing. The hanks of yarn are rinsed and dried. The yarns are dyed a bright yellow shade and exhibit a bright yellow fluorescence under ultra-violet light.
- the yarns may also be dyed a yellow color substantially identical with the yellow fluorescent color under ultra-violet light employing a dyebath containing 0.5 part by weight of Artol Yellow SG on the weight of the yarn being dyed dissolved in 30 parts by weight of a 25% aqueous solution of ethyl alcohol containing 2% of sodium thiocyanate.
- the dyeing is carried out by padding with the dyebath at 68 C.
- Colored, fluorescent cellulose acetate filamentary materials exhibiting substantially the same color under visible as well as ultra-violet illumination having a finely divided pigment consisting of zinc sulfide fluorescent in a red color incorporated therein and colored with a fluorescent dyestufl' consisting of p-nitro-benzene-azo- 4-methyl-2-di-hydroxyethy1-amino-benzene.
Description
Patented Jan. 4, 1949 OFFICE- 2,457,838 FLUORESCENT CELLULOSE ACETATE FILAMENTS Richard R. Sitzler ind George E. Dennison, Cumberland, Md., assignors to Celanese Corporation of America, a corporation of Delaware Serial No. 667,499
No Drawing. Application May 4, 1946,
1 2 Claims.
This invention relates to the preparation of colored fabrics, and relates more particularly to the production of fabrics woven of continuous or staple lengths of artificial filamentary materials such as, for example, regenerated cellulose. cellulose acetate, or other organic derivative of cellulose, dyed in shades which are extremely fast to light and which, in addition, exhibit a pronounced fluorescence under the excitation of ultra-violet light.
An object of this invention is the provision of colored fabrics made of or containing artificial filamentary materials which are dyed in shades fast to light and capable of fluorescence under the excitation of ultra-violet light in a color substantially identical with that of the fabric under visible light.
Another object of this invention is to provide colored fabrics of artificial filamentary materials containing fluorescent pigments and dyed in shades fast to light whereby the respective colorations produced will not interfere with each other, the fabric obtained being of the same color whether viewed by visible light or under ultraviolet light.
Other objects of this invention will appear from the following detailed description.
Artificial filaments or fibers which have been dyed with fluorescent dyestuffs so that they may glow under ultra-violet light have found some use in the arts. Thus, they may be employed in the manufacture of cloth for use in making uniforms and garments for show girls to produce spectacular stage effects. Also, they may be used in the manufacture of floor coverings in apartment buildings or in theatres, and the like, for indicating the presence of aisles, steps, etc. Usually, the fluorescent filaments or fibers are woven into the floor covering in a predetermined pattern. However, since the fluorescent dyestuffs may be entirely colorless when the ultra-violet source is withdrawn the pattern is no longer visible when illuminated by ordinary light. Furthermore, even when such portions of the floor covering which are also dyed with a dyestuif visible under ordinary illumination, as well aswith a fluorescent dyestuff, are exposed to ultra-violet light so as to bring out the desired fluorescence, the ultra-violet light has an undesirable eifect on the visible dyestuff, frequently causing fading, or even a complete change in shade on com 2 subjected to continued exposure to sunlight as during daylight hours when the sunlight reaches the fioor coverings through windows. 7
We have now found that artificial filamentary materials exhibiting the identical color under both daylight ,and the excitation of ultra-violet light may be obtained by incorporating a finelydivided fluorescent pigment in the spinning solution from which the artificial filaments are spun and then dyeing the filaments obtained in hank, bobbin or. fabric form with a dyestuff highly resistant to changes in shade on continued exposure to ultra-violet light. The fluorescent pigment and the dyestufi to be employed therewith must be such that together they yield a color which does not vary appreciably when viewed by visible light or under ultra-violet light. Thus, various fabric materials may be formed wherein a decorative or identifying colored pattern is present in a color which is substantially identical regardless of whether the dyed materials are viewed by daylight or are illuminated by invisible, ultra-violet light.
