US3862073A - Emulsifier compositions for creaseproofing textile materials which contain copolymers of unsaturated carboxylic acids and their esters - Google Patents

Emulsifier compositions for creaseproofing textile materials which contain copolymers of unsaturated carboxylic acids and their esters Download PDF

Info

Publication number
US3862073A
US3862073A US266608A US26660872A US3862073A US 3862073 A US3862073 A US 3862073A US 266608 A US266608 A US 266608A US 26660872 A US26660872 A US 26660872A US 3862073 A US3862073 A US 3862073A
Authority
US
United States
Prior art keywords
weight
copolymer
parts
mixture
acid
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
US266608A
Other languages
English (en)
Inventor
Heinz Bille
Ernst Wilheim Hann
Gerhard Luetzel
Guenther Schmidt
Dieter Voelker
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Application granted granted Critical
Publication of US3862073A publication Critical patent/US3862073A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
    • D06M15/29—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides containing a N-methylol group or an etherified N-methylol group; containing a N-aminomethylene group; containing a N-sulfidomethylene group
    • 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
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having amino or quaternary ammonium groups
    • 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

Definitions

  • ABSTRACT Emulsifier compositions containing, apart from water and conventional surfactants, a copolymer of unsaturated carboxylic acids and their esters and optionally other comonomers for creaseproofing cellulosic textile materials with amino resin forming substances.
  • Emulsifiers are materials capable of maintaining organic substances, primarily liquids, in a stable mixture with other liquids where such substances are not miscible with each other or soluble in each other. Such emulsifiers are important when it is desired to distribute organic, water-immiscible or water-insoluble substances in water in such a manner that they are uniformly present in the aqueous medium as if they were physically dissolved therein.
  • Emulsifiers of this kind have hitherto been used for the said purpose in resin finishing processes.
  • German Published Applications 1,594,954 and 1,594,965 describe textile treatment baths based on methylolated amino resin-forming substances which contain organic solvents and include emulsifiers for stabilizing the emulsion, which emulsifiers are based on ethoxylated fatty acid amides and, according to German Published Application 1,594,965, must also exhibit specific physical characteristics.
  • the above object is achieved using emulsifier compositions for creaseproofing textile materials containing cellulose and/or regenerated cellulose in an aqueous liquor which may or may not contain organic solvents and which contains methylolated amino resin-forming substances and optionally amino resin-forming substances which have been etherified at the methylol group, said emulsifier compositions being characterized by contents of:
  • B from 30 to 80 parts by weight of the composition of a known cationic, anionic or non-ionic surfaceactive compound and C. from 30 to 70 parts by weight of the composition of water.
  • Suitable comonomers (a) of component (A) are afi'ethylenically unsaturated carboxylic acids of the aliphatic and aliphatic/aromatic series having from 3 to 10 carbon atoms. They may also be substituted by hetero atoms such as halogen atoms and in particular chlorine atoms, or by hetero atom-containing groups such as hydroxyl groups and alkoxyl groups. Also of commerical interest are mixtures of two or more of these acids, specific examples of which are acrylic acid, methacrylic acid, chloracrylic acid, crotonic acid, phenylacrylic acid, maleic acid, fumaric acid, itaconic acid and citraconic acid.
  • the monomer units (a) are conveniently incorporated in the copolymers in amounts ranging from 1 to 10% and preferably from 2 to 7 by weight.
  • the comonomers (b) are esters of said acids (a) or mixtures of said esters. Of commerical interest are ester mixtures containing from 2 to 4 esters.
  • the alcohols from which the esters are derived are of the saturated aliphatic series and contain-from l to 8 and preferably from 1 to 6 carbon atoms. Particular examples thereof are methanol, ethanol, n-propanol, isopropanol, nbutanol, isobutanol, t-butanol, the amyl alcohols, hexyl alcohols and octyl alcohols, preferably methanol, ethanol, n-propanol, n-butanol and n-hexanol.
  • esters are conveniently incorporated in the copolymers in amounts ranging from 99 to 70% and preferably from 98 to Suitable comonomers (c) are copolymerizable monomers which may be present in the copolymers in amounts of up to 20% by weight and which may, if desired, contain materials having a crosslinking effect.
