US3833397A - Process for the resin finishing of cellulosic fabrics and cellulosic blend fabrics with simultaneous improvement of their affinity for optical brighteners - Google Patents

Process for the resin finishing of cellulosic fabrics and cellulosic blend fabrics with simultaneous improvement of their affinity for optical brighteners Download PDF

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US3833397A
US3833397A US15851871A US3833397A US 3833397 A US3833397 A US 3833397A US 15851871 A US15851871 A US 15851871A US 3833397 A US3833397 A US 3833397A
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copolymer
fabrics
cellulosic
units
vinyl alcohol
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K Poppenwimmer
H Roedel
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Sandoz AG
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    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63H—TOYS, e.g. TOPS, DOLLS, HOOPS OR BUILDING BLOCKS
    • A63H33/00—Other toys
    • A63H33/30—Imitations of miscellaneous apparatus not otherwise provided for, e.g. telephones, weighing-machines, cash-registers
    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D06M15/3562—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing nitrogen
    • 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
    • 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
    • Y10T442/2369—Coating or impregnation improves elasticity, bendability, resiliency, flexibility, or shape retention of the fabric
    • Y10T442/2393—Coating or impregnation provides crease-resistance or wash and wear characteristics
    • 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
    • Y10T442/2582—Coating or impregnation contains an optical bleach or brightener or functions as an optical bleach or brightener [e.g., it masks fabric yellowing, etc.]

Definitions

  • the cellulosic fabrics for finishing by the present process may be of natural or regenerated cellulosic fibre (cotton, linen, hemp, ramie, jute or viscose rayon, cu-
  • ' prammonium rayon, polynosic fibre or blends of a cellulosic fibre and a natural fibre such as wool or silk or a synthetic fibre such as polyamide, polyurethane, polyacrylonitrile, polypropylene or preferably polyester fibre (p0lyethyleneterephthalate and the condensation product deriving from terephthalic acid and 1,4- dimethylol-cyclohexane).
  • N-methylol and N- alkoxymethylol compounds are the polymethylol and polyalkoxymethyl compounds of triazinones, melamine, melamine derivatives, carbamates, urea and cyclic ureas of formula where R represents The polyalkoxymethyl compounds are produced by etherification of polymethylol compounds using low molecular weight alcohols (CHgOH, C H Ol-l, nC H Ol-l).
  • the curing agents suitable for the N-methylol compounds include the colourless salts formed by multivalent metals and strong inorganic acids, such as magnesium, zinc, cadmium and aluminium chlorides, bromides, nitrates, sulphates and other halides, zirconyl chloride, acid phosphates such as Mg(H PO Al(H- P0, and Zn(H PO the colourless salts of multivalent metals and organic acids, such as magnesium and zinc acetate and propionate; compounds which act acid under the curing conditions, e. g.
  • ammonium and amine salts such as ammonium bromide, chloride and sulphate, monoammonium and diammonium phosphate, ammonium oxalate, monomethyl, dimethyl and trimethy] aminohydrochloride, monoethyl, diethyl and triethyl aminohydrochloride, monoethanol, diethanol and triethanol aminohydrochloride, mono-, diand tripropanol aminohydrochloride.
  • N-methylol and N-alkoxymethyl compounds impart the actual finish, While the copolymers (c) improve the affinity for opticalbrighteners.
  • the degree of polymerization of the copolymers (c) is not critical so long as they are soluble'in water at room temperature. Products polymerized to a high degree, with an average'molecular weight greater than 50,000, or others of a low degree of polymerization with average molecular weights of 5,000 or less can'be employed. But since high polymers form very viscous aqueous solutions and thelow polymers are'difficultto synthesize in a homogeneous state,'preference is given to polymers and copolymers with molecular weights in the range of 5,000 t 50,000, e.g. 10,000 to 30,000.
  • Copolymers consisting of 5.5 to 55 weight'percent of vinyl alcohol units and94.5 to 45 weight percent N- vinylpyrrolidone units greatly increase the affinity.
