US2782090A - Stabilization of cellulosic fabrics by applying alkyl silicon halide vapors - Google Patents
Stabilization of cellulosic fabrics by applying alkyl silicon halide vapors Download PDFInfo
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- US2782090A US2782090A US444917A US44491754A US2782090A US 2782090 A US2782090 A US 2782090A US 444917 A US444917 A US 444917A US 44491754 A US44491754 A US 44491754A US 2782090 A US2782090 A US 2782090A
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- fabric
- vapors
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- tensioning
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- 239000004744 fabric Substances 0.000 title claims description 110
- -1 alkyl silicon halide Chemical class 0.000 title claims description 18
- 229910052710 silicon Inorganic materials 0.000 title claims description 14
- 239000010703 silicon Substances 0.000 title claims description 14
- 230000006641 stabilisation Effects 0.000 title description 4
- 238000011105 stabilization Methods 0.000 title description 4
- 238000000034 method Methods 0.000 claims description 27
- 230000003472 neutralizing effect Effects 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000006227 byproduct Substances 0.000 claims description 15
- 230000000087 stabilizing effect Effects 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 3
- 239000012433 hydrogen halide Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 18
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 16
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 14
- 229910000077 silane Inorganic materials 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 230000008569 process Effects 0.000 description 12
- 239000005055 methyl trichlorosilane Substances 0.000 description 9
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 9
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 8
- 239000000835 fiber Substances 0.000 description 8
- 239000005049 silicon tetrachloride Substances 0.000 description 8
- 239000005051 trimethylchlorosilane Substances 0.000 description 8
- 229920000742 Cotton Polymers 0.000 description 7
- 229920000297 Rayon Polymers 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 description 6
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 6
- 239000005048 methyldichlorosilane Substances 0.000 description 6
- 239000002964 rayon Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000000443 aerosol Substances 0.000 description 5
- 239000000080 wetting agent Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920002113 octoxynol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000005303 weighing Methods 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
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
- D06M13/517—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond containing silicon-halogen bonds
Definitions
- the present invention constitutes an improvement ove the invention of ,applicants prior application whereby better shrinkage stabilization isattained, either with or without imparting water repellency to the fabric.
- the process of this invention avoids the difficulties previously encountered in treating cellulosic, fabrics with organo halogeno silanes of degradation caused by acidic reaction by-products, r
- shrinkage maybe reduced to less than 1%.
- the process of this invention compares favorably with the well-known compressive shrinkage process (sanforizing) Where it is. desired that the treated fabric shall be waterrepellent in addition to being stabilized, the fabric should, prior to exposure to the silane vapors, have a moisture content such as attained by equilibrating the fabric with an atmosphere of about 30-90% relative humidity. Howevenit may be desired that the fabric be temperature of 200 F. or higher.
- Silanes preferred for practicing the invention are the 'n'iethyl chloro silanes, such as methyl trichloro silane, Ql-IsSiClg, dimethyl dichloro silaneKCHahSiClz, methyl tlichlorosilane, CHs-SiHClz, and commerciallyavail'able methyl chloro silane compositions consisting principally of methyl trichloro silane, climethyl dichloro silane and trimethyl chloro silane (CHs)3SiCl (together with some methyl dichloro silane, and silicon tetrachloride SiClr, as these result from the method of manufacture), as they are readily available and sufficiently volatile to be formed into vapors at low temperatures.
- methyl trichloro silane Ql-IsSiClg
- dimethyl dichloro silaneKCHahSiClz methyl tlichlorosilane
- CHs-SiHClz commercially
- silane may be allowed to evaporate. in air, or other inert gas, but is preferably atomized to produce an aerosol mixture, in the form of a noticeable fog. In this manner, the silane concentration of the gas mixture may be greatly increased over that attainable by true vaporization within the temperature limitations.
- An aerosol formed by condensation, as by cooling a saturated atmosphere of silane, may also be employed.
- the fabric is exposed to the silane atmosphere for be tween about one second and five minutes, preferably for less than a minute, and is then immediately immersed in a mildly basic aqueous neutralizing bath, preferably one buffered at a pH of between 7 and 11.
- Alkaline neutralizing agents particularly suitable for forming the bath include sodium carbonate, sodium bicarbonate, calcium hydroxide, disodium phosphate, trisodium phosphate, sodium acetate, and similar water-soluble basic compounds which form slightly basic aqueous solutions of high neutralizing capacity. Strongly basic solutions, e. g. of pH higher than 11.0, are preferably avoided since they tend to remove the silicone from the fabric.
- the neutralizing bath preferably also includes a wetting agent effective to aid the wetting ofv cellulosic fabrics, preferably a nonionic or cationic wetting agent, examples of which are well-known in the art.
- the fabric is. preferably rinsed in water to remove residual alkaline solution and is then tensioned and dried.
- the tensioning of the fabric is preferably widthwise, that is, in the direction of the fill threads, with little or' no tensioning warpwise, to permit normal contractionof the warp threads during drying;
- Tensioning and drying is preferably carried out in a standard commercial tenter-dryer, preferably one adapted to be overfed to permit warpwise contraction during drying. In so tensioning the fabric it is preferably drawn out at least to substantially its original dimension preceding exposure to the silane vapors, and is typically stretched by between about one and five percent.
