US1776052A - Process for treating cellulosic fibers with alkali - Google Patents
Process for treating cellulosic fibers with alkali Download PDFInfo
- Publication number
- US1776052A US1776052A US218109A US21810927A US1776052A US 1776052 A US1776052 A US 1776052A US 218109 A US218109 A US 218109A US 21810927 A US21810927 A US 21810927A US 1776052 A US1776052 A US 1776052A
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- US
- United States
- Prior art keywords
- alkali
- cellulosic fibers
- lye
- mixture
- mercerizing
- 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.)
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- 238000000034 method Methods 0.000 title description 11
- 239000000835 fiber Substances 0.000 title description 10
- 239000003513 alkali Substances 0.000 title description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 25
- 239000000203 mixture Substances 0.000 description 15
- 235000011121 sodium hydroxide Nutrition 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 239000004744 fabric Substances 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920000742 Cotton Polymers 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 229920000297 Rayon Polymers 0.000 description 3
- 238000005517 mercerization Methods 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 150000001896 cresols Chemical class 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 150000004780 naphthols Chemical class 0.000 description 2
- MTQKMPGBALVEDL-ZPCKWCKBSA-N (z,12r)-12-hydroxy-2-sulfooctadec-9-enoic acid Chemical class CCCCCC[C@@H](O)C\C=C/CCCCCCC(C(O)=O)S(O)(=O)=O MTQKMPGBALVEDL-ZPCKWCKBSA-N 0.000 description 1
- MQWCXKGKQLNYQG-UHFFFAOYSA-N 4-methylcyclohexan-1-ol Chemical compound CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101150004141 Vcan gene Proteins 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000004707 phenolate Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/325—Amines
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- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
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- D06M11/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with hydrogen peroxide or peroxides of metals; with persulfuric, permanganic, pernitric, percarbonic acids or their salts
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- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
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- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/152—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen having a hydroxy group bound to a carbon atom of a six-membered aromatic ring
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- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
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- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
- D06M13/256—Sulfonated compounds esters thereof, e.g. sultones
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- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/325—Amines
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- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
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- D06M13/338—Organic hydrazines; Hydrazinium compounds
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- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
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- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
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- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/402—Amides imides, sulfamic acids
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- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
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- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/46—Compounds containing quaternary nitrogen atoms
- D06M13/463—Compounds containing quaternary nitrogen atoms derived from monoamines
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/17—Natural resins, resinous alcohols, resinous acids, or derivatives thereof
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- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/53—Polyethers
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- 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
- Y10S162/00—Paper making and fiber liberation
- Y10S162/03—Wetting agent
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- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
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- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
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- Y10S516/03—Organic sulfoxy compound containing
- Y10S516/05—Organic amine, amide, or n-base containing
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- Y10S516/06—Protein or carboxylic compound containing
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- Y10S516/07—Organic amine, amide, or n-base containing
Definitions
- the following hydrogenated aromatic substances come into consideration for the present process:
- the products of hydrogenation of naphthalene, naphthols and phenols as for instance tetrahydroand decahydronaphthalene, hydrogenated naphthols, cyclohexanol, methylcylohexanols and mixtures of these substances.
- phenolic substances ordinary phenol, then especially the cresols and mixtures of them, further the higher phenol homologues may be used.
- a raw and unbowked cotton fabric is mercerized with a caustic soda lye'of 34 B. to which 1 of a mixture of 91% of a cresol mixture 'and 9% of a methylcycloincreased elasticity together with a deeper mercerization than that mercerized according to the old mercerizing process. Further the operation is carried out in a shorter time than is the ca e Without the mixt re.
- Emample 2 fil of a mixture of 95% of cresols and 5% of tetrahydronaphthalene is added a to a mercerizing lye of 36 B. the same efl'ect 5 as described in Example 1 is observed.