  • the N-methylol and N-alkoxymethyl compounds are best employed in the padding liquor in amounts of 50150 g/l, or preferably 70-120 g/l.
  • the curing agent is added in amounts of -30 g/l, preferably -20 g/l, in crystalline form.
  • the amount of copolymer (c) is preferably 3-50 g/l, the optimum range being 75-30 phosphate, or condensed-phosphates. It may alsocontain per salts such as sodium perborate as bleaching agents.
  • non ionic detergents suitable for this-purpose include the adducts of ethylene oxide or propylene oxide on hydrophobic compounds such as fatty alcohols,
  • fatty acids fatty acid amides, monoalkyland polyalkyl-phenols, monoalkyland polyalkylnaphthols, alkylmercaptans, alkylthiophenols, saccharic acid esters, methylalkyl sulphoxides, N-oxides of al-kyl-di (lower alkyl)-amines or phosphines, and the weakly basic adducts of ethylene oxide on fatty amines.
  • Suitable anioic detergents include alkylbenzene sulphonates, alkyl sulphonates,'primary and secondary alkyl sulphates, alkyl, alkylphenyl, dialkylphenyl, alkylnaphthyl and dialkylnaphthyl polyglycolether sulphates, phosphates and oxyacetates, fatty acid amides of Z-am'inoethane sulp'honate, Z-N-methylaminoethane sulphonate, 2- aminoethyl sulphate, aminobenzene sulphonates and aminoalkoxybenzene sulphonates.
  • Cellulosic fabrics and blend fabrics finished as described above have higher dry and wet crease resistance values than comparable unfinished fabrics, and show higher affinity for anionic optical brighteners such as those in domestic detergents which build up on the fabric from the wash bath.
  • a typical formulation for such a detergent is as follows:
  • a merit of the process describedherein is thatit lessens the loss of tensile strength caused by the resin finishing of'the fabric.
  • EXAMPLE I A 50/50 percentblendfabr'ic of cotton and polyester fibreis added with an aqueous solution containing per litre.
  • the fabric is dried at 100 to 120 and the resin cured by treatment for 4 to 5 'minutes at 160C.
  • the fabric is washed 5 times at 98 with an aqueous solution of 5 'g/l of a commercial detergent.
  • the detergent has the composition given above,the active wash substance being sodium dodecylbenzenesulphonate, the condensed phosphate sodium tripolyphosphate and the anionic optical brightener the compound designated P in the above enumeration.
  • the vinyl pyrrolidone-vinyl alcohol copolymer used here was produced as follows. 50parts of vinyl acetate, 50 parts of vinyl pyrrolidone, parts of demineralized water, 41 parts of methanol and 0.2 parts of a,a-azoiso-butyric acid dinitrile are mixed in a nitrogen atmosphere. The mixture is raised tov 60 in 30 to 40 minutes. The polymerization reaction is slightly exothermic and its progress can be recognized from the increase in viscosity.
  • the temperature is slowly increased to to 98 and in 6 hours a mixture of methanol, methyl acetate and water is distilled.
  • the distilled methanol is replaced by water.
  • the product is 90 parts of colourless vinyl pyrrolidone-vinyl alcohol copolymer in solution in 5 lo'parts of water. It consists of 34 percent vinyl alcohol units and 66 percent vinyl pyrrolidone units and in the following is termed copolymer 34/66.
  • Example l washed, either once at 60 or times at 98, with the detergent used in Example l at a concentration of 5 g/l, then rinsed and dried.
  • the improvement whereby the affinity of the fabric for anionic optical brighteners is increased which comprises including in said solution (c) a copolymer consisting of N-vinylpyrrolidone units and at least 5.5 weight percent vinyl alcohol units, said components (a), (b), and (c) being present in the solution in amounts of 50l50 g/l, 5-30 g/l, and 3-50 g/I, respectively.
  • copolymer has a molecular weight in the range 5,000 to 50,000.
  • copolymer consists of 5 .5 to 55 weight percent vinyl alcohol units and 94.5 to 45 weight N-vinylpyrrolidone units and has a molecular weight in the range 5,000 to 50,000.