- Warpwise tensioning particularly when accompanied by widthwise tensioning, is also satisfactory but generally results in greater initial relaxation and contraction when the tension is released,
- Example 1 An enclosed chamber was supplied with an atmosphere of: an aerosol mixture of methyl chloro silanes consisting chiefly of methyl trichloro silane and dimethyl dichloro silane (GE Drifilm, sold by the General Electric Company, Schenectady, New York), by atomizing the silane in the container until it was filled with a noticeable fog, at a temperature of about 75 F.
- An unfinished cotton muslin piece measure 60" x 60" and equilibrated at room temperature at a relative humidity of about 60% was then placed in the chamber for about seconds, and then removed and immediately immersed in a warm (ca. 100 F.) concentrated aqueous solution of sodium bicarbonate, containing a small amount (e. g.
- a wetting agent such as the nonionic wetting agent Triton X 100 sold by Rohm & Haas Co., Philadelphia, Pennsylvania, and described as an alkyl aryl polyether alcohol
- Triton X 100 sold by Rohm & Haas Co., Philadelphia, Pennsylvania, and described as an alkyl aryl polyether alcohol
- Example 2 The same procedure described in Example 1 was followed with the exception that prior to exposure to the silane vapors the fabric was dried in an oven at 220 F.
- the treated fabric showed substantially the same stability as that treated in accordance with Examplc 1, but was not water-repellent. Water showered on this sample was readily absorbed, wetting the fabric.
- Example 3 In a continuous process a plain weave rayon 60 inches wide, having a warp count of 90 threads/ inch and a filling count of threads/inch, and weighing 16 oz. per linear yard, was passed through a chamber having an aerosol atmosphere as described in Example 1. The fabric was passed through the chamber at rate providing a dwell therein of about 20 seconds, and fresh silane was atomized in the chamber at a rate of 2 parts by weight for each 100 parts of fabric.
- the fabric After passing through the chamber, the fabric was passed through a neutralizing bath, of composition the same as given in Example I, and then through rinse water to remove excess alkali.
- the fabric was then finally dried in a standard tenterdrier adjusted to grasp the selvedge edges and expand the fabric to a width of about 61 inches, and to overfeed the fabric by about 10%.
- a standard tenterdrier adjusted to grasp the selvedge edges and expand the fabric to a width of about 61 inches, and to overfeed the fabric by about 10%.
- the fabric was released from the tenter, upon which the width returned to inches, and was found not to shrink during ten subsequent washings by more than about 1.5%.
- the process of this invention may be used advantageously with other cellulosic fabrics and includesin general, the treatment of fabrics of such fibers as cotton, rayon, and cellulose acetate.
- the method of stabilizing water insoluble cellulosic fabrics having free hydroxy groups comprising exposing the said fabric for not more than about 5 minutes and at a temperature of less than about 100 F. to organo silicon halide vapors, having as organo substituents alkyl groups with between one and four carbon atoms, the conditions of time and temperature being such that reaction takes place between the halogen of said organo silicon halide and said free hydroxy groups with the liberation of free hydrogen halide, immediately thereafter neutralizing and removing the resulting by-products by immersing the fabric in a basic aqueous solution having a pH between 7 and 11, then tensioning the fabric at least to substantially its original dimension preceding exposure to said vapors and drying it while held under tension at said dimension, whereby said fabric is stabilized against shrinkage.
- the method of stabilizing water insoluble cellulosic fabrics having free hydroxy groups comprising exposing said fabric for not more than about 5 minutes and at a temperature of less than about 100 F. to vapors comprising a material selected from the group consisting of: methyl trichlorosilane; dimethyl dichlorosilane; methyl dicholorsilane; trimethylchlorosilane in admixture with silicon tetrachloride; and mixtures of the foregoing materials, the conditions of time and temperature being such that reaction takes place between the chloride of said material and said hydroxy groups with the liberation of hydrogen chloride, immediately thereafter neutralizing and removing the resulting by-products by immersing the fabric in a basic aqueous solution having a pH between 7 and 11, then tensioning the fabric at least to substantially its original dimension preceding exposure to said vapors and drying it while held under tension at said dimension, whereby said fabric is stabilized against shrinkage.
- the method of stabilizing water insoluble cellulosic fabrics having free hydroxy groups comprising exposing said fabric at a temperature of about F. to no higher than about F. and for a time between about I second and 5 minutes to organo silicon salide vapors having as organo substituents alkyl groups with between one and four carbon atoms, immediately thereafter neutralizing and removing the resulting by-products by immersing the fabric in a basic aqueous solution having a pH between 7 and 11, then tensioning the fabric at least to substantially its original dimension preceding exposure to said vapors and drying it while held under tension at said dimension, whereby said fabric is stabilized against shrinkage.
- the method of stabilizing water insoluble cellulosic fabrics having free hydroxy groups comprising exposing said fabric at a temperature of about 75 F. to no higher than about 100 F. and for a time between about 1 second and 5 minutes to vapors comprising a material selected from the group consisting of: methyl trichlorosilane; dimethyl dichlorosliane; methyl dichlorosilane; trimethylchlorosilane in admixture with silicon tetrachloride; and mixtures of the foregoing materials, immediately thereafter neutralizing and-removing the resulting by-products by immersing the fabric in a basic aqueous solution having a pH between 7 and 11, then tensioning the fabric at least to substantially its original dimension preceding exposure to said vapors and drying it while held under tension at said dimension, whereby said fabric is stabilized against shrinkage.
