US3677694A - Imparting crease resistance to fibrous silk structures through treatment with gaseous formaldehyde - Google Patents

Imparting crease resistance to fibrous silk structures through treatment with gaseous formaldehyde Download PDF

Info

Publication number
US3677694A
US3677694A US88361A US3677694DA US3677694A US 3677694 A US3677694 A US 3677694A US 88361 A US88361 A US 88361A US 3677694D A US3677694D A US 3677694DA US 3677694 A US3677694 A US 3677694A
Authority
US
United States
Prior art keywords
silk
fabric
formaldehyde
fibrous structure
crease
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
US88361A
Other languages
English (en)
Inventor
Yoshitaka Sugimoto
Isao Sannomiya
Kazunobu Noumi
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.)
Kanegafuchi Spinning Co Ltd
Original Assignee
Kanegafuchi Spinning 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
Priority claimed from JP6383470A external-priority patent/JPS4824437B1/ja
Priority claimed from JP6708570A external-priority patent/JPS4841797B1/ja
Application filed by Kanegafuchi Spinning Co Ltd filed Critical Kanegafuchi Spinning Co Ltd
Application granted granted Critical
Publication of US3677694A publication Critical patent/US3677694A/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
    • 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
    • D06M13/10—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 oxygen
    • D06M13/12—Aldehydes; Ketones
    • D06M13/127—Mono-aldehydes, e.g. formaldehyde; Monoketones
    • 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
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423—Amino-aldehyde resins
    • 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
    • D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423—Amino-aldehyde resins
    • D06M15/429—Amino-aldehyde resins modified by compounds containing sulfur

