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
  • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
  • D06P3/58—Material containing hydroxyl groups
  • D06P3/60—Natural or regenerated cellulose
  • D06P3/6025—Natural or regenerated cellulose using vat or sulfur dyes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
  • C09B35/02—Disazo dyes
  • C09B35/039—Disazo dyes characterised by the tetrazo component
  • C09B35/227—Disazo dyes characterised by the tetrazo component the tetrazo component being a derivative of a diaryl sulfide or a diaryl polysulfide
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B43/00—Preparation of azo dyes from other azo compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B49/00—Sulfur dyes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
  • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
  • C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
  • C09B62/08—Azo dyes
  • C09B62/085—Monoazo dyes
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
  • D06B3/00—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating
  • D06B3/10—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of fabrics
• • 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
  • D06P1/30—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 sulfur dyes
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
  • D06B2700/00—Treating of textile materials, e.g. bleaching, dyeing, mercerising, impregnating, washing; Fulling of fabrics
  • D06B2700/09—Apparatus for passing open width fabrics through bleaching, washing or dyeing liquid
• • 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
  • Y10S534/00—Organic compounds -- part of the class 532-570 series
  • Y10S534/01—Mixtures of azo compounds

Definitions

• the present invention relates to a method for printing dyestuffs on textile fibers, and more particularly to a method for printing dyestuffs selected from the group consisting of sulfur dye, azo-disulfide dyestuff,and mixture of sulfur dye and azo-disulfide dyestuff on textile fibers, and to printing pastes useful therein.
• the method of the present invention is particularly characterized in that a delayed action reducing agent selected from the group consisting of HOOCR1S SRaCOOH wherein R and R are alkylene groups having 1-5 carbon atoms, a salt of said and sodium S-sodiocarboxymethyl thiosulphate, and dyestuff selected from the group consisting of sulfur dye, azo-disulfide dyestuff, and mixture of sulfur dye and azodisulfide dyestutf; steaming the fibers to activate the reducing agent and reduce the dyestuff; and oxidizing the dyestuff
• a solubilizing agent and hydroscopic agent may be advantageously included in the printing paste.
• the printing paste of the present invention comprises water, thickening agent, alkali, a reducing agent selected from the group consisting of wherein R and R are alkylene groups having 1-5 carbon atoms, a salt of said sodium S-sodiocarboxymethyl thiosulphate, dye selected from the group consisting of sulfur dye, azo-disulfide dyestuff and mixture of sulfur dye. and azo-disulfide dyestuff,
• Azo-disulfide dyestuffs have been known for more than fifty years, but have not gone into commercial production or use, one of the principal reasons being that a commercially acceptable method for dyeing and printing the azo-disulfide dyestuffs has remained unknown. Insofar as can be determined, no one has previously suggesteda method for printing azo-disulfide dyes.
• the azo groups may either be connected to the same aromatic nuclei to which the disulfide group is connected, or they may be found elsewhere in the color bodies.
• Illustrative examples of the above three types of azo-disulfide dyestuffs are the dyestuif formed by coupling one mole of diazotized 5- thiocyano-2-amino-toluene to one mole of beta-naphthol,
• glucose-carbonate nor sodium formaldehyde hydrosulfite may be used as the reducing agent in printing azo-disulfide dyestufis, or mixtures of sulfur dye and azo-disulfide dyestuff.
• sulfur dye, azo-disulfide dyestuff and mixture of sulfur dye and azo-disulfide dyestuif may be printed on cellulosic textile fibers without oorroding the engraved printing rollers by the method and with the printing paste of the present invention. Additionally, the method provides improved color yield and improved brightness of shade for some of the sulfur dyes.
• the above reducing agents utilized in the present invention are of delayed action type in the sense that they do not reduce the dyestuff until it is in the steamer.
• the printing paste is applied to the fibers by means of the printing rollers and the printing rollers are not attacked by any of the components in the printing paste.
• the reduction of the dyestuif occurs in the steamer as evidenced by the fact that those azo-disulfide dyestuffs and sulfur dyes which have a characteristic color change on being converted to the reduced state undergo this color change in the steamer.
• the delayed action reducing agent is converted into its active reducing components in the steamer, and corrosion of the printing rollers 3 4 is thus avoided.
• R and R are alkylene groups having 1-5 caraction 'reducing agents break down in the steamer into bon atoms, which may be generally referred to as salts of thioglycollic acid salts or a higher homologue thereof, di(carboxyalkyl) trithiocarbonates, and are suitable for which are the active reducing agents.