- the method of stabilizing water insoluble cellulosic fabrics having free hydroxy groups comprising exposing the said fabric for not more than about minutes and at a temperature of less than about 100 F. to organo silicon halide vapors having as organosubstituents alkyl groups with between one and four carbon atoms, the conditions of time and temperature being such that reaction takes place between the halogen of said organo silicon halide and said free hydroxy groups with the liberation of free hydrogen halide, immediately thereafter neutralizing and removing the resulting by-products by immersing the fabric in a basic aqueous solution having a pH between 7 and 11, then tensioning the fabric fillwise at least to substantially its original width preceding exposure to said vapors anddrying it while held under tension at said width, whereby said fabric is stabilized against shrinkage.
- the method of stabilizing water insoluble cellulosic fabrics having free hydroxy groups comprising exposing said fabric for not more than about 5 minutes and at a temperature of less than about 100 F. to vapors comprising a material selected from the group consisting of: methyl trichlorosilane; dimethyl dichlorosilane; methyl dichlorosilane; trimethylchlorosilane in admixture with silicon tetrachloride; and mixtures of the foregoing materials, the conditions of time and temperature being such that reaction takes place between the chloride of said material and said hydroxy groups with the liberation of hydrogen chloride, immediately thereafter neutralizing and removing the resulting by-products by immersing the fabric in a basic aqueous solution having a pH between 7 and 11, then tensioning the fabric fillwise at least to substantially its original width preceding exposure to said vapors and drying it while held under tension at said width, whereby said fabric is stabilized against shrinkage.
- the method of stabilizing water insoluble cellulosic fabrics having free hydroxy groups comprising exposing said fabric at a temperature of about 75 F. to no higher than about 100 F. and for a time between about 1 second and 5 minutes to organo silicon halide vapors having as organo substituents alkyl groups with between one and four carbon atoms, immediately thereafter neutralizing and removing the resulting by-products by immersing the fabric in a basic aqueous solution having a pH between 7 and 11, then tensioning the fabric fillwise at least to substantially its original width preceding exposure to said vapors and drying it while held under tensecond and 5 minutes to vapors comprising a material width preceding exposure to said vapors and drying it while held under tension at said width, whereby said fabric is stabilized against shrinkage.
- the method of stabilizing water insoluble cellulosic fabrics having free hydroxy groups comprising exposing said fabric at a temperature of about 75 F. to no higher than about F. and for a time, between about 1 second and 5 minutes to organo silicon halide vapors having as organo substituents alkyl groups with between one and four carbon atoms, immediately thereafter neutralizing and removing the resulting by-products by immersing the fabric in a basic aqueous solution having a pH between 7 and 11, then tensioning the fabric fillwise to stretch it by at least about 1% and drying it while held under tension at said width, whereby said fabric is stabilized against shrinkage.
- the method of stabilizing water insoluble cellulosic fabrics having free hydroxy groups comprising exposing said fabric at a temperature of about 75 F. to no higher than about 100 F. and for a time between about 1 second and 5 minutes to vapors comprising a material selected from the group consisting of: methyl trichlorosilane; dimethyl dichlorosilane; methyl dichlorosilane; trimethylchlorosilane in admixture with silicon tetrachloride; and mixtures of the foregoing materials, immediately thereafter neutralizing and removing the resulting by-products by immersing the fabric in a basic aqueous solution having a pH between 7 and 11, then tensioning the fabric fillwise to stretch it by at least about 1% and drying it while held under tension at said width, whereby said fabric is stabilized against shrinkage.
- the method of stabilizing fabrics including a material selected from the group consisting of cotton fibers and cellulosic rayon fibers having free hydroxy groups comprising exposing said fabric at a temperature of about 75 F. to no higher than about 100 F. and for a time between about 1 second and 5 minutes to organo silicon halide vapors having as organo substituents alkyl groups with between one and four carbon atoms, immediately thereafter neutralizing and removing the resulting by-products by immersing the fabric in a basic aqueous solution having a pH between 7 and 11, then tensioning the fabric fillwise at least to substantially its original width preceding exposure to said vapors and drying it while held under tension at said width, whereby said fabric is stabilized against shrinkage.
- the method of stabilizing fabrics including a material selected from the group consisting of cotton fibers and cellulosic rayon fibers having free hydroxy groups comprising exposing said fabric at a temperature of about 75 F. to no higher than about 100 F. and for a time between about 1 second and 5 minutes to vapors comprising a material selected from the group consisting of: methyl trichlorosilane; dimethyl dichlorosilane; methyl dichlorosilane; trimethylchlorosilane in admixture with silicon tetrachloride; and mixtures of the foregoing materials, immediately thereafter neutralizing and removing the resulting by-products by immersing the fabric in a basic aqueous solution having a pH between 7 and 11, then tensioning the fabric fill-wise at least to substantially its original width preceding exposure to said vapors and drying it while held under tension at said width, whereby said fabric is stabilized against shrinkage.