  • acylonitrile methacrylonitrile
  • acrylamide methacrylamide
  • styrene ethylene
  • propylene vinyl esters of saturated carboxylic acids such as vinyl acetate and vinyl propionate
  • vinyl ethers such as vinyl ethyl ether
  • vinyl chloride vinylidene chloride
  • butadiene isoprene
  • monomers having crosslinking groups such as N-methylolacrylamide and N-methylolmethacrylamide, 2-chloro-3-hydroxypropyl acrylate, 1,3-butanediol monoacrylate and 1,3- butanediol diacrylate.
  • copolymers arev prepared by known methods.
  • any of the free radical generating substances normally used for such copolymerization and generally known in the art of the manufacture of dispersions may be used for the present purpose.
  • free radical substances such as benzoyl peroxide, lauroyl peroxide. benzoic peroxide. peracetic acid, azoisobutyronitrile or other free radical substances may be used.
  • Conventional molecular weight regulators and plasticizers, as commonly used for polymerizations, may also be present.
  • Suitable components (B), which may be present in the composition in amounts ranging from 30 to 80 parts by weight and preferably from 30-to 60 parts by weight, are all cationic, anionic and/or non-ionic surfactants such as have been conventionally used in the textile industry over many years. It is immaterial whether the surface-active agents are anionic, cationic or non-ionic. However, it is more convenient to use non-ionic or anionic compounds.
  • alkali metal or ammonium salts of long-chain fatty acids or long-chain sulfonic acids and sulfuric acid half esters of polyoxyalkylated compounds which have been prepared from alcohols, carboxylic acids, carboxamides and alkylphenols by reaction with from 5 to 90 moles of ethylene oxide and/or propylene oxide.
  • Suitable alcohols and carboxylic acids for this purpose are for example coconut fatty alcohol, sperm oil alcohol, wax alcohol, sperm oil fatty acid, stearic acid, palmitic acid, oleic acid, ricinoleic acid and corresponding products of paraffin oxidation.
  • oxyalkylated alkylphenols are also highly suitable surfactants.
  • oxyalkylated alkylphenols having a degree of oxyalkylation of between and 60and in which the alkyl radicals contain from 6 to 14 carbon atoms and may be branched-chain'or unbranched, may be used after conversion to the alkali metal or ammonium salts of their sulfuric acid half esters.
  • Suitable alkylphenols from which these compounds are derived are for example iso-octylphenol, decylphenol, dodecylphenol and nonylphenol or the corresponding naphthols.
  • the amides of the carboxylic acids are also highly suitable.
  • Component (C) which is present in the compositions in amounts ranging from 30 to 70 parts by weight, is water.
  • compositions described above constitute excellent emulsifier systems for creaseproofing textile materials containing cellulose'or regenerated cellulose.
  • the basic component of a creaseproofing agent consists in a methylolated amino resinforming substance, in which some or all of the methylol groups may be etherified by lower alcohols.
  • alcohols which are suitable as etherifying components are preferably those containing from 1 to 5 carbon atoms.
  • amino resin-forming substances we mean for example ethylene urea, propylene urea, melamine, carbamates, and urone.
  • methylolated amino resins are as follows: N,N'- dimethylolethylene urea, N,N'-dimethylolpropylene urea, N,N'-dimethylol-4-methoxy-5 ,5-dimethylpropylene urea, N-methylol-2-methoxyethylene carbamate, hexamethylolmelamine, dimethylol urea and N,N- dimethylol urone.
  • etherified or partially etherified methylolated amino resins are N,N-dimethoxymethylethylene urea, N,N-dimethoxymethyl-4,5- hydroxyethylene urea, N,N'-methoxymethylpropylene urea, N,N-dimethoxymethyl-4-methoxy-5,S-dimethylpropylene urea, N,N'-isopropoxymethyl-4-methoxy- 5,5-dimethylpropylene urea, N,N,N-hexamethoxymelamine, N,N-dimethylol-2-methoxyethyl carbamate, N,N-dimethoxymethyl-2-methoxymethyl carbamate and N,N-dimethoxymethyl urone.
  • the finishing bath may additionally include protective colloids derived for example from water-soluble copolymers or saponification products of polymers such as polyvinyl alcohol and methyl cellulose.
  • a finishing bath containing the emulsifier compositions of the invention generally comprises from about 5 to 60% by weight of one of the aforementioned, optionally partially etherified methylol compounds, from about 0.01 to 20% by weight of the emulsifier of the invention, from about 5 60% by weight of water and from about 5 to by weight of chlorinated hydrocarbon.
  • Suitable hydrocarbons are, for example, carbon tetrachloride, trichloroethylene, perchloroethylene, 1,1,1- trichloroethane, l,2-dichloropropane and hexachloroethane.
  • Creaseproofing is carried out in known manner with the addition of so-called curing catalysts.
