US2536050A - Treatment of cellulosic textile materials and products thereof - Google Patents

Treatment of cellulosic textile materials and products thereof Download PDF

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US2536050A
US2536050A US78518847A US2536050A US 2536050 A US2536050 A US 2536050A US 78518847 A US78518847 A US 78518847A US 2536050 A US2536050 A US 2536050A
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melamine
fabric
weight
thermoplastic
methylated
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Jr Linton A Fluck
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Wyeth Holdings LLC
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS, OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS, OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/267Macromolecular 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
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS, OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39Aldehyde resins; Ketone resins; Polyacetals
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS, OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/39Aldehyde resins; Ketone resins; Polyacetals
    • D06M15/423Amino-aldehyde resins
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31855Of addition polymer from unsaturated monomers
    • Y10T428/3188Next to cellulosic
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20Coated 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
    • Y10T442/2369Coating or impregnation improves elasticity, bendability, resiliency, flexibility, or shape retention of the fabric
    • Y10T442/2393Coating or impregnation provides crease-resistance or wash and wear characteristics

Description

tatented Jan. 2, 1951 TREATMENT OF CELLULOSIC TEXTILE MATERIALS AND PRODUCTS THEREG F Linton A. l'luck, Jr., Norwalk, Conn., assignor to American Cyanamid Company,

New York,

N. Y., a corporation of Maine No Drawing. Application November 10, 1947, Serial No. 785,188

16 Claims.

This invention relates to the treatment of cellulosic textile materials and to the products thereof. Mo e articularly the invention is concerned with the production of cellulosic textiles. specifically cotton fabrics, having improved properties (e. g., better resistance to creasing or wrinkling) by a process which comprises impregnating the textile with a particular combination of impregnants within a definite range of proportions of each. Conditions also are so maintained that the amount of combined impregnants which are retained by the textile is kept within definite limits.

Generally described, my process of improvin the properties of cotton and other cellulosic textiles comprises impregnating such textiles with ,a combination of (1) a curable (more particularly heat-curable) product of partial reaction of ingredients comprising melamine and formaldehyde, e. g., dimethylol melamine, trimethylol melamine, the heat-curable or thermosetting alkylated, specifically methylated, methylol melamines, etc., which partial reaction product is at least partly soluble and preferably substant: ally completely soluble in Water, and (2) a film-iorming, substantially water-insoluble, thermopastic product of polymerization of a polymerizable mass including a lower alkyl acrylate, e. g., methyl acrylate, ethyl acrylate, npropyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec.-butyl acrylate, etc., or mixtures thereof with each other or with other monomers or partial polymers which are copolymerizable therewith to yield film-forming, substantially water-insoluble, thermoplastic copolymers or interpolymers. The products of (l) and (2) should be used in a weight ratio corresponding to form 1 to 3 parts of the latter for each part of the former. After the cellulosic textile material has been impregnated with the aforementioned combination of impregnants in any suitable manner, but preferably by treating the textile material, as by immersion, with a substantially homogeneous aqueous composition containing the mixed impregnants in dispersed or other form, the partial reaction product of 1) is cured in situ in intimate contact with the polymerization product of (2) to a substantially water-insoluble state. The total amount of the products of (1) and (2) that are applied to the cellulosic textile material is such that the finished textile contains from abouts to about 40%, more particularly from to 30%, by weight of the dry (net dry) textile, of a substantially washfast impregnant consisting of the product of (1) III-139.4)

2 in a cured or substantially water-insoluble state and the substantially water-insoluble product of (2).

The treatment of cellulosic textile materials with a water-soluble, curable methylated methylol melamine heretofore has been known and is described, for example, in Patent No. 2,339,203 of Harold W. Stiegler and Linton A. Fluck, Jr., issued January 11, 1944. It was also suggested prior to my invention that textile materials, including cotton textiles, be impregnated with various thermoplastic materials, among which polymers of unsaturated aliphatic aldehydes and polymeric esters of unsaturated aliphatic acids, e. g., polymeric methyl acrylate, specifically have been mentioned. In some cases it has been contended that such thermoplastic materials impart increased resistance to creasing or wrinkling to the textile, but, at least in the case of cotton fabrics or cloths, such contentions are inconsistent with available evidence. In general, a thermoplastic impregnant when applied alone to a cellulosic textile material, specifically a cotton fabric, in amounts such as are employed in practicing my invention merely imparts a permanent non-spring finish to the fabric. There is no substantial improvement, if any, in the resistance of the fabric to creasing or wrinkling, and in many cases the tendency of the treated fabric to crease or wrinkle is even greater than that of the untreated fabric.

When cotton fabrics are impregnated with a water soluble, curable methylated methylol melamine, e. g., in the form of an aqueous solution, and the treated fabric thereafter dried and heated to cure the impregnant to a substantially water-insoluble condition, the resistance of the fabric to shrinking and creasing is considerably increased. However, the tensile strength of the fabric is materially lowered by this treatment, the percentage loss in tensile strength in some cases being as much as 35% or more of that of the original fabric.

The present invention is a solution to the problem of imparting a higher degree of crease resistance to cotton textiles, and e pecially to mercerized cotton fabrics, than has been obtained with the prior treating agents and to effect this result while at the same time obviating or minimizing losses in the tensile strength of the and specifically cotton fabrics, can be rendered resistant to creasing and the losses in tensile strength either obviated or materially lessened by treating the fabric as briefly described in the first and second paragraphs of this specification and more fully hereafter. In. general, the degree of crease resistance imparted to the fabric is greater than that obtained by using only a curable methylated methylol melamine or other curable, water-soluble or -dispersible product of partial reaction of ingredients comprising melamine and formaldehyde. This was wholly unexpected and unpredictable, since the thermoplastic polymerization product alone does not impart markedcrease resistance, if any, to a cotton fabric. It also was surprising and unexpected that the thermoplastic polymerization product would obviate or decrease the loss in 'tensile strength which'normally results when a cotton textile is impregnated with a curable methylated methylol melamine, v or equivalent curable product of partial reaction of ingredients comprising melamine and formaldehyde, and thereafter dried and cured, since from the known properties of thermoplastic polymers and copolymers it would not be expected that such materials would co-act, physically or otherwise, with the methylated methylol melamine or equivalent material so that the embrittlement of the textile, as evidenced by a decrease in its tensile strength, would be obviated or minimized. v The impregnated cotton and other cellulosic textiles of my invention also are resistant to shrinking, as well as to wear and abrasion. The finish is durable and is not removed by washing in water. The hand may be varied considerably, for example, by varying the kind and amount of thermoplastic modifier employed and by variations in the impregnating and finishing operations. In some cases. it may be stiffer than that of fabrics containing a cured methylated methylol melamine alone, which is a characteristic that is desired in many types of cellulosic textiles.