Definitions

  • a method of finishing silk fibrous structure which comprises treating the silk fibrous structure with a solution containing at least one compound selected from the following group: (a) urea of thiourea; (b) a mixture of formaldehyde-containing low grade condensation resin and urea or thiourea; (c) aliphatic, alicyclic or aromatic compounds having at least two hydroxyl groups and having molecular weight of no more than 400; (d) aliphatic amines having at least two groups selected from hydroxyl and amino and having molecular weight of no more than 400; drying the treated fibrous structure until the moisture content of said fibrous structure reaches no more than 10% and then, treating said fibrous structure with gaseous formaldehyde at a temperature of no less than 100 C. Durable and high crease-resistance is obtained without adversely affecting excellent properties peculiar to silk fibrous structure.
  • This invention relates to a crease-resisting finish of silk fibrous structures, and particularly to a creaseproofing method for remarkably reducing the creation of creases at the time of wearing without adversely affecting excellent properties peculiar to silk fibrous structures.
  • Silk fibrous structures exhibit unique hand-feeling and luster as well as excellent mechanical properties such as tensile strength, elasticity, etc. On the contrary, they have a defect, that is, they crease easily at wearing.
  • the creation of crease is seriously afiected by relative humidity in an atmosphere surrounding the fibrous structure; it considerably increases with increase of the relative humidity.
  • creases are easily created at the seat and the waist portions of silk clothes because relative humidity of the above portions is high, i.e., usually 73 to 95%, and the resultant crease is persistent. It is very difiicult to prevent the creation of such creases.
  • dyed silk fibrous structure is inferior in color fastness, particularly in Wet color fastness such as washing fastness and sweat fastness. Therefore, in the case where a printed article of silk fibrous material is washed at home, a part of the dyestuif comes out furiously and stains the fields of white or other colors and accordingly, coloring is changed. In the case of a dip dyed article, coloring is also changed and mottles are created due to loss of dyestulf. Still further, the creation of crease at the time of washing at home and the loss of shape are brought about. Accordingly, all of the dyed articles of silk fibrous 3,677,694 Patented July 18, 1972 ice material are obliged to be only dry-cleaned in the existing circumstances.
  • Liquid phase process comprising treating the fibrous structure with a solution containing, for example, isocyanates-organic acid, urea-formalin, methylol acrylamide-stannic chloride, etc. and then polymerizing the above component inside the fiber.
  • crease-resistance may also be achieved by covering fibrous material with the polymerized resin from the cross-linking agent or by filling up the gaps between molecules with the resin, besides by cross-linking molecules as described above, or by the combination of cross-linking, covering and filling-up.
  • the covering layer of the polymerized resin from, for example, isocyanates-organic acid etc.
  • a liquid phase process is not industrially practicable because sufiicient cross-linkings cannot be produced and additionally covering or filling-up of polymerized resins does not create satisfactory crease-resistance and damages silks own characteristic such as hand-feeling and luster.
  • I 1 Testing method is as follows: each specimen is cut 4 cm. by 1 cm. along the warp and weft, respectively, and left at RH 65% for a period of one night. The strip is then folded in half so that it measures 2 cm. by 1 cm. and weighted with 2 kg. for a period of 5 min., after which it is removed. Then the strip is suspended on a strained wire for 3 min. The distance (a mm.) between the extremities is measured.
  • the crease-resistance may be calculated from the following formula and expressed as a percentage Grease resistance X 100
  • a liquid and gaseous phase-2 stage process for cellulose fibrous structure i.e., a compromised process between the above two processes is disclosed in Japanese patent publication Sho. 374596.
  • the process comprises lipping the fibrous structure with an aqueous solution of oxy acid salt of melamine and thereafter, treating the same with vaporized formaldehyde in the presence of water.
  • the resultant fibrous structure develops the similar defects to those described above; roughening and hardening of the hand-feeling, reduction of luster and discoloration are caused and therefore, satisfactory results cannot be obtained.
  • dyed or printed silk fibrous structure is inferior in wet fastness such as washing fastness and sweat fastness.
  • polymerized resin is usually produced as a surface layer 'over the fibrous material and internally in gaps between the molecules by the conventional creaseresisting finish, the internal production of polymerized resin is insufficient in the case of taking care that the excellent hand-feeling is not lost and accordingly, bonds due to van der Waals force and hydrogen bond between the polymerized resin and dyestuff molecule penetrated into the fibrous material are not fully formed.
  • An object of the present invention is to provide a creaseresisting finish for silk fibrous structure whereby the fibrous structure is given durable and high crease-resistance and it maintains its own characteristics such as handfeeling, luster, etc. as well as its own physical properties such as tenacity, elongation, etc.
