US3788884A - Textile material coated with a waterproofing agent - Google Patents

Textile material coated with a waterproofing agent Download PDF

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Publication number
US3788884A
US3788884A US3788884DA US3788884A US 3788884 A US3788884 A US 3788884A US 3788884D A US3788884D A US 3788884DA US 3788884 A US3788884 A US 3788884A
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US
United States
Prior art keywords
tolylene
bis
waterproofing
fabric
desmodur
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Expired - Lifetime
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English (en)
Inventor
J Neel
A Bernard
G Gras
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SOLTEX SOC CIV
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SOLTEX SOC CIV
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
    • C07C273/1809—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety
    • C07C273/1818—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety from -N=C=O and XNR'R"
    • C07C273/1827—X being H
    • 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
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • 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
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/405—Acylated polyalkylene polyamines
    • 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
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/425—Carbamic or thiocarbamic acids or derivatives thereof, e.g. urethanes
    • 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
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/402—Amides imides, sulfamic acids
    • D06M13/432—Urea, thiourea or derivatives thereof, e.g. biurets; Urea-inclusion compounds; Dicyanamides; Carbodiimides; Guanidines, e.g. dicyandiamides
    • 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
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/10—Processes in which the treating agent is dissolved or dispersed in organic solvents; Processes for the recovery of organic solvents thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2221—Coating or impregnation is specified as water proof
    • Y10T442/2246—Nitrogen containing