- the method of stabilizing fabrics including a material selected from the group consisting of cotton fibers and cellulosic rayon fibers having free hydroxy groups comprising exposing said fabric at a temperature of about 75 F. to no higher than about 100 F. and for a time between about 1 second and 5 minutes to vapors comprising a material selected from the group consisting of: methyl trichlorosilane; dimethyl dichlorosilane; methyl dichlorosilane; trimethylchlorosilane in admixture with silicon tetrachloride; and mixtures of the foregoing materials, immediately thereafter neutralizing and removing the resulting by-products by immersing the fabric in a basic aqueous solution having a pH'between 7 and 11, then tensioning the fabric fillwise to stretch it by at least about 1% and drying it while held under tension at said width, whereby said fabric is stabilized against shrinkage.
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
A 2,782,090 Patented Feb. 19, 1957 United States Patent Ofifice STABILIZATION OF CELLULOSIC FABRICS BY APPLYING ALKYL SILICON HALIDE VAPORS Edward Robbart, Cambridge, Mass.
No Drawing. Application July 21, 1954, Serial No. 444,917
13 Claims. (Cl. 8-11 6) t This invention consists in a process of treating cellulosic fabrics with organo halogenosilanes to improve their stability against shrinkage.
.A major problem in finishing fabrics of cellulosic fibers, such as cotton, acetate or rayon fabrics, is in minimizing shrinkage during subsequent washing of the fabric or of articles made from the fabric. In applicantscopending application, Serial No. 318,734, filed November 4, 1952, is disclosed process of treating fabrics with .organo 'halogeno sila es which, among other things, improves That process consists in gentheir shrinkage resistance. eral of exposing the fabric to vapors of the silane under carefully controlled conditions of time and temperature, and then neutralizing the reaction by-products in a mildly alkaline solution and drying the fabric.
The present invention constitutes an improvement ove the invention of ,applicants prior application whereby better shrinkage stabilization isattained, either with or without imparting water repellency to the fabric. In addition, the process of this inventionavoids the difficulties previously encountered in treating cellulosic, fabrics with organo halogeno silanes of degradation caused by acidic reaction by-products, r
The process of this invention consists in general of. ex-
posing the fabric togaseous mixture, preferably an aerosol, of an organo halogeno silane and an inert gas .at a temperature no higher than about 100 F., and preferably below 80 F., for a brief period of time generally between one second and five minutes, then immediately thereafter From the foregoing brief description, it will be seen that applicants 'presen'tlinvention differs from the process of his copending application primarily in that the fabric is tensionedduring'drying. Why tensioning should result I in better stabilization against shrinkage is not fully understood, but it has been found that whereas the prior process is etfective to reduce shrinkage of a cotton muslin to less thanabout 3%, by the process of the present invention, shrinkage maybe reduced to less than 1%. From this it will be seen that the process of this invention compares favorably with the well-known compressive shrinkage process (sanforizing) Where it is. desired that the treated fabric shall be waterrepellent in addition to being stabilized, the fabric should, prior to exposure to the silane vapors, have a moisture content such as attained by equilibrating the fabric with an atmosphere of about 30-90% relative humidity. Howevenit may be desired that the fabric be temperature of 200 F. or higher.
Silanes preferred for practicing the invention are the 'n'iethyl chloro silanes, such as methyl trichloro silane, Ql-IsSiClg, dimethyl dichloro silaneKCHahSiClz, methyl tlichlorosilane, CHs-SiHClz, and commerciallyavail'able methyl chloro silane compositions consisting principally of methyl trichloro silane, climethyl dichloro silane and trimethyl chloro silane (CHs)3SiCl (together with some methyl dichloro silane, and silicon tetrachloride SiClr, as these result from the method of manufacture), as they are readily available and sufficiently volatile to be formed into vapors at low temperatures. Mixtures of trimethyl chloro silane and silicon tetrachloride are also satisfactory. It is contemplated, however, that other organo halogeno silanes may be used particularly the lower alkyl silicon halides (e. g. ethyl, propyl, butyl, etc., silicon halides). In forming the gaseous mixture for treating the fabric, the silane may be allowed to evaporate. in air, or other inert gas, but is preferably atomized to produce an aerosol mixture, in the form of a noticeable fog. In this manner, the silane concentration of the gas mixture may be greatly increased over that attainable by true vaporization within the temperature limitations. An aerosol formed by condensation, as by cooling a saturated atmosphere of silane, may also be employed.
The fabric is exposed to the silane atmosphere for be tween about one second and five minutes, preferably for less than a minute, and is then immediately immersed in a mildly basic aqueous neutralizing bath, preferably one buffered at a pH of between 7 and 11. Alkaline neutralizing agents particularly suitable for forming the bathinclude sodium carbonate, sodium bicarbonate, calcium hydroxide, disodium phosphate, trisodium phosphate, sodium acetate, and similar water-soluble basic compounds which form slightly basic aqueous solutions of high neutralizing capacity. Strongly basic solutions, e. g. of pH higher than 11.0,, are preferably avoided since they tend to remove the silicone from the fabric. Dilute solutions of such strongly basic materials as sodium hydroxide having a pH below 11 could be used, but the neutralizing capacity is quite low because of the extreme dilution of the solution necessary to such low alkalinity. Ammonia and amines are also preferably avoided as neutralizing agent's. since their salts, formed during neutralization, tend to be retained by the fabric and cause gradual degradation. The neutralizing bath preferably also includes a wetting agent effective to aid the wetting ofv cellulosic fabrics, preferably a nonionic or cationic wetting agent, examples of which are well-known in the art.
