US3484272A - Process for coating a substrate of keratinous fibers with polyamide - Google Patents

Process for coating a substrate of keratinous fibers with polyamide Download PDF

Info

Publication number
US3484272A
US3484272A US585404A US3484272DA US3484272A US 3484272 A US3484272 A US 3484272A US 585404 A US585404 A US 585404A US 3484272D A US3484272D A US 3484272DA US 3484272 A US3484272 A US 3484272A
Authority
US
United States
Prior art keywords
wool
bis
sebacate
mmol
hexamethylene diamine
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
US585404A
Other languages
English (en)
Inventor
Helmut Zahn
Mamoun Bahra
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.)
IWS Nominee Co Ltd
Original Assignee
IWS Nominee Co 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
Application filed by IWS Nominee Co Ltd filed Critical IWS Nominee Co Ltd
Application granted granted Critical
Publication of US3484272A publication Critical patent/US3484272A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • 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
    • D06M15/59—Polyamides; Polyimides
    • 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
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2964—Artificial fiber or filament
    • Y10T428/2967—Synthetic resin or polymer
    • Y10T428/2969—Polyamide, polyimide or polyester

Definitions

  • the present invention relates to the coating of fibrous or filamentary, flexible substrates with a polymer.
  • substrates are preferably natural fibrous substrates, such as keratinous fibers, cotton, silk etc.
  • substrates also means products which have been manufactured from the fibrous or filamentary materials, such as slivers, yarns, combings, woven or knitted fabrics etc. Further examples of bercontaining materials are paper, cardboard and the like.
  • Filamentary substrates in the sense of the invention, which are not of natural origin, include for example synthetic threads or fibers.
  • a special object of the present invention is to coat keratinous or keratin-containing fibers, the coating being effected with a polyamide film.
  • Keratin-containing fibers in this sense include wool fibers in particular.
  • the expression wool or wool fibers when used in connection with the invention is to be understood as including all kinds of keratincontaining fibers, and in particular fibers which are obtained from the fleece of sheep, goats, llamas, vicunas7 alpacas etc., where nothing to the contrary is said in the specification.
  • the present invention arises from the problem of avoiding the obvious and known disadvantages, which result from the use of acid chlorides and organic solvents and ICC which arise particularly in the treatment of natural fibrous or filamentary materials such as have been mentioned above. This applies particularly to the non-felting treatment of keratinous fibers. It has been found, surprisingly, that these disadvantages can be overcome if treatment is carried out in an aqueous emulsion or solution Without the use of an acid chloride.
  • the process for coating fibrous or filamentary substrates with a polymer is characterised in that a diamine and a dicarboxylic acid ester in dilute form are reacted in the presence of the substrate, in some cases using elevated temperatures.
  • the substrates are preferably present in cleaned or purified form, in order that the layer formed as a film on the substrate may be unitary as far as possible.
  • the reaction is preferably carried out in an aqueous medium, and possibly in the presence of small quantities of an inert organic solvent.
  • concentrations used should be so chosen that a coating of the required thickness is formed on the substrate. The thickness of the coating depends, apart from the concentration of the aqueous solution or dispersion employed, on the type of substrate.
  • Absorbent substrates which therefore take up a certain quantity of the aqueous solution or dispersion, will therefore receive, even with low concentrations, thicknesses of coating such as can be obtained only with higher concentrations in the case of non-absorbent substrates.