  • These include all acids and potential acids known to be valuable for this purpose. These are acids or Lewis acids such as zinc chloride, zinc acetate and magnesium chloride. Examples of acids are monochloroacetic acid, secondary diammonium phosphate, benzoic acid, organic sulfonic acids suchas p-toluenesulfonic acid and also acid-liberating compounds such as p-toluenesulfonic chloride.
  • the components When preparing the finishing baths, the components may generally be added in any order.
  • a finishing bath containing the emulsifier compositions of the invention is eminently suitable for effecting creaseproofing from organic solvent emulsions.
  • a smooth emulsion may be obtained simply by stirring one of the methylol compounds with the emulsifier composition of the invention followed by the addition of organic solvents. Surprisingly, even a small amount of emulsifier is sufficient to stabilize such an emulsion.
  • the conventional curing catalyst is added to the liquor simultaneously or subsequently.
  • a liquor of user consistency is obtained from this mixture by further dilution with said organic solvents, which may themselves contain water if desired, to form clear to opalescent solutions of stable'water-in-oil emulsions.
  • the water required for the creaseproofing process may be included in the emulsifier composition of the invention. Alternatively, it may be added when the tinishing liquor is prepared.
  • plasticizers fillers or water or oil repellents may also be added to the finishing baths with the catalysts.
  • the textiles are impregnated with the above liquors, freed from excess liquor and dried and then, advantageously, heated to temperatures between 110 and 190C. Textiles treated in this manner exhibit considerably higher tensile strength and tear resistance than textiles treated with aqueous emulsifier-free baths or textiles treated in baths containing organic solvents and conventional emulsifiers. In addition, the losses of abrasion resistance are much less in the present case, whilst the crease recovery is at the same level as that obtained when working according to the prior art.
  • our novel emulsifier compositions permits energysaving drying and the treatment of very sensitive fabrics due to the controlled swelling of the cellulose fibers made possible by varying the amount of water contained in the finishing liquors.
  • Finishing agents prepared with the compositions of the invention are suitable for finishing textile materials of all kinds, provided they contain cellulose or regenerated cellulose.
  • EXAMPLE 1 A mixture of 60 parts by weight of an approximately 70% emulsifier composition prepared in the manner described in supplement 1 below and 150 parts by weight of a 50% aqueous solution of N,-
  • N'-dimethylol-4,S-dihydroxyethylene urea is emulsified and made up to 970 parts by volume with 1,1,1-trichloroethane with stirring.
  • composition of the invention which contain 3.47% by weight of emulsifier, 6.2% by weight of methylol compound, 9.3% by weight of water and 83% by weight of 1,1,1-trichloroethane, there are added parts by weight of monochloroacetic acid dissolved in 27 parts by weight of water.
  • White mercerized and beached cotton poplin weighing about 118 g/m is impregnated with the above 1iquor.
  • the impregnated fabric is dried, conditioned and then condensed at 150C for 5 minutes.
  • the fabric thus treated exhibits good crease recovery in both the dry and wet states and shows low losses of tensile strength, tear resistance and abrasion resistance compared with purely aqueous treatments.
  • EXAMPLE 2 A mixture of 60 parts by weight of an emulsifier composition as described in supplement 1 of Example 1 and 100 parts by weight of a aqueous solution of N,-
  • N-dimethylol-4,S-dihydroxyethylene urea are emulsified and made up to 940 parts by volume with 1,1,1-trichloroethane with stirring. The pH is then adjusted to 5 with monochloroacetic acid and the mixture is made up to 1,000 parts by volume with water.
  • This finishing bath is used to treat white cotton poplin as described in Example 1.
  • the treated fabric has good crease recovery, particularly when wet, whilst the losses of tensile strength, tear resistance and abrasion resistance are only slight.
  • EXAMPLE 3 parts by weight of the approximately 35% emulsifier composition described in supplement 1 below are homogeneously mixed with a solution of 136 parts by weight of N,N-di(methoxymethyl)ethylene urea in 360 parts by weight of 1,1,1-trichloroethane.
  • Emulphor 0U is a polyoxyethylated fatty alcohol having a melting point of 3540C., a drop-forming temperature of 464'9C., and a turbidity point l% aqueous solution) of ca. 100C. or (2% solution in aqueous NaCl solution) of 7378'C.