- Example 3 A viscose fabric containing fibers which have been produced in different manufacturing operations is passed through a mercerizing lye of 20 B. to which 1 (calculated on the weight of the lye) of a mixture oiE 90% of a cresolimixtu're and 10% of methylcyclohexanolmixture are added. The fabric is then squeezed out. The fabric thus treated vcan be dyed in more even shades than without this treatment. 7 What I claim is:
- An improved process for thetreatment of natural and artificial cellulose fibers with alkali consisting in adding a mixture of a phenol and hydrogenated aromatic substances to the alkaline medium.
- An improved process for the treatment of natural and artificial cellulosic fibers with alkali consisting in adding. a mixture of a 1 cresol mixture and a methylcyclohexanol mixture to the alkaline medium.
- An improvedprocess for the treatment of natural and artificial cellulosic fibers with alkali consisting in adding a mixture of 212% of hydrogenated aromatic substances and of 98-88% of phenolic substances to the ⁇ 35 alkaline lye, said mixture being added in quantities of 12% reckoned on .the weight of the lye.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Coloring (AREA)
- Treatment Of Fiber Materials (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Detergent Compositions (AREA)
Description
Patented Sept. 116, I93@ UN HT GIGVANNI TAG-LIANI, F BASEL, SWITZERLAND, ASSIGNOR TO THE FIRM: CHEMICAL WORKS FORMERLY SANDOZ, OF BASEL, SWITZERLAND PROCESS FOR TREATING CELLULOSIC FIBERS WITH ALKALI Ito Drawing. Application filed September 7, 1927, Serial No. 218,109, and in Germany October :39, 1926.
Various attempts have been made to improve the alkaline treatment of natural and artificial cellulosic fibers, such as is realized for instance in the mercerizing process, by the use of convenient admixtures. Soaps, sulphoricinoleic acids, alcohols and other substances have been proposed for this purpose. These admixtures have only little ef feet, so that large quantities are necessary to obtain a satisfactory result, which renders the process expensive. For instance, 20- 30% of alcohol, calculated on the mercerizing lye, is necessary to merceriz e satisfac torily a raw and sized cotton fabric Without a previous bowking.
, It has unexpectedly been found that this process can be considerably improved, if small quantities of a suitable mixtureof phenolic substances and hydrogenated aromatic substances are added to the mercerizing lye, the action of the alkali is then quicker and more uniform. By the aid ofthese admixtures it is possible ,to mercerize raw and sized cotton fabrics without previous bowking. These fabrics would otherwise not produce uniform effects without a previous bowkin Theaddition of henol alone to mercerizing lyes is already nown. According to the U. S. specification 1,343,139 textile fabrics o composed of mercerizable cellulosic fibers intermixed with artificial silk-filaments of viscose are mercerized with a lye containing 5% of phenol. :This addition has the only oblject to allow the performance of the mercerization of the cellulosic fiber without injury to the viscose silk, because, as is proved by many tests, phenol as well as its homologues do not effect at all the mercerizing operation of ordinary cotton. The hydrogenated aro- 40 matic compounds being entlrely insoluble in the concentrated alkaline lyes used for mercerization would not by themselves improve I the process;
, with phenols as set forth above they act as very good wetting-out agents and greatly improve the wetting-out ca acity of the alkaline lyes. This remarkably good action is based on the fact that the alkali phenolates formed in the mercerizing lye act as solvent and dispersing agent for the hydrogenated But if they are used jointly aromatic compounds so as to allow to practically utilize their excellent wetting-out action.
The following hydrogenated aromatic substances come into consideration for the present process: The products of hydrogenation of naphthalene, naphthols and phenols, as for instance tetrahydroand decahydronaphthalene, hydrogenated naphthols, cyclohexanol, methylcylohexanols and mixtures of these substances. As phenolic substances, ordinary phenol, then especially the cresols and mixtures of them, further the higher phenol homologues may be used.