After neutralization, the fabric is. preferably rinsed in water to remove residual alkaline solution and is then tensioned and dried. ,The tensioning of the fabric is preferably widthwise, that is, in the direction of the fill threads, with little or' no tensioning warpwise, to permit normal contractionof the warp threads during drying; Tensioning and drying is preferably carried out in a standard commercial tenter-dryer, preferably one adapted to be overfed to permit warpwise contraction during drying. In so tensioning the fabric it is preferably drawn out at least to substantially its original dimension preceding exposure to the silane vapors, and is typically stretched by between about one and five percent.
When drying is complete the tension is released, and after a few minutes during which the fabric relaxes and contracts, the fabric will be stable and undergo generally not more than 1% shrinkage during subsequent washings.
Warpwise tensioning, particularly when accompanied by widthwise tensioning, is also satisfactory but generally results in greater initial relaxation and contraction when the tension is released,
The following examples describe in detail representative and preferred embodiments of this invention, and are presented as illustrative thereof.
Example 1 An enclosed chamber was supplied with an atmosphere of: an aerosol mixture of methyl chloro silanes consisting chiefly of methyl trichloro silane and dimethyl dichloro silane (GE Drifilm, sold by the General Electric Company, Schenectady, New York), by atomizing the silane in the container until it was filled with a noticeable fog, at a temperature of about 75 F. An unfinished cotton muslin piece measure 60" x 60" and equilibrated at room temperature at a relative humidity of about 60% was then placed in the chamber for about seconds, and then removed and immediately immersed in a warm (ca. 100 F.) concentrated aqueous solution of sodium bicarbonate, containing a small amount (e. g. about 0.02% by weight) of a wetting agent such as the nonionic wetting agent Triton X 100 sold by Rohm & Haas Co., Philadelphia, Pennsylvania, and described as an alkyl aryl polyether alcohol), and was agitated therein for about 1 minute. After rinsing the muslin in cold water, it was stretched on a pin frame to a width (fillwise) of 63", the other edges remaining free, and was permitted to dry. When the fabric was removed the width returned to 60 inches. did not shrink more than 1% in either direction. This fabric showed a pronounced Water-repellency in that water showered on it formed droplets which were readily shed.
Example 2 The same procedure described in Example 1 was followed with the exception that prior to exposure to the silane vapors the fabric was dried in an oven at 220 F. The treated fabric showed substantially the same stability as that treated in accordance with Examplc 1, but was not water-repellent. Water showered on this sample was readily absorbed, wetting the fabric.
Example 3 In a continuous process a plain weave rayon 60 inches wide, having a warp count of 90 threads/ inch and a filling count of threads/inch, and weighing 16 oz. per linear yard, was passed through a chamber having an aerosol atmosphere as described in Example 1. The fabric was passed through the chamber at rate providing a dwell therein of about 20 seconds, and fresh silane was atomized in the chamber at a rate of 2 parts by weight for each 100 parts of fabric.
After passing through the chamber, the fabric was passed through a neutralizing bath, of composition the same as given in Example I, and then through rinse water to remove excess alkali.
The fabric was then finally dried in a standard tenterdrier adjusted to grasp the selvedge edges and expand the fabric to a width of about 61 inches, and to overfeed the fabric by about 10%. When dried the fabric was released from the tenter, upon which the width returned to inches, and was found not to shrink during ten subsequent washings by more than about 1.5%.
By way of comparison, a similar fabric, treated in the same way but dried without being tentered, shrunk by about 3-4% after three washings. It will accordingly be seen that tensioning of the fabric during the final drying and after treatment with the silane results in a marked improvement in the stability of cellulosic fabrics.
The foregoing examples have been presented as illustrative of applicants invention and it is contemplated that obvious modifications will occur to those skilled in the art and may be made without departing from the scope of this invention.
In addition to the fabric disclosed in the examples, the process of this invention may be used advantageously with other cellulosic fabrics and includesin general, the treatment of fabrics of such fibers as cotton, rayon, and cellulose acetate.
The chemical mechanism by which the process func tions is not fully understood but it is theorized that a reaction takes place on and within the fibers between the silane and hydroxyl groups in the cellulose molecule During ten subsequent washings, the fabric (see in this connection Schuyten, Weaver, Reid and Jergens, J. Am. Chem. Soc. 70, 1919 (1948)) and between adsorbed moisture on the fibers and the silane. The latter reaction is believed to account for the water repellency characteristics of the treated fabric, for presumably by it is formed a surface coating of a silicone. As evidenced by the fact that a dried fabric may be treated as described in Example 2, to impart shrink resistance without substantial water repellency, it appears that the theorized reaction with cellulose hydroxyl groups somehow accounts largely for the improved shrink resistance resulting from the treatment, probably by altering the ability of the fibers to absorb water and relax during subsequent washings.
The foregoing explanation is presented as hypothesis and is not intended as limiting in any way this invention to the theorized mechanism.