The curable partial reaction products of ingredients comprising melamine and formaldehyde which are used in practicing my invention are at least partly soluble in water, the preferred reaction products being those which are substantially completely soluble therein, either in the form of a true solution or a colloidal dispersion. Examples of melamine reaction products that may be employed are those which comprise one or more polymethylol melamines, more particularly di-, tri-, tetra-, pentaor hexamethylol melamine or mixtures thereof. Such products may be produced in known manner by effecting reaction under neutral or alkaline conditions between melamine and an aqueous solution of formaldehyde in the ratio of 1 mol of the former to from 2 Lo 6 or more mols of the latter. To avoid the formation of the crystalline material which has lower water-solubility and to obtain the amorphous product of higher water solubility, the mass advantageously is maintained at a temperature not less than about 70 C. during the reaction.

In order to minimize polymerization of the monomer, it is usually desirable to keep the reaction temperature from exceeding about 90 C.

The curable, methylated or methyl alcoholreacted methylol melamines, moreparticularly methylated polymethylol melamines, are especially suitable for use in practicing my invention. They may be prepared, for example, by effecting reaction under acidic conditions between a polymethylol melamine and methyl alcohol in the ratio of 1 mol of the former to from 2 to 6 mols of the latter, depending upon the number of methylol groupings in the melamine derivative and the extent of methylation (or etherification) desired. The reaction is stopped before the product becomes hydrophobic, alkali is added in an amount at least sufficient to neutralize the reaction mass, after which the mass is dehydrated under vacuum. Advantageously the methylated methylol melamine, more particularly poly- (methoxymethyl) melamine, is prepared in a manner such as is disclosed and claimed in the copending application of Herbert J. West and William .T. Watt, Serial No. 568,780, filed December 18,1944. now Patent No. 2,529,856. Such methylated methylol melamines are miscible with water in all proportions at room temperature and are stable on storage at F. for at least two weeks.

The thermoplastic polymerization products are prepared by known methods. Although a polymer of a lower alkyl (e. g., methyl, ethyl, propyl, tert.-butyl, amyl, etc.) ester of acrylic acid may be used as the thermoplastic modifier, I prefer to employ copolymers or interpolymers of such esters (or mixtures thereof) with a suitable proportion of one or more other monomers which are compatible and copolymerizable therewith to yield a water-insoluble, fllm-forming thermoplastic copolymerization product which is flexible or pliable in film form. Illustrative examples of monomers which may be employed in the production of copolymers useful in practicing my invention are compounds different from the lower alkyl acrylate component and which contain a single CH2=C grouping, for instance: the monovinyl compounds (both aliphatic and armomatic), including the vinyl esters of saturated aliphatic monocarboxylic acids (e. g., vinyl acetate, vinyl propionate, vinyl butyrate, etc); the monovinylsubstituted cyclic compounds, for instance styrene and the various nuclearly substituted styrenes (e. g., the monoand dimethyl styrenes, the chloro, fluoro and other halogeno styrenes, the cyano styrenes, etc.), a-p-dimethyl styrene (isopropenyl toluene) and other a-substituted, nuclearly substituted styrenes, vinyl pyridines, vinyl thiophenes, vinyl fiuorenes, etc.; the vinyl and vinylidene halides, e. g., the chlorides, bromides and fluorides; acrylic acid, acrylonitrile and the amides of acrylic acid, e. g., acrylamide and the N-monoand -di-alky1 acrylamides (e. g., N- methyl acrylamide, N-diethylacrylamide, etc. alkacrylic compounds, including the acids, esters, nitriles and amides, e. g., methacrylic, ethacrylic, etc., acids, methacrylamide, ethacrylamide, etc., and the N-monoalkyl and -dialkyl substitution products thereof, methacrylonitrile, ethacrylonitrile and other hydrocarbon-substituted acrylonitriles, the methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, amyl, e.c., esters of methacrylic, ethacrylic, etc., acids; the allyl and methallyl esters of saturated monocarboxylic acids, e. g., allyl and methallyl acetates, propionates, laurates, etc.; and numerous other vinyl, vinylidene, acrylic and other compounds containing a single CH2=C grouping. In some cases compounds containing a plurality of CH2=C groups, e. g., 1,3-butadiene, may comprise the comonomer employed in forming the copolymer. Suitable compounds of this class are those which, like 1,3-butadiene, are compatible and copolymerizable with the lower alkyl acrylate to yield a water-insoluble, film-forming thermoplastic copolymerization product which is flexible or pliable in film form.

It will be understood, of course, by those skilled in the art that the particular monomeric material which is employed in producing the copolymer is so selected and is used in such a proportion with the lower alkyl acrylate, e. g., ethyl acrylate, as to obtain a film-forming material which, when applied to the cellulosic textile in combination with the curable melamine-formaldehyde reaction product, will impart to the treated textile the desired finish and hand.

Particularly good results have been obtained with copolymers of a lower alkyl acrylate, specifically ethyl acrylate, and styrene or acrylonitrfle. However, as has been mentioned previously, a polymer instead of a copolymer of a lower alkyl acrylate may be used as the thermoplastic modifier. Thus, I may employ the product of polymerization of a polymerizable mass containing, by weight, from 50 to 100% of a lower alkyl acrylate, specifically ethyl acrylate, and from 50 to 0% of a different monomer which is copolymerizable therewith and which contains a CH2=C grouping, specifically styrene or acrylonitrile. In some cases the monomeric material which is copolymerized with the monomeric lower alkyl acrylate may constitut as much as 90% by weight of the mixture of monomers, but usually I employ a thermoplastic modifier obtained by polymerization of a mixture containing, by weight, from 70 to 90% of the lower alkyl acrylate and from 30 to 10% of the other copolymerizable monomer. I prefer to use copolymers of, by weight, from '70 to 90% of ethyl acrylate and from 30 to 10% of styrene or acrylonitrile. The polymers and copolymers used in practicing my invention are either substantially water-insoluble per se or yield substantially water-insoluble compositions when the reactive melamine derivative is cured in intimate contact with the polymer or copolymer.