  • the person skilled in the art can easily determine the optimum conditions for each substrate by tests. In general, coatings having a weight of about 1-4%, preferably about 2-3%, referred to the dry weight of the coated substrate, are required.
  • Suitable starting materials within the meaning of the invention are, in particular, aliphatic diamines and esters of aliphatic dicarboxyl acids, in particular dicarboxylic acid derivatives and diamines such as are customarily used in the manufacture of polyamides (nylon).
  • aliphatic diamines and esters of aliphatic dicarboxyl acids in particular dicarboxylic acid derivatives and diamines such as are customarily used in the manufacture of polyamides (nylon).
  • dicarboxylic acid derivatives and diamines such as are customarily used in the manufacture of polyamides (nylon).
  • nylon polyamides
  • dicarboxylic esters which can be used for the purposes of the invention include the activated esters of succinic acid, adipic acid, suberic acid and dodecandioic acid.
  • activated dicarboxylic acid ester are to be understood those in the sense of R. Schwyzer, B. Iselin and M. Feuver (Helv. chim. Acta, '38 (1955), 69).
  • the activation is effected by electron-attracting groups, whereby the carbonyl carbon atom is made positive and is rendered more readily accessible to a nucleophilic attack by amino groups.
  • the steeping of the substrate with the solution or emulsion of the reaction components may be carried out in a one-bath or a two-bath operation.
  • the substrate is preferably steeped with a mixture of an aqueous solution of hexamethylene diamine and an aqueous emulsion of a sebacic acid ester prepared at about 5 C. and the reaction components are caused to react together on the wool by warming to room temperature or above.
  • This process may be used in particular when the velocity of reaction between the reaction components, for example between the sebacic ester and hexamethylene diamine, is not too high.
  • Sebacic esters having such relatively high reaction velocities are, for example, bis-2,4,5-trichlorophenyl sebacate, bis-o-nitro phenyl sebacate and bis-p-nitrophenyl sebacate.
  • the reaction components are then caused to react together on the substrate.
  • the wool or wool fibers are impregnated with the aqueous solution and emulsion, preferably until a weight increase of 8090% based on the weight of the conditioned wool has occurred. After steeping, the wool is preferably treated with steam, which brings about the formation of the polyamide.
  • the speed of formation of the polyamide is essentially a function of the reaction temperature and time. The higher the reaction temperature the shorter the reaction time.
  • the formation of the polyamide may, for example, be effected by warming the wool, steeped with the above-mentioned mixture of aqueous solution and aqueous emulsion prepared at 5 C., to room temperature.
  • the reaction times are relatively long in this case and amount to many hours. With heating to 40, 60, 80 C. and above the reaction time is shortened considerably and amounts only to a few minutes. Since extended reaction times are harmful to the wool, short reaction times are desirable.
  • the Wet tensile strength and wet elongation, under tension fall sharply at high reaction temperatures of, for example, 80 C. and 95 C.
  • sebacic esters as are highly activated, that is, exhibit a high reaction velocity with hexamethylcne diamine, are particularly suitable for the process according to the invention.
  • very slight damage was obtained with bis 2,4,5 trichlorophenyl sebacate.
  • Hexamethylene diamine is preferably used in the lowest possible concentrations, for example in the form of aqueous solutions which contain about -35 mmol per
  • the quantity of nylon covering obtained is essentially Cit wool material, for example, after 2 hours of effective washing time is reduced from to 3%.
  • the uptake of moisture falls, owing to the treatment, from 0.6 to 1.4%.
  • the reaction temperature appears to inuence the extent of the non-shrinking effect only to the extent that it determines the thickness of the nylon coating. The higher the reaction temperature employed, the thicker is the nylon coating, as a rule.