  • Another object of the present invention is to provide a wash-and-wear finish for silk fibrous structure, particularly dyed or printed silk fibrous structure whereby the fibrous structure is given excellent color fastness.
  • a finishing process for a silk fibrous structure which comprises treating the silk fibrous structure with a solution containing at least one member selected from the group consisting of (a) Urea or thiourea,
  • Formaldehyde-containing low grade condensational resin which is used together with urea or thiourea in the process of the present invention, includes urea resins such as methylolurea, methylol ethylene urea, methylolthiourea, methylol ethylene thiourea, methylol propylene urea and methylol propylene thiourea, etc.; glyoxal resins such as dimethylol glyoxal nonurein, tetramethylol glyoxal diurein, etc.; melamine resins such as trimethylolmelamine and hexamethylolmelamine, etc.; urone resins such as dimethylol urone, etc.; triazine resins such as triethyleneiminotriazine, etc.; triazone resins such as dimethyloltriazone, etc.; and methylol acrylamide. They may be used alone or in combination.
  • Formaldehyde-containing low grade condensational resin can be present in the mixture in a wide range of concentrations such as, for example, at a resin-to-urea or thiourea ratio of from 1:9 to 9:1 and preferably in the range from 3:7 to 7:3.
  • a resin-to-urea or thiourea ratio of from 1:9 to 9:1 and preferably in the range from 3:7 to 7:3.
  • the resin-tourea or thiourea ratio is less than 1:9, the object of addition of the condensational resin is not attainable.
  • the ratio is more than 9:1, high crease-resistance is not obtainable.
  • Typical aliphatic compounds having at least two hydroxyl groups and having molecular weight of no more than 400 whichare used in the present invention, are ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, triethylene glycol, 1,2,6-hexanetriol, tartaric acid, glycerine and mannitol, etc.
  • Typical alicyclic compounds are cycloheXane-1,3-diol, cyclohexane-l,4-diol, cyclohexane-l,2,3-triol, etc.
  • Typical aromatic compounds are 2,5-dioxybenzoic acid, 2,4-dioxybenzoic acid, 1,2-dioxybenzoic acid, 4,6-dioxy-O-toluylic acid, 3,5- dioxytoluene, 3,5-dioxypropyl benzene, etc.
  • Typical aliphatic amines having at least two groups selected from hydroxyl and amino and having molecular weight of no more than 400 are ethanolamine, ethylenediamene, trimethylenediamene, tetramethylenediamine, pentamethylenediamine, hexamethylenediamene, heptamcthylencdiamene and octamethylenediamene, etc.
  • a preferred average molecular weight is no more than 100 for the aliphatic and alicyclie hydroxy compound, no more than 150 for the aromatic hydroxy compound and no more than 100 for the aliphatic amine.
  • ethylene glycol as aliphatic hydroxy compound ethylene glycol as aliphatic hydroxy compound, cyclohexane-1,3-diol as alicyclic hydroxy compound, 2,5-dioxybenzoic acid as aromatic hydroxy compound and ethanol amine as aliphatic amine are most preferable.
  • These compounds may be used alone or in combination. These compounds or mixtures are dissolved in water or organic solvent such as methanol, ethanol, etc. A preferred concentration range of the compound or mixture in solution is from 1 to 30% by weight, particularly from 5 to 25% by weight. If desired, polymerizationpromoting catalyst may be added to the solution.
  • the solution is applied to silk fibrous structure by conventional method such as padding, spraying and dipping, etc. and, if desired, squeezed by, for example, a mangle so that an adhered amount of the compound or mixture is from 2.5 to 25% OWF and preferably from 5 to 15% OWF. In the case where the amount is less than 2.5% OWF, suflicient cross-links cannot be formed. On the contrary, an amount of more than 25 OWF results in a coarse and hard hand-feeling.
  • ,As catalysts which are used in the present invention, for example, inorganic ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, etc.; inorganic metal salts such as magnesium chloride and zinc nitrate, etc.; organic acids such as tartaric acid, etc. and organic amines such as 2-amino-2-methylpropanol hydrochloride, etc. are enumerated.
  • a preferred amount of catalyst varies depending upon the particular catalyst, temperature of gaseous formaldehyde and reaction period, etc. and it is in the range from 0.5 to 30% based on the weight of the above-said compound or mixture. In the case where the amount is less than 0.5%, the desired object is not attainable. On the other hand, in the case of more than 30%, reaction rate is not so improved and degree of polycondensation is reduced due to degradation.
  • Silk fibrous structure having picked up the above compound is then dried until the moisture content of the fibrous structure reaches no more than by weight and is successively treated with gaseous formaldehyde at a temperature of no less than 100 C. Drying may be effected by heating, air-drying or any other drying means. Drying should be made as fully as possible, i.e. until the moisture content reaches no more than 10% and preferably no more than 7%, so that the trouble due to moisture will not arise in the gaseous phase reaction process. In this connection, if moisture exceeding 10% exists in the silk fibrous structure during the reaction, handfeeling of the structure is made coarse and hard.
  • Gaseous formaldehyde may be produced, for example, by heating paraformaldehyde or by adding concentrated sulfuric acid to trioxane.