The thermoplastic polymerization products may be prepared in any suitable manner but advantageously are produced by emulsion polymerization (or copolymerization) technique, for example as described in the copending application of Edward. L. Kropa, Serial No. 636,279, now abandoned, .filed December 20, 1945, with particular reference to the emulsion copolymerization of styrene and certain acrylic esters.

The "curable, methylated methylol melamine, more particularly methylated polymethylol melamine, or other curable partial reaction product of ingredients comprising melamine and formaldehyde and the thermoplastic polymerization productare ordinarily, and preferably, applied to the cellulosic material in the form of an aqueous dis-- persion or emulsion containing the aforemen tionedingredients, e. g., in a concentration of from 8 to 40%, more particularly from 10 to 30%,

by weight thereon The reactive melamine resin may be in dissolved state and the thermoplastic modifier dispersed in the aqueous solution of the dissolved melamine resin. When the textile is impregnated with 100%, by weight of the dry' formaldehyde and to decrease the heating time, a suitable catalyst may be added to the aqueous dispersion. e. g., oxalic acid, acetic acid, phosphoric acid, diammonium hydrogen phosphate, ethyl ammonium phosphate, diammonium phthalate, ammonium chloride, zinc chloride, and others which are known to be catalysts for ouring such reaction products. The amount of catalyst may be varied as desired or as conditions may require, but ordinarily the catalyst is employed in an amount corresponding to from 0.5 to 5% by weight of the melamine derivative.

The curable methylated methylol melamine or other melamine derivative of the kinds aforementioned and thermoplastic polymerization product are employed in the ratio of, by weight, 1 part of the former to from 1 to 3 parts (preferably from 1 to 2 parts) of the latter. The thermoplastic modifier must be used in a weight ratio which is at least equal to that of the melamine derivative in order to obtain the results (e. g., better crease resistance, minimizing or obviating tensile strength losses, etc.) hereinbefore set forth. If a weight ratio of thermoplastic modifier to melamine derivative materially above 3 to 1 be employed,-the impregnated cloth is excessively weighted, usually has a non-drapey hand and is not satisfactory for use in applications (e. g., in dresses and other clothing) where the weight and feeling to th touch are important. Good results are obtained by using the curable melamine derivative and thermoplastic modifier in a weight ratio of approximately 1 to 1. or with a relatively small excess of the latter, e. g., up to 50% excess by weight of the thermoplastic additive.

The melamine derivative and thermoplastic polymerization product may be applied to the cotton fabric or other cellulosic textile material in various ways. For example, if the curable reaction product and thermoplastic modifier are applied in the form of an aqueous dispersion, the dry or substantially dry cellulosic fabric to be treated may be immersed in the dispersion. and then passed through pressure rolls or padders to secure uniform impregnation and a controlled removal of the excess dispersion. The fabric or other textile, however, may be impregnated by other methods, e. g., by spraying or by means of suitable boxes located on a mangle.

The term "aqueous dispersion as used generally herein with reference tothe aqueous composition containing the reactive melamine resin and thermoplastic modifier includes within its meaning aqueous dispersions in which the reactive melamine resin is present either dissolved in the aqueous phase in the form of a true solution or colloidal dispersed in the said phase.

The pick-up of aqueous dispersion by the cotton or other cellulosic material being treated should be adjusted so that the finished textile will contain from 8 to 40%, more particularly from 10 to 30%, by weight Of the dry textile, of the cured resin (e. g., cured methylated methylol melamine) admixed with the particular thermoplastic modifier employed in the ratio of, by weight, from 1 to 3 parts (preferably from 1 to 2 parts) of the latter for each part of the former. The amount of aqueous dispersion picked up by the cellulosic textile, that is, the so-called "wet pick-up," may be varied as desired or as conditions may require and may range, for example, from about 40 to about or more by weight of the dry textile depending, for example, upon the particular textile treated, method and conditions of treatment, concentration of solids in methylated polymethylol melamine.

the impregnating bath, amount of solids and properties desired in the finished textile, etc.

The wet, impregnated cotton fabric or' other cellulosic textile material is then dried and cured. The drying and curing temperatures may be varied considerably, but ordinarily temperatures within the range of about 200 F. to about 400 I".

' are employed. The impregnated fabric may be ployed) admixed with the thermoplastic poly-- merization product, e. g., polymeric ethyl acrylate a copolymer of ethyl acrylate and styrene or acrylonitrile, etc., to a substantially water-insoluble condition. 'The drying and curing operation is flexible and may be varied to suit ,the available equipment. Continuous methods are preferred. However, drying and curing also may be effected by framing the impregnated fabric to width, as on a pin tenter, drying the framed fabric, batching it upon a shell and then allowing it to stand hot for a period sumcient to complete the drying (if not entirely dried Previously) and to convert the solid impregnant in situ to a water-insoluble state. In some cases drying and curing for 2 r 3 hours at 200 F. may be required. Heating the dried fabric for 1 minute at 340 F. or for a shorter time at a higher temperature has effectively water-insolubilized the impregnant.

The finishing treatment usually consists in washing the treated textile, e. g., in an aqueous 150'-190 F. solution containing. by weight, from 0.1 to 0.2% of soapand 0.1% soda ash, followed by rinsing in hot water at the same temperature, drying and then calendering either hot or cold.

The process of the present invention may be used in treating both uncolored and colored goods. It is applicable to the treatment of both bleached and unbleached cotton goods, as well as mercerized cotton fabrics. Surprisingly, the results are generally better, especially in plant operations, on mercerized, more particularly scoured and mercerized or bleached and mercerized, materials than on unmercerized cotton textiles.

In order .that those skilled in the art better may understand how the present invention may be carried into effect, the following examples are given by way of illustration and not by way of limitation. All partsand percentages are by weight.

The methylated methylol melamine used in all of the examples was a substantially completely water-soluble, heat-curable or thermosetting This material is prepared by the following process: One mol of melamine is mixed with 3.3 mol's of aqueous 37% formaldehyde previously adjusted to a pH of approximately 8.0, the temperature being raised to 70 C. and maintained at this point until a clear solution is obtained. The solution powder is alkylated by admixture with twice its weight of 95% methanol containing 0.5% of oxalic acid crystals, based on the weight of the methylol melamine. The mixture is heated to 70 C. and held at this temperature for approximately minutes, or

7 parts of the latter.

until a clear solution is obtained, whereupon it is immediately neutralized by the addition of suillcient sodium hydroxide solution to raise the pH to' approximately 9.0. The neutralized reaction mass is then evaporated to 80% solids under reduced pressure so that the temperature does not rise above C.