  • copolymer (c) is the reaction product of N- vinylpyrrolidone and vinyl acetate.
  • a composition comprising an aqueous solution of (a) an N-methylol or a lower N-alkoxymethyl compound, (b) an acid curing catalyst for the N-methylol or N-alkoxymethyl compound, and (c) a copolymer consisting of N-vinylpyrrolidone units and at least 5.5 weight percent vinyl alcohol units, said components (a), (b), and (c) being present in amounts of -150 g/I, 5-30 g/l, and 3-50 g/l, respectively.
  • composition according to claim 7 wherein the copolymer has a molecular weight in the range 5,000
  • composition according to claim 7 wherein the copolymer (6) is the reaction product of N- vinylpyrrolidone and vinyl acetate.
  • a composition consisting essentially of an aqueous solution of (a) an N-methylol or a lower N- alkoxymethyl compound, (b) an acid curing catalyst of 50-150 g/l, 530 g/l, and 3-50 g/I, respectively.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Toys (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Detergent Compositions (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

A process for the resin finishing of cellulosic blend fabrics with improvement of their affinity for anionic optical brighteners by treating the fabrics with a solution of a) an Nmethylol or N-alkoxymethyl compound b) an acid curing catalyst c) a copolymer consisting of vinyl pyrrolidone units and at least 5.5 weight percent vinyl alcohol units and curing by dry heat treatment at 120*-180*C.

Description

United States Patent Poppenwimmer et al.
Sept. 3, 1974 July 10, 1970 PROCESS FOR THE RESIN FINISHING OF CELLULOSIC FABRICS AND CELLULOSIC BLEND FABRICS WITH SIMULTANEOUS IMPROVEMENT OF THEIR AFFINITY FOR OPTICAL BRIGHTENERS Inventors: Kurt Poppenwimmer,
Allschwil/Basel-Land; Hilmar Roedel, Therwil/Basel-Land, both of Switzerland Assignee: Sandoz Ltd., Basle, Switzerland Filed: June 30, 1971 Appl. N0.: 158,518
Foreign Application Priority Data Switzerland 10452/70 US. Cl. 117/335 T, 8/115.6, 8/116.2, 117/139.4,117/139.5 A, 117/1395 CQ Int. Cl C09j 3/00, D06m 13/34 Field of Search 117/335 T, 139.4, 139.5 CQ, 117/1395 A; 260/296 HN, 29.6 B, 29.6
WA, 29.6 RB; 8/116.2, 1 W, 100, 115.5,
[56] References Cited UNITED STATES PATENTS 3,232,691 2/1966 Wilhelm et al 117/335 T X 3,238,166 3/1966 Kawai et al. 117/139.4 X 3,322,569 5/1967 Faulhaber et al 117/1394 3,402,987 9/1968 Dalton et al. 260/296 HN X 3,533,728 lO/1970 Shippee et al. 8/17 X Primary Examiner-Alfred L. Leavitt Assistant Examiner-Caleb Weston Attorney, Agent, or FirmGerald D. Sharkin [5 7 ABSTRACT 11 Claims, N0 Drawings UUDEEOU 011 a2 I050 I950 w O o mo 050 Z 050 o mo .J B 3 FL 6 8 mo m o mz mo m o mz Z 5Z 2 Ez o o mo mo mz mz o o mo mo mz 0 dz mz oo mo mo wz mz oo mo H355 moqmo 2 mz w o z mz w o z a2 EOQHNO ZOUENO I m mo m o moi o /Z v NZ I 1 I I I I 1 l I v w I 1 n MEMO NO I! m m2 I 259m mm waam 262a ww oEmw NQHOQHHNOVZ| NQHOQHNOVZI 0 QHWO w w O .Z 0 IWZ IEZ 2 Q2 m o JMNO 1 I I I I m O Z wn az |HHZ {HZ Z 0 w 2% O m EOIHHOH DIE OIHHZ! EOIWOE OIEOIHHZI SA EZI Ez mo momo fio mz mo o z om a m w V @Z EO HHQEO EO EZ smo mo mo mo m HO O QZ EO MOQO EO HHZ mo momo fio mz @z mo momo mo mz mo momo fio mz 02 y PW um Gm @Z 5 wd 25m 95% 3 05am mo m o :o m o Z VE/TO MZQ wz o o fi o 7 0 o fi o 4 Q2 52! 