Having thus disclosed my invention and described in detail preferred embodiments thereof, I claim and desire to secure by Letters Patent:
1. The method of stabilizing water insoluble cellulosic fabrics having free hydroxy groups, comprising exposing the said fabric for not more than about 5 minutes and at a temperature of less than about 100 F. to organo silicon halide vapors, having as organo substituents alkyl groups with between one and four carbon atoms, the conditions of time and temperature being such that reaction takes place between the halogen of said organo silicon halide and said free hydroxy groups with the liberation of free hydrogen halide, immediately thereafter neutralizing and removing the resulting by-products by immersing the fabric in a basic aqueous solution having a pH between 7 and 11, then tensioning the fabric at least to substantially its original dimension preceding exposure to said vapors and drying it while held under tension at said dimension, whereby said fabric is stabilized against shrinkage.
2. The method of stabilizing water insoluble cellulosic fabrics having free hydroxy groups, comprising exposing said fabric for not more than about 5 minutes and at a temperature of less than about 100 F. to vapors comprising a material selected from the group consisting of: methyl trichlorosilane; dimethyl dichlorosilane; methyl dicholorsilane; trimethylchlorosilane in admixture with silicon tetrachloride; and mixtures of the foregoing materials, the conditions of time and temperature being such that reaction takes place between the chloride of said material and said hydroxy groups with the liberation of hydrogen chloride, immediately thereafter neutralizing and removing the resulting by-products by immersing the fabric in a basic aqueous solution having a pH between 7 and 11, then tensioning the fabric at least to substantially its original dimension preceding exposure to said vapors and drying it while held under tension at said dimension, whereby said fabric is stabilized against shrinkage.
3. The method of stabilizing water insoluble cellulosic fabrics having free hydroxy groups comprising exposing said fabric at a temperature of about F. to no higher than about F. and for a time between about I second and 5 minutes to organo silicon salide vapors having as organo substituents alkyl groups with between one and four carbon atoms, immediately thereafter neutralizing and removing the resulting by-products by immersing the fabric in a basic aqueous solution having a pH between 7 and 11, then tensioning the fabric at least to substantially its original dimension preceding exposure to said vapors and drying it while held under tension at said dimension, whereby said fabric is stabilized against shrinkage.
4. The method of stabilizing water insoluble cellulosic fabrics having free hydroxy groups comprising exposing said fabric at a temperature of about 75 F. to no higher than about 100 F. and for a time between about 1 second and 5 minutes to vapors comprising a material selected from the group consisting of: methyl trichlorosilane; dimethyl dichlorosliane; methyl dichlorosilane; trimethylchlorosilane in admixture with silicon tetrachloride; and mixtures of the foregoing materials, immediately thereafter neutralizing and-removing the resulting by-products by immersing the fabric in a basic aqueous solution having a pH between 7 and 11, then tensioning the fabric at least to substantially its original dimension preceding exposure to said vapors and drying it while held under tension at said dimension, whereby said fabric is stabilized against shrinkage.
5. The method of stabilizing water insoluble cellulosic fabrics having free hydroxy groups, comprising exposing the said fabric for not more than about minutes and at a temperature of less than about 100 F. to organo silicon halide vapors having as organosubstituents alkyl groups with between one and four carbon atoms, the conditions of time and temperature being such that reaction takes place between the halogen of said organo silicon halide and said free hydroxy groups with the liberation of free hydrogen halide, immediately thereafter neutralizing and removing the resulting by-products by immersing the fabric in a basic aqueous solution having a pH between 7 and 11, then tensioning the fabric fillwise at least to substantially its original width preceding exposure to said vapors anddrying it while held under tension at said width, whereby said fabric is stabilized against shrinkage.
6. The method of stabilizing water insoluble cellulosic fabrics having free hydroxy groups, comprising exposing said fabric for not more than about 5 minutes and at a temperature of less than about 100 F. to vapors comprising a material selected from the group consisting of: methyl trichlorosilane; dimethyl dichlorosilane; methyl dichlorosilane; trimethylchlorosilane in admixture with silicon tetrachloride; and mixtures of the foregoing materials, the conditions of time and temperature being such that reaction takes place between the chloride of said material and said hydroxy groups with the liberation of hydrogen chloride, immediately thereafter neutralizing and removing the resulting by-products by immersing the fabric in a basic aqueous solution having a pH between 7 and 11, then tensioning the fabric fillwise at least to substantially its original width preceding exposure to said vapors and drying it while held under tension at said width, whereby said fabric is stabilized against shrinkage.
7. The method of stabilizing water insoluble cellulosic fabrics having free hydroxy groups comprising exposing said fabric at a temperature of about 75 F. to no higher than about 100 F. and for a time between about 1 second and 5 minutes to organo silicon halide vapors having as organo substituents alkyl groups with between one and four carbon atoms, immediately thereafter neutralizing and removing the resulting by-products by immersing the fabric in a basic aqueous solution having a pH between 7 and 11, then tensioning the fabric fillwise at least to substantially its original width preceding exposure to said vapors and drying it while held under tensecond and 5 minutes to vapors comprising a material width preceding exposure to said vapors and drying it while held under tension at said width, whereby said fabric is stabilized against shrinkage.