Mixtures of 52-12% of hydrogenated aromaticsubstances with 98-88% of phenols are most suitable for carrying out the new process, but this does not mean that mixtures of other proportions would be useless.
The effect of these admixtures is obtained even with small quantities (12% of the weight of the mercerizing lye). It consists in an increase of the wetting properties of the cellulosic fibers to an unexpected degree. This strong increase is the more unex- 'pected as neither the phenols nor the hydrogenated' aromatic substances by them selves cause appreciable increase of the wetting'properties; only mixtures of such substances have this effect. The increase of the wetting properties of the fibers results not only in a quicker action of the alkali, but also in a more uniform effect.
Emample 1;
A raw and unbowked cotton fabric is mercerized with a caustic soda lye'of 34 B. to which 1 of a mixture of 91% of a cresol mixture 'and 9% of a methylcycloincreased elasticity together with a deeper mercerization than that mercerized according to the old mercerizing process. Further the operation is carried out in a shorter time than is the ca e Without the mixt re.
Emample 2 fil of a mixture of 95% of cresols and 5% of tetrahydronaphthalene is added a to a mercerizing lye of 36 B. the same efl'ect 5 as described in Example 1 is observed.
Example 3 A viscose fabric containing fibers which have been produced in different manufacturing operations is passed through a mercerizing lye of 20 B. to which 1 (calculated on the weight of the lye) of a mixture oiE 90% of a cresolimixtu're and 10% of methylcyclohexanolmixture are added. The fabric is then squeezed out. The fabric thus treated vcan be dyed in more even shades than without this treatment. 7 What I claim is:
1. An improved process for thetreatment of natural and artificial cellulose fibers with alkali, consisting in adding a mixture of a phenol and hydrogenated aromatic substances to the alkaline medium.
2. An improved process for the treatment of natural and artificial cellulosic fibers with alkali, consisting in adding. a mixture of a 1 cresol mixture and a methylcyclohexanol mixture to the alkaline medium.
3. An improvedprocess for the treatment of natural and artificial cellulosic fibers with alkali, consisting in adding a mixture of 212% of hydrogenated aromatic substances and of 98-88% of phenolic substances to the\ 35 alkaline lye, said mixture being added in quantities of 12% reckoned on .the weight of the lye.
In witness whereof Ihave hereunto signed my name this 25th day of August 1927.
. GIOVANNI TAGLIANI.
Applications Claiming Priority (11)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEC38909D DE591923C (en) | 1926-10-29 | 1926-10-29 | Process to increase the wetting ability of mercerising liquors |
DEC43256D DE669426C (en) | 1926-10-29 | 1929-06-17 | Process for mercerizing |
DE1930C0000330 DE593048C (en) | 1926-10-29 | 1930-01-15 | Process to increase the wetting ability of mercerising liquors |
DE1930C0000630 DE661428C (en) | 1926-10-29 | 1930-01-16 | Mercerize |
DE374214X | 1930-04-23 | ||
DE1930C0005330 DE614913C (en) | 1926-10-29 | 1930-05-27 | Process to increase the wetting ability of mercerising liquors |
DE360472X | 1930-06-14 | ||
DE361865X | 1930-06-16 | ||
DE1930C0007930 DE674894C (en) | 1926-10-29 | 1930-07-31 | Process for improving mercerising liquors |
