US3832228A - Process for rendering keratinous fibers resistant to shrinkage - Google Patents

Process for rendering keratinous fibers resistant to shrinkage Download PDF

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Publication number
US3832228A
US3832228A US00286518A US28651872A US3832228A US 3832228 A US3832228 A US 3832228A US 00286518 A US00286518 A US 00286518A US 28651872 A US28651872 A US 28651872A US 3832228 A US3832228 A US 3832228A
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US
United States
Prior art keywords
radicals
shrinkage
substituents
keratinous fibers
wool
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
Application number
US00286518A
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English (en)
Inventor
W Gardiner
F Saunders
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Silicones UK Ltd
Original Assignee
Dow Corning Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to GB4047171A priority Critical patent/GB1396509A/en
Priority to AU45916/72A priority patent/AU447659B2/en
Application filed by Dow Corning Ltd filed Critical Dow Corning Ltd
Priority to FR7230344A priority patent/FR2150866B1/fr
Priority to US00286518A priority patent/US3832228A/en
Priority to DE2242297A priority patent/DE2242297A1/de
Application granted granted Critical
Publication of US3832228A publication Critical patent/US3832228A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain

Definitions

  • This invention relates to a shrink resistant treatment for keratinous fibers.
  • Wool fibers are known to have a scaly, ratchet-like surface which, by reason of interlocking of scales and fiber travel, gives rise to such properties as fulling, felting and shrinking. Unless wool is given a shrinkproofing treatment garments will shrink or felt in use or during washing. Several methods for shrinkproofing are available, these being generally either chemical treatments which modify the structure of the wool by removing the scales or treatments which depend for their elfect on the woollen fibers being coated with a resin. Neither type of treatment has been completely successful. The chemical treatments tend to degrade the fibers and the resin treatments tend to be difficult to apply uniformly over the fiber surface and are also liable to give the treated fabric an unsatisfactory hand.
  • this invention provides a process for rendering keratinous fibers resistant to shrinkage which comprises applying thereto from 0.5 to 10% by weight based on the weight of the fibers of one or more organopolysiloxanes of the unit general formula R SiO wherein n has an average value of from 1.9 to 2.1 and R represents an organic radical attached to silicon through a silicon to carbon bond, from 0.25 to 50 percent of the total R substituents being monovalent radicals having less than 30 carbon atoms and containing at least 3 carbon Patented Aug. 27, 1974 atoms and at least one primary or secondary amino radical NX wherein X represents hydrogen, an alkyl radical or an aryl radical, the remaining R groups (i.e.
  • R substituents being selected from the group consisting of hydrogen atoms, monovalent hydrocarbon radicals, halohydrocarbon radicals, carboxyalkyl radicals and cyanoalkyl radicals containing 1 to 30 carbon atoms, and at least 70 percent of said remaining R substituents being monovalent hydrocarbon radicals having less than 19 carbon atoms.
  • the invention also includes a shrink resistant keratinous fibers whenever treated according to said process.
  • At least 0.25 percent and up to 50 percent of the total R substituents should consist of the specified amino and imino-containing monovalent radicals.
  • the preferred organopolysiloxanes are, however, those in which the amino and imino-containing substituents comprise from 1 to 5 percent of the total R substituents.
  • the amino radicals present in the R substituents are those of the formula NX wherein X represents a hydrogen atom, an alkyl radical or an aryl radical, at least one X being hydrogen.
  • X represents a hydrogen atom, an alkyl radical or an aryl radical, at least one X being hydrogen.
  • the alkyl and aryl radicals represented by X are those having less than 19 carbon atoms and are, e.g. methyl, ethyl, propyl, butyl, octadecyl or phenyl.
  • the amino and imino-containing substituents may contain up to 30, preferably from 3 to 11, carbon atoms.
  • the nitrogen atom of any imino or amino radical in R should be linked to the silicon atom through a chain of at least 3 carbon atoms.
  • the operative imino and amino-containing substituents are the radicals, the first and third of these being preferred on the basis of commercial availability.
  • Also operative are polyalkyleneimine radicals, eg those of the general formula wherein each R" is a hydrogen atoms, an alkyl radical or an aryl radical of 1 to 18 carbon atoms, x has a value from 1 to 10 inclusive, y is 1 or 2 and R is a saturated divalent or trivalent hydrocarbon radical having at least 3 carbon atoms.
  • the remaining R groups bonded to silicon can be hydrogen atoms, hydrocarbon radicals, halohydrocarbon radicals, cyanoalkyl radicals or carboxyalkyl radicals.
  • the organic substituents contain 1 to 30 (preferably 1 to 18) carbon atoms. At least 70 percent of the remaining R substituents in the polyorganosiloxane are monovalent hydrocarbon radicals having less than 19 carbon atoms.
  • Such radicals include alkyl radicals, e.g. methyl, ethyl, propyl, nonyl, tetradecyl and octadecyl, aryl radicals, e.g.