32? 8 32m 1 255 [i255 EZ Q m 5 2 m2 .mzl 050 0E0 H4 Z Z NHZI EH21. Hm IQ d onw mm 25% 2055 S055 /Z /Z Z N mzl 52! E6 E6 3 dz HHOqHHHOIHHZI HHO HH-O|HHZ|. IOWHHNO IIOMHHNU H055 i055 2 MZ Q w 55A 54 G w m m z Z 50 E0 m4 Z5 1 w 2 505534 EQE VZ 94 :Z HHOQHHHOIIHHZI HHOJHHDIIHHZI [OSHO IIOHHHO I |O i5 m 25 w E055 E055 lmzl IET @Z E0 50 m4 m mZU m o z mz m 5 2 2 523192 xmoqmovz d E Q HEU Z mz flo CZEO a 2 9% C un Gm where R, in both positions represents OCH:
morpholine soaNa derivatives of 7-aminoeomarin such as derivatives of stilbenyl naphthotriazole such as derivatives of oxacyanine such as 3, 3, 5, 5, 7, 7- hexamethyloxacyanine-p-sulphonate =AW' derivatives of bis-azoles such as the sodium salt of sulphonated 2,2-bis-[(phenyl vinylidene)-6,6- oxazole] =AX derivatives of sulphonated 2,2-bis-[(phenyl vinylidederivatives of sulphonated [(phenylvinylidene)-6,6-imidazole] =AZ derivatives of diphenylazoles such as the sodium salt of sulphonated-Z-styryl-S-phenyloxazole =BA derivatives of sulphonated Z-naphthyl-S- phenylthiazole BB derivatives of sulphonated 2-naphthyl-5- phenylimidazole BC derivatives of an a, B-di-(benzimidazyl)-ethylene such as the sodium salt of sulphonated a,B-di-(benzimidazyl- 2)-ethylene BD derivatives of diphenylimidazolone such as the sodium salt of sulphonated 4,5-diphenylimidazole BE.
The cellulosic fabrics for finishing by the present process may be of natural or regenerated cellulosic fibre (cotton, linen, hemp, ramie, jute or viscose rayon, cu-
' prammonium rayon, polynosic fibre), or blends of a cellulosic fibre and a natural fibre such as wool or silk or a synthetic fibre such as polyamide, polyurethane, polyacrylonitrile, polypropylene or preferably polyester fibre (p0lyethyleneterephthalate and the condensation product deriving from terephthalic acid and 1,4- dimethylol-cyclohexane).
Examples of suitable N-methylol and N- alkoxymethylol compounds are the polymethylol and polyalkoxymethyl compounds of triazinones, melamine, melamine derivatives, carbamates, urea and cyclic ureas of formula where R represents The polyalkoxymethyl compounds are produced by etherification of polymethylol compounds using low molecular weight alcohols (CHgOH, C H Ol-l, nC H Ol-l).
The curing agents suitable for the N-methylol compounds include the colourless salts formed by multivalent metals and strong inorganic acids, such as magnesium, zinc, cadmium and aluminium chlorides, bromides, nitrates, sulphates and other halides, zirconyl chloride, acid phosphates such as Mg(H PO Al(H- P0, and Zn(H PO the colourless salts of multivalent metals and organic acids, such as magnesium and zinc acetate and propionate; compounds which act acid under the curing conditions, e. g. ammonium and amine salts such as ammonium bromide, chloride and sulphate, monoammonium and diammonium phosphate, ammonium oxalate, monomethyl, dimethyl and trimethy] aminohydrochloride, monoethyl, diethyl and triethyl aminohydrochloride, monoethanol, diethanol and triethanol aminohydrochloride, mono-, diand tripropanol aminohydrochloride.