  • the size of the nylon coating is of course determined, apart from the reaction temperature employed, by the concentrations and quantities of the reaction components.
  • the treated Wool is washed as soon as possible, preferably firstly with a soda solution and then with water. If the alcohol component of the sebacic ester split off in the formation of the nylon is insoluble in Water and in soda solution, washing is preferably effected with a solvent by 'which the said alcohol component can be removed. For example, when using bis-p-thiocresyl sebacate, the pthiocresol that is liberated may be removed by Washing with alcohol. f
  • the production of the activated sebacic esters employed in accordance with the invention may be carried out by known methods, in particular by the so-called mixed anhydride method (Th. Wieland and H. Bernhard, Liebigs Ann. Chem., 572, 190 (1951); R. A. Boissonais, Helv. Chim. Acta, 34 874 (1951); I. R. Vaughan, Jr. and R. L. Osato, I. Amer. Chem. Soc., 74, 676 (1952); N. F. Albertson, Organic Reactions, 12, p. 157), the carbodi-imide method (I. C. Sheehan and G. P. Hess, I. Amer. Chem. Soc., 77, 1067 (1955)); the acid chloride method or other known processes.
  • the best yields with a high degree of purity are obtained with the acid chloride method. In this case one may, for
  • the mixture is kept in a refrigerator for a few hours and is then poured into 2 litres of water, whereupon the ester precipitates. After a few hours the deposit precipitate is filtered off at the pump, washed several times with water and then recrystallised. Very pure products are obtained even after a single recrystallisation.
  • Bis-thiophenyl sebaeate Ethanol Colourless needles 58-59.
  • Bis-o-nitrophenyl sebaeate Greenish rods BrS-ZA-dmitrophenyl Sebacate Very light yellow cr tals. 83. 5-84 Brs-p-mtro'thlophenyl sebacate. Bright yellow rods.
  • the area shrinkage of knitted wool is particularly low in the case of wool treated by the process according to the invention, if a nylon covering of about 1-4%, preferably about 2-3%, based on the dry weight of the wool, is formed.
  • a nylon covering of about 1-4%, preferably about 2-3%, based on the dry weight of the wool is formed.
  • bis-2,4,5-trichlorophenyl sebacate and forming a coating of about 2.5% the area shrinkage of knitted In carrying out the process according to the invention, stable emulsions in water must -be formed from these sebacic esters.
  • Such stable emulsions are obtained by dissolving the ester in question in a solvent immiscible with water, such as benzene or methylene chloride, and adding it to an aqueous emulsifying solution whilst vibrating it.
  • a solvent immiscible with water such as benzene or methylene chloride
  • emulsifiers are employed.
  • Emulphor O is suitable, for example.
  • the products known under the trademark Nekanil O (BASF) and Stokopal T (Stockhausen) may for example also be used.
  • the bis-onitro phenyl, bis-p-nitrophenyl, bis2,4,5trichlorophenyl and bis-p-thiocresyl esters are particularly suitable for the process according to the invention.
  • the other activated esters have disadvantages when -used for the process according to the invention, such as:
  • Unpleasant odour e.g. of thiophenyl ester
  • the polyamide formed on the wool fibers is not chemically bound to the wool, but is deposited mechanically on the surface of the fibers in the form of a thin film. The same applies to wool treated by the IFP process.
  • the unbleached, combed wool yarn used for the test treatment was, in accordance with the requirement of a standard process for testing the -felting property of wool yarns, knitted into a tubular article (Z. ges. Textiland, 66 (1964), 358; see also H. J. Fleuning, Melliand Textilber, 44 (1963), 189, 288).
  • This knitted wool article was extracted for 12 hours with ethanol. Frequently the carded wool yarn was of a degree of purity such that extraction with ethanol was unnecessary. In these cases a conventional isoionic washing with water is sufficient. After this treatment the article was rinsed with water, dried and conditioned.
  • the sebacic ester was dissolved in water and mixed, whilst being vibrated, with ml. of a 20% aqueous emulsifying solution (Emulphor O 0.20% based onthe weight of ester).