  • Supplement 2 EXAMPLE 4 120 parts by weight of the emulsifier composition described in supplement 1 of Example 1 but containing 3% of acrylic acid in place of 2% thereof .are homogeneously mixedwith a solution of 172 parts by weight of N,N-di(methoxymethyl)propylene urea in 470 parts by weight of perchloroethylene.
  • the resulting emulsion is used to treat fabric as described in Example 1.
  • the treated fabric shows good crease recovery in both the dry and wet states with moderate losses of tensile strength and tear resistance and very small losses of abrasion resistance.
  • EXAMPLE 5 120 parts by weight of the emulsifier composition described in Example 2 are mixed to a homogeneous emulsion with a solution of 176 parts by weight of N,N-di(methoxymethyl)urone in 464 parts by weight of perchloroethylene.
  • This emulsion is used toimpregnate white mercerized and bleached cotton poplin weighing about 118 g/m
  • the fabric is then dried and condensed for l minute at 180C.
  • the treated fabric shows good crease recovery in both the dry and wet states with low losses of tensile strength, tear resistance and abrasion resistance.
  • EXAMPLE 6 146 parts byweight of N,N-di(methoxymethyl)propylene urea are dissolved in 120 parts by weight of the emulsifier composition described in Example 1, with stirring. 5 parts by weight of p-toluenesulfonic acid, dissolved m 22 parts by weight of water, are added and the mixture is made up to 1,000 parts by volume with l,l,l-trichloroethane so as to give a stable finishing emulsion.
  • Cotton fabric is treated with this emulsion, dried and condensed in the manner described in Example 1. It is then rinsed in the usual manner.
  • the fabric shows good crease recovery in both the wet and dry states with low losses of tensile strength, tear resistance and abrasion resistance.
  • EXAMPLE 7 100 parts by weight of the emulsifier composition described in Example 1 but containing a polymer dispersion of the following composition: 1
  • EXAMPLE 9 A mixture of 1 part by weight of an approximately 70% emulsifier composition described in the Supplement below,
  • methoxyethylene urea is emulsified with stirring with perchloroethylene which is added to make up to 950 parts by volume.
  • composition of the invention which contains 0.051% by weight of emulsifier, 15.8% by weight of etherified methylol compound, 7.3% by weight of water and 77% by weight of perchloroethylene, there are added 17 parts by weight of zinc nitrate dissolved in 50 parts by weight of water.
  • This finishing bath is used to impregnate white mercerized and bleached cotton poplin weighing approximately 1 18 g/m
  • the fabric is dried and condensed for 1 minute at 180C.
  • the fabric thus treated shows good crease recovery in both the dry and wet states with low losses of tensile strength,-tear resistance and abrasion resistance.
  • a mixture for creaseproofing textile materials containing cellulose and/or regenerated cellulose in an aqueous liquor which may or may not contain organic solvents and which contains methylolated amino resinforming substances and optionally amino resin-forming substances which have been etherified at the methylol group, and an emulsifier composition comprising A. from 5 to 70 parts by weight of the emulsifier composition of a copolymer containing polymerized units of the following monomers:
  • copolymer (A) is a copolymer of ll0% acrylic acid, methacrylic acid or both of said acids, 99-70% of one or more acrylate esters optionally together with a methacrylate ester, and 020% of methacrylamide; and the surface active compound (B) is a polyoxyethylated fatty alcohol.
  • copolymer (A) is a copolymer of 1-10% of acrylic acid and 9970% of butyl acrylate and ethyl acrylate optionally together with methylmethacrylate, and 020% of methacrylamide; and the surface active compound (B) is a polyoxyethylated fatty alcohol.
  • An emulsifier composition for creaseproofing a cellulosic textile material in an aqueous liquor which optionally may contain an organic solvent and which contains a methylolated amino resin-forming substance and optionally an amino resinforming substance which has been etherified at the methylol group, comprising A. from 5 to 70 parts by weight of the composition of a copolymer containing polymerized units of the following monomers: v a. from 1 to 10% by weight of the copolymer of an alpha, beta-ethylenically unsaturated vmonocarboxylic acid which contains from 3 to 10 carbon atoms or a mixture of said acids,
  • B from 30 to parts by weight of the composition of a surfactant selected from the group consisting of a polyoxyethylated fatty alcohol and the sodium salt of paraffinsulfonic acid and a polyoxyethylated fatty alcohol and C. from 30 to 70 parts by weight of the composition of water.
  • a surfactant selected from the group consisting of a polyoxyethylated fatty alcohol and the sodium salt of paraffinsulfonic acid and a polyoxyethylated fatty alcohol
  • C from 30 to 70 parts by weight of the composition of water.