EXALCPLEI hydrogen phosphate (curing catalyst) and hexamethylene tetramine (buffering agent) in the ratio of about-30 parts of the. former to about 4 The bath was made by diluting with water a composition comprising about 80% methylated methylol melamine and 20% water. and the resulting product was then stirred into an emulsion ofthe polymerization product.

Impregnation was carried out by soaking the fabric material for about V minute in the bath and squeezing the impregnated fabric through a padder so that the amount of liquid impregnant retained by the fabric .(so called "wet pick-up") was about 90% by weight of the dry fabric. The squeezed fabric was then heated for 6. minutes at 290 F. to dry the fabric and to cure the applied resinous composition, that is, curable methylated methylol melamine admixed with the particular polymerization product employed, to a substantially water-insoluble state.

The dried textile was then given a mild washing for 2 minutes in an aqueous 160 F. solution containing 0.1% soap and 0.1% sodium bicarbonate, followed by thorough rinsing in water at 160 F. and squeezing of the rinsed fabric. The

- rinsed'and squeezed fabric was then pressed dry on a flat bed electric press.

The fabrics employed in this example were x 80 cotton percale and mercerized cotton twill. The bath compositions each contained 30% by weight of solids, of which 10% of the bath composition was methylated methylol melamine and 20% was a thermoplastic polymerization product. For purpose of comparison a bath containing 10% by weight of methylated methylol melamine and no thermoplastic additive was included in the series of tests. The wet pick-up was about by weight of the dry fabric. The finished fabric contained about 27 by weight of the dry fabric, of solid, resinous impregnant of which A; was cured methylated methylol melamine resin and 3:; was thermoplastic modifier. Tables I and 11 show the thermoplastic materials employed and test data on the treated and lightly washed fabrics.

For purpose of comparison data also are given on the untreated fabrics. In these tables and in others which follow W" means 'warp" and F means filling. The total tensile strength (warp plus filling in pounds) is determined using the apparatus and method of the American Society for Testing Materials described under D-76-45.

Total T. B. Lpcrease Resistance (W plus F in cm.) in the tables refers to the total values of crease resistance of samples of the treated fabrics out along the warp and along the weft, using the apparatus and procedure developed by Tootal Broadhurt Lee Company. Ltd. (Manchester, England) and described in publications of this company. In this test, strips of fabric time the distance between theends of the sample is measured by means of a calibrated plane mir- EXAMPLE 2 Same as Example 1 with the exception that the bath contained 22%% solids (736% methylated methylol melamine plus 15% of the thermoplastic modifier). The wet pick-up was about 90% by weight of the dry cloth. Table III shows the thermoplastic materials employed and test data on the treated and lightly washed fabrics.

Table [IL-80 a: 80 cotton parcels-7% methylated methulol melamine and 15% thermoplastic modifier Tensile Total .Qg Loss Due 'r. B. L Test No. Thermoplastic Additive BtrgnFgtll; ggg mg, (Approx. (W lus F Percent) in cm.)

Untreated cot- 91 3.6

ton percale. 10 raw m1 1: d20'7styre 68 25 11 opo ymero e y acry a ean ne. 82 6.0 12 couplolymer 0180;, ethyl acrylate and 20% acryloni 88 3 6. 6

ror mounted directly below the sample. The EXAMPLE 3 T. B. L. crease-resistance rating is the distance in centimeters between the ends of the sample after it has been subjected to the treatment described above. The total T. B. L. crease-resistance values reported in the tables are in each case the sum of the values obtained upon testing a strip of the fabric out along the warp and another strip out along the weft or filling.

Same as Example 1 with the exception that the bath contained 15% solids (5% methylated methylol melamine plus 10% of the thermoplastic modifier). The wet pick-up was about 90% by 5 weight of the dry cloth. Table IV shows the thermoplastic modifiers employed and test data on the treated and lightly washed fabrics.

Table I.-80 :c 80 cotton impale-40% methylated methylol melamine and thermoplastic modifier Tensile Total Loss '1. n. L. Tensm Due to Crease Test No. Thermoplastic Additive Sa e n gh Treatment Resistance (Approx. (W plus F lbs) percent) in cm.

Untreated cotton 91 3. 6 perca e.

1-.-. None 69 24 5. 5 2 Copoiymer of 70% ethyl acrylate and styrene. 89 2 5. 7 3 Ctzpflolymer 0! 90% ethyl aerylate and 10% acryioni- 84 8 6.4

e. 4 Copolymer of 80% ethyl wylate and 20% aeryloni- 84 8 6. 9

r e. 5 Comiymer of ethyl acrylate and 30% acryloni- 84 8 6. 0

e. 6 Copol er of 79% ethyl acrylate and 21% dimethyl 88 3 6. 0

styrene.

Table II.-Mercerieed cotton twill-10 methylated methulol melamine and 20% thermoplastic modifier Tensile Total ig fl Loss Due 'r. e. L. Test No. Thermoplastic Additive su g n g g g' (Approx. plus F lbs) Percent) incm.)

Untreated mercerized 192 4 2 cotton twill. 7- None 153 20 6. 1 8 Polymeric ethyl aerylate 174 9 8. 4 9 Copoiymer of ethyl acrylate and 217% styl77 8 6. 4

rene.

Table IV.Mercerized cotton twlll-% metlwlated methylol melamine and thermoplastic modifier 'r I] 'r tal ggg o: '1. is. L. Test No. Thermoplastic Additive Strength g: gfi ifg @5 (Approx. (w plus F Percent) in cm Untreated mercerized 192 4.2

cotton twill. 13 None 166 14 5 4 14 Polymeric ethyl acrylate 104 1 a 5.9 15 Copolymer of 90% ethyl acrylate and 10% 178 7 ,1

' ene. 16 c p oiymer of 90% ethyl acrylate and 10% 188 2 5 g ecrylonitrile.