DE1930C0009130 DE679766C (en) | 1926-10-29 | 1930-08-21 | Process for mercerizing |
DE382373X | 1930-09-16 |
Publications (1)
Publication Number | Publication Date |
---|---|
US1776052A true US1776052A (en) | 1930-09-16 |
Family
ID=31950999
Family Applications (8)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US218109A Expired - Lifetime US1776052A (en) | 1926-10-29 | 1927-09-07 | Process for treating cellulosic fibers with alkali |
US459122A Expired - Lifetime US1851914A (en) | 1926-10-29 | 1930-06-03 | Manufacture and use of new wetting preparations |
US473773A Expired - Lifetime US1851393A (en) | 1926-10-29 | 1930-08-07 | Preparation of wetting agents for use in mercerizing lyes |
US475373A Expired - Lifetime US1851394A (en) | 1926-10-29 | 1930-08-14 | Preparation of wetting agents |
US506507A Expired - Lifetime US2008459A (en) | 1926-10-29 | 1931-01-03 | Process for increasing the wettingout power of alkaline lyes |
US506506A Expired - Lifetime US2008458A (en) | 1926-10-29 | 1931-01-03 | Process for increasing the wettingout power of alkaline lyes |
US537225A Expired - Lifetime US1976886A (en) | 1926-10-29 | 1931-05-13 | Preparation of wetting agents for use in alkalizing lyes |
US552547A Expired - Lifetime US1998550A (en) | 1926-10-29 | 1931-07-22 | Preparation of wetting agents for use in mercerizing lyes |
Family Applications After (7)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US459122A Expired - Lifetime US1851914A (en) | 1926-10-29 | 1930-06-03 | Manufacture and use of new wetting preparations |
US473773A Expired - Lifetime US1851393A (en) | 1926-10-29 | 1930-08-07 | Preparation of wetting agents for use in mercerizing lyes |
US475373A Expired - Lifetime US1851394A (en) | 1926-10-29 | 1930-08-14 | Preparation of wetting agents |
US506507A Expired - Lifetime US2008459A (en) | 1926-10-29 | 1931-01-03 | Process for increasing the wettingout power of alkaline lyes |
US506506A Expired - Lifetime US2008458A (en) | 1926-10-29 | 1931-01-03 | Process for increasing the wettingout power of alkaline lyes |
US537225A Expired - Lifetime US1976886A (en) | 1926-10-29 | 1931-05-13 | Preparation of wetting agents for use in alkalizing lyes |
US552547A Expired - Lifetime US1998550A (en) | 1926-10-29 | 1931-07-22 | Preparation of wetting agents for use in mercerizing lyes |
Country Status (5)
Country | Link |
---|---|
US (8) | US1776052A (en) |
DE (2) | DE669426C (en) |
FR (7) | FR38872E (en) |
GB (11) | GB279784A (en) |
NL (6) | NL28346C (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE751172C (en) * | 1932-04-27 | 1954-01-04 | Boehme Fettchemie Ges M B H | Wetting agent for mercerising liquors |
DE753403C (en) * | 1935-11-20 | 1952-11-24 | Ig Farbenindustrie Ag | Detergents, wetting agents, cleaning agents, foaming agents and dispersants |
US2497519A (en) * | 1946-12-04 | 1950-02-14 | Alrose Chemical Company | Art of stabilizing rayon type fabric |
US2971918A (en) * | 1957-01-07 | 1961-02-14 | Solventol Chemical Products In | Paint stripper composition |
US3027223A (en) * | 1957-12-11 | 1962-03-27 | Dow Chemical Co | Caustic mercerizing solutions |
US3279901A (en) * | 1963-08-30 | 1966-10-18 | Exxon Research Engineering Co | Distillate fuels |
US4384113A (en) * | 1982-03-23 | 1983-05-17 | The Dow Chemical Company | Stabilization of alkali polysaccharides |