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)
US266608A 1971-07-05 1972-06-27 Emulsifier compositions for creaseproofing textile materials which contain copolymers of unsaturated carboxylic acids and their esters Expired - Lifetime US3862073A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19712133351 DE2133351A1 (de) 1971-07-05 1971-07-05 Emulgatorzubereitungen fuer die knitterfestausruestung von cellulose- und/oder regeneratcellulosehaltigem textilgut

Publications (1)

Publication Number Publication Date
US3862073A true US3862073A (en) 1975-01-21

Family

ID=5812704

Family Applications (1)

Application Number Title Priority Date Filing Date
US266608A Expired - Lifetime US3862073A (en) 1971-07-05 1972-06-27 Emulsifier compositions for creaseproofing textile materials which contain copolymers of unsaturated carboxylic acids and their esters

Country Status (9)

Country Link
US (1) US3862073A (enrdf_load_stackoverflow)
CA (1) CA987458A (enrdf_load_stackoverflow)
CH (2) CH895972A4 (enrdf_load_stackoverflow)
DE (1) DE2133351A1 (enrdf_load_stackoverflow)
FR (1) FR2144796B1 (enrdf_load_stackoverflow)
GB (1) GB1395782A (enrdf_load_stackoverflow)
IT (1) IT965879B (enrdf_load_stackoverflow)
NL (1) NL7209316A (enrdf_load_stackoverflow)
SE (1) SE393644B (enrdf_load_stackoverflow)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4442258A (en) * 1979-07-04 1984-04-10 Nitto Electric Industrial Co., Ltd. Water-soluble pressure-sensitive adhesive composition
US5621030A (en) * 1994-02-01 1997-04-15 Moore Business Forms, Inc. Printable release
US20050076810A1 (en) * 2002-08-13 2005-04-14 Mitteldeutsche Harstein-Industrie Ag Method and device for manufacturing a bitumen-bonded construction material mixture

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3062686A (en) * 1955-04-30 1962-11-06 Bayer Ag Process of treating textile with a copolymer and a cross-linking agent
US3090762A (en) * 1957-08-02 1963-05-21 Ciba Ltd Aqueous coating and impregnating preparations comprising acrylic resins
US3096524A (en) * 1961-04-11 1963-07-09 Williamson Dickie Mfg Company Process for improving crease-retention properties of cotton garments
US3116967A (en) * 1958-01-09 1964-01-07 Sun Chemical Corp Creaseproofing compositions for textiles
US3240740A (en) * 1959-06-24 1966-03-15 Bayer Ag Aqueous dispersions of self-crosslinking copolymers