Gain. V I

EXAMPLE 4 fabric is approximately the same as that of the Same as Example 1 with the exception that 20 untreated fabric- 5 impregnating baths comprising, by weight, 10% of methylated methylol melamine and 10%, 15%, Same as Example 1 with the exception that im- 20% and of a copolymer of 80% ethyl acrylpregnating baths comprising, by weight, 10% oi.

ate and 20% acrylonitrile were used in treating 2 methylated methylol melamine and 10%. 15% samples of 80 x 80 cotton percale. In addition and 20% of a copolymer of 90% ethyl acrylate to the light wash of 2 minutes described in Exand 10% of styrene were used in treating samples ample 1, the treated samples also were given a of 136 x 60 mercerized cotton broadcloth. For l-hour wash using the same soap solution and purpose of comparison samples also were treated procedure except for the difference intime. The by immersion in baths containing, by weight, resin solids in the various baths are shown in 10% of methylated methylol melamine (with no Table V. The wet pick-up was about 90% by copolymer present), and 10%, 15% and 20% of weight of the dry cloth. the same copolymer (with no methylated methylol melamine present). The baths containing Table V' Resm solids bath methylated methylol melamine also contained a h t Th 1 U A llllng accelerator of the kind and in the perfig gfi i as centage mentioned under Example 1. The resin Test Mel solids in the various baths are shown in Table VII.

Per Cent Per Cent Description Table VII.Resm solids in bath 10 None. h l 40 10 10 gg gfi gigghg g} acry ate Math lated Thermoplastic Additive 10 15 D0. T t get I101 10 20 Do. (1mm 1o 25 Per Cent Per Cent Description Table VI shows test data obtained on the None 10 ggg ethylacrylm treated and washed samples. For purpose of None 15 1mg 10% sty comparison data also were given on the untreated None 20 10 10 Do. cotton percale. 10 15 Do. Table VI Total Tensile Total T -B L Table VIII ShOWS test data obtained on the W sltrellggthlb (g'leaie Rgsistanoe treated and washed samples. For purpose of TestNm pus m pus mcm') comparison data also are given on a sample of Li ht 1 Hr Li ht Hr the untreated mercerized broadcloth which had 5 was}; i been immersed in water and dried prior to testing for tensile strength and crease resistance.

Untreated 80 x 80 cotton cal 93 94 3.2 3.3 Table VH1 38 $1 2-2 83 1a 615 6:6 Total Tot 86 so 6.4 6.5 Tensile T. B. L. 88 86 Test No. Strength l esistance W Egg w plus F In all the foregoing examples each oi. the baths m also contained a curing accelerator of the kind 05 U H t d 1% 60 r d n and in the percentage mentioned under Exiks k and fi giff jlfi 126 m ample 1. 22 2;;

When the thermoplastic modifiers mentioned 128 in Tables I to IV, inclusive, are employed alone in treating cotton percale or mercerized cotton ms twill, that is, in the absence of methylated meth- 07 5.9 ylol melamine but with other conditions the same as when the methylated methylol melamine alone From the results of the above tests it will be or with the thermoplastic modifier is used, the noted that the combination of the thermoplastic total T. B. L. crease resistance of the impregnated copolymer and methylated methylol melamine 13 provides a treated cloth having a materially improved crease resistance as compared with the untreated cloth and much better than that shown by cloths which have been treated with the a '14 treatment herein described also may be applied to other textiles which are composed substantially or mainly of cellulose or regenerated-celluloses, e. g., linen, hemp, jute, ramie, sisal, cellulose methylated methylol melamine alone or with acetate rayons, cellulose acetate-butyrate rayons, various percentages of the thermoplastic copclysaponified acetate rayons, viscose rayons, cuprammer alone. Furthermore, the combination of monium rayons, ethyl cellulose, etc., and mixtures treating agents yields a treated cloth having a thereof with each other or with cotton. The higher tensile strength than that obtained by invention is particularly applicable to the treatusing methylated methylol melamine alone. ment of cotton fabric material, specifically mer- Similar results are obtained when other 00- cerized cotton cloth, and hence such textiles are polymers, e. g., copolymers of, by weight, 70-85% preferred for treating to improve their properethyl acrylate and 30-15% styrene, copolymers ties as hereinbefore described. of, by weight, 70-90% ethyl acrylate and 30-10% Thermoplastic polymerization products other acrylonitrile, etc., are substituted for the particuthan those comprising polymers and copolymers larethyl acrylate-styrene copolymer employed in of lower alkyl acrylates may be combined with a the above illustrative example. curable methylated methylol melamine or other Ex I I LE 6 curable product of partial reaction of ingredients Pounds comprising melamine and formaldehyde and the resulting combination or admixture may be used Aqueous methylated methylol melamine in treating cotton or other cellulosic textile masmds) terials in a manner similar to that hereinbefore Emulsion of a copolymer of 90% ethyl acrylate and 10 styrene solids) 300 set forth. Examples of such polymerization products are the polymers (or copolymers) obtained Curing accelerator as in Example 1 2 water Sumcient to make 100 gallons by polymerizing, alone or admixed 1th each other or with other monomers, the monomeric The above ingredients were mixed to yield an materials hereinbefore mentioned with particuimpregnflting b which had a D 0 This lar reference to compounds that may be copolybath was used in a plant run in treating four merized with a lower alkyl acrylate to yield codiiferent cellulosic fabric materials. The dry polymers suitable for use in practicing the presfabrics were passed continuously at 48 yards per ent invention. Such polymers and copolymers, minute through the bath (2 dips and 2 nips). however, are not equivalent, in the relationship in the bath temperature being 80 F. The impregwhich they are used, to the polymers and copolynated fabrics were dried in a pre-drier at 220 F. mers of the lower alkyl acrylates. and then in a tenter frame at 300 F., followed The terms textile and "textile material" as by heating for 1 minute at 340 F. to cure the used generally herein and in the appended claims methylated methylol melamine admixed with include within their meaning filaments, fibers, the ethyl acrylate-styrene copolymer to a subthreads, yarns, twisted yarns, etc., as such or stantially water-insoluble state. The fabrics in woven, felted or otherwise formed fabrics, were washed in 190 F. water containing 0.2% sheets, cloths and the like. soap and 0.1% sodium carbonate, followed by I claim: rinsing in clear water at 190 P. All but a cotton 1. The process of improving the properties of cord fabric (cloth No. 4) were finished by drying a cellulosic textile material which comprises imand cold calendering. The wet pick-up of the pregnating the said textile material with a com cloths averaged of the dry weight of the 4b bination of (1) a curable product of partial reindividual cloth. The amount of resin (cured action of ingredients comprising melamine and methylated methylol melamine plus copolymer) formaldehyde, said product being at least partly on the goods (after drying and curing) averaged soluble in water,and (2) a film-forming substance about 11.8% by weight of the dried fabric, of consisting essentially of a substantially waterwhich about 5% was cured methylated methylol insoluble, thermoplastic product of polymerizamelamine and the remainder ethyl acrylatetion of polymerizable monomers, said olymerizstyrene copolymer. able monomers consisting of, by weight, from 50% A description of the goods treated and the reto of a lower alkyl acrylate and up to 50% sults obtained are given in Table IX. of a different monomeric compound containing Table IX Cloth No. l Cloth N0. 2 Cloth No. 3 Cloth No. 4

Quantity treated 200yds 200yds 2fl0yds 3 0 yds. Descriptionand properties oicloths. Bleached andmer- Bleachedand mer- Bleached only. Bleachedand mcrcenzed,

cerized. cerized. 3-ply cor Color Stripes Stripes Stripes Brown and white. Blue and white. 0 100% cotton 100% cotton Ravon blend" 100%ootton. Filling do do 100% ootton- Do. PerI tcleit shrinkage of untreated 6.80 11.39 4.5.

