US2130150A - Process for the treatment of textiles - Google Patents
Process for the treatment of textiles Download PDFInfo
- Publication number
- US2130150A US2130150A US443633A US44363330A US2130150A US 2130150 A US2130150 A US 2130150A US 443633 A US443633 A US 443633A US 44363330 A US44363330 A US 44363330A US 2130150 A US2130150 A US 2130150A
- Authority
- US
- United States
- Prior art keywords
- textiles
- acid
- water
- treatment
- anhydride
- 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
- 239000004753 textile Substances 0.000 title description 16
- 238000000034 method Methods 0.000 title description 10
- 230000008569 process Effects 0.000 title description 9
- 239000000463 material Substances 0.000 description 14
- -1 lauryl chloride Chemical class 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000005871 repellent Substances 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 229920000742 Cotton Polymers 0.000 description 5
- 229920002955 Art silk Polymers 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 230000002940 repellent Effects 0.000 description 3
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 2
- VUQPJRPDRDVQMN-UHFFFAOYSA-N 1-chlorooctadecane Chemical compound CCCCCCCCCCCCCCCCCCCl VUQPJRPDRDVQMN-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- YAYNEUUHHLGGAH-UHFFFAOYSA-N 1-chlorododecane Chemical compound CCCCCCCCCCCCCl YAYNEUUHHLGGAH-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229940053200 antiepileptics fatty acid derivative Drugs 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- 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
- D06M13/10—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
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
Definitions
- This invention relates to the manufactures of textiles whichare rendered water-repellent without their other properties being unfavorably affected thereby.
- One object of the invention is v e the manufacture of water-repellent textiles which do not lose their soft feel.
- Another object of the invention is the ,manufacture of water-proof textile goods which do not lose their permeability to air.
- a further object of the invention is the i manufacture of water-proof woollen materials which retain their heat-insulating property.
- a further object of the invention is the manufacture of water repellent textiles which do not lose their water-repellent property either 15 through extraction with organic solvents or on treatment with warm soap suds.
- a still further object of the invention is the manufacture of water repellent textiles which have the same properties in dyeing as the non-treated textiles of the same kind. Further objects of the invention are mentioned in the following.
- textiles of the most various kinds such as cotton, linen, hemp, jute, artificial silk, wool, silk, etc.
- higher fatty acids are understood here: acids with at least 12 carbon atoms such 30 as lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, oleic acid, ricinoleic acid, etc.
- the corresponding halides such as lauryl chloride, etc.
- acid anhydrides such as lauryl anhydride, etc.
- the process may be carried out equally well with raw textiles as with those previously submitted to a process of improvement such as for instance bucking, bleaching, dyeing, mercerizing 40 and the like. It could also be applied in the yarn or to raw or finished woven fabrics, knitted fabrics, hosiery and the like.
- One method of carrying the process into practical effect consistsin dipping the material to be 45 treated into a solution which contains -1% stearyl anhydride in benzine, benzol, alcohol,
- tetrachloride of carbon and .the like, in thereupon expressing, drying and exposing the material for several hours to a temperature above 35 C. It 50 is preferable to use for the purpose temperatures between 70 and 100 C. the material being exposed to the said temperature for about 6 hours.
- the concentration of the anhydride may be made higher, but this does not result in any 56 great advantage. In such a case, for instance,
- the process may be carried out also by replacing the stearyl anhydride by stearyl chloride.
- a weak organic base such as dimethyl-aniline, diethyl-anilin and the like, so that the hydrochloric acid produced is bound.
- the process may be carried out also by heating the textiles to be treated in the solutions de- 19 scribed, for instance for 6 hours to the boiling point, and-by thereupon drying the materials. In such 'a case a subsequent treatment at a higher temperature is not necessary.
- the process may also be carried out by impregnating the textiles with a molten mass of the above mentioned acid anhydrides and by expose ing them in that state for a number of hours, say for 6 hours, to an increased temperature for instance of 70 C. In such a case the excess of anhydride must be washed out.
- the process may be carried out also with the assistance of an emulsion of fatty acid anhydride.
- stearyl anhydride is energetically stirred in a solution of about 0.2% ammonia preferably under addition of 1% of dis- ,solved starch, gum or the like so that a milky 40 liquid is produced.
- the textile material is impregnated with the said liquid, dried and exposed then to a temperature of about 80 C. for 6 hours.
- the materials treatedin the manner described 7 possess pronounced water repellent property. They can be used for the manufacture of waterproof fabrics for any purposes, which are permeable to the air as no materials choking or'clogging up the pores are used in their manufacture. In the case of finer fabrics, more particularly of artificial silk, there is a great advantage that the water drops falling on them, run ofl directly without leaving any stains.