  • gaseous formaldehyde for example, low grade polyoxymethylene glycol, a-polyoxymethylene, fi-polyoxymethylene, polyoxymethylene glycol derivatives and 'y-polyoxymethylene are enumerated.
  • temperature should be no less than 100 C. and preferably no less than 120 C. In the case of high temperature exceeding 180 C.,
  • Suitable treating conditions such as concentration of formaldehyde, temperature, pressure, period and impurities contained in gaseous formaldehyde, etc. vary depending upon the particular compound reacted with formaldehyde, the particular catalyst, etc. Therefore, it is difiicult to stably maintain formaldehyde monomer during the reaction, because formaldehyde monomer is easily changed to polymer.
  • the resulting formaldehyde polymer is deposited on the surface of the fibrous structure and form: protective coatings, which prevent the penetration of formaldehyde monomer into the inner part of the fibrous structure.
  • gaseous formaldehyde is maintained at a temperature higher than the equilibrium condensation temperature determined depending upon the particular pressure so that gaseous formaldehyde is not transformed into polymer during the reaction.
  • equilibrium condensation temperature is meant the upper limit of a temperature range at which gaseous formaldehyde monomer or its low molecular weight polymer can be transformed into solid polymer under the particular pressure.
  • low molecular weight polymer is meant that of gaseous, for example, trioxane, tetraoxane land the like.
  • Gaseous formaldehyde which is produced by heating a convenient formaldehyde source, for example, formaldehyde polymer such as paraformaldehyde, trioxane, etc. or formalin containing 30 to 40% of formaldehyde, is fed through a feeding pipe into a treating chamber.
  • a convenient formaldehyde source for example, formaldehyde polymer such as paraformaldehyde, trioxane, etc. or formalin containing 30 to 40% of formaldehyde
  • the pipe and the chamber are heated at a temperature higher than the equilibrium condensation tempreature, and preferably, gaseous formaldehyde is additionally heated at a temperature higher than the equilibrium condensation temperature by a superheater so that the formaldehyde polymer formation is eifectively prevented and formaldehyde polymer contained in gaseous formaldehyde is decomposed to form monomer.
  • equilibrium condensation pressure is meant by the lower limit of a pressure range at which gaseous formaldehyde monomer or its low molecular weight polymer can be transformed into solid polymer under the particular temperature.
  • gaseous formaldehyde monomer should be penetrated into the fibrous structure, which is attainable by replacing air existing at the inner part of the fibrous structure with formaldehyde. Accordingly, gaseous formaldehyde is forced to penetrate the fabric in one direction by creating the difference of pressure or the partial pressure of air surrounding and existing inside the fibrous structure is previously reduced to no more than 150 mm. Hg and preferably no more than 60 mm. Hg by sucking out air by a vacuum pump and thereafter, formaldehyde is fed into the chamber. If silk fabric is left in the chamber at a temperature of more than 100 C.
  • air existing at the inner part of the fibrous structure is replaced with formaldehyde or air surrounding and existing inside the fibrous structure is sucked out by a vacuum pump before or at the beginning of treatment.
  • temperatures of the chamber, the fabric and the feed pipe must be kept at higher than the saturated vapor temperature determined depending upon the particular partial pressure, which is similar to the case of gaseous formaldehyde, as described above.
  • the partial pressure of steam and temperature should be regulated so that the moisture content is maintained at no more than 10% and preferably no more than 7% during gaseous phase treatment.
  • cross-linking between functional groups in silk fiber molecule and filling up effect of resin which heretofore could not be expected, are properly achieved. That is, polycondensation of the compound such as urea or thiourea with formaldehyde occurs at solid-gaseous phase and the resultant product reacts on functional groups in silk fiber and hence, a cross-link between the functional groups is formed. Additionally, the condensation product fills in the fibrous structure. Consequently, it is presumed that cross-linking and filling up go hand-in-hand to achieve high crease resistance.
  • the silk fabric which has been treated by the method of the present invention, exhibits remarkably improved crease-resisting property even at a high humidity.
  • the method of the present invention does not adversely affect hand-feeling and drapery of silk fabric in the least and achieves a weighting effect of approximately resulting in dignified silk fabric.
  • the crease-resisting finish using low grade formaldehyde condensational resin together with urea or thiourea superior to the finish only using urea or thiourea. Because the former finish does not make silk fabric opaque in the least and crease resistance of the resulting fabric does not deteriorate.
  • urea or thiourea forms relatively low grade resin at the inner part of the fiber, but, the above-said low grade resin staying on the surface increase still more to form a water-insoluble and relatively high molecular weight resin. Because the low grade resin staying on the surface is directly heated in the presence of a catalyst. Thus, a protective layer of the water-insoluble resin prevents migration of the relatively low grade resin.
