US3338661A - Cellulosic fabrics rendered crease resistant and water repellant through treatment with compositions comprising catalyst-water repellant silicones and sulfone crosslinking agents - Google Patents

Cellulosic fabrics rendered crease resistant and water repellant through treatment with compositions comprising catalyst-water repellant silicones and sulfone crosslinking agents Download PDF

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Publication number
US3338661A
US3338661A US407210A US40721064A US3338661A US 3338661 A US3338661 A US 3338661A US 407210 A US407210 A US 407210A US 40721064 A US40721064 A US 40721064A US 3338661 A US3338661 A US 3338661A
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United States
Prior art keywords
water repellant
siliconate
sulfone
fabric
group
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Expired - Lifetime
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US407210A
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English (en)
Inventor
John W Gilkey
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 Corp
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Dow Corning Corp
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Filing date
Publication date
Application filed by Dow Corning Corp filed Critical Dow Corning Corp
Priority to US407210A priority Critical patent/US3338661A/en
Priority to FR32274A priority patent/FR1449152A/fr
Priority to GB44281/65A priority patent/GB1131047A/en
Priority to DE19651469334 priority patent/DE1469334A1/de
Priority to AT968065A priority patent/AT256773B/de
Priority to NL6513899A priority patent/NL6513899A/xx
Application granted granted Critical
Publication of US3338661A publication Critical patent/US3338661A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
    • D06M13/272—Unsaturated compounds containing sulfur atoms
    • D06M13/278—Vinylsulfonium compounds; Vinylsulfone or vinylsulfoxide compounds
    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups

Definitions

  • This invention relates to a method of producing a fabric which is both crease resistant and water repellent.
  • Z is of the group consisting of -SSO M, -OSO M, quaternary ammonium salt residues attached to the CH CH group through carbon-nitrogen bonds, and OR groups in which M is an anion,
  • 'R' is of the group hydrogen, lower aliphatic hydro- .car-bon radicals and acyl radicals derived frpm lower aliphatic carboxylic acids,
  • R is a divalent hydrocarbon radical, any valence of the N of the NR N group not satisfied by R groups and the CH CH group being satisfied by monovalent hydrocarbon radicals,
  • n is an integer from 1 to 2 inclusive and X is of the group divalent hydrocarbon radicals and divalent radicals attached to the S by a CS linkage, and being composed of C, H and O atoms in the form of ether linkages and (2) Alkali metal salt of an aliphatic hydrocarbon siliconate having an average of .9 to 1.3 hydrocarbon radicals per silicon atom, said hydrocarbon radicals having from 1 to 4 inclusive carbon atoms, in amount such that the weight pickup of (1) and (2) on the fabric is at least 1% by weight and .5% by weight respectively andthereafter heating the treated fabric to a degree sufficient to give a crease resistant and water repellent fabric.
  • the cellulosic fabric such as cotton, rayon, acetate, linen, or the like or blends of cellulosic fibers with other fibers such as cotton and polyester, is contacted in any desired manner with an aqueous dispersion of (1) and (2).
  • the fabric can be dipped, sprayed or padded with the dispersion.
  • the fabric is then dried and heated to such an extent that the sulfone reacts with the cellulose to crosslink it imparting the crease resistant property.
  • the siliconate makes the fabric water repellent.
  • the treating medium be alkaline.
  • the siliconate When the siliconate is employed in amount of at least 1% by weight of the treating solution, it alone will furnish sufficient alkalinity to cause the sulfone to react with the cellulose.
  • the siliconate when the siliconate is employed in an amount less than 1%, it is often desirable to add additional alkali to the solution in the form of materials such as sodium hydroxide or potassium carbonate in order to obtain the desired degree of alkalinity. If desired, additional alkali can be employed in any event.
  • the sulfones which are operative in this invention are divinylsulfone and sulfones of the formula in which Z can be thiosul-fate salt groups of the formula $50 M, in which M can be any anion such as sodium, potassium, ammonium, cesium, or other metals. Prefera- 'bly the anion is one which will render the sulfone water soluble or at least water dispersible. Z can also be the sulfate group OSO M where M is any anion as shown above.
  • Z can also be any quaternary amonium salt residue such as those derived from pyridine hydrochloride, quinoline hydrochloride, trimethylamine, ethyldimethylamine, benzyldimethylamine, allyldiethylamine, or any other tertiary amine.
  • Z can be a hydroxyl, a lower alkoxy group such as methoxy, ethoxy, butoxy, or 2-ethylhexoxy or an unsaturated aliphatic hydrocarbonoxy group such as allyloxy or hexenyloxy or Z can be an acyl group derived from any lower aliphatic carboxylic acid. Examples of such groups are formyl, acetyl, propionyl, acrylyl or methacrylyl.
  • X can also be a hydrocarbon ether radical such as CH3 C2115 CHzCHzOCHzCHz, CHOHgOCHzCHz,CHCH2OCHzCHz and CH CH OCH CH CH CH (1)
  • Can also be a disulfone of the formula CH CHSO CH CH NR NCH CH SO CH CHQ in which R is a divalent hydrocarbon radical.
  • the NR N grouping is derived from a bis-secondary amine and can be of two types. When n is 1, the group has the formula in which R is a divalent hydrocarbon radical, and R" is a monovalent hydrocarbon radical. These groups, of course, are derived from linear bis-secondary amines. The second type of NR N group arises when n is 2.
  • the group is of a cyclic structure and there are two monovalent hydrocarbon radicals between the nitrogens, the latter, of course, being a part of the cyclic structure.
  • These groups are derived from bis-secondary cyclic amines such as in which x is an integer. Specific examples of such amines are those in which x is 2, 3 and 5.
  • Ingredient (2) can be any alkali metal salt of an aliphatic hydrocarbon siliconate in which the hydrocarbon groups are from 1 to 4 carbon atoms.
  • the siliconates can contain some unsubstituted silicon atoms and some di-substituted silicon atoms such as dimethylsiliconate, ethylmethylsiliconate, methylvinyl siliconate, etc.
  • some of the silicon atoms in the siliconate structure can be linked through alkylene bridges in which the bridges are methylene, ethylene, trimethylene, or butylene.
  • the above alkali metal siliconates are well-known materials and are available commercially.
  • the alkali metal can be any alkali metal such as lithium, sodium, potassium or cesium and the alkali metal can be present in ratios from 1 to 3 alkali metal atoms per silicon.
  • the solubility of the alkali metal siliconate varies with the alkali metal and with the size and number of hydrocarbon groups attached to the silicon.
  • the lithium salts are the least soluble and the cesium salts are most soluble of the alkali metal siliconates.
  • the amount of (1) and (2) employed should be such that the fabric will pickup at least 1% by weight of (1) and at least /2% by weight of (2).
  • the upper limit of these ingredients is not critical although for cost reasons it is preferable that the fabric contain no more than 5% by weight silicone.
  • (1) should be employed in amount of from 1 to by weight although more can be employed if desired.
  • Fabrics treated in accordance with this invention are both crease resistant and water repellent and they retain these properties after repeated washings. Consequently, the fabrics so treated are useful in a wide variety of applications.
  • the crease recovery of the fabrics in the following examples was determined in accordance with AATCC Method 66-1959T and the spray rating was determined in accordance with AATCC Method 22-1964.
  • Example 1 A solution of 9.37 g. of bis-beta-hydroxyethyl sultone and 1.87 g. of sodium methyl siliconate diluted to 100 g. in distilled water was prepared. Samples of 80 x 80 cotton cloth were padded with this solution, air dried and cured 1 /2 minutes at 350 F. The cured samples were bleached with hydrogen peroxide (2%) in a .5%
  • the bleached fabric was rinsed with warm water and air :dried.
  • the spray rating was determined and the crease recovery angles measured after overnight conditioning in a constant temperature room at 72 F. and 50% relative humidity.
  • the crease recovery angle is the sum of the average of three measurements in the warp and three measurements in the fill directions of the fabric. For comparison a run was made in which no alkaline material was added to the bath and one was made in which sodium carbonate was used in place of the siliconate.
  • Example 1 The procedure of Example 1 was repeated employing 8% bis-beta-hydroxyethyl sulfone and varying concentrations of sodium methyl siliconate and sodium propyl siliconate as shown below.
  • Example 3 Washes Crease Recovery, Spray Rating Initial 243 so 1 234 70 255 70 243 70
  • Example 4 A solution was made by dissolving 9.37 g. of bis-betahydroxyethyl sulfone and 1.87 g. of potassium butyl siliconate in g. of distilled water containing some ethanol. 80 x 80 cotton cloth was padded in accordance with the procedure of Example 1. The fabric was then laundered under the conditions of Example 3. The results are as follows:
  • Example 5 Equivalent results are obtained when sodium vinyl siliconate and a siliconate composed of a mixture of sodium ethyl siliconate and one of the structure CH (NaO)3S iCH2OH2Si(ONn)3 are employed in the procedure of Example 1.
  • Z is selected from the group consisting of -SSO M, OSO M, quarternary ammonium salt residues attached to the CHgCHz group through a carbon-nitrogen bond and OR groups, in which M is an anion,
  • R is selected from the group consisting of hydrogen, lower aliphatic hydrocarbon radicals and acyl radicals derived from lower aliphatic carboxylic acids,
  • R is a divalent hydrocarbon radical, any valence of the nitrogen of the group NR N not satisfied by R groups and the CH CH group being satisfied by monovalent hydrocarbon radicals,
  • n is an integer from 1 to 2 inclusive
  • X is selected from the group consisting of divalent hydrocarbon radicals and divalent radicals attached to the S by a CS linkage and being composed of carbon, hydrogen and oxygen atoms in the form of ether linkages and (2) an alkali metal salt of an aliphatic hydrocarbon siliconate having an average of from .9 to 1.3 hydrocarbon radicals per silicon, said hydrocarbon radicals having from 1 to 4 inclusive carbon atoms in amount such that the weight pickup of (1) and (2) on the fabric is at least 1% by weight and .5 by weight respectively and thereafter heating the treated fabric to a degree sufiicient to give a crease resistant and water repellent fabric.
  • composition of matter an aqueous dispersion containing at least 1% by weight based on the weight of the dispersion of composition (1) of claim 1 and at least .5 by weight based on the weight of the dispersion of composition (2) of claim 1.
  • composition in accordance with claim 5 in which (1) is bis-beta-hydroxyethyl sulfone.
  • composition in accordance with claim 5 in which (1) is bis-beta-hydroxyethyl sulfone and (2) is sodium methyl siliconate.
  • composition in accordance with claim 5 in which (1) is his beta-hydroxyethyl sulfone and (2) is sodium propyl siliconate.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
US407210A 1964-10-28 1964-10-28 Cellulosic fabrics rendered crease resistant and water repellant through treatment with compositions comprising catalyst-water repellant silicones and sulfone crosslinking agents Expired - Lifetime US3338661A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US407210A US3338661A (en) 1964-10-28 1964-10-28 Cellulosic fabrics rendered crease resistant and water repellant through treatment with compositions comprising catalyst-water repellant silicones and sulfone crosslinking agents
FR32274A FR1449152A (fr) 1964-10-28 1965-09-22 Tissus cellulosiques hydrofuges, infroissables
GB44281/65A GB1131047A (en) 1964-10-28 1965-10-19 Crease-resistant, water-repellent cellulosic fabrics
DE19651469334 DE1469334A1 (de) 1964-10-28 1965-10-21 Verfahren zur wasserabweisenden und knitterfesten Ausruestung von Cellulosegeweben in einem Arbeitsgang
AT968065A AT256773B (de) 1964-10-28 1965-10-26 Verfahren zur wasserabweisenden und knitterfesten Ausrüstung von Cellulosegeweben
NL6513899A NL6513899A (esLanguage) 1964-10-28 1965-10-27