0 Pgr centshrinkage of treated cloths 2.0 Tensile strength (in lbs.) oi un- 65143.4 741162-2- treated cloths (warp x filling). Tensile strength (in lbs.) of treated 66.2 x 42 4 69.2 x 250 60.0 x323.-." 77 x $2.5.

cloths (warp x filling). Total T. B. L. crease resistance of 5.2 4.8 5.3 6.0.

untreated cloths (W plus F in cm.) Total T. B. L. crease resistance of 6.3 6.2 6.5 6.9.

treated cloths (W plus F in cm.) Hand and finish of treated cloths... G0od... Good Good Very good.

Although I have described my invention hereinbefore with particular reference to the treatment of cotton, specifically cotton fabrics, the

a CH2=C grouping and which is copolymerizable with said acrylate, the products of (1) and (2) being employed in a weight ratio corre- 15 sponding to from 1 to 3 parts of the latter for each part of the former, and curing in situ the paitial reaction product of (1) in intimate contact with the polymerization product of (2) to a substantially water-insoluble state, the amount of the products of (1) and (2) applied to the said textilematerial being-such that the finished textile contains from 8 to 40%, by weightof the dry textile, of a substantially washfast impregnant consisting of the product of (1) in cured state and the product of (2).

2. A process as in claim 1 which includes the additional steps of washing the treated textile material in an aqueous soap-containing solution followed by rinsing in water; drying the washed and rinsed textile; and calendering thedried textile.

3. A process as in claim 1 wherein ethyl acrylate is the lower alkyl acrylate.

4. A process as in claim 1 wherein the com-.

late and the remainder styrene.

5. A process as in claim 1 wherein the component of (2) is a thermoplastic product of polymerization of a mixture of monomers of which not less than 50% by weight thereof is ethyl acrylate and the remainder acrylonitrile.

6. The process of rendering cotton fabric material resistant to creasing which comprises impregnating said fabric material with from 1-0 to 30%, by weight of the dry fabric, of a mixture comprising (1) a curable methylated methylol melamine and (2) a film-forming substance consisting essentially of a substantially water-insoluble, thermoplastic product of polymerization of polymerizable monomers consisting of, by weight, from 50 to 100% of ethyl acrylate and up to 50% of styrene, the components of (1) and (2) being present in the said mixture in a weight ratio corresponding to from 1 to 3 parts of the latter for each part of the former, and the said mixture being applied to the said fabric material in the form of a substantially homogeneous aqueous composition containing the same, and thereafter drying the impregnated fabric material and curing the methylated methylol melamine in the presence of the said polymerization product to a substantially water-insoluble state, thereby ob-' taining an impregnated cotton fabric material containing a substantially washfast solid impregnant and which has a higher tensile strength and a better crease resistance than the same cotton fabric material which has been similarly impregnated with an aqueous composition containing the same amount of the methylated methylol melamine of (1) but none of the thermoplastic material of (2) and thereafter has been similarly dried and cured.

7. A process as in claim 6 wherein the filmforming substance of (2) is a copolymer of monomers consisting of, by weight, from about 70% to about 90% of ethyl acrylate and from about 30% to about 10% of styrene.

8. A process as in claim 6 wherein the methylated methylol melamine of (l) and the film-forming substance of (2) are present in the aqueous composition in a weight ratio corresponding to from 1 to 2 parts of the latter for each part of the former, and the thermoplastic material of 2) is a copolymer of monomers consisting of, by weight, about 90% ethyl acrylate and about 10% styrene.

9. A process as in claim 6 wherein the cotton fabric material is a mercerlzed cotton cloth.

assapao 10. The process of rendering cellulosic fabric material resistant to creasing which comprises impergnating said fabric material with from 10 to 30%. by weight of the dry fabric, of a mixture comprising (1) a water-soluble methylated methylol melamine and (2) a thermoplastic material which is a copolymer of monomers consisting of by weight, from about 70% to about of ethyl acrylate and from about 30% to about 10% of styrene, the components of (1) and (2) being present in the said mixture in a weight ratio corresponding to from 1 to 2 parts of the latter for each part of the former, and the said mixture being applied to the said fabric material in the form M a substantially homogeneous aqueous composition containing the same, drying the impregnated fabric material and thereafter heat-v ing thedried material at'a temperature within the range of 250 F. to 400 F. to convert the said methylated methylol melamine admixed with the said copolymer to a'substantially water-insoluble condition.

11. A cellulosic textile material' which is resistant to creasing and which contains'from 8 to 40%, by weight of the dry textile material, of a combination of (1) a substantially water-insoluble, curedproduct which, prior to curing, is a curable product of partial reaction of ingredients comprising melamine and formaldehyde, said curable product being at least partly soluble in water, and (2) a film-forming substance consisting essentially of a substantially water-in oluble product of polymerization of polymerizable monomers, said polymerizable monomers consisting of, by weight, from 50%to of a lower alkyl acrylate and up to 50% of a different monomeric compound containing a CH2='C grouping and which is copolymerizable with said acrylate, the said polymerization product being present in the combination thereof with the said curable product, before curing of the latter, in a weight ratio corresponding to from 1 to 3 parts of the former for each'part of the latter.