  • the crease-resisting finish using a single compound or mixture selected from aliphatic hydroxy compounds, amines and aromatic hydroxy compounds, or a mixture of the above compound and urea or thiourea provides the fabric which is particularly excellent in crease resistance to washing and colorfastness to washing.
  • reduction of wet crease resistance and fading of the fabric was scarcely recognized even after repeated launderings of 20 times.
  • the method it is presumed that formation of cross-link between functional groups in silk molecule and filling up of waterinsoluble resin are effectively obtained.
  • the method provides a practical wash-and-wear finish.
  • silk fibrous structure is meant not only the fibrous structure wholly composed of silk fiber, but also yarns or threads, woven fabric, knitted fabric and cords or strings prepared by mix spinning or mix weaving from silk fiber and other natural or man-made fibers.
  • gloss, whiteness degree and wash-and-wear characteristic are determined by the following methods:
  • Crease resistance Crease resistance is determined by measuring the angular recovery as directed in JIS-L1041-(c) method. Procedure is as follows: Fabric is out 1.5 cm. by 4 cm. to obtain a specimen strips. The strip is inserted between two superimposed metal leaves of the holder of Monsantotype tester, and an exposed end of the specimen is lifted over and back on the shorter metal leaf. The holder and specimen are inserted in a press holder, on which a load of 500 g. is applied. After min., the load is removed and the exposed end of the specimen holder is carefully inserted in the mount on the face of the tester. Care is taken so as not to roll the exposed end of the specimen, and the specimen holder is aligned properly on the mounting shelf. In order to eliminate gravitational effects, the
  • dangling specimen leg is .kept aligned with the vertical guide line during the 5 min. recovery period. Angle of the specimen in degrees is measured and angular recovery is calculated from the following equation:
  • Angle in degrees Angular recovery (percent) An average value for the warp and filling directions, each being 5 times, is calculated. Before the above determinations, the specimen is conditioned at a relative humidity of 65%, 85%, 90% and 95% and a temperature of 20 C. for to hours.
  • Whiteness degree is determined using photoelectric spectrophotometer EPU-2Atype (made by Hitachi, Japan). The whiteness is expressed by a percentage in comparison with whiteness of the scoured silk fabric at 440 III/1., the latter whiteness degree being 100% as standard for comparison.
  • Test specimen is Wetted by the method as directed in JIS-L1076-5.22.1-(2) and then, test is made by the method of JIS-L1076-5.22.2-(B). Crease-resistance is calculated by the method of JIS-L107 65.22.3.
  • the crease resistance is referred to as wet crease resistance in the specification.
  • EXAMPLE 1 Scoured silk Habutai (plain weave fabric prepared from silk filament yarn) was dipped in an aqueous bath containing 10% of thiourea and 1% of zinc nitrate as catalyst at room temperature and then squeezed to a pick-up of 100%. After it was dried so that the fabric had a moisture content of 6% it was placed in a closed chamber filled with gaseous formaldehyde at a temperature of 0., 100 C. and 120 C., evolved from paraformaldehyde.
  • the dried fabric was placed in a closed chamber and heated to 80 C. to 120 C. Then, air existing inside the chamber was sucked out by a vacuum pump so that internal air pressure was reduced to less than 150 mm. Hg and thereafter, a mixed gas of formaldehyde and steam was fed into the vessel until the internal pressure reached 0.5 to 1.2 kg./cm. abs. A ratio of the partial pressure of steam-to-that of formaldehyde was to /2.
  • a gaseous formaldehyde-evolving apparatus, a gas-feeding pipe and the above chamber were maintained at a temperature of no less than 120 C. so that formaldehyde did not polymerize at the applied pressure, i.e., 0.5 to 1.2 kg./cm. abs.
  • the fabric was maintained at the above temperature and pressure for a period of 30 min. to 3 hours.
  • FIG. 1 Crease-resisting properties of the resultant fabrics are shown in FIG. 1.
  • crease-resisting property indicated as angular recovery in percent
  • relative humidity that is, creaseresistance proportionally increases with increase of the temperature of gaseous formaldehyde and there is a critical point in a temperature range between 80 C. and 100 C.
  • angular recovery in percent creaseresisting property proportionally increases with increase of the temperature of gaseous formaldehyde and there is a critical point in a temperature range between 80 C. and 100 C.
  • EXAMPLE 2 Scoured Fuji silk (plain weave fabric prepared from silk spun yarn) and scoured silk Habutai were dipped in a mixed bath of an aqueous solution containing thiourea and an aqueous solution containing thiourea and a catalyst at room temperature and then squeezed to a pick up of 100%. After the fabrics were dried with hot air so that they had a moisture content of 5%, they were treated with gaseous formaldehyde vaporized from paraformaldehyde in the similar manner to those described in Example 1. After soaping, rinsing and drying, the fabrics were tested. Results are given in Table 2.
  • FIG. 2 shows relationship between angular recovery and relative humidity, both data of which are listed in Table 2.