  • R substituents may be other than hydrocarbon radicals, for example, hydrogen atoms, halogenated hydrocarbon radicals, e.g. chlorophenyl and other substituted hydrocarbon r-adicals, e.g. carboxyalkyl and cyanoalkyl.
  • substantially all of the remaining R substituents are methyl radicals.
  • the preferred polyorganosiloxanes therefore, include copolymers of dimethylsiloxane units with delta-aminobutyl(methyl)siloxane units or gamma-aminopropyl (methyl)siloxane units, copolymers of dimethylsiloxane units with methyl(N beta aminoethyl-gamma-aminopropyl)siloxane units and copolymers of dimethylsiloxane units with methyl(N-beta-aminoethyl-gamma-aminoisobutyl)siloxane units.
  • the copolymers can be end-stopped with suitable chain terminating units, for example, trimethylsiloxane units, dimethylphenylsiloxane units and dimethylvinylsiloxane units. Also, if desired, at least some of the imino and amino-containing substituents can be present in the chain terminating units.
  • the polyorganosiloxanes can vary in consistency from low molecular weight freely flowing liquids having a viscosity of 100 cs. or less at 25 C. to viscous gummy materials having viscosities in excess of 100,000 cs. at 25 C.
  • the molecular weight of the polysiloxane used will depend primarily on the desired nature of the shrinkproofing coating. Lower molecular weights make for a harder, more durable coating but require a higher pick up of siloxane by the fiber for a given shrink-proofing effect than do the higher molecular weights.
  • Organopolysiloxanes having an average degree of polymerization in the range from 50 to 400 are generally preferred.
  • any suitable coating of impregnating technique may be employed in carrying out the application of the polyorganosiloxane to the fiber according to the process of this invention.
  • the organosiloxane may be applied as such or, more preferably, as a dispersion or solution in a liquid carrier.
  • Suitable carriers include organic solvents, for example, hydrocarbons and halogenated hydrocarbons, e.g. benzene, hexane or perchloroethylene.
  • the polyorganosiloxane is applied by spraying or by immersion of the fiber in an organic solvent solution of the polyorganosiloxane.
  • keratinous fibers as employed herein includes fibers of any animal hair, for example, sheep wool, mohair, cashmere, alpaca wool and vicuna wool.
  • the fibers may be treated in any desired form, for example, as yarn, as fabric or as made up or partially made up goods. In general, the best results are obtained with keratinous fibers which have been chlorinated.
  • the application conditions should be chosen such that the pick up of polyorganosiloxane by the fiber is from 0.5 to 10% by weight of polyorganosiloxane based on the weight of the fiber. In most cases, the desired property is attained with less than 10% by weight and it is preferred to use from 0.5 to 5%.
  • the fibers After application of the organopolysiloxane, the fibers are dried and aged to fix the siloxane on the fiber. Although some fixation may occur on aging at room temperature, inconveniently long aging periods are required to obtain optimum results. Drying of the fiber and fixing of the siloxane is, therefore, preferably achieved by heating the treated fibers to temperatures in the range from 40 to 160 C. for from one minute to one hour.
  • the polyorganosiloxane may be applied in conjunction with organosiloxanes of the type normally employed as water repellent treatments for fibers, for example, polydimethylsiloxanes, methylhydrogenpolysiloxanes and mixtures of the two.
  • Example 1 An organopolysiloxane having a viscosity of 20,000 cs. at 25 C. and composed of 3 mole percent of methyl(N- beta,aminethyl-garnma-aminoisobutyl)siloxy units, 97 mole percent of dimethylsiloxy units and end-stopped with trimethylsiloxy units was dissolved in toluene in a proportion of 5 parts by weight of polysiloxane to 95 parts by weight of toluene.
  • This solution was used to treat 3 samples of 1:1 cover factor knitted botany wool fabric by padding at 100% mangle expression. After treatment, the samples were allowed to air dry at 22 C. for 1 hour and then placed in an air circulating oven for 5 minutes at 110 C.
  • Percent area felting shrinkage (FS) [peroent width shrinkage (WS) [WSXLS] percent length shrinkage (LS)]-
  • the width shrinkage and length shrinkage were determined according to the formula Width or length shrinkage dimension after 5 minutes dimension after 3 hours.
  • n has an average value of from 1.9 to 2.1 and R represents an organic radical attached to silicon through a silicon to carbon bond, from 0.25 to 50 percent of the total R substituents being monovalent radicals composed of carbon, hydrogen and nitrogen, said radicals having less than 30 carbon atoms and containing at least 3 carbon atoms distant from the silicon atom at least one imino and at least one primary or secondary amino radical NX wherein X represents a hydrogen atom, an alkyl radical or an aryl radical, the remaining R substituent being selected from the group consisting of hydrogen atoms, monovalent hydrocarbon radicals, monovalent halogenated hydrocarbon radicals, carboxyalkyl radicals and cyanoalkyl radicals, said radicals containing 1 to 30 carbon atoms, at least 70 percent of the remaining R substituents being monovalent hydrocarbon radicals having less than 19 carbon atoms and thereafter drying the fiber and fixing the siloxane by heating the treated fibers to a temperature in the range from 40 to C. for from one minute to one