Definitions

  • the present invention relates to new agents for making textiles water-repellent. It also relates to a process of applying these agents to textiles.
  • One aspect of the invention relates to organic compounds intended for waterproofing textiles. Another aspect relates to a process of applying those compounds, providing an excellent water-repellency to all the types of textile materials, such water-repellency having especially the advantage of permanency, that is the ability to resist to repeated washings and degreasings.
  • the new waterproofing agents according to the invention are organic compounds having the general formula:
  • R is a tolylene or hexamethylene radical
  • a and B identical or different, may be groups NHR, or NHR N(R or N(R OR, or 0R R or R in which R and R identical or different, are aliphatic hydrocarbon radicals of the formula C H L n being an integer comprised between 12 and 22.
  • Those compounds may be obtained by means of any classical techniques in the field of the contemplated products.
  • they may be formed from tolyleneor hexamethylene-diisocyanate.
  • Tolylene diisocyanate may be constituted by a mixture of isomers and especially be the commercial product containing 20% isomer 2,6 and 80% isomer 2,4 known under the name of Desmodur T80 (registered trademark).
  • About symmetric derivatives, that is derivatives of which the radicals A and B are identical, bis-ureas may be prepared by reaction of the convenient isocyanate and amine, in an organic solvent which is inert under reaction conditions, specially a chlorobenzene or acetone.
  • Biscarbamates are obtained by heating of convenient isocyanate and alcohol in an inert solvent in the presence of a tertiary amine as a catalyst.
  • bis-amides may be prepared by reacting hexamethylene or tolylene-diisocyanate with an aliphatic acid, in the presence of a catalyst which may be a tertiary amine.
  • the asymmetric derivatives may have either different hydrocarbon radicals R and R or different functional groupsureacarbamateamide, or those two differences at the same time.
  • R and R hydrocarbon radicals
  • the compounds are obtained by means of the precited methods in reacting simultaneously on isocyanate the two types of necessary reagents; in the other cases a two-stage process is necessary.
  • Examples of the present compounds are hexamethylenebis (3 octadecylurea) hexamethylene-bis-octadecanamide; hexamethylene-bis (O-tetradecyl carbamate); the 2,4 and 2,6 isomers, alone or in admixture, of tolylene-bis(3- dodecylurea), of tolylene-bis(3-tetradecylurea), of tolylene-bis(3 hexadecylurca), of tolylene-bis( 3 octadecylurea), of tolylene-bis(3-dioctadecylurea), tolylene-bis (O- tetradecyl carbamate), tolylene-bis (O-octadecyl carbamate), of tolylene-bis (O-eicosyl carbamate), of tolylenebis-hexadecanamide, of tolylene-bis-oct
  • the process of applying such waterproofing agents to textiles which is also an object of the present invention, consists'essentially of impregnating textiles with organic solutions of such agents, then of cross-linking the agents by means of polyisocyanates. Practically the process is generally carried out by providing organic solutions of the waterproofing agent, to which is added the polyisocyanate used for further cross-linking, and possibly a catalyst of known type which accelerates this reaction, then in applying this solution on the fabric by any classical method such as spraying or padding, and then, after solvent removing, in submitting the fabric to a thermal treatment in order to obtain cross-linking.
  • the concentration of the waterproofing agent in the organic solution may vary within large limits. It is, however, advantageous to use between 20 and gm. per liter of solution.
  • the solvents which may be used are the ones which have been quoted hereinabove as suitable for dissolving the compounds of Formula I in the hot or cold. At the hereinabove given concentrations the obtained solutions are slightly viscous and have a translucid appearance.
  • isocyanates for cross-linking the waterproofing agents all the types of known diand polyisocyanates may be used, and for example hexamethylene-diisocyanate or its reaction product with water having the commercial name of Desmodur N (registered trademark); tolylene-diisocyanate and especially the mixture of precited isomers, known under the name of Desmodur T80; diphenyl-methane diisocyanate; the mixture of diphenylmethane diisocyanate and of its higher homologs having the commercial name of Desmodur VL (registered trademark); a polyisocyanate having an isocyanurate structure, such as Desmodur IL (registered trademark); a triisocyanate resulting from condensing trimethylol propane and tolylene diisocyanate, such as Desmodur L (registered trademark), etc.
  • Desmodur N registered trademark
  • tolylene-diisocyanate and especially the mixture of precited isomers known under the
  • the quantity of isocyanate to be used must be at least equal to that theoretically necessary to cross-link the waterproofing agent. However, it is preferred to use an excess of isocyanate, for example, 50 to 150% excess, i.e. ISO-250% based on 100% agent.
  • the convenient accelerating agents are, for example, tertiary amines such as methyl diethyl amine, triethyl amine, N- methyl morpholine, organo-metallic compounds, such as tetramethyl tin, dibutyl tin dilaurate, metal salts of organic acids such as zinc octanoate, cobalt naphthenate, etc.
  • mixtures prepared in this way containing the derivative of Formula I in solution, polyisocyanate and optionally, reaction accelerating agent, are stable in the cold and may be kept as such for several days. They are applied on fabrics at room temperature or at a higher temperature, for example at 50 80 C.
  • the textile material is impregnated according to classical technique such as spraying or padding, followed by squeezing.
  • the quantity of impregnating solution is adjusted, taking into account its concentration, in order to obtain the desired proportion of dry extract (calculated on the basis of waterproofing agent +polyisocyanate) on fabric.
  • This proportion is favorably comprised between 0.5 and preferably 1 to 3% with regard to the weight of the treated textile.
  • the new waterproofing agents and the application process according to the invention may be used for all the types of textiles, constituted either by natural fibers such as cotton, linen, wool or blends, or artificial fibers such as viscose, rayon, cellulose acetates, or synthetic fibers such as polyacrylic fibers, polyesters, polyamides, or still by their mixtures as for example associations polyestercotton, polyester-viscose, etc. They are especially interesting for synthetic textiles such as polyamides, which, it is known, are the most difiicult to hydrofuge.
  • the obtained waterproofing is at the beginning generally superior than the one brought about by known products and it resists conveniently to washings and/ or degreasings much better than the known materials.
  • Examples 1 to 5 describe the preparation of waterproofing agents.
  • the following examples relate to tests of waterproofing various textiles.
  • EXAMPLE 1 For this test a device has been used which was contituted by a reactor provided with a stirrer, a thermocouple, a system for introducing isocyanate and surmounted by a cooler.
  • the product has been identified as being a mixture of the 2,4 and 2,6 isomers of tolylene-bis (3-octadecylurea).
  • EXAMPLE 2 In a device identical to the one of Example 1, there was loaded kg. of acetone and 80 kg. of dioctadecylamine, at room temperature. Then there was introduced in 45 min. under strong stirring 13.4 kg. of Desmodur T80 in solution in 50 kg. of acetone, maintaining the temperature near 30 C. After the end of addition, the reaction mixture was heated under reflux for 1 hour. After cooling, the formed white crystalline solid was isolated by filtration; after air drying, it weighed 80 kg.
  • This product has been identified as being a mixture of the 2,4 and 2,6 isomers of tolylene-bis (3-dioctadecylurea)-(nitrogen content: calculated 4.60; found 4.65).
  • EXAMPLE 3 In a device of the same type as in Example 1, there was introduced 1 kg. of trichlorethylene, 320 g. of 1- octadecanol and 1 g. of triethylamine, to which 110 g. of Desmodur T80 was added slowly. After cooling at 20 C. the reaction mixture was filtered and the isolated white solid was washed with acetone; this solid had a weight of 330 g. and has been identified as being a mixture of the 2,4 and 2,6 isomers of tolylene-bis (O-octadecyl carbamate). Its melting point is 90-92 C. (nitrogen content: calculated 3.92; found 4.03).
  • the numbers correspond to the average of 4 measures achieved in 4 different points of the samples.
  • compositions were used to pad samples of poly- 15 amide to obtain a deposit of 2 to 3% of dry mate wherein R is a tolylene or hexamethylene radical,
  • R is a tolylene or hexamehtylcne radical
  • a 50 and B are selected from the group consisting of WILLIAM MARTIN Pnmary Exammer NHR NHR N(R N(R 0R 0R R and T. G. DAVIS, Assistant Examiner R, in which R and R are selected from the group consisting of aliphatic hydrocarbon radicals of for- .”U.S. Cl. X.R.
  • mula CnHZnw being an integer betwm 12 and 55 117-138.8 F, 138.8 N, 138.8 UA, 141, 143 R, 144 22, inclusive;