  • reference marks (A), (B), (C) and (D) designate silk Habutai having been treated by the method of the present invention (No. 4), commercially available polyester/ cotton blended crease-resisting finished shirt (No. 11), Fuji silk having been treated by the conventional method (No. 10) and untreated silk Habutai (No. 12) respectively.
  • the dried fabric was placed in the closed chamber.
  • the chamber was heated to a temperature of 130 C. and the fabric was heated to a temperature of 80 C. by stirring and circulating hot air. After it was stopped, to stir and circulate hot air, air existing inside the chamber was sucked out by a vacuum pump so that internal air pressure was reduced to 150 mm. Hg. Thereafter, a mixed gas of formaldehyde and steam was fed through a feeding pipe heated at a temperature of 120 C. into the chamber. A ratio of the partial pressure of steam-to-that of formaldehyde was /2. A temperature of the fabric in the chamber was measured and a feeding amount of steam was so controlled that internal pressure of the chamber did not exceed the pressure of gaseous formaldehyde corresponding to that at the treating temperature.
  • a temperature of the fabric in the chamber was raised by conductive heat and radiant heat from the inside wall of the chamber and by heat of the mixed gas of steam and formaldehyde fed into the chamber.
  • Internal pressure of the chamber was increased to 1.0 kg./cm. while a feeding amount of the mixed gas was controlled according to the rise of temperature as described above, and thereafter, the internal pressure was maintained at 1.0 kg./cm. abs.: 0.1 kg./cm. for a period of two hours while a feeding amount of gaseous formaldehyde was controlled at two positions according to the internal pressure of the chamber. Then, the mixed gas inside the chamber was sucked out and discharged by a vacuum pump from the chamber until the internal pressure reached less than 160 mm.
  • EXAMPLE 5 of the silk fabric reached less than 5% immediately placed in a chamber filled with gaseous formaldehyde at a temperature of 150 C., which was produced from trioxane and cone. H S0 and did not contain moisture. After five minutes, the fabric was taken out of the chamber and cooled. Then, it was subjected to soaping and rinsing. Crease-resistance of the resultant fabric is shown in Table 6 in comparison with those of the untreated fabric and the fabric treated by the conventional method.
  • EXAMPLE 6 Scoured silk twill Habutai was dipped in a solution containing trimethylolmelamine low grade condensation product (trademark Sumitex resin M-3, made by Sumitomo Chemical, Japan), thiourea and 3% by weight of zinc nitrate catalyst (trademark Sumitex Accelerator KX, made by Sumitomo Chemical, Japan) and then, squeezed to a pick up of 170% with a mangle made of silicone rubber. After the fabric was dried at a temperature of 100 C. for 5 min. it was placed in a test tube, at the bottom portion of which paraformaldehyde was stuffed. The fabric was treated with gaseous formaldehyde for 3 hours which was evolved by heating the paraformaldehyde at a temperature of C. Crease resistance of the resultant fabric is given in Table 9.
  • EXAMPLE 7 Secured milk twill Habutai was dipped in a solution containing trimethylolmelamine-low grade condensation product (trademark Sumitex Resin M-3, made by Surnitomo Chemical, Japan), magnesium chloride catalyst (trademark Sumitex Accelerator MK, made by Sumitomo Chemical, Japan), and thiourea and then squeezed to a pick up of 200%. Thereafter, it was dried and treated with gaseous formaldehyde in the same man ner as that described in Example 7. Then, the fabric was subjected to soaping at a temperature of 50 C. for three min. with aqueous solution containing 0.2% of nonionic surface active agent (trademark Scourol 450, made by Kao Sekken, Japan) and thereafter, Washed and dried.
  • aqueous solution containing 0.2% of nonionic surface active agent trademark Scourol 450, made by Kao Sekken, Japan
  • the resultant fabric was dyed at a temperature of 90 C. for min. in a bath containing 3% OWF of Kayanol Milling Red PG (trademark; made by Nihon Kayaku, Japan), 1% OWF of acetic acid and 30% OWF of anhydrous sodium sulfate; a bath ratio was 1: 100.
  • Kayanol Milling Red PG trademark; made by Nihon Kayaku, Japan
  • Scoured silk Habutai was dipped in a'solution containing 3% by weight of 'trimethylolmelamine-low grade resin (trade mark U-ramine T-10l, made by Mitsui-Toatsu Chemical, Japan), 3% of zinc nitrate catalyst (trademark Catalyst Z, made by Mitsui-Toatsu Chemical, Japan) and 10% of urea, squeezed with the same mangle as that of Example 6 to a pick up of 180% and then TABLE 10 Crease resistance Crease resistance 7 before dyeing Handafter dyeing Hand- (percent) cling (percent feeling Tear before after strength N0.
  • RH RH 95% dyeing RH 65% RH 95% dyeing (g) 1 92. 1 87. 8 Good--..- 86. 6 2, 750 2 90.5 84.6 do 90.2 2,600
  • Formaldehyde-low grade condensational resins and catalysts which were used in this example, were as follows:
  • EXAMPLE 1 1 5 0 they were dried with hot air until the moisture content descreased to 8% and thereafter, treated with gaseous formaldehyde at a temperature of C. for 3 hours, which was evolved by heating paraformaldehyde. Then, the fabrics were subjected to soaping using an aqueous solution containing 0.5% of nonionic surface active agent (trademark Scourol, made by Kao Sekken, Japan) and then washed and dried. Crease resistance and fading of the resultant fabrics are given in Table 15.