US5379807A (en) * | 1993-11-22 | 1995-01-10 | Kelley; Jerry | Shuttle weft yarn control |
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0
- NL NL30506D patent/NL30506C/xx active
- NL NL30262D patent/NL30262C/xx active
- NL NL30555D patent/NL30555C/xx active
-
1927
- 1927-06-10 GB GB15544/27A patent/GB279784A/en not_active Expired
- 1927-09-07 US US218109A patent/US1776052A/en not_active Expired - Lifetime
-
1929
- 1929-06-17 DE DEC43256D patent/DE669426C/en not_active Expired
-
1930
- 1930-06-03 US US459122A patent/US1851914A/en not_active Expired - Lifetime
- 1930-06-11 FR FR38872D patent/FR38872E/en not_active Expired
- 1930-06-16 GB GB18408/30A patent/GB359399A/en not_active Expired
- 1930-06-16 NL NL52154A patent/NL28346C/en active
- 1930-08-04 FR FR38915D patent/FR38915E/en not_active Expired
- 1930-08-06 GB GB23562/30A patent/GB360472A/en not_active Expired
- 1930-08-07 US US473773A patent/US1851393A/en not_active Expired - Lifetime
- 1930-08-12 FR FR39219D patent/FR39219E/en not_active Expired
- 1930-08-14 US US475373A patent/US1851394A/en not_active Expired - Lifetime
- 1930-08-21 DE DE1930C0009130 patent/DE679766C/en not_active Expired
- 1930-08-25 GB GB25356/30A patent/GB361865A/en not_active Expired
-
1931
- 1931-01-03 US US506507A patent/US2008459A/en not_active Expired - Lifetime
- 1931-01-03 US US506506A patent/US2008458A/en not_active Expired - Lifetime
- 1931-01-09 NL NL55095A patent/NL28668C/en active
- 1931-01-09 GB GB831/31A patent/GB364844A/en not_active Expired
- 1931-01-12 FR FR39681D patent/FR39681E/en not_active Expired
- 1931-01-16 GB GB1521/31A patent/GB365323A/en not_active Expired
- 1931-04-20 FR FR40131D patent/FR40131E/en not_active Expired
- 1931-04-23 GB GB12102/31A patent/GB374214A/en not_active Expired
- 1931-05-13 US US537225A patent/US1976886A/en not_active Expired - Lifetime
- 1931-05-21 NL NL56978A patent/NL30340C/en active
- 1931-05-21 FR FR40318D patent/FR40318E/en not_active Expired
- 1931-05-22 GB GB15194/31A patent/GB368606A/en not_active Expired
- 1931-07-22 US US552547A patent/US1998550A/en not_active Expired - Lifetime
- 1931-07-24 FR FR40615D patent/FR40615E/en not_active Expired
- 1931-07-29 GB GB21692/31A patent/GB378194A/en not_active Expired
- 1931-08-12 GB GB22803/31A patent/GB382345A/en not_active Expired
- 1931-09-11 GB GB25545/31A patent/GB382373A/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
GB382345A (en) | 1932-10-27 |
GB378194A (en) | 1932-08-11 |
US2008459A (en) | 1935-07-16 |
NL30555C (en) | |
GB361865A (en) | 1931-11-25 |
GB360472A (en) | 1931-11-06 |
FR39681E (en) | 1932-02-17 |
FR40615E (en) | 1932-07-27 |
NL30340C (en) | 1933-07-15 |
GB359399A (en) | 1931-10-16 |
GB364844A (en) | 1932-01-14 |
US1851914A (en) | 1932-03-29 |
FR38915E (en) | 1931-08-07 |
US1851394A (en) | 1932-03-29 |
GB368606A (en) | 1932-03-10 |
NL28346C (en) | 1932-11-15 |
FR38872E (en) | 1931-08-07 |
US1976886A (en) | 1934-10-16 |
GB365323A (en) | 1932-01-21 |
GB374214A (en) | 1932-06-09 |
GB279784A (en) | 1927-12-22 |
DE679766C (en) | 1939-08-12 |
NL28668C (en) | 1932-12-15 |
DE669426C (en) | 1938-12-24 |
US1998550A (en) | 1935-04-23 |
US2008458A (en) | 1935-07-16 |
GB382373A (en) | 1932-10-27 |
FR40131E (en) | 1932-04-20 |
NL30506C (en) | |
NL30262C (en) | |
US1851393A (en) | 1932-03-29 |
FR40318E (en) | 1932-06-09 |
FR39219E (en) | 1931-10-21 |
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