The colored fluorescent filaments prepared in accordance with the process of our invention may have a basis of any suitable filament-forming -material. The filamentsmay be formed by extruding a solution of the desired filament-forming material-containing the desired finely-divided fluorescent pigment through a spinning jet containing a plurality of orifices into a medium adapted to effect the formation or solidification of the filaments. 7 Thus, for example, thefilaments may have a basis of regenerated cellulose which may be made by the viscose, cuprammonium, nitro cellulose, or any other process adapted for the production of said regenerated cellulose filaments. They may also have a basis of a synthetic linear polyamide condensation product or other suitable polymeric material such as polyvinyl chloride, polymerized vinylidene chloride, or a co-bolymer of vinyl chloride and viny tinued exposure, which shade may be undesirable.
derivative of cellulose may be prepared by dismamas a 3 solving the organic derivative of cellulose in a suitable volatile solvent, such as acetone, and extruding such solution, after the desired amount of finely-divided fluorescent pigment has been added thereto, through an orifice or plurality of orifices into an evaporative atmosphere as in the dry spinning method or into a liquid coagulating medium as in the wet spinning method, which spinning methods are well known in the art.
Prior to incorporation in the spinning solution, the fluorescent pigment-is reduced to a very finely-divided form by a suitable treatment which may comprise grinding the pigment in a ball mill, colloid mill or the like, adapted to reduce the pigment to the desired finely-divided form.
Preferably, the particles are reduced in size to a diameter of from less than 0.1 up to about 5 microns. The amount of pigment added will vary depending upon the particular shade which is desired in thefilaments and the nature of the pigment employed. A satisfactory color of high intensity and brilliance under both daylight and ultra-violet light may beobtained by adding to the spinning solution an amount of fluorescent pigment of from about 0.01% to about 5 to by weight, based on the amount of the filamentforming material present in the spinning solution.
The finely-divided colored fluorescent pigment may be added at any point in the manufacture of the filaments prior to extrusion. Thus, for
example, a spinning solution may be prepared with the desired amount of fluorescent pigment incorporated therein and the pigmented spinning solution thus obtained then extruded through orifices to form filaments in the manner well known to the art. Most advantageously, however, the pigments may be added to the spinning dope at a point near the spinning jet or orifices through which it is extruded so that the system employed for spinning the filaments will not be contaminated with any particular color. This avoids extensive and time-consuming cleaning operations if it is desired'to spin filaments in various other colors. 4
Because of the extremely flne particle size of the fluorescent pigments, the filaments obtained possess substantially the same tenacity and elongation characteristics as filaments which do not contain a finely-divided pigment. Consequently, the pigmented filaments prepared in accordance with my invention may be employed satisfactorily y in any application where substantial tenacity and elongation characteristics are necessary.
As examples of fluorescent pigments which may be employed to impart the desired brilliant fluorescent color to the filaments, the following may be mentioned. For a yellow fluorescent color specially prepared mixtures of zinc sulfide and cadmium sulfide, or cadmium tungstate are satisfactory. For a red fluorescent color, specially prepared zinc sulfide, or mercuric oxide, potassium dichromate, magnesium dichromate,.barium chromate, thorium dichromate, rhodium thiocyanate, as well as Rhodamine BX tungstate lake and Barium red lakeC toner, are suitable. For a blue fluorescent color, we may employ pigments,v such as specially prepared zinc sulfide of a blue fluorescent color, Peacock blue lake or certain blue dyestufl's in substance such as Milling Blue BC;
Alizarine Blue SE. For a green fluorescent color, I have found that the addition of specially prepared zinc' sulfide of a green daylight color as well as a green fluorescent color is suitable, as well as other pigments such as brilliant Green tungstate or Auramine 00 tungstate lake or Malaobtain any other colors, the fluorescent pigments may be mixed as is well understood in the art.