  • Tniourea-treating method The method was as follows: Silk Habutai was dipped in a solution contaimng 10% thiourea and 3% catalyst (2- amino-2-methylpro anol salt ACX.” made by Sumitomo Chemical, Japan) for a perio of 30 111111. and then squeezed to a pick up of 30%. After the fabric was dried until the moisture content reached less than 5%, it was treated with gaseous formaldehyde at a temperature of 120 C. for 3 hours which was evolved by heating paraformaldehyde and then soaped, rinsed and dried. The above method is hereinafter referred to as thiourea-treating method.
  • Shrinkage percentage is defined by the followmg equation: A1 th ft 1 d t eng a or aun enng imes Shrinkage percentage (percent) An mginal length wherein the shrinkage percentage is an average value of both shrinkage percentage in the warp and the filling directions.
  • the fabric which has been treated by the conventional method exhibits low crease resistance in all relative humidities of 6 5%, and on the other hand, the fabric which has been treated by the method of the present invention has remarkably high crease resistance being nearly equal to that of a commercially available wash-and-wcar finished polyester/cotton blended shirt nd accordingly, does not crease at the time of wearing.
  • the fabric of the present invention exhibits higher Wet crease resistance and higher wet crease resistance after laundering at home 10 times and 20utimes, both resistances being nearly equal to that of the above polyester/cotton blended shirt, than that of the conventional method.
  • the fabric having been treated by the method of the present invention has been remarkably improved as compared with untreated Habntai or Fuji silk.
  • the fabric exhibits extremely low fading even after the repeated laundering of 10 or 20 times, which is the reverse of the fabric treated by the conventional method, it is not too much to say that the method of the present invention has actualized the washand-wear finish of silk fabrics.
  • EXAMPLE 13 Dyed silk Habutai was dipped in a solution containing aliphatic hydroxy compound, thiourca, urea and catalyst at room temperature for 5 min. and then squeezed to a pick up of After the fabric was dried with hot air until the moisture content reached 6% it was treated with gaseous formaldehyde at a temperature of C. for 3 hours which was evolved by heating paraformaldchyde and thereafter, soapcd, rinsed and dried.
  • EXAMPLE 14 EXAMPLE '17 Dyed silk Habutai was dipped in a solution containing Scoured silk Habutai was dipped in an aqueous solution aliphatic amine, thiourea and catalyst at room temperacontaining of one of aliphatic hydroxy compounds ture for 5 min. and then squeezed to a pick up of 100%. having various molecular weight, of thiourea and 3% After the fabric was dried until the moisture content 5 of zinc nitrate catalyst at a temperature of 50 C. for 5 reached less than 7%, it was treated with gaseous formalmin. and then squeezed with a angle to a pick up of dehyde in the same manner as that of Example 13. Re- 100%. sults are given in Table 18.
  • EXAMPLE 19 resultant fabric was finished by the conventional method scoured Fuji Silks were dipped in a Solution containing usually applied to wool fabrics. Results are given in 5% of ethylene glycol, 10% of thiourea and 3% of zinc Table TABLE 24 After laundering at home times Crease resistance (percent) Wet crease Shrinkage RH RH RH resistance percentage Dye- Fad- 65% 85% 95% Wet (percent) (percent) stufis ing Untreated 85.4 78.5 65.0 60.2 60.2 6.8 g 1 I A 4 Treated 90.1 89.1 87.1 80.0 80.0 2.0 B 4 nitrate catalyst at room temperature for 5 min. and then EXAMPLE 21 squeezed in the same manner as that of Example 17. After the fabric were dried under various conditions so that they had a moisture content different from each other, they were treated by the same method as that of Example 17. Results are given in Table 23.
  • a method of finishing silk fibrous structure which ous formaldehyde comprises treating said silk fibrous structure with a solu- R f e Cit d tion containing at least one member selected from the UNITED STATES PATENTS group consisting of (a) urea or thiourea, (b) a mixture of formaldehyde-containing low grade condensation resin and urea or thiourea, (c) aliphatic, alicylic or aromatic compounds having 2,434,247 1/1948 Lewls et at least two hydroxyl groups and having molecular 2,512,195 6/1950 Bener' weight of no more than 400, FOREIGN PATENTS (d) aliphatic amines having at least two groups se- 437,642 11/1935 Great Britain lected from hydroxyl and amino and having molecular Weight of no more than 400, OTHER REFERENCES drying the
  • tent of said fibrous structure reaches no more than 10% 31-3 l 9, 19 2 and then, treating Said fibrous Structure with gaseous 40 Gonzales et aL, American Dyestuif Reporter, Sept. 13, formaldehyde at a temperature of no less than C. 19 5, 74 and -19 2-
  • a meth d as claimed in claim wherein said y- Mehta et al., Journal of the Textile Institute, vol. 58, ing is efiected until the moisture content of said fibrous 279-292 (1967) structure reaches no more than 7% 3.
  • LESMES Primary Examiner ing of said fibrous structure with gaseous formaldehyde is effected at a temperature of no less than C.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
US88361A 1969-11-10 1970-11-10 Imparting crease resistance to fibrous silk structures through treatment with gaseous formaldehyde Expired - Lifetime US3677694A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP9036969 1969-11-10
JP6383470A JPS4824437B1 (enrdf_load_html_response) 1970-07-21 1970-07-21
JP6708570A JPS4841797B1 (enrdf_load_html_response) 1970-07-30 1970-07-30