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3062686A (en) * 1955-04-30 1962-11-06 Bayer Ag Process of treating textile with a copolymer and a cross-linking agent
US3090762A (en) * 1957-08-02 1963-05-21 Ciba Ltd Aqueous coating and impregnating preparations comprising acrylic resins
US3116967A (en) * 1958-01-09 1964-01-07 Sun Chemical Corp Creaseproofing compositions for textiles
US3240740A (en) * 1959-06-24 1966-03-15 Bayer Ag Aqueous dispersions of self-crosslinking copolymers
US3096524A (en) * 1961-04-11 1963-07-09 Williamson Dickie Mfg Company Process for improving crease-retention properties of cotton garments

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4442258A (en) * 1979-07-04 1984-04-10 Nitto Electric Industrial Co., Ltd. Water-soluble pressure-sensitive adhesive composition
US5621030A (en) * 1994-02-01 1997-04-15 Moore Business Forms, Inc. Printable release
US20050076810A1 (en) * 2002-08-13 2005-04-14 Mitteldeutsche Harstein-Industrie Ag Method and device for manufacturing a bitumen-bonded construction material mixture

Also Published As

Publication number Publication date
FR2144796B1 (enrdf_load_stackoverflow) 1976-05-14
FR2144796A1 (enrdf_load_stackoverflow) 1973-02-16
DE2133351A1 (de) 1973-01-18
CH561813A (enrdf_load_stackoverflow) 1975-05-15
NL7209316A (enrdf_load_stackoverflow) 1973-01-09
SE393644B (sv) 1977-05-16
GB1395782A (en) 1975-05-29
CA987458A (en) 1976-04-20
IT965879B (it) 1974-02-11
CH895972A4 (enrdf_load_stackoverflow) 1974-11-29

Similar Documents

Publication Publication Date Title
US3462296A (en) Fluorinated oil- and water-repellent copolymer and process for treating fibrous materials with said copolymer
US3378609A (en) Oil- and water-repellent compositions
US3544537A (en) Poly(perfluoroalkoxy)polyfluoroalkyl acrylate-type esters and their polymers
US2606810A (en) Treatment of wool-containing textile materials and products thereof
US4455342A (en) Acrylic resin dispersions
US2244703A (en) Water soluble salts of interpolymers containing methacrylic acid
US3645990A (en) Fluorinated oil- and water-repellent and dry soil resistant polymers
US3256230A (en) Polymeric water and oil repellents
US3459696A (en) Water-repellent compositions
US3361695A (en) Film-forming copolymers from acrylates, acrylic acid and n-methylolmethacrylamide
US3220869A (en) Process for improving textile fabrics
US3178380A (en) New copolymers, process for their preparation and their use
US3752783A (en) Water and oil repellent compositions containing fluoro resins and water soluble salt of guanidine
US3533977A (en) Organic solvent composition for textiles and process for its application
US3288740A (en) Process for the preparation of stable emulsions from nu-methylol substituted amides of acrylic acid or the ethers of such nu-methylolamides
US2763578A (en) Process of finishing cellulosic fabric and product resulting therefrom
US3125405A (en) Method of crease-proofing cellulosic
US3595944A (en) Oil- and water-repellent fluorine-containing compositions
US3535156A (en) Method of employing aqueous fluorocarbon concentrates in chlorinated solvent application to textiles
US3690942A (en) Stain release and durable press finishing using solution polymers
US3096524A (en) Process for improving crease-retention properties of cotton garments
US3521993A (en) Soil releasing textiles
US3862073A (en) Emulsifier compositions for creaseproofing textile materials which contain copolymers of unsaturated carboxylic acids and their esters
US3446761A (en) Stain-resistant article,and composition for preparing same
US3246946A (en) Method of crease-proofing cellulosic fabrics and fabrics obtained