The N-methylol and N-alkoxymethyl compounds impart the actual finish, While the copolymers (c) improve the affinity for opticalbrighteners.
The degree of polymerization of the copolymers (c) is not critical so long as they are soluble'in water at room temperature. Products polymerized to a high degree, with an average'molecular weight greater than 50,000, or others of a low degree of polymerization with average molecular weights of 5,000 or less can'be employed. But since high polymers form very viscous aqueous solutions and thelow polymers are'difficultto synthesize in a homogeneous state,'preference is given to polymers and copolymers with molecular weights in the range of 5,000 t 50,000, e.g. 10,000 to 30,000.
Copolymers consisting of 5.5 to 55 weight'percent of vinyl alcohol units and94.5 to 45 weight percent N- vinylpyrrolidone units greatly increase the affinity.
The N-methylol and N-alkoxymethyl compounds are best employed in the padding liquor in amounts of 50150 g/l, or preferably 70-120 g/l. The curing agent is added in amounts of -30 g/l, preferably -20 g/l, in crystalline form. The amount of copolymer (c) is preferably 3-50 g/l, the optimum range being 75-30 phosphate, or condensed-phosphates. It may alsocontain per salts such as sodium perborate as bleaching agents.
The non ionic detergents suitable for this-purpose include the adducts of ethylene oxide or propylene oxide on hydrophobic compounds such as fatty alcohols,
fatty acids, fatty acid amides, monoalkyland polyalkyl-phenols, monoalkyland polyalkylnaphthols, alkylmercaptans, alkylthiophenols, saccharic acid esters, methylalkyl sulphoxides, N-oxides of al-kyl-di (lower alkyl)-amines or phosphines, and the weakly basic adducts of ethylene oxide on fatty amines. Suitable anioic detergents include alkylbenzene sulphonates, alkyl sulphonates,'primary and secondary alkyl sulphates, alkyl, alkylphenyl, dialkylphenyl, alkylnaphthyl and dialkylnaphthyl polyglycolether sulphates, phosphates and oxyacetates, fatty acid amides of Z-am'inoethane sulp'honate, Z-N-methylaminoethane sulphonate, 2- aminoethyl sulphate, aminobenzene sulphonates and aminoalkoxybenzene sulphonates.
Cellulosic fabrics and blend fabrics finished as described above have higher dry and wet crease resistance values than comparable unfinished fabrics, and show higher affinity for anionic optical brighteners such as those in domestic detergents which build up on the fabric from the wash bath.
A typical formulation for such a detergent is as follows:
percent active washing substance .(see above) 2 percent lauroyl diethanolamide 3 40 percent condensed phosphate, eg sodium tripolyp'hosphate 5 1 percent sodium metasilicate 5=percent sodium carbonate 10 percent sodium sulphate Zpercent carboxymethyl cellulose I 10 percent sodium perborate(NaBO 'HQO '3HQO) 0.5 percent anionic optical'br'ightener 5.5 percent moisture etc.
A merit of the process describedherein is thatit lessens the loss of tensile strength caused by the resin finishing of'the fabric. y
In thefollowing Examples, which illustrate the invention without'limiting'its scope, theparts and percentages are by weight and the temperatures in degrees Centigrade.
EXAMPLE I A 50/50 percentblendfabr'ic of cotton and polyester fibreis added with an aqueous solution containing per litre.
100 g dimethylolethylene urea (100 percent strength),
30 g magnesium chloride Mg Cl 6H O and 15 g of a vinylpyrrolidone-vinyl alcohol copolymer produced as described below.
The fabric is dried at 100 to 120 and the resin cured by treatment for 4 to 5 'minutes at 160C.
The fabric is washed 5 times at 98 with an aqueous solution of 5 'g/l of a commercial detergent. The detergent has the composition given above,the active wash substance being sodium dodecylbenzenesulphonate, the condensed phosphate sodium tripolyphosphate and the anionic optical brightener the compound designated P in the above enumeration.