9. The method of stabilizing water insoluble cellulosic fabrics having free hydroxy groups comprising exposing said fabric at a temperature of about 75 F. to no higher than about F. and for a time, between about 1 second and 5 minutes to organo silicon halide vapors having as organo substituents alkyl groups with between one and four carbon atoms, immediately thereafter neutralizing and removing the resulting by-products by immersing the fabric in a basic aqueous solution having a pH between 7 and 11, then tensioning the fabric fillwise to stretch it by at least about 1% and drying it while held under tension at said width, whereby said fabric is stabilized against shrinkage.
10. The method of stabilizing water insoluble cellulosic fabrics having free hydroxy groups comprising exposing said fabric at a temperature of about 75 F. to no higher than about 100 F. and for a time between about 1 second and 5 minutes to vapors comprising a material selected from the group consisting of: methyl trichlorosilane; dimethyl dichlorosilane; methyl dichlorosilane; trimethylchlorosilane in admixture with silicon tetrachloride; and mixtures of the foregoing materials, immediately thereafter neutralizing and removing the resulting by-products by immersing the fabric in a basic aqueous solution having a pH between 7 and 11, then tensioning the fabric fillwise to stretch it by at least about 1% and drying it while held under tension at said width, whereby said fabric is stabilized against shrinkage.
11. The method of stabilizing fabrics including a material selected from the group consisting of cotton fibers and cellulosic rayon fibers having free hydroxy groups comprising exposing said fabric at a temperature of about 75 F. to no higher than about 100 F. and for a time between about 1 second and 5 minutes to organo silicon halide vapors having as organo substituents alkyl groups with between one and four carbon atoms, immediately thereafter neutralizing and removing the resulting by-products by immersing the fabric in a basic aqueous solution having a pH between 7 and 11, then tensioning the fabric fillwise at least to substantially its original width preceding exposure to said vapors and drying it while held under tension at said width, whereby said fabric is stabilized against shrinkage.
12. The method of stabilizing fabrics including a material selected from the group consisting of cotton fibers and cellulosic rayon fibers having free hydroxy groups comprising exposing said fabric at a temperature of about 75 F. to no higher than about 100 F. and for a time between about 1 second and 5 minutes to vapors comprising a material selected from the group consisting of: methyl trichlorosilane; dimethyl dichlorosilane; methyl dichlorosilane; trimethylchlorosilane in admixture with silicon tetrachloride; and mixtures of the foregoing materials, immediately thereafter neutralizing and removing the resulting by-products by immersing the fabric in a basic aqueous solution having a pH between 7 and 11, then tensioning the fabric fill-wise at least to substantially its original width preceding exposure to said vapors and drying it while held under tension at said width, whereby said fabric is stabilized against shrinkage.
13. The method of stabilizing fabrics including a material selected from the group consisting of cotton fibers and cellulosic rayon fibers having free hydroxy groups comprising exposing said fabric at a temperature of about 75 F. to no higher than about 100 F. and for a time between about 1 second and 5 minutes to vapors comprising a material selected from the group consisting of: methyl trichlorosilane; dimethyl dichlorosilane; methyl dichlorosilane; trimethylchlorosilane in admixture with silicon tetrachloride; and mixtures of the foregoing materials, immediately thereafter neutralizing and removing the resulting by-products by immersing the fabric in a basic aqueous solution having a pH'between 7 and 11, then tensioning the fabric fillwise to stretch it by at least about 1% and drying it while held under tension at said width, whereby said fabric is stabilized against shrinkage.
References Cited in the file of this patent UNITED STATES PATENTS Patnode Dec. 22, 1942 Norton Dec. 10, 1946 Pfett'er et a1. Feb. 17, 1948 Thayer June 28, 1949
Claims (1)
1. THE METHOD OF STABILIZING WATER INSOLUBLE CELLULOSIC FABRICS HAVING A TREE HYDROXY GROUPS, COMPRISING EXPOSING THE SAID FABRIC FOR NOT MORE THAN ABOUT 5 MINUTES AND AT A TEMPERATURE OF LESS THAN ABOUT 100*F. TO ORGANO SILICON HALIDE VAPORS, HAVING AS ORGANO SUBSTITUTES ALKYL GROUPS WITH BETWEEN ONE AND FOUR CARBON ATOMS, THE CONDITIONS OF TIME AND TEMPERATURE BEING SUCH THAT REACTION TAKES PLACE BETWEEN THE HALOGEN OF SAID ORGANO SILICON HALIDE AND SAID FREE HYDROXY GROUPS WITH THE LIBERATION OF FREE HYDROGEN HALIDE, IMMEDIATELY THEREAFTER NEUTRALIZING AND REMOVING THE RESULTING BY-PRODUCTS BY IMMERSING THE FABRIC IN A BASIC AQUEOUS SOLUTION HAVING A PH BETWEEN 7 AND 11, THEN TENSIONING THE FABRIC AT LEAST TO SUBSTANTIALLY ITS ORIGINAL DIMENSION PRECEDING EXPOSURE TO SAID VAPORS AND DRYING IT WHILE HELD UNDER TENSION AT SAID DIMENSION, WHEREBY SAID FABRIC IS STABILIZED AGAINST SHRINKAGE.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US444917A US2782090A (en) | 1954-07-21 | 1954-07-21 | Stabilization of cellulosic fabrics by applying alkyl silicon halide vapors |