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
US00286518A 1971-08-28 1972-08-25 Process for rendering keratinous fibers resistant to shrinkage Expired - Lifetime US3832228A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
GB4047171A GB1396509A (en) 1971-08-28 1971-08-28 Treatment of keratinous fibres
AU45916/72A AU447659B2 (en) 1971-08-28 1972-08-24 Shrink resistant treatment for keratinous fibres
FR7230344A FR2150866B1 (cs) 1971-08-28 1972-08-25
US00286518A US3832228A (en) 1971-08-28 1972-08-25 Process for rendering keratinous fibers resistant to shrinkage
DE2242297A DE2242297A1 (de) 1971-08-28 1972-08-28 Verfahren zur veredelung von fasern

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB4047171A GB1396509A (en) 1971-08-28 1971-08-28 Treatment of keratinous fibres
US00286518A US3832228A (en) 1971-08-28 1972-08-25 Process for rendering keratinous fibers resistant to shrinkage

Publications (1)

Publication Number Publication Date
US3832228A true US3832228A (en) 1974-08-27

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US00286518A Expired - Lifetime US3832228A (en) 1971-08-28 1972-08-25 Process for rendering keratinous fibers resistant to shrinkage

Country Status (4)

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US (1) US3832228A (cs)
DE (1) DE2242297A1 (cs)
FR (1) FR2150866B1 (cs)
GB (1) GB1396509A (cs)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4247592A (en) * 1980-03-12 1981-01-27 Dow Corning Corporation Method for treating synthetic textiles with aminoalkyl-containing polydiorganosiloxanes
US4248590A (en) * 1978-03-16 1981-02-03 Th. Goldschmidt Ag Preparation for shrinkproofing wool
US4277242A (en) * 1977-02-07 1981-07-07 Australian Atomic Energy Commision Ionizing radiation treatment of wool textiles with resin for shrink resistance
US4283191A (en) * 1979-03-23 1981-08-11 Th. Goldschmidt Ag Preparation for shrinkproofing wool
US4403011A (en) * 1980-12-18 1983-09-06 Ciba-Geigy Corporation Process for the treatment of wool containing material

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1565241A (en) * 1976-07-21 1980-04-16 Goldschmidt Ag Th Process for rendering wool shrink-resistant

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4277242A (en) * 1977-02-07 1981-07-07 Australian Atomic Energy Commision Ionizing radiation treatment of wool textiles with resin for shrink resistance
US4248590A (en) * 1978-03-16 1981-02-03 Th. Goldschmidt Ag Preparation for shrinkproofing wool
US4283191A (en) * 1979-03-23 1981-08-11 Th. Goldschmidt Ag Preparation for shrinkproofing wool
US4247592A (en) * 1980-03-12 1981-01-27 Dow Corning Corporation Method for treating synthetic textiles with aminoalkyl-containing polydiorganosiloxanes
US4403011A (en) * 1980-12-18 1983-09-06 Ciba-Geigy Corporation Process for the treatment of wool containing material

Also Published As

Publication number Publication date
AU4591672A (en) 1974-02-28
FR2150866A1 (cs) 1973-04-13
GB1396509A (en) 1975-06-04
DE2242297A1 (de) 1973-03-01
FR2150866B1 (cs) 1975-01-03

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