In comparison with a fabric finished without the copolymer, the fabric finished according to this process "has a far higher degree of whiteness after five washes under the same conditions, as these values show:
Fluorimeter values The vinyl pyrrolidone-vinyl alcohol copolymer used here was produced as follows. 50parts of vinyl acetate, 50 parts of vinyl pyrrolidone, parts of demineralized water, 41 parts of methanol and 0.2 parts of a,a-azoiso-butyric acid dinitrile are mixed in a nitrogen atmosphere. The mixture is raised tov 60 in 30 to 40 minutes. The polymerization reaction is slightly exothermic and its progress can be recognized from the increase in viscosity. The mixture is stirred for 3 hours at 60 to 65 then a-further 76 parts of demineralized water, 60 parts of methanol and 0.08 parts of a-a'-azo-iso butyric acid dinitrile are added and stirring continued for 5 hours at 60 to 65 till polymerization is complete. After the ad- .dition of 470 parts of methanol, 100 parts of a solution of 10 parts of 87 percent potassium hydroxide in 90 parts of methanol are dropped in slowly.
The temperature is slowly increased to to 98 and in 6 hours a mixture of methanol, methyl acetate and water is distilled. The distilled methanol is replaced by water.
The product is 90 parts of colourless vinyl pyrrolidone-vinyl alcohol copolymer in solution in 5 lo'parts of water. It consists of 34 percent vinyl alcohol units and 66 percent vinyl pyrrolidone units and in the following is termed copolymer 34/66.
The following polymers and copolymers can be synthesized in an analogous manner to the above:
washed, either once at 60 or times at 98, with the detergent used in Example l at a concentration of 5 g/l, then rinsed and dried.
5 D C t' P )d d f naetsiLgn OmpOSI IOI'I H uce rom 3 82/l8 8271 vinyl alcohol, 90% vinyl acetate, ep e E p 2 1S p y Wlth the 18% vinyl pyrrolidone i071 67% vinyl pyrrolidone follow ng res n solutions: 67/33 67% vinyl alcohol, 80% vinyl acetate,
33% vinyl pyrrolidone 2071 vinyl pyrrolidone IO I8/82 I871 vinyl alcohol, 30% vinyl acetate, I
82% vinyl pyrrolidone .707: vinyl pyrrolidone A 75 g/l of a I:I mlxture of dlmethylolethylene urea and dimethylolpropylene urea 20 g/l MgCI 't'JH O g/I copolymer 34/66 EXAMPLE 2 B 75 g/l dimethylol methylcarbamate /I ZnCI- A cotton fabric IS padded with a solutlon contalnlng g 'mpufymer 34/66 75 g/l of a 1:1 mixture. of dlmethylolethylene urea and S 1 dimethylolpropylene urea, 20 g/l MgCI '6H O and 7.5 C 75 '5;figgfl fifg" g/l of one of the copolymers lished in Example 1. After /lv copolymer 34/66 intermediate drying at 100 to 120 the finish is cured 20 by treatment for 5 minutes at 160. The fabric is The results are listed in Tables 2 to 4.