Publications (1)

Publication Number Publication Date
US3677694A true US3677694A (en) 1972-07-18

Family

ID=27298296

Family Applications (1)

Application Number Title Priority Date Filing Date
US88361A Expired - Lifetime US3677694A (en) 1969-11-10 1970-11-10 Imparting crease resistance to fibrous silk structures through treatment with gaseous formaldehyde

Country Status (6)

Country Link
US (1) US3677694A (enrdf_load_html_response)
CA (1) CA937706A (enrdf_load_html_response)
CH (2) CH1669170A4 (enrdf_load_html_response)
FR (1) FR2070190B1 (enrdf_load_html_response)
GB (1) GB1330153A (enrdf_load_html_response)
SE (1) SE382473B (enrdf_load_html_response)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3849848A (en) * 1971-05-20 1974-11-26 Iws Nominee Co Ltd Method for the treatment of textile fibres
US4343617A (en) * 1981-03-16 1982-08-10 Baur Jr Paul S Suture and prosthesis material
US20130224134A1 (en) * 2010-11-02 2013-08-29 L'oreal Nitrocellulose-free nail polish compositions

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3849848A (en) * 1971-05-20 1974-11-26 Iws Nominee Co Ltd Method for the treatment of textile fibres
US4343617A (en) * 1981-03-16 1982-08-10 Baur Jr Paul S Suture and prosthesis material
US20130224134A1 (en) * 2010-11-02 2013-08-29 L'oreal Nitrocellulose-free nail polish compositions
US9713588B2 (en) * 2010-11-02 2017-07-25 L'oreal Nitrocellulose-free nail polish compositions

Also Published As

Publication number Publication date
GB1330153A (en) 1973-09-12
CH1669170A4 (enrdf_load_html_response) 1973-09-14
CA937706A (en) 1973-12-04
FR2070190B1 (enrdf_load_html_response) 1974-04-05
FR2070190A1 (enrdf_load_html_response) 1971-09-10
DE2055260B2 (de) 1975-08-28
SE382473B (sv) 1976-02-02
CH550278A (enrdf_load_html_response) 1974-06-14
DE2055260A1 (de) 1971-05-27

Similar Documents

Publication Publication Date Title
US2657151A (en) Coating of fabrics
US3183054A (en) Aldehyde condensation products and their use in treating fibrous materials
US2763574A (en) Method for protection of cellulosic fibrous material from attack by micro-organisms
US3044891A (en) Textile sheet material and process for producing same
US3472606A (en) Two-component wet fixation process for imparting durable press to cellulosecontaining materials
US3216779A (en) Textile materials and process for manufacturing them
US3709657A (en) Wet fixation of resins in fiber systems for durable press products
US3677694A (en) Imparting crease resistance to fibrous silk structures through treatment with gaseous formaldehyde
US4162275A (en) Flame-resistant fiber
US3627556A (en) Durable press finish for wool/cellulosic fabrics (melamine/dihydroxy-imidazolidinone resins)
US5015261A (en) Pre-treatment of cellulosic fibres or cellulosic fibres in blends with synthetic fibres for subsequent transfer printing
Lewin et al. The role of liquid ammonia in functional textile finishes
US3026216A (en) Treatment of textile fabrics with methylglycidyl ethers
EP0268368B1 (en) Fabric treatment
Murphy et al. Yarn mercerization techniques in preparing high-strength wash-wear cottons
US3526474A (en) Abrasion-resistant durably-pressed cellulosic textiles
JPH08188921A (ja) 耐候性の改善されたポリエステル系繊維およびその製造方法ならびにその繊維を用いてなる繊維製品
US3950589A (en) Melt-resistant synthetic fiber and process for preparation thereof
US5902355A (en) Method for pattern dyeing of textile fabrics containing blends of cellulose regenerated fiber
US3506390A (en) Process of reacting cellulosic fibers with sultones and optionally with other creaseproofing agents and resulting products
US3634019A (en) Metal acetate-acidic catalyst system for cellulosic fabric treatment
US3094371A (en) Textile treatment with aminoplast and polyacrylamides and the textile so treated
US2988416A (en) Process of creaseproofing linen fabric by applying resin, mercerizing and reapplyingresin and product produced thereby
US3533728A (en) Inorganic and/or organic cellulose swelling agents used in conjunction with cross-linking agents in fabric modification process
US3738864A (en) Fiber bearing antistatic composition