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| Application Number | Priority Date | Filing Date | Title |
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| US444917A US2782090A (en) | 1954-07-21 | 1954-07-21 | Stabilization of cellulosic fabrics by applying alkyl silicon halide vapors |
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| US2782090A true US2782090A (en) | 1957-02-19 |
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| US444917A Expired - Lifetime US2782090A (en) | 1954-07-21 | 1954-07-21 | Stabilization of cellulosic fabrics by applying alkyl silicon halide vapors |
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| US2961338A (en) * | 1958-05-07 | 1960-11-22 | Robbart Edward | Process for treating wool and other fibrous materials to impart water repellency and resistance to shrinkage |
| DE1129923B (en) * | 1958-05-23 | 1962-05-24 | Freudenberg Carl Fa | Process for the production of anti-sticking agents from rayon |
| US4151327A (en) * | 1978-02-24 | 1979-04-24 | Lawton William R | Complex amine/silane treated cellulosic materials |
| US4339479A (en) * | 1966-01-24 | 1982-07-13 | Edward Robbart | Treatment of cellulose |
| US4390692A (en) * | 1982-06-21 | 1983-06-28 | The Dow Chemical Company | Trimethylsilylation of cellulose |
| US4721587A (en) * | 1985-06-12 | 1988-01-26 | E. I. Du Pont De Nemours And Company | Process of making heat-strengthened yarn |
| US4770936A (en) * | 1985-06-12 | 1988-09-13 | E. I. Du Pont De Nemours And Company | Heat-strengthened yarn |
| US4789564A (en) * | 1987-03-31 | 1988-12-06 | Union Carbide Corporation | Hydridoaminosilane treatment for rendering surfaces water-repellent |
| US20070107630A1 (en) * | 2000-06-06 | 2007-05-17 | Edwin Neal | Preservative compositions for materials and method of preserving same |
| US20080014110A1 (en) * | 2000-06-06 | 2008-01-17 | Thompson Michael M | Preservative compositions for wood products |
| US20080276970A1 (en) * | 2007-05-09 | 2008-11-13 | John Christopher Cameron | Apparatus and method for treating materials with compositions |
| US20090261297A1 (en) * | 2000-06-06 | 2009-10-22 | Neal Edwin A | Compositions for treating materials and methods of treating same |
| US20100267303A1 (en) * | 2007-11-08 | 2010-10-21 | Aike Wypke Wijpkema | Hydrophobic surface finish and method of application |
| US20110100258A1 (en) * | 2000-06-06 | 2011-05-05 | Edwin Neal | Compositions For Treating Materials And Methods Of Treating Same |
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| US2961338A (en) * | 1958-05-07 | 1960-11-22 | Robbart Edward | Process for treating wool and other fibrous materials to impart water repellency and resistance to shrinkage |
| DE1129923B (en) * | 1958-05-23 | 1962-05-24 | Freudenberg Carl Fa | Process for the production of anti-sticking agents from rayon |
| US4339479A (en) * | 1966-01-24 | 1982-07-13 | Edward Robbart | Treatment of cellulose |
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| US20080047460A1 (en) * | 2000-06-06 | 2008-02-28 | Edwin Neal | Preservative compositions for materials and method of preserving same |
| US8721783B2 (en) | 2000-06-06 | 2014-05-13 | Dow Corning Corporation | Compositions for treating materials and methods of treating same |
| US20090053545A1 (en) * | 2000-06-06 | 2009-02-26 | Woodholdings Environmental, Inc. | Preservative compositions for materials and method of preserving same |
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| US20090261297A1 (en) * | 2000-06-06 | 2009-10-22 | Neal Edwin A | Compositions for treating materials and methods of treating same |
| US7754288B2 (en) | 2000-06-06 | 2010-07-13 | Woodholdings Environmental, Inc. | Preservative compositions for materials and method of preserving same |
| US7758924B2 (en) | 2000-06-06 | 2010-07-20 | Dow Corning Corporation | Preservative compositions for wood products |
| US7964031B2 (en) | 2000-06-06 | 2011-06-21 | Dow Corning Corporation | Compositions for treating materials and methods of treating same |
| US7838124B2 (en) | 2000-06-06 | 2010-11-23 | Dow Corning Corporation | Preservative compositions for wood products |
| US7846505B2 (en) | 2000-06-06 | 2010-12-07 | Dow Corning Corporation | Preservative compositions for materials and method of preserving same |
| US20110100258A1 (en) * | 2000-06-06 | 2011-05-05 | Edwin Neal | Compositions For Treating Materials And Methods Of Treating Same |
| US20090252873A1 (en) * | 2007-05-09 | 2009-10-08 | John Christopher Cameron | Apparatus and method for treating materials with compositions |
| US20080276970A1 (en) * | 2007-05-09 | 2008-11-13 | John Christopher Cameron | Apparatus and method for treating materials with compositions |
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| US20100267303A1 (en) * | 2007-11-08 | 2010-10-21 | Aike Wypke Wijpkema | Hydrophobic surface finish and method of application |
| US9017760B2 (en) * | 2007-11-08 | 2015-04-28 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Hydrophobic surface finish and method of application |
| US9297077B2 (en) | 2010-02-11 | 2016-03-29 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno | Method and apparatus for depositing atomic layers on a substrate |
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| US9157190B2 (en) | 2011-01-18 | 2015-10-13 | Petra International Holdings, Llc | Method for treating substrates with halosilanes |
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