12. A cotton fabric material which is resistant to creasing and which contains from 10 to 30%, by weight of the dry fabric material, of a combination of (l) a substantially water-insoluble, cured product which, prior to curing, is a curable methylatedmethylol melamine and (2) a filmforming substance consisting essentially of a substantially water-insoluble, thermoplastic product of polymerization of polymerizable monomers, said polymerizable monomers consisting of, by weight, from 50 to 100% of ethyl acrylate and up to 50% of styrene. thesaid polymerization product being present in the combination thereof with i the said curable methylated methylol melamine, before curing of the latter, in a weight ratio corresponding to from 1 to 3 parts thereof for each part of the said curable methylated methylol melamine, and the said cotton fabric material from 10 to 30%, by weight of the dry fabric material, of a combination of (1) a substantially water-insoluble, cured product which, prior to curing, is a water-soluble, curable methylated methyl melamine and (2) a thermoplastic material which is a copolymer of monomers consistin: of, by weight, from about 70% to about 90% asaaoao of ethyl acrylate and from about 30% to about of styrene, the said copolymer being present in the combination thereof with the said curable methylated methylol melamine, before curing of the latter, in a weight ratio corresponding to from 1 to 2 parts thereof for each part of the said curable methylated methylol melamine, and the said cellulosic fabric material having a higher tensile strength and a better crease resistance than the same cellulosic fabric material which has been similarly impregnated with the same amount of the same product of (l) but none of the thermoplastic material of (2).

14. A cellulosic fabric material which is resistant to creasing and which is impregnated with from about 10% to about 30%, by weight of the dry fabric material, of a combination of (1) a substantially water-insoluble, cured product which, prior to curing, is a water-soluble, curable methylated methylol melamine and (2) a copolymer of 90% ethyl acrylate and 10% styrene, the said copolymer being present in the combination thereof with the said curable methylol melamine, before curing of the latter, in a weight ratio corresponding to from 1 to 2 parts thereof for each part of the said curable methylated methylol melamine, and the said cellulosic fabric material having a higher tensile strength and a better crease resistance than the same celluloslc fabric material which has been similarly impregnated with the same amount of the same product of (1) but none of the copolymer of (2).

15. The method of rendering a cotton-containing fabric material resistant to shrinking and otherwise improving its properties which comprises immersing the material to be treated in an impregnating bath maintained at a temperature of about 80 F., said bath having a pH of about 'I and being constituted of Emulsion ofa copolymer of ethyl acrylate and 10% styrene (25% solids) Curing accelerator consisting essentially of a mixture of diammonium hydrogen ph osphate (curing catalyst) and hexamethylene tetramine (buffering agent) in the ratio of about 30 parts of the former to about 4 parts of the latter 2 Water Sufiicient to make gallons adjusting the wet pick-up of the fabric so that the amount of cured methylated methylol melamine plus the aforementioned copolymer of ethyl acrylate and styrene on the fabric (after drying and curing) averages about 11.8% by weight of the dried fabric, of which about 5% is cured methylated methylol melamine and the remainder ethyl acrylate-styrene copolymer; drying the wet impregnated fabric at a temperature up to 300 F. followed by further heating at a temperature of 340 F. for a brief period to advance the cure of the methylated methylol melamine in situ to a substantially water-insoluble state; washing the resulting fabric in an aqueous soapcontaining solution followed by rinsing in water; and drying the washed and rinsed fabric.

16. A method as in claim 15 which includes the additional step of cold calendering the dried fabric.

LINTON A. FLUCK, JR-

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,187,383 Ludwig Jan. 16, 1940 2,339,203 Stiegler Jan. 11, 1944 2,378,365 Swain et al June 12, 1945 2,499,653 Kropa Mar. 7, 1950 Certificate of Correction Patent No. 2,536,050 January 2, 1951 LINTON A. FLUGK, JR.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Column 1, line 38, for the Word form read from; column 2, line 26, for non-spring read non-springy; column 4, line 37, for armomatic read aromatic; column 6, line 57, r'or colloidal read colloidally; column 11, line 17 r'or were read are; line 6 1, after all insert of; column 16, line 3, for impergnating read impregnating; line 73, for methyl read mcthylol; and that the said Letters Patent should be read as corrected above, so that the same may conform to the record of the case in the Patent Oflice.

Signed and sealed this 27th day of March, A. D. 1951.

[smAt] THOMAS F. MURPHY,

Assistant Commissioner of Patents.

Certificate of Correction Patent No. 2,536,050 January 2, 1951 LINTON A. FLUGK, JR.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Column 1, line 38, for the Word form read from; column 2, line 26, for non-spring read non-springy; column 4, line 37, for armomatic read aromatic; column 6, line 57, r'or colloidal read colloidally; column 11, line 17 r'or were read are; line 6 1, after all insert of; column 16, line 3, for impergnating read impregnating; line 73, for methyl read mcthylol; and that the said Letters Patent should be read as corrected above, so that the same may conform to the record of the case in the Patent Oflice.

Signed and sealed this 27th day of March, A. D. 1951.

[smAt] THOMAS F. MURPHY,

Assistant Commissioner of Patents.

Certificate of Correction Patent No. 2,536,050 January 2, 1951 LINTON A. FLUCK, JR.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Column 1, line 38, for the Word form read from; column 2, line 26, for

non-spring read non spri ngy; column 42, line 37, for ar1no1natic" rea aromatw; column 6, hne 57, for colloidal read colloidal/Z1 column 11, hne

47, for were read are; hne 6%, after all 1nsert of; column 16, line 3, for

' line impergnating read impregnwtmg; 73, for methyl read mlethylol;

and that the said Letters Patent should be read as corrected the same may conf he Patent above, so that orm to the record of the case in t Office.

Signed and sealed this 27th day of March, A. D. 1951.

[SEAL] THOMAS F. MURPHY,

Assistant Commz'ssz'oner of Patents.

Claims (1)