Table l Fluorilneter values Finished without Finished with the addition copolymer of a copolymer (7.5 g/I) addition Washed once 24 82/18 67/33 34/66 I8/82 41 44 60 58 Washed five 29 44 47 58 58 times at 98 Table 2 Fluorimeter values of Finished Fabric Resin Number of washes Amount of copolymer 34/66 Solution .v 0 g/l 7.5 g/l I5 g/I g/l A once at 60 26 64 74 five tilnes at 98 29 58 63 72 B once at 60 33 65 69 five times at 98 42 67 8i C once at 60 20 56 66 five times at 98 20 38 58 70 Table 3 Dry crease recovery angle of finished fabric (Averages ol' determinations in the warp and wet directions) Resin Number of washes Amount of copolymer 34/66 solution 0 g/l 7.5 g/l I5 g/l 30 g/l Unwashed I 37 I 37 I35 I25 A once at 60 I I47 I37 I3I five times at 98 I40 I3) I37 I32 Unwashed I4I I27 I I3 B once at 60 I40 I30 I21 t'lve times at 98" I40 I32 I I9 Unwashed I4) I43 I40 I32 C once at 60 I I47 I42 I25 five times at 98 I46 I40 I40 I23 Table 4 Wet crease recovery angle of finished fabric (Averages ofdeterminations in the warp and weft directions) Resin Number of washes Amount of co ol mer 34/66 solution X g/l 7.5 g/l I g/] 30 g/l Unwashed l3l I34 I36 I 37 A once at 60 I34 I34 I37 I37 five times at 98 I35 I34 I37 I37 Unwashed I34 I33 I 33 B once at 60" I34 I34 I34 five times at 98 I33 I35 I29 Unwashed I33 I33 I36 I36 C once at 60 I38 I40 I43 I39 five times at 98 I36 I33 134 I38 Table 5 Mean crease recover angle of finished fabric (Averages of the dry and \vet crease recover angles) Resin Number of washes Amount of copolymer 34/66 solution .v 0 g/l 7.5 g/l g/l g/l Unwashed 134 I I35 I3I A once at (10 I40 I41 I37 I34 five times at 98 I38 I36 I37 I35 Unwashed I38 I30 I 23 B once at 60 I37 I32 I28 five times at 98 I36 I33 I24 linwashcd I41 I38 I38 I34 C once at 60 I44 I43 I43 I33 five times at 98 l4l I37 I37 I30 The loss in tensile strength caused by resin finishing is significantly reduced by the inclusion in the finish of an additive according to this invention.
Very similar results to those given above are obtained with cotton fabrics.
Having thus disclosed the invention what we claim is:
1. In a process for the resin finishing of cellulosic fabrics and cellulosic blend fabrics by padding the fabric with an aqueous solution of (a) an N-methylol or a lower N-alkoxymethyl compound and (b) an acid curing catalyst for the N-methylol or N-alkoxymethyl compound and treating the fabric at 120 to 180C. to cure the resin, the improvement whereby the affinity of the fabric for anionic optical brighteners is increased which comprises including in said solution (c) a copolymer consisting of N-vinylpyrrolidone units and at least 5.5 weight percent vinyl alcohol units, said components (a), (b), and (c) being present in the solution in amounts of 50l50 g/l, 5-30 g/l, and 3-50 g/I, respectively.
2. A process according to claim 1 wherein the copolymer contains 5.5 to 55 weight percent of vinyl alcohol units.
3. A process according to claim 1 wherein the padded fabric is dried before the resin is cured.
4. A process according to claim 1 wherein the copolymer has a molecular weight in the range 5,000 to 50,000.
5. A process according to claim 1 wherein the copolymer consists of 5 .5 to 55 weight percent vinyl alcohol units and 94.5 to 45 weight N-vinylpyrrolidone units and has a molecular weight in the range 5,000 to 50,000.
6. A process according to claim 1 wherein the copolymer (c) is the reaction product of N- vinylpyrrolidone and vinyl acetate.
7. A composition comprising an aqueous solution of (a) an N-methylol or a lower N-alkoxymethyl compound, (b) an acid curing catalyst for the N-methylol or N-alkoxymethyl compound, and (c) a copolymer consisting of N-vinylpyrrolidone units and at least 5.5 weight percent vinyl alcohol units, said components (a), (b), and (c) being present in amounts of -150 g/I, 5-30 g/l, and 3-50 g/l, respectively.
8. A composition according to claim 7 wherein the copolymer has a molecular weight in the range 5,000
9. A composition according to claim 7 wherein the copolymer (6) is the reaction product of N- vinylpyrrolidone and vinyl acetate.
10. Fabric of cellulosic fibre or cellulose-containing blended fibres having crease resistance and improved affinity for anionic optical brighteners and produced by the process of claim 1.