• salts of thioglycollic acid salts or a higher homologue thereof, di(carboxyalkyl) trithiocarbonates and are suitable for which are the active reducing agents.
• thioglycollic acid salts or a higher homologue thereof di(carboxyalkyl) trithiocarbonates
• H H H delayed action reducing agent s 0 NaO-i,cHl-siis0Hlii-0Na Na-0-g-CH -sgs-0H,-g 0-Na di(s0d10carboxymethyl) trlthlocarbonate which does not attack the printing rollers, is used as the H H H delayed action reducing agent and NaO-H is used as the 19 alkali in the printing paste, two moles of H w D ye y t oca bon-ate d1 sodlocarboxypropyl) trithtocarbonate (disodium salt of thioglyoollic acid) and one mole of 0 II II I H NaOC-CHrCH2-CH2-CH7S-C-S-CHrCHr-CHz-CHr-C-ON8 Na.
• the salts of the di(cardl(carboxypropyl) trlthiocarbonate boxyalkyl) trithioc-arbonates are preferably formed in the o H O-E-CHl-CHr-CHKCHPS( SCH!'-CHQ CH2CHH(OH dl(carboxybutyl) trl thiocarbonate H H 55 printing paste when alkali is added to di(carboxya1kyl) trlthlocarbonates, and subsequently break down into the B active reducing agents under the influence of steam. How- H ever, these salts may be prepared prior to their being incorporated into the printing paste.
• S-sodiocarboxymethyl thiosulphate is the sodif H g um salt of S-carboxymethyl thiosulfuric acid, and may be O :'CHr?H-CH1SCSCHa-(fH--CH:-CHr-COH prepared by reacting sodium chloroacetate with sodium CH3 CH3 thiosulphate.
• reducing agent while in the steamer, reduces the 0 CH 8 CH; 0 sulfur dye at its normal reducible site, and reduces azo- (EH H st-uif contalns a dlsulfide linkage, RS-S-R, it is u y y yn trithiooirbaonate considered to be in its normal oxidized state.
• azo- EH H st-uif contalns a dlsulfide linkage, RS-S-R, it is u y y yn trithiooirbaonate considered to be in its normal oxidized state.
• di(carboxyalkyl) trithiocarbona-tes may be pre- Steamer one molecule of the dyestufl 1S reduced by forming into two molecules of RS-Na.
• the dyestulf Upon subgigigg fiigi g tnthlocarbonate wlth a sequent oxidation, the dyestulf is returned to its normal oxidized condition, RSSR.
• the salts dyestufi is one which upon reduction and Subsequent oxidation produces a disulfide group connected to aromatic nuclei, two molecules of the dyestutf (R--S-X), wherein X may be such as a cyano or sulfonic group, are
• delayed action reducing agents which render them suitable for use in the method of the present invention are that they are water soluble in the printing paste, do not corrode the printing rollers, do not form into active reducing agents until heated in the steamer, neither the delayed action reducing agents nor the active reducing agents produced therefrom have an objectionable odor, the active reducing agents formed from the delayed action reducing agents are water soluble and are therefore easily removed from the fibers following oxidation, and the delayed action reducing agents are comparatively inexpensive when calculated on the basis of cost per square yard of printed material. 7
• One of the important advantages of the method of the present invention is that a printing paste containing sulfur dye and azo-disulfide dyestulf may now be applied to the fibers.
• This is an important development because it provides shades and hues that cannot be obtained by use of sulfur dye or azo-disulfide dyestuif alone, and provides increased brightness of shades over that attainable by use of sulfur dye alone.
• Sulfur dyes are among the least expensive dyes which have generally good fastness properties, but they do not have the extraordinary brightness of color that is characteristic of the azo-disulfide dyes.
• the printing paste should comprise a dyestutf selected from the group consisting of sulfur dye, azo-disulfide dyestuff, and mixture of sulfur dye and azo-disulfide dyestutf, water, thickening agent, alkali, a delayed action reducing agent selected from the group consisting of wherein R and R are alkylene groups having 1-5 carbon atoms, a salt of said and sodium S-sodiocarboxymethyl thiosulphate, and may additionally comprise solubilizing agent and hydroscopic agent.
• the suggested composition of the printing paste based on percent by weight of the printing paste, is given below.
• the amount of dyestutf to be used in the printing paste willbe determined by the depth of shade desired. Generally speaking about l5%, and preferably about 3% of concentrated dye will be suitable for most purposes.
• the amount of delayed action reducing agent to be utilized in the printing paste will be determined by the amount of dyestuff and to some extent by the particular dye that is used, for example the sulfur blacks require somewhat more reducing agent than an equivalent amount of the other sulfur dyes.
• the printing paste will have 0.54%, and preferably about 1% of delayed action reducing agent.
• the amount of alkali to be used in the printing paste will be determined by the amount of reducing agent used in the printing paste, the alkalinity of the base selected, and also by whether the salt of the di(carboxyalkyl) trithiocarbonate is formed before the di(carboxyalkyl) trithiocarbonate is incorporated into the printing paste or subsequently, more alkali being required in the printing paste when di(carboxyalkyl) trithiocarbonate has not been formed into a salt prior to its incorporation into the paste.