- cotton or artificial silk which comprises regenerated cellulose, can be dyed by means of direct dyestuffs in exactly the same way as the non-treated fibre.
- organic fat-dissolving liquids such as benzine, benzol, tetrachloride of carbon.
- the material can also be washed in the ordinary way, for although it is not wetted by cold water, it
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
Patent ed Sept. 13, 1938 PATENT OFFLCE 2,130,150 PROCESS FOR .THE TREATMENT OF TEXTILES Alexander Nathansohn, Berlin-Wilmersdorf,
Germany No Drawing. Application April 11, 1930, Serial No. 443,633. In Germany April 19, 1929 1 claim. (c1. s-120) This invention relates to the manufactures of textiles whichare rendered water-repellent without their other properties being unfavorably affected thereby. One object of the invention is v e the manufacture of water-repellent textiles which do not lose their soft feel. Another object of the invention is the ,manufacture of water-proof textile goods which do not lose their permeability to air. A further object of the invention is the i manufacture of water-proof woollen materials which retain their heat-insulating property. A further object of the invention is the manufacture of water repellent textiles which do not lose their water-repellent property either 15 through extraction with organic solvents or on treatment with warm soap suds. A still further object of the invention is the manufacture of water repellent textiles which have the same properties in dyeing as the non-treated textiles of the same kind. Further objects of the invention are mentioned in the following.
I have found that textiles of the most various kinds such as cotton, linen, hemp, jute, artificial silk, wool, silk, etc., can be made to repel water 25 without changing their other physicalgand textile-technical properties by treating them in a special careful manner with derivatives of higher fatty acids. By higher fatty acids are understood here: acids with at least 12 carbon atoms such 30 as lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, oleic acid, ricinoleic acid, etc. As to the derivatives, the corresponding halides, such as lauryl chloride, etc., and acid anhydrides such as lauryl anhydride, etc., are
36 illustrative.
The process may be carried out equally well with raw textiles as with those previously submitted to a process of improvement such as for instance bucking, bleaching, dyeing, mercerizing 40 and the like. It could also be applied in the yarn or to raw or finished woven fabrics, knitted fabrics, hosiery and the like.
" One method of carrying the process into practical effect consistsin dipping the material to be 45 treated into a solution which contains -1% stearyl anhydride in benzine, benzol, alcohol,
tetrachloride of carbon and .the like, in thereupon expressing, drying and exposing the material for several hours to a temperature above 35 C. It 50 is preferable to use for the purpose temperatures between 70 and 100 C. the material being exposed to the said temperature for about 6 hours.
The concentration of the anhydride may be made higher, but this does not result in any 56 great advantage. In such a case, for instance,
when using a concentration of 5%, the material must be subsequently washed out.
The process may be carried out also by replacing the stearyl anhydride by stearyl chloride. In such a case, however, it is preferable to add such 5 a quantity of a weak organic base such as dimethyl-aniline, diethyl-anilin and the like, so that the hydrochloric acid produced is bound.
The process may be carried out also by heating the textiles to be treated in the solutions de- 19 scribed, for instance for 6 hours to the boiling point, and-by thereupon drying the materials. In such 'a case a subsequent treatment at a higher temperature is not necessary.
The process may also be carried out by impregnating the textiles with a molten mass of the above mentioned acid anhydrides and by expose ing them in that state for a number of hours, say for 6 hours, to an increased temperature for instance of 70 C. In such a case the excess of anhydride must be washed out.
Instead of impregnating the textile material with a molten mass of acid anhydride,-it may be impregnated also with a molten mixture of acid anhydride and of a non-volatile substance such 5 as paraflin, and treated in the same way as just described.
In the treatment of artificial silk composed of others or esters of cellulose, it is necessary to avoid such liquids wherein the fibers are dissolving or swelling. Otherwise the material is destroyed or altered in an unfavorable manner.
In such cases benzine is the best solvent for the esterifying agents.
The process may be carried out also with the assistance of an emulsion of fatty acid anhydride. For instance, stearyl anhydride is energetically stirred in a solution of about 0.2% ammonia preferably under addition of 1% of dis- ,solved starch, gum or the like so that a milky 40 liquid is produced. The textile material is impregnated with the said liquid, dried and exposed then to a temperature of about 80 C. for 6 hours.
The materials treatedin the manner described 7 possess pronounced water repellent property. They can be used for the manufacture of waterproof fabrics for any purposes, which are permeable to the air as no materials choking or'clogging up the pores are used in their manufacture. In the case of finer fabrics, more particularly of artificial silk, there is a great advantage that the water drops falling on them, run ofl directly without leaving any stains.
The effect produced in the manner described does not alter in any way the textile-technical 2 a,1so,1so
properties of the material, which remains exactly as soft and porous as the raw material, does not lose any strength and chiefly does not lose its property of being dyed by or taking up the dyes with which the fibre could be dyed before the treatment. Thus, for instance, cotton or artificial silk which comprises regenerated cellulose, can be dyed by means of direct dyestuffs in exactly the same way as the non-treated fibre.