11. A composition consisting essentially of an aqueous solution of (a) an N-methylol or a lower N- alkoxymethyl compound, (b) an acid curing catalyst of 50-150 g/l, 530 g/l, and 3-50 g/I, respectively.

Claims (10)

  1. 2. A process according to claim 1 wherein the copolymer contains 5.5 to 55 weight percent of vinyl alcohol units.
  2. 3. A process according to claim 1 wherein the padded fabric is dried before the resin is cured.
  3. 4. A process according to claim 1 wherein the copolymer has a molecular weight in the range 5,000 to 50,000.
  4. 5. A process according to claim 1 wherein the copolymer consists of 5.5 to 55 weight percent vinyl alcohol units and 94.5 to 45 weight N-vinylpyrrolidone units and has a molecular weight in the range 5,000 to 50,000.
  5. 6. A process according to claim 1 wherein the copolymer (c) is the reaction product of N-vinylpyrrolidone and vinyl acetate.
  6. 7. A composition comprising an aqueous solution of (a) an N-methylol or a lower N-alkoxymethyl compound, (b) an acid curing catalyst for the N-methylol or N-alkoxymethyl compound, and (c) a copolymer consisting of N-vinylpyrrolidone units and at least 5.5 weight percent vinyl alcohol units, said components (a), (b), and (c) being present in amounts of 50-150 g/l, 5-30 g/l, and 3-50 g/l, respectively.
  7. 8. A composition according to claim 7 wherein the copolymer has a molecular weight in the range 5,000 to 50,000.
  8. 9. A composition according to claim 7 wherein the copolymer (c) is the reaction product of N-vinylpyrrolidone and vinyl acetate.
  9. 10. Fabric of cellulosic fibre or cellulose-containing blended fibres having crease resistance and improved affinity for anionic optical brighteners and produced by the process of claim 1.
  10. 11. A composition consisting essentially of an aqueous solution of (a) an N-methylol or a lower N-alkoxymethyl compound, (b) an acid curing catalyst for the N-methylol or N-alkoxymethyl compound, and (c) a copolymer consisting of N-vinylyrrolidone units and at least 5.5 weight percent vinyl alcohol units, said components (a), (b) and (c) being present in amounts of 50-150 g/l, 5-30 g/l, and 3-50 g/l, respectively.
US15851871 1970-05-04 1971-06-30 Process for the resin finishing of cellulosic fabrics and cellulosic blend fabrics with simultaneous improvement of their affinity for optical brighteners Expired - Lifetime US3833397A (en)

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US5288262A (en) * 1991-12-13 1994-02-22 Phillips E Lakin Crazy wheels toy
US6270349B1 (en) 2000-01-13 2001-08-07 Frederick M. Ng Educational tool for defensive driving
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US8100736B2 (en) * 2008-06-09 2012-01-24 Mattel, Inc. Simulated engine sound device for bicycles or the like
US10130191B2 (en) 2015-09-09 2018-11-20 Kids Ii, Inc. Convertible children's walker
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US3402987A (en) * 1964-01-20 1968-09-24 Gaf Corp Dyeing of polymeric articles treated with a graft copolymer of an n-vinyl lactam polymer
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US3238166A (en) * 1961-10-10 1966-03-01 Sumitomo Chemical Co Brocess for endowing permanent dirtpreventing property and hardness to fabrics of synthetic fibers, and resin composition therefor
US3322569A (en) * 1962-11-10 1967-05-30 Basf Ag Treatment of cellulosic textiles with a crease resisting finish and a copolymer of a n-methylolamide of an acrylic acid for the purpose of reducing wet soiling
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GB1301062A (en) 1972-12-29
CH1045270A4 (en) 1972-06-30
DE2133528A1 (en) 1972-01-13
FR2098302B1 (en) 1974-03-15
CH531089A (en) 1972-11-30
FR2098302A1 (en) 1972-03-10
US3659375A (en) 1972-05-02
FR2092302A5 (en) 1971-01-21
DE2060928B2 (en) 1975-10-09
GB1269880A (en) 1972-04-06
DE2060928A1 (en) 1971-11-25

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