• alkali about 2-12% of alkali will be suitable, and preferably about 6% when the salt of the di(carboxyalkyl) trithiocarbonate is used and preferably'about 7% when the di(carboxyalkyl) trithiocarbonate is used.
• Any of the alkalis such as the caustic alkalis or alkali carbonates, examples of which are NaOH, KOH, Na CO K cO jand NaHCO may be used.
• Enough water is used to form an aqueous, alkaline dispersion of the dyestulf.
• the printing paste should contain a tot-a1 of about 75-85%, and preferably about of water.
• the printing paste is thickened in the conventional manner, enough thickener being used to give the printing paste a viscosity suitable for the specific pattern desired.
• Any of the conventional thickeners which are compatible with free alkali may be used, such as starch, converted starches, natural gums, starch-tragacanth, water and oil emulsions, synthetic polymer thickeners, etc. Generally, about 17%, and preferably about 4% of thickener will be used.
• a hydroscopic agent such as diethylene glycol, monoethylene glycol, and glycerine may be advantageously used in the printing paste. About 04% of hydroscopic agent, and preferably about 3%, will be utilized. The hydroscopic agent is recommended, as it appears to improve color yield, but is not essential.
• a solubilizing agent or assistant such as urea, thiodiethylene glycol and glycol ethyl ether also may be advantageously used in the printing paste.
• solubilizing agent and preferably about 3% of solubilizing agent is recommended, as it appears to improve fastness, but is not essential.
• the components of the printing paste may be blended in any order, and should form a homogenous, aqueous, alkaline dispersion.
• the printing paste may be prepared and applied to the fibers at room temperature, and it is recommended that the printing not be heated enough to activate the delayed action reducing agent therein prior to application to the fibers.
• the above printing paste may be applied to textile 'fibers, such as yarn-s or fabrics of cotton or regenerated cellulose, singly or in blends with other fibers.
• the printing paste may be applied to the fibers by any selected method, such as by a screen or by contacting the fibers with a rotating, engraved, chromium plated cop er printing roller which has received the printing paste by contacting a furnish roll that rotates through and is partially immersed in a color box, a doctor blade being used to remove the paste from all except the engravings of the printing roller. It will be understood that multicolor prints and designs requiring more than one printing roller may be obtained by using additional color boxes and printing rollers.
• the fibers are dried sufiiciently to prevent marking 01f of the printed areas on other areas.
• the fibers are steamed to activate the delayed action reducing agent and reduce the dyestutl.
• the fibers may be subjected to neutral air-free steam at 212225 F. for 2-10 minutes to accomplish this result.
• the dyestuff is oxidized. Oxidation may be accomplished by passing the fibers through a bath containing an oxidizing agent. Any of the conventional oxidizing baths used in connection with sulfur dyestuffs may be used, such as an aqueous solution of acetic acid and sodium bichromate, and aqueous solution of acetic acid and hydrogen peroxide, or an aqueous solution of ammonium persulfate. Enough oxidizing agent will be used to oxidize the dyestuff. The oxidizing agent will be customarily applied by the pad-nip method, and a bath containing 1.5 fluid oz. of glacial acetic acid and 1 oz.
• the print should be Washed and .ried. This may be accomplished by rinsing the print with later, soaping, rinsing with water, and drying in the onventional manner.
• the method of the present inention may be conducted in a continuous manner on ligh speed equipment positioned in tandem, such as multi- 10101 print machine, drying cans or loop drier, rapid ager, lad boxes with nip rolls, and drying cans or oven.
• Example I An aqueous, alkaline, dispersion of printing paste is nade by blending together the following components in :he order listed, at room temperature, all parts by weight:
• the fabric is dried to prevent marking off by serpentining it about 4-6 rotating, steam-heated, stainless steel, drying cans six feet in diameter and maintained at an internal steam pressure of 15-30 p.s.i.
• the dyestufl is reduced by passing the fabric through a neutral ager with air-free steam at 216220 F. for 5 minutes.
• the dyestuff Upon emergence from the steam ager, the dyestuff is oxidized by passing the fabric at 50 yards per minute through a three bowl padder containing 1.5 fluid oz. of glacial acetic acid and 1.0 oz. by weight of sodium bichromate per gallon of Water at 130 F.
• the fabric is finally rinsed, scoured and dried in the conventional manner by passing it through a pad box containing water at 150 F., through a pad box containing 0.5 oz. by weight of soap per gallon of water at 160 F., through two pad boxes containing water at 170 F., and by serpentining it about 16 rotating, cylindrical, steamheated, stainless steel drying cans thirty inches in diameter maintained at an internal steam pressure of 50 p.s.i.