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US407210A US3338661A (en) 1964-10-28 1964-10-28 Cellulosic fabrics rendered crease resistant and water repellant through treatment with compositions comprising catalyst-water repellant silicones and sulfone crosslinking agents

Publications (1)

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US3338661A true US3338661A (en) 1967-08-29

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US (1) US3338661A (esLanguage)
AT (1) AT256773B (esLanguage)
DE (1) DE1469334A1 (esLanguage)
GB (1) GB1131047A (esLanguage)
NL (1) NL6513899A (esLanguage)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3000762A (en) * 1960-08-25 1961-09-19 Stevens & Co Inc J P Process for reacting polymeric materials with sulfones and products resulting therefrom
US3031435A (en) * 1960-10-05 1962-04-24 Giuliana C Tesoro Products of polyvinyl alcohol compounds with divinyl sulfone and processes for preparation thereof
US3178250A (en) * 1961-07-10 1965-04-13 Gen Aniline & Film Corp Fiber improving process and product
US3194627A (en) * 1956-04-03 1965-07-13 Deering Milliken Res Corp Processes for producing modified cellulosic textile materials
US3218118A (en) * 1958-07-23 1965-11-16 Rohm & Haas Crease-proofing cellulosic fabrics, the fabrics obtained and methods of making them
US3222119A (en) * 1959-03-10 1965-12-07 Monsanto Co Process for treating cellulosic textile materials with bis(beta-methoxyethyl) sulfone

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3194627A (en) * 1956-04-03 1965-07-13 Deering Milliken Res Corp Processes for producing modified cellulosic textile materials
US3218118A (en) * 1958-07-23 1965-11-16 Rohm & Haas Crease-proofing cellulosic fabrics, the fabrics obtained and methods of making them
US3222119A (en) * 1959-03-10 1965-12-07 Monsanto Co Process for treating cellulosic textile materials with bis(beta-methoxyethyl) sulfone
US3000762A (en) * 1960-08-25 1961-09-19 Stevens & Co Inc J P Process for reacting polymeric materials with sulfones and products resulting therefrom
US3031435A (en) * 1960-10-05 1962-04-24 Giuliana C Tesoro Products of polyvinyl alcohol compounds with divinyl sulfone and processes for preparation thereof
US3178250A (en) * 1961-07-10 1965-04-13 Gen Aniline & Film Corp Fiber improving process and product

Also Published As

Publication number Publication date
NL6513899A (esLanguage) 1966-04-29
AT256773B (de) 1967-09-11
GB1131047A (en) 1968-10-16
DE1469334A1 (de) 1968-12-19

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