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US3788884D 1968-12-19 1971-02-16 Textile material coated with a waterproofing agent Expired - Lifetime US3788884A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR69050775A FR1604745A (fr) 1968-12-19 1968-12-19
FR6938618A FR2069844B2 (fr) 1968-12-19 1969-11-06

Publications (1)

Publication Number Publication Date
US3788884A true US3788884A (en) 1974-01-29

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ID=33436242

Family Applications (1)

Application Number Title Priority Date Filing Date
US3788884D Expired - Lifetime US3788884A (en) 1968-12-19 1971-02-16 Textile material coated with a waterproofing agent

Country Status (9)

Country Link
US (1) US3788884A (fr)
BE (1) BE743372A (fr)
CH (2) CH1887269A4 (fr)
DE (1) DE1963574C3 (fr)
FR (2) FR1604745A (fr)
GB (1) GB1279109A (fr)
IL (1) IL33550A (fr)
NL (1) NL6918935A (fr)
SE (1) SE372569B (fr)

Also Published As

Publication number Publication date
DE1963574C3 (de) 1974-12-12
GB1279109A (en) 1972-06-28
CH1887269A4 (fr) 1973-02-28
IL33550A (en) 1973-03-30
DE1963574B2 (de) 1973-06-14
FR2069844A2 (fr) 1971-09-10
SE372569B (fr) 1974-12-23
NL6918935A (fr) 1970-06-23
FR2069844B2 (fr) 1975-02-14
IL33550A0 (en) 1970-02-19
BE743372A (fr) 1970-05-28
CH540384A (fr) 1973-02-28
DE1963574A1 (de) 1970-07-02
FR1604745A (fr) 1972-01-24

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