• Example III This example is the same as Example l'above, except that 15 pounds of a 20% aqueous dispersion of Sulfur Red 5 solids, 0.1. Part II No. 53830, is substituted for the dye and 1 pound of di(sodiocarboxypropyl) trithiocarbonate is substituted for the delayed action reducing agent used in Example I.
• Example IV This example is the same as Example I above, except that 15 pounds of a 20% aqueous dispersion of Sulfur Black 11 solids, (3.1. Part II No. 53290, is substituted for the dye used in Example I, and the amount of delayed action reducing agent used in Example I is increased to 2.0 pounds.
• Example V This example is the same as Example I, except that 15 pounds of a 20% aqueous dispersion of Sulfur Brown 10 solids, C.I. Part -II No. 53055, is substituted for the dye and 1 pound of di(carboxymethyl) trithiocarbonate is substituted for the delayed action reducing agent used in Example I. Also, the amount of Na CO used in Example I is increased to 7.0 pounds.
• Example VI This example is the same as Example I above, except that 15 pounds of a 20% aqueous dispersion of Sulfur Green 14 solids is substituted for the dye used in Example 1.
• Example VII This example is the same as Example I, except that 1 pound of di(sodiocarboxyethyl) trithiocarbonate is substituted for the delayed action reducing agent utilized in Example I, and 15 pounds of a 20% aqueous dispersion of the azo-disulfide dyestulf solids formed by coupling one mole of tetrazotized 4:4'-diaminodiphenyldisulfide to two moles of 5'-chloro-3-hydroxy 2',4 dimethoxy-Z-naphthanilide is substituted for the dye used in Example 1.
• Example IX This example is the same as Example I above, except that 1 pound of di(carboxymethyl) trithiocarbonate is substituted for the delayed action reducing agent used in Example I; 7 pounds of NaHCO is substituted for the alkali used in Example I; and 15 pounds of a 20% aqueous dispersion of the azo-disulfide dyestuff solids formed bycoupling one mole of tetrazotized 2,2-dichloro-4:4'-diaminodiphenyldisulfide to two moles of 3-hydroxy-2-naphthortho-anisidide is substituted for the dye used in Example I.
• Example XI This example is the same as Example I, except that 15 pounds of a 20% aqueous dispersion of the dye formed by coupling one mole of diazotized S-thiocyano-Z-aminotoluene to one mole of beta-naphthol is substituted for 9 the dye used in Example I, and 2 pounds of NaOH is substituted for the Na CO used in Example 1.
• Example XII Example XIII This example is the same as Example I above except that 10 pounds of a 20% aqueous dispersion of Sulfur Red 5 solids, C.I. Part II No. 53830, and 5 pounds of a 20% aqueous dispersion of the azo-disulfide dyestuif solids formed by coupling one mole of diazotized paranitroaniline to one mole of 1-phenyl-3-methyl-5-pyrazolone, reducing the coupled product with sodium sulfhydrate, filtering, drying, condensing the resulting dried product with one mole of 2,4,6-trichloro-1,3,5-triazine in the presence of acetone and soda ash at 5 C., and reacting one mole of the resulting product with one-half mole of 4:4'-diaminodiphenyldisulfide at 20 C. are substituted for the dye used in Example I.
• Example XIV This example is the same as Example I above, except that 7.5 pounds of a 20% aqueous dispersion of the azodisulfide dyestulf solids described in Example XIII above and 7.5 pounds of a 20% aqueous dispersion of Sulfur Brown 52 solids, C.I. Part II No. 53320, are substituted for the dye used in Example I.
• Example XV This example is the same as Example I above, except that 6 pounds of a 20% aqueous dispersion of the azodisulfide dyestuff solid-s described in Example IX above and 9 pounds of a 20% aqueous dispersion of Sulfur Red 5 solids are substituted for the dye used in Example I.
• Example XVI This example is the same as Example I above, except that 7 pounds of a 20% aqueous dispersion of the azodisulfide dyestuff solids described in Example IX above and 8 pounds of a 20% aqueous dispersion of Sulfur Brown 52 solids are substituted for the dye utilized in Example I.
• Example XVII Example XVIII This example is the same as Example I above, except that 3 pounds of sodium S-sodiocarboxymethyl thiosulphate is substituted for the delayed action reducing agent utilized in Example I.
• Example XIX This example is the same as Example VII above, except that 3 pounds of sodium S-sodiocarboxymethyl thiosulphate is substituted for the delayed action reducing agent utilized in Example VII.
• Example XX This example is the same as Example XIV above, ex-
• a method for printing dyestuif on cellulosic textile fibers comprising the steps of applying to said fibers a printing paste comprising water, alkali, thickening agent, a dyestuff selected from the group consisting of sulfur dye, azo-disulfide dyestuff, and a mixture of sulfur dye and azo-disulfide dyestuff, and a delayed action reducing agent selected from the group consisting of prises a hydroscopic agent and a solubilizing agent.
• a printing paste comprising water, alkali, thickening agent, a dyestuff selected from the group consisting of sulfur dye, azo-disulfide dyestufi, and mixture of sulfur dye and azo-disulfide dyestuif, and a reducing agent selected from the group consisting of HooGR1s( isR,0o0H wherein R and R are alkylene groups having 1-5 carbon atoms, a salt of said and sodium S-sodiocarboxymethyl thiosulphate.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Coloring (AREA)