The artificial filamentary materials containing the above finely-divided fluorescent pigments are then dyed with a suitable dyestufl resistant to the detrimental eflects of ultra-violet light. The filaments may be dyed in hankor in bobbin form or they may be woven in the desired fabric form and the fabric obtained then dyed in the piece. The dyestufl's preferably employed in dyeing pigmented cellulose acetate or other pigmented organic derivative of cellulose filaments comprise acid dyestuffs, such as those normally employed in the dyeing of wool, and those dyestuffs which are applied in dispersed form in the dyeing of cellulose acetate or other organic derivative of cellulose materials. Examples of said acid dyestufls are Brilliant Sulfanine Red B, Artol Blue GL, Artol Yellow SG, Xylene Brilliant Cyanine G and. Fast Red A, whileexamples of satisfactory dyestuffs applied in dispersed form are 1,4-dimethylaminoanthraquinone, the azo dyestuif obtained by coupling p-aminoiacetanilide with p-cresol, and the azo dyestufl. obtained by conpling p-nitro-analine and dihydroxyethyl-m-tolyarns having a basis of cellulose acetate, or other organic acid ester of cellulose, to a stretching operation whereby the filaments are stretched to 200, 300, 500 or even 1000, to 2000% of their original length. The yarns may be stretched to the desired degree when they are in a somewhat softened condition, which condition may be obtained by treating the fluorescent pigmented cellulose acetate yarns, or other organic ester of cellulose yarns, with organic solvents, latent sol-' vents, or swelling agents therefor, or by subjecting the yarns to the action of hot water or steam at elevated temperature 'or pressure. The stretching of the yarns may be effected during, continuously with, or after their formation and the stretched yarns may then be taken up in suitable package form. The stretching operation causes cellulose acetate yarns to acquire a relatively high tenacity and this increased tenacity may be enhanced by subjecting the stretched cellulose acetate or other organic acid ester of cellulose yarns to saponification with a suitable alkaline medium.
The saponifying agent employed may be inorganic, such as, for example, sodium hydroxide, potassium hydroxide, ammonium hydroxide or other organic basic agent, or may be an organic saponifying agent, such as, methyl amine, ethylene diamine, triethanolamine, or other organic base. The saponifying agents may be employed in varying concentrations in aqueous, alcoholic or aqueous/alcoholic solutions and saponification may be effected satisfactorily at temperatures of 20 to C. I The stretched cellulose acetate or' other organic acid ester of cellulose yarns containing a fluorescent pigment may be dyed after stretching with any of the dyestufls heretofore mentioned or the stretched yam may be dyed, after saponification, with suitable dyestuffs resistant to light and having an affinity for the regenerated cellulose material formed by saponification. The finelydivided fluorescent pigment contained therein does not afiect the tenacity of the stretched and saponifled yarns and they may be employed wherever such dyed, fluorescent yarns of high tenacity characteristics are desired.
In order further to illustrate our invention, but without being limited thereto, the following examples are given:
Example I Cellulose acetate filaments containing a finelydivided fluorescent pigment are prepared by adding 1 part'by weight of specially prepared zinc sulfide, fluorescent in a red color, to 400 parts by weight of a 25% solution of cellulose acetate in acetone and then extruding the mixture obtained through a spinning jet into an evaporative atmosphere where-the volatile solvent is removed and the desired pigmented filaments are formed. The yarn obtained is then dyed in hank form by padding the hank of yarn with an aqueous dyebath comprising 0.5 part by weight of p-nitrobenzene-azo-4-methyl-2-di-hydroxyethyl amino-benzene on the weight of the yarn dispersed in 30 parts by weight of water, on the weight of the yarn, with the aid of sulfonated ricinoleic acid. Dyeing is effected at a temperature of 180 F. After being rinsed and dried, the yarn obtained is dyed in a bright red color and is fluorescent under ultra-violet light in a bright red color substantially identical with that under daylight. The yarn may also be dyed by padding the hank with 0.5 part by weight of Fast Red A (Color Index No. 176) on the weight of the yarn dispersed in 30 parts by weight of a 25% aqueous solution of ethyl alcohol containing 2% of sodium thiocyanate at 68 F. The yarn isdyed a bright color red and is fluorescent under ultraviolet light in a bright red color substantially I identical with that under daylight.