1. THE PROCESS OF IMPROVING THE PROPERTIES OF A CELLULOSIC TEXTILE MATERIAL WHICH COMPRISES IMPREGNATING THE SAID TEXTILE MATERIAL WITH A COMBINATION OF (1) A CURABLE PRODUCT OF PARTIAL REACTION OF INGREDIENTS COMPRISNG MELAMINE AND FORMALDEHYDE, SAID PRODUCT BEING AT LEAST PARTLY SOLUBLE IN WATER, AND (2) A FILM-FORMING SUBSTANCE CONSISTING ESSENTIALLY OF A SUBSTANTIALLY WATERINSOLUBLE, THERMOPLASTIC PRODUCT OF POLYMERIZATION OF POLYMERIZABLE MONOMERS, SAID POLYMERIZABLE MONOMERS CONSISTING OF, BY WEIGHT, FROM 50% TO 100% OF A LOWER ALKYL ACRYLATE AND UP TO 50% OF A DIFFERENT MONOMERIC COMPOUND CONTAINING A CH2=C< GROUPING AND WHICH IS COPOLYMERIZABLE WITH SAID ACRYLATE, THE PRODUCTS OF (1) AND (2) BEING EMPLOYED IN A WEIGHT RATIO CORRESPONDING TO FROM 1 TO 3 PARTS OF THE LATTER FOR EACH PART OF THE FORMER, AND CURING IN SITU THE PARTIAL REACTION PRODUCT OF (1) IN INTIMATE CONTACT WITH THE POLYMERIZATION PRODUCT OF (2) TO A SUBSTANTIALLY WATER-INSOLUBLE STATE, THE AMOUNT OF THE PRODUCTS OF (1) AND (2) APPLIED TO THE SAID TEXTILE MATERIAL BEING SUCH THAT THE FINISHED TEXTILE CONTAINS FROM 8 TO 40%, BY WEIGHT OF THE DRY TEXTILE, OF A SUBSTANTIALLY WASHFAST IMPREGNANT CONSISTING OF THE PRODUCT OF (1) IN CURED STATE AND THE PRODUCT OF (2).
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ES185807A ES185807A1 (en) 1947-11-10 1948-11-03 A method of treating a cellulosic textile material
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US2739908A (en) * 1950-10-24 1956-03-27 Tootal Broadhurst Lee Co Ltd Method of impregnating textile fabric with resin
US2774687A (en) * 1952-09-03 1956-12-18 Nottebohm Carl Ludwig Process for the manufacture of porous flexible sheet material
US2780562A (en) * 1950-10-30 1957-02-05 Bayer Ag Process of decorating textile materials
US2819237A (en) * 1953-09-22 1958-01-07 American Cyanamid Co Aqueous dispersions of a copolymer of an ethylenically unsaturated monomer containing a primary hydroxy group and a thermosetting resin forming reaction product
US2862901A (en) * 1958-12-02 Aqueous solution of amino-aldehyde
US2864093A (en) * 1954-10-20 1958-12-16 Chicopec Mfg Corp Washable garment part
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US2987421A (en) * 1955-09-19 1961-06-06 Goodrich Co B F Composition for treating textile materials, method, and article produced thereby
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US2998326A (en) * 1956-04-04 1961-08-29 Nat Starch Products Inc Cleaning and sizing of fabrics
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US3068183A (en) * 1959-07-20 1962-12-11 Du Pont Coating compositions containing styrene, ethyl acrylate, methacrylic acid interpolymers
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US2862901A (en) * 1958-12-02 Aqueous solution of amino-aldehyde
US2739908A (en) * 1950-10-24 1956-03-27 Tootal Broadhurst Lee Co Ltd Method of impregnating textile fabric with resin
US2780562A (en) * 1950-10-30 1957-02-05 Bayer Ag Process of decorating textile materials
US2719831A (en) * 1951-01-20 1955-10-04 Basf Ag Production of pigmented prints and coatings on fibrous material
US2674741A (en) * 1951-03-21 1954-04-13 Cluett Peabody & Co Inc Shirt collar
US2908658A (en) * 1951-08-22 1959-10-13 Bayer Ag Printing paste and process of decorating textile therewith
US2774687A (en) * 1952-09-03 1956-12-18 Nottebohm Carl Ludwig Process for the manufacture of porous flexible sheet material
US2819237A (en) * 1953-09-22 1958-01-07 American Cyanamid Co Aqueous dispersions of a copolymer of an ethylenically unsaturated monomer containing a primary hydroxy group and a thermosetting resin forming reaction product
US2864093A (en) * 1954-10-20 1958-12-16 Chicopec Mfg Corp Washable garment part
US2987421A (en) * 1955-09-19 1961-06-06 Goodrich Co B F Composition for treating textile materials, method, and article produced thereby
US2998326A (en) * 1956-04-04 1961-08-29 Nat Starch Products Inc Cleaning and sizing of fabrics
US2994676A (en) * 1958-04-18 1961-08-01 Rohm & Haas Interpolymer of acrylonitrile, acrylamide, ethyl acrylate, and higher alkyl acrylate, and aqueous dispersions thereof
US3068121A (en) * 1958-09-29 1962-12-11 Johnson & Johnson Pressure sensitive adhesive tape and paper backing element impregnated with an acrylic ester copolymer and a water-dispersible aldehyde resin
US3030325A (en) * 1958-12-23 1962-04-17 Plax Corp Coating composition comprising an aqueous emulsion of vinylidene chloride and amine-aldehyde resin, method of coating polystyrene therewith, and article thus coated
US3220869A (en) * 1959-03-13 1965-11-30 Basf Ag Process for improving textile fabrics
US3068183A (en) * 1959-07-20 1962-12-11 Du Pont Coating compositions containing styrene, ethyl acrylate, methacrylic acid interpolymers
US3252932A (en) * 1959-08-10 1966-05-24 Minnesota Mining & Mfg Resin compositions comprising a segmented fluorine-containing copolymer and an aminoplast
US3087905A (en) * 1960-05-03 1963-04-30 American Cyanamid Co Durable fluorochemical-melamine resin textile finish
US3095320A (en) * 1960-10-24 1963-06-25 Geigy Chem Corp Low temperature pigment binder compositions for textile fabrics
US3214488A (en) * 1961-08-24 1965-10-26 American Cyanamid Co Composition comprising polymethyl ether of polymethylol melamine and copolymer of olefin and carboxyl monomer
US3316123A (en) * 1964-01-28 1967-04-25 American Cyanamid Co Paper carrying non-blocking flexible grease-proof vinyl polymer coating
US3448462A (en) * 1964-09-14 1969-06-10 Deering Milliken Res Corp Collar and cuff-like garment member and method of making it
US3425856A (en) * 1964-09-15 1969-02-04 Riegel Textile Corp Process for producing permanent creases and other desirable properties in textile fabrics
US3288553A (en) * 1964-09-21 1966-11-29 Beacon Mfg Co Process for treating napped fabrics
DE1294925B (en) * 1964-09-21 1969-05-14 Beacon Mfg Co A method for finishing a pile surface having textile fabrics
US3473948A (en) * 1966-09-29 1969-10-21 Burlington Industries Inc Method of improving resin finished textiles
US7063895B2 (en) 2001-08-01 2006-06-20 National Starch And Chemical Investment Holding Corporation Hydrophobically modified solution polymers and their use in surface protecting formulations

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DE936029C (en) 1955-12-01 grant
FR974362A (en) 1951-02-21 grant
GB664993A (en) 1952-01-16 application
ES185807A1 (en) 1949-02-01 application
BE485717A (en) grant

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