Priority Applications (22)

Applications Claiming Priority (7)

Publications (1)

Family

ID=27569510

Family Applications (3)

Family Applications After (2)

Country Status (4)

Cited By (2)

Families Citing this family (12)

Citations (6)

Family Cites Families (2)

• 1963
  • 1963-03-11 US US264044A patent/US3329477A/en not_active Expired - Lifetime
  • 1963-03-11 US US264045A patent/US3225025A/en not_active Expired - Lifetime
  • 1963-09-06 US US307014A patent/US3299040A/en not_active Expired - Lifetime
• 1964
  • 1964-03-04 NL NL6402179A patent/NL6402179A/xx unknown
  • 1964-03-04 NL NL6402181A patent/NL6402181A/xx unknown
  • 1964-03-04 NL NL6402183A patent/NL6402183A/xx unknown
  • 1964-03-04 NL NL6402184A patent/NL6402184A/xx unknown
  • 1964-03-04 NL NL6402180A patent/NL6402180A/xx unknown
  • 1964-03-04 NL NL6402178A patent/NL6402178A/xx unknown
  • 1964-03-10 BE BE644980D patent/BE644980A/xx unknown
  • 1964-03-10 BE BE644985D patent/BE644985A/xx unknown
  • 1964-03-10 BE BE644979D patent/BE644979A/xx unknown
  • 1964-03-10 GB GB10155/64A patent/GB1020706A/en not_active Expired
  • 1964-03-10 GB GB10154/64A patent/GB1016085A/en not_active Expired
  • 1964-03-10 GB GB10156/64A patent/GB1014703A/en not_active Expired
  • 1964-03-10 GB GB10160/64A patent/GB1018459A/en not_active Expired
  • 1964-03-10 GB GB10159/64A patent/GB1025043A/en not_active Expired
  • 1964-03-10 GB GB10157/64A patent/GB1016850A/en not_active Expired
  • 1964-03-10 BE BE644983D patent/BE644983A/xx unknown
  • 1964-03-10 BE BE644984D patent/BE644984A/xx unknown
  • 1964-03-10 BE BE644982D patent/BE644982A/xx unknown

Patent Citations (6)

Also Published As

Similar Documents