The effect obtained is not destroyed by. the
treatment with organic fat-dissolving liquids such as benzine, benzol, tetrachloride of carbon. The material can also be washed in the ordinary way, for although it is not wetted by cold water, it
takes up directly warm water, more particularly when it contains soap. After rinsing and drying after the washing, it regains its water-repelling property; Nor does repeated washing destroy the effect.
The most important point is to treat the textiles in a very mild manner with the fatty acid derivatives, for instance not to impregnate them with alkali before the treatment with stearyl chloride. If this is done, the whole surface of the textile fibre will be esterified in the well known manner, and therefore simultaneously with the appearance of the water-repelling force, there will take place a change in the textiletechnical properties, more particularly in the ability to take up dyes. The materials in which owing to the intensive simultaneous action of alkali and acid chloride, there takes place an esterification-of the whole surface, change their textile-technical properties, more particularly their ability to be dyed by, or to take up the dride of a higher fatty acid, impregnating cotton;- 20 therewith in the absence of alkalies, drying the cotton and thereafter heating the impregnated cotton at a temperature within the range of from about 35 C. to 100 C. for several hours.
ALEXANDER m'rnmsoim.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEN30270D DE535283C (en) | 1929-04-19 | 1929-04-19 | Process for the refinement of artificial structures made of cellulose or its derivatives by esterifying treatment |
DEN30269D DE572613C (en) | 1929-04-19 | 1929-04-19 | Process for the finishing of cleaned textile fabrics |
Publications (1)
Publication Number | Publication Date |
---|---|
US2130150A true US2130150A (en) | 1938-09-13 |
Family
ID=25989086
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US443633A Expired - Lifetime US2130150A (en) | 1929-04-19 | 1930-04-11 | Process for the treatment of textiles |
Country Status (2)
Country | Link |
---|---|
US (1) | US2130150A (en) |
GB (1) | GB355256A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2429644A (en) * | 1940-08-08 | 1947-10-28 | Joseph G Denny Jr | Art of esterification |
US2460777A (en) * | 1946-02-18 | 1949-02-01 | Peter J Gaylor | Waterproofing cellulosic material with higher aliphatic acyl peroxides |
US2762270A (en) * | 1949-10-06 | 1956-09-11 | Hercules Powder Co Ltd | Process of sizing paper with an aqueous emulsion of ketene dimer |
US2986445A (en) * | 1960-01-06 | 1961-05-30 | Nathan H Koenig | Treatment of wool with acid anhydrides in the presence of dimethylformamide |
FR2767270A1 (en) * | 1997-08-14 | 1999-02-19 | Daniel Gamain | Hydrophobic material made by treating solid material |
US20140338944A1 (en) * | 2013-05-14 | 2014-11-20 | Robert Bosch Gmbh | Hand tool device |
-
1930
- 1930-04-11 US US443633A patent/US2130150A/en not_active Expired - Lifetime
- 1930-04-16 GB GB12061/30A patent/GB355256A/en not_active Expired
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2429644A (en) * | 1940-08-08 | 1947-10-28 | Joseph G Denny Jr | Art of esterification |
US2460777A (en) * | 1946-02-18 | 1949-02-01 | Peter J Gaylor | Waterproofing cellulosic material with higher aliphatic acyl peroxides |
US2762270A (en) * | 1949-10-06 | 1956-09-11 | Hercules Powder Co Ltd | Process of sizing paper with an aqueous emulsion of ketene dimer |
US2986445A (en) * | 1960-01-06 | 1961-05-30 | Nathan H Koenig | Treatment of wool with acid anhydrides in the presence of dimethylformamide |
FR2767270A1 (en) * | 1997-08-14 | 1999-02-19 | Daniel Gamain | Hydrophobic material made by treating solid material |
WO1999008784A1 (en) * | 1997-08-14 | 1999-02-25 | Daniel Samain | Method for treating a solid material to make it hydrophobic, material obtained and uses |
US6342268B1 (en) | 1997-08-14 | 2002-01-29 | Daniel Samain | Method for treating a solid material to make it hydrophobic, material obtained and uses |
US20140338944A1 (en) * | 2013-05-14 | 2014-11-20 | Robert Bosch Gmbh | Hand tool device |
US10046449B2 (en) * | 2013-05-14 | 2018-08-14 | Robert Bosch Gmbh | Hand tool device |
US10780562B2 (en) | 2013-05-14 | 2020-09-22 | Robert Bosch Gmbh | Hand tool device |
Also Published As
Publication number | Publication date |
---|---|
GB355256A (en) | 1931-08-17 |
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