  • the emulsion was cooled to 5 C. and treated with hexamethylene diamine. Wool samples of about g. were dipped into this emulsion, twice Wrung out by hand and then squeezed out to about 80-90% increase in weight.
  • the samples, rolled in filter paper, were then fixed in a vacuum steam bath. The steam pressure was controlled so that the liquid content of the wool remained constant.
  • the samples were rolled in plastic and placed in a desiccator. The following subsequent treatments were then carried out:
  • the samples were then centrifuged, dried and conditioned. The weight increase after alcohol extraction for six hours was determined.
  • the testing of the felting capacity was carried out by a washing machine test in accordance with the abovementioned standard procedure.
  • the alkalinity of the wool was determined by the method of M. Harris and A. Smith in accordance with the I.W.V. specification. (Amer. Dyestuff Reptr., 25, 542 (1936), see also Spezikationen fur Test-Methoden; Internationale Wollierinung, Techn. Ausschuss, published by the Internat. Wool Secretariat, London (1960).)
  • the urea bisulphite solubility was determined by the method of K. Lees and F. F. Elsworth (Proc. Int. Wool Text. Res. Conf. Australia, vol. C, 363 (1955)).
  • the wool was dyed with an acid dye (Supranol Cyanine G) in accordance with the manufacturers instructions.
  • Emulsier (Emulphor O) 50% hexamethylene diamine solution 11.6 g. (50.0 mmol). With water made up to 120.0 m1.
  • Bis-p-thiocresyl sebacate 10.3 g. (25.0 mmol). Benzene 20.0ml.
  • Emulsier (Stokopal T) 2.0 g. 50% heXamethylene diamine solution 15.6 g. (67.5 mmol). With water made up to ⁇ 100.0 m1.
  • FIGS. 1 to 9 Shrinkage curves of knitted samples treated in accordance with the examples are shown in FIGS. 1 to 9 of the accompanying drawings.
  • FIGS. 1 to 9 Shrinkage curves of knitted samples treated in accordance with the examples are shown in FIGS. 1 to 9 of the accompanying drawings.
  • FIG. 1 shows shrinkage curves for knitted samples treated with nylon 610 made from bis-o-nitrophenyl sebacate and hexarnethylene diamine (bath A) at four different temperatures;
  • FIG. 2 shows shrinkage curves for knitted samples treated with nylon 610 made from bis-p-nitrophenyl sebacate and hexamethylene diamine (bath B) at four different temperatures;
  • FIG. 3 shows shrinkage curves for knitted samples treated with nylon 610 made from bis-o-nitrophenyl sebacate and hexamethylene diamine (bath C) at two dfferent temperatures;
  • FIG. 7 shows shrinkage curves for' knitted samples treated with nylon 610 made from bis-2,4,5-trichlorohs A and C) at two phenyl sebacate and hexamethylene diamine (bath D) at four different temperatures; itted samples 5
  • FIG. 8 shows shrinkage curves for knitted samples lbis-p-nitrophenyl sebatreated with nylon 610 made from bis-p-thiocresyl seba- (baths B and D) at cate and hexamethylene diamine (bath A) at two different temperatures; and
  • FIG. 9 shows shrinkage curves for knitted samples 10 treated with nylon 610 made from bis-p-thiocresyl sebae (baths B, C, cate and hexamethylene diamine (baths B and C) at three different temperatures.
  • FIG. 4 shows shrinkage curves for knitted sam treated with nylon 610 made from bis-p-nitrophenyl sebacate ad hexamethylene diamine (bat different temperatures;
  • FIG. 5 shows shrinkage curves for kn treated with nylon 610 made from cate and hexamethylene diamine four different temperatures
  • FIG. 6 shows shrinkage curves for knitted samples treated with nylon 610 made from bis-2,4,5-trichlorophenyl sebacate and hexamethylene diamin E) at four different temperatures;
  • a process for coating a substrate of'keratinous bers with polyamide which comprises reacting a solution or suspension of hexamethylene diamine and an activated ester of sebacic acid in the presence of the substrate at a temperature between about 25-95 C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Polyamides (AREA)
  • Laminated Bodies (AREA)
US585404A 1965-10-09 1966-10-10 Process for coating a substrate of keratinous fibers with polyamide Expired - Lifetime US3484272A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DED0048396 1965-10-09