Example If Pigmented cellulose acetate fllaments fluorescent in a yellow color are prepared by adding 1 part by weight of a mixture of specially prepared zinc sulfide and cadmium sulfide, fluorescent in a yellow color. to 400 parts by weight of a 25% solution of cellulose acetate in acetone and then'extruding the mixture obtained through a maintained at F. during dyeing. The hanks of yarn are rinsed and dried. The yarns are dyed a bright yellow shade and exhibit a bright yellow fluorescence under ultra-violet light. The yarns may also be dyed a yellow color substantially identical with the yellow fluorescent color under ultra-violet light employing a dyebath containing 0.5 part by weight of Artol Yellow SG on the weight of the yarn being dyed dissolved in 30 parts by weight of a 25% aqueous solution of ethyl alcohol containing 2% of sodium thiocyanate. The dyeing is carried out by padding with the dyebath at 68 C.
It is to be understood that the foregoing detailed description is given merely by way of illustration and that many variations may be made therein without departing from the spirit of our invention.
Having described our invention, what we desire to secure by Letters Patent is:
1( In a process for the production of colored, fluorescent cellulose acetate filamentary materials exhibiting substantially the same color under visible as well as ultra-violet illumination, the step of dyeing the cellulose acetate textile material having incorporated therein a finely divided pigment consisting of zinc sulfide fluorescent in a red color with a dyebath comprising p-nitro-benzene-azo-4-methyl-2-di hydroxyethyl aminobenzene, water and sulfonated ricinoleic acid.
2. Colored, fluorescent cellulose acetate filamentary materials exhibiting substantially the same color under visible as well as ultra-violet illumination having a finely divided pigment consisting of zinc sulfide fluorescent in a red color incorporated therein and colored with a fluorescent dyestufl' consisting of p-nitro-benzene-azo- 4-methyl-2-di-hydroxyethy1-amino-benzene.
RICHARD R. SITZLER, GEORGE E. DENNISON.
REFERENCES arm!) The following references are of record in the file of this patent:
UNITED STATES PATENTS Great Britain Oct. 31, 1929
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US667499A US2457838A (en) | 1946-05-04 | 1946-05-04 | Fluorescent cellulose acetate filaments |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US667499A US2457838A (en) | 1946-05-04 | 1946-05-04 | Fluorescent cellulose acetate filaments |
Publications (1)
Publication Number | Publication Date |
---|---|
US2457838A true US2457838A (en) | 1949-01-04 |
Family
ID=24678469
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US667499A Expired - Lifetime US2457838A (en) | 1946-05-04 | 1946-05-04 | Fluorescent cellulose acetate filaments |
Country Status (1)
Country | Link |
---|---|
US (1) | US2457838A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3380798A (en) * | 1962-11-19 | 1968-04-30 | Monsanto Co | Preparation of dyeable acrylonitrile polymer fibers using 4, 4'-diaminostilbene-2, 2'-disulfonic acid |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB275553A (en) * | 1926-08-03 | 1928-05-25 | Ste Chim Usines Rhone | Process for colouring cellulose esters and ethers |
US1791199A (en) * | 1927-12-29 | 1931-02-03 | Henry A Gardner | Luminous filament |
GB348094A (en) * | 1928-11-03 | 1931-04-28 | Camille Baillod | Process for making coloured artificial textile fibres |
US1875894A (en) * | 1929-05-08 | 1932-09-06 | James A Singmaster | Artificial silk filament and method of making same |
US2033976A (en) * | 1936-03-17 | Treatment op textile or other | ||
US2086591A (en) * | 1934-01-19 | 1937-07-13 | Celanese Corp | Artificial material and method of making same |
US2089413A (en) * | 1937-08-10 | Production of novel effects on | ||
US2142717A (en) * | 1935-02-01 | 1939-01-03 | Celanese Corp | Manufacture of cellulose derivative materials |
US2169657A (en) * | 1938-07-22 | 1939-08-15 | Calco Chemical Co Inc | Luminous or fluorescent floor covering |
US2382355A (en) * | 1942-09-03 | 1945-08-14 | Jr Richard F Warren | Luminous rope |
US2412817A (en) * | 1944-08-03 | 1946-12-17 | American Cyanamid Co | Aminophthalimides |
-
1946
- 1946-05-04 US US667499A patent/US2457838A/en not_active Expired - Lifetime
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2033976A (en) * | 1936-03-17 | Treatment op textile or other | ||
US2089413A (en) * | 1937-08-10 | Production of novel effects on | ||
GB275553A (en) * | 1926-08-03 | 1928-05-25 | Ste Chim Usines Rhone | Process for colouring cellulose esters and ethers |
US1791199A (en) * | 1927-12-29 | 1931-02-03 | Henry A Gardner | Luminous filament |
GB348094A (en) * | 1928-11-03 | 1931-04-28 | Camille Baillod | Process for making coloured artificial textile fibres |
US1875894A (en) * | 1929-05-08 | 1932-09-06 | James A Singmaster | Artificial silk filament and method of making same |
US2086591A (en) * | 1934-01-19 | 1937-07-13 | Celanese Corp | Artificial material and method of making same |
US2142717A (en) * | 1935-02-01 | 1939-01-03 | Celanese Corp | Manufacture of cellulose derivative materials |
US2169657A (en) * | 1938-07-22 | 1939-08-15 | Calco Chemical Co Inc | Luminous or fluorescent floor covering |
US2382355A (en) * | 1942-09-03 | 1945-08-14 | Jr Richard F Warren | Luminous rope |
US2412817A (en) * | 1944-08-03 | 1946-12-17 | American Cyanamid Co | Aminophthalimides |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3380798A (en) * | 1962-11-19 | 1968-04-30 | Monsanto Co | Preparation of dyeable acrylonitrile polymer fibers using 4, 4'-diaminostilbene-2, 2'-disulfonic acid |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3974251A (en) | Production of flameproof fibers of regenerated cellulose | |
US2347508A (en) | Process for dyeing vinyl copolymer fibers | |
US2457838A (en) | Fluorescent cellulose acetate filaments | |
US2206278A (en) | Textile and other materials | |
US2504183A (en) | Production of organic derivative of cellulose staple fibers by solvent dyeing, mechanical crimping, and cutting in that order | |
US2457808A (en) | Fluorescent red cellulose acetate fibers | |
US2384001A (en) | Coloration of textile materials | |
US2328682A (en) | Dyeing cellulose esters | |
US2273305A (en) | Production of color effects on | |
US2292433A (en) | Dyeing process | |
GB609197A (en) | Improvements in the production of coloured artificial textile materials | |
US3493316A (en) | Dyed fiber products | |
Yang et al. | Dyeing Behavior of 100% Poly (trimethylene terephthalate)(PTT) Textiles. | |
US2380503A (en) | Dyeing | |
US2899421A (en) | Monoazo-dyestuffs insoluble in water | |
TW201825149A (en) | Anti-uv mask | |
US2105519A (en) | Colored artificial yarn and like materials and method of making same | |
US2671250A (en) | Method of blending fibers | |
US2160839A (en) | Method of making textile materials | |
US2373191A (en) | Process for chlorinating textiles colored with dyestuffs sensitive to chlorine | |
US2383995A (en) | Colored material | |
US2278540A (en) | Production or treatment of pigments and textile and other materials containing them | |
US2211861A (en) | Textile material | |
US2216793A (en) | Manufacture of colored artificial materials | |
US2143883A (en) | Manufacture of artificial silk |