Publications (1)

Publication Number Publication Date
US3484272A true US3484272A (en) 1969-12-16

Family

ID=7051139

Family Applications (1)

Application Number Title Priority Date Filing Date
US585404A Expired - Lifetime US3484272A (en) 1965-10-09 1966-10-10 Process for coating a substrate of keratinous fibers with polyamide

Country Status (7)

Country Link
US (1) US3484272A (en))
BE (1) BE688053A (en))
DE (1) DE1469332A1 (en))
FR (1) FR1515019A (en))
GB (1) GB1162228A (en))
NL (1) NL6614231A (en))
SE (1) SE329145B (en))

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5573553A (en) * 1992-04-24 1996-11-12 Milliken Research Corporation Method for improving the bleach resistance of dyed textile fiber and product made thereby
US9586745B1 (en) * 2012-05-17 2017-03-07 JoAnne L. Givler Reusable, moisture wicking liner apparatus for produce containers and associated method

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110104747A (zh) * 2019-05-16 2019-08-09 上海出版印刷高等专科学校 一种用于柔性版印刷水墨废水处理的复合絮凝药粉及其应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2191556A (en) * 1936-07-01 1940-02-27 Du Pont Polyamides
US2696448A (en) * 1949-03-17 1954-12-07 Montclair Res Corp Shrinkproofed wool and method for producing same
US2862836A (en) * 1955-03-14 1958-12-02 Texas Co In situ polyamide coating method
US2957783A (en) * 1956-05-16 1960-10-25 Basf Ag Process of finishing leather
US3078138A (en) * 1960-04-15 1963-02-19 Lowell A Miller Shrinkproofing wool with polyamides
US3355409A (en) * 1965-04-29 1967-11-28 Du Pont Preparation of stable film forming aqueous polyamide dispersions

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2191556A (en) * 1936-07-01 1940-02-27 Du Pont Polyamides
US2696448A (en) * 1949-03-17 1954-12-07 Montclair Res Corp Shrinkproofed wool and method for producing same
US2862836A (en) * 1955-03-14 1958-12-02 Texas Co In situ polyamide coating method
US2957783A (en) * 1956-05-16 1960-10-25 Basf Ag Process of finishing leather
US3078138A (en) * 1960-04-15 1963-02-19 Lowell A Miller Shrinkproofing wool with polyamides
US3355409A (en) * 1965-04-29 1967-11-28 Du Pont Preparation of stable film forming aqueous polyamide dispersions

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5573553A (en) * 1992-04-24 1996-11-12 Milliken Research Corporation Method for improving the bleach resistance of dyed textile fiber and product made thereby
US9586745B1 (en) * 2012-05-17 2017-03-07 JoAnne L. Givler Reusable, moisture wicking liner apparatus for produce containers and associated method

Also Published As

Publication number Publication date
GB1162228A (en) 1969-08-20
SE329145B (en)) 1970-10-05
FR1515019A (fr) 1968-03-01
BE688053A (en)) 1967-04-10
DE1469332A1 (de) 1969-08-07
NL6614231A (en)) 1967-04-10

Similar Documents

Publication Publication Date Title
US2165265A (en) Process of imparting hydrophobic properties to cellulose fibers
US3429650A (en) Including finishing agents in at least one of two mutually immiscible solutions containing coreactants and serially applying said solutions to fibrous materials
US3007763A (en) Cross-linking fibers with diisocyanates in dimethylsulfoxide
US2327162A (en) New water-repellent agent and process of making same
KR940007742B1 (ko) 우레탄을 함유하는 수성 분산제
US3484272A (en) Process for coating a substrate of keratinous fibers with polyamide
US2445064A (en) Alkali metal hydroxide liquid reagent
US2071419A (en) Treatment of textile material
JPH02760A (ja) 脂肪族弗化アルコール、イソシアネートおよび置換芳香族化合物より成るウレタン、その製造方法およびその用途
US2873206A (en) Process for the optical brightening of polyester fibers
US2313742A (en) Process of treating textile fiber
DE2421888C2 (de) Verfahren zum Schrumpffestmachen von Textilmaterialien bei gleichzeitiger Verbesserung des Griffs
US2304157A (en) Process for improving textiles
US2303363A (en) Process for rendering textiles water-repellent and product therefrom
EP0075170A1 (de) Imidazolinderivate
GB839891A (en) A process for the improvement of shaped products containing carbonamide groups
US2207740A (en) Process for producing water-repellent cellulose-containing materials and products therefrom
US4210415A (en) Shrinkproofing of fabrics of wool
US2955954A (en) Process for treating shaped articles prepared from synthetic linear polyesters
US2241542A (en) Manufacture of nitrogen derivatives of cellulose
US3163552A (en) Process for making fibrous material hydrophobic
US2185795A (en) Process for the treatment of vegetable fibers and artificial threads
US2220856A (en) Process for rendering textiles water-repellent and products therefrom
US3079216A (en) Shrinkproofing wool with polyesters
US3206274A (en